committee on materials and pavements...tech subcommittee 3a annual meeting 2020 page 1 of 5...

Tech Subcommittee 3a Annual Meeting 2020 of 5

COMMITTEE ON MATERIALS AND PAVEMENTS

Meeting (Annual or Mid-Year) Annual Date August 5, 2020 Scheduled Time 11:00-12:30 EST Technical Subcommittee & Name TS 3a Hydraulic Cement and Lime Chair Name and (State) John Staton - MI Vice Chair Name and (State) Brett Trautman - MO Research Liaison Name and (State) Vacant

I. Introduction and Housekeeping

II. Call to Order and Opening Remarks

A. Brief Summary of Activities

III. Roll Call of Voting Members

Present Member Name State Present Member Name State ☒ John Staton MI ☐ Russell Thielke NY ☒ Brett Trautman MO ☒ A. Brown MS ☒ Brian Egan Mike Doran TN ☐ Clement Fung MA ☒ Richard Barezinsky KS ☒ Kurt Williams WA ☒ Scott George Steven Ingram AL ☐ Paul Farley WV ☒ Daniel Miller OH ☐ Brian Ikehara HI ☒ Jose Lima RI ☒ Curt Turgeon MN ☒ Kenny Seward OK ☒ Jose L. Armenteros FL ☐ Robert Lauzon CT ☒ Richard Bradbury ME ☒ Nicholas R. Van Den Berg VT ☒ Todd Wittington NC ☒ Joseph Robinson Dave Kuniega PA ☒ Anne Holt ON ☒ Changlin Pan NV ☒ Andy Naranjo TX ☒ Charles Babish VA ☒ James Krstulovich IL ☐ Richard Douds Monica Flournoy GA ☒ Jim Reilman IN ☐ Justin Morris LA ☐ ☒ Merrill Zwanka SC ☐

Quorum Rules Met? Annual Meeting: Simple majority of voting members (☒y/ ☐n)

A. Review of Membership (New members, exiting members, etc.)

IV. Approval of Technical Subcommittee Minutes – Attachment A

Motion to approve the mid-year meeting as presented: ME Second by: OK No discussion, motion passed. Meeting minutes were accepted.

V. Old Business

A. Outstanding items from Mid-Year Meeting 1. 2019 Ballot Items to Publications

Tech Subcommittee 3a Mid-Year Meeting 2020 of 5

B. Technical Subcommittee Ballot (May 27 – June 17, 2020) COMP_TS3a-20-01 – Attachment B 1. M85 – Standard Specification for Portland Cement, Change 1.1.1 on Type I cements 2. M85 – Standard Specification for Portland Cement, Clarification of Bogue Phase Adjustments 3. M240 – Standard Specification for Blended Hydraulic Cement, Add Type HE Blended Cement 4. M240 – Standard Specification for Blended Hydraulic Cement, Add an example mill test report 5. M240 – Standard Specification for Blended Hydraulic Cement, Permit Air Jet Sieving 6. T106 – Standard Method of Test for Compressive Strength of Hydraulic Cement Mortar (Using 50-

mm or 2-in. Cube Specimens), Fixed water for Type IL cements 7. T105 – Standard Method of Test for Chemical Analysis of Hydraulic Cement, Revisions to subsection

7.3.1 8. M201 – Standard Specification for Mixing Rooms, Moist Cabinets, Moist Rooms, and Water Storage

Tanks Used in the Testing of Hydraulic Cements and Concretes, Revisions

TS Ballot # Standard

Results (Affirm/Neg/NV) Comments Action

1 M85 27/0/3 None No Action Required: motion to move to full committee ballot: MN; second by ME no discussion

2 M85 27/0/3 None No Action Required: motion to move to full committee ballot OH; second by NC

3 M240 27/0/3 None No Action Required: motion by KS; OK seconds moves to committee ballot

4 M240 27/0/3 Vermont, Illinois Resolve Comments: the harmonization TF is looking for clarification on nomenclature surrounding certification/mfg certification OH motion to send to COMP ballot; WA seconds

5 M240 27/0/3 Tennessee Resolve Comments: motion to carry to a full committee ballot MN; second by KS. No discussion, motion carries

6 T106 27/0/3 None No Action Required. Motion to move to COMP ballot ME; second by TX. No discussion and moves to COMP ballot.

7 T105 27/0/3 Washington State Resolve Comments. Discussion about timing of paper dissolution based on comments from FL. Fused pellet discussion usage discussed in open discussion session. Motion to move to COMP ballot by ME; Second by SC. No discussion.

8 M201 27/0/3 None No Action Required. Motion to move to COMP ballot by MN; second by OH. No discussion.

Comment from NRMCA: Revision to M201 Sec 6.1 does not seem to be correct where the control of RH seems to be changed to be optional. TN (steward) will investigate this issue. CCRL could have an issue with this revision. Until this particular issue is resolved, the COMP ballot will be submitted with the original language used in Sec 6.1. All of the other changes will be submitted to COMP ballot.


C. Task Force Reports 1. TF 09-1 – Harmonization Task Group (JAAHTG) – Naranjo (TX) Just a few membership changes with

new NY representation. The comments from the recent TS ballots were covered during the ballot items. a. Comment about certification nomenclature is going to be covered and balloted next year

potentially. b. Looking at autoclave expansion tests and what they are really telling us – might look at some

potential changes to the testing requirements. c. FL: Can the harmonization group bring the maceration of filter paper in T105 to ASTM C114?

Paul Tennis can bring to the attention of the appropriate ASTM subcommittee.

The chair thanked the harmonization task forces for all their work and leadership.

VI. New Business

A. AASHTO Re:source/CCRL/NTPEP 2. CCRL will be resuming their inspections virtually 3. Matt Bluman is working on a survey regarding use of Datamine and will be sent out soon.

B. Presentation by Industry/Academia None

C. Revisions/Work on Standards for Coming Year 4. T 105 Discussion regarding rolling fused pellets in with the pressed pellets. OK would like to use

fused pellets and proposes a change for the coming year. MO said that the newer machines use fused pellets and that this standard may need updating to keep up with technology. MO (steward) will draft some wording in the procedure as well as a draft definition for fused vs pressed specimens. d. ME, FL, NE agree that there needs to be some adjusted wording e. FL: also, requests adding use of porcelain crucible f. PA – proposed having definitions between fused and pressing to distinguish between powder

that has been pressed and a fused glass bead, FL agrees. g. Motion to move this as a concurrent ballot to include fused pellets as an option as well as

including a definition of fused pellets and pressed pellets by MN; second by ME. No objections. Discussion noted above.

D. Review of Stewardship List – Attachment C 5. There are many standards in need of stewardship. Please get in touch with John or Brett if you

would like to be a steward. h. Prior to the meeting GA volunteered for M303 and VT volunteered to steward T192 i. RI will volunteer to steward T131 and T137 j. James from IL will take Normal Consistency and Air. k. OK will volunteer to steward of T303

E. Proposed New Standards None

F. NCHRP Issues Amir mentioned it has been awhile since this technical subcommittee has submitted a research problem statement. Research problem statements are due by November 2, 2020.

G. Correspondence, Calls, Meetings None

H. Proposed New Task Forces None


I. Fall Reconfirmation/Equivalency Standards There are no reconfirmations this coming year. There are four equivalency standards to be reviewed this year.

J. New TS Ballots Not aware of any at this time.

VII. Open Discussion

A. Awards and Accomplishments None

B. Volunteer for Research Liaison Chair mentioned the Research Liaison position is currently vacant. If interested in serving as the Research Liaison for this technical subcommittee, please contact John or Brett

C. Other l. Should the new ACI cement tester certification be a requirement for testing cement? Mr.

Tennis suggests maybe taking this up again when the industry is a bit more robust. Colorado spoke to the high quality of the ACI course and how useful it was for his colleagues.

a. Concern about rolling a personnel qualification into a test method was expressed. It was suggested to use personnel certifications as part of a contract or qualification rather than putting in a test method

6. Mark Felag and the TS recognized the Task Force and John Melander for his hard work in keeping this task force going through the last 17 years.

VIII. Adjourn


TS Meeting Summary

Meeting Summary Items Approved by the TS for Ballot (Include reconfirmations.)

Standard Designation Summary of Changes Proposed Ballot Type

M 85 Change 1.1.1 on Type I cements ☐TS ☒COMP ☐CONCURRENT M 85 Clarification of Bogue Phase Adjustments ☐TS ☒COMP ☐CONCURRENT

M 240 Add Type HE Blended Cement ☐TS ☒COMP ☐CONCURRENT

M 240 Add an example mill test report ☐TS ☒COMP ☐CONCURRENT

M 240 Permit Air Jet Sieving ☐TS ☒COMP ☐CONCURRENT

T 105

Revisions. Comment to include fused pellets (beads) will not be added to revision due to post-meeting concerns. Fused pellet issue will be discussed at later date. ☐TS ☒COMP ☐CONCURRENT

T 106 Fixed water for Type IL cement ☐TS ☒COMP ☐CONCURRENT

M 201

Moist/Moist/curing/Storage Room revisions. The RH issue in Section 6.1 will need to be investigated prior to submitting the ballot. ☐TS ☒COMP ☐CONCURRENT

T 129 ASTM Equivalency ☐TS ☐COMP ☒CONCURRENT



M 216 ASTM Equivalency ☐TS ☐COMP ☒CONCURRENT

☐TS ☐COMP ☐CONCURRENT New Task Forces Formed Task Force Name Summary of Task TF Member Names and (States)

Research Proposals (Include number/title/states interested.)

Other Action Items

Tech Subcommittee 3a Mid-Year Meeting 2019 Page 1 of 7

Attachment A

COMMITTEE ON MATERIALS AND PAVEMENTS

Meeting (Annual or Mid-Year) Mid-Year

Date Thursday, November 7, 2019

Scheduled Time 11:00-12:00

Technical Subcommittee & Name TS 3a, Hydraulic Cement and Lime

Chair Name and (State) John Staton (MI)

Vice Chair Name and (State) Brett Trautman (MO)

Research Liaison Name and (State) Vacant

I. Introduction and Housekeeping

II. Call to Order and Opening Remarks - Staton

A. Brief Summary of Activities

III. Roll Call of Voting Members – Trautman

Present Member Name State Present Member Name State ☒ John Staton MI ☐ Russell Thielke NY

☒ Brett Trautman MO ☒ James Williams III – Adam Browne MS

☐ Brian Egan – Mike Doran TN ☐ Mark Brum MA

☒ Richard Barezinsky KS ☒ Kurt Williams Joe Devol, Garrett Webster, Erica Legaspi

WA

☐ Scott George AL ☐ Paul Farley WV

☒ Daniel Miller OH ☐ Brian Ikehara HI

☐ Jose Lima RI ☐ Curt Turgeon MN

☒ Kenny Seward OK ☒ Harvey DeFord, Awilda Merced FL

☒ Robert Lauzon CT ☒ Richard Bradbury ME

☒ Mladen Gagulic - Nick Van Den Berg

VT ☐ Todd Wittington NC

☐ Joseph Robinson PA ☐ Becca Lane ON

☐ Darin Tedford NV ☐ Andy Naranjo TX

☐ Charles Babish VA ☒ James Krstulovich IL

☐ Monica Flourenoy GA ☐ Bill Lawrence UT

☐ Justin Morris LA ☒ Jim Reilman IN

Quorum Rules Met?

Mid-Year Meeting: Voting members present (☒y/ ☐n)

A. Review of Membership (New members, exiting members, etc.)

IV. Approval of Technical Subcommittee Annual Meeting Minutes – Attachment A

a. Motion to approve annual meeting minutes from: OK made motion to accept the annual meeting

minutes as they exist. OH second. No discussion. Motion past approving meet minutes as is.


V. Old Business

A. Outstanding items from Annual Meeting

B. COMP Ballot Items (Include any ASTM changes/equivalencies, including ASTM standards’ revision years.)

COMP Ballot # Standard

Results (affirm/neg/NV) Comments/Negatives Action

19-02 M85 45/0/6 No Comments No Action Required

M240 45/0/6 KS, Penn, TN - Comments Investigate comments

T105 45/0/6 AR, OR, Penn Comments Investigate comments

T131 45/0/6 VA Comment Investigate comments

T153 45/0/6 Penn Comment Investigate comments

T186 45/0/6 OR, VA Comments Investigate comments

M240:

KS - ASTM C114 is not referenced in Section 2 of this standard. It seems that we usually include the whole name (ASTM C114) when we reference an ASTM document in an AASHTO standard.

Penn - Editorial comment:1) In Section 15.6, revise from "as determined using C114" to "as determined according to ASTM C114".

TN - Comment- Should section 15.6 reference AASHTO T 105 instead of ASTM C114 especially if the harmonized version (Ballot #3) is affirmed. The intent was to reference the AASHTO version but was inadvertently not included on the ballot. There was discussion about the use of the phrase "as determined using" and "as detemined according to" in the AASHTO vs ASTM standards. None of the members present expressed a preference which phrase to utilize.

T105:

AR - Section 3.1.2.1 - space is missing between evaporation and Section 3.1.2.2. - the word “removed” is missing

“…after which they are removed by an acid……” T 105 continues to carry an error in Section 23.2.2 when it

references neutralizing the acid solution with NH4OH as described in 15.3.1. This reference should be to 23.2.1.

Section 15.3.1. is the acidification of the filtrates by the addition of HCl. This comment needs be reviewed

because there is a reference error in the standard. The standard is referencing the wrong section. MO will review

this comment along with the others.

FL proposed a change to the standard for future consideration. Currently, Section 7.3.1 requires adding

the filter paper and contents to a beaker followed by adding 100 mL of NaOH to macerate the paper. FL has

experienced issues with the filter paper floating in the solution. They propose adding a small amount of NaOH, to

the beaker then added the filter paper to be macerate. This would then be followed by adding the rest of the

NaOH solution to the beaker.

This topic will require some additional discussion or the possible formation of a task force to address

this propose change. MO (as steward of the standard) volunteered to take the information from FL and begin

discussion on this topic. Awilda Merced will be the point of contact for FL. This could be a TS ballot come spring

pending the results of the discussion and investigation.

OR - There is a missing space between "evaporationand" section 3.1.2.1.- Missing the word "removed" in section 3.1.2.2.-"Large" should be "larger" in section 3.1.2.3-"for"should be "from" in section 3.1.2.3


Penn - Editorial comments:1) In Section 3.1.2.1, add a space between the words "evaporation" and "and".2) In

Section 3.1.2.2, 2nd line, the text "'after which they are by an acid absorbent or synthetic resin" does not read

well. Perhaps add something after the word "are" such as "passed".

T131:

VA - Paragraph 9.1 states temp of mixing room to be 23±3°C but both AASHTO M201 (listed as reference) and ASTM C511 (not listed) state 23±4°C. May want to consider editing for consistency if appropriate. Moving forward as an editorial change. This was considered mis-typed.

T153:

Penn - Editorial comment:1) In Section 3.1.1, suggest revising from "refer to Terminology ASTM C125 and C219"

to "refer to ASTM C125 and ASTM C219".

T186:

OR - "Foir" should be "for" (3rd "for" in the note) in section 6.8 Note 1.

VA - Paragraph 9.1 states temp of mixing room to be 23±3°C but both AASHTO M201 (listed as reference) and

ASTM C511 (not listed) state 23±4°C. May want to consider editing for consistency if appropriate.

This will be a TS ballot in the Spring or will be brought to the annual meeting for a vote for concurrent ballot in

the fall. This is considered a techinical change since adding a reference from another standard. This was

considered adding technical content to the standard.

C. Reconfirmation Ballots

Reconf. Ballot # Standard

Results (affirm/neg/NV) Comments/Negatives Action

COMP TS3A-19-04

M152 21/0/6 No Comments No Action Required

M201 21/0/6 No Comments No Action Required

R71 21/0/6 No Comments No Action Required

T137 21/0/6 No Comments No Action Required




D. Task Force Reports

Task Force # Title Members Status/Update

TF 09- 1 Harmonization Task Group Update

Andy Naranjo (TX) Update from John Melander – went over AASHTO and ASTM ballots. Both items passed and will be going into the 2019 standard. List of new business items to consider: 2 on M85 / C150


Task Force # Title Members Status/Update

2 on M240 / C595 There’s an ASTM meeting of Committee C01 in December 2019. Next TF meeting is scheduled for January 2020.

VI. New Business

A. AASHTO re:source/CCRL/NTPEP (Observations from assessments, as applicable.)

1. AASHTO re:source is working on updating the accreditation directory to list some of the standards differently. A survey will be sent to the states to get an idea of how standards can be better shown on the directory (specifically involving concrete, cement, masonry)

B. Presentation by Industry/Academia

2. None

C. Revisions/Work on Standards for Coming Year - Attachment B1 and B2

Standard # Title Task/Summary Assigned to

M201 Mixing Room, Moist Cabinets, Moist Room, and Water Storage Tanks Used in the Testing of Hydraulic Cements and Concretes

TNDOT submitted proposed revisions after the Annual Meeting that the Chair considered to be beyond the scope of editorial.

TN/Chair – attachment includes specific changes to standard. These changes may go to TS ballot in the spring or ahead of the annual meeting after the newest M 201 has been published in April.

D. Review of Stewardship List - Attachment C (List of subcommittee’s standards flagging those requiring action; include as separate attachment.)

3. If you are interested in becoming a steward of the standard, please get in touch with John or Brett.

E. Proposed New Standards

4. None

F. NCHRP Issues

5. None

G. Correspondence, Calls, Meetings

6. Nothing new outside of what was already discussed

H. Proposed New Task Forces (Include list of volunteers to lead and/or join TF.)

7. It may be determined later by Brett Trautman (MO – T105 Steward) and Awilda Merced (FL) whether a TF is necessary for T 105. They will investigate the issue with their technical staffs and report to the Chair on their findings. No other task forces were formed at this time.

I. New TS Ballots

1. M201 - Mixing Room, Moist Cabinets, Moist Room, and Water Storage Tanks Used in the Testing of Hydraulic Cements and Concretes.

VII. Open Discussion

No open discussion


VIII. Adjourn

11:48 EST


TS Meeting Summary

Meeting Summary

Items Approved by the TS for Ballot (Include reconfirmations.)

Standard Designation Summary of Changes Proposed Ballot Type

M 201

Based on TN’s suggestions for revisions. This will be balloted in the spring based on the newest revision of M 201 to be published in April ☒TS ☐COMP ☐CONCURRENT

T 105 Possibly balloting based on the results of MO’s investigation into wording as well as solvent (pending) ☒TS ☐COMP ☐CONCURRENT

T 186 Referencing M 201 into the standard ☐TS ☐COMP ☒CONCURRENT

☐TS ☐COMP ☐CONCURRENT








New Task Forces Formed

Task Force Name Summary of Task TF Member Names and (States)

Research Proposals (Include number/title/states interested.)

Other Action Items


Attendance list as generated by GoToWebinar:

Last Name First Name Email Address

Barezinsky Rick [email protected]

Bradbury Rick [email protected]

DeFord Harvey [email protected]

DeVol Joe [email protected]

Doran Michael [email protected]

Felag Mark [email protected]

Fragapane Ryan [email protected]

Holter Pete [email protected]

Innis Al [email protected]

Johnson Brian [email protected]

Krstulovich James [email protected]

Lauzon Bob [email protected]

Legaspi Erica [email protected]

MERCED AWILDA [email protected]

Melander John [email protected]

Miller Dan [email protected]

Reilman Jim [email protected]

Seward Kenny [email protected]

Staton John [email protected]

Tennis Paul [email protected]

Trautman Brett [email protected]

Van Den Berg Nick [email protected]

browne adam [email protected]

Babish Andy [email protected]

Hall Chris [email protected]

Attachment B

Technical Subcommittee Ballot (May 27 – June 17, 2020)

COMP_TS3a-20-01

1. M85 – Standard Specification for Portland Cement, Change 1.1.1 on Type I cements 2. M85 – Standard Specification for Portland Cement, Clarification of Bogue Phase Adjustments 3. M240 – Standard Specification for Blended Hydraulic Cement, Add Type HE Blended Cement 4. M240 – Standard Specification for Blended Hydraulic Cement, Add an example mill test report 5. M240 – Standard Specification for Blended Hydraulic Cement, Permit Air Jet Sieving

6. T106 – Standard Method of Test for Compressive Strength of Hydraulic Cement Mortar (Using 50-mm or 2-in. Cube Specimens), Fixed water for Type IL cements

7. T105 – Standard Method of Test for Chemical Analysis of Hydraulic Cement, Revisions to subsection 7.3.1

8. M201 – Standard Specification for Mixing Rooms, Moist Cabinets, Moist Rooms, and Water Storage Tanks Used in the Testing of Hydraulic Cements and Concretes, Revisions

Item #: TS 3a_20_01 Description: Revision of AASHTO M 85, Change 1.1.1 on Type I cements Rationale: The phrase “general use” is used to describe hydraulic cements without special properties. Its use to describe Type I cements is appropriate and would improve communication with readers of the standard. This ballot item is based on AASHTO M 85-20, and includes changes approved on prior ballots. Only additions to text shown in underline font and deletions shown in strikethrough font are being balloted. Other text is included for information only. Where necessary, tables, figures, notes, footnotes, and section numbers will be renumbered editorially. This proposal has been developed by TS 3a TF09-1, the Joint AASHTO-ASTM Harmonization Task Force, and a parallel proposal is being considered by ASTM Committee C01 for ASTM C150. Please note this proposal has 2 pages. Detailed Changes:

Standard Specification for

Portland Cement AASHTO Designation: M 85-201

Technical Subcommittee: 3a, Hydraulic Cement and Lime

Release: Group 1 (April)

ASTM Designation: C150/C150M-20

American Association of State Highway and Transportation Officials 555 12th Street NW, Suite 1000 Washington, DC 20004

TS-3a M 85-1 AASHTO


Portland Cement

AASHTO Designation: M 85-201




1. SCOPE

1.1. This specification covers ten types of portland cement as follows (see Note 1):

1.1.1. Type I—For general use, when the special properties specified for any other type are not required;

1.1.2. Type IA—Air-entraining cement for the same uses as Type I, where air entrainment is desired;

1.1.3. Type II—For general use, more especially when moderate sulfate resistance is desired;

1.1.4. Type IIA—Air-entraining cement for the same uses as Type II, where air entrainment is desired;

1.1.5. Type II(MH)—For general use, more especially when moderate heat of hydration and moderate sulfate resistance are desired.

1.1.6. Type II(MH)A—Air-entraining cement for the same uses as Type II(MH), where air entrainment is desired.

1.1.7. Type III—For use when high early strength is desired;

1.1.8. Type IIIA—Air-entraining cement for the same use as Type III, where air entrainment is desired;

1.1.9. Type IV—For use when low heat of hydration is desired; and

1.1.10. Type V—For use when high sulfate resistance is desired. Note 1—Some cements are designated with a combined type classification, such as Type I/II, indicating that the cement meets the requirements of the indicated types and is being offered as suitable for use when either type is desired.

1.2.

1 In essential equivalence with ASTM C150/C150M-2021.

Item #: TS 3a_20_02 Ballot Action: Revision of AASHTO M 85, Clarification of Bogue Phase Adjustments Rationale: To improve clarity of existing requirements, it is proposed that Section A1.6.2 be revised to note that the adjusted Bogue phase composition is used in calculations that use those values. This impacts the so-called “heat index,” C3S+4.75C3A, and the sum of tetracalcium aluminoferrite and twice the tricalcium aluminate (C4AF+2(C3A)) or solid solution (C4AF+C2F). The final sentence of A1.6.1 is proposed to be moved to A1.6.3 to make it clearer that it is not part of Note A1.3. This ballot item is based on AASHTO M 85-20, and includes changes approved on prior ballots. Only additions to text shown in underline and deletions shown in strikethrough font are being balloted. Other text is included for information only. Where necessary, tables, figures, notes, footnotes, and section numbers will be renumbered editorially. This proposal has been developed by TS 3a TF09-1, the Joint AASHTO-ASTM Harmonization Task Force, and a parallel proposal is being considered by ASTM Committee C01 for ASTM C150. Please note this proposal has 4 pages. Detailed Changes:


Portland Cement AASHTO Designation: M 85-201





TS-3a M 85-1 AASHTO

ANNEX A

(Mandatory Information)

A1. CALCULATION OF POTENTIAL CEMENT PHASE COMPOSITION

A1.1. All values calculated as described in this annex shall be rounded according to ASTM E29. When evaluating conformance to a specification, round values to the same number of places as the corresponding table entry before making comparisons. The expressing of chemical limitations by means of calculated assumed phases does not necessarily mean that the oxides are actually or entirely present as such phases.

A1.2. When expressing phases, C = CaO, S = SiO2, A = Al2O3, F = Fe2O3. For example, C3A = 3CaO·Al2O3. Titanium dioxide and phosphorus pentoxide (TiO2 and P2O5) shall not be included with the Al2O3 content. See Note A1. Note A1—When comparing oxide analyses and calculated phases from different sources or from different historic times, be aware that they may not have been reported on exactly the same basis. Chemical data obtained by Reference and Alternate Test Methods of T 105 (wet chemistry) may include titania and phosphorous as alumina unless proper correction has been made (see T 105), while data obtained by rapid instrumental methods usually do not. This can result in small differences in the calculated phases. Such differences are usually within the precision of the analytical methods, even when the methods are properly qualified under the requirements of T 105.

A1.3. When the ratio of percentages of aluminum oxide to ferric oxide is 0.64 or more, the percentages of tricalcium silicate, dicalcium silicate, tricalcium aluminate, and tetracalcium aluminoferrite shall be calculated from the chemical analysis as follows:

(A1.1)

(A1.2)

(A1.3)

(A1.4)

When the alumina-ferric oxide ratio is less than 0.64, a calcium aluminoferrite solid solution (expressed as ss(C4AF + C2F)) is formed. No tricalcium aluminate will be present in cements of this composition. Dicalcium silicate shall be calculated as in Equation A1.2. Contents of this solid solution and of tricalcium silicate shall be calculated by the following formulas:

(A1.5)

(A1.6)

( ) ( )( ) ( )( )

3 2

2 3 2 3

3

tricalcium silicate (C S) 4.071 % CaO 7.600 % SiO

6.718 % Al O 1.430 % Fe O

2.852 % SO

= ´ - ´ -

´ - ´ -

´

2 2 3dicalcium silicate (C S) = (2.867 %SiO ) (0.7544 %C S)´ - ´

3 2 3 2 3tricalcium aluminate (C A) = (2.650×%Al O ) (1.692×%Fe O )-

4 2 3tetracalcium aluminoferrite (C AF) = 3.043×%Fe O )

( ) ( ) ( )4 2 2 3 2 3ss C AF C F 2.100 % Al O 1.702 % Fe O+ = ´ + ´

( ) ( )( ) ( )( )

3 2

2 3 2 3

3

tricalcium silicate (C S) 4.071 % CaO 7.600 % SiO

4.479 % Al O 2.859 % Fe O

2.852 % SO

= ´ - ´ -

´ - ´ -

´

TS-3a M 85-2 AASHTO

A1.4. If no limestone or inorganic processing additions are used in the cement, or in the absence of information on limestone or inorganic processing additions used in the cement, phases shall be calculated using procedures in Equations A1.1 to A1.6 without adjustment.

A1.5. In the absence of information on limestone or inorganic processing additions content, results shall note that no adjustment has been made for possible use of limestone or inorganic processing additions.

A1.6. When inorganic processing additions, limestone, or both are used with the base cement (portland cement clinker and any added calcium sulfate), the contents of C3S, C2S, C3A, and C4AF shall be adjusted as follows:

The percentage of C3S, C2S, C3A, and C4AF in the base cement (see Note A2) shall be determined based on chemical analyses using methods in T 105 and using Equations A1.1 to A1.6 as appropriate. The contents of each of these phases shall be adjusted to account for the use of limestone or inorganic processing additions as follows:

(A1.7)

where: Xb = the percentage by mass of C3S, C2S, C3A, or C4AF in the base cement (portland cement

clinker and any calcium sulfate); L = the percentage by mass of limestone; P = the percentage by mass of inorganic processing addition; and Xf = the percentage by mass of C3S, C2S, C3A, or C4AF in the finished cement.

The adjusted values for the finished cement shall be reported on the manufacturer’s report. Note A2—When the oxide analysis of the finished cement, the limestone, and inorganic processing addition are known along with the mass percentage of limestone (L) and mass percentage of inorganic processing addition (P), one method of determining the base cement oxide composition is to use the following equation:

where: Ob = the base cement oxide content (% by mass of base cement); Of = the finished cement oxide content (% by mass of finished cement); Ol = the limestone oxide content (% by mass of limestone); and Op = the inorganic processing addition oxide content (% by mass of inorganic processing

addition).

The base cement phase composition can be determined using these values of oxide analyses in Equations A1.1 to A1.6. Equation A1.7 is used to calculate the adjusted phase composition. Note A3—For example, where the cement includes 3.5 percent limestone and 3.0 percent of an inorganic processing addition and the base cement has 60 percent C3S, 15 percent C2S, 7 percent C3A, and 10 percent C4AF, the adjusted phase composition is:

(100 )100f bL PX X - -

= ´

( ) ( ){ } ( )100 /100 /100 / 100b f l pO O L O P O L P= ´ é ù- ´ - ´ - -é ùë û ë û

360 (100 3.5 3.0)C S 56%

100f´ - -

= =

TS-3a M 85-3 AASHTO

Only the percentages of C3S, C2S, C3A, and C4AF shall be adjusted by the procedure in Section A1.6.1. These adjusted values for the finished cement shall be reported on the manufacturer’s report, and used in determining compliance with specification limits, including those based on calculated values, such as the sums of C3S + 4.75 C3A, and C4AF + 2 (C3A).

215 (100 3.5 3.0)C S 14%

100f´ - -

= =

37 (100 3.5 3.0)C A 7%

100f´ - -

= =

410 (100 3.5 3.0)C AF 9%

100f´ - -

= =

Item #: TS 3a_20_03

Description: AASHTO M 240, Add Type HE Blended Cement

Rationale: Some blended cements can meet high early strength requirements, but there are

no provisions to define those requirements in M 240. This proposal would define those

requirements, to be consistent with Type III strength requirements in M 85 and Type HE cements

in C1157.

This ballot item is based on AASHTO M240-20. Only additions to text shown in underline and

deletions shown in strikethrough font are being balloted. Other text is included for information

only. Where necessary, tables, figures, notes, footnotes, and section numbers will be renumbered

editorially.

This proposal has been developed by TS 3a TF09-1, the Joint AASHTO-ASTM Harmonization

Task Force, and a parallel proposal is being considered by ASTM Committee C01 for ASTM

C595.

Please note this proposal has 5 pages.


Blended Hydraulic Cement

AASHTO Designation: M 240M/M 240-201





4. CLASSIFICATION

4.1. This specification applies to the following types of blended cement that generally are intended for

use as directed.

4.1.1. Blended hydraulic cements for general concrete construction.

4.1.1.1. Type IS—Portland blast-furnace slag cement.

4.1.1.2. Type IP—Portland-pozzolan cement.

4.1.1.3. Type IL—Portland-limestone cement.

4.1.1.4. Type IT—Ternary blended cement.

4.2. Reporting:

4.2.1. The naming practice for blended cements shall be made by adding the suffix (X) to the type

designation under Section 4.1.1, where (X) equals the targeted percentage of slag, pozzolan, or

limestone in the product expressed as a whole number by mass of the final blended product, within

the allowable variation as stated in Section 15.3.

4.2.2. The naming practice for ternary blended cements shall be made by adding the suffixes (AX) and

(BY) to the Type IT designation under Section 4.1.1, where:

4.2.2.1. A is “S” for slag, “P” for pozzolan, or “L” for limestone, whichever is present in a larger amount

by mass;

4.2.2.2. X is the targeted percentage by mass of constituent A;

4.2.2.3. B is “S” for slag, “P” for pozzolan, or “L” for limestone; and

4.2.2.4. Y is the targeted percentage by mass of constituent B.

4.2.2.5. Both X and Y values are expressed as a whole number by mass of the final blended product,

within the allowable variation as stated in Section 15.3. If X and Y are the same, list the two

constituents in alphabetical order by constituent type (limestone, pozzolan, or slag).

Note 3—Examples of the naming practice per Sections 4.2.1 and 4.3 are shown below (all

percentages by mass):

Binary blended cement with 80 percent portland cement and 20 percent slag = Type IS(20);

Binary blended cement with 85 percent portland cement and 15 percent pozzolan = Type

IP(15);

Binary blended cement with 90 percent portland cement and 10 percent limestone = Type

IL(10).

Ternary blended cement with 70 percent portland cement, 20 percent slag, and 10 percent

pozzolan = Type IT(S20)(P10);

Ternary blended cement with 65 percent portland cement, 25 percent of one pozzolan, and

10 percent of another pozzolan = Type IT(P25)(P10);


pozzolan = Type IT(P20)(S20);

Ternary blended cement with 80 percent portland cement, 10 percent limestone, and

10 percent pozzolan = Type IT(L10)(P10); and


limestone = Type IT(S15)(L10).

4.2.3. A simplified naming practice is used in this standard for practicality and clarity when referring to

specific requirements for binary and ternary blended cements that are applicable to a range of

products or in ternary blended cements when requirements are applicable to only one constituent

within a specific range (percent). (See Note 4.)

Note 4—Examples of the simplified naming practices per Section 4.2.3 are shown below:

An example when requirements are applicable to a range of products can be found in Table 1,

where the maximum SO3 content of 3 percent applies to binary blended cements with slag

contents <70 percent, indicated as IS(<70) and ternary blended cements with a pozzolan

content less than the slag content, and the slag content is less than 70 percent, indicated as

Type IT(P < S < 70).

An example when requirements are applicable to only one constituent within a specific

range (percent) of that constituent can be found in Section 9.2, where testing is required

only when the slag content is <25 percent. Because the requirement is based on the slag

content only with no relation to the pozzolan or limestone content, a simplified naming

practice is employed and the range of ternary blended cements is indicated as Type

IT(S < 25).

4.3. Special Properties:

4.3.1. Air-entraining cement, when desired by the purchaser, shall be specified by adding the suffix (A)

to the type designation under Section 4.1.1. (See Note 5.)

Note 5—A given mass of blended cement has a larger absolute volume than the same mass of

portland cement. This should be taken into consideration in purchasing cements and in

proportioning concrete mixtures.

4.3.2. Moderate heat of hydration, when desired by the purchaser, shall be specified by adding the suffix

(MH) to the type designation under Section 4.1.1.

4.3.3. Moderate sulfate resistance, when desired by the purchaser, shall be specified by adding the suffix

(MS) to the type designation under Section 4.1.1.

4.3.4. High sulfate resistance, when desired by the purchaser, shall be specified by adding the suffix

(HS) to the type designation under Section 4.1.1.

4.3.5. Low heat of hydration, when desired by the purchaser, shall be specified by adding the suffix (LH)

to the type designation under Section 4.1.1.

Note 6—Special properties attributable to slag, pozzolan, or limestone will vary based on

quantities contained within the blended cements.

Note 7—R 80 provides guidance on use of blended hydraulic cements in concrete mixtures where

potential for deleterious alkali–silica reaction is of concern.

4.3.6. High early strength, when desired by the purchaser, shall be specified by adding the suffix (HE) to

the type designation under 4.1.1.

5. ORDERING INFORMATION

5.1. Orders for material under this specification shall include the following:

5.1.1. Specification number;

5.1.2. Type or types required; and

5.1.2.1. Indicate allowable slag, pozzolan, or limestone maximum or minimum percentage by mass, if

required.

5.1.3. Optional special properties required (see Section 4.3):

5.1.3.1. MS if moderate sulfate resistance is required;

5.1.3.2. HS if high sulfate resistance is required;

5.1.3.3. MH if moderate heat of hydration is required;

5.1.3.4. LH if low heat of hydration is required;

5.1.3.5. HE if high early strength is required;

5.1.3.5.5.1.3.6. A if air entraining is required;

5.1.3.6.5.1.3.7. Accelerating addition, if required;

5.1.3.7.5.1.3.8. Retarding addition, if required;

5.1.3.8.5.1.3.9. Water-reducing addition, if required;

5.1.3.9.5.1.3.10. Water-reducing and accelerating addition, if required; and

5.1.3.10.5.1.3.11. Water-reducing and retarding addition, if required.

5.1.4. Certification, if desired. (See Section 15.)

Note 8—It is important to check for availability of various options. Some multiple options are

mutually incompatible or unattainable.

Table 3—Physical Requirements for Blended Cements with Special Properties

Special Property

Designationa

Applicable

Test

Method A MS HS MH LH HE HE(A)

Air content of mortar:

min, volume %

max, volume %

T 137

16b

22b

—

12

—

12

—

12

—

12

—

12

16

22

Compressive strength,c min,

MPa [psi]:

3 days

7 days

28 days

T 106M/

T 106

10.0 [1450]

16.0 [2320]

22.0 [3190]

13.0 [1890]

20.0 [2900]

25.0 [3620]

13.0 [1890]

20.0 [2900]

25.0 [3620]

10.0 [1450]

17.0 [2470]

22.0 [3190]

—

11.0 [1600]

21.0 [3050]

12.0 [1740]

24.0 [3480]

—

10.0 [1450]

19.0 [2760]

Heat of hydration, max, kJ/kg

[cal/g]:

3 days

7 days

ASTM

C1702

—

—

—

—

—

—

335 [80]

—

200 [50]

225[55]

—

—

—

—

Water requirement, max

weight % of cement

T 106M/

T 106

—

—

—

—

64

—

—

Sulfate resistance, max, %:

Expansion at 180 days

Expansion at 1 year

ASTM

C1012

—

—

0.10

—

0.05d

0.10d

—

—

—

—

—

—

—

—

a These requirements apply only if specified and are designated by suffixes A, MS, HS, MH, or LH, HE or HE(A) as appropriate to type designations IL, IP,

IS(<70), or IT(S<70). See Section 4.3. Requirements for fineness, autoclave expansion, autoclave contraction, and time of setting shall conform to Table 2. b These air content requirements apply to cements with multiple special property designations when one of those designations is (A). c When multiple special property designations are applied that do not include HE or HE(A), the set of strength requirements for the special property designation

with the lowest 7-day minimum strength requirement shall apply. When the HE or HE(A) designation is applied to a cement with multiple special property

designations, the HE or HE(A) strength requirements apply. d Testing at 1 year shall not be required when the cement meets the 180-day limit. A cement failing the 180-day limit shall not be rejected unless it also fails the

1-year limit.

Item #: TS 3a_20_04

Description: Revision of M 240, Add an example mill test report

Rationale: This ballot proposes to add a new non-mandatory appendix that would provide

guidance on reporting mill certification test results for M 240 cements. Included would be text

with background information and an example mill test report. This format could optionally be

used by manufacturers to report tests results and other provisions of the standard, while retaining

flexibility to report additional information requested by specific purchasers. Although these

reports are routinely provided by blended cement manufacturers, this report provides an example

format that can be used to simplify review to verify that the provisions of M 240 are met. The

proposed appendix is based largely on that used in AASHTO M 85 and ASTM C150.

Given the variety of cement types specified under M 240, it would be awkward to provide

examples covering all of them. However, this example provides a broad outline that show how

various provisions may be communicated. This example is for a Type IL cement.

This ballot item is based on ASTM M 240-20. Only additions to text shown in underline and

deletions shown in strikethrough font are being balloted. Other text is included for information

only. Where necessary, tables, figures, notes, footnotes, and section numbers will be renumbered

editorially.



C595.


Detailed Changes:

15. CERTIFICATION

15.1. At the request of the purchaser, the manufacturer shall state in writing the source, targeted amount,

and composition of the essential constituents used in manufacture of the blended cement and the

composition of the blended cement purchased.

15.2. At the request of the purchaser, the manufacturer shall state in writing the nature, amount, and

identity of any processing, functional, or air-entraining addition used, and also, if requested, shall

supply test data showing compliance of any such processing addition with the provisions of

M 327, of any such functional addition with the provisions of ASTM C688, and of any such air-

entraining addition with the provisions of ASTM C226.

15.3. At the request of the purchaser, the manufacturer shall also state in writing that the amount of a

constituent in the finished cement will not vary more than the percentages listed in Table 5 with a

99 percent probability of compliance, between lots or within a lot (see Note 13).

Table 5—Permitted Variation in Mass Percentage of Constituent

Constituent

Maximum Variation in Amount from Target,

% by Mass of Blended Cement

Silica fume, metakaolin, limestone ± 2.5

All other constituents ± 5.0

Note 1—To satisfy the 99 percent probability of compliance, the manufacturing process must be

capable of producing a cement such that the standard deviation of the determined mass percentage

of silica fume, metakaolin, or limestone in the cement is less than 1 percent. For all other

ingredients, the standard deviations of their determined mass percentages have to be less than

1.9 percent. The variation in determined mass percentage includes that due to the amount and

chemistry of the constituent, as well as that due to variation in verification testing. As an example,

Type IP(5) made with silica fume indicates a blended hydraulic cement determined to contain

between 2.5 percent and 7.5 percent silica fume by mass. A Type IP(20) cement made with fly

ash indicates a blended cement determined to contain between 15 percent and 25 percent fly ash

by mass.

15.4. Upon request of the purchaser in the contract or order, a manufacturer’s certification shall be

furnished indicating that the material was tested during production or transfer in accordance with

this specification, that it complies with this specification, and a report of the test results shall be

furnished at the time of shipment (to include amount retained on the 45-m (No. 325) sieve,

specific surface by the air permeability method, and density).

Note 214— Guidance on preparing the manufacturer’s report is provided in Appendix X1.

15.5. Upon request of the purchaser in the contract or order, the manufacturer shall report the following

characteristics of constituents of the blended cement: the equivalent alkali content (Na2Oe =

%Na2O + 0.658 × %K2O) of any portland cement, slag, fly ash, natural pozzolan, or silica fume;

the CaO content of any fly ash; and the SiO2 content of any silica fume. (See Note 1415.)

Note 215—The characteristics listed in Section 15.5 may be requested in order to follow

guidance provided in R 80 to reduce the risk of deleterious expansion due to alkali–silica reaction

in concrete.

15.6. Upon request of the purchaser, the manufacturer shall report the chloride content as determined

according to T105, in percent by mass of the blended cement, in the manufacturerʼs report (see

Note 15 16).

Note 316—Chlorides in concrete come from multiple ingredients and blended cement chloride

content may be required to estimate concrete chloride content. Requirements for concrete chloride

content are provided in building codes and other documents.

APPENDIX

(Nonmandatory Information)

X1. MANUFACTURER’S CERTIFICATION (MILL TEST REPORT)

X1.1. To provide uniformity for reporting the results of tests performed on blended cements under this

specification, as required by Section 15 of M 240, Manufacturer’s Certification, an example Mill

Test Report is shown in Figure X1.1.

X1.2. The identity information given should unambiguously identify the cement production represented

by the Mill Test Report and may vary, depending on the manufacturer’s designation and

purchaser’s requirements.

X1.3. The Manufacturer’s Certification statement may vary, depending on the manufacturer’s

procurement order or legal requirements, but should certify that the blended cement shipped is

represented by the certificate and that the blended cement conforms to applicable requirements of

the specification at the time it was tested (or retested) or shipped.

X1.4. The sample Mill Test Report has been developed to reflect the chemical and physical requirements

of this specification and recommends reporting all analyses and tests normally performed on

blended cements meeting M 85. Purchaser reporting requirements should govern if different from

normal reporting by the manufacturer or from those recommended here.

X1.5. Blended cements may be shipped prior to later-age test data being available. In such cases, the test

value may be left blank. Alternatively, the manufacturer can generally provide estimates based on

historical production data. The report should indicate if such estimates are provided.

X1.6. In reporting limits from the tables in M 240 on the Mill Test Report, only those limits specifically

applicable should be listed. In some cases, M 240 table limits are superseded by other provisions.

X1.7. When limestone or inorganic processing additions or both are used in the cement, additional data

are reported by the manufacturer. An example additional data report is shown in Figure X1.2.

NOTE X1. The example in Figure X1.1 is specific to Type IL blended cement and other blended

cement types will have different reporting requirements.

Vermont - Consider re-wording note X1.5: 'Blended cements may be shipped prior to later-age test

data being available. In such cases, the test value may be left blank. Alternatively, the manufacturer

may can generally provide estimates based on historical production data. The report must should

indicate if test data such estimates are provided. It doesn't seem good practice to allow estimated

values to be used and then not require the manufacturer to disclose that those values are estimated.

JAAHTG - Blended cements may be shipped prior to later-age test data being available. In such

cases, the test value may be left blank. Alternatively, the manufacturer may can generally provide

estimates based on historical production data. The report should indicate if such estimates are

provided.

Vermont - In Appendix X1.1 it refers to 'Section 15 of M 240, Manufacturer's Certification'.

Section 15 of M 240 in this draft is titled simply 'Certification', not 'Manufacturer's Certification'.

These should be reconciled.

Illinois - New note in subsection 15.4 should be Note 14, and thus, references to subsequent notes

in subsections 15.5 and 15.6 should be updated (e.g., see parenthetical sentence of 15.5) along with

the note numbers themselves.

JAAHTG – See revisions above.

ABC Portland Cement Company Qualitytown, N.J.

Plant Example Blended Cement Type: IL(13) Date April 15, 20xx

Production Period March 1, 20xx – March 31, 20xx

AASHTO M 240

REQUIREMENTS

Chemical Physical

Item Spec. Limit

Test Result

Item Spec.

Limit Test

Result

Sulfate as SO3 (%) 3.0 max A 3.2 Blaine fineness (m2/kg) B 479

Loss on ignition (%) 10.0 max 5.4 Fineness, No. 325 sieve (% retained)

B 2.6

Equivalent alkali content of portland cement (Na2Oeq %)

B 0.65 Density (g/cm3) B 3.06

Air content of mortar (volume %) 12 max 6.0

Autoclave test

Expansion (%)

Contraction (%)

0.80 max 0.20 max

0.04

Time of initial setting (Vicat)

Not less than (minutes) Not more than (hours)

45

7 120 minutes

Compressive strength (MPa) min:

3 days 13.0 min 28.9

7 days 20.0 min 34.8

28 days 25.0 min 42.9 C

Mortar Bar Expansion, C1038, (%) 0.020 max,AD 0.005 A Default table maximum may be exceeded if C1038 limit is met. Required only if percent SO3 exceeds the limit in Table 1. B Not applicable. C Test result for this production period not available. Most recent test result provided. D Required only if percent SO3 exceeds the limit in Table 1.

We certify that the above described blended cement, at the time of shipment, meets the chemical and physical requirements of the AASHTO M 240 or (other) _______________ specification.

Signature: ________________________________________ Title: ________________________________________

Figure X1.1 Example mill test report for a M240 Type IL blended cement.

JAAHTG – Editorial revisions.

Item #: TS 3a_20_05

Description: Revision of AASHTO M 240, Permit Air Jet Sieving

Rationale:

ASTM C1891 is a new standard to determine fineness of hydraulic cement, as indicated by the

percent retained on a No. 325 (45-µm) sieve, by air jet sieving. This ballot proposes to permit the

new test method to be used as an option to AASHTO T 192. Both methods require

standardization of sieves using standard reference materials, therefore no bias between the

methods is expected.

This ballot item is based on AASHTO M 240-20. Only additions to text shown in underline font

and deletions shown in strikethrough font are being balloted. Other text is included for

information only. Where necessary, tables, figures, notes, footnotes, and section numbers will be

renumbered editorially.



C595.


Detailed Changes:


Blended Hydraulic Cement

AASHTO Designation: M 240M/M 240-201





2 REFERENCED DOCUMENTS

2.1 AASHTO Standards:

M 85, Portland Cement

M 201, Mixing Rooms, Moist Cabinets, Moist Rooms, and Water Storage Tanks Used in the

Testing of Hydraulic Cements and Concretes

M 327, Processing Additions for Use in the Manufacture of Hydraulic Cements

R 71, Sampling and Amount of Testing of Hydraulic Cement

R 80, Determining the Reactivity of Concrete Aggregates and Selecting Appropriate

Measures for Preventing Deleterious Expansion in New Concrete Construction

T 105, Chemical Analysis of Hydraulic Cement

T 106M/T 106, Compressive Strength of Hydraulic Cement Mortar (Using 50-mm or 2-in.

Cube Specimens)

T 107M/T 107, Autoclave Expansion of Hydraulic Cement

T 129, Amount of Water Required for Normal Consistency of Hydraulic Cement Paste

T 131, Time of Setting of Hydraulic Cement by Vicat Needle

T 133, Density of Hydraulic Cement

T 137, Air Content of Hydraulic Cement Mortar

T 153, Fineness of Hydraulic Cement by Air Permeability Apparatus

T 192, Fineness of Hydraulic Cement by the 45-m (No. 325) Sieve

2.2 ASTM Standards:

C51, Standard Terminology Relating to Lime and Limestone (as used by the Industry)

C219, Standard Terminology Relating to Hydraulic Cement

C226, Standard Specification for Air-Entraining Additions for Use in the Manufacture of Air-

Entraining Hydraulic Cement

C311/C311M, Standard Test Methods for Sampling and Testing Fly Ash or Natural

Pozzolans for Use in Portland-Cement Concrete

C563, Standard Guide for Approximation of Optimum SO3 in Hydraulic Cement

C688, Standard Specification for Functional Additions for Use in Hydraulic Cements

C821, Standard Specification for Lime for Use with Pozzolans

C1012/C1012M, Standard Test Method for Length Change of Hydraulic-Cement Mortars

Exposed to a Sulfate Solution

C1038/C1038M, Standard Test Method for Expansion of Hydraulic Cement Mortar Bars

Stored in Water

C1157/C1157M, Standard Performance Specification for Hydraulic Cement

C1702, Standard Test Method for Measurement of Heat of Hydration of Hydraulic

Cementitious Materials Using Isothermal Conduction Calorimetry

C1891, Standard Test Method for Fineness of Hydraulic Cement by Air Jet Sieving at 45-µm

(No. 325)

Manual of Cement Testing, Annual Book of ASTM Standards, Volume 04.01

2.3 IEEE/ASTM Standard:

SI10, American National Standard for Metric Practice

Table 2—Physical Requirements for Blended Cements

Cement Type Applicable Test Method

IL,

IP,

IS(<70),

IT(S < 70)

IS(70),

IT(S 70)

Fineness T 153,,and T 192 or

ASTM C1891

a a

Density T 133 a a

Autoclave expansion, max, %b T 107M/T 107 0.80 0.80

Autoclave contraction, max, %b T 107M/T 107 0.20 0.20

Time of initial setting, Vicat testc:

Set, minutes, not less than

Set, hours, not more than

T 131

45

7

45

7

Air content of mortar, volume %, max T 137 12 12

Compressive strength, minimum, MPa

[psi]:

3 days

7 days

28 days

T 106M/T 106

13.0 [1890]

20.0 [2900]

25.0 [3620]

—

5.0 [720]

11.0 [1600]

a The amount retained when wet-sieved on 45-m (No. 325) sieve, specific surface by air permeability apparatus, m2/kg, and density, g/cm3, shall be

reported on all mill test reports requested under Section 15.4. b The specimens shall remain firm and hard and show no signs of distortion, cracking, checking, pitting, or disintegration when subjected to the

autoclave expansion test. c The time of setting of cements containing a user-requested accelerating or retarding functional addition need not meet the limits of this table, but

shall be stated by the manufacturer.

JAAHTG – Editorial Comment

Table 4—Requirements for Pozzolan for Use in Blended Cements and

for Slag for Use in Portland Blast-Furnace Slag Cement Type IS(<25)

and Ternary Blended Cement Type IT(S < 25)

Pozzolan Applicable Test Method

Fineness:

Amount retained when wet-

sieved on 45-m (No. 325)

sieve, max, %

T 192 or C1891 20.0

Slag or pozzolan activity index

with portland cement, at

28 days, min, %

See Annex A 75.0

Loss on ignition of pozzolan, max, %:

Natural pozzolan

Fly ash

Silica fume

ASTM C311

10.0

6.0

6.0

11. TEST METHODS

11.1. Determine the applicable properties enumerated in this specification in accordance with the

following test methods:

11.1.1. Chemical Analysis—T 105, with the special provisions noted therein applicable to blended

cement analyses.

11.1.2. Fineness by Sieving—T 192 or ASTM C1891.

11.1.3. Fineness by Air-Permeability Apparatus—T 153.

1

Item #: TS 3a_20_06 Description: Revision of AASHTO T 106, Fixed water for Type IL cements Rationale: In order to simplify laboratory procedures and reduce the chance for errors, it is proposed that Type IL cements be tested with a fixed water content, as are portland cements. A brief survey of manufacturers appears to indicate that water contents are generally comparable tested using a fixed flow or a fixed water expressed as percent of cement and strengths of portland-limestone cements are comparable as well. Limestone contents in the Type IL cements represented below are from 10% to 12% by mass. Existing Sections 10.1.1 and 10.1.2 contain duplicate information on test mortar composition. Body text describes mortar proportions, while Table 2 in Section 10.1.2 explicitly defines proportions in table format. Provisions of Sections 10.1.1 and 10.1.2 are simplified and combined. Table 2 is revised to proportion Type IL test mortars at a fixed water content rather than a fixed flow, and is referenced in the revised Section 10.1.1. Table 2 title is revised to better reflect subject matter and to be consistent with proposed parallel change to ASTM C109. Sections 10.3.1 and 10.3.2 are revised to be parallel in form. A new Note 8 is included to provide descriptive information about Table 2 ratios of water and sand to portland and portland-limestone cements. The existing references in 10.4.5.1 to Table 2 should reference Table 4. That correction is also included in this ballot item. This ballot item is based on AASHTO T 106-18. Only additions to text shown in underline and deletions shown in strikethrough font are being balloted. Other text is included for information only. Where necessary, tables, figures, notes, footnotes, and section numbers will be renumbered editorially. This proposal has been developed by TS 3a TF09-1, the Joint AASHTO-ASTM Harmonization Task Force, and a parallel proposal is being considered by ASTM Committee C01 for ASTM C109. Please note this proposal has 16 pages.

2

0%

20%

40%

60%

80%

100%

120%

Plant A Plant B Plant C Plant D Plant E Plant F Plant G

Rat

io o

f Wat

er c

onte

nt:

Fixe

d wa

ter:

Fixe

d Fl

ow

Water Content of Type IL cementsfixed water: fixed flow

0%

20%

40%

60%

80%

100%

120%

Plant A Plant B Plant C Plant D Plant E Plant F Plant G

Stre

gnth

rat

io:

Fixe

d wa

ter:

Fixe

d Fl

ow

Strength ratio of Type IL cementsfixed water: fixed flow

1 d3 d7 d28 d

3

Detailed Changes:

Standard Method of Test for

Compressive Strength of Hydraulic Cement Mortar (Using 50-mm or 2-in. Cube Specimens)

AASHTO Designation: T 106M/T 106-18





4


Compressive Strength of Hydraulic Cement Mortar (Using 50-mm or 2-in. Cube Specimens)

AASHTO Designation: T 106M/T 106-18




1. SCOPE

1.1. This test method covers determination of the compressive strength of hydraulic cement mortar using 50-mm ([or 2-in.)] cube specimens (see Note 1). Note 1—ASTM C349 provides an alternative procedure for this determination (not to be used for acceptance tests).

1.2. This test method covers the application of the test using either inch-pound or SI units. The values stated in either SI units or inch-pound units are to be regarded separately as standard. Within the text, the inch-pound units are shown in brackets. The values stated in each system may not be exact equivalents; therefore, each system shall be used independently of the other. Combining values from the two systems may result in nonconformance with the standard.

1.3. Values in SI units shall be obtained by measurement in SI units or by appropriate conversion, using the Rules for Conversion and Rebounding given in Standard IEEE/ASTM SI 10, of measurements made in other units.

1.4. This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use. Warning—Fresh hydraulic cementitious mixtures are caustic and may cause chemical burns to skin and tissue upon prolonged exposure.

2. REFERENCED DOCUMENTS

2.1. AASHTO Standards: < M 85, Portland Cement < M 152M/M 152, Flow Table for Use in Tests of Hydraulic Cement < M 201, Mixing Rooms, Moist Cabinets, Moist Rooms, and Water Storage Tanks Used in the

Testing of Hydraulic Cements and Concretes < M 240M/M 240, Blended Hydraulic Cement < M 295, Coal Fly Ash and Raw or Calcined Natural Pozzolan for Use in Concrete < M 302, Slag Cement for Use in Concrete and Mortars

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< T 105, Chemical Analysis of Hydraulic Cement < T 162, Mechanical Mixing of Hydraulic Cement Pastes and Mortars of Plastic Consistency

2.2. ASTM Standards: < C91/C91M, Standard Specification for Masonry Cement < C349, Standard Test Method for Compressive Strength of Hydraulic-Cement Mortars (Using

Portions of Prisms Broken in Flexure) < C670, Standard Practice for Preparing Precision and Bias Statements for Test Methods for

Construction Materials < C778, Standard Specification for Standard Sand < C1005, Standard Specification for Reference Masses and Devices for Determining Mass and

Volume for Use in the Physical Testing of Hydraulic Cements < C1157/C1157M, Standard Performance Specification for Hydraulic Cement < C1328/C1328M, Standard Specification for Plastic (Stucco) Cement < C1329/C1329M, Standard Specification for Mortar Cement

2.3. IEEE/ASTM Standard: < SI10, American National Standard for Metric Practice

3. SUMMARY OF TEST METHOD

3.1. The mortar used consists of one part cement and 2.75 parts of sand proportioned by mass. Portland, or air-entraining portland, portland-limestone, and air-entraining portland-limestone cements are mixed at a specified water content-cement ratios. Water content for other cements is that sufficient to obtain a flow of 110 ± 5 in 25 drops of the flow table. Fifty- millimeter [or 2-in.] test cubes are compacted by tamping in two layers. The cubes are cured 24 h in the molds, and then stripped and immersed in lime water until tested.

4. SIGNIFICANCE AND USE

4.1. This test method provides a means of determining the compressive strength of hydraulic cement and other mortars, and results may be used to determine compliance with specifications. Further, this test method is referenced by numerous other specifications and test methods. Caution must be exercised in using the results of this test method to predict the strength of concretes.

5. APPARATUS

5.1. Weights and Weighing Devices—Shall conform to the requirements of ASTM C1005. The weighing device shall be evaluated for precision and accuracy at a total load of 2000 g.

5.2. Glass Graduates—Of suitable capacities (preferably large enough to measure the mixing water in a single operation) to deliver the indicated volume at 20°C. The permissible variation shall be ±2 mL. These graduates shall be subdivided to at least 5 mL, except that the graduation lines may be omitted for the lowest 10 mL for a 250-mL graduate and for the lowest 25 mL for a 500-mL graduate. The main graduation lines shall be circles and shall be numbered. The least graduations shall extend at least one-seventh of the way around, and intermediate graduations shall extend at least one-fifth of the way around.

5.3. Specimen Molds—For the 50-mm [or 2-in.] cube specimens shall be tight fitting. The molds shall have no more than three cube compartments and shall be separable into no more than two parts.

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The parts of the molds when assembled shall be positively held together. The molds shall be made of hard metal not attacked by the cement mortar. For new molds, the Rockwell hardness number of the metal shall be not less than 55 HRB. The sides of the molds shall be sufficiently rigid to prevent spreading or warping. The interior faces of the molds shall be plane surfaces and shall conform to the tolerances of Table 1.

Table 1—Permissible Variations of Specimen Molds

Parameter 50-mm Cube Molds 2-in. Cube Molds

New In Use New In Use Planeness of sides <0.025 mm <0.05 mm <0.001 in. <0.002 in. Distance between opposite sides

50 mm ± 0.13 mm 50 mm ± 0.50 mm 2 in. ± 0.005 2 in. ± 0.02

Height of each compartment

50 mm + 0.25 mm to – 0.13 mm

50 mm + 0.25 mm to – 0.38 mm

2 in. + 0.01 in. to – 0.005 in.

2 in. + 0.01 in. to – 0.015 in.

Angle between adjacent facesa

90 ± 0.5o 90 ± 0.5o 90 ± 0.5o 90 ± 0.5o

a Measured at points slightly removed from the intersection. Measured separately for each compartment between all the interior faces and the adjacent face and between interior faces and top and bottom planes of the mold.

5.4. Mixer, Bowl, and Paddle—An electrically driven mechanical mixer of the type equipped with paddle and mixing bowl, as specified in T 162.

5.5. Flow Table and Flow Mold—Conforming to the requirements of M 152M/M 152.

5.6. Tamper—A nonabsorptive, nonabrasive, nonbrittle material such as a rubber compound having a Shore A durometer hardness of 80 ± 10 or seasoned oak wood rendered nonabsorptive by immersion for 15 min in paraffin at approximately 200°C [392°F], shall have a cross section of 13 by 25 mm [1/2 by 1 in.] and a convenient length of about 120 to 150 mm [5 to 6 in.]. The tamping face shall be flat and at right angles to the length of the tamper.

5.6.1. Tampers shall be checked for conformance to the design and dimensional requirements of this test method at least once every six months. Note 2—A visual inspection of the tamper should be performed each day before use to confirm that the end is flat and at a right angle to the long axis of the tamper. Rounded or peeling tampers should not be used.

5.7. Trowel—Having a steel blade 100 to 150 mm [4 to 6 in.] in length, with straight edges.

5.8. Moist Cabinet or Room—Conforming to the requirements of M 201.

5.9. Testing Machine—Either the hydraulic or the screw type, with sufficient opening between the upper bearing surface and the lower bearing surface of the machine to permit the use of verifying apparatus. The load applied to the test specimen shall be indicated with an accuracy of ±1.0 percent. If the load applied by the compression machine is registered on a dial, the dial shall be provided with a graduated scale that can be read to at least the nearest 0.1 percent of the full scale load (see Note 3). The dial shall be readable within 1 percent of the indicated load at any given load level within the loading range. In no case shall the loading range of a dial be considered to include loads below the value that is 100 times the smallest change of load that can be read on the scale. The scale shall be provided with a graduation line equal to zero and so numbered. The dial pointer shall be of sufficient length to reach the graduation marks, and the width of the end of the pointer shall not exceed the clear distance between the smallest graduations. Each dial shall be equipped with a zero adjustment that is easily accessible from the outside of the dial case, and with a suitable device that at all times, until reset, will indicate to within 1 percent accuracy the maximum load applied to the specimen.

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Note 3—“As close as can be read” is considered 0.5 mm [0.02 in.] along the arc described by the end of the pointer. Also, one half of the scale interval is about as close as can reasonably be read when the spacing on the load indicating mechanism is between 1 mm [0.04 in.] and 1.6 mm [0.0625 in.]. When the spacing is between 1.6 mm [0.0625 in.] and 3.2 mm [0.125 in.], one third of the scale interval can be read with reasonable certainty. When the spacing is 3.2 mm [1/8 in.] or more, one fourth of the scale interval can be read with reasonable certainty.

5.9.1. If the testing machine load is indicated in digital form, the numerical display must be large enough to be easily read. The numerical increment must be equal to or less than 0.10 percent of the full scale load of a given loading range. In no case shall the verified loading range include loads less than the minimum numerical increment multiplied by 100. The accuracy of the indicated load must be within 1.0 percent for any value displayed within the verified loading range. Provision must be made for adjusting to indicate true zero at zero load. There shall be provided a maximum load indicator that at all times, until reset, will indicate within 1 percent system accuracy the maximum load applied to the specimen.

5.9.2. The upper bearing assembly shall be a spherically seated, hardened metal block firmly attached at the center of the upper head of the machine. The center of the sphere shall coincide with the surface of the bearing face within a tolerance of ±5 percent of the radius of the sphere. Unless otherwise specified by the manufacturer, the spherical portion of the bearing block and the seat that holds this portion shall be cleaned and lubricated with a petroleum-type oil such as motor oil at least every 6 months. The block shall be closely held in its spherical seat, but shall be free to tilt in any direction. A hardened metal bearing block shall be used beneath the specimen to minimize wear of the lower platen of the machine. To facilitate accurate centering of the test specimen in the compression machine, one of the two surfaces of the bearing blocks shall have a diameter or diagonal between 70.7 mm [2.83 in.] (see Note 4) and 73.7 mm [2.9 in.]. When the upper block bearing surface meets this requirement, the lower block bearing surface shall be greater than 70.7 mm [2.83 in.]. When the lower block bearing surface meets this requirement, the diameter or diagonal of upper block bearing surface shall be between 70.7 and 79.4 mm [2.83 and 31/8 in.]. When the lower block is the only block with a diameter or diagonal between 70.7 and 73.7 mm [2.83 and 2.9 in.], the lower block shall be used to center the test specimen. In that case, the lower block shall be centered with respect to the upper bearing block and held in position by suitable means. The bearing block surfaces intended for contact with the specimen shall have a Rockwell hardness number not less than 60 HRC. These surfaces shall not depart from plane surfaces by more than 0.013 mm [0.0005 in.] when the blocks are new and shall be maintained within a permissible variation of 0.025 mm [0.001 in.]. Note 4—The diagonal of the 50-mm [2-in.] cube is 70.7 mm [2.83 in.].

6. MATERIALS

6.1. Graded Standard Sand:

6.1.1. The sand (see Note 5) used for making test specimens shall be natural silica sand conforming to the requirements for graded standard sand in ASTM C778. Note 5—Segregation of Graded Sand—The graded standard sand should be handled in such a manner as to prevent segregation because variations in the grading of the sand cause variation in the consistency of the mortar. In emptying bins or sacks, care should be exercised to prevent the formation of mounds of sand or craters in the sand, down the slopes of which the coarser particles will roll. Bins should be of sufficient size to permit these precautions. Devices for drawing the sand from bins by gravity should not be used.

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7. TEMPERATURE AND HUMIDITY

7.1. Temperature—The temperature of the air in the vicinity of the mixing slab, the dry materials, molds, base plates, and mixing bowl shall be maintained between 23.0 ± 3.0°C [73.5 ± 5.5°F]. The temperature of the mixing water, moist closet, or moist room and water in the storage tank shall be set at 23 ± 2°C [73.5 ± 3.5°F].

7.2. Humidity—The relative humidity of the laboratory shall be not less than 50 percent. The moist closet or moist room shall conform to the requirements of M 201.

8. TEST SPECIMENS

8.1. Make two or three specimens from a batch of mortar for each period of test or test age.

9. PREPARATION OF SPECIMEN MOLDS

9.1. Apply a thin coating of release agent to the interior faces of the mold and nonabsorptive base plates. Apply oils and greases using an impregnated cloth or other suitable means. Wipe the mold faces and the base plate with a cloth as necessary to remove any excess release agent and to achieve a thin, even coating on the interior surfaces. When using an aerosol lubricant, spray the release agent directly onto the mold faces and base plate from a distance of 150 to 200 mm [6 to 8 in.] to achieve complete coverage. After spraying, wipe the surface with a cloth as necessary to remove any excess aerosol lubricant. The residue coating should be just sufficient to allow a distinct fingerprint to remain following light finger pressure (see Note 6). Note 6—Because aerosol lubricants evaporate, molds should be checked for a sufficient coating of lubricant immediately prior to use. If an extended period of time has elapsed since treatment, retreatment may be necessary.

9.2. Seal the surfaces where the halves of the mold join by applying a coating of light cup grease such as petrolatum. The amount should be sufficient to extrude slightly when the two halves are tightened together. Remove any excess grease with a cloth.

9.3. Seal molds to their base plates with a watertight sealant. Use microcrystalline wax or a mixture of three parts paraffin to five parts rosin by mass. Paraffin wax is permitted as a sealant with molds that clamp to the base plate. Liquefy the wax by heating it to a temperature of between 230 and 248°F or [110 and 120°C]. Effect a watertight seal by applying the liquefied sealant at the outside contact lines between the mold and its base plate (see Note 7). Note 7—Watertight Molds—The mixture of paraffin and rosin specified for sealing the joints between molds and base plates may be found difficult to remove when molds are being cleaned. Use of straight paraffin is permissible if a watertight joint is secured; however, due to the low strength of paraffin, it should be used only when the mold is not held to the base plate by paraffin alone. When securing clamped molds with paraffin, an improved seal can be obtained by slightly warming the mold and base plate prior to applying the wax. Molds so treated should be allowed to return to room temperature before use.

9.4. Optionally, a watertight sealant of petroleum jelly is permitted for clamped molds. Apply a small amount of petroleum jelly to the entire surface of the face of the mold that will be contacting the base plate. Clamp the mold to the base plate, and wipe any excess sealant from the interior of the mold and base plate.

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10. PROCEDURE

10.1. Composition of Mortars:

10.1.1. The proportions of materialsMaterials for the standard mortar shall be 1 part of cement, to 2.75 parts of graded standard sand, and water by mass. The quantities of materials to be mixed at one time in the batch of mortar for making six, nine, and twelve test specimens shall be in accordance with Table 2. Use a specified water content -cement ratio of 0.485 for all portland, portland-limestone, cements and 0.460 for all air-entraining portland, and air-entraining portland-limestone cements. The amount of mixing water for other than portland and air-entraining portland cements shall be such as to produce a flow of 110 ± 5 as determined in accordance with Section 10.3 and shall be expressed as mass percent of cement.

10.1.2. The quantities of materials to be mixed at one time in the batch of mortar for making six, nine, and twelve test specimens shall be as follows in Table 2: Note 8—The water-to-portland-cement and water-to-portland-limestone-cement ratio used in Table 2 is 0.485 by mass. For air-entraining cements the water-to-portland-cement or water-to portland-limestone-cement ratio is 0.460 by mass. The sand-to-cement ratio is 2.75.

Table 2—Mixing Proportions for 2-in. Cubes Standard Test Mortar Proportions

No. of Specimens 6 9 12 Cement, g 500 740 1060

Sand, g 1375 2035 2915

Water, mL:

Portland or portland-limestone cements (0.485)

242 359 514

Air-entraining portland or air-entraining portland-limestone cements (0.460)

230 340 488

Other cements (to flow of 110 ± 5)

— — —

10.2. Preparation of Mortar:

10.2.1. Mechanically mix in accordance with the procedure given in T 162.

10.3. Determination of Flow:

10.3.1. Carefully wipe the flow-table top clean and dry, and place the flow mold at the center. Place a layer of mortar about 25 mm [1 in.] in thickness in the mold and tamp 20 times with the tamper. The tamping pressure shall be just sufficient to ensure uniform filling of the mold. Then fill the mold with mortar and tamp as specified for the first layer. Cut off the mortar to a plane surface, flush with the top of the mold, by drawing the straight edge of a trowel (held nearly perpendicular to the mold) with a sawing motion across the top of the mold. Wipe the table top clean and dry, being especially careful to remove any water from around the edge of the flow mold. Lift the mold away from the mortar 60 s after completing the mixing operation. Immediately drop the table through a height of 13 mm [1/2 in.], 25 times in 15 s.

10.3.2. Using the calipers, determine the flow by measuring the diameters of the mortar along the four lines scribed in the table top, recording each diameter as the number of caliper divisions, estimated to one-tenth of a division. If some other caliper is being used, measure the diameter of the mortar along the four lines scribed in the table top, recording each diameter to the nearest millimeter.

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10.3.3. For portland, portland-limestone, and air-entraining portland, and air-entraining portland-limestone cements, merely record the flow.

10.3.4. In the case of cements other than portland, portland-limestone, or air-entraining portland, and air-entraining portland-limestone cements, make trial mortars with varying percentages of water until the specified flow is obtained. Make each trial with fresh mortar. Record the water content used to achieve the specified flow as weight percent of cement.

10.3.5. Immediately following completion of the flow test, return the mortar from the flow table to the mixing bowl. Quickly scrape the bowl sides and transfer into the batch the mortar that may have collected on the side of the bowl, and then remix the entire batch 15 s at medium speed. Upon completion of mixing, the mixing paddle shall be shaken to remove excess mortar into the mixing bowl.

10.3.6. When a duplicate batch is to be made immediately for additional specimens, the flow test may be omitted and the mortar allowed to stand in the mixing bowl 90 s without covering. During the last 15 s of this interval, quickly scrape the bowl sides and transfer into the batch the mortar that may have collected on the side of the bowl. Then remix for 15 s at medium speed.

10.4. Molding Test Specimens:

10.4.1. Complete the consolidation of the mortar in the molds by either hand tamping or a qualified alternative method. Alternative methods include, but are not limited to, the use of a vibrating table or mechanical devices.

10.4.2. Hand Tamping:

10.4.2.1. Start molding the specimens within a total elapsed time of not more than 2 min and 30 s after completion of the original mixing of the mortar batch. Place a layer of mortar about 25 mm [1 in.] (approximately one-half of the depth of the mold) in all of the cube compartments. Tamp the mortar in each cube compartment 32 times in about 10 s in four rounds, each round to be at right angles to the other and consisting of eight adjoining strokes over the surface of the specimen, as illustrated in Figure 1. The tamping pressure shall be just sufficient to ensure uniform filling of the molds. The four rounds of tamping (32 strokes) of the mortar shall be completed in one cube before going to the next. When the tamping of the first layer in all of the cube compartments is completed, fill the compartments with the remaining mortar and then tamp as specified for the first layer.

10.4.2.2. During tamping of the second layer, bring in the mortar forced out onto the tops of the molds after each round of tamping by means of the gloved fingers and the tamper upon completion of each round and before starting the next round of tamping. On completion of the tamping, the tops of all cubes should extend slightly above the tops of the molds. Bring in the mortar that has been forced out onto the tops of the molds with a trowel and smooth off the cubes by drawing the flat side of the trowel (with the leading edge slightly raised) once across the top of each cube at right angles to the length of the mold.

10.4.2.3. Then, for the purpose of leveling the mortar and making the mortar that protrudes above the top of the mold of more uniform thickness, draw the flat side of the trowel (with the leading edge slightly raised) lightly once along the length of the mold. Cut off the mortar to a plane surface flush with the top of the mold by drawing the straight edge of the trowel (held nearly perpendicular to the mold) with a sawing motion over the length of the mold.

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Figure 1—Order of Tamping in Molding of Test Specimens

10.4.3. Alternative Methods—Any consolidation method may be used that meets the qualification requirements of this section. The consolidation method consists of a specific procedure, equipment, and consolidation device, as selected and used in a consistent manner by a specific laboratory. The mortar batch size of the method may be modified to accommodate the apparatus, provided the proportions maintain the same ratios as given in Section 10.1.2.

10.4.3.1. Separate qualifications are required for the following classifications:

10.4.3.2. Class A, Non-Air Entrained Cements—For use in concrete. Refer to M 85, M 240M/M 240, and ASTM C1157/C1157M.

10.4.3.3. Class B, Air-Entrained Cements—For use in concrete. Refer to M 85, M 240M/M 240, and ASTM C1157/C1157M.

10.4.3.4. Class C, Masonry, Mortar, and Stucco Cements—Refer to ASTM C91/C91M, ASTM C1328/C1328M, and ASTM C1329/C1329M.

10.4.3.5. An alternative method may only be used to test the cement types as given in Section 10.4.3.1 above, for which it has been qualified.

10.4.3.6. It can also be used for Strength Activity Index determinations for fly ash and slag (refer to M 295 and M 302), provided the alternative method has qualified for both Class A and Class C cements.

10.4.4. Qualification Procedure—Contact Cement and Concrete Reference Laboratory (CCRL) to purchase cement samples that have been used in the Proficiency Sample Program (PSP). Four samples (5 kg each) of the class to be qualified will be required to complete a single qualification (see Note 89). Note 89—It is recommended that a large homogenous sample of cement be prepared at the time of qualification for use as a secondary standard and for method evaluation. Frequent testing of this sample will give early warning of any changes in the performance of the apparatus.

10.4.4.1. In 1 day, prepare replicate 6-cube or 9-cube batches using one of the cements and cast a minimum of 36 cubes. Complete one round of tests on each cement on different days. Store and test all specimens as prescribed in the sections below. Test all cubes at the age of 7 days.

10.4.4.2. Tabulate the compressive strength data and complete the mathematical analyses as instructed in Annex A1.

10.4.5. Requalification of the Alternate Compaction Method:

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10.4.5.1. Requalification of the method shall be required if any of the following occur: < Evidence that the method may not be providing data in accordance with the requirements of

Table 24. < Results that differ from the reported final average of a CCRL-PSP sample with a rating of

three or less. < Results that differ from the accepted value of a known reference sample with established

strength values by more than twice the multilaboratory 1s percent values of Table 24. Before starting the requalification procedure, evaluate all aspects of cube fabrication and the testing process to determine if the offending result is due to some systematic error or just an occasional random event.

10.4.5.2. If the compaction equipment is replaced, significantly modified, repaired, or has been recalibrated, requalify the equipment in accordance with Section 10.4.4.

10.5. Storage of Test Specimens—Immediately upon completion of molding, place the test specimens in the moist closet or moist room. Keep all test specimens, immediately after molding, in the molds on the base plates in the moist closet or moist room from 20 to 72 h with their upper surfaces exposed to the moist air but protected from dripping water. If the specimens are removed from the molds before 24 h, keep them on the shelves of the moist closet or moist room until they are 24 h old. Then immerse the specimens, except those for the 24-h test, in saturated lime water in storage tanks constructed of noncorroding materials. Keep the storage water clean by changing as required.

10.6. Determination of Compressive Strength:

10.6.1. Test the specimens immediately after their removal from the moist closet in the case of 24-h specimens, and from storage water in the case of all other specimens. All test specimens for a given test age shall be broken within the permissible tolerance prescribed as follows in Table 3:

Table 3—Testing Time Tolerances Test Age Permissible Tolerance

24 h ±1/2 h 3 days ±1 h 7 days ±3 h 28 days ±12 h 56 days ±24 ho

If more than one specimen at a time is removed from the moist closet for the 24-h tests, keep these specimens covered with a damp cloth until time of testing. If more than one specimen at a time is removed from the storage water for testing, keep these specimens in water at a temperature of 23 ± 2°C [73.5 ± 3.5°F] and of sufficient depth to completely immerse each specimen until time of testing.

10.6.2. Wipe each specimen to a surface-dry condition, and remove any loose sand grains or incrustations from the faces that will be in contact with the bearing blocks of the testing machine. Check these faces by applying a straightedge (see Note 910). If there is appreciable curvature, grind the face or faces to plane surfaces or discard the specimen. A periodic check of the cross-sectional area of the specimen should be made. Note 910—Specimen Faces—Results much lower than the true strength will be obtained by loading faces of the cube specimen that are not truly plane surfaces. Therefore, it is essential that the specimen molds be kept scrupulously clean; otherwise, large irregularities in the surface will occur. Instruments for cleaning molds should always be softer than the metal in the molds to prevent wear. In case grinding specimen faces is necessary, it can be accomplished best by

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rubbing the specimen on a sheet of fine emery paper or cloth glued to a plane surface, using only a moderate pressure. Such grinding is tedious for more than a few hundredths of a millimeter (thousandths of an inch); where more than this is found necessary, it is recommended that the specimen be discarded.

10.6.3. Apply the load to specimen faces that were in contact with the true plane surfaces of the mold. Carefully place the specimen in the testing machine below the center of the upper bearing block. Prior to the testing of each cube, it shall be ascertained that the spherically seated block is free to tilt. Use no cushioning or bedding materials. Bring the spherically seated block into uniform contact with the surface of the specimen. Apply the load rate at a relative rate of movement between the upper and lower platens corresponding to a loading on the specimen with the range of 900 to 1800 N/s [200 to 400 lb/s]. Obtain this designated rate of movement of the platen during the first half of the anticipated maximum load and make no adjustment in the rate of movement of the platen in the latter half of the loading, especially while the cube is yielding before failure. (See Note 10.11) Note 1011—It is advisable to apply only a very light coating of a good quality, light mineral oil to the spherical seat of the upper platen.

11. CALCULATION

11.1. Record the total maximum load indicated by the testing machine, and calculate the compressive strength as follows:

(1) where: fm = compressive strength in MPa [psi], P = total maximum load in N [lbf], and A = area of loaded surface in mm2 [in.2]. Either 50-mm or 2-in. cube specimens may be used for the determination of compressive strength, whether SI or inch-pound units are used. However, consistent units for load and area must be used to calculate strength in the units selected. If the cross-sectional area of the specimen varies more than 1.5 percent from the nominal, use the actual area for the calculation of the compressive strength. The compressive strength of all acceptable test specimens (see Section 13) made from the same sample and tested at the same period shall be averaged and reported to the nearest 0.1 MPa [10 psi].

12. REPORT

12.1. Report the flow to the nearest 1 percent and the water used to the nearest 0.1 percent. Average compressive strength of all specimens from the same sample shall be reported to the nearest 0.1 MPa [10 psi].

13. FAULTY SPECIMENS AND RETESTS

13.1. In determining the compressive strength, do not consider specimens that are manifestly faulty.

13.2. The maximum permissible range between specimens from the same mortar batch, at the same test age, is 8.7 percent of the average when three cubes represent a test age and 7.6 percent when two cubes represent a test age (see Note 1112). Note 1112—The probability of exceeding these ranges is 1 in 100 when the within-batch coefficient of variation is 2.1 percent. The 2.1 percent is an average for laboratories participating

/fm P A=

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in the portland cement and masonry cement reference sample programs of the Cement and Concrete Reference Laboratory (CCRL).

13.3. If the range of three specimens exceeds the maximum in Section 13.2, discard the result that differs most from the average and check the range of the remaining two specimens. Make a retest of the sample if fewer than two specimens remain after discarding faulty specimens or discarding tests that fail to comply with the maximum permissible range of two specimens. (See Notes 1213 and 1314.) Note 1213—Example for Permissible Range—For a data set of three cubes (31.0, 34.0, and 35.0 MPa) the average strength is 33.3 MPa with a range of 4.0 MPa. According to the 8.7% limit, the range should not be more than 2.9 MPa (33.3 × 0.087). Since the range here is greater than 2.9 MPa, discard the value most different from the average, in this case 31.0 MPa. Now, the new average based on only two specimens is 34.5 MPa and the range should not be more than 2.6 MPa (34.5 × 0.076). Since the difference between the two values is less than the range this is an acceptable data set and the reported average should be 34.5 MPa. Note 1314—Reliable strength results depend upon careful observance of all the specified requirements and procedures. Erratic results at a given test period indicate that some of the requirements and procedures have not been carefully observed (e.g., those covering the testing of the specimens as prescribed in Sections 10.6.2 and 10.6.3). Improper centering of specimens resulting in oblique fractures or lateral movement of one of the heads of the testing machine during loading will often cause lower strength results.

14. PRECISION AND BIAS

14.1. Precision—The precision statements for this test method are listed in Table 4 and are based on results from the CCRL Reference Sample Program. They are developed from data where a test result is the average of compressive strength tests of three cubes molded from a single batch of mortar and tested at the same age. A significant change in precision will not be noted when a test result is the average of two cubes rather than three.

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Table 4—Precision

Test Age, Days

Coefficient of

Variation 1s, Percenta

Acceptable Range of Test Results d2s,

Percenta

Portland cements: Constant water as percent of cement-cement ratio:

Single-laboratory 3 4.0 11.3 7 3.6 10.2 Av 3.8 10.7 Multilaboratory 3 6.8 19.2 7 6.4 18.1 Av 6.6 18.7 Blended cements (excluding portland-limestone cements):

Constant flow mortar: Single-laboratory 3 4.0 11.3 7 3.8 10.7 28 3.4 9.6 Av 3.8 10.7 Multilaboratory 3 7.8 22.1 7 7.6 21.5 28 7.4 20.9 Av 7.6 21.5 Masonry cements: Constant flow mortar: Single-laboratory 7 7.9 22.3 28 7.5 21.2 Av 7.7 21.8 Multilaboratory 7 11.8 33.4 28 12.0 33.9 Av 11.9 33.7

a These numbers represent, respectively, the (1s percent) and (d2s percent) limits as described in ASTM C670. Precision data for tests at ages of 24 hours and 56 days are not available.

14.2. These precision statements are applicable to mortars made with cements mixed and tested at the ages as noted. The appropriate limits are likely somewhat larger for tests at younger ages and slightly smaller for tests at older ages.

14.3. Bias—The procedure in this test method has no bias because the value of compressive strength is defined in terms of the test method.

15. KEYWORDS

15.1. Compressive strength; hydraulic cement mortar; hydraulic cement strength; mortar strength; strength.

16

16. REFERENCE

16.1. Goodspeed, C. H., S. Vanikar, and R. Cook. High Performance Concrete Defined for Highway Structures. Concrete International, Vol. 18, No. 2, February 1996, pp. 62–67.


COMP_TS3a-20-01

Item 7: T105 – Standard Method of Test for Chemical Analysis of

Hydraulic Cement, Revisions to subsection 7.3.1


Chemical Analysis of

Hydraulic Cement

AASHTO Designation: T 105-201



ASTM Designation: C114-18


TS-3a T 105-1 AASHTO


Chemical Analysis of Hydraulic Cement

AASHTO Designation: T 105-201




1. SCOPE

1.1. These test methods cover the chemical analyses of hydraulic cements. Any test methods of

demonstrated acceptable precision and bias may be used for analysis of hydraulic cements,

including analyses for referee and certification purposes, as explained in Section 4. Specific

chemical test methods are provided for ease of reference for those desiring to use them. They are

grouped as Reference Test Methods and Alternate Test Methods. The reference test methods are

long accepted classical chemical test methods, which provide a reasonably well-integrated basic

scheme of analysis for hydraulic cements. The alternative test methods generally provide

individual determination of specific analytes and may be used alone or as alternates and

determinations within the basic scheme at the option of the analyst and as indicated in the

individual method. The individual analyst must demonstrate achievement of acceptable precision

and bias, as explained in Section 4, when these methods are used.

1.2. Contents:

Section Subject

2 Referenced Documents

3 Terminology

4 Description of Referee Analyses

4.1 Referee Analyses

5 Qualification for Different Analyses

5.1 Certified Reference Materials

5.2 Requirements for Qualification Testing

5.3 Alternative Analyses

5.4 Performance Requirements for Rapid Test Methods

6 General

6.1 Interferences and Limitations

6.2 Apparatus and Materials

6.3 Reagents

6.4 Sample Preparation

6.5 General Procedures

6.6 Recommended Order for Reporting Analyses


Section Reference Test Methods

7 Insoluble Residue

8 Silicon Dioxide

8.1 Selection of Test Method

8.2 Silicon Dioxide in Portland Cements and Cements with Low Insoluble Residue

8.3 Silicon Dioxide in Cements with Insoluble Residue Greater Than 1 Percent

9 Ammonium Hydroxide Group

10 Ferric Oxide

11 Phosphorus Pentoxide

12 Titanium Dioxide

13 Zinc Oxide

14 Aluminum Oxide

15 Calcium Oxide

16 Magnesium Oxide

17 Sulfur

17.1 Sulfur Trioxide

17.2 Sulfide

18 Loss on Ignition

18.1 Portland Cement

18.2 Portland Blast-Furnace Slag Cement and Slag Cement

19 Sodium and Potassium Oxides

19.1 Total Alkalis

19.2 Water-Soluble Alkalis

20 Manganic Oxide

21 Chloride

22 Chloroform-Soluble Organic Substances

Alternative Test Methods

23 Calcium Oxide

24 Carbon Dioxide

25 Magnesium Oxide

26 Loss on Ignition

26.1 Portland Blast-Furnace Slag Cement and Slag Cement

27 Titanium Dioxide

28 Phosphorus Pentoxide

29 Manganic Oxide

30 Free Calcium Oxide

Appendixes

Appendix X1 Example of Determination of Equivalence Point for the Chloride Determination

Appendix X2 CO2 Determinations in Hydraulic Cements

1.3. The values stated in SI units are to be regarded as the standard.

1.4. This standard does not purport to address all of the safety concerns, if any, associated with its use.

It is the responsibility of the user of this standard to consult and establish appropriate safety and


health practices and determine the applicability of regulatory limitations prior to use. See

Sections 8.3.2.1 and 16.4.1 for specific caution statements.


2.1. ASTM Standards:

C25, Standard Test Methods for Chemical Analysis of Limestone, Quicklime, and Hydrated

Lime

E29, Standard Practice for Using Significant Digits in Test Data to Determine Conformance

with Specifications

E275, Standard Practice for Describing and Measuring Performance of Ultraviolet and Visible

Spectrophotometers

E350, Standard Test Methods for Chemical Analysis of Carbon Steel, Low-Alloy Steel,

Silicon Electrical Steel, Ingot Iron, and Wrought Iron

E617, Standard Specification for Laboratory Weights and Precision Mass Standards

E832, Standard Specification for Laboratory Filter Papers

3. TERMINOLOGY

3.1. Definition:

3.1.1. analyte, n—A substance of interest when performing a quantitative analysis.

3.1.1.1. Discussion—For the purposes of this test method, analytes are considered to be those items listed

in Column 1 of Table 1.

3.1.2. reagent water, n—water purified by the process of distillation, deionization, reverse osmosis, or

any combination of the three processes.

3.1.2.1. distillation, n—the process of purification by the evaporation and vaporization of water and its

subsequent condensation and collection.

3.1.2.2. deionization, n—the process of purification using the two-step process of converting soluble salts

into acids by passing them through a hydrogen exchanger, after which they are removed by an

acid absorbent or synthetic resin.

3.1.2.3. reverse osmosis, n—water purification technology that uses a semipermeable membrane to

remove ions, molecules, and larger particles for from drinking water.

3.1.3. water (potable), n—water that is suitable for drinking.

4. DESCRIPTION OF REFEREE ANALYSES

4.1. Referee Analyses—When conformance to chemical specification requirements is questioned,

perform referee analyses as described in Section 4.1.1. The reference test methods that follow in

Sections 7 through 22, or other test methods qualified according to Section 5.4, Performance

Requirements for Rapid Test Methods, are required for referee analysis. A cement shall not be

rejected for failure to conform to chemical requirements unless all determinations of constituents

involved and all necessary separations prior to the determination of any one constituent are made

entirely by these methods. When reporting the results of referee analyses, specify which test

methods were used.


4.1.1. Referee analyses shall be made in duplicate and on different days. If the two results do not agree

within the permissible variation given in Table 1, the determination shall be repeated until two or

three results agree within the permissible variation. When two or three results do agree within the

permissible variation, their average shall be accepted as the correct value. When an average of

either two or three results can be calculated, the calculation shall be based on the three results. For

the purpose of comparing analyses and calculating the average of acceptable results, the

percentages shall be calculated to the nearest 0.01 (or 0.001 in the case of chloroform-soluble

organic substances), although some of the average values are reported to 0.1 as indicated in the

test methods. When a blank determination (see Note 1) is specified, one shall be made with each

individual analysis or with each group of two or more samples analyzed on the same day for a

given analyte.

Note 1—A blank determination is a procedure that follows all steps of analysis, but in the

absence of a sample. It is used for detection and compensation of systematic bias.


Table 1—Maximum Permissible Variation in Resultsa

(Column 1)

Analyte

(Column 2)

Maximum Difference

between Duplicatesb

(Column 3)

Maximum Difference

of the Average of

Duplicates from CRM

Certificate Valuesb ,c ,d

SiO2 (silicon dioxide) 0.16 0.20

Al2O3 (aluminum oxide) 0.20 0.20

Fe2O3 (ferric oxide) 0.10 0.10

CaO (calcium oxide) 0.20 0.30

MgO (magnesium oxide) 0.16 0.20

SO3 (sulfur trioxide) 0.10 0.10

LOI (loss on ignition) 0.10 0.10

Na2O (sodium oxide) 0.03 0.05

K2O (potassium oxide) 0.03 0.05

TiO2 (titanium dioxide) 0.02 0.03

P2O5 (phosphorus pentoxide) 0.03 0.03

ZnO (zinc oxide) 0.03 0.03

Mn2O3 (manganic oxide) 0.03 0.03

S (sulfide sulfur) 0.01 e

Cl (chloride) 0.003 ±0.005e

IR (insoluble residue) 0.10 e

Cx (free calcium oxide) 0.20 e

CO2 (carbon dioxide) 0.12 e, f

Alksol (water-soluble alkali)g 0.75/ w g e

Chlsol (chloroform-soluble organic substances) 0.004 e

a When all seven Certified Reference Material (CRM) cements are required, as for demonstrating performance of rapid test methods,

at least six of the seven shall be within the prescribed limits, and the seventh shall differ by no more than twice that value. When more

than seven CRMs are used, as for demonstrating the performance of rapid test methods, at least 77 percent shall be within the

prescribed limits, and the remainder no more than twice the value. When a lesser number of CRM cements are required, all of the

values shall be within the prescribed limits. b Where no value appears in Column 3, CRM certificate values do not exist. In such cases, only the requirement for differences

between duplicates shall apply. c Interelement corrections may be used for any oxide standardization provided improved accuracy can be demonstrated when

correction is applied to all seven CRM cements.

d Where a CRM certificate value includes a subscript number, that subscript number shall be treated as a valid significant figure. e Not applicable. No certificate value given. f Demonstrate performance by analysis, in duplicate, of at least one portland cement. Prepare three standards, each in duplicate:

Standard A shall be selected portland cement, Standard B shall be Standard A containing 2.00 percent Certified CaCO3

(e.g., NIST 915a), Standard C shall be Standard A containing 5.00 percent Certified CaCO3. Weigh and prepare two separate

specimens of each standard. Assign the CO2 content of Standard A as the average of the two values determined, provided they agree

within the required limit of Column 2. Assign CO2 values to Standards B and C as follows: Multiply the Certified CaCO3 value (Y)

for CO2 (from the certificate value) by the mass fraction of Certified CaCO3 added to that standard (percentage added divided by 100);

multiply the value determined for Standard A by the mass fraction of Standard A in each of the other standards (i.e., 0.98 and 0.95

for Standards B and C, respectively); add the two values for Standards A and B, respectively; call these values B and C.

Example:

B = 0.98A + 0.02Y.

C = 0.95A + 0.05Y.

where for Certified CaCO3, if Y= 39.9 percent

B = 0.98A + 0.80 percent by mass.

C = 0.95A + 2.00 percent by mass.

Maximum difference between the duplicate CO2 values for Standards B and C, respectively, shall be 0.17 and 0.24 percent by mass.

Averages of the duplicate values for Standards B and C shall differ from their assigned values (B and C) by no more than 10 percent

of those respective assigned values. g w = mass, in grams, of samples used for the test.


5. QUALIFICATION FOR DIFFERENT ANALYSES

5.1. Certified Reference Materials—A Certified Reference Material (CRM) must be used in the

qualification of test methods and analysts. Acceptable reference cements are National Institute of

Standards and Technology (NIST) CRMs or other reference cements traceable to the NIST CRMs.

The reference cement must have an assigned value for the analyte being determined. Traceability

consists of documentary evidence that the assigned values of the reference cement are compatible

with the certified values of NIST CRMs. To demonstrate traceability for a given analyte, perform

a referee analysis (as defined in Section 4.1) on the proposed reference cement, using an NIST

CRM for demonstration of precision and accuracy. The reference cement is acceptable if its

assigned value agrees with the average referee value within the limits given in Column 3 of

Table 1. If the reference cement, as supplied, has no documented guarantee of homogeneity,

establish its homogeneity by analyzing at least six randomly selected samples. No result shall

deviate from the assigned value by more than the limits given in Column 2 of Table 1. An

acceptable reference cement must be accompanied by a document showing the data produced in

demonstrating traceability and homogeneity.

5.2. Requirements for Qualification Testing—Qualified test methods are required whenever testing is

performed for the following reasons: (1) Referee analyses, (2) analyses intended for use as a basis

for acceptance or rejection of a cement, or (3) manufacturer’s certification. When Reference

methods are used, qualification testing of the analyst is required as described in Section 5.2.1.

When Rapid methods are used, qualification testing of both the analyst and the test method are

required as described in Sections 5.2.1 and 5.4. Such demonstration may be made concurrently

with analysis of the cement being tested. The requirements for qualification of a test method and

analyst are summarized in Table 2.

Table 2—Minimum Number of CRMs Required for Qualification of Chemical Testing

Equipment Qualification

Operator Qualificationc

Method Type

Referencea Otherb

None 7

1 1

a Reference methods are those outlined in Sections 7 through 22. b These may be any test method as described in Section 5.3, Alternative Analyses, or any instrumental or rapid test method,

which must be qualified in accordance with Section 5.4, Performance Requirements for Rapid Test Methods. c Each analyst performing acceptance or reference analyses must be qualified in accordance with Section 5.2.1, Performance

Requirements for Rapid Test Methods, at a frequency of 2 years. If qualification of the instrument is completed by a

single analyst, the analyst has demonstrated individual qualifications per Section 5.2.1.

Initial qualification of the analyst shall be demonstrated by analysis of each constituent of concern

in at least one CRM cement in duplicate, no matter what test method is used (Note 2)). Duplicate

samples shall be run on different days. The same test methods to be used for analysis of cement

being tested shall be used for analysis of the CRM cement. If the duplicate results do not agree

within the permissible variation given in Table 1, the determinations shall be repeated, following

identification and correction of problems or errors, until a set of duplicate results do agree within

the permissible variation. Requalification of the analyst is required every two years.

Note 2—When qualifying a rapid method with seven CRMs in accordance with Section 5.4.2, the

analyst performing the qualification of the test method may simultaneously qualify for the

requirement of Section 5.2.1.

5.2.1. The average of the results of acceptable duplicate determinations for each constituent may differ

from the CRM assigned value by no more than the value shown in Column 3 of Table 1 after

necessary corrections for minor analytes are made.

5.2.2. Qualification data demonstrating that the same operator or analyst making the acceptance

determination obtained precise and accurate results with CRM cements as per Section 5.4 shall be


made available on request to all parties concerned when there is a question of acceptance of a

cement. If the CRM used is not an NIST cement, the traceability documentation of the CRM used

shall also be made available on request.

5.3. Alternative Analyses—The alternative test methods provide, in some cases, procedures that are

shorter or more convenient to use for routine determination of certain constituents than are the

reference test methods (see Note 3). Longer, more complex procedures, in some instances, have

been retained as alternative test methods to permit comparison of results by different procedures or

for use when unusual materials are being examined, where unusual interferences may be

suspected, or when unusual preparation for analysis is required. Test results from alternative test

methods may be used as a basis for acceptance or rejection when it is clear that a cement does or

does not meet the specification requirement. Any change in test method procedures from those

procedures listed in Sections 7 through 30 requires method qualification in accordance with

Section 5.4, Performance Requirements for Rapid Test Methods.

Note 3—It is not intended that the use of reference test methods be confined to referee analysis.

A reference test method may be used in preference to an alternative test method when so desired.

A reference test method must be used where an alternative test method is not provided.

5.3.1. Duplicate analyses and blank determinations are not required when using the alternative test

methods. If, however, a blank determination is desired for an alternative test method, one may be

used, and it need not have been obtained concurrently with the analysis. The final results, when

corrected for blank values, should, in either case, be so designated.

5.4. Performance Requirements for Rapid Test Methods2, 3:

5.4.1. Definition and Scope—When analytical data obtained in accordance with this test method are

required, any test method may be used that meets the requirements of Section 5.4.2, Qualification

of a Test Method. A test method is considered to consist of the specific procedures, reagents,

supplies, equipment, instrument, and so forth, selected and used in a consistent manner by a

specific laboratory. See Note 4 for examples of procedures.

Note 4—Examples of test methods used successfully by their authors for analysis of hydraulic

cement are given in the list of references. Included are test methods using atomic absorption X-ray

spectrometry and spectrophotometry-EDTA.

5.4.1.1. If more than one instrument, even though substantially identical, is used in a specific laboratory

for the same analyses, use of each instrument shall constitute a separate test method and each must

be qualified separately.

5.4.2. Qualification of a Test Method—Prior to use for analysis of hydraulic cement, each test method

(see Section 5.4.1) must be qualified individually for such analysis. Qualification data, or if

applicable, requalification data, shall be made available pursuant to the Manufacturer’s

Certification section of the appropriate hydraulic cement specification.

5.4.2.1. Using the test method chosen, make single determinations for each analyte under consideration on

at least seven CRM samples. Requirements for a CRM are listed in Section 5.1, Certified

Reference Materials. Complete two rounds of tests on different days repeating all steps of sample

preparations. Calculate the differences between values and averages of the values from the two

rounds of tests.

5.4.2.2. When seven CRMs are used in the qualification procedure, at least six of the seven differences

between duplicates obtained of any single analyte shall not exceed the limits shown in Column 2

of Table 1 and the remaining differences by no more than twice that value. When more than seven

CRMs are used, the values for at least 77 percent of the samples shall be within the prescribed

limits, while the values for the remainder shall differ by no more than twice that value.


5.4.2.3. For each analyte and each CRM, the average obtained shall be compared to the certified

concentrations. Where a certificate value includes a subscript number, that subscript shall be

assumed to be a significant number. When seven CRMs are used in the qualification procedure, at

least six of the seven averages for each analyte shall not differ from the certified concentrations by

more than the value shown in Column 3 of Table 1, and the remaining average by more than twice

that value. When more than seven CRMs are used in the qualification procedure, at least

77 percent of the averages for each analyte shall not differ from the certified concentrations by

more than the value shown in Column 3 of Table 1, and the remaining average(s) by more than

twice that value.

5.4.2.4. The standardization, if needed, used for qualification and analysis of each constituent shall be

determined by valid curve-fitting procedures. A point-to-point, sawtooth curve that is artificially

made to fit a set of data points does not constitute a valid curve-fitting procedure. A complex

polynomial drawn through the points is similarly not valid. For the same reason, empirical

interelement corrections may be used only if (N – 3)/2 is employed, where N is the number of

different standards used. The qualification testing shall be conducted with specimens newly

prepared from scratch, including all the preparation stages applicable for analysis of an unknown

sample, and employing the reagents currently in use for unknown analyses.

5.4.3. Partial Results—Test methods that provide acceptable results for some analytes but not for others

may be used only for those analytes for which acceptable results are obtained.

5.4.4. Report of Results—When performing chemical analysis and reporting results for Manufacturer’s

Certification, the type of method (Reference or Rapid) and the test method used, along with any

supporting qualification testing, shall be available on request.

5.4.5. Rejection of Material—See Section 4.1, Referee Analyses, and Section 5.3, Alternative Analyses.

5.4.6. Requalification of a Test Method:

5.4.6.1. Requalification of a test method shall be required upon receipt of substantial evidence that the test

method may not be providing data in accordance with Table 1 for one or more constituents. Such

requalification may be limited to those constituents indicated to be in error and shall be carried out

prior to further use of the method for analysis of those constituents.

5.4.6.2. Substantial evidence that a test method may not be providing data in accordance with Table 1 shall

be considered to have been received when a laboratory is informed that analysis of the same

material by Reference Test Methods run in accordance with Section 4.1.1, the final average of a

Cement and Concrete Reference Laboratory (CCRL) sample, a certificate value of an NIST CRM,

the assigned value of an alternate CRM, or an accepted value of a known secondary standard

differs from the value obtained by the test method in question by more than twice the value shown

in Column 2 of Table 1 for one or more constituents. When indirect test methods are involved, as

when a value is obtained by difference, corrections shall be made for minor constituents to put

analyses on a comparable basis prior to determining the differences. For any constituents affected,

a test method also shall be requalified after any substantial repair or replacement of one or more

critical analytes of an instrument essential to the test method.

5.4.6.3. If an instrument or piece of equipment is replaced, even if by one of identical make or model, or is

significantly modified, a previously qualified test method using such new or modified instrument

or equipment shall be considered a new method and must be qualified in accordance with

Section 5.4.2.

5.4.7. Precision and Bias—Different analytical test methods are subject to individual limits of precision

and bias. It is the responsibility of the user to demonstrate that the test methods used at least meet

the limits of precision and bias shown in Table 1.


6. GENERAL

6.1. Interferences and Limitations:

6.1.1. These test methods were developed primarily for the analysis of portland cements. However,

except for limitations noted in the procedure for specific constituents, the reference test methods

provide for accurate analyses of other hydraulic cements that are completely decomposed by

hydrochloric acid, or where a preliminary sodium carbonate fusion is made to ensure complete

solubility. Some of the alternative test methods may not always provide accurate results because

of interferences from elements that are not removed during the procedure.

Note 5—Instrumental analyses can usually detect only the element sought. Therefore, to avoid

controversy, the actual procedure used for the elemental analyses should be noted when actual

differences with reference procedures can exist. For example, P2O5 and TiO2 are included with

Al2O3 in the usual wet test method and sulfide sulfur is included in most instrumental procedures

with SO3.

6.1.2. When using a test method that determines total sulfur, such as most instrumental test methods,

sulfide sulfur will be determined with sulfate and included as such. In most hydraulic cements, the

difference resulting from such inclusion will be insignificant, less than 0.05 weight percent. In

some cases, notably slags and slag-containing cements but sometimes other cements as well,

significant levels of sulfide may be present. In such cases, especially if there is a question of

meeting or not meeting a specification limit or when the most accurate results are desired,

analytical test methods shall be chosen so that sulfate and sulfide can be reported separately.

Where desired, when using instrumental test methods for sulfate determination, if sulfide has been

determined separately, correct the total sulfur results (expressed as an oxide) in accordance with

the following calculation:

SO3 = Stotal – (2.5S –) (1)

where:

SO3 = sulfur trioxide excluding sulfur,

Stotal = total sulfur in the sample, expressed as the oxide, from instrumental results,

2.5 = molecular ratio of SO3/S– to express sulfur as SO3, and

S – = sulfide sulfur present.

6.2. Apparatus and Materials:

6.2.1. Balance—The analytical balance used in the chemical determinations shall conform to the

following requirements:

6.2.1.1. The balance shall be capable of reproducing results within 0.0002 g, with an accuracy of

0.0002 g. Direct-reading balances shall have a sensitivity not exceeding 0.0001 g (see Note 6).

Conventional two-pan balances shall have a maximum sensibility reciprocal of 0.0003 g. Any

rapid weighing device that may be provided, such as a chain, damped motion, or heavy riders,

shall not increase the basic inaccuracy by more than 0.0001 g at any reading and with any load

within the rated capacity of the balance.

Note 6—The sensitivity of a direct-reading balance is the weight required to change the reading

one graduation. The sensibility reciprocal for a conventional balance is defined as the change in

weight required on either pan to change the position of equilibrium one division on the pointer

scale at capacity or at any lesser load.

6.2.2. Weights—Weights used for analysis shall conform to Types I or II, Grades S or O, Classes 1, 2,

or 3, as described in ASTM E617. They shall be checked at least once a year, or when questioned,

and adjusted at least to within allowable tolerances for Class 3 weights (see Note 7). For this

purpose, each laboratory shall also maintain, or have available for use, a reference set of standard


weights from 50 g to 10 mg, which shall conform at least to Class 3 requirements and be

calibrated at intervals not exceeding 5 years by the NIST. After initial calibration, recalibration by

the NIST may be waived, provided it can be shown by documented data obtained within the time

interval specified that a weight comparison between summations of smaller weights and a single

larger weight nominally equal to that summation establishes that the allowable tolerances have not

been exceeded. All new sets of weights purchased shall have the weights of 1 g and larger made of

stainless steel or other corrosion-resisting alloy not requiring protective coating, and shall meet the

density requirements for Grades S or O.

Note 7—The scientific supply houses do not presently list weights as meeting ASTM E617. They

list weights as meeting NIST or International Organization of Legal Metrology (OIML) standards.

The situation with regard to weights is in a state of flux because of the trend toward

internationalization. Hopefully, this will soon be resolved. NIST Classes S and S-1 and OIML

Class F1 weights meet the requirements of this standard.

6.2.3. Glassware and Laboratory Containers—Standard volumetric flasks, burets, and pipets should be

of precision grade or better. Standard-taper, interchangeable, ground-glass joints are recommended

for all volumetric glassware and distilling apparatus, when available. Wherever applicable, the use

of special types of glassware (e.g., colored glass for the protection of solutions against light,

alkali-resistant glass, and high-silica glass having exceptional resistance to thermal shock) is

recommended. Polyethylene containers are recommended for all aqueous solutions of alkalis

and for standard solutions where the presence of dissolved silica or alkali from the glass would be

objectionable. Such containers shall be made of high-density polyethylene having a wall thickness

of at least 1 mm.

6.2.4. Desiccators—Desiccators shall be provided with a good desiccant such as magnesium perchlorate,

activated alumina, or sulfuric acid. Anhydrous calcium sulfate may also be used, provided it has

been treated with a color-change indicator to show when it has lost its effectiveness. Calcium

chloride is not a satisfactory desiccant for this type of analysis.

6.2.5. Filter Paper—Filter paper shall conform to the requirements of ASTM E832, Type II,

Quantitative. When coarse-textured paper is required, Class E paper shall be used; when medium-

textured paper is required, Class F paper shall be used; and when retentive paper is required,

Class G paper shall be used.

6.2.6. Crucibles:

6.2.6.1. Platinum Crucibles—For ordinary chemical analysis, platinum crucibles should preferably be

made of pure unalloyed platinum and be of 15 to 30 mL capacity. Where alloyed platinum is used

for greater stiffness or to obviate sticking of crucible and lid, the alloyed platinum shall not

decrease in weight by more than 0.2 mg when heated at 1200°C for 1 h.

6.2.6.2. Porcelain Crucibles—Should be glazed inside and out, except for the outside bottom and rim, and

be of 5–10 mL capacity.

6.2.7. Muffle Furnace—The muffle furnace shall be capable of operation at the temperatures required

and shall have an indicating pyrometer accurate within 25°C, as corrected, if necessary, by

calibration. More than one furnace may be used, provided each is used within its proper operating

temperature range.

6.3. Reagents:

6.3.1. Purity of Reagents—Reagent grade chemicals shall be used in all tests. Unless otherwise

indicated, it is intended that all reagents shall conform to the specifications of the Committee on

Analytical Reagents of the American Chemical Society, where such specifications are available.4


Other grades may be used, provided it is first ascertained that the reagent is of sufficiently high

purity to permit its use without lessening the accuracy of the determination.

6.3.2. Use reagent water as defined in Section 3.1.2 for all tests.

6.3.3. Concentration of Reagents:

6.3.3.1. Prepackaged Reagents—Commercial prepackaged standard solutions or diluted prepackaged

concentrations of a reagent may be used whenever that reagent is called for in the procedures,

provided the purity and concentrations are as specified. Verify purity and concentration of such

reagents by suitable tests.

6.3.3.2. Concentrated Acids and Ammonium Hydroxide—When acids and ammonium hydroxide are

specified by name or chemical formula only, it shall be understood that concentrated reagents of

the following specific gravities or concentrations by weight are intended:

Acetic acid (HC2H3O2) 99.5 percent

Hydrochloric acid (HCl) sp gr 1.19

Hydrofluoric acid (HF) 48 percent

Nitric acid (HNO3) sp gr 1.42

Phosphoric acid (H3PO4) 85 percent

Sulfuric acid (H2SO4) sp gr 1.84

Ammonium hydroxide (NH4OH) sp gr 0.90

6.3.3.3. The desired specific gravities or concentrations of all other concentrated acids shall be stated

whenever they are specified.

6.3.4. Diluted Acids and Ammonium Hydroxide—Concentrations of diluted acids and ammonium

hydroxide, except when standardized, are specified as a ratio stating the number of volumes of the

concentrated reagent to be added to a given number of volumes of water (e.g., HCl (1+99) means

1 volume of concentrated HCl (sp gr 1.19) added to 99 volumes of water).

6.3.5. Standard Solutions—Concentrations of standard solutions shall be expressed as normalities (N) or

as equivalents in grams per milliliter of the analyte to be determined (e.g., 0.1 N Na2S2O3 solution

or K2Cr2O7 (1 mL = 0.004 g Fe2O3)). The average of at least three determinations shall be used for

all standardizations. When a material is used as a primary standard, reference has generally been

made to the standard furnished by NIST. However, when primary standard grade materials are

otherwise available, they may be used, or the purity of a salt may be determined by suitable tests.

6.3.6. Nonstandardized Solutions—Concentrations of nonstandardized solutions prepared by dissolving

a given weight of the solid reagent in a solvent shall be specified in grams of the reagent per liter

of solution, and it shall be understood that water is the solvent unless otherwise specified (e.g.,

NaOH solution (10 g/L) means 10 g of NaOH dissolved in water and diluted with water to 1 L).

Other nonstandardized solutions may be specified by name only, and the concentration of such

solutions will be governed by the instructions for their preparation.

6.3.7. Indicator Solutions:

6.3.7.1. Methyl Red—Prepare the solution on the basis of 2 g of methyl red/L of 95 percent ethyl alcohol.

6.3.7.2. Phenolphthalein—Prepare the solution on the basis of 1 g of phenolphthalein/L of 95 percent

ethyl alcohol.

6.4. Sample Preparation:


6.4.1. Before testing, pass representative portions of each sample through a No. 20 (850 μm) sieve or any

other sieve having approximately 20 openings per 1 in. to mix the sample, break up lumps, and

remove foreign materials. Discard the foreign materials and hardened lumps that do not break up

on sieving or brushing.

6.4.2. By means of a sample splitter or by quartering, the representative sample shall be reduced to a

laboratory sample of at least 50 g. Where larger quantities are required for additional

determinations such as water-soluble alkali, chloride, and duplicate testing, and so forth, prepare a

sample of at least 100 g.

6.4.3. Pass the laboratory sample through a No. 100 (150-μm) sieve. Further grind the sieve residue so

that it also passes the No. 100 sieve. Homogenize the entire sample by again passing it through the

sieve.

6.4.4. Transfer the sample to a clean, dry, glass container with an airtight lid, and further mix the sample

thoroughly.

6.4.5. Expedite the above procedure so that the sample is exposed to the atmosphere for a minimum

time.

6.5. General Procedures:

6.5.1. Weighing—The calculations included in the individual test methods assume that the exact weight

specified has been used. Accurately weighed samples, that are approximately but not exactly equal

to the weight specified, may be used provided appropriate corrections are made in the calculations.

Unless otherwise stated, weights of all samples and residues should be recorded to the nearest

0.0001 g.

6.5.2. Tared or Weighed Crucibles—The tare weight of crucibles shall be determined by preheating the

empty crucible to constant weight at the same temperature and under the same conditions as shall

be used for the final ignition of a residue and cooling in a desiccator for the same period of time

used for the crucible containing the residue.

6.5.3. Constancy of Weight of Ignited Residues—To definitely establish the constancy of weight of an

ignited residue for referee purposes, the residue shall be ignited at the specified temperature and

for the specified time, cooled to room temperature in a desiccator, and weighed. The residue shall

then be reheated for at least 30 min, cooled to room temperature in a desiccator, and reweighed. If

the two weights do not differ by more than 0.2 mg, constant weight is considered to have been

attained. If the difference in weights is greater than 0.2 mg, additional ignition periods are required

until two consecutive weights agree within the specified limits. For ignition loss, each reheating

period shall be 5 min.

6.5.4. Volatilization of Platinum—The possibility of volatilization of platinum or alloying constituents

from the crucibles must be considered. On reheating, if the crucible and residue lose the same

weight (within 0.2 mg) as the crucible containing the blank, constant weight can be assumed.

Crucibles of the same size, composition, and history shall be used for both the sample and the

blank.

6.5.5. Calculation—In all operations on a set of observed values such as manual multiplication or

division, retain the equivalent of at least two more places of figures than in the single observed

values. For example, if observed values are read or determined to the nearest 0.1 mg, carry

numbers to the nearest 0.001 mg in calculation. When using electronic calculators or computers

for calculations, perform no rounding, except in the final reported value.


6.5.6. Rounding Figures—Rounding of figures to the number of significant places required in the report

should be done after calculations are completed to keep the final results substantially free of

calculation errors. The rounding procedure should follow the principle outlined in ASTM E29.5 In

assessing analyst and method qualification in accordance with Section 5, the individual duplicate

results, the difference between them, the average of duplicates on CRMs, and the difference of this

average from the certificate value shall be left unrounded for comparison with the required limits.

(See Note 8.) Round results for reporting as shown in Table 3.

Note 8—The rounding procedure referred to in Section 6.5.6, in effect, drops all digits beyond

the number of places to be retained if the next figure is less than 5. If it is more than 5 or equal to 5

and subsequent places contain a digit other than 0, then the last retained digit is increased by one.

When the next digit is equal to 5 and all other subsequent digits are 0, the last digit to be retained

is unchanged when it is even and increased by one when it is odd. For example, 3.96 (50) remains

3.96, but 3.95 (50) becomes 3.96.

6.6. Recommended Order for Reporting Analyses—The following order is recommended for reporting

the results of chemical analysis of hydraulic cement:

SiO2 (silicon dioxide)

Al2O3 (aluminum oxide)

Fe2O3 (ferric oxide)

CaO (calcium oxide)

MgO (magnesium oxide)

SO3 (sulfur trioxide)

Na2O (sodium oxide)

K2O (potassium oxide)

TiO2 (titanium dioxide)

P2O5 (phosphorus pentoxide)

ZnO (zinc oxide)

Mn2O3 (manganic oxide)

Insoluble residue

Free calcium oxide

CO2 (carbon dioxide)

Water-soluble alkali

Chloroform-soluble organic substances


Table 3—Rounding of Reported Results

Analyte Decimal Places

SiO2 (silicon dioxide) 1

Al2O3 (aluminum oxide) 1

Fe2O3 (ferric oxide) 2

CaO (calcium oxide) 1

MgO (magnesium oxide) 1

SO3 (sulfur trioxide) 2

LOI (loss on ignition) 1

Na2O (sodium oxide) 2

K2O (potassium oxide) 2

SrO (strontium oxide) 2

TiO2 (titanium dioxide) 2

P2O5 (phosphorous pentoxide) 2

ZnO (zinc oxide) 2

Mn2O3 (manganic oxide) 3

S (sulfide sulfur) 2

Cl (chloride) 3

IR (insoluble residue) 2

Cx (free calcium oxide) 1

CO2 (carbon dioxide) 1

Alksol (water-soluble alkali) 2

Chlsol (chloroform-soluble organic substances) 3

REFERENCE TEST METHODS

7. INSOLUBLE RESIDUE (REFERENCE TEST METHOD)

7.1. Summary of Test Method:

7.1.1. In this test method, insoluble residue of a cement is determined by digestion of the sample in

hydrochloric acid followed, after filtration, by further digestion in sodium hydroxide. The

resulting residue is ignited and weighed (see Note 9).

Note 9—This test method, or any other test method designed for the estimation of an acid-

insoluble substance in any type of cement, is empirical because the amount obtained depends on

the reagents and the time and temperature of digestion. If the amount is large, there may be a little

variation in duplicate determinations. The procedure should be followed closely to reduce the

variation to a minimum.

7.1.2. When this test method is used on blended cement, the decomposition in acid is considered to be

complete when the portland cement clinker is decomposed completely. An ammonium nitrate

solution is used in the final washing to prevent finely ground insoluble material from passing

through the filter paper.

7.2. Reagents:

7.2.1. Ammonium Nitrate Solution (20 g NH4NO3/L).

7.2.2. Sodium Hydroxide Solution (10 g NaOH/L).


7.3. Procedure:

7.3.1. To 1 g of the sample (see Note 10), add 25 mL of cold water. Disperse the cement in the water and

while swirling the mixture, quickly add 5 mL of HCl. If necessary, warm the solution gently and

grind the material with the flattened end of a glass rod for a few minutes until it is evident that

decomposition of the cement is complete (see Note 11). Dilute the solution to 50 mL with hot

water (nearly boiling) and heat the covered mixture rapidly to near boiling by means of a high-

temperature hot plate. Then digest the covered mixture for 15 min at a temperature just below

boiling (see Note 12). Filter the solution through a medium-textured paper into a 400mL beaker;

wash the beaker, paper, and residue thoroughly with hot water; and reserve the filtrate for the

sulfur trioxide determination, if desired (see Note 13). Transfer the filter paper and contents to the

original beaker, add 100 mL of hot (near boiling) NaOH solution (10 g/L), and digest at a

temperature just below boiling for 15 min. During the digestion, occasionally stir the mixture and

macerate the filter paper. Transfer the filter paper and contents to the original beaker, add a small

portion from a total of 100 mL of hot (near boiling) NaOH solution (10 g/L). Macerate the filter

paper using a glass rod. After complete maceration, add remaining NaOH solution and proceed to

digest covered mixture at temperature just below boiling for 15 minutes. Acidify the solution with

HCl using methyl red as the indicator and add an excess of 4 or 5 drops of HCl. Filter through

medium-textured paper and wash the residue at least 14 times with hot NH4NO3 solution (20 g/L),

making sure to wash the entire filter paper and contents during each washing. Ignite the residue in

a weighed platinum crucible at 900 to 1000°C, cool in a desiccator, and weigh.

Note 10—If sulfur trioxide is to be determined by turbidimetry, it is permissible to determine the

insoluble residue on a 0.5-g sample. In this event, the percentage of insoluble residue should be

calculated to the nearest 0.01 by multiplying the weight of residue obtained by 200. However, the

cement should not be rejected for failure to meet the insoluble residue requirement unless a 1-g

sample has been used.

Note 11—If a sample of portland cement contains an appreciable amount of manganic oxide,

there may be brown compounds of manganese that dissolve slowly in cold diluted HCl but rapidly

in hot HCl in the specified strength. In all cases, dilute the solution as soon as decomposition is

complete.

Note 12—To keep the solutions closer to the boiling temperature, it is recommended that these

digestions be carried out on an electric hot plate rather than in a steam bath.

Note 13—Continue with the sulfur trioxide determination (see Sections 17.1.2.1 through 17.1.3)

by diluting to 250 mL or 200 mL, as required by the appropriate section.

7.3.2. Blank—Make a blank determination, following the same procedure and using the same amounts

of reagents, and correct the results obtained in the analysis accordingly.

7.4. Calculation—Calculate the percentage of the insoluble residue to the nearest 0.01 by multiplying

the weight in grams of the residue (corrected for the blank) by 100.

8. SILICON DIOXIDE (REFERENCE TEST METHOD)

8.1. Selection of Test Method—For cements other than portland and for which the insoluble residue is

unknown, determine the insoluble residue in accordance with Section 7 of these test methods. For

portland cements and other cements having an insoluble residue less than 1 percent, proceed in

accordance with Section 8.2. For cements having an insoluble residue greater than 1 percent,

proceed in accordance with Section 8.3.

8.2. Silicon Dioxide in Portland Cements and Cements with Low Insoluble Residue:

8.2.1. Summary of Test Method—In this test method, silicon dioxide (SiO2) is determined

gravimetrically. Ammonium chloride is added, and the solution is not evaporated to dryness. This

test method was developed primarily for hydraulic cements that are almost completely


decomposed by hydrochloric acid, and should not be used for hydraulic cements that contain large

amounts of acid-insoluble material and require a preliminary sodium carbonate fusion. For such

cements, or if prescribed in the standard specification for the cement being analyzed, the more

lengthy procedure in Section 8.3 shall be used.

8.2.2. Reagent—Ammonium chloride (NH4Cl).

8.2.3. Procedure:

8.2.3.1. Mix thoroughly 0.5 g of the sample and about 0.5 g of NH4Cl in a 50mL beaker, cover the beaker

with a watch glass, and add cautiously 5 mL of HCl, allowing the acid to run down the lip of the

covered beaker. After the chemical action has subsided, lift the cover, add 1 or 2 drops of HNO3,

stir the mixture with a glass rod, replace the cover, and set the beaker on a steam bath for 30 min

(see Note 14). During this time of digestion, stir the contents occasionally and break up any

remaining lumps to facilitate the complete decomposition of the cement. Fit a medium-textured

filter paper to a funnel, transfer the jellylike mass of silicic acid to the filter as completely as

possible without dilution, and allow the solution to drain through. Scrub the beaker with a

policeman, and rinse the beaker and policeman with hot HCl (1+99). Wash the filter two or three

times with hot HCl (1+99) and then with 10 or 12 small portions of hot water, allowing each

portion to drain through completely. Reserve the filtrate and washings for the determination of the

ammonium hydroxide group (see Note 15).

Note 14—A hot plate may be used instead of a steam bath if the heat is so regulated as to

approximate that of a steam bath. Under conditions where water boils at a lower temperature than

at sea level, such as at higher elevations, 30 min may not be sufficient to recover all of the silica.

In such cases, increase the time of digestion as necessary to get complete recovery of the silica. In

no case should this time exceed 60 min.

Note 15—Determine the ammonium hydroxide group in accordance with the procedure described

in Sections 9.1 through 9.3.

8.2.3.2. Transfer the filter paper and residue to a weighed platinum crucible, dry, and ignite, at first slowly

until the carbon of the paper is completely consumed without inflaming, and finally at 1100 to

1200°C for 1 h. Cool in a desiccator and weigh. Reignite to constant weight. Treat the SiO2 thus

obtained, which will contain small amounts of impurities, in the crucible with 1 or 2 mL of water,

2 drops of H2SO4 (1+1), and about 10 mL of HF, and evaporate cautiously to dryness. Finally, heat

the small residue at 1050 to 1100°C for 5 min, cool in a desiccator, and weigh. The difference

between this weight and the weight previously obtained represents the weight of SiO2. Consider

the weighed residue remaining after the volatilization of SiO2 as combined aluminum and ferric

oxides, and add it to the result obtained in the determination of the ammonium hydroxide group.

8.2.3.3. If the HF residue exceeds 0.0020 g, the silica determination shall be repeated, steps should be

taken to ensure complete decomposition of the sample before a silica separation is attempted and

the balance of the analysis (ammonium hydroxide group, CaO, and MgO) determined on the new

silica filtrate, provided the new silica determination has an HF residue of 0.0020 g or less, except

as provided in Sections 8.2.3.4 and 8.2.3.5.

8.2.3.4. If two or three repeated determinations of a sample of portland cement consistently show HF

residues higher than 0.0020 g, this is evidence that contamination has occurred in sampling or the

cement has not been burned properly during manufacture. In such a case, do not fuse the large HF

residue with pyrosulfate for subsequent addition to the filtrate from the silica separation. Instead,

report the value obtained for the HF residue. Do not ignite the ammonium hydroxide group in the

crucible containing this abnormally large HF residue.

8.2.3.5. In the analysis of cements other than portland, it may not always be possible to obtain HF residues

under 0.0020 g. In such cases, add 0.5 g of sodium or potassium pyrosulfate (Na2S2O7 or K2S2O7)

to the crucible and heat below red heat until the small residue of impurities is dissolved in the melt


(see Note 16). Cool, dissolve the fused mass in water, and add it to the filtrate and washings

reserved for the determination of the ammonium hydroxide group.

Note 16—A supply of nonspattering pyrosulfate may be prepared by heating some pyrosulfate in

a platinum vessel below red heat until the foaming and spattering cease, cooling, and crushing the

fused mass.

8.2.3.6. Blank—Make a blank determination, following the same procedure and using the same amounts


8.2.4. Calculation—Calculate the percentage of SiO2 by multiplying the mass in grams of SiO2 by 200

(100 divided by the mass (see Section 8.2.3.1) or equivalent mass (see Section 8.3.2.1) of the

sample used (0.5 g)). Round in accordance with Table 3.

8.3. Silicon Dioxide in Cements with Insoluble Residue Greater Than 1 Percent:

8.3.1. Summary of Test Method—This test method is based on the sodium carbonate fusion followed by

double evaporation to dryness of the hydrochloric acid solution of the fusion product to convert

silicon dioxide (SiO2) to the insoluble form. The solution is filtered, and the insoluble siliceous

residue is ignited and weighed. Silicon dioxide is volatilized by hydrofluoric acid, and the loss of

weight is reported as pure SiO2.

8.3.2. Procedure:

8.3.2.1. Weigh a quantity of the ignited sample equivalent to 0.5 g of the as-received sample calculated as

follows:

W = [(0.5(100.00 – I )]/100 (2)

where:

W = weight of ignited sample, g, and

I = loss of ignition, percent.

The ignited material from the loss on ignition determination may be used for the sample.

Thoroughly mix the sample with 4 to 6 g of Na2CO3 by grinding in an agate mortar. Place a thin

layer of Na2CO3 on the bottom of a platinum crucible of 20- to 30-mL capacity, add the cement-

Na2CO3 mixture, and cover the mixture with a thin layer of Na2CO3. Place the covered crucible

over a moderately low flame, increase the flame gradually to a maximum (approximately 1100°C),

and maintain this temperature until the mass is quiescent (about 45 min). Remove the burner, lay

aside the cover of the crucible, grasp the crucible with tongs, and slowly rotate the crucible so that

the molten contents spread over the sides and solidify as a thin shell on the interior. Set the

crucible and cover aside to cool. Rinse off the outside of the crucible and place the crucible on its

side in a 300-mL casserole about one-third full of water. Warm the casserole and stir until the cake

in the crucible disintegrates and can be removed easily. By means of a glass rod, lift the crucible

out of the liquid, rinsing it thoroughly with water. Rinse the cover and crucible with HCl (1+3),

and then add the rinse to the casserole. Very slowly and cautiously add 20 mL of HCl (sp gr 1.19)

to the covered casserole. Remove the cover and rinse. If any gritty particles are present, the fusion

is incomplete and the test must be repeated, using a new sample.

Warning—Subsequent steps of the test method must be followed exactly for accurate results.

8.3.2.2. Evaporate the solution to dryness on a steam bath (until it no longer appears gelatinous). Without

heating the residue any further, treat it with 5 to 10 mL of HCl, wait at least 2 min, and then add

an equal amount of water. Cover the dish and digest for 10 min on the steam bath or a hot plate.

Dilute the solution with an equal volume of hot water, immediately filter through medium-

textured paper and wash the separated SiO2 thoroughly with hot HCl (1+99), then with hot water.

Reserve the residue.


8.3.2.3. Again evaporate the filtrate to dryness, and bake the residue in an oven for 1 h at 105 to 110°C.

Cool, add 10 to 15 mL of HCl (1+1), and digest on the steam bath or hot plate for 10 min. Dilute

with an equal volume of water, filter immediately on a fresh filter paper, and wash the small SiO2

residue thoroughly as described in Section 8.3.2.2. Stir the filtrate and washings, and reserve for

the determination of the ammonium hydroxide group in accordance with Sections 9.1 through 9.3.

8.3.2.4. Continue the determination of silicon dioxide in accordance with Section 8.2.3.2.

9. AMMONIUM HYDROXIDE GROUP (REFERENCE TEST METHOD)

9.1. Summary of Test Method—In this test method, aluminum, iron, titanium, and phosphorus are

precipitated from the filtrate, after SiO2 removal, by means of ammonium hydroxide. With care,

little if any manganese will be precipitated. The precipitate is ignited and weighed as the oxides.

9.2. Procedure:

9.2.1. To the filtrate reserved in accordance with Section 8.2.3.1 (see Note 17), which should have a

volume of about 200 mL, add HCl if necessary to ensure a total of 10 to 15 mL of the acid. Add a

few drops of methyl red indicator and heat to boiling. Then treat with NH4OH (1+1) (see Note 18)

dropwise until the color of the solution becomes distinctly yellow, and add one drop in excess (see

Note 19). Heat the solution containing the precipitate to boiling and boil for 50 to 60 s. In the

event difficulty from bumping is experienced while boiling the ammoniacal solution, a digestion

period of 10 min on a steam bath, or on a hot plate having the approximate temperature of a steam

bath, may be substituted for the 50- to 60-s boiling period. Allow the precipitate to settle (not more

than 5 min) and filter using medium-textured paper (see Note 20). Wash, with hot ammonium

nitrate (NH4NO3, 20 g/L) (see Note 21), twice for a small precipitate to about four times for a

large one.

Note 17—If a platinum evaporating dish has been used for the dehydration of SiO2, iron may

have been partially reduced. At this stage, add about 3 mL of saturated bromine water to the

filtrate and boil the filtrate to eliminate the excess bromine before adding the methyl red indicator.

If difficulty from bumping is experienced during the boiling, the following alternate techniques

may be helpful: (1) a piece of filter paper, approximately 1 cm2 in area, positioned where the

bottom and side of the beaker merge and held down by the end of a stirring rod may solve the

difficulty, and (2) use of 400-mL beakers supported inside a cast aluminum cup has also been

found effective.

Note 18—The NH4OH used to precipitate the hydroxides must be free of contamination with

carbon dioxide (CO2).

Note 19—It usually takes 1 drop of NH4OH (1+1) to change the color of the solution from red to

orange and another drop to change the color from orange to yellow. If desired, the addition of the

indicator may be delayed until ferric hydroxide (Fe(OH)3) is precipitated without aluminum

hydroxide (Al(OH)3) being completely precipitated. In such a case, the color changes may be

better observed. However, if the content of Fe2O3 is unusually great, it may be necessary to

occasionally let the precipitate settle slightly so that the color of the supernatant liquid can be

observed. If the color fades during the precipitation, add more of the indicator. Observation of the

color where a drop of the indicator strikes the solution may be an aid in the control of the acidity.

The boiling should not be prolonged as the color may reverse and the precipitate may be difficult

to retain on the filter. The solution should be distinctly yellow when it is ready to filter. If it is not,

restore the yellow color with more NH4OH (1+1) or repeat the precipitation.

Note 20—To avoid drying of the precipitate with resultant slow filtration, channeling, or poor

washing, the filter paper should be kept nearly full during the filtration and should be washed

without delay.

9.2.2. Set aside the filtrate, and transfer the precipitate and filter paper to the same beaker in which the

first precipitation was effected. Dissolve the precipitate with hot HCl (1+2). Stir to thoroughly


macerate the paper, and then dilute the solution to about 100 mL. Reprecipitate the hydroxides as

described in Section 9.2.1. If difficulty from bumping is experienced while boiling the acid

solution containing the filter paper, it may be obviated by diluting the hot 1+2 solution of the

mixed oxides with 100 mL of boiling water and thus eliminate the need for boiling. Filter the

solution and wash the precipitate with about four 10-mL portions of hot NH4NO3 solution (20 g/L)

(see Note 21). Combine the filtrate and washings with the filtrate set aside, and reserve for the

determination of CaO in accordance with Section 15.3.1.

Note 21—Two drops of methyl red indicator solution should be added to the NH4NO3 solution in

the wash bottle, followed by NH4OH (1+1) added dropwise until the color just changes to yellow.

If the color reverts to red at any time due to heating, it should be brought back to yellow by the

addition of a drop of NH4OH (1+1).

9.2.3. Place the precipitate in a weighed platinum crucible, heat slowly until the papers are charred, and

finally ignite to constant weight at 1050 to 1100°C, taking care to prevent reduction, and weigh as

the ammonium hydroxide group.



9.3. Calculation—Calculate the percentage of ammonium hydroxide group by multiplying the

weight in grams of ammonium hydroxide group by 200 (100 divided by the weight of sample

used (0.5 g)).

10. FERRIC OXIDE (REFERENCE TEST METHOD)

10.1. Summary of Test Method—In this test method, the Fe2O3 content of the cement is determined on a

separate portion of the cement by reducing the iron to the ferrous state with stannous chloride

(SnCl 2) and titrating with a standard solution of potassium dichromate (K2Cr2O7). This

determination is not affected by any titanium or vanadium that may be present in the cement.

10.2. Reagents:

10.2.1. Barium Diphenylamine Sulfonate Indicator Solution—Dissolve 0.3 g of barium diphenylamine

sulfonate in 100 mL of water.

10.2.2. Potassium Dichromate, Standard Solution (1 mL = 0.004 g Fe2O3)—Pulverize and dry primary

standard potassium dichromate (K2Cr2O7) reagent, the current lot of NIST 136, at 180 to 200°C to

constant weight. Weigh accurately an amount of dried reagent equal to 2.45700 g times the

number of liters of solution to be prepared. Dissolve in water and dilute to exactly the required

volume in a single volumetric flask of the proper size. This solution is a primary standard and

requires no further standardization.

Note 22—Where large quantities of standard solution are required, it may be desirable for certain

laboratories to use commercially produced primary standard potassium dichromate for most

determinations. Such a material may be used provided that the first solution made from the

container is checked as follows: Using a standard solution of NIST 136, prepared as described in

Section 10.2.2, analyze, in duplicate, samples of an NIST CRM cement, by the procedure given in

Section 10.3.1. Repeat using a similar solution prepared from the commercial primary standard

dichromate. The average percentages of Fe2O3 found by each method should not differ by more

than 0.06 percent.

10.2.3. Stannous Chloride Solution—Dissolve 5 g of stannous chloride (SnCl2 · 2H2O) in 10 mL of HCl

and dilute to 100 mL. Add scraps of iron-free granulated tin and boil until the solution is clear.

Keep the solution in a closed dropping bottle containing metallic tin.


10.3. Procedure—For cements other than portland and for which the insoluble residue is unknown,

determine the insoluble residue in accordance with the appropriate sections of these test methods.

When insoluble residue is known, proceed in accordance with Section 10.3.1 or Section 10.3.2 as

is appropriate for the cement being analyzed.

10.3.1. For portland cements and cements having insoluble residue lower than 1 percent, weigh 1 g of the

sample into a 500-mL Phillips beaker or other suitable container. Add 40 mL of cold water and,

while the beaker is being swirled, add 10 mL of HCl. If necessary, heat the solution and grind the

cement with the flattened end of a glass rod until it is evident that the cement is completely

decomposed. Continue the analysis in accordance with Section 10.3.3.

10.3.2. For cements with insoluble residue greater than 1 percent, weigh a 0.500 g sample, blend with 1 g

LiBO2 using a mortar and pestle, and transfer to a previously fired 8-mL carbon crucible that has

0.1 g LiBO2 sprinkled in the bottom (see Note 23). Cover with 0.1 g LiBO2 that was used to

chemically wash the mortar and pestle (see Note 24). Place the uncovered crucible in a furnace set

at 1100°C for 15 min. Remove the crucible from the furnace and check for complete fusion (see

Note 25). If the fusion is incomplete, return the crucible to the furnace for another 30 min. Again,

check for complete fusion. If the fusion is still incomplete, discard the sample and repeat the

fusion procedure using 0.250 g sample or a smaller quantity with the same amount of LiBO2.

When the fusion is complete, gently swirl the melt and pour into a 150-mL glass beaker containing

10 mL concentrated HCl and 50 mL water. Stir continuously until the fusion product is dissolved,

usually 10 min or less (see Note 26). If a stirring bar is used, remove and rinse the bar. Continue

the analysis in accordance with Section 10.3.3.

Note 23—The firing loosens the carbon on the surface, reducing the possibility of the fusion

product sticking to the crucible.

Note 24—A chemical wash is a dry rinse of the equipment in which the blending was done so

that any sample adhering to this equipment will be loosened and transferred to the crucible.

Note 25—When fusion is incomplete, the sample may not be completely melted, or there may be

particles on top of the bead. Usually, if the bead forms a small smooth spherical ball when taken

from the furnace and before it is swirled, the sample is completely fused.

Note 26—There are usually some carbon particles that are in suspension, undissolved in the

solution, but they will not interfere with the completion of the analysis.

10.3.3. Heat the solution to boiling and treat it with the SnCl2 solution, added dropwise while stirring and

boiling, until the solution is decolorized. Add 1 drop in excess and cool the solution to room

temperature by placing the beaker in a pan of cool water. After cooling and without delay, rinse

the inside of the vessel with water, and add all at once 10 mL of a cool, saturated mercuric

chloride (HgCl2) solution. Stir the solution vigorously for 1 min by swirling the beaker and add

10 mL of H3PO4 (1+1) and 2 drops of barium diphenylamine sulfonate indicator. Add sufficient

water so that the volume after titration will be between 75 and 100 mL. Titrate with the standard

K2Cr2O7 solution. The end point shall be taken as the point at which a single drop causes an

intense purple coloration that remains unchanged on further addition of standard K2Cr2O7 solution.

10.3.4. Blank—Make a blank determination following the same procedure and using the same amounts of

reagents. Record the volume of K2Cr2O7 solution required to establish the end point as described

in Section 10.3.3. Because some iron must be present to obtain the normal end point, if no definite

purple color is obtained after the addition of 4 drops of the standard K2Cr2O7 solution, record the

blank as zero.

10.4. Calculation:

10.4.1. Calculate the percentage of Fe2O3 as follows:

Fe2O3, % = E (V – B) 100/W (3)

where:


E = Fe2O3 equivalent of the K2Cr2O7 solution, g/mL;

V = milliliters of K2Cr2O7 solution required by the sample determination;

B = milliliters of K2Cr2O7 solution required by the blank determination; and

W = mass of sample within 0.1 mg.

Round in accordance with Table 3.

11. PHOSPHORUS PENTOXIDE (REFERENCE TEST METHOD)

11.1. Summary of Test Method—This colorimetric test method is applicable to the determination of

P2O5 in portland cement. Under the conditions of the test, no constituent normally present in

portland cement will interfere.

11.2. Apparatus:

11.2.1. Spectrophotometer (see Note 27):

11.2.1.1. The instrument shall be equipped to measure absorbance of solutions at a spectral wavelength of

725 nm.

11.2.1.2. Wavelength measurements shall be repeatable within 1 nm or less.

11.2.1.3. In the absorbance range from 0.1 to 1.0, the absorbance measurements shall be repeatable within

1 percent or less.

11.2.1.4. To establish that the spectrophotometer will permit a satisfactory degree of accuracy, qualify the

instrument in accordance with Section 5.4.2 using the procedure in Sections 11.4.1 through 11.4.9.

Note 27—For the measurement of the performance of the spectrophotometer, refer to

ASTM E275.

11.3. Reagents:

11.3.1. Ammonium Molybdate Solution—Into a 1-L volumetric flask introduce 500.0 mL of 10.6 N H2SO4

(see Section 11.3.7). Dissolve 25.0 g of ammonium molybdate ((NH4)6Mo7O24 · 4H2O) in about

250 mL of warm water and transfer to the flask containing the H2SO4, while swirling the flask.

Cool, dilute to 1 L with water, and store in a plastic bottle.

11.3.2. Ascorbic Acid Powder—For ease in dissolving, the finest mesh available should be used.

11.3.3. Hydrochloric Acid, Standard (6.5 0.1 N)—Dilute 540 mL of concentrated HCl (sp gr 1.19) to

1 L with water. Standardize against standard NaOH solution (see Section 11.3.6) using

phenolphthalein as indicator. Determine the exact normality and adjust to 6.5 0.1 N by dilution

with water. Restandardize to ensure the proper normality has been achieved.

11.3.4. Phosphate, Standard Solution A—Dissolve 0.1917 g of oven-dried potassium dihydrogen

phosphate (KH2PO4) in water and dilute to 1 L in a volumetric flask.

11.3.5. Phosphate, Standard Solution B—Dilute 50.0 mL of phosphate solution A to 500 mL with water.

11.3.6. Sodium Hydroxide, Standard Solution (1 N)—Dissolve 40.0 g of sodium hydroxide (NaOH) in

water, add 10 mL of a freshly filtered saturated solution of barium hydroxide (Ba(OH)2), and

dilute to 1 L with water that has been recently boiled and cooled. Shake the solution from time to

time during a several-hour period, and filter into a plastic bottle. Keep the bottle tightly closed to


protect the solution from CO2 in the air. Standardize against acid potassium phthalate or benzoic

acid acidimetric standards furnished by NIST (Standard Samples No. 84f and 350) using the test

methods in the certificates accompanying the standard samples. Determine the exact normality of

the solution.

11.3.7. Sulfuric Acid, Standard (10.6 0.1 N)—To a 1-L volumetric flask cooled in water, add about

600 mL of water and then, slowly, with caution, add 300 mL of concentrated H2SO4 (sp gr 1.84).

After cooling to room temperature, dilute to 1 L with water. Standardize against the standard

NaOH solution (see Section 11.3.6) using phenolphthalein as indicator. Determine the normality

and adjust to 10.6 0.1 N by dilution with water. Restandardize to ensure the proper normality has

been achieved.

11.4. Procedure:

11.4.1. Prepare a series of phosphate solutions to cover the range from 0 to 0.5 percent P2O5. Prepare each

solution by adding a suitable volume of standard phosphate solution B and 25.0 mL of the 6.5 N

hydrochloric acid to a 250-mL volumetric flask (see Note 28). Dilute to the mark with water.

Note 28—One milliliter of standard phosphate solution B/250 mL of solution is equivalent to

0.004 percent P2O5 for a 0.25-g cement sample. Aliquots of 0, 12.5, 25, 50, 75, 100, and 125 mL

are equivalent to P2O5 contents in the sample of 0, 0.05, 0.10, 0.20, 0.30, 0.40, and 0.50 percent.

11.4.2. Prepare a blank by adding 25.0 mL of the standard HCl to a 250-mL volumetric flask and diluting

to 250 mL with water.

11.4.3. Develop colors in the series of phosphate solutions and in the blank, in accordance with Sections

11.4.6 through 11.4.8.

11.4.4. Plot the net absorbance (absorbance of standard minus that of the blank) values obtained as

ordinates and the corresponding P2O5 concentrations as abscissas. Draw a smooth curve through

the points.

Note 29—A suitable paper for plotting the calibration curve is a 10-by-15-in. (254-by-381-mm)

linear cross-section paper having 20 by 20 divisions to the inch (25.4 mm). The percentage of

P2O5 can then be plotted on the long dimension using five divisions equal to 0.01 percent P2O5. A

scale of one division equal to 0.005 absorbance units is suitable as the ordinate (short dimension of

the paper). Scales other than this may be used, but under no circumstances should a scale division

less than 0.05 in. (1.3 mm) be used for 0.005 units of absorbance or for 0.005 percent P2O5. A

separate calibration curve should be made for each spectrophotometer used, and the calibration

curve checked against standard phosphate solution whenever a new batch of ammonium

molybdate reagent is used.

11.4.5. Transfer 0.250 g of the sample to a 250-mL beaker and moisten with 10 mL of cold water to

prevent lumping. Add 25.0 mL of the standard HCl and digest with the aid of gentle heat and

agitation until solution is complete. Filter into a 250-mL volumetric flask, and wash the paper and

the separated silica thoroughly with hot water. Allow the solution to cool, and then dilute with

water to 250 mL.

11.4.6. Transfer a 50.0-mL aliquot (see Note 30) of the sample solution to a 250-mL beaker, and add

5.0 mL of ammonium molybdate solution and 0.1 g of ascorbic acid powder. Mix the contents of

the beaker by swirling until the ascorbic acid has dissolved completely. Heat the solution to

vigorous boiling, and then boil, uncovered, for 1.5 0.5 min. Cool to room temperature and

transfer to a 50-mL volumetric flask. Rinse the beaker with one small portion of water and add the

rinse water to the flask. Dilute to 50 mL with water.

Note 30—The range of the test can be extended by taking a smaller aliquot of the sample

solution. In such instances, the decrease in the aliquot volume must be made up by the blank


solution (see Section 11.4.5) to maintain the proper acidity of the final solution. Thus, if a 25-mL

aliquot of the sample solution is taken (instead of the usual 50 mL), a 25-mL aliquot of the blank

solution should be added before proceeding with the test. The result of the test must then be

calculated accordingly.

11.4.7. Measure the absorbance of the solution against water as the reference at 725.0 nm.

11.4.8. Develop on a 50.0-mL aliquot of the blank solution prepared in Section 11.4.2 in the same manner

as was used in Section 11.4.6 for the sample solution. Measure the absorbance in accordance with

Section 11.4.7 and subtract this absorbance value from that obtained for the sample solution in

Section 11.4.6 to obtain the net absorbance for the sample solution.

11.4.9. Using the net absorbance value found in Section 11.4.8, record the percentage of P2O5 in the

cement sample as indicated by the calibration curve. Report the percentage of P2O5 rounded in

accordance with Table 3.

12. TITANIUM DIOXIDE (REFEREE TEST METHOD)

12.1. Summary of Test Method—In this test method, titanium dioxide (TiO2) in portland cement is

determined colorimetrically using Tiron reagent. Under the conditions of the test, iron is the only

constituent of portland cement causing a very slight interference equivalent to 0.01 percent for

each 1 percent of Fe2O3 present in the sample.

12.2. Apparatus:

12.2.1. Spectrophotometer (see Note 31):

12.2.1.1. The instrument shall be equipped to measure absorbance of solutions at a spectral wavelength of

410 nm.

12.2.1.2. Wavelength measurements shall be repeatable within 1 nm or less.

12.2.1.3. In the absorbance range from 0.1 to 1.0, the absorbance measurements shall be repeatable within

1 percent or less.

12.2.1.4. To establish that the spectrophotometer will permit a satisfactory degree of accuracy, qualify the

instrument in accordance with Section 5.4.2 using the procedure in Sections 12.4.1 through 12.4.6

of this test method.

Note 31—For the measurement of the performance of the spectrophotometer, refer to ASTM

E275.

12.3. Reagents:

12.3.1. Buffer (pH 4.7)—68 g of NaC2H3O2 · 3H2O (sodium acetate trihydrate), plus 380 mL of water,

plus 100 mL of 5.0 N CH3COOH (acetic acid).

12.3.2. Ethylenedinitrilo Tetraacetic Acid Disodium Salt, Dihydrate (0.2 M EDTA)—Dissolve 37.5 g of

EDTA in 350 mL of warm water and filter. Add 0.25 g of FeCl3 · 6H2O (ferric chloride

hexahydrate) and dilute to 500 mL.

12.3.3. Hydrochloric Acid (1+6).

12.3.4. Hydrochloric Acid, Standard (6.5 N)—Dilute 540 mL of concentrated HCl (sp gr 1.19) to 1 L

with water.


12.3.5. Ammonium Hydroxide (NH4OH, 1+1).

12.3.6. Potassium Pyrosulfate (K2S2O7).

12.3.7. Titanium Dioxide, Stock Solution A—Fuse slowly in a platinum crucible over a very small flame

0.0314 g of NIST SRM 154b (TiO2 = 99.74 percent) or its replacements with about 2 or 3 g of

K2S2O7. Allow to cool, and place the crucible in a beaker containing 125 mL of H2SO4 (1+1). Heat

and stir until the melt is completely dissolved. Cool, transfer to a 250-mL volumetric flask, and

dilute the solution to volume.

12.3.7.1. Titanium Dioxide, Dilute Standard Solution B (1 mL = 0.0125 mg TiO2)—Pipet 50 mL of stock

TiO2 solution into a 500-mL volumetric flask, and dilute to volume. One milliliter of this solution

is equal to 0.0125 mg of TiO2, which is equivalent to 0.05 percent TiO2 when used as outlined in

Sections 12.4.4 through 12.4.6.

12.3.8. Sulfuric acid (1+1).

12.3.9. Tiron (disodium-1,2-dihydroxybenzene-3,5 disulfonate).

12.4. Procedure:

12.4.1. Prepare a series of TiO2 solutions to cover the range from 0 to 1.0 percent TiO2. Prepare each

solution in a 50-mL volumetric flask (see Note 32).

Note 32—One milliliter of dilute TiO2 standard solution B per 50 mL (see Section 12.3.7.1) is

equivalent to 0.05 percent TiO2 for a 0.2500-g cement sample. Aliquots of 0, 5, 10, 15, and 20 mL

of dilute TiO2 standard solution are equivalent to TiO2 contents in the sample of 0, 0.25, 0.50, 0.75,

and 1.0 percent. Dilute each to 25 mL with water.

12.4.2. Develop color in accordance with Section 12.4.4 starting with second sentence. Measure

absorbance in accordance with Section 12.4.5.

12.4.3. Plot absorbance values obtained as ordinates and the corresponding TiO2 concentrations as

abscissas. Draw a smooth curve through the points.

Note 33—A suitable paper for plotting the calibration curve is a linear cross-section paper having

10 by 10 divisions to 1 cm. A scale division equivalent to 0.002 absorbance and 0.002 percent

TiO2 should be used. A separate calibration curve should be made for each spectrophotometer

used.

12.4.4. Transfer a 25.0-mL aliquot of the sample solution prepared in Section 11.4.5 into a 50-mL

volumetric flask (see Note 34). Add 5 mL Tiron and 5 mL EDTA, mix, and then add NH4OH

(1+1) dropwise, mixing thoroughly after each drop, until the color changes through yellow to

green, blue, or ruby red. Then, just restore the yellow color with HCl (1+6) added dropwise and

mixing after each drop. Add 5 mL buffer, dilute to volume and mix.

Note 34—The range of the test can be extended by taking a smaller aliquot. The results of the test

must then be calculated accordingly.

12.4.5. Measure the absorbance of the solution against water as the reference at 410 nm.

12.4.6. Using the absorbance value determined in Section 12.4.5, record the percentage of TiO2 in the

cement sample as indicated by the calibration curve. Correct for the iron present in the sample to

obtain the true TiO2 as follows: True TiO2 = measured percent TiO2 − (0.01 percent Fe2O3).

Report the percent of TiO2 rounded in accordance with Table 3.


13. ZINC OXIDE (REFERENCE TEST METHOD)6

13.1. Any test method may be used that meets the requirements of Section 5.4 and Table 1.

13.2. Report the result rounded in accordance with Table 3.

14. ALUMINUM OXIDE (REFERENCE TEST METHOD)

Note 35—In the reference test method, Al2O3 is calculated from the ammonium hydroxide group

by subtracting the separately determined constituents that usually are present in significant

amounts in the ammonium hydroxide precipitate. These are Fe2O3, TiO2, and P2O5. Most

instrumental test methods for Al2O3 analysis give Al2O3 alone if standardized and calibrated

properly.

14.1. Calculation:

14.1.1. Calculate the percentage of Al2O3 by deducting the percentage of the sum of the Fe2O3, TiO2, and

P2O5 from the percentage of ammonium hydroxide group, using unrounded values of all four

quantities. All determinations shall be by referee test methods described in the appropriate sections

herein. Report the Al2O3 rounded in accordance with Table 3. For nonreferee analyses, the

percentages of Fe2O3, TiO2, and P2O5 can be determined by any procedure for which qualification

has been shown.

15. CALCIUM OXIDE (REFERENCE TEST METHOD)


15.1.1. In this test method, manganese is removed from the filtrate after the determination of SiO2 and the

ammonium hydroxide group. Calcium is then precipitated as the oxalate. After filtering, the

oxalate is redissolved and titrated with potassium permanganate (KMnO4). (See Note 36.)

Note 36—For referee analysis or for the most accurate determinations, removal of manganese in

accordance with Section 15.3.2 must be made. For less accurate determinations, and when only

insignificant amounts of manganese oxides are believed present, Section 15.3.2 may be omitted.

15.1.2. Strontium, usually present in portland cement as a minor constituent, is precipitated with calcium

as the oxalate and is subsequently titrated and calculated as CaO. If the SrO content is known and

correction of CaO for SrO is desired as, for example, for research purposes or to compare results

with CRM certificate values, the CaO obtained by this method may be corrected for SrO. In

determining conformance of a cement to specifications, the correction of CaO for SrO should not

be made.

15.2. Reagents:

15.2.1. Ammonium Oxalate Solution (50 g/L).

15.2.2. Potassium Permanganate, Standard Solution (0.18 N)—Prepare a solution of potassium

permanganate (KMnO4) containing 5.69 g/L. Let this solution stand at room temperature for at

least 1 week, or boil and cool to room temperature. Siphon off the clear solution without

disturbing the sediment on the bottom of the bottle, and then filter the siphoned solution through a

bed of glass wool in a funnel or through a suitable sintered glass filter. Do not filter through

materials containing organic matter. Store in a dark bottle, preferably one that has been painted

black on the outside. Standardize the solution against 0.7000 to 0.8000 g of primary standard

sodium oxalate, according to the directions furnished with the sodium oxalate, and record the

temperature at which the standardization was made (see Note 37).


Note 37—Because of the instability of the KMnO4 solution, it is recommended that it be

restandardized at least bimonthly.

15.2.2.1. Calculate the CaO equivalent of the solution as follows:

1 mL of 1 N KMnO4 solution is equivalent to 0.06701 g of pure sodium oxalate.

4

4

weight of sodium oxalate fraction of its puritynormality of KMnO

mL of KMnO solution 0.06701

=

(4)

1 mL of 1 N KMnO4 solution is equivalent to 0.02804 g of CaO.

4normality of KMnO solution 0.02804 100

0.5F

=

where:

F = CaO equivalent of the KMnO4 solution in percent CaO/mL based on a 0.5-g sample

of cement.

15.3. Procedure:

15.3.1. Acidify the combined filtrates obtained in the precipitations of the ammonium hydroxide group

(see Section 9.2.2). Neutralize with HCl to the methyl red end point, make just acid, and add

6 drops of HCl in excess.

15.3.2. Removal of Manganese—Evaporate to a volume of about 100 mL. Add 40 mL of saturated

bromine water to the hot solution and immediately add NH4OH until the solution is distinctly

alkaline. Addition of 10 mL of NH4OH is generally sufficient. A piece of filter paper, about 1 cm2

in area, placed in the heel of the beaker and held down by the end of a stirring rod aids in

preventing bumping and initiating precipitation of hydrated manganese oxides (MnO). Boil the

solution for 5 min or more, making sure that the solution is distinctly alkaline at all times. Allow

the precipitate to settle, filter using medium-textured paper, and wash with hot water. If a

precipitate does not appear immediately, allow a settling period of up to 1 h before filtration.

Discard any manganese dioxide that may have been precipitated. Acidify the filtrate with HCl

using litmus paper as an indicator, and boil until all the bromine is expelled (see Note 38).

Note 38—Potassium iodide starch paper may be used to indicate the complete volatilization of

the excess bromine. Expose a strip of moistened paper to the fumes from the boiling solution. The

paper should remain colorless. If it turns blue bromine is still present.

15.3.3. Add 5 mL of HCl, dilute to 200 mL, and add a few drops of methyl red indicator and 30 mL of

warm ammonium oxalate solution (50 g/L) (see Note 39). Heat the solution to 70 to 80°C, and add

NH4OH (1+1) dropwise while stirring until the color changes from red to yellow (see Note 40).

Allow the solution to stand without further heating for 60 5 min (no longer), with occasional

stirring during the first 30 min.

Note 39—If the ammonium oxalate solution is not perfectly clear, it should be filtered before use.

Note 40—This neutralization must be made slowly; otherwise, precipitated calcium oxalate may

have a tendency to run through the filter paper. When a number of these determinations are being

made simultaneously, the following technique will assist in ensuring slow neutralization. Add 2 or

3 drops of NH4OH to the first beaker while stirring, then 2 or 3 drops to the second, and so on,

returning to the first beaker to add 2 or 3 more drops, etc., until the indicator color has changed in

each beaker.

15.3.4. Filter, using retentive paper, and wash the precipitate eight to ten times with hot water, the total

amount of water used in rinsing the beaker and washing not to exceed 75 mL. During this

washing, water from the wash bottle should be directed around the inside of the filter paper to


wash the precipitate down, and then a jet of water should be gently directed toward the center of

the paper to agitate and thoroughly wash the precipitate. Acidify the filtrate with HCl and reserve

for the determination of MgO.

15.3.5. Place the beaker in which the precipitation was made under the funnel, pierce the apex of the filter

paper with the stirring rod, place the rod in the beaker, and wash the precipitate into the beaker by

using a jet of hot water. Drop about 10 drops of H2SO4 (1+1) around the top edge of the filter

paper. Wash the paper five more times with hot water. Dilute to 200 mL, and add 10 mL of H2SO4

(1+1). Heat the solution to a temperature just below boiling, and titrate it immediately with the

0.18 N KMnO4 solution (see Note 41). Continue the titration slowly until the pink color persists

for at least 10 s. Add the filter paper that contained the original precipitate and macerate it. If the

pink color disappears, continue the titration until it again persists for at least 10 s.

Note 41—The temperature of the 0.18 N KMnO4 solution at time of use should not vary from its

standardization temperature by more than 10°F (5.5°C). Larger deviations could cause serious

error in the determination of CaO.


of reagents (see Note 42), and record the milliliters of KMnO4 solution required to establish the

end point.

Note 42—When the amount of calcium oxalate is very small, its oxidation by KMnO4 is slow to

start. Before the titration, add a little MnSO4 to the solution to catalyze the reaction.

15.4. Calculation:

15.4.1. Calculate the percentage of CaO as follows:

CaO, % = E (V – B) (5)

where:

E = CaO equivalent of the KMnO4 solution in percent CaO/mL based on a 0.5-g sample,

V = milliliters of KMnO4 solution required by the sample, and

B = milliliters of KMnO4 solution required by the blank.

Report the result rounded in accordance with Table 3.

15.4.2. If desired, calculate the percentage of CaO corrected for SrO as follows:

CaOc, % = CaOi, % – 0.54 SrO, % (6)

where:

CaOc = CaO corrected for SrO,

CaOi = initial CaO as determined in Section 15.4.1, and

0.54 = 56.08

103.62 = molecular weight ratio

CaO

SrO.

16. MAGNESIUM OXIDE (REFERENCE TEST METHOD)

16.1. Summary of Test Method—In this test method, magnesium is precipitated as magnesium

ammonium phosphate from the filtrate after removal of calcium. The precipitate is ignited and

weighed as magnesium pyrophosphate (Mg2P2O7). The MgO equivalent is then calculated.

16.2. Reagent—Ammonium phosphate, dibasic (100 g/L) (NH4)2HPO4.

16.3. Procedure:


16.3.1. Acidify the filtrate from the determination of CaO (see Section 15.3.4) with HCl and evaporate by

boiling to about 250 mL. Cool the solution to room temperature, add 10 mL of ammonium

phosphate, dibasic, (NH4)2HPO4 (100 g/L), and 30 mL of NH4OH. Stir the solution vigorously

during the addition of NH4OH, and then for 10 to 15 min longer. Let the solution stand for at least

8 h in a cool atmosphere and filter. Wash the residue five or six times with NH4OH (1+20) and

ignite in a weighed platinum or porcelain crucible, at first slowly until the filter paper is charred

and then burn off (see Section 16.4.1), and finally at 1100°C for 30 to 45 min. Weigh the residue

as magnesium pyrophosphate (Mg2P2 O7).


reagents, and correct the results obtained in the analysis accordingly.

16.4. Calculation:

16.4.1. Calculate the percentage of MgO to the nearest 0.1 as follows:

MgO, % = W 72.4 (7)

where:

W = grams of Mg2P2O7, and

72.4 = molecular ratio of 2MgO to Mg2P2O7 (0.362) divided by the weight of the

sample used (0.5 g) and multiplied by 100.


Warning—Extreme caution should be exercised during this ignition. Reduction of the phosphate

precipitate can result if carbon is in contact with it at high temperatures. There is also danger of

occluding carbon in the precipitate if ignition is too rapid.

17. SULFUR

Note 43—When an instrumental test method is used for sulfur or when comparing results of

classical wet and instrumental test methods, consult Section 6.1.2 of these test methods.

17.1. Sulfur Trioxide (Reference Test Method):

17.1.1. Summary of Test Method—In this test method, sulfate is precipitated from an acid solution of the

cement with barium chloride (BaCl2). The precipitate is ignited and weighed as barium sulfate

(BaSO4), and the SO3 equivalent is calculated.

17.1.2. Procedure:

17.1.2.1. To 1 g of the sample, add 25 mL of cold water, and, while the mixture is stirred vigorously, add

5 mL of HCl (see Note 44). If necessary, heat the solution and grind the material with the flattened

end of a glass rod until it is evident that decomposition of the cement is complete (see Note 45).

Dilute the solution to 50 mL and digest for 15 min at a temperature just below boiling. Filter

through a medium-textured paper and wash the residue thoroughly with hot water. Dilute the

filtrate to 250 mL and heat to boiling. Add slowly, dropwise, 10 mL of hot BaCl2 (100 g/L) and

continue the boiling until the precipitate is well formed. Digest the solution for 12 to 24 h at a

temperature just below boiling (see Note 46). Take care to keep the volume of solution between

225 and 260 mL and add water for this purpose, if necessary. Filter through a retentive paper,

wash the precipitate thoroughly with hot water, place the paper and contents in a weighed

platinum crucible, and slowly char and consume the paper without inflaming. Ignite at 800 to

900°C, cool in a desiccator, and weigh.

Note 44—The acid filtrate obtained in the determination of the insoluble residue (see

Section 7.3.1) may be used for the determination of SO3 instead of using a separate sample.


Note 45—A brown residue due to compounds of manganese may be disregarded (see Note 11).

Note 46—If a rapid determination is desired, immediately after adding the BaCl2, place the

beaker with the solution in an ultrasonic bath for 5 min, and then continue the determination

starting with “Filter through a retentive paper…”. Qualify the method in accordance with the

Performance Requirements for Rapid Test Methods.

17.1.2.2. Blank—Make a blank determination following the same procedure and using the same amounts of


17.1.3. Calculation—Calculate the percentage of SO3 to the nearest 0.01 as follows:

SO3, % = W 34.3 (8)

where:

W = grams of BaSO4, and

34.3 = molecular ratio of SO3 to BaSO4 (0.343) multiplied by 100.


17.2. Sulfide (Reference Test Method):

17.2.1. Summary of Test Method—In this test method, sulfide sulfur is determined by evolution as

hydrogen sulfide (H2S) from an acid solution of the cement into a solution of ammoniacal zinc

sulfate (ZnSO4) or cadmium chloride (CdCl2). The sulfide sulfur is then titrated with a standard

solution of potassium iodate (KIO3). Sulfites, thiosulfates, and other compounds intermediate

between sulfides and sulfates are assumed to be absent. If such compounds are present, they may

cause an error in the determination.

17.2.2. Apparatus:

17.2.2.1. Gas-Generating Flask—Connect a dry 500-mL boiling flask with a long-stem separatory funnel

and a small connecting bulb by means of a rubber stopper. Bend the stem of the funnel so that it

will not interfere with the connecting bulb, adjust the stem so that the lower end is close to the

bottom of the flask, and connect the opening of the funnel with a source of compressed air.

Connect the bulb with an L-shaped glass tube and a straight glass tube about 200 mm in length.

Insert the straight glass tube in a tall-form, 400-mL beaker. A three-neck distilling flask with a

long glass tubing in the middle opening, placed between the source of compressed air and the

funnel, is a convenient aid in the regulation of the airflow. Rubber used in the apparatus shall be

pure gum grade, low in sulfur, and shall be cleaned with warm HCl.

17.2.3. Reagents:

17.2.3.1. Ammoniacal Cadmium Chloride Solution—Dissolve 15 g of cadmium chloride (CdCl2 · 2H2O) in

150 mL of water and 350 mL of NH4OH. Filter the solution after allowing it to stand at least 24 h.

17.2.3.2. Ammoniacal Zinc Sulfate Solution—Dissolve 50 g of zinc sulfate (ZnSO4 · 7H2O) in 150 mL of

water and 350 mL of NH4OH. Filter the solution after allowing it to stand at least 24 h.

17.2.3.3. Potassium Iodate, Standard Solution (0.03 N)—Prepare a solution of potassium iodate (KIO3) and

potassium iodide (KI) as follows: Dry KIO3 at 180°C to constant weight. Weigh 1.0701 g of the

KIO3 and 12 g of KI. Dissolve and dilute to 1 L in a volumetric flask. This is a primary standard

and requires no standardization (see Note 47). One milliliter of this solution is equivalent to

0.0004809 g of sulfur.


Note 47—The solution is very stable but may not maintain its titer indefinitely. Whenever such a

solution is more than 1 year old, it should be discarded or its concentration checked by

standardization.

17.2.3.4. Stannous Chloride Solution—To 10 g of stannous chloride (SnCl2 · 2H2O) in a small flask, add

7 mL of HCl (1+1), warm the mixture gently until the salt is dissolved, cool the solution, and add

95 mL of water. This solution should be prepared as needed because the salt tends to hydrolyze.

17.2.3.5. Starch Solution—To 100 mL of boiling water, add a cool suspension of 1 g of soluble starch in

5 mL of water and cool. Add a cool solution of 1 g of sodium hydroxide (NaOH) in 10 mL of

water, and then add 3 g of potassium iodide (KI) and mix thoroughly.

17.2.4. Procedure:

17.2.4.1. Place 15 mL of the ammoniacal ZnSO4 or CdCl2 solution (see Note 48) and 285 mL of water in a

beaker. Put 5 g of the sample (see Note 49) and 10 mL of water in the flask, and shake the flask

gently to wet and disperse the cement completely. This step and the addition of SnCl2 should be

performed rapidly to prevent the setting of the cement. Connect the flask with the funnel and bulb.

Add 25 mL of the SnCl2 solution through the funnel and shake the flask. Add 100 mL of

HCl (1+3) through the funnel and shake the flask. During these shakings, keep the funnel closed

and the delivery tube in the ammoniacal ZnSO4 or CdCl2 solution. Connect the funnel with the

source of compressed air, open the funnel, start a slow stream of air, and heat the flask and

contents slowly to boiling. Continue the boiling gently for 5 or 6 min. Cut off the heat, and

continue the passage of air for 3 or 4 min. Disconnect the delivery tube and leave it in the solution

for use as a stirrer. Cool the solution to 20 to 30°C (see Note 50), add 2 mL of the starch solution

and 40 mL of HCl (1+1), and titrate immediately with the 0.03 N KIO3 solution until a persistent

blue color is obtained (see Note 51).

Note 48—In general, the ZnSO4 is preferable to the CdCl2 solution because ZnSO4 is more

soluble in NH2OH than is CdCl2. The CdCl2 solution may be used when there is doubt as to the

presence of a trace of sulfide sulfur because the yellow cadmium sulfide (CdS) facilitates the

detection of a trace.

Note 49—If the content of sulfur exceeds 0.20 or 0.25 percent, a smaller sample should be used

so that the titration with the KIO3 solution will not exceed 25 mL.

Note 50—The cooling is important because the end point is indistinct in a warm solution.

Note 51—If the content of sulfur is appreciable but not approximately known in advance, the

result may be low due to the loss of H2S during a slow titration. In such a case, the determination

should be repeated with the titration carried out more rapidly.

17.2.4.2. Make a blank determination, following the same procedure and using the same amounts of

reagents. Record the volume of KIO3 solution necessary to establish the end point, as described in

Section 17.2.4.1.

17.2.5. Calculation—Calculate the percentage of sulfide sulfur (see Section 17.2.1) as follows:

sulfide, % = E(V – B) 20 (9)

where:

E = sulfide equivalent of the KIO3 solution, g/mL;

V = milliliters of KIO3 solution required by the sample;

B = milliliters of KIO3 solution required by the blank; and

20 = 100 divided by the weight of sample used (5 g).



18. LOSS ON IGNITION (REFERENCE TEST METHOD)

18.1. Portland Cement:

18.1.1. Summary of Test Method—In this test method, the cement is ignited in a muffle furnace at a

controlled temperature. The loss is assumed to represent the total moisture and CO2 in the cement.

This procedure is not suitable for the determination of the loss on ignition of portland blast-

furnace slag cement and of slag cement. A test method suitable for such cements is described in

Sections 18.2.1 through 18.2.3.

18.1.2. Procedure—Weigh 1 g of the sample in a tared platinum or porcelain crucible. Cover and ignite

the crucible and its contents to constant weight in a muffle furnace at a temperature of 950 50°C.

Allow a minimum of 15 min for the initial heating period and at least 5 min for all subsequent

periods.

18.1.3. Calculation—Calculate the percentage of loss on ignition to the nearest 0.1 by multiplying the loss

of weight in grams by 100. Report the result rounded in accordance with Table 3.

18.2. Portland Blast-Furnace Slag Cement and Slag Cement:

18.2.1. Summary of Test Method—Because it is desired that the reported loss on ignition represent

moisture and CO2, this test method provides a correction for the gain in weight due to oxidation of

sulfides usually present in portland blast-furnace slag cement and slag cement by determining the

increase in SO3 content during ignition. An optional test method providing for a correction based

on the decrease in sulfide sulfur during ignition is given in Sections 26.1.1 through 26.1.3.

18.2.2. Procedure:

18.2.2.1. Weigh 1 g of cement into a tared platinum or porcelain crucible and ignite in a muffle furnace at a

temperature of 950 50°C for 15 min. Cool to room temperature in a desiccator and weigh.

Without checking for constant weight, carefully transfer the ignited material to a 400-mL beaker.

Break up any lumps in the ignited cement with the flattened end of a glass rod.

18.2.2.2. Determine the SO3 content by the test method given in Sections 17.1.2 through 17.1.3 (see

Note 52). Also determine the SO3 content of a portion of the same cement that has not been ignited

using the same procedure.

Note 52—Some of the acid used for dissolving the sample may first be warmed in the platinum

crucible to dissolve any adhering material.

18.2.3. Calculation—Calculate the percentage loss of weight occurring during ignition, and add 0.8 times

the difference between the percentages of SO3 in the ignited sample and the original cement (see

Note 53). Report the corrected percentage, rounded in accordance with Table 3, as loss on

ignition.

Note 53—If a gain in weight is obtained during ignition, subtract the percentage gain from the

correction for SO3.

19. SODIUM AND POTASSIUM OXIDES (REFERENCE TEST METHOD)

19.1. Total Alkalis:

19.1.1. Summary of Test Method—This test method7 covers the determination of sodium oxide (Na2O)

and potassium oxide (K2O) by flame photometry or atomic absorption (see Note 54).


Note 54—This test method is suitable for hydraulic cements that are completely decomposed by

hydrochloric acid and should not be used for determination of total alkalis in hydraulic cements

that contain large amounts of acid-insoluble material, for example, pozzolan cements. It may be

used to determine acid-soluble alkalis for such cements. An alternate test method of sample

dissolution for such cements is in preparation.

19.1.2. Apparatus:

19.1.2.1. Instrument—Any type of flame photometer or atomic absorption unit may be used, provided it

can be demonstrated that the required degree of accuracy and precision is as indicated in

Section 19.1.3 (see Notes 55 and 56).

Note 55—After such accuracy is established for a specific instrument, further tests of instrument

accuracy are not required, except when it must be demonstrated that the instrument gives results

within the prescribed degree of accuracy by a single series of tests using the designated standard

samples.

Note 56—For normal laboratory testing, it is recommended that the accuracy of the instrument be

routinely checked by the use of either an NIST cement or cement of known alkali content.

19.1.2.2. The instrument shall consist at least of an atomizer and burner, suitable pressure-regulating

devices and gages for fuel and oxidant gas, an optical system capable of preventing excessive

interference from wavelengths of light other than that being measured, and a photosensitive

indicating device.

19.1.3. Initial Qualification of Instrument—Qualify the instrument in accordance with Section 5.4.2 to

establish that an instrument provides the desired degree of precision and accuracy.

19.1.4. Reagents and Materials:

19.1.4.1. Laboratory Containers—All glassware shall be made of borosilicate glass, and all polyethylene

shall comply with the requirements of Section 6.2.3.

19.1.4.2. Calcium Carbonate—The calcium carbonate (CaCO3) used in the preparation of the calcium

chloride stock solution (see Section 19.1.5.1) shall contain not more than 0.020 percent total

alkalis as sulfate.

Note 57—Materials sold as a primary standard or ACS “low alkali” grade normally meet this

requirement. However, the purchaser should assure himself that the actual material used conforms

with this requirement.

19.1.4.3. Potassium Chloride (KCl).

19.1.4.4. Sodium Chloride (NaCl).

19.1.4.5. Commercially available solutions may be used in place of those specified in Section 19.1.5.

19.1.5. Preparation of Solutions:

19.1.5.1. Calcium Chloride Stock Solution—Add 300 mL of water to 112.5 g of CaCO3 in a 1500-mL

beaker. While stirring, slowly add 500 mL of HCl. Cool the solution to room temperature, filter

into a 1-L volumetric flask, dilute to 1 L, and mix thoroughly. This solution contains the

equivalent of 63,000 ppm (6.30 percent) CaO.

19.1.5.2. Sodium-Potassium Chloride Stock Solution—Dissolve 1.8858 g of sodium chloride (NaCl) and

1.583 g of potassium chloride (KCl) (both dried at 105 to 110°C for several hours prior to

weighing) in water. Dilute to 1 L in a volumetric flask and mix thoroughly. This solution contains


the equivalent of 1000 ppm (0.10 percent) each of Na2O and K2O. Separate solutions of Na2O and

of K2O may be used, provided that the same concentration solutions are used for calibration for

cement analysis as were used for the calibration when qualifying the instrument in accordance

with Section 19.1.3.

19.1.5.3. Standard Solutions—Prepare the standard solutions prescribed for the instrument and method

used. Measure the required volume of NaCl-KCl stock solutions in calibrated pipets or burets. The

calcium chloride stock solutions, if needed, may be measured in appropriate graduated cylinders.

If the instrument being used requires an internal standard, measure the internal standard solution

with a pipet or buret. Place each solution in a volumetric flask, dilute to the indicated volume, and

mix thoroughly.

19.1.5.4. If more dilute solutions are required by the method in use, pipet the required aliquot to the

proper sized volumetric flask, add any necessary internal standard, dilute to the mark, and mix

thoroughly.

19.1.6. Calibration of Apparatus (see Note 58):

Note 58—No attempt is made in this section to describe in detail the steps for putting the

instrument into operation because this will vary considerably with different instruments. The

manufacturer’s instructions should be consulted for special techniques or precautions to be

employed in the operation, maintenance, or cleaning of the apparatus.

19.1.6.1. Turn on the instrument and allow it to warm up in accordance with the manufacturer’s

instructions. (A minimum of 30 min is required for most instruments.) Adjust the fuel and oxidant

gas pressures as required by the instrument being used. Light and adjust the burner for optimum

operation. Make any other adjustments that may be necessary to establish the proper operating

conditions for the instrument.

19.1.7. Procedure:

19.1.7.1. Solution of the Cement—Prepare the solution of the cement in accordance with the procedure

specified by the instrument manufacturer. If no procedure is specified, or if desired, proceed as

specified in Section 19.1.7.1.1 through 19.1.7.1.3 (see Note 59).

Note 59—The presence of SiO2 in solution affects the accuracy of some flame photometers. In

cases where an instrument fails to provide results within the prescribed degree of accuracy

outlined in Sections 5.4.2.1 through 5.4.3, tests should be made on solutions from which the SiO2

has been removed. For this removal, proceed as in Section 19.1.7.2.

19.1.7.1.1. Place 1.000 0.001 g of the cement in a 150-mL beaker and disperse with 20 mL of water using a

swirling motion of the beaker. While still swirling, add 5.0 mL of HCl all at once. Dilute

immediately to 50 mL with water. Break up any lumps of cement remaining undispersed with a

flat-end stirring rod. Digest on a steam bath or hot plate for 15 min, and then filter through a

medium-textured filter paper into a 100-mL volumetric flask. Wash beaker and paper thoroughly

with hot water, cool contents of the flask to room temperature, dilute to 100 mL, and mix the

solution thoroughly. Continue as given in Section 19.1.7.2.

19.1.7.1.2. Place 1.000 0.001 g of cement into a platinum evaporating dish and disperse with 10 mL of

water using a swirling motion. While still swirling, add 5.0 mL of HCl all at once. Break up any

lumps with a flat-end stirring rod and evaporate to dryness on a steam bath. Make certain that the

gelatinous appearance is no longer evident. Treat the residue with 2.5 mL of HCl and about 20 mL

of water. Digest on a steam bath for 5 to 10 min and filter immediately through a 9-cm medium-

textured filter paper into a 100-mL volumetric flask. Wash thoroughly with repeated small

amounts of hot water until the total volume of solution is 80 to 95 mL. Cool to room temperature,

dilute to the mark, and mix thoroughly.


19.1.7.1.3. When it has been demonstrated that the removal of SiO2 is necessary to obtain the required

accuracy described in Sections 5.4.2.1 through 5.4.3 for a specific flame photometer, SiO2 must

always be removed when making analyses that are used as the basis for rejection of a cement for

failure to comply with specifications or where specification compliance may be in question. When

there is no question as to specification compliance, analyses may be made by such instruments

without SiO2 removal, provided the deviations from certificate values obtained by the tests

prescribed in Sections 5.4.2.1 through 5.4.3 are not more than twice the indicated limits.

19.1.7.2. If the test method in use requires more dilute solutions, an internal standard, or both, carry out the

same dilutions as in Section 19.1.5.4, as needed. The standard and the sample solutions to be

analyzed must be prepared in the same way and to the same dilution as the solutions of standard

cements analyzed for the qualification of the instrument.

19.1.7.3. Procedure for Na2O—Warm up and adjust the instrument for the determination of Na2O as

described in Section 19.1.6.1. Immediately following the adjustment and without changing any

instrumental settings, atomize the cement solution and note the scale reading (see Note 60). Select

the standard solutions that immediately bracket the cement solution in Na2O content and observe

their readings. Their values should agree with the values previously established during calibration

of the apparatus. If not, recalibrate the apparatus for that constituent. Finally, alternate the use of

the unknown solution and the bracketing standard solutions until readings of the unknown agree

within one division on the transmission or meter scale, or within 0.01 weight percent for

instruments with digital readout, and readings for the standards similarly agree with the calibration

values. Record the average of the last two readings obtained for the unknown solution.

Note 60—The order in determining Na2O or K2O is optional. In all cases, however, the

determination should immediately follow the adjustment of the instrument for that particular

constituent.

19.1.7.4. If the reading exceeds the scale maximum, either transfer a 50-mL aliquot of the solution prepared

in Section 19.1.7.1 to a 100-mL volumetric flask or, if desired, prepare a new solution by using

0.500 g of cement and 2.5 mL of HCl (instead of 5.0 mL) in the initial addition of acid. In the

event silica has to be removed from the 0.5-g sample of cement, treat the dehydrated material with

1.25 mL of HCl and about 20 mL of water, then digest, filter, and wash. In either case, add 5.0 mL

of calcium chloride stock solution (see Section 19.1.5.1) before diluting to mark with water. Dilute

to the mark. Proceed as in Section 19.1.5.4 if more dilute solutions are required by the test method

in use. Determine the alkali content of this solution as described in (see Section 19.1.7.3) and

multiply by a factor of 2 the percentage of alkali oxide.

19.1.7.5. Procedure for K2O—Repeat the procedure described in Section 19.1.7.3, except that the

instrument shall be adjusted for the determination of K2O. For instruments that read both Na2O

and K2O simultaneously, determine K2O at the same time as determining Na2O.

19.1.8. Calculation and Report—From the recorded averages for Na2O and K2O in the unknown sample,

report each oxide rounded in accordance with Table 3.

19.2. Water-Soluble Alkalis (see Note 61):

Note 61—The determination of water-soluble alkali should not be considered as a substitute for

the determination of total alkali according to Sections 19.1.2.1 to 19.1.8. Moreover, it is not to be

assumed that in this method all water-soluble alkali in the cement will be dissolved. Strict

adherence to the procedure described is essential where there is a specified limit on the content

of water-soluble alkali or where several lots of cement are compared on the basis of water-soluble

alkali.

19.2.1. Procedure:


19.2.1.1. Weigh 25.0 g of sample into a 500-mL Erlenmeyer flask and add 250 mL of water. Stopper the

flask with a rubber stopper and shake continuously for 10 min at room temperature. Filter through

a Büchner funnel that contains a well-seated retentive, dry filter paper, into a 500-mL filtering

flask, using a weak vacuum. Do not wash.

19.2.1.2. Transfer a 50-mL aliquot (see Note 62) of the filtrate to a 100-mL volumetric flask and acidify

with 0.5 mL of concentrated HCl (sp gr 1.19). Add 9.0 mL of stock CaCl2 solution (63,000 ppm

CaO), described in Section 19.1.5.1, to the 100-mL flask, and dilute the solution to 100 mL. If the

test method in use requires more dilute solutions, an internal standard, or both, carry out the same

dilutions as in Section 19.1.5.4, as needed. Determine the Na2O and K2O contents of this solution

as described in Sections 19.1.7.3 and 19.1.7.5. Record the parts per million of each alkali in the

solution in the 100-mL flask.

Note 62—The aliquot of the filtrate taken for the analysis should be based on the expected water-

soluble alkali content. If the expected level of either K2O or Na2O is more than 0.08 weight

percent of cement, or if the water-soluble alkali level is unknown, a 50-mL aliquot as given in

Section 19.2.1.2 should be used to make up the initial test solution. If either the Na2O or K2O

exceeds 0.16 percent, place a 50-mL aliquot of the solution from Section 19.2.1.2 in a 100-mL

volumetric flask, add 5 mL of CaCl2 stock solution, and dilute to 100 mL. When the level of either

K2O or Na2O is less than 0.08 percent, take a 100-mL aliquot from the original filtrate (obtained

by Section 19.2.1.1), add 1 mL of HCl, and evaporate on a hot plate in a 250-mL beaker to about

70 mL. Add 8 mL of stock CaCl2 solution and transfer the sample to a 100-mL volumetric flask,

rinsing the beaker with a small portion of distilled water. Cool the solution to room temperature

and dilute to 100 mL.

19.2.2. Calculations—Calculate the percentage of the water-soluble alkali, expressed as Na2O, as follows:

Total water-soluble alkali, as Na2O = A + E (10)

A = B/(V 10)

C = D/(V 10)

E = C 0.658

where:

A = percentage of water-soluble sodium oxide (Na2O),

B = parts per million of Na2O in the solution in the 100-mL flask,

V = milliliters of original filtrate in the 100-mL flask,

C = percent of water-soluble potassium oxide (K2O),

D = parts per million of K2O in the 100-mL flask,

E = percentage Na2O equivalent to K2O determined, and

0.658 = molecular ratio of Na2O to K2O.


20. MANGANIC OXIDE (REFERENCE TEST METHOD)

20.1. Summary of Method—In this procedure, manganic oxide is determined volumetrically by titration

with sodium arsenite solution after oxidizing the manganese in the cement with sodium

metabismuthate (NaBiO3).

20.2. Reagents:

20.2.1. Sodium Arsenite, Standard Solution (1 mL = 0.0003 g Mn2O3)—Dissolve in 100 mL of water

3.0 g of sodium carbonate (Na2CO3) and then 0.90 g of arsenic trioxide (As2O3), heating the

mixture until the solution is as complete as possible. If the solution is not clear or contains a


residue, filter the solution. Cool it to room temperature, transfer to a volumetric flask, and dilute

to 1 L.

20.2.1.1. Dissolve 0.58 g of potassium permanganate (KMnO4) in 1 L of water and standardize it against

about 0.03 g of sodium oxalate (Na2C2O4) oxidimetric standard furnished by NIST (Standard

Sample No. 40 or its replacement) according to the directions furnished with the sodium oxalate.

Put 30.0 mL of the KMnO4 solution in a 250-mL Erlenmeyer flask. Add 60 mL of HNO3 (1+4)

and 10 mL of sodium nitrite (NaNO2, 50 g/L) to the flask. Boil the solution until the HNO2 is

completely expelled. Cool the solution, add NaBiO3, and finish by titrating with the standard

sodium arsenite (NaAsO2) solution, as described in Section 20.3.2. Calculate the manganic oxide

(Mn2O3) equivalent of the NaAsO2 solution, g/mL, as follows:

E = (A 7.08)/BC (11)

where:

E = Mn2O3 equivalent of the NaAsO2 solution, g/mL;

A = grams of Na2C2O4 used;

B = milliliters of KMnO4 solution required by the Na2C2O4;

C = milliliters of NaAsO2 solution required by 30.0 mL of KMnO4 solution; and

7.08 = molecular ratio of Mn2O3 to 5 Na2C2O4(0.236) multiplied by 30.0 (milliliters of

KMnO4 solution).

20.2.2. Sodium Metabismuthate (NaBiO3).

20.2.3. Sodium Nitrite Solution (50 g NaNO2/L).

20.3. Procedure:

20.3.1. Weigh 1.0 to 3.0 g of the sample (see Note 63) into a 250-mL beaker and treat it with 5 to 10 mL

of water, and then with 60 to 75 mL of HNO3 (1+4). Boil the mixture until the solution is as

complete as possible. Add 10 mL of NaNO2 solution (50 g/L) to the solution and boil it until the

nitrous acid is completely expelled (see Note 64), taking care not to allow the volume of the

solution to become so small as to cause the precipitation of gelatinous SiO2. There may be some

separated SiO2, which may be ignored, but if there is still a red or brown residue, use more NaNO2

solution (50 g/L) to effect a complete decomposition, and then boil again to expel the nitrous acid.

Filter the solution through a medium-textured paper into a 250-mL Erlenmeyer flask and wash the

filter paper with water.

Note 63—The amount of cement taken for analysis depends on the content of manganese,

varying from 1 g for about 1 percent of Mn2O3 to 3 g for 0.25 percent or less of Mn2O3.

Note 64—When NaNO2 is added, the expulsion of HNO2 by boiling must be complete. If any

HNO2 remains in the solution, it will react with the added NaBiO3 and decrease its oxidizing value.

If there is any manganese in the cement, the first small quantity of NaBiO3 should bring out a

purple color.

20.3.2. The solution should have a volume of 100 to 125 mL. Cool it to room temperature. To the

solution, add a total of 0.5 g of NaBiO3 in small quantities while shaking intermittently. After the

addition is completed, shake the solution occasionally for 5 min and then add to it 50 mL of cool

HNO3 (1+33), which has been previously boiled to expel nitrous acid. Filter the solution through a

pad of ignited asbestos in a Gooch crucible or a carbon or fritted-glass filter with the aid of

suction. Wash the residue four times with the cool HNO3 (1+33). Titrate the filtrate immediately

with the standard solution of NaAsO2. The end point is reached when a yellow color is obtained

free of brown or purple tints and does not change upon further addition of NaAsO2 solution.




20.4. Calculate the percentage of Mn2O3 to the nearest 0.01 as follows:

Mn2O3, % = (EV/S) 100 (12)

where:

E = Mn2O3 equivalent of the NaAsO2 solution, g/mL;

V = milliliters of NaAsO2 solution required by the sample; and

S = grams of sample used.


21. CHLORIDE (REFERENCE TEST METHOD)

21.1. Summary of Test Method—In this test method, acid-soluble chloride content of cement is

determined by the potentiometric titration of chloride with silver nitrate (see Note 65). The

procedure is also applicable to clinker and portland cement raw mix. Under the conditions of the

test, no constituent normally present in these materials will interfere (see Note 66).

Note 65—In most cases, acid-soluble chloride content of a portland cement is total chloride

content.

Note 66—Species that form insoluble silver salts or stable silver complexes in acid solution

interfere with potentiometric measurements. Thus, iodides and bromides interfere, but fluorides

will not. Sulfide salts in concentrations typical of these materials should not interfere because they

are decomposed by acid treatment.

21.2. Apparatus:

21.2.1. Chloride, Silver/Sulfide Ion Selective Electrode—Or a silver billet electrode coated with silver

chloride (see Note 67), with an appropriate reference electrode.

21.2.2. Potentiometer—With millivolt scale readable to 1 mV or better. A digital readout is preferred but

not required.

21.2.3. Buret—Class A, 10-mL capacity with 0.05-mL divisions. A buret of the potentiometric type,

having a displaced delivery tip, is convenient but not required.

Note 67—Suitable electrodes are available from Orion, Beckman Instruments, and Leeds and

Northrup. Carefully following the manufacturer’s instructions, add filling solution to the

electrodes. The silver billet electrodes must be coated electrolytically with a thin, even layer of

silver chloride. To coat the electrode, dip the clean silver billet of the electrode into a saturated

solution of potassium chloride (about 40 g/L) in water, and pass an electric current through the

electrode from a 1.5- to 6-V dry cell with the silver billet electrode connected to the positive

terminal of the battery. A carbon rod from an all-dry cell or other suitable electrode is connected to

the negative terminal and immersed in the solution to complete the electrical circuit. When the

silver chloride coating wears off, it is necessary to rejuvenate the electrode by repeating the above

procedure. All of the old silver chloride should first be removed from the silver billet by rubbing it

gently with fine emery paper, followed by water rinsing of the billet.

21.3. Reagents:

21.3.1. Sodium Chloride (NaCl)—Primary standard grade.

21.3.2. Silver Nitrate (AgNO3)—Reagent grade.

21.3.3. Potassium Chloride (KCl)—Reagent grade (required for silver billet electrode only).


21.3.4. Reagent Water—Use reagent water as defined in Section 3.1.2.

21.4. Preparation of Solutions:

21.4.1. Sodium Chloride, Standard Solution (0.05 N NaCl)—Dry sodium chloride (NaCl) at 105 to 110°C

to a constant mass. Weigh 2.9222 g of dried reagent. Dissolve in water and dilute to exactly 1 L

in a volumetric flask and mix thoroughly. This solution is the standard and requires no

further standardization.

21.4.2. Silver Nitrate, Standard Solution (0.05 N AgNO3)—Dissolve 8.4938 g of silver nitrate (AgNO3) in

water. Dilute to 1 L in a volumetric flask and mix thoroughly. Standardize against 5.00 mL of

standard 0.05 N sodium chloride solution diluted to 150 mL with water following the titration test

method given in Section 21.5.4 beginning with the second sentence. The exact normality shall be

calculated from the average of three determinations as follows:

N = 0.25/V (13)

where:

N = normality of AgNO3 solution;

0.25 = milliequivalents NaCl (5.0 mL 0.05 N); and

V = volume of AgNO3 solution, mL.

Commercially available standard solutions may be used provided the normality is checked

according to the standardization procedure.

21.4.3. Methyl Orange Indicator—Prepare a solution containing 2 g of methyl orange per liter of

95 percent ethyl alcohol.

21.5. Procedure:

21.5.1. Weigh a 5.0-g sample of the cement into a 250-mL beaker (see Note 68). Disperse the sample with

75 mL of water. Without delay slowly add 25 mL of dilute (1+1) nitric acid, breaking up any

lumps with a glass rod. If the smell of hydrogen sulfide is strongly evident at this point, add 3 mL

of hydrogen peroxide (30 percent solution) (see Note 69). Add three drops of methyl orange

indicator and stir. Cover the beaker with a watch glass and allow to stand for 60 to 120 s. If a

yellow to yellow-orange color appears on top of the settled solids, the solution is not sufficiently

acidic. Add additional dilute nitric acid (1+1) dropwise while stirring until a faint pink or red color

persists. Then add 10 drops in excess. Heat the covered beaker rapidly to boiling. Do not allow to

boil for more than a few seconds. Remove from the hot plate (see Note 70).

Note 68—Use a 5-g sample for cement and other materials having an expected chloride content

of less than about 0.15 percent Cl. Use proportionally smaller samples for materials with higher

chloride concentrations. Use cement and other powdered materials as is without grinding. Coarse

samples require grinding to pass a No. 20 mesh sieve. If a sample is too fine, excessive silica gel

may form during digestion with nitric acid, thereby slowing subsequent filtration.

Note 69—Slags and slag cements contain sulfide sulfur in concentrations that can interfere with

the determination.

Note 70—It is important to keep the beaker covered during heating and digestion to prevent the

loss of chloride by volatilization. Excessive amounts of acid should not be used because this

results in early removal of the silver chloride coating from the silver billet electrode. A slurry that

is only slightly acidic is sufficient.

21.5.2. Wash a 9-cm coarse-textured filter paper with four 25-mL increments of water using suction

filtering provided by a 250-mL or 500-mL Büchner funnel and filtration flask. Discard the

washings and rinse the flask once with a small portion of water. Reassemble the suction apparatus

and filter the sample solution. Rinse the beaker and the filter paper twice with small portions of


water. Transfer the filtrate from the flask to a 250-mL beaker and rinse the flask once with water.

The original beaker may be used (see Note 71). Cool the filtrate to room temperature. The volume

should not exceed 175 mL.

Note 71—It is not necessary to clean all the slurry residue from the sides of the beaker nor is it

necessary that the filter remove all of the fine material. The titration may take place in a solution

containing a small amount of solid matter.

21.5.3. For instruments equipped with dial readout, it is necessary to establish an approximate

“equivalence point” by immersing the electrodes in a beaker of water and adjusting the instrument

to read about 20 mV lower than midscale. Record the approximate millivoltmeter reading.

Remove the beaker and wipe the electrodes with absorbent paper.

21.5.4. To the cooled sample (see Note 72) beaker from Section 21.5.2, carefully pipet 2.00 mL of

standard 0.05 N NaCl solution. Place the beaker on a magnetic stirrer and add a TFE-

fluorocarbon-coated magnetic stirring bar. Immerse the electrodes into the solution, taking care

that the stirring bar does not strike the electrodes, and begin stirring gently. Place the delivery tip

of the 10-mL buret, filled to the mark with standard 0.05 N silver nitrate solution, in (preferably)

or above the solution (see Note 73).

Note 72—It is advisable to maintain constant temperature during measurement because the

solubility relationship of silver chloride varies markedly with temperature at low concentrations.

Note 73—If the tip of the buret is out of the solution, any adhering droplet should be rinsed onto

the beaker with a few milliliters of water following each titration increment.

21.5.5. Gradually titrate and record the amount of standard 0.05 N silver nitrate solution required to bring

the millivoltmeter reading to –60.0 mV of the equivalence point determined in the water.

21.5.6. Continue the titration with 0.20-mL increments. Record the buret reading and the corresponding

millivoltmeter reading in Columns 1 and 2 of a four-column recording form like that shown in

Appendix X1. Allow sufficient time between each addition for the electrodes to reach equilibrium

with the sample solution. Experience has shown that acceptable readings are obtained when the

minimum scale reading does not change within a 5-s period (usually within 120 s).

21.5.7. As the equivalence point is approached, the equal additions of AgNO3 solution will cause larger

and larger changes in the millivoltmeter readings. Past the equivalence point, the change per

increment will again decrease. Continue to titrate until three readings past the approximate

equivalence point have been recorded.

21.5.8. Calculate the difference in millivolt readings between successive additions of titrant and enter the

values in Column 3 of the recording form. Calculate the difference between consecutive values in

Column 3 and enter the results in Column 4. The equivalence point of the titration will be within

the maximum mV interval recorded in Column 3. The precise equivalence point can be

interpolated from the data listed in Column 4, as shown in Appendix X1.

21.5.9. Blank—Make a blank determination using 75 mL of water in place of the sample, following the

same procedure starting with the third sentence of Section 21.5.1 without delay. Correct the results

obtained in the analysis accordingly (see Note 74) by subtracting the blank.

21.6. Calculations—Calculate the percent chloride to the nearest 0.001 percent as follows:

1 23.545( – ) – 0.10Cl, %

V V N

W= (14)

where:

V1 = milliliters of 0.05 N AgNO3 solution used for sample titration (equivalence point);

V2 = milliliters of 0.05 N AgNO3 solution used for blank titration (equivalence point);


N = exact normality of 0.05 N AgNO3 solution; and

W = weight of sample, g.


Note 74—For nonreferee analysis, the blank may be omitted.

22. CHLOROFORM-SOLUBLE ORGANIC SUBSTANCES (REFERENCE TEST METHOD)

22.1. Summary of Test Method—This test method was specially designed for the determination of

Vinsol resin and tallow in portland cement, although mineral oil, common rosin, calcium stearate,

and other fatty acid compounds, and probably some other substances, if present, will be included

in the determination. Extreme care is necessary during the entire procedure. The test method may

be applied to types of cement other than portland cement, although if the cement contains a large

amount of acid-insoluble matter, the emulsions may separate slowly, and less vigorous shaking,

more chloroform, and more washing may be necessary.

22.2. Reagents:

22.3. Chloroform—If the blank determination as described in Section 22.3.5 exceeds 0.0015 g, the

chloroform should be distilled before use. Chloroform recovered in the procedure may be slightly

acid but can be reused for the portions to be shaken with the aqueous acid solution of the sample

in the 1-L funnel. Chloroform used for washing the filter and transferring the extract should be

fresh or distilled from fresh chloroform.

22.3.1. Stannous Chloride (SnCl2).

22.4. Procedure:

22.4.1. Place 40 g of cement in a 1-L Squibb separatory funnel (see Note 75) and mix it with 520 mL of

water added in two approximately equal portions. Shake vigorously immediately after the addition

of the first portion to effect complete dispersion. Then add the second portion and shake again. At

once add rapidly 185 mL of HCl in which 10 g of SnCl2 (see Note 76) has been dissolved, and

then rapidly insert the stopper in the funnel, invert, and shake with a swirling motion for a few

seconds to loosen and disperse all the cement, taking care to avoid the development of great

internal pressure due to unnecessarily violent shaking. Release internal pressure immediately by

opening and closing the stopcock. Repeat the shaking and release the pressure until the

decomposition of the cement is complete. If necessary, break up persistent lumps with a long glass

rod. Cool to room temperature rapidly by allowing tap water to run on the flask.

Note 75—The use of grease to lubricate the stopcocks and glass stoppers of the separatory

funnels should be avoided. Wetting the stopcocks with water before using will assist in their

easy operation.

Note 76—The purpose of the SnCl2 is to prevent the oxidation of sulfide sulfur to elemental

sulfur, which is soluble in chloroform.

22.4.2. Add 75 mL of chloroform to the solution, stopper the funnel, shake it vigorously for 5 min, and

allow the water and chloroform to stand 15 min to separate. Draw off the lower chloroform layer

into a 125-mL Squibb separatory funnel, including the scum (see Note 77) and a few milliliters of

the aqueous layer, making sure all the scum is transferred. Keep the amount of the aqueous layer

transferred to an absolute minimum because excessive water in the 125-mL funnel may result in

incomplete extraction of the scum and may cause an emulsion that does not separate readily.

Shake the funnel vigorously to ensure the complete extraction of the scum. Allow the chloroform

to separate and draw it into a 250-mL Squibb separatory funnel that contains 50 mL of water and a


few drops of HCl, making sure to keep the scum behind in the 125-mL funnel. Shake the 250-mL

funnel and draw the chloroform into another 250-mL funnel that contains 50 mL of water and a

few drops of HCl. Shake this funnel as in the case of the first 250-mL funnel. When the

chloroform separates, draw it into a standard-taper flat-bottom boiling flask (see Note 78), taking

care not to allow any water to enter the flask.

Note 77—There is usually a dark-colored scum at the liquid interface. It may contain chloroform-

soluble organic substance after shaking in the funnel, where the proportion of water to chloroform

is great. It may be concentrated and confined to a small volume by gently twirling the funnel after

the scum has been drawn into the narrower part of the funnel.

Note 78—The liquid is later distilled. No cork or rubber stoppers should be used. A 250- or

300-mL soil analysis flask, fitted with a condenser tube by means of a ground joint, is satisfactory.

The tube may be bent near the neck, and the remaining part fitted with a water-cooling jacket.

Chloroform thus recovered may be reused as described in Section 22.2.1.

22.4.3. Add 25 mL of chloroform to the solution in the original 1-L separatory funnel and carry out the

operations as described in Section 22.3.2, retaining the original wash water in the 250-mL funnels.

Repeat, using another 25-mL portion of chloroform.

22.4.4. Distill the combined chloroform extracts in the boiling flask until their volume is reduced to 10 to

15 mL. Filter the remaining liquid into a weighed 100-mL glass beaker or platinum dish (see

Note 79) through a small medium-textured filter paper that has been washed with fresh

chloroform. Rinse the flask and wash the paper with several small portions of fresh chloroform.

Evaporate the extracts at a low temperature (not over 63°C) to dryness (see Note 80) and heat it in

an oven at 57 to 63°C for 3 min. Pass dry air into the vessel for 15 s, cool, and determine the mass.

Repeat the heating and mass determinations until two successive mass determinations do not differ

by more than 0.0010 g. The higher of the last two mass determinations shall be taken as the true

mass.

Note 79—A platinum dish is preferable because it quickly attains the temperature of the balance.

If a glass beaker is used, it should be allowed to stand in the case of the balance for at least 20 min

before determining the mass.

Note 80—Care should be taken in drying the extract because many of the chloroform-soluble

organic substances are somewhat volatile when heated for a long time at even moderate

temperatures. With protection from the accumulation of dust, the solution may be evaporated at

room temperature overnight.

When a quick evaporation is desired, the solution may be evaporated on a hot plate at low heat

under a stream of dry air through a glass tube (about 10 mm in inside diameter) until it is about

3 mm in depth. Then remove the vessel from the hot plate and continue a slow stream of dry air

until the residue appears dry. Then continue with a more rapid stream of dry air for 5 min at room

temperature before placing the vessel in the oven at 57 to 63°C. After each 3-min heating period in

the oven, pass dry air into the vessel for about 15 s before determining the mass. The air may be

dried by passing it through a cheap desiccant such as calcium chloride or sulfuric acid, followed

by a desiccant of high efficiency such as magnesium perchlorate or anhydrous calcium sulfate,

with care taken to avoid the carrying of dust from the desiccant by the air. Instead of using

compressed air, which is often contaminated with oil, dirt, and moisture, one can place the

chloroform solution under a bell glass and induce a stream of air through the desiccants by means

of an aspirator or vacuum pump.

When Vinsol resin is known to be the only substance present, the residue is more stable and

may be heated at 100 to 105°C, instead of 57 to 63°C, to expel all possible traces of chloroform.

22.4.5. Blank—Make a blank determination. Ignite a 40-g sample of the cement at 950 to 1000°C for 1 h

(see Note 81) and regrind. Treat this ignited sample by the same procedure using the same

reagents as in the analysis, and correct the results accordingly.

Note 81—Care should be taken to completely burn off the organic substance. A 100-mL flat

platinum dish, in which the sample is well spread out, and a muffle furnace are advised for this


purpose. If such a furnace is not available, a large high-temperature burner of the Meker type may

be used. Thorough stirring of the sample should be done frequently—every 5 min when a burner

is used.

22.5. Calculation—Calculate the percentage of chloroform-soluble organic substances to the nearest

0.001 by multiplying the mass in grams of residue (see Note 82) by 2.5 (100 divided by the mass

of the sample used (40 g)). Report the result rounded in accordance with Table 3.

Note 82—If the organic substance in the cement is tallow, the residue is the fatty acids

resulting from the hydrolysis of the tallow in the hot acid solution, and its mass should be

multiplied by 1.05 to give the mass of the original glycerides in the tallow. If the original

substance is calcium stearate, the residue is stearic acid, and its mass multiplied by 1.07 gives

the mass of calcium stearate.

ALTERNATIVE TEST METHODS

23. CALCIUM OXIDE (ALTERNATIVE TEST METHOD)


23.1.1. This test method covers the gravimetric determination of CaO after removal of SiO2 and the

ammonium hydroxide groups and double precipitation of calcium as the oxalate. The precipitate is

converted to CaO by ignition, and the mass is determined.

23.1.2. Strontium, usually present in portland cement as a minor constituent, is precipitated with calcium

as the oxalate and is subsequently calculated as CaO. If the SrO content is known and correction

of CaO for SrO is desired, as, for example, for research purposes or to compare results with CRM

certificate values, the CaO obtained by this test method may be corrected by subtracting percent

SrO. In determining conformance of a cement to specifications, the correction of CaO for SrO

should not be made.

23.2. Procedure (see Note 83):

23.2.1. Acidify the combined filtrates obtained in the determination of the ammonium hydroxide group

(see Sections 9.1 through 9.3) and, if necessary, evaporate to a volume of about 200 mL. Add

5 mL of HCl, a few drops of methyl red indicator solution, and 30 mL of warm ammonium

oxalate solution (50 g/L) (see Note 39). Heat the solution to 70 to 80°C and add NH4OH (1+1)

dropwise while stirring until the color changes from red to yellow (see Note 40). Allow the

solution to stand without further heating for 1 h (not longer), with occasional stirring during the

first 30 min. Filter using a retentive paper and wash moderately with cold ammonium oxalate

solution (1 g/L). Reserve the filtrate and washings.

Note 83—When analyses are being made for determining conformity to specifications and there

is a possibility that sufficient manganese will be present to cause the percentage of magnesium

determined by alternate test methods to exceed the specification limit, manganese may be removed

as directed in Section 15.3.2 before CaO is determined by this alternative test method.

23.2.2. Transfer the precipitate and filter paper to the beaker in which the precipitation was made.

Dissolve the oxalate in 50 mL of hot HCl (1+4) and macerate the filter paper. Dilute to 200 mL

with water, add a few drops of methyl red indicator and 20 mL of ammonium oxalate solution,

heat the solution nearly to boiling, and precipitate calcium oxalate again by neutralizing the acid

solution with NH4OH, as described in Section 15.3.123.2.1. Allow the solution to stand 1 to 2 h

(standing for 2 h at this point does no harm), filter, and wash as before. Combine the filtrate with

that already obtained and reserve for the determination of MgO (see Section 16.3.1).


23.2.3. Dry the precipitate in a tared covered platinum crucible. Char the paper without inflaming; burn

the carbon at as low a temperature as possible; and, finally, heat with the crucible tightly covered

in an electric furnace or over a blast lamp at a temperature of 1100 to 1200°C. Cool in a desiccator

and determine the mass as CaO. Repeat the ignition to constant mass.



23.3. Calculation:

23.3.1. Calculate the percentage of CaO to the nearest 0.1 by multiplying the mass in grams of CaO by

200 (100 divided by the mass of sample used (0.5 g)).

23.3.2. Correct the percent CaO for SrO, if desired, by subtracting the percent SrO.

24. CARBON DIOXIDE (REFERENCE TEST METHOD)

24.1. Any test method may be used, provided that acceptable performance has been demonstrated in

accordance with Section 24.2. See Appendix X2 for guidance on methods.

24.2. Demonstrate performance by analysis, in duplicate, of at least one portland cement. Prepare three

standards, each in duplicate: Standard A shall be the selected portland cement; Standard B shall be

Standard A containing 2.00 percent Certified CaCO3 (e.g., NIST 915a); Standard C shall be

Standard A containing 5.00 percent Certified CaCO3. Prepare duplicate specimens of each

standard. Assign the CO2 content of Standard A as the average of the two values determined,

provided they agree within the required limit of Table 1, Column 2. Assign CO2 values to

Standards B and C as follows: Multiply the Certified CaCO3 value (Y) for CO2 (from the certificate

value) by the mass fraction of Certified CaCO3 added to that standard (percentage added divided

by 100); multiply the value determined for Standard A by the mass fraction of Standard A in each

of the other standards (i.e., 0.98 and 0.95 for Standards B and C, respectively); add the two values

for Standard A and for Standard B, respectively; call these values B and C.

Example:

B = 0.98A + 0.02Y

C = 0.95A + 0.05Y

where for Certified CaCO3, if Y = 44.01 percent, then

B = 0.98A + 0.88 percent by mass

C = 0.95A + 2.20 percent by mass

The difference between the duplicate CO2 values for Standards B and C, respectively, shall not

exceed 0.17 and 0.24 percent by mass. The difference between the average of the duplicate values

for Standards B and C and their assigned values (B and C) shall not exceed 0.13 and 0.26 percent

by mass, respectively.

24.3. Report the results rounded in accordance with Table 3.


25. MAGNESIUM OXIDE (ALTERNATIVE TEST METHOD)

25.1. Summary of Test Method—This alternative test method is a volumetric procedure suitable for use

when the determination of silicon dioxide (SiO2), aluminum oxide (Al2O3), ferric oxide (Fe2O3),

and calcium oxide (CaO) are omitted.

25.2. Rapid Volumetric Test Method (Titration of Magnesium Oxyquinolate):

25.3. Reagents:

25.3.1. Ammonium Nitrate Solution (20 g NH4NO3/L).

25.3.2. Ammonium Oxalate Solution (50 g/L).

25.3.3. Hydroxyquinoline Solution—Dissolve 25 g of 8-hydroxyquinoline in 60 mL of acetic acid. When

the solution is complete, dilute to 2 L with cold water. One milliliter of this solution is equivalent

to 0.0016 g of MgO.

25.3.4. Potassium Bromate-Potassium Bromide, Standard Solution (0.2 normal)—Dissolve 20 g of

potassium bromide (KBr) and 5.57 g of potassium bromate (KBrO3) in 200 mL of water and dilute

to 1 L. Obtain the ratio of the strength of this solution to that of the 0.1 N Na2S2O3 solution (see

Section 23.2.6) as follows: To 200 mL of water in a 500-mL Erlenmeyer flask, add 25.0 mL of the

0.2 N KBrO3-KBr solution, measured from a pipet or buret. Add 20 mL of HCl, stir, and add

immediately 10 mL of potassium iodide (KI) (250 g/L). Mix well and titrate at once with the

Na2S2O3 solution until nearly colorless. Add 2 mL of starch solution and titrate to the

disappearance of the blue color. Calculate the ratio in strength of the KBrO3-KBr solution to the

Na2S2O3 solution by dividing the volume of Na2S2O3 solution by the volume of KBrO3-KBr

solution used in the titration.

25.3.5. Potassium Iodide Solution (250 g KI/L).

25.3.6. Sodium Thiosulfate, Standard Solution (0.1 N)—Dissolve 25 g of sodium thiosulfate

(Na2S2O3·5H2O) in 200 mL of water, add 0.1 g of sodium carbonate (Na2CO3), and dilute to 1 L.

Let stand at least 7 days. Standardize this solution directly against primary standard potassium

dichromate (K2Cr2O7). One milliliter of 0.10 N Na2S2O3 solution is equivalent to 0.000504 g

of MgO.

25.3.7. Starch Solution—To 500 mL of boiling water, add a cold suspension of 5 g of soluble starch in

25 mL of water, cool to room temperature, add a cool solution of 5 g of sodium hydroxide

(NaOH) in 50 mL of water, add 15 g of KI, and mix thoroughly.

25.4. Procedure:

25.4.1. Disperse 0.5 g (see Note 84) of the sample of cement in a 400-mL beaker with 10 mL of water,

using a swirling motion. While still swirling, add 10 mL of HCl all at once. Dilute immediately to

100 mL. Heat gently and grind any coarse particles with the flattened end of a glass rod until

decomposition is complete, add two or three drops of HNO3 and heat to boiling (see Note 85).

Note 84—If SiO2, ammonium hydroxide group, and CaO are separated and determined in

accordance with the appropriate sections for either the reference or alternative test methods, the

remaining filtrate may be used for the determination of MgO as described in Section 25.4.1,

starting with the third from the last sentence of Section 25.4.2, “Add 5 mL of HCl…”.

Note 85—In the case of cements containing blast-furnace slag or a significant quantity of sulfide

sulfur, add 12 drops of HNO3 and boil for 20 min to oxidize iron and remove sulfide.


25.4.2. Add three drops of methyl red indicator to the solution, and then add NH4OH until the solution is

distinctly yellow. Heat this solution to boiling and boil for 50 to 60 s. In the event difficulty from

bumping is experienced while boiling the ammoniacal solution, a digestion period of 10 min on a

steam bath, or a hot plate having the approximate temperature of a steam bath, may be substituted

for the 50- to 60-s boiling period. Remove from the burner, steam bath, or hot plate and allow to

stand until the precipitate has settled. Using medium-textured paper, filter the solution without

delay, wash the precipitate twice with hot NH4NO3 (20 g/L), and reserve the filtrate. Transfer the

precipitate with the filter paper to the beaker and dissolve in 10 mL of HCl (1+1). Macerate the

filter paper. Dilute to about 100 mL and heat to boiling. Reprecipitate, filter, and wash the

hydroxides as above. Combine this filtrate and washings with those from the first precipitation

taking care that the volume does not exceed 300 mL (see Note 86). Add 5 mL of HCl, a few drops

of methyl red indicator solution, and 30 mL of warm ammonium oxalate solution (50 g/L). Heat

the solution to 70 to 80°C and add NH4OH (1+1) dropwise, while stirring, until the color changes

from red to yellow (see Note 40). Allow the solution to stand without further heating for 15 min

on a steam bath.

Note 86—In the case of cements containing blast-furnace slag, or which are believed to contain a

significant quantity of manganese, acidify with HCl, evaporate to about 100 mL, and remove the

manganese, using the procedure described in Section 15.3.1.

25.4.3. Add 10 to 25 mL of the 8-hydroxyquinoline reagent (see Note 87) and then 4 mL of the

NH4OH/100 mL solution. Stir the solution on a mechanical stirring machine for 15 min and set

aside until the precipitate has settled (see Note 88). Filter the solution using medium-textured

paper and wash the precipitate with hot NH4OH (1+40). Dissolve the precipitate in 50 to 75 mL of

hot HCl (1+9) in a 500-mL Erlenmeyer flask. Dilute the resulting solution to 200 mL and add

15 mL of HCl. Cool the solution to 25°C and add 10 to 35 mL of the 0.2 N KBrO3-KBr solution

(see Note 89) from a pipet or buret. Stir the solution and allow to stand for about 30 s to ensure

complete bromination. Add 10 mL of KI (250 g/L). Stir the resulting solution well and then titrate

with the 0.1 N Na2S2O3 solution until the color of the iodine becomes faintly yellow. At this point,

add 2 mL of the starch solution and titrate the solution to the disappearance of the blue color.

Note 87—An excess of the 8-hydroxyquinoline reagent is needed to avoid a low result for MgO,

but too great an excess will yield high results. The following guide should be used to determine

the amount of reagent added:

Appropriate Content

of MgO, %

Appropriate Amount

of Reagent Required,

mL

0 to 1.5 10

1.5 to 3.0 15

3.0 to 4.5 20

4.5 to 6.0 25

Note 88—The precipitate should be filtered within an hour. Prolonged standing may cause

high results.

Note 89—The amount of the standard KBrO3-KBr solution used should be as follows:


Appropriate Content

of MgO, %

Amount of Standard

KBrO3-KBr Solution,

mL

0 to 1 10

1 to 2 15

2 to 3 20

3 to 4 25

4 to 5 30

5 to 6 35



25.5. Calculation—Calculate the percentage of MgO to the nearest 0.1 as follows (see Note 90):

( )1 2MgO, % 200E V R V= − (15)

where:

E = MgO equivalent of the Na2S2O3 solution, g/mL;

V1 = milliliters of KBrO3-KBr solution used;

R = ratio in strength of the KBrO3-KBr solution to the Na2S2O3;

V2 = milliliters of Na2S2O3 solution used; and

200 = 100 divided by the mass of sample used (0.5 g).


Note 90—V1R represents the volume of Na2S2O3 solution equivalent to the volume of KBrO3-

KBr solution used. V2 represents the amount of Na2S2O3 required by the excess KBrO3-KBr that is

not reduced by magnesium oxyquinolate.

26. LOSS ON IGNITION (ALTERNATIVE TEST METHOD)

26.1. Portland Blast-Furnace Slag Cement and Slag Cement (Alternative Test Method):

26.1.1. Summary of Test Method—This test method covers a correction for the gain in weight due to

oxidation of sulfides usually present in such cement by determining the decrease in the sulfide

sulfur content during ignition. It gives essentially the same result as the reference test method (see

Sections 18.2.1 through 18.2.3) that provides for applying a correction based on the increase in

SO3 content.

26.1.2. Procedure:

26.1.2.1. Weigh 1 g of cement in a tared platinum crucible, cover, and ignite in a muffle furnace at a

temperature of 950 50°C for 15 min. Cool to room temperature in a desiccator and weigh. After

weighing carefully, transfer the ignited material to a 500-mL boiling flask. Break up any lumps in

the ignited cement with the flattened end of a glass rod.

26.1.2.2. Determine the sulfide sulfur content of the ignited sample using the procedure described in

Sections 17.2.1 through 17.2.5. Using the same procedure, also determine the sulfide sulfur

content of a portion of the cement that has not been ignited.

26.1.3. Calculation—Calculate the percentage loss of weight (see Note 91) occurring during ignition (see

Section 26.1.2.1), and add twice the difference between the percentages of sulfide sulfur in the


original sample and ignited sample as determined in Section 26.1.2.2. Report this value as the loss

on ignition, rounded in accordance with Table 3.

Note 91—If a gain of weight is obtained during the ignition, subtract the percentage of gain from

the correction for sulfide oxidation.

27. TITANIUM DIOXIDE (ALTERNATIVE TEST METHOD)

27.1. Summary of Test Method—In this test method, titanium dioxide (TiO2) is determined

colorimetrically by comparing the color intensity of the peroxidized solution of the titanium in the

sample with the color intensity of a peroxidized standard solution of titanic sulfate.

27.2. Interferences—Interfering elements in the peroxide method for TiO2 are vanadium, molybdenum,

and chromium. In very small quantities, the interference of the last two is negligible. However,

vanadium in very small quantities causes interference and, because some cements contain this

element, the Na2CO3 fusion (see Section 27.5.4) and extraction with water are necessary.

27.3. Apparatus:

27.3.1. Colorimeter—The apparatus shall consist of a colorimeter of the Kennicott or Duboscq type, or

other colorimeter or spectrophotometer designed to measure light transmittancy and suitable for

measurements at wavelengths between 400 and 450 nm.

27.4. Reagents:

27.4.1. Ammonium Chloride (NH4Cl).

27.4.2. Ammonium Nitrate (20 g NH4NO3/L).

27.4.3. Ferrous Sulfate Solution (1 mL = 0.005 g Fe2O3)—Dissolve 17.4 g of ferrous sulfate

(FeSO4 · 7H2O) in water containing 50 mL of H2SO4 and dilute to 1 L. One milliliter is

equivalent to 1 percent of Fe2O3 in 0.5 g of sample.

27.4.4. Hydrogen Peroxide (30 percent)—Concentrated hydrogen peroxide (H2O2).

27.4.5. Sodium Carbonate (20 g Na2CO3/L).

27.4.6. Sodium or Potassium Pyrosulfate (Na2S2O7 or K2S2O7).

27.4.7. Titanic Sulfate, Standard Solution (1 mL = 0.0002 g TiO2)—Use standard TiO2 furnished by NIST

(Standard Sample No. 154 or its replacements). Dry for 2 h at 105 to 110°C. Transfer a weighed

amount, from 0.20 to 0.21 g of the TiO2, to a 125-mL Phillips beaker. Add 5 g of ammonium

sulfate ((NH4)2SO4) and 10 mL of H2SO4 to the beaker, and insert a short-stem glass funnel in the

mouth of the beaker. Heat the mixture cautiously to incipient boiling while rotating the flask over

a free flame. Continue the heating until the complete solution has been effected and no unattacked

material remains on the wall of the flask (see Note 92). Cool and rapidly pour the solution into

200 mL of cold water while stirring vigorously. Rinse the flask and funnel with H2SO4 (1+19),

stir, and let the solution and washings stand for at least 24 h. Filter into a 1-L volumetric flask,

wash the filter thoroughly with H2SO4 (1+19), dilute to the mark with H2SO4 (1+19), and mix.

Note 92—There may be a small residue, but it should not contain more than a trace of TiO2 if the

operations have been properly performed.

27.4.8. Calculate the TiO2 equivalent of the titanic sulfate solution, g/mL, as follows:

E = AB/1000 (16)


where:

E = TiO2 equivalent of the Ti(SO4)2 solution, g/mL;

A = grams of standard TiO2 used (corrected for loss on drying);

B = percentage of TiO2 in the standard TiO2 as certified by the NIST, divided by 100;

and

1000 = number of milliliters in the volumetric flask.

27.5. Procedure:

27.5.1. Mix thoroughly 0.5 g of the sample of cement and about 0.5 g of NH4Cl in a 50-mL beaker, cover

the beaker with a watch glass, and add cautiously 5 mL of HCl, allowing the acid to run down the

lip of the covered beaker. After the chemical action has subsided, lift the cover, stir the mixture

with a glass rod, replace the cover, and set the beaker on a steam bath for 30 min (see Note 93).

During this time of digestion, stir the contents occasionally and break up any remaining lumps to

facilitate the complete decomposition of the cement. Fit a medium-textured filter paper to a funnel

and transfer the precipitate to the filter. Scrub the beaker with a rubber policeman, and rinse the

beaker and policeman. Wash the filter two or three times with hot HCl (1+99), and then with 10 or

12 small portions of hot water, allowing each portion to drain through completely.

Note 93—A hot plate may be used instead of a steam bath if the heat is so regulated as to

approximate that of a steam bath.

27.5.2. Transfer the filter and residue to a platinum crucible (see Note 94), dry, and ignite slowly until the

carbon of the paper is completely consumed without inflaming. Treat the SiO2 thus obtained with

0.5 to 1 mL of water, about 10 mL of HF, and 1 drop of H2SO4, and evaporate cautiously to

dryness (see Note 95).

Note 94—When it is desired to shorten the procedure for purposes other than referee analysis,

usually with little sacrifice of accuracy, the procedure given in Section 27.5.2 may be omitted.

Note 95—When a determination of SiO2 is desired in addition to one of TiO2, the SiO2 may be

obtained and treated with HF, as directed in Sections 8.2.3.1 through 8.2.4.

27.5.3. Heat the filtrate to boiling and add NH4OH until the solution becomes distinctly alkaline, as

indicated by an ammoniacal odor. Add a small amount of filter paper pulp to the solution and boil

for 50 to 60 s. Allow the precipitate to settle, filter through a medium-textured paper, and wash

twice with hot NH4NO3 solution (20 g/L). Place the precipitate in the platinum crucible in which

the SiO2 has been treated with HF and ignite slowly until the carbon of the paper is consumed.

Note 96—When a determination of ammonium hydroxide group is desired in addition to one of

TiO2, the precipitation and ignition may be made as described in Sections 9.2.1 through 9.2.4.

However, the crucible must contain the residue from the treatment of the SiO2 with HF unless

circumstances permit its omission, as indicated in Note 95.

27.5.4. Add 5 g of Na2CO3 to the crucible and fuse for 10 to 15 min (see Section 27.2). Cool, separate the

melt from the crucible, and transfer to a small beaker. Wash the crucible with hot water, using a

policeman. Digest the melt and washings until the melt is completely disintegrated, and then filter

through a 9-cm medium-textured filter paper and wash a few times with Na2CO3 (20 g/L). Discard

the filtrate. Place the precipitate in the platinum crucible and ignite slowly until the carbon of the

paper is consumed.

27.5.5. Add 3 g of Na2S2O7 or K2S2O7 to the crucible and heat below red heat until the residue is dissolved

in the melt (see Note 97). Cool and dissolve the fused mass in water containing 2.5 mL of H2SO4.

If necessary, reduce the volume of the solution (see Note 98), filter into a 100-mL volumetric flask

through a 7-cm medium-textured filter paper, and wash with hot water. Add 5 mL of H3PO4, and

cool the solution to room temperature. Add H2O2 (1.0 mL of 30 percent strength or its equivalent)

(see Note 99), dilute to the mark with water, and mix thoroughly.


Note 97—Start the heating with caution because pyrosulfates (also known as fused bisulfates) as

received often foam and spatter in the beginning due to an excess of H2SO4. Avoid an

unnecessarily high temperature or unnecessarily prolonged heating because fused pyrosulfates

may attack platinum. A supply of nonspattering pyrosulfates may be prepared by heating some

pyrosulfate in a platinum vessel to eliminate the excess H2SO4 and crushing the cool fused mass.

Note 98—If the solution is evaporated to too small a volume and allowed to cool, there may be a

precipitate of sulfates difficult to redissolve. In case of overevaporation, do not permit the contents

to cool, but add hot water and digest on a steam bath or hot plate until the precipitate is

redissolved, with the possible exception of a small amount of SiO2.

Note 99—Hydrogen peroxide deteriorates on standing. Its strength may be determined by adding

a measured volume of the solution to 200 mL of cold water and 10 mL of H2SO4 (1+1) and

titrating with a standard solution of potassium permanganate (KMnO4) prepared in accordance

with Section 15.2.2. If the standard solution contains 0.0056357 g of KMnO4/mL, 49.5 mL of it

will be required by 0.50 mL of H2O2 (30 percent).

27.5.6. Prepare from the standard Ti(SO4)2 solution a suitable reference standard solution or a series of

reference standard solutions in 100-mL volumetric flasks, depending on the type of colorimeter to

be used. To each solution, add 3 g of Na2S2O7 or K2S2O7 dissolved in water, an amount of FeSO4

solution equivalent to the Fe2O3 content in 0.5 g of the cement under test, 2.5 mL of H2SO4, and

5 mL of H3PO4 (see Note 100). When the solution is at room temperature, add H2O2 (1.0 mL of

30 percent strength or its equivalent), dilute to the mark with water, and mix thoroughly (see

Note 101).

Note 100—The color imparted to the solution by Fe2(SO4)2 is partly offset by the bleaching effect

of H2SO4, H3PO4, and alkali salts on ferric and peritanic ions. The directions should be followed

closely for the highest degree of precision. However, when it is desired to shorten this procedure

for purposes other than referee analysis, the addition of pyrosulfate, FeSO4 solution, and H3PO4 to

the color comparison solutions may be omitted, provided the Fe2O3 of the sample cement is less

than 5 percent. This usually leads to little sacrifice to accuracy.

Note 101—The color develops rapidly and is stable for a sufficient period of time, but if the

peroxidized solution is allowed to stand a long time, bubbles of oxygen may appear and interfere

with color comparison. When the contents of a tube are first mixed, there may be fine bubbles that

should be allowed to clear up before the comparison is made. Comparison between the standard

and unknown solution should be made not less than 30 min after the addition of H2O2.

27.5.7. Compare the color, light transmittancy, or absorbance of the unknown solution with the reference

standard solution. The technique of comparing colored solutions or measuring transmittancy or

absorbance depends on the type of apparatus (see Sections 27.5.8 through 27.5.10) and should be

in accordance with standard practice appropriate to the particular type used or with instructions

supplied by the manufacturer of the equipment. If the peroxidized solution of cement is compared

with a single standard peroxidized solution, bear in mind that a single peroxidized solution cannot

be used for the whole range in TiO2 content that may be encountered. The difference in volume or

depth for the two liquids should not exceed 50 percent of the smaller value. All solutions should

contain the prescribed concentrations of H2SO4, H3PO4, Fe2(SO4)3, and persulfate, except under

the circumstances indicated in Note 101.

27.5.8. Colorimeter of the Kennicott Type—By means of a plunger in a reservoir of standard peroxidized

solution, adjust the amount of solution through which light passes until it gives the same color

intensity as the peroxidized solution of the sample.

27.5.9. Colorimeter of the Duboscq Type—Lower or raise the plungers in the cups until the two solutions

give the same color intensity when viewed vertically. The color matching may be done either

visually or photoelectrically.

27.5.10. Colorimeter Designed to Measure Light Transmittancy—The measurement should be made

between 400 to 450 nm and may be made either visually or photoelectrically. In most colorimeters


of this type, the instrument is calibrated with standard solutions, and a calibration curve showing

the relation of light transmittancy or absorbance to TiO2 content is prepared in advance of the

analysis of the sample for TiO2.


of reagent, and correct the results obtained in the analysis accordingly.

27.6. Calculation—Calculate the percentage of TiO2, rounded in accordance with Table 3. When a

colorimeter designed to measure light transmittancy is used, read the percentage of TiO2 from a

calibration curve showing the relation of light intensity to TiO2 content. When the peroxidized

solution of the sample is compared with a single reference standard solution, calculate the

percentage of TiO2 as follows (see Note 102):

27.6.1. For Colorimeters of the Kennicott Type:

TiO2, % = (100 VE/S ) (D/C) (17)

27.6.2. For Colorimeters of the Duboscq Type:

TiO2, % = (100 VE/S ) (F/G) (18)

where:

V = milliliters of standard Ti(SO4)2 solution in the peroxidized standard solution;

E = TiO2 equivalent of the standard Ti(SO4)2 solution, g/mL;

S = grams of sample used;

D = volume of peroxidized reference standard solution that matches the peroxidized solution

of the sample, mL;

C = total volume of the peroxidized reference standard solution, mL;

F = depth of peroxidized reference standard solution through which light passes; and

G = depth of peroxidized solution of the sample through which light passes.

Note 102—The difference between D and C or between F and G should not exceed 50 percent of

the smaller value.

28. PHOSPHORUS PENTOXIDE (ALTERNATIVE TEST METHOD)

28.1. Summary of Test Method—In this test method, phosphorus is determined volumetrically by

precipitation of the phosphorus as ammonium phosphomolybdate and titration with NaOH

and H2SO4.

28.2. Reagents:

28.2.1. Ammonium Molybdate Solution—Prepare the solution in accordance with Section 11.3.1.

28.2.2. Ammonium Nitrate (NH4NO3).

28.2.3. Potassium Nitrate Solution (10 g/L)—Dissolve 10 g of potassium nitrate (KNO3) in water freshly

boiled to expel CO2 and cooled, and dilute to 1 L.

28.2.4. Sodium Hydroxide, Standard Solution (0.3 N)—Dissolve 12 g of sodium hydroxide (NaOH) in 1 L

of water that has been freshly boiled to expel CO2 and cooled. Add 10 mL of a freshly filtered,

saturated solution of barium hydroxide (Ba(OH)2). Shake the solution frequently for several hours,

and filter it. Protect it from contamination by CO2 in the air. Standardize the solution against

standard acid potassium phthalate (Standard Sample No. 84) or benzoic acid (Standard Sample


No. 39) furnished by NIST, according to the directions furnished with the standard. Calculate the

phosphorus pentoxide (P2O5) equivalent (see Note 103) of the solution, g/mL, as follows:

E = N 0.003086 (19)

where:

E = P2O5 equivalent of the NaOH solution, g/mL;

N = normality of the NaOH solution; and

0.003086 = P2O5 equivalent of 1 N NaOH solution, g/mL.

Note 103—The value of the solution is based on the assumption that the phosphorus in cement is

precipitated as ammonium phosphomolybdate (2(NH4)3PO4 · 12MoO3) and that the precipitate

reacts with the NaOH solution thus:

2(NH4)3 PO4 12MoO3 + 46NaOH =

2(NH4)2HPO4 + (NH4)2MoO4 + 23Na2 MoO4 + 22H2O (20)

The number 0.003086 is obtained by dividing the molecular weight of P2O5 (141.96) by 46 (for 46

NaOH in the equation) and by 1000 (number of milliliters in 1 L).

Because the actual composition of the precipitate is influenced by the conditions under which the

precipitation is made, it is essential that all the details of the procedure are followed closely as

prescribed.

28.2.5. Sodium Nitrite (50 g NaNO2/L).

28.2.6. Sulfuric Acid, Standard Solution (0.15 N)—Dilute 4.0 mL of H2SO4 to 1 L with water that has

been freshly boiled and cooled. Standardize against the standard NaOH solution. Determine the

ratio in strength of the standard H2SO4 solution to the standard NaOH solution by dividing the

volume of NaOH solution by the volume of H2SO4 solution used in the titration.

28.3. Procedure:

28.3.1. Weigh 1 to 3 g of the sample (see Note 104) and 10 g of NH4NO3 into a 150-mL beaker. Mix the

contents, add 10 mL of HNO3, and stir quickly, using the flattened end of a glass rod to crush

lumps of cement until the cement is completely decomposed and the thick gel of silica (SiO2) is

broken up. Cover the beaker with a watch glass, place it on a water bath or a hot plate at

approximately 100°C for 15 to 20 min, and stir the contents occasionally during the heating. Add

20 mL of hot water to the beaker and stir the contents. If the cement contains an appreciable

amount of manganese, as shown by the presence of a red or brown residue, add a few milliliters of

NaNO2 (50 g/L) to dissolve this residue. Boil the contents of the beaker until all nitrous fumes are

completely expelled. This procedure should not take more than 5 min, and water should be added

to replace any lost by evaporation. Filter, using medium-textured paper, into a 400-mL beaker

under suction and with a platinum cone to support the filter paper. Wash the residue of SiO2 with

hot water until the volume of filtrate and washings is about 150 mL.

Note 104—The amounts of sample and reagents used depend on the content of phosphorus in the

cement. The minimum requirements are sufficient if the cement contains 0.5 percent P2O5 or more.

The maximum amounts are required if the content of P2O5 is 0.1 percent or less.

28.3.2. Heat the solution to 69 to 71°C, remove it from the heat source, and immediately add 50 to

100 mL of the ammonium molybdate solution. Stir the solution vigorously for 5 min, wash down

the sides of the beaker with cool KNO3 solution (10 g/L), cover the beaker with a watch glass, and

allow to stand 2 h. Using suction, filter the precipitate (see Note 105), decanting the solution with

as little disturbance to the precipitate as possible. Stir the precipitate in the beaker with a stream of

the cool KNO3 solution, decant the liquid, and then wash the precipitate onto the filter. Scrub the

stirring rod and beaker with a policeman, and wash the contents onto the filter. Wash and


precipitate until it is acid-free (see Note 106), allowing each portion of wash solution to be sucked

completely through before adding the next.

Note 105—The filter may be a small medium-textured filter paper supported by a platinum cone,

or a small Hirsch funnel may be used with filter paper cut to fit and a thin mat of paper pulp or

acid-washed asbestos pulp. The filtration should be carried out with care to avoid any loss of the

precipitate. The filter should fit well, and the suction should be started before filtration and

maintained until the end of the washing.

Note 106—About ten washings are usually required. Test the tenth washing with one drop of

neutral phenolphthalein indicator and half a drop of the standard NaOH solution. If a definite pink

color lasts at least 5 min, the precipitate is considered to be acid-free; otherwise, continue the

washing.

28.3.3. Transfer the filter and precipitate to the beaker in which the precipitation took place, using small

damp pieces of paper to wipe out the funnel and pick up portions of the precipitate that may

remain on it. Add 20 mL of cool CO2-free water to the beaker, and break up the filter by stirring

rapidly with the policeman that was used to scrub the beaker. Add an excess of the 0.3 N NaOH

solution; stir the contents until all trace of yellow has disappeared; wash down the policeman

and sides of the beaker with 50 mL of cool, CO2-free water; and add 2 drops of neutral

phenolphthalein indicator solution. Treat the solution with a measured quantity of the

0.15 N H2SO4 solution, sufficient to destroy completely the pink color. Complete the titration

with the NaOH solution until there is a definite faint pink color that lasts at least 5 min.



28.4. Calculation—Calculate the percentage of P2O5 to the nearest 0.01 as follows:

P2O5, % = [E(V1 – V2R)/S] 100 (21)

where:

E = P2O5 equivalent of the NaOH solution, g/mL;

V1 = milliliters of NaOH solution used;

V2 = milliliters of H2SO4 solution used;

R = ratio in strength of the H2SO4 solution to the NaOH solution; and

S = grams of sample used.


29. MANGANIC OXIDE (ALTERNATIVE TEST METHOD)

29.1. Summary of Test Method—In this test method, manganic oxide is determined volumetrically by

titration with potassium permanganate solution.

29.2. Reagents:

29.2.1. Potassium Permanganate, Standard Solution (0.18 N)—Prepare a solution of potassium

permanganate (KMnO4) and standardize as described in Section 15.2.2, except that the manganic

oxide (Mn2O3) equivalent of the solution is calculated instead of the calcium oxide (CaO)

equivalent. Calculate the Mn2O3 equivalent of the solution as follows:

( )0.3534BE

A

= (22)

where:

E = Mn2O3 equivalent of the KMnO4 solution, g/mL;


B = grams of Na2C2O4 used;

A = milliliters of KMnO4 solution required by the Na2C2O4; and

0.3534 = mole ratio of 3 Mn2O3 to 10 Na2C2O4.

29.2.2. Zinc Oxide (ZnO)—Powder.

29.3. Procedure:

29.3.1. Place 2 g of the sample in a 250-mL beaker and add about 50 mL of water to the cement. Stir the

mixture until it is in suspension, and then add about 15 mL of HCl. Heat the mixture gently until

the solution is as complete as possible. Add 5 mL of HNO3 and 50 mL of water to the solution and

boil it until most of the chlorine has been expelled. If necessary, add hot water to maintain the

solution at a volume of about 100 mL. Stop the boiling and add ZnO powder to the solution until

the acid is neutralized. Add an excess of 3 to 5 g of ZnO powder to the solution and boil it for a

few minutes.

29.3.2. Without filtering, and while keeping the solution hot (90 to 100°C) by intermittent or continuous

heating, titrate the solution with the 0.18 N KMnO4 solution until a drop of it gives a permanent

pink color (see Note 107). When the end point is approached, add the standard solution dropwise.

After each drop, stir the solution, allow the precipitate to settle a little, and observe the color of the

stratum of the solution by looking through the side of the beaker.

Note 107—In the case of a cement in which the approximate content of Mn2O3 is unknown, a

preliminary determination may be made with rapid titration, 0.5 to 1 mL of the standard solution

being added at a time, and without an attempt to keep the solution close to the boiling point.



29.4. Calculation—Calculate the percentage of Mn2O3 to the nearest 0.01 as follows:

2 3Mn O , % 50EV= (23)

where:

E = Mn2O3 equivalent of the KMnO4 solution, g/mL;

V = milliliters of KMnO4 solution used; and

50 = 100 divided by the mass of sample used (2 g).


30. FREE CALCIUM OXIDE (ALTERNATIVE TEST METHOD)

30.1. Summary of Test Methods—These are rapid test methods for the determination of free calcium

oxide in fresh clinker. When applied to cement or aged clinker, the possibility of the presence of

calcium hydroxide should be kept in mind because these methods do not distinguish between free

CaO and free Ca(OH)2. Two test methods are provided. Alternate Test Method A is a modified

Franke procedure in which uncombined lime is titrated with dilute perchloric acid after solution in

an ethylacetoacetate-isobutyl alcohol solvent. Alternate Test Method B is an ammonium acetate

titration of the alcohol-glycerin solution of uncombined lime with Sr(NO3)2 as an accelerator.

30.2. Modified Franke Test Method (Alternative Method A):

30.2.1. Apparatus:


30.2.1.1. Refluxing Assembly—Consisting of a flat-bottom, short-neck Erlenmeyer flask with

250-mL capacity. The water-cooled refluxing condenser should have a minimum length of

300 mm. The flask and reflux condenser shall be connected with standard tapered ground glass

joints. The reflux condenser shall be fitted with an absorption tube containing a desiccant, such as

indicating silica gel and a material for the removal of CO2 such as Ascarite. The absorption tube

shall be inserted with a rubber stopper in the upper end of the reflux column.

30.2.1.2. Buret—Having a 10-mL capacity and graduated in units not more than 0.05 mL.

30.2.1.3. Vacuum Filtration Assembly—Consisting of a Gooch crucible size No. 3, 25-mL capacity in

which is placed a suitable filter paper (21-mm size), a Walter crucible holder, a 500-mL vacuum

flask, and vacuum source. The crucible is half filled with compressed filter pulp.

30.2.1.4. Glass Boiling Beads.

30.2.2. Solutions Required:

30.2.2.1. Ethyl Acetoacetate-Isobutyl Alcohol Solvent—Three parts by volume of ethyl acetoacetate and

20 parts by volume of isobutyl alcohol.

30.2.2.2. Thymol Blue Indicator—Dissolve 0.1 g of thymol blue indicator powder in 100 mL of

isobutyl alcohol.

30.2.2.3. Perchloric Acid, Standard Solution (0.2 N)—Dilute 22 mL of 70 to 72 percent perchloric acid to

1 L with isobutyl alcohol. Standardize this solution as follows: Ignite 0.1000 g of primary standard

calcium carbonate in a platinum crucible at 900 to 1000°C. Cool the crucible and contents in a

desiccator, and determine the mass to the nearest 0.0001 g to constant mass. Perform the mass

determinations quickly to prevent absorption of water and CO2. Immediately transfer the CaO

without grinding to a clean, dry Erlenmeyer flask and again determine the mass of the empty

crucible to the nearest 0.0001 g to determine the amount of CaO added. Then follow procedure

beginning with “Add 70 mL of the ethyl acetoacetate isobutyl alcohol . . .” in Section 30.2.3.1.

Calculate the CaO equivalents of the standard perchloric acid solution in grams per milliliter by

dividing the mass of CaO used by the volume of perchloric acid required for the titration.

30.2.3. Procedure:

30.2.3.1. Transfer 1.0000 g of ground sample (see Note 108) into a clean, dry 250-mL Erlenmeyer flask.

Add four to five glass boiling beads. Add 70 mL of prepared ethyl acetoacetate-isobutyl alcohol

solvent. Agitate the flask to disperse the sample.

Note 108—Thorough grinding of the sample is essential for proper exposure of the free lime

grains that often are occluded in crystals of tricalcium silicate in the cement. However, exposure

of the sample to the air must be kept at a minimum to prevent carbonation of the free lime.

Caution—In particular, direct breathing into the sample must be avoided. The sample should be

sufficiently fine to easily pass a No. 200 (75-µm) sieve, but actual sieving is not recommended. If

the sample is not to be immediately tested, it must be kept in an airtight container to avoid

unnecessary exposure to the atmosphere.

30.2.3.2. Attach the flask to a reflux condenser and bring the material to a boil. Reflux for 15 min.

30.2.3.3. Remove flask from condenser, stopper, and cool rapidly to room temperature.

30.2.3.4. Filter the sample and solution using the vacuum assembly. Wash the flask and residue with

small increments (10 to 15 mL) of isobutyl alcohol until a total of 50 mL has been used for the

wash solution.


30.2.3.5. Add 12 drops of the thymol blue indicator to the filtrate and immediately titrate with

0.2 N perchloride acid to the first distinct color change.

30.2.4. Calculations—Calculate the percent free calcium oxide to the nearest 0.1 percent as follows:

100free CaO, %

EV

W

= (24)

where:

E = CaO equivalent of the perchloric acid, g/mL;

V = milliliters of perchloric acid solution required by sample; and

W = mass of the sample, g.


30.3. Rapid Sr(NO3)2 Test Method (Alternative Test Method B):

30.3.1. Reagents:

30.3.1.1. Ammonium Acetate, Standard Solution (1 mL = 5 mg CaO)—Prepare a standard solution of

ammonium acetate (NH4C2H3O2) by dissolving 16 g of desiccated ammonium acetate in 1 L of

ethanol in a dry, clean, stoppered bottle. Standardize this solution by the same procedure as

described in Section 30.3.2.1, except use the following in place of the sample: Ignite to constant

mass approximately 0.1 g of calcium carbonate (CaCO3) in a platinum crucible at 900 to 1000°C,

cool the contents in a desiccator, and determine the mass to the nearest 0.1 mg. Perform the mass

determinations quickly to prevent absorption of water and CO2. Immediately transfer the CaO

without grinding to a 250-mL boiling flask (containing glycerin-ethanol solvent and Sr(NO3)2),

and again determine the mass of the empty crucible to determine the mass of CaO to the nearest

0.1 mg. Continue as described in Sections 30.3.2.1 and 30.3.2.2. Calculate the CaO equivalent of

the ammonium acetate in grams per milliliter by dividing the mass of CaO used by the volume of

solution required.

30.3.1.2. Phenolphthalein Indicator—Dissolve 1.0 g of phenolphthalein in 100 mL of ethanol (Formula 2B)

(see Note 109).

Note 109—Ethanol denatured in accordance with Formula 2B (99.5 percent ethanol and

0.5 percent benzol) is preferred but may be replaced by isopropyl alcohol, A.R.

30.3.1.3. Glycerin-Ethanol Solvent (1+2)—Mix one volume of glycerin with two volumes of ethanol

(Formula 2B). To each liter of this solution, add 2.0 mL of phenolphthalein indicator solution.

30.3.1.4. Strontium Nitrate (Sr(NO3)2)—Reagent grade.

30.3.2. Procedure:

30.3.2.1. Transfer 60 mL of the glycerin-ethanol solvent into a clean, dry, 250-mL standard-taper flat-

bottom boiling flask. Add 2 g of anhydrous strontium nitrate (Sr(NO3)2), and adjust the solvent to

slightly alkaline with a dropwise addition of a freshly prepared dilute solution of NaOH in ethanol

until a faint pink color is formed. Weigh 1.000 g of the finely ground sample (see Note 108) into

the flask, add encapsulated stirring bar, and immediately attach a water-cooled condenser (with a

standard 24/40 glass joint). Boil the solution in the flask on a magnetic stirrer hot plate for 20 min

with mild stirring.

30.3.2.2. Remove the condenser and filter the contents of the flask on a small polypropylene Büchner

funnel under vacuum, using a 250-mL filtering flask with side tube. Bring the filtrate to a boil and

immediately titrate with standard ammonium acetate solution to a colorless end point.


30.3.3. Calculation—Calculate the percent free CaO to the nearest 0.1 percent as follows:

free CaO, % 100EV= (24)

where:

E = CaO equivalent of the ammonium acetate solution, g/mL; and

V = milliliters of ammonium acetate solution required by the sample.


31. KEYWORDS

31.1. Chemical analysis; compositional analysis; hydraulic cements.

32. REFERENCES

32.1. Bean, B. L. Improvements in the Rapid Analysis of Portland Cement by Atomic Absorption

Spectrophotometry. Report No. FHWA RD-73-4. Department of Transportation, Federal Highway

Administration, March 1973. (Order copies from National Technical Information Service,

Springfield, VA 22151, by Order No. PB-220-549.)

32.2. Bean, B. L. and T. H. Arni. A New Rapid Test Method for Cement Analysis (Atomic Absorption

Spectrophotometry), Report No. FHWA RD-72-41. Department of Transportation, Federal

Highway Administration, September 1972. (Order copies from National Technical Information

Service, Springfield, VA 22151, by Order No. PB-243-622.)

32.3. Crow, R. F. and J. D. Connolly. Atomic Absorption Analysis of Portland Cement and Raw Mix

Using Lithium Metaborate Fusion. In Journal of Testing and Evaluation, Vol. 1, No. 5, September

1973, pp. 382–393.

32.4. Jugovic, Z. T. Applications of Spectrophotometric and EDTA Methods for Rapid Analysis of

Cement and Raw Materials. In Analytical Techniques for Hydraulic Cement and Concrete,

ASTM STP 395. ASTM, 1966, pp. 65–93.

32.5. Moore, C. W. Suggested Method for Spectrochemical Analysis of Portland Cement by Fusion

with Lithium Tetraborite Using an X-Ray Spectrometer. E-2 SM 10–26 in Test Methods for

Emission Spectrochemical Analysis. ASTM, 1971.


APPENDIXES

(Nonmandatory Information)

X1. EXAMPLE OF DETERMINATION OF EQUIVALENCE POINT FOR THE CHLORIDE DETERMINATION

(Column 1)

AgNO3, mL

(Column 2)

Potential, mV

(Column 3)

ΔmV a

(Column 4)

Δ2mV b

1.60 125.3

5.8

1.80 119.5 1.4

7.2

2.00 112.3 1.3

8.5

2.20 103.8 1.3

9.8

2.40 94.0 0.6

9.2

2.60 84.8 2.3

6.9

2.80 77.9 0.8

6.1

3.00 71.8 1.3

4.8

3.20 67.0

The equivalence point is in the maximum ∆mV interval (Column 3), and thus between 2.20 and 2.40 mL. The exact equivalence point in this 0.20 increment is

calculated from the ∆2mV (Column 4) data as follows:

E = 2.20 + (1.3/(1.3 + 0.6)) 0.20 = 2.337 mL. Round to 2.34.

a Differences between successive readings in Column 2. b Differences between successive readings in Column 3 “second differentials.”

X2. CO2 DETERMINATIONS IN HYDRAULIC CEMENTS

X2.1. Scope:

X2.1.1. This appendix contains information about methods for determination of carbon dioxide (CO2)

in hydraulic cement. The methods listed received a favorable evaluation by ASTM Task

Group C01.23.04.

X2.1.2. Section X2.2 lists the analytical methods that received a favorable evaluation, briefly describes

each method, suggests analytical techniques or cautions that may be useful, and indicates

limitations to some of the methods.

X2.1.3. The methods listed in Sections X2.2.1, X2.2.4, X2.2.5, and X2.2.6 determine total carbon

calculated as CO2. For that reason, they are not appropriate for determination of carbon dioxide in

fly ash, limestones containing carbon in the form of graphite or kerogen, in other carbon-bearing

materials, or in blended cements produced from these materials.

X2.1.4. The methods listed in Sections X2.2.2 and X2.2.3 can determine actual CO2 directly rather than by

calculation from total carbon. They are suggested for analysis of blended cement and blended

cement ingredients that are likely to contain noncarbonate carbon.


X2.1.5. The split loss on ignition method in Section X2.2.1 can give misleading results when used with

materials containing CaOH2 (calcium hydroxide). This can occur with aged cement, cement made

from aged clinker, or high free lime clinker, in addition to cements with a lime or hydrated lime

ingredient.

X2.2. Analytical Methods:

X2.2.1. Split Loss on Ignition—This procedure is comparable to the analytical method described in

ASTM C114, Section 17.1.1, with the following modifications:

1. A crucible of known mass and containing a sample of known mass is initially heated at 550°C

for 2 h.

2. After being cooled to room temperature in a desiccator, and its mass determined, the crucible

with sample is then heated at 950°C for 2 h.

3. Finally, the crucible with sample is cooled and its mass is determined as per step No. 2.

4. The difference in residue masses after the respective heat treatments is assumed to be

carbon dioxide.

TGA results indicated that Ca(OH)2 can lose a significant portion of its mass above 500°C.

Thus, the Split on Loss of Ignition procedure should not be used when situations described in

Section X2.1.5 exist.

X2.2.2. Thermogravimetric Analysis (TGA)—This method involves the determination of sample mass loss

at various temperatures. The heating of a sample through a temperature range allows for mass loss

differentiation based on mineral form (e.g., CaCO3, MgCO3, CaOH2). Specific operational

information is provided by the equipment manufacturers. If free carbon is present, an inert

atmosphere (e.g., nitrogen) should be used for sample analysis.

X2.2.3. ASTM C25, Section 22—“Standard Test Methods for Chemical Analysis of Limestone, Quicklime,

and Hydrated Lime.” This method involves decomposition of the sample with HCl. The liberated

CO2 is then passed through a series of scrubbers to remove water and sulfides. The CO2 is

absorbed with special Sodium Hydroxide Absorbent (Ascarite). The gain in mass of the absorption

tube is determined and calculated as percent CO2. Calcium carbonate, for instance, can be

calculated by multiplying the determined CO2 content by a conversion factor (e.g.,

CO2 2.2742 = CaCO3).

X2.2.4. X-Ray Fluorescence Spectroscopy—In this method, the sample is ground to a fine particle size,

pressed into a flat pellet, and irradiated with the chosen instrument. Carbon content is determined

by comparing the collected carbon emissions to calibration standards.

X2.2.5. Combustion by Induction Furnace/IR—This method involves volatilization by induction furnace

and detection by infrared absorption. Suitable calibration standards (e.g., calcium carbonate and

synthetic carbon) are available from some instrument manufacturers. NIST cement SRMs with

known additions of NIST argillaceous limestone (or other suitable standards) should also be

considered to check instrument calibration.

X2.2.6. ASTM E350—This method, “Total Carbon by the Combustion Gravimetric” from “Test Methods

for Chemical Analysis of Carbon Steel, Low-Alloy Steel, Silicon Electrical Steel, Ingot Iron, and

Wrought Iron,” is suitable for the determination of carbon in concentrations from 0.05 to

1.80 percent (as carbon dioxide 0.18 to 6.60 percent). The test method involves burning the

sample in a stream of oxygen; the carbon dioxide in the evolved gases is then collected in a

suitable absorbent and its mass determined. Time of analysis is less than 10 min.

Washington State - Comment on X2.2.4: Shouldn't section X2.2.4 X-Ray Fluorescence also be

changed to allow for fused pellets and not just pressed pellets?


X2.3. Cooperative Test Results:

X2.3.1. Tables X2.1 and X2.2 list results from two series of cooperative tests using several of the

analytical methods evaluated by the Task Force Group. In all, five of the six methods

receiving favorable ratings were included. The sixth method, ASTM C25, was specifically

not tested in these cooperative series but was rated favorably because of long history of use

with related materials.

X2.3.2. Table X2.1 includes results of single determinations using three of the different analytical

methods. The methods used were Split Loss on Ignition, ASTM E350, and Combustion by

Induction Furnace with Infrared Detection.

X2.3.3. Table X2.2 includes results based on the average of three determinations. Results from four of the

different analytical methods are included. Methods used were Split Loss on Ignition, X-Ray

Fluorescence Analysis, Induction Furnace with Infrared Detection, and Thermo-Gravimetric

Analysis. ASTM E350 was not used in this series of tests.

Table X2.1—Cooperative Test Series No. 1

Single Determinations

Carbon Dioxide

Unknowna

Determinations

Base

Cementb

Added

CO2, %

Determinedc

Added

CO2, %

Knownd

Split LOI 2.40 0.45 1.97 2.00

2.52 0.56 1.99

2.41 0.36 2.07

2.39 0.32 2.09

2.41 0.36 2.07

2.28 0.27 2.02

ASTM E350 2.00 0.02 1.98

2.00 0.02 1.98

Induction Furnace/IR 2.46 0.40 2.07

2.53 0.48 2.08

2.38 0.40 2.00

2.42 0.48 1.97

2.02

Average Standard Deviation 0.05

a The Unknown was prepared by blending/grinding a mixture of 5.00 percent NIST SRM 1C Argillaceous Limestone and 95.00 percent CCRL Portland

Cement Reference Sample No. 85. According to the Certificate of Analysis, SRM 1C had a loss on ignition of 39.9 percent. For the purpose of the

cooperative test series, the loss on ignition was assumed to be CO2 only. b The Base Cement was CCRL Portland Cement Reference Sample No. 85. c The Determined Percent Added CO2 was obtained by subtracting the Base Cement Percent CO2 from the Unknown Percent CO2. d The addition of 5.00 percent NIST SRM 1C (with a loss on ignition value of 39.9 percent) would provide 2.00 percent Added CO2. (Again, it was

assumed that the SRM 1C loss on ignition was only carbon dioxide.)


Table X2.2—Cooperative Test Series No. 2

Average from Three Determinations

Carbon Dioxide

Unknowna

Determinations

Base

Cementb

Added

CO2, %

Determinedc

Added

CO2, %

Knownd

Split LOI 2.00 0.41 1.59 1.60

1.65 0.32 1.33

2.02 0.46 1.56

1.91 0.35 1.56

2.10 0.43 1.67

1.91 0.41 1.50

1.98 0.46 1.52

XRFA 1.68e 0.00e 1.68e

Induction Furnace/IR 2.23 0.28 1.95

1.96 0.28 1.68

1.95 0.40 1.55

TGA 1.77 0.20 1.57

1.87 0.25 1.62

1.60

Average Standard Deviation 0.14

a The Unknown was prepared by blending/grinding a mixture of 4.00 percent NIST SRM 1C Argillaceous Limestone and 96.00 percent CCRL Portland

Cement Reference Sample No. 85. According to the Certificate of Analysis, the SRM 1C had a loss on ignition of 39.9 percent. For the purpose of the

cooperative test series, the loss on ignition was assumed to be CO2 only. b The Base Cement was CCRL Portland Cement Reference Sample No. 85. c The Determined Percent Added CO2 was obtained by subtracting the Base Cement Percent CO2 from the Unknown Percent CO2. d The addition of 4.00 percent NIST SRM 1C (with a loss on ignition value of 39.9 percent) would provide 1.60 Added CO2. (Again, it was assumed that the

SRM 1C loss on ignition was only carbon dioxide.) e The XRF instrument was calibrated using standards composed of the Base Cement (i.e., CCRL No. 85) and NIST SRM 1C. It was assumed that

the Base Cement contained 0 percent CO2.

1 Similar to ASTM C114-15, except for terminology related to mass and weights. 2 Gebhardt, R. F. Rapid Methods for Chemical Analysis of Hydraulic Cement. ASTM STP 985, 1988. 3 Barger, G. S. A Fusion Method for the X-Ray Fluorescence Analysis of Portland Cements, Clinker and Raw

Materials Utilizing Cerium (IV) Oxide in Lithium Borate Fluxes. In Proceedings of the Thirty-Fourth Annual

Conference on Applications of X-Ray Analysis, Denver, CO, Volume 29, August 5, 1985, pp. 581–585. 4 ACS Committee on Analytical Reagents. Reagent Chemicals: Specifications and Procedures, 10th Edition.

American Chemical Society, Washington, DC, August 2005. For suggestions on the testing of reagents not listed by

the American Chemical Society, see Reagent Chemicals and Standards, by Joseph Rosin, D. Van Nostrand Co.,

Inc., New York, NY, and the United States Pharmacopeia, U.S. Pharmacopeia Convention, Inc., Rockville, MD. 5 See also the ASTM Manual on Presentation of Data and Control Charts Analysis, STP 15D, 1976. 6 The 1988 revision of these test methods deleted the colorimetric method for determination of ZnO using the

extraction with CCl4. 7 The 1963 revision of these test methods deleted the classical (J. L. Smith) gravimetric method for the

determination of Na2O and K2O in cements. The 1983 revision of these test methods deleted the details of the flame

photometric procedure for the determination of Na2O and K2O.


COMP_TS3a-20-01

Item 8: M201 – Standard Specification for Mixing Rooms, Moist

Cabinets, Moist Rooms, and Water Storage Tanks Used in the

Testing of Hydraulic Cements and Concretes, Revisions


Mixing Rooms, Moist Cabinets,

Moist Rooms, and Water Storage

Tanks Used in the Testing of

Hydraulic Cements and Concretes

AASHTO Designation: M 201-15 (2020)





TS-3a M 201-1 AASHTO


Mixing Rooms, Moist Cabinets, Moist Rooms,

and Water Storage Tanks Used in the Testing

of Hydraulic Cements and Concretes

AASHTO Designation: M 201-15 (2020)




1. SCOPE

1.1. This specification includes requirements for mixing rooms, where paste and mortar specimens are

prepared, and for moist cabinets, moist rooms, and water storage tanks, where paste, mortar, and

concrete test specimens are stored.

1.2. The values stated in SI units are to be regarded as standard. No other units of measurement are

included in this standard. Values in SI units shall be obtained by measurement in SI units or by

appropriate conversion, using the Rules for Conversion and rounding given in Standard

IEEE/ASTM SI 10, of measurements made in other units.

1.3. This standard does not purport to address all of the safety concerns, if any, associated with its use.

It is the responsibility of the user of this standard to establish appropriate safety and health

practices and determine the applicability of regulatory limitations prior to use.


2.1. ASTM Standards:

C51, Standard Terminology Relating to Lime and Limestone (as used by the Industry)

E77, Standard Test Method for Inspection and Verification of Thermometers

C125 Terminology Relating to Concrete and Concrete Aggregates

C219 Terminology Relating to Hydraulic Cement

2.2. IEEE/ASTM Standard:

SI10, American National Standard for Metric Practice

3. TERMINOLOGY

3.1. Definitions:

http://www.astm.org/Standards/C51.htm

http://www.astm.org/Standards/E77.htm


3.1.1. Refer to Terminology C125 and Terminology C219 for definitions of terms used in this test

method.

3.2. Definitions of Terms Specific to This Standard:

3.1.1.3.2.1. mixing room, n—a room with controlled temperature and relative humidity where cement paste

and mortar specimens are prepared.

3.1.2.3.2.2. moist cabinet, n—a compartmented storage facility of moderate dimensions with controlled

temperature and relative humidity.

3.2.3. moist room, n—a walk-in storage facility with controlled temperature and relative humidity,

commonly called a “fog room” when the prescribed relative humidity is achieved by the

atomization of water.

3.2.4. water tank, n—a container of sufficient size to fully submerge samples and holds saturated lime

water at a controlled temperature.

3.1.3.

4. REQUIREMENTS FOR CEMENT MIXING ROOMS

4.1. The temperature of the air in the vicinity of the mixing slab, molds, and baseplates shall be

maintained at 23.0 ± 4.0°C and at a relative humidity of not less than 50 percent.

4.2. The temperature of the mixing water used to prepare cement paste and mortar specimens shall be

23.0 ± 2.0°C.

5. TEMPERATURE MEASURING DEVICES

5.1. Reference Temperature Measuring Devices—Used to verify standardize the temperature recorder,

must shall be accurate and readable to 0.5°C. A copy of theThe certificate or report that verifies

the accuracy calibration report for the reference thermometer shall be available in the

laboratoryindicate a measurement uncertainty of not more than 0.5°C.

Note 1—The ice-point method described in ASTM E77 may be used to ensure that no damage to

the reference thermometer has occurred during shipping.

5.2. Temperature Recorder—Shall record temperatures every 15 min or less and shall be accurate and

readable to 1°C. The data from the recorder shall be evaluated at a minimum of once each week. A

record of this evaluation documenting the date checked, a confirmation that the data are within the

required temperature range, and the name of the individual performing this evaluation shall be

maintained in the laboratory. (See Note 2.)

5.2. Note 2—This requirement may be satisfied by an initialed and dated temperature recorder chart.

Brief changes in the temperature due to door openings should be ignored.

5.2.1. The temperature recorder shall be standardized during the normal operation of the moist cabinet,

moist room, or water storage tanksverified at least every 6 months or whenever there is a question

of accuracy in accordance with the following procedure.

5.2.1.1. For moist cabinets and rooms, position the reference temperature measuring device in a readable

position in air as near as practical to the temperature recorder probe. Keep the door closed for at

least 5 min prior to taking readings. Record the temperature readings of both the temperature


recorder and the reference temperature measuring device. When taking these readings, the

reference temperature measuring device shall remain in the moist cabinet or room and be read

immediately on opening the door.

5.2.1.2. For water storage tanks, position the reference temperature measuring device in a readable

position in water as near as practical to the temperature recorder probe. Without removing the

reference temperature measuring device from the water, record the temperature readings of both

the temperature recorder and the reference temperature measuring device after the temperatures

have stabilized.

5.2.1.3. Verify the accuracy of the temperature recorder by comparingCompare the reading of the

temperature recorder with that of the reference temperature measuring device during the normal

operation of the moist cabinet, moist room, or water storage tanks. If the difference between the

temperature readings is greater than 0.51°C, the temperature recorder shall be adjusted to within

0.5°C of the reference temperature measuring device.

5.2.2. The data from the recorder shall be evaluated at a minimum of once each week.

5.2.2.1. A record of this evaluation shall be documented on the record of the data itself and include the

following information:

5.2.2.1.1. the start date of the data;

5.2.2.1.2. the end date of the data;

5.2.2.1.3. the name of the individual evaluating the data;

5.2.2.1.4. the date of the evaluation; and

5.2.2.1.5. a confirmation that the data are within the required temperature range. (See Note 1.)

Note 1—Brief changes in the temperature due to door openings should be ignored.

5.2.3. The laboratory shall demonstrate the ability to maintain the required temperature in the moist

cabinet, moist room, or water tank, over a 12 month period of time. Data from the temperature

recorder that indicate that the temperatures are within the temperature limits shall be required as

evidence of this ability.

5.2.1.3.

6. REQUIREMENTS FOR MOIST CABINETS AND MOIST ROOMS

6.1. General—Except during those times when specimens are being placed into or removed from

storage, maintain the atmosphere in a moist cabinet or moist room at a temperature of 23.0 ±

2.0°C and a relative humidity of not less than 95 percent. Maintain atmospheric conditions within

a moist cabinet or moist room such that test specimens in storage are saturated with moisture to

the degree needed to ensure that the exposed surfaces of all specimens in storage both look moist

and feel moist (see Note 54). Equip all moist cabinets and moist rooms with a temperature

recorder. The use of humidity recording devices is optional and if used should maintain a humidity

of not less than 95 percent. Keep shelves on which fresh specimens are placed level.

6.1.1. The air temperature inside the moist cabinet or moist room shall be controlled with provisions

made for heating or cooling, or both, as may be necessary. This shall be accomplished in one of

two ways:


6.1.1.1. Thermostatically control the air temperature within the moist cabinet or moist room when

surrounding space is not conditioned. In this case, the sensing element for the controls shall be

located inside the moist cabinet or moist room.

6.1.1.2. Thermostatically control the space surrounding the moist cabinet or moist room and manually

control the temperature within the moist cabinet or moist room.

6.1.2. In either of the preceding cases, the laboratory shall demonstrate the ability of the controls to

maintain the required temperature in the moist cabinet or moist room over an extended period of

time. Data from the temperature recorder that indicate that the temperatures are within the

temperature limits specified in Section 6.1 shall be required as evidence of this ability.

6.2. Moist Cabinets—A moist cabinet shall be constructed of durable materials, and the doors shall be

tight fitting. The specified relative humidity shall be maintained by the use of one or more fog

sprays, water sprays, or curtains of water on the inner walls that are directed such that the

discharge will collect in a pool at or near the bottom of the moist storage section.

6.3. Moist Rooms:

6.3.1. General—The walls of a moist room shall be constructed of durable materials, and all openings

shall be provided with tight-fitting doors or windows (see Note 32). Maintain theThe specified

relative humidity may be maintained inby any convenient and suitable manner (see Note 43).

Note 32—Well-insulated walls will substantially help maintain necessary conditions.

Note 43—A fog spray found suitable for this purpose is shown in Figure 1.

Figure 1—Example of a Fog Spray for Maintaining Relative Humidity in Moist Rooms (Full Scale)1

Water Line

Approx. 20 mL/min

Hollow Stainless Steel Sphere,

40-mm Dia with Welded Fitting

Horizontal Slots Described in Note.

(Only two slots are shown, the third

slot is on the back side of the sphere.)

Air Line, Approx. 700 kPa

Note: Cut three horizontal air slots around circumference of hollow sphere

using a 0.20-mm-thick diamond lapidary saw covering 120º to 150º

each and spaced approximately 5 mm apart. Air passing through these

slots strikes the water, which is flowing over the outer surface of the

sphere, to produce a spray.


6.3.2. Moist Rooms Used in Cement Testing—Durable shelving that is properly shielded to prevent

droplets of water from falling on the surfaces of freshly molded specimens shall be available

within each moist room.

6.3.3. Moist Rooms Used in Concrete Testing—Maintain atmospheric conditions within each moist room

such that test specimens in storage both look and feel moist (see Note 54). Do not expose

specimens to dripping or running water.

Note 54—Maintenance of adequate water spray(s) and adequate spray distribution in the moist

room will result in stored specimens looking and feeling moist and will maintain the required

humidity. Inadequate numbers of spray nozzles, partially obstructed spray nozzles, or disturbances

in the moist air system such as open doors, air-conditioning or heating drafts, or overly crowded

shelf space may result in relative dry spots. Specimen surface texture and age can influence the

surface appearance and should be considered when specimens in localized areas do not look and

feel moist.

7. REQUIREMENT FOR WATER STORAGE TANKS

7.1. General—Tanks shall be constructed of noncorroding materials. Maintain storage water

temperature at 23.0 ± 2.0°C, except for those times when specimens are being placed into or

removed from storage, or tank maintenance is being performed.

7.2.7.1.1. Tank Temperature Controls—Provision for automatic control of water temperature at 23.0 ±

2.0°C shall be made when a tank is located in a room not having temperature controlled within

that range and in any other instance where difficulty in maintaining temperatures within the

specified range is encountered. With the exception of water storage tanks located in a moist room

or moist cabinet, water storage tanks shall be equipped with a temperature recorder with its

sensing element in the storage water. For the purpose of temperature recording, a group of water

storage tanks may be considered one tank if the following three conditions are met: (1) the tanks

are interconnected with tubing that allows the water to flow between tanks, (2) some means of

circulation is provided between tanks, and (3) temperature variation between tanks must not

exceed 1.0°C when checked and recorded weekly.

7.3.7.2. Tank Storage Water—The water in a storage tank shall be saturated with calcium hydroxide to

prevent leaching of calcium hydroxide from the specimens (see Note 65). Water not saturated with

calcium hydroxide (high-calcium hydrated lime) may affect test results due to leaching of lime

from the test specimens and shall not be used in storage tanks. To maintain saturation with

calcium hydroxide, excess calcium hydroxide shall be present. For the purposes of lime saturation

to prevent leaching, lime means high-calcium hydrated lime, not calcium carbonate (limestone);

see ASTM C51. The water in the storage tank shall be thoroughly stirred at intervals not to exceed

1 month to help replace calcium ions that have depleted. Tanks shall be cleaned and refilled with

water containing 3 g/L of calcium hydroxide at intervals not to exceed 24 months (see Note 76).

Note 65—pH is not a reliable indicator of lime saturation in storage tank water because severe

reductions in dissolved calcium ions can occur before pH values are significantly reduced.

Note 76—The 3 g/L level is intended to provide a quantity of calcium hydroxide approximately

two times that required for initial saturation.

7.3.1.7.2.1. Do not use continuously running fresh water or demineralized water in storage tanks because it

may affect test results due to excessive leaching. The use of aA closed system, circulating the

saturated limewater between or among storage tanks, is permittedmay be used.

8. KEYWORDS

8.1. Cement paste; concrete; mixing rooms; moist cabinets; moist rooms; mortar; water storage tanks.


1 One spray will supply sufficient water to provide moisture to a space of 25 m3. Hollow spheres are available

through McMaster Carr Supply Co., P.O. Box 4355, Chicago, IL 60680-4355.

TECHNICAL SUBCOMMITTEE 3A, HYDRAULIC CEMENT LIME

AASHTO STEWARDS

Attachment C

C977-18North Carolina - Chris Peoples; Tennessee - Brian

Egan

BLENDED HYDRAULIC

CEMENTS

M 240M/M 240-

19C 595/C 595M-19 Texas - Andy Naranjo

LIME FOR SOIL STAB. M 216-13 (2017)

LIME FOR ASPHALT

MIXTURESM 303-89 (2019) NONE

AUTOCLAVE EXPANSION

OF PORTLAND CEMENTT 107M/T 107-18

FINENESS OF PC BY THE

TURBIDIMETERT 98-12(2016) C 115-10e1

CHEMICAL ANALYSIS

HYDRAULIC CEMENT

COM. STRENGTH OF

HYDRAULIC CEMENT OF

MORTAR CUBES

T 106M/T 106 - 18 C 109/C109M-16a Kansas - Rick Barezinski

C 151/C151M-18Oklahoma - Kenny Seward; Kansas - Rick

Barezinski

PROCESSING ADDITIONS M 327-19 ASTM C 465-19 Texas - Andy Naranjo

T 105-161 C 114-18 Missouri - Brett Trautman

APP. FOR MEAS. LENGTH

CHANGE OF PASTE,

MORTAR, CONCRETE

C490/C 490M-17

SAMPLING HYDRAULIC

CEMENTR 71 - 161 C 183-16

R 70-18

TITLE AASHTO # ASTM # AASHTO COMP Steward

M 152M/M 152 -

16

M 85-19

M 201-15 C511-13 Re:source - Pete Holter; Tennessee - Brian Egan

C150/C150M-19a

C230/C230M-14 Oklahoma - Kenny Seward

Texas - Andy Naranjo

MOIST CAB, ROOMS, ETC.

USED IN TESTING CEM. &

CONCRETE

FLOW TABLE FOR USE IN

TESTING HYD. C.

PORTLAND+A3:K50

CEMENT

TECHNICAL SUBCOMMITTEE 3A, HYDRAULIC CEMENT LIME

AASHTO STEWARDS

SAMPLING HYDRATED

LIME

T 192-19 C 430-17

FINENESS OF HYDRAULIC

CEMENT BY THE NO. 325

SIEVE

EARLY STIFFENING OF

PORTLAND CEMENT

(PASTE METHOD)

T 185-15 C 359-18

EARLY STIFFENING OF

PORTLAND CEMENT

(MORTAR METHOD)

T 186-151 C 451-18

T 218-86 (2018) NONE

C 187-16NORMAL CONSISTENCY OF

HYDRAULIC T 129-14 (2018)

DET. OF LIME CONTENT BY

TITRATIONNONET 232-90 (2018)

T 219-87 (2018) NONETESTING LIME FOR CHEM.

CON. AND PART. SIZES

PARTICLE SIZE BY LIGHT

SCATTERINGNONET 353-14 (2018)

C 204-18e1 Illinois - James KrstulovichFINENESS OF P.C. BY AIR

PERM. APPARATUS

AIR CONTENT OF

HYDRAULIC CEMENT

MORTAR

T 137-12 (2016) C 185-15a

T 162-16 C305-14

MECHANICAL MIXING OF

HYDRAULIC CEMENT

PASTES AND MORTARS

T 154-181 C 266-18

TIME OF SETTING OF

HYDRAULIC CEMENT BY

GILLMORE NEEDLES

T 153-13 (2017)

DENSITY OF HYDRAULIC

CEMENTT 133-19 C 188-17

TIME OF SETTING OF

HYDRAULIC CEMENT BY

VICAT NEEDLE

T 131-15 C 191-18a

TENSILE STRENGTH OF

HYDRAULIC CEMENT

MORTARS

NONET 132-87 (2018)