packaging hm for shipment - labelmaster€¦ · packaging hm for shipment: considerations for...

Packaging HM for shipment:Considerations for Selection and Filling under the HMR

Dangerous Goods Instructors Symposium, 2015

Jaycox Consulting, LLC 2015

Identify• Is this material “hazardous” for transportation?

Classify• Determination of Hazard Class and Packing Group

Describe• Determination of Basic Description

Package• Selection, filling and closing

Communicate• Marking, labeling, placarding, documentation

Loading• Loading, blocking and bracing

Process flow for the HMR: “Person who offers”


§171.1 Applicability of Hazardous Materials Regulations (HMR) to persons and functions.(b) Pre-transportation functions.……..(2) Selecting a hazardous materials packaging.(3) Filling a hazardous materials packaging, including a bulk packaging.(4) Securing a closure on a filled or partially filled hazardous materials package or container or on a package or container containing a residue of a hazardous material.


Basic Description:UN ID#, PSN, Class, PG

172.101HMT: Column 8 and 7

173.***

Package selection based on:Physical statePacking GroupDensity (SG) or weight

May I use this packaging for this material?:How it looks to be done in “the real world”.


173.22 Shipper's Responsibilities

(a)(2) The person shall determine that the packaging or container is an authorized packaging, includingpart 173 requirements, and that it has been manufactured, assembled, and marked in accordance with:

§173.24 General requirements for packagings and packages.

c) Authorized packagings. (1) A packaging is authorized for a hazardous material only if—(i) The packaging is prescribed or permitted for the hazardous material in a packaging section specifiedfor that material in Column 8 of the §172.101 table and conforms to applicable requirements in thespecial provisions of Column 7 of the §172.101 table and...

172.101Hazardous Materials Table

Columns 7 + 8

Basic Description ofHazardous Material

May I use this packaging for this material?:The “path” through the HMR


PART 173—SHIPPERS—GENERAL REQUIREMENTS FOR SHIPMENTS AND PACKAGINGS

§173.1 Purpose and scope.(a) This part includes:(1) Definitions of hazardous materials for transportation

purposes;(2) Requirements to be observed in preparing hazardous

materials for shipment by air, highway, rail, or water, or any combination thereof; and


Part 173: Subpart B--PREPARATION OF HAZARDOUS MATERIALS FOR TRANSPORTATION

§ 173.24 General requirements for packagings and packages.

§ 173.24a Additional general requirements for non-bulk packagings and packages.

§ 173.24b Additional general requirements for bulk packagings. [Note: Contains stacking regulations for IBC]

§173.35 Hazardous materials in IBCs.

§173.22 Shipper's responsibility.

§ 173.24 General requirements for packagings and packages.

Non-bulk No IBC

No

§ 173.24b Additional generalrequirements for bulk packagings

.

[Except IBC stacking 173.24b(e)]

Yes §173.35 Hazardous materials in IBCs.

[Except IBC stacking 173.24b(e)]Yes

§ 173.24a Additional generalrequirements for non-bulkpackagings and packages.

Subpart B—Preparation of Hazardous Materials for Transportation


173.24 General requirements for packagings and packages.

(a) Applicability(b) Effectiveness in transportation (“filled, its contents so limited,”)(c) Authorized(d) Meets specification requirements(e) Compatible with lading (packaging & mixed contents)(f) Closures effective(g) Venting(h) Outage and filling limits(i) Air Transportation


173.24a Additional general requirements for non-bulk packagings and packages.

(a) Packaging design(b) Filling limits(c) Mixed contents(d) Additional outage requirement for non-bulk packages.


Process Questions

• What needs to be done?• What “functions” are prescribed?• Are we doing “this”?• Do we have the information needed to perform the functions?

• Who is doing it?• Are they trained in the “specific function”?

• Have we documented what we do (have done)?


Packaging/Material relationships

Hazardous Material PackagingBasic Description Design type and performance level

Physical Characteristics of the Hazardous Material

Physical Characteristics of the Test Material

Density (Specific Gravity) Maximum rated weight (or SG) Vapor Pressure Hydrostatic pressure rating

[Also: 173.27(c)]Coefficient of Expansion Volumetric capacityChemical composition Material(s) of construction


How much may I put in the package?

• Weight (or Specific Gravity)• Vapor Pressure• Outage (Ullage)


Filling Limits (Non-bulk): Weight/Specific Gravity

173.24a(b) Non-bulk packaging filling limits(1) A single or composite non-bulk packaging may be filled with a liquid

hazardous material only when..(2) a non-bulk packaging may not be filled with a hazardous material to a gross

mass greater than the maximum gross mass marked on the packaging….(3) …a single or composite non-bulk packaging which is tested and marked for

liquid hazardous materials may be filled with a solid hazardous material…(4) Vapor Pressure evaluation (Single packagings for liquids.)


Filling Limits (IBC): Weight/Specific Gravity

173.35(l) Hazardous Materials in IBC(1)…an IBC may not be filled with a hazardous material in excess of the maximum gross mass marked on that container…..

(3) An IBC which is tested and marked for liquid hazardous materials may be filled with a solid hazardous material to a gross mass not exceeding the maximum gross mass marked on that container


Vapor Pressure/Outage: Why?

Temperature Increase =Product expansion + Increased Vapor Pressure =

Increase in Internal Pressure!!!


Volume Differential /Temperature Change


173.24(h), 173.24a(d), 173.35(d)

Outage (Ullage)


Outage: Non-bulk

173.24(h) “When filling packagings and receptacles for liquids, sufficient ullage (outage) must be left to ensure that neither leakage nor permanent distortion of the packaging or receptacle will occur as a result of an expansion of the liquid caused by temperatures likely to be encountered during transportation. Requirements for outage and filling limits for non-bulk and bulk packagings are specified in §§173.24a(d) and 173.24b(a), respectively.”

Additionally:173.24a(d) Liquids must not completely fill a receptacle at a temperature of 55 °C (131 °F) or less.


Outage: IBC

173.24(h) No leakage or permanent deformation

Additionally: 173.35(d) Notwithstanding requirements in §173.24b of this subpart, when filling an IBC with liquids, sufficient ullage must be left to ensure that, at the mean bulk temperature of 50 °C (122 °F), the IBC is not filled to more than 98 percent of its water capacity.


Definition: COEFFICIENT OF EXPANSION

the ratio of the increase of length, area, or volume of a body per degree rise in temperature to its length, area, or volume, respectively, at some specified temperature, commonly 0° C, the pressure being kept constant —called also expansivity.

For our purposes, temperature range (usually) = Filling temp 15°C (59°F) 55°C (131°F) [or: 50°C (122°F)]


Examples: Coefficient of Expansion

LiquidVolumetric Coefficient of Expansion(1/K, 1/oC) (1/oF)

Acetic acid 0.00110 0.00061Acetone 0.00143 0.00079

Alcohol, ethyl (ethanol) 0.00109 0.00061Alcohol, methyl

(methanol,wood alcohol, wood naphtha, wood

spirits, CH3OH)

0.00149 0.00083

Ammonia 0.00245 0.00136Chloroform 0.00127 0.00071

Water 0.000214 0.00012


Methanol Expansion (Simplified version): 15°C-55°C

208 liters x (ΔT: 40) x (CoE: .00149) = 12.4 liters 208 liters (@15°C)+ 12.4 liters = 220.4 liters @ 55°C


Volume Differential /Temperature Change


173.24a(b)(4); 173.35(h)(1)

Vapor Pressure Evaluation


Definition: Vapor Pressure

“The vapor pressure of a liquid is the equilibrium pressure of a vapor above its liquid (or solid); that is, the pressure of the vapor resulting from evaporation of a liquid (or solid) above a sample of the liquid (or solid) in a closed container.”


173.24a(b)…(4) Packagings tested as prescribed in §178.605 of this subchapter and marked with the hydrostatic test pressure as prescribed in §178.503(a)(5) of this subchapter may be used for liquids only when the vapor pressure of the liquid conforms to one of the following:(i) The vapor pressure must be such that the total pressure in the packaging (i.e., the vapor pressure of the liquid plus the partial pressure of air or other inert gases, less 100 kPa (15 psia)) at 55 °C (131 °F), determined on the basis of a maximum degree of filling in accordance with paragraph (d) of this section and a filling temperature of 15 °C (59 °F)), will not exceed two-thirds of the marked test pressure;(ii) The vapor pressure at 50 °C (122 °F) must be less than four-sevenths of the sum of the marked test pressure plus 100 kPa (15 psia); or(iii) The vapor pressure at 55 °C (131 °F) must be less than two-thirds of the sum of the marked test pressure plus 100 kPa (15 psia).


Non-bulk: Vapor Pressure Material/Test Pressure Packaging173.24a(b)(4)

(ii) The vapor pressure at 50 °C (122 °F) must be less than four-sevenths of the sum of the marked test pressure plus 100 kPa (15 psia); orVP50C (kPa) ≤ .571 [Pmarked (kPa) + 100]

178.605(d)(5)

…The hydraulic pressure (gauge) applied, taken at the top of the receptacle, and determined by any one of the following methods must be:………(2) Not less than 1.75 times the vapor pressure at 50 °C (122 °F) of the material to be transported minus 100 kPa (15 psi), but with a minimum test pressure of 100 kPa (15 psig); orPmarked (kPa) ≥ 1.75 VP50C (kPa) - 100


Non-bulk: Vapor Pressure Material/Test Pressure Packaging

173.24a(b)(4)(iii) The vapor pressure at 55 °C (131 °F) must be less than two-thirds of the sum of the marked test pressure plus 100 kPa (15 psia).VP55C (kPa) ≤ .666 [Pmarked (kPa) + 100]

178.605(d)….The hydraulic pressure (gauge) applied, taken at the top of the receptacle, and determined by any one of the following methods must be:…….(3) Not less than 1.5 times the vapor pressure at 55 °C (131 °F) of the material to be transported minus 100 kPa (15 psi), but with a minimum test pressure of 100 kPa (15 psig).Pmarked (kPa) ≥ 1.5 VP55C (kPa) – 100


IBC: Vapor Pressure Material/Test Pressure Packaging173.35(h)(1)(iii) The absolute pressure (vapor pressure of the hazardous material plus atmospheric pressure) in the IBC at 55 °C (131 °F). This absolute pressure must not exceed two-thirds of the sum of the marked test pressure and 100 kPa (14.5 psia).

178.814(d)(5)(i) The pressure determined by any one of the following methods:........(C) If absolute pressure (vapor pressure of the hazardous material plus atmospheric pressure) is used, 1.75 multiplied by the vapor pressure of the hazardous material at 50 °C (122 °F) minus 100 kPa (14.5 psi). If this method is chosen, the hydrostatic test pressure applied must be at least 100 kPa gauge pressure (14.5 psig); or


Vapor Pressure: Chloroform

P kPa = P mm Hg x .134 760 mm Hg x .134 = 102 kPa @ approx. 60 C

P in mm Hg 1 10 40 100 400 760 T in °C –58.0 –29.7 –7.1 10.4 42.7 61.3


173.24a(b)(4) Chloroform

(iii) VP55C (kPa) ≤.666 [Pmarked (kPa) + 100]Pmarked (kPa) ≥ 1.5 VP55C (kPa) – 100

Pmarked (kPa) ≥ 1.5 102(kPa) – 100Pmarked (kPa) ≥ 53 kPa (minimum 100 kPa)


IMDG 4.1.1.10


Examples of required marked test pressures for packagings, including IBCs, calculated as in 4.1.1.10.3

UN No. Name Class Packing

group Vp55 (kPa)

Vp55 x 1.5 (kPa)

(Vp55 x 1.5) minus

100 (kPa)

Required minimum

test pressure (gauge) under

6.1.5.5.4.3 (kPa)

Minimum test

pressure (gauge)

to be marked

on the

packaging (kPa)

2056 2247 1593 1155

Tetrahydrofuran n-Decane

Dichloromethane Diethyl ether

3 3

6.1 3

II III III I

70 1.4 164 199

105 2.1 246 299

5 -97.9 146 199

100 100 146 199

100 100 150 250

Note 1: For pure liquids the vapour pressure at 55° C (Vp55) can often be obtained from scientific tables.

Note 2: The table refers to the use of 4.1.1.10.3 only, which means that the marked test pressure shall exceed 1.5 times the vapour pressure at 55°C less 100 kPa. When, for example, the test pressure for n-decane is determined according to 6.1.5.5.4.1, the minimum marked test pressure may be lower.

Single or compositepackaging marked at

100 kPa or higher?

Vapor PressureQualification

YesYou may use

173.24a(b)(4)(ii) or (iii)No

You must use173.24a(b)(4)(i) and

perform required analysis.

Is the VP of the materialbelow the required

threshold of the ratingon the packaging

YesPackage may beused if properlyfilled (outage).

NoFind packaging with

higher VP rating; or usemethod in 173.24a(b)(4)(i)

Select Packagebased on result of

analysis

Vapor Pressure Analysis: non-bulk


If: Marked test pressure of all packagings is greater than or equal to 100 kPa

And: Highest vapor pressure component of your compound is less than orequal to:

VP50: 110kPa @ 50° C or VP55: 130 kPa @ 55°C

Then: Material meets VP requirements of 173. 24a(b)(4)(ii) or (iii) as applicable

Initial VP screen for 173.24a(b)(4)


Compatibility173.24(e)


Packaging Materials

• Glass-For packaging purposes considered a “barrier” material with few exceptions.

• Metal-Barrier material for most common permeants, but has many compatibility issues.

• Plastic-Not considered a barrier material. Some plastics have barrier capabilities to some permeants.


THE FRONT IN OUR WAR AGAINST ENTROPY

Schematic diagram of permeation parameters through a package wall.

Same general process for scalping or permeation.

From: Plastics Packaging; Selke, Cutler, Hernandez; Hanser


Container Fights Forces of Equilibration: Container always loses, only question—when?


§173.24 General requirements for packagings and packages

(e) Compatibility. (1) Even though certain packagings are specified in this part, it is,nevertheless, the responsibility of the person offering a hazardous material fortransportation to ensure that such packagings are compatible with their lading.This particularly applies to corrosivity, permeability, softening, premature aging andembrittlement.

(2) Packaging materials and contents must be such that there will be no significant chemicalor galvanic reaction between the materials and contents of the package.

(3) Plastic packagings and receptacles. (i) Plastic used in packagings and receptacles mustbe of a type compatible with the lading and may not be permeable to an extent that ahazardous condition is likely to occur during transportation, handling or refilling.


(ii) Each plastic packaging or receptacle which is used for liquid hazardous materials must be capable ofwithstanding without failure the procedure specified in appendix B of this part (“Procedure for Testing ChemicalCompatibility and Rate of Permeation in Plastic Packagings and Receptacles”). The procedure specified in appendixB of this part must be performed on each plastic packaging or receptacle used for Packing Group I materials.

PG I liquid inplastic

receptacleYes Appendix B Test on Receptacle

No

Meet maximum permeation rates listed in (ii)(A)-(C)

Documentation???See IATA: 5.0.2.6.3


Appendix B

7. Each of the following constitute test failure:a. Visible evidence of permanent deformation due to vapor

pressure build-up or collapse of walls, deterioration, swelling, crazing, cracking, excessive corrosion, oxidization, embrittlement, leakage, rupture or other defects likely to cause premature failure or a hazardous condition.


Think they’ll

notice?


Closure, gasket and liner materials are susceptible to chemical attack and the same types of diffusion effects as container walls. Compatibility determination should include intended closures.

Closures are part of the package.


This is an exception that may prove useful.


Possible compatibility clue?

PSN Class/Divis-

ion UN ID # PG Label

Codes Special provisions

(172.102) Packaging (173.***)

Excep-tions

Non Bulk Bulk

(2) (3) (4) (5) (6) (7) (8A) (8B) (8C)

Methanol 3 UN1230 II 3, 6.1 IB2, T7, TP2 150 202 242

Diallyether 3 UN2360 II 3,6.1 IB2, N12, T7, TP1, TP13 150 202 243

Hydrogen peroxide, aqueous solutions with not less than 20 percent but not more than 40 percent hydrogen peroxide (stabilized as necessary)

5.1 UN2014 II 5.1, 8 A2, A3, A6, B53, IB2, IP5, T7, TP2, TP6, TP24, TP37

None 202 243

Ammonia solutions, relative density between 0.880 and 0.957 at 15 degrees C in water, with more than 10 percent but not more than 35 percent ammonia

8 UN2672 III 8 336, IB3, IP8, T7, TP1

154 203 241


Chloroform: Stability and Reactivity

Incompatibility with various substances: Reactive with metals, alkalis.Corrosivity: Non-corrosive in presence of glass.Special Remarks on Reactivity: Light Sensitive. Incompatible with triisopropyl phosphine, acetone, disilane, fluorine, strong bases and reactive metals (aluminum, magnesium in powdered form), light.Special Remarks on Corrosivity: It will attack some forms of plastics, rubber, and coatings.


Additional compatibility considerations:(4) Mixed contents. Hazardous materials may not be packed or mixed together in the same outer packaging with other hazardous or nonhazardous materials if such materials are capable of reacting dangerously with each other and causing—

(i) Combustion or dangerous evolution of heat;(ii) Evolution of flammable, poisonous, or asphyxiant gases; or(iii) Formation of unstable or corrosive materials.

(5) Packagings used for solids, which may become liquid at temperatures likely to be encountered during transportation, must be capable of containing the hazardous material in the liquid state.


Questions?

Thank You,Lonnie [email protected]


mailto:[email protected]

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