i june 1963 - apps.dtic.mil · the synthesis of colemanite single crystals in 1959 and the...
Post on 18-Oct-2020
1 Views
Preview:
TRANSCRIPT
"ii4OLC1L!!RT 583
I JUNE 1963
HYDROTHERMAL SYNTHESIS OF VEATCHITE
AND ITS CALCIUM ISOMORPH
C. R. PAR ERSON
RESEARCH DEPARTMENT
/
JU
NAVAL ORDNANCE LABORATORY CORONACORONA, CALIFORNIA
NAVAL ORDNANCE LABORATORY CORONA
W. Rt. KURTZ. CAPT.. USN. r.5. ATCHISON. Ph.D.Commanding Officer Technical Director
ABSTRACT
The hydrated strontium borate, veatchite (SrO. 3BO'7 2820). andits calcium isomorph (CaO. 3B203. 2H2O) have been prepared by hydro-thermal synthesis at 260 C. Veatchite was prepared by the reaction ofSr(OH) 4 and H'BO4 solution and also by the conversion of tunellite(SrO.3 3jO.4H{03 in H3BO 3 solution at 260 The calcium isomorph3 " 7 ° 7 7
was prepared in a similar manner by the reaction of Ca(OH)2 and H3BO 3solution and also by the conversion of gowerite (CaO. 3BO .5H O) in'
H3BO 3 solution at 260 0C. The observed densities of the syntheticveatchite and the calcium .isomorph, as determined with a pycnometel.and using water as the liquid, were 2.77 * 0.04 and 2.31 * 0.02 g/'-.._respectively, for 0.5-g samples of fine crystals. The highest and
lowest indices of refraction (white light) for the synthetic veatchite andits calcium isomorph were determined to be 1.546 and 1.619 * 0.003,and 1.555 and 1.620 * 0.002, respectively.
FOREWORD
The Naval Ordnance Laboratory Corona is making a continuingstudy of the chemistry and synthesis of crystals of ferroelectric cole-manite (2CaO. 3B 2 0 3 5H 20), its strontium isomorph (2SrO 3B 2 0 3 5H 2 0),and other related calcium and strontium borate hydrates of potentialuse in ferroelectric devices. As part of this study, the chemistry andmethods of synthesis of veatchite (SrO. 3B 2 0 3 " 2H 2 0) and its calciumisomorph (CaO. 3B 2 0 3* 2H 2 0) are reported herein. The dielectric,ferroelectric, and pyroelectric properties of the materials synthesizedwill be reported later. All the above work is authorized by ONR ContractPO 1-0008 NR 048-119.
C. J. HUMPHREYSHead, Research Department
CONTENTS
0 ABSTRACT ............ ... .. .. Inside front cover
FORIEWIORD. ........... .. ... . .. .. . . . .* .
INTRODUCTION . . .. .. .. .. .. ... .. ... ... 1
PREPARATION OF SYNTHETIC VEATCHITE . . . . . . . . 1
PREPARATION OF THE CALCIUM ISOMORPH OF
VEATCHITE. ....................... 2
DENSITY AND REFRACTIVE INDEX OF SYNTHETIC
VEATCHITE AND THE CALCIUM ISOMORPH . . . . . . 3
INTRODUCTION
The synthesis of colemanite single crystals in 1959 and the prepara-tion of deuterated colemanite in 1961 have been reported in NOLC Techni-cal Memorandums (Refs. 1, 2, 3), and in 1962 a comparison of theferroelectric and pyroelectric properties of mineral and syntheticcolemanite was made (Ref. 4). The synthesis of the hydrated calciumborates was then investigated further to improve the quality and sizeof the crystals produced, and a limited study was made of the hydro-thermal reactions that produce hydrated calcium and strontium boratesand the transformation these borates undergo with increased temperature.
The work reported in this document is only a small part of theoverall investigation of the calcium and strontium borate hydrates thatmight prove of interest to those people who are concerned with ferro-electric devices. Since, to the author's knowledge, there has been noprevious laboratory synthesis of the mineral veatchite (SrO 3B 2 0 3 " 2H 2 0),
and no mention of the existence of a calcium isomorph (CaO' 3B 2 O 3 " 2H 2 0),this work is'considered sufficiently important to be reported separatelyfrom the results of the entire investigation, which will appear in a reportnow in process of publication (Ref. 5).
PREPARATION OF SYNTHETIC VEATCHITE
It was found that synthetic veatchite could be prepared by two methods.By the first method, strontium hydroxide is reacted with boric acid inaqueous-solution at 260"C for 64 hours. By the second method, theveatchite is prepared by the transformation of synthetic "tunellite"(SrO'3B2 0 3 ' 4H 2 0) in boric acid solutionat 260"C for 40 hours. Thesecond method produces the best quality of crystals.
Method I. Reaction of Sr(OH) 2 and H3 BO 3 . In this method and also
in Method II, the reaction is carried out in a sealed, stainless steelbomb, 'which has a capacity of 76 ml and is equipped with a platinumliner. The platinum liner is not absolutely necessary, but it serves toreduce the contamination of the product. The reaction mixture consistsof 8.50 ml H 2 0 (CO 2 free), 1.42 g anhydrous SrO, and 7.30 g boric acid
2 2
crystals. The reaction is completed within 64 hours at 260°C to formveatchite.
Method II. Transformation of tunellite (SrO. 3B 2 0 3 4H 2 0) in boric
acid solution. The reaction mixture consists of 22.6 ml H 2 0 (CO 2 free),
1.89 g synthetic tunellite, and 4.52 g boric acid crystals. The reaction
is completed within 40 hours at 260°C to form veatchite. In the absence
of boric acid, this reaction does not produce veatchite.
Table 1 gives the X-ray diffraction analysis for-both the synthetic• veatchite produced by the above methods and the calcium isomorph ofveatchite discussed below. For comparison purposes, X-ray data arepresented from investigations of the mineral veatchite by others (Refs.6, 7. 8).
PREPARATION OF THE CALCIUM ISOMORPH OF VEATCHITE
Reactions similar to those described above produce the calcium" isomorph(CaO" 3B 2 03 " 2H 2 0). The.reactions are identical, except that
for Method I an equivalent amount of Ca(OH)2 is substituted for the SrO,""and in Method II gow.er'ite (CaO 3B 2 0 3 " 5H 2 0) is substituted for tunellite.
;The reaction time is reduced to 40 hours at 260:C in the formation ofthe calcium compound, since longer- reaction time favors the formation-
• of other r'eaction.products. See Table 1ifor the X-ray diffraction datafor the synthetic calcium isomorph produced by these reactions. Detailsof other reaction times and resultant products will be published in the
. forthcoming report-on the entire investigation (Ref. 5).
• *This isomorph can.also be produced by the conversion reaction of. synthetic ginorite (2CaO--7B 2 0 3 ' 8H 2 0) in boric acid solution .in a manner
identical with that given for the transformation of gowerite. Inthepresence'of boric acid solution of the strength used in the above reactions,gowerite'is cohipletely transformed to ginorite at 170°C and to the veatch-
• ite isomorph at 2600C.
The compound CaO" 3B 2 0 3 . 2H 2 0 is also one component of the reaction•-product resulting when a mixture containing 0.20 g colemanite and 1.00 gpriceite is reacted for 5 days at 200°C with 50 g of 20% boric acid solutionin a 76-ml bomb. The second component of this reaction product will be
S.discussed in the report cited in Ref. 5.
• • ...
DENSITY AND REFRACTIVE INDEX OF SYNTHETICVEATCHITE AND THE CALCIUM ISOMORPH
Two determinations of density were made with a pycnometer onseparate samples of the synthetic veatchite crystals, using water asthe liquid. The values obtained for the two specimens (approximately0.5 g each) of fine crystals were 2.73 and 2.80 g/cm3 . This comparesfavorably with the value of 2.78 ± 0.03 reported by Clark, Mrose,
*Perloff, and Burley (Ref. 6).
Two determinations of density of the synthetic CaO" 3B 2 0 3 " 2H 2 0were also made by the pycnometer method. The values obtained for
the two specimens (approximately 0.5 g each) of fine crystals were2.29 and 2.32 g/cm 3 .
The highest and lowest refractive indices were determined for thesynthetic veatchite and CaO 3B 2 0 3 * 2H 2 0 by using the immersion methodand white light. The values for synthetic veatchite are 1.546 and 1.619(* 0.003), and for the calcium isomorph, 1.555 and 1.620 (±0.002).
3
0 .- 0 -4 0 1-1 0 e" 0 4 o4 0 -4 -4 0 -4 0 -4
-4 -
1.441)oY U o -(,-a m NL noL 0P. 4 Ln - . 0 - v o r4 ON 0. o4 oo r- N No' 0 o. N U
U. In v w '%.' na, L a
0M
ooL
en 0
41 >4
01 NY n0c ,r., WU
u (d -4CN0 '
1.0 >A '0NNa .'Q)~.>) I A~c,'
-4 k4C~
-) a' C '*
Ca m0. r- 00 0 0
0-4
I4e) > 4)
0 0_ _ _ _ _ _ _ _ _
p4
r- -a -jao r- r- a, LA-N O N2X 0 ~LA N -4aN m -0N' r- D
(nx e 4 A. * *
~~~~~~ A ~ 41 A A~4J~~~. 0n
0 A0
u -4 co en L a ON 10 m w m t- w
o 0.04j En kU c Cen :) 0 Le--4-envv vvN mN m N
U a, N
41 - 4 - 4 -
- . o 0 - -4 - o IN N N m . o ~ 0 4 0 N N --~I Ft
o %0 w -n nM o
- n -4, r_ m N4j a a n q _ 0 n " 0 0
0 >1- 0*
r~ v ~ N 0 0en N
-. 4 U)
"0
ccc1-4 Ul
*m . .
'dU
U)~41
) ena, a, 0
0 k0'z .cC) a., En ..
N .- 4
4)4-0
U) en N -
1-4 4)a,)
*~+ 4 _4 Nm0Ll 0 4 ca, N4 000 0'0'
1-. A.
- -, N 4 N N (4 qN - N 4o -4 N oe4
a' (
o z
00 (Y f
a, cc e0 a,'0a' '0 '0 a
L') U o0'- -. . L0
NN
4-4
-44
4) U)
4-4.
a, .. %. m
-44 OD 4)0 0 Q. 00 000
4 N. N ' L
:5 N N N .
-4* .0
en .o . n .
- 'O~N N ' '0 O -
(n. A* .. In
G) IsoILf'.0o'D 00Lo
- .
a)
$4. . N 4-4a'
-4 c
-q. U f r- .o 0
UU
-4 ar'. Ln N0,c a
(D .!4 .4 0. . a, ,.~~~ *4 . .* 4 a
* ~ ~ ~ ~ 0 z ... 1
L)4
~'d
41N .:. v~ -V *-n .. .N o a.
f- LoO. r- 'N. * N NN.- N 4 a ,
-4 4 1
-4 0 Ny% r- .oLn m--'N r- ow
* ~ )~ ~. . -4-4 4 0 0 0'-4
N N5N 14- -4 4
0).50 ) (n *n oo Ln -4L~4N N41) (A
-4
a- u
N4- a) U)
-4- N.00-)0 0
00 -- r -1 oU
au 'a) U)
U)-
0>0
* . . .a
u. c r ~ c ' .. . U
F-4 (d -4 N 4- - .- (4
-4 00 000 - r -
*~~~- -4 * 0 -4> ). U
* -ui (
00 .t 00 c. .D m (N o. -0 v (n 0 .% -L
o .4 U)i . .0
*- 4 ~ '--
-4 (4 -*' .- 4 4 fI 4
REFERENCES
1. Naval Ordnance Laboratory Corona. Progress Report on theSynthesis of Colemanite Single Crystals, by C. R. Parkerson.Corona, California, NOLC, January 1959. (Technical Memorandum42-24.)
2. Naval Ordnance Laboratory Corona. Progress Report on theSynthesis of Colemanite Single Crystals, by C. R. Parkerson.Corona, California, NOLC, June 1959. (Technical Memorandum
* 42-31.)
3. Naval Ordnance Laboratory Corona. Preparation of DeuteratedColernanite, by C. R. Parkerson. Corona, California, NOLC,September 1961. (Technical -Memorandum 42-56.)
4. Wieder, H. H., A. R. Clawson, and C. R. Parkerson. "Ferro-* electric and Pyroelectric Properties of Mineral and Synthetic
Colemanite, " J. Appl. Phys., Vol. 33, No. 5. (May 1962), pp.* ' 1720-25.
. ' 5. Naval Ordnance Laboratory Corona. Hydrothermal Synthesis ofHydrated Calcium Borates, by C. R. Parkerson. (NOLC Report
* 584, *in process.)
6. Clark, J. R., M. E. Mrose, A. Perloff, and G. Burley. "Studiesof Borate Minerals (VI);'Investigation of Veatchite," Am. Mineral.,
i:Vol. 44 (November -December 195.6), pp. 1141-49.
7. Kramer, H., and R. D. Allen. "A Restudy of Bakerite, Priceite,and Veatchite, " Am. Mineral., Vol. 41 (September-October 1956),pp. 689-700.
8. Stewart, F. H., R. A. Chalmers, and R. Phillips. "Veatchite Fromthe Permian Evaporites of Yorkshire," Mineral. Mag., Vol. 30(1954), pp. 389-392.
9
NOLC Report 583, ONR PO 1-0008 NR 048-119
INITIAL DISTRIBUTION
Copies Copies
Chief, Bureau of Naval Weapons. CommanderNavy Department Naval Weapons LaboratoryWashington 25, D. C. Dahlgren, Va.
Attn: Code R3 I Attn: G. H. GleissnerRAAV 1RMWC 1. Commanding OfficerRUDC 1 Naval Avionics FacilityDLI-31 4 21st and Arlington Avenue
Indianapolis 18, Ind.
Chief, Bureau of Ships Attn: Code 031.2, Libr.•.Navy Department'
Washington 25, D. C. Chief, Bureau of SuppliesAttn: Code 607A, NTDS 1 and Accounts
671AZ,' (LCDR.E.B. Navy DepartmentMahinske) 1 Washington, D. C..
• 686" *1 . Attn: Code W3 .
Commanding Officer . Commanding OfficerNaval Ordnance Laboratory Navy Electronics' LaboratoryWhite Oak San Diego 52, Calif.
Silve'r Spring 19, Md. Attn: Technical Library IAttn: Technical Library Y
Director
Chief of Naval Operations . Naval Research LaboratoryNavy Department Washington 25, D. C.Washington 25, D. C. Attn: Code 5266, G. Abraham 1
Attn: Code OP-07T-12 Tech. Info. Officer,Code 2000 6
Chief of Naval ResearchNavy Department Office of Technical ServicesWashington 25, D. C.' Department of Commerce
Attn: Code 437, Info. Sys. Br. 2 Washington 25, D. C.Attn: Tech. Reports Section 1
Commanding Officer 10Office of Naval Research Commanding Officer INavy #100, Fleet Post Office ONR Branch OfficeNew York, N. Y. 1030 E. Green Street
Pasadena, Calif.
10
Copies Copies
Commanding Officer 1 Harry Diamond Laboratories
ONR Branch Office Connecticut Ave. & Van Ness St.
1000 Geary Street Washington 25, D. C.
San Francisco 9, Calif Attn: E. W. Channel, ORDTL-012 1
Commanding Officer I Technical Information Officer
ONR Branch Office Army Signal Research and
John Crerar Library Building Development Laboratory
86 East Randolph Street Fort Monmouth, N. J.
Chicago 1, Ill. Attn: Data Equipment Branch 1
Dr. H. Jacobs, Solid 1
Commanding Officer State Devices Branch
ONR Branch Office M. Tenzer 1
495 Summer Street
Bostoh'10, Mass. Office of the Chief of Research
and Development
Commanding Officer 1 Department of the Army
ONR Branch Office' Pentagon, Rm. 3D442
.346 Broadway Washington.25, D. C.
.New York 13, N. Y'. Attn: L. H. Geiger 1
Federal Aviation Agency . Commander
Bureau of Research j& Development Air Force Cambridge Research
Washington 25, D. C. . Laboratories
Attn: Code RD-375, H. Hayman 1 Laurence G. Hanscom Field
Bedford, Mass.
Director Attn: Research Lib., CRX2-R 1
National Bureau' of Standards CRRB, Dr. H. H. Zschirnt 1
Data Processing Systems. Div.,
Rm.'239, Bldg. 10 Commander
Washington 25, D. C. Wright Air Development Division
Attn: R. D. Elbourn 1 Electronic Technology Laboratory
A. K. Smilow 1 Wright Patterson AFB, Ohio
Attn: Lt. Col. L. M. Butsch, Jr.,(ASRUEB) I
Assistant Secretary of Defense 2
for Research & Engineering Defense Documentation Center 10
Information Office Library Branch Arlington Hall Station
Pentagon Building Arlington 12, Va.
Washington 25, D. C.
Commanding General Director
Aberdeen Proving Ground, BRL National Security Agency
Aberdeen Proving Ground, Md. Fort George G. Meade, Md.
Attn: J. H. Giese, Chief, I Attn: R-4, Howard Campaigne 1
'Comput. Lab.
11
Copie s Copies
Aeronutronic s Division Harvard UniversityFord Motor Company Cambridge, Mass.
Ford Road Attn: Dean H. Brook. School
Newport Beach, Calif. of Applied Science
Attn: C. L. Wanlass
Institute for Defense AnalysisCalifornia Institute of Technology Communications Research DivisionJet Propulsion Laboratory Von Neumann Hall
Pasadena, Calif. Princeton, N. J.
Attn: Dr. F. B. Humphrey 1
Laboratory for Electronics, Inc.Columbia University 1079 Commonwealth Avenue
New York 27, N. Y. Boston 15, Mass.Attn: Prof. L. Brillouin, 1 Attn: Dr. H. Fuller
Dept. of Physics
Laboratories RCA Ltd.Applied Physics Laboratory Zurich, SwitzerlandThe Johns Hopkins University Attn: Dr. W. J. Merz
8621 Georgia Avenue Via: Chief, BuWeps, Code DSC-3
Silver Spring, Md.Attn: Documen' Library 1 Lincoln Laboratory
Massachusetts Institute of
David Taylor Mlodel Basin TechnologyWashington 7. 1). C. Lexington 73, Mass.
Attn: Technical Library 1 Attn: Library
Division of Electronics Materials Lockheed Research Laboratory
Kyoto University 3251 Hanover, 52-40, Bldg. 202Kyoto, Japan Palo Alto, Calif.
Attn: Tetsuro Tenaka I Attn: M. E. Browne
Via: Chief, BuWeps, Code DSC-3McDonnell Aircraft Corporation
General Electric Research Missile Engineering DivisionLaboratory Municipal Airport
P. 0. Box 1088 St. Louis, Mo.
Schenectady, N. Y. Attn: R. E. Acker, Mgr.,Attn: V. L. Newhouse, I Adv. Digital Techniques
Applied Physics SectionNational Physical Laboratory
Harshaw Chemical Company Teddington, Middlesex1945 East 97th Street England
Cleveland 6, Ohio Attn: Dr. A. M. UttleyAttn: A. E. Middleton 1 Via: Chief, BuWeps, Code DSC-3
12
Copies Copies
National Aeronautics & Space University of California atAdministration Los Angeles
Goddard Space Flight Center Los Angeles 24, Calif.Greenbelt, Md. Attn: Prof. G. Estrin, Dept.
Attn: C. V. L. Smith, Chief, 1 of Engr.
Data Systems Division
University of Illinois
New York University Urbana, Ill.Washington Square Attn: D. Alpert, Cont. Sys. Lab. 1
New York 3, N. Y. Dr. J. E. Robertson, IAttn: Dr. H. Kallmann 1 Digital Comp. Lab.
The Rand Corporation University of Maryland
1700 Main Street Physics DepartmentSanta Monica, Calif. College Park, Md.
Attn: W. H. Ware, Numerical 1 Attn: Prof. R. E. Glover
Analysis Dept.
University of Michigan
Space Technology Labs, Inc. College of Engineering
Physical Research Laboratory Ann Arbor, Mich.
P. 0. Box 95002 Attn: Prof. H. Diamond
Los Angeles 45, Calif.
Attn: F. S. Gardner 1 Institut for Angewandte Physik
University of Munster
Stanford Research Institute Munster, West Germany
Menlo Park, Calif. Attn: Dr. Muser IAttn: H. D. Crane, Computer 1 Via: Chief, BuWeps, Code DSC-3
Laboratory University of Pennsylvania
Dr. C. Rosen, Appl. 1 Moore School of Electrical
Phys. Group Engineering200 South 33rd Street
Stanford University Philadelphia 4, Pa.
Stanford, Calif. Attn: A. L. Campion 1Attn: Prof. J. G. Linvill, 1
Elect. Lab. Varo Manufacturing Company
2201 Walnut StreetTransitron Electronic Corporation Garland, Tex.
168-182 Albion Street Attn: F. P. Granger, Jr.
Wakefield, Mass.
Attn: Dr. H. G. Rudenbert, 1 Waddell Dynamics, Inc.
Director R&D 5770 Soledad Road
LaJolla, Calif.
University of California Attn: B. L. Waddell,Department of Physics President
Berkeley, 4, Calif.Attn: Prof. E. L. Hahn 1
13
Copies
Westinghouse Electric Research
Laboratories
Beulah Road, Churchill BoroughPittsburgh 35, Pa.
Attn: G. Shirane, Magnetics I& Solid State Dept.
NOLC:
C. J. Humphreys, Code 40 1R. L. Ccnger, Code 42 1Arthur Clawson, Code 423 2C. R. Parkerson, Code 423 5H. H. Wieder, Code 423 2D. J. White, Code 423 2
Technical Library, Code 234 2
NOLC 6-63-135
14
a' 0
0~ 0 i
44 4 . z 4. 4W a. Z
0•, 4 4 01
Go z.
0 14 0 n c4
u) .1 ~4 0 NINa~a 0- d -. aaau 0 4o
oU 'a
o uu 'a o o,
o 0 o( 2 ..
.... N o °N I o. >u 0 z r c 'I Iu , 'd 4t o E: m>
0 k. Q, >0 o o
~ 0. .4 o U2o4W4 W . .0
o z 0 6z
q In
44 " . ° 4°r, .'I "' . ' W4W o. -,° ... 4
u u
a 0 N a r 00.r
o A UL, (1 (3 ; u -8E4 44)4 'o, uw. - T* > -o o4. N . ", 4.4)
0 0 . 1 0 g S . . 4 .a _, 4 4~ n Uu'
N - qE0 u W • o N u v ., .,
.00.,z4.0 4• .. O.0
.4,"
4 ll . - 4. -
o E. 4 0 a 0 a.4
A , u o v- ' A o rs M ., :: S ,' vv. "o~~~ ~ z .- O" r 9.,, . , I o -' ,- .
0 o > 4 e.
a .: ... IdHI I -1 Ia 0
- u .* V . C~ 4 U xw"
0 0 v M t " '4 ow, r , '25
'm N 0 'd o" D.jo,- =
t UU 0.. . . 4W
0' u 0' d
v Id - k m .
$4 '0, N. o,' o Z.- E -ax n ' '
00 v 4. 0 (00
4W ' .-" 4W -, z1 t 0 > 0 * 'i
0 .. 4 v p0L lU '6 n 0 E .4
4 aU .vI o 0 u o4 u 0k, , H , z 4 V o .x o , .d a , .00
-0 N- u -0 4 - 0>X z:
w .4 u4 .4 Id u
~~~~~ v' 0o 0.W EN0~.
4, 0. - . ~
U 41 4o u,~ ' 1 .
v 4 ~j O~ o 0 0
4.7 .4.4 r44~ 0 4 n~~j 0>.,4 -u
o '0 ~ ~ . .E 4 '~a~
2 I . ~ '~Eg-~z
N m .0 0 04 0 o
C1U4 or or.44 :1 o NC-H1 4.1 4
,: ,6 um . 44 ON E ~ -o V1) o 0 U E v%~ Ul 0 *6~
0 n - 0 0
top related