"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).

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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

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