US3356463A - Synthetic quartz growth - Google Patents

Synthetic quartz growth Download PDF

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Publication number
US3356463A
US3356463A US490018A US49001865A US3356463A US 3356463 A US3356463 A US 3356463A US 490018 A US490018 A US 490018A US 49001865 A US49001865 A US 49001865A US 3356463 A US3356463 A US 3356463A
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US
United States
Prior art keywords
growth
quartz
nutrient
temperature
seed
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Expired - Lifetime
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US490018A
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English (en)
Inventor
Albert A Ballman
Robert A Laudise
David W Rudd
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AT&T Corp
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Western Electric Co Inc
Bell Telephone Laboratories Inc
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Publication date
Application filed by Western Electric Co Inc, Bell Telephone Laboratories Inc filed Critical Western Electric Co Inc
Priority to US490018A priority Critical patent/US3356463A/en
Priority to IL26375A priority patent/IL26375A/en
Priority to GB40112/66A priority patent/GB1153802A/en
Priority to BE687141D priority patent/BE687141A/xx
Priority to NL6613410A priority patent/NL6613410A/xx
Priority to DE1592308A priority patent/DE1592308C3/de
Priority to DK494766AA priority patent/DK112518B/da
Priority to FR77519A priority patent/FR1495138A/fr
Priority to SE12839/66A priority patent/SE315270B/xx
Application granted granted Critical
Publication of US3356463A publication Critical patent/US3356463A/en
Assigned to AT & T TECHNOLOGIES, INC., reassignment AT & T TECHNOLOGIES, INC., CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). EFFECTIVE JAN. 3,1984 Assignors: WESTERN ELECTRIC COMPANY, INCORPORATED
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/16—Oxides
    • C30B29/20—Aluminium oxides

Definitions

  • This invention relates to improved synthetic quartz crystals and to methods for their preparation. More particularly, it concerns a novel additive which has been found to significantly improve the resonator efficiency of synthetic quartz crystal bodies.
  • the anion in solution can be extremely significant. Specifically, it hasbeen discovered that the use of lithium nitrite, and to a lesser extent lithium nitrate, in the hydrothermal growth solution profoundly improves the acoustic performance'of' the final crystal product.
  • the useful lithium nitrate and lithium nitrite concentrations are from 0.02 molar to 0.5 molar. The preferred range is 0.04 molar to 0.15 molar.
  • the basic hydrothermal solution may have a conventional composition, i.e., at least 0.2 molar andpreferably 1.0 molar soluble sodium salt such as sodium hydroxide, sodium carbonate, sodium silicate or mixtures thereof.
  • the figure is a perspective view, partly in section, of an autoclave used for the growth of quartz crystals.
  • the growing of the crystals was carried out in a pressure bomb adapted for hydrothermal crystal growth.
  • Various types of apparatus are appropriate for such procedures.
  • One such apparatus is described in detail in the 1 aforementioned patent.
  • the particular autoclave used in these experiments was a modified Bridgeman closure as shown in the figure.
  • the main body of the autoclave 10 contains a chamber 11 having approximate dimensions of 6 inches x 132 inches.
  • a main nut 12 is threaded into the upper portion of the chamber.
  • a plunger 13 is fitted into the bore 11 and is free to use under the influence of pressure within the chamber. As the plunger rises it contacts a steel seal ring 14 and is finally stopped by bearing against the main nut 12 through the seal ring.
  • the chamber is initially temporarily sealed by means of the set screws 15 which compress a resilient washer 48 against the shank of the plunger.
  • the chamber 11 is charged with nutrient quartz crystals in an amount and size as hereinafter specified.
  • An aqueous medium of a sodium salt and the aforementioned lithium salt is added in an amount sufficient to fill at least 60 percent of the chamber at room temperature (excluding the volume of the nutrient, seeds and supporting means).
  • the seed crystals 16 are suspended as shown.
  • a bafile 17 was interposed between the nutrient mass and the seed crystals so as to divide the chamber into essentially two thermal zones. This bafiie maintains a reliable temperature differential between the nutrient crystals and the crystallization zone.
  • This particular baffle had 4 percent open area.
  • the design and op-- eration of this type of baffle is fully treated in United States Patent 2,895,812 issued to G. T. Kohman, July 21, 195 9. V
  • the quartz used as the nutrient should possess a particle size suc has to present a sufficient surface area to the solvent thereby permitting the quartz to be dissolved-to an extent adequate to sustain the desired rapid growth of 1 the seed crystal. It has been found that with proper conmentor cut of natural or synthetic quartz.
  • the seed should be free of twinning if it is desired to produce an untwinned crystal. Growth on the seed crystal has been obtained by the process of the present invention when the aqueous medium used for transporting the silica from the nutrient to the seed has contained sodium ions.
  • Suitable compounds for supplying the sodium ions have been found to be sodium hydroxide, sodium carbonate and sodium silicate. Since sodium silicate is the reaction product of silica and sodium hydroxide, it is apparent that whether sodium hydroxide or sodium silicate is added initially, the solute will include sodium silicate during the operation of the process.
  • Sodium carbonate is a desirable compound for use since it permits the rapid growth of quartz with a small temperature differential between nutrient and seed.
  • sodium hydroxide or sodium silicate
  • Salts of sodium with organic acids which are stable against substantial decomposition at the temperatures and concentrations used may also be employed.
  • the concentration of sodium ions in the aqueous solution should be at least about 0.2 molar and preferably at least 1.0 molar. In general, as the concentration is increased, the rate of growth increases somewhat until concentrations of about 4 molar or 5 molar are reached. Further increase in concentration appears to produce only a slight increase in growing rate, but obviously higher concentrations may be used, if desired, provided quartz remains as the stable phase.
  • the growing of the quartz crystals by the process of the present invention is carried out with the aqueous solution at pressures above the pressure at which the liquid phase completely fills the autoclave.
  • the temperature in the growth part of the chamber should not fall below 300 C. and should preferably be at least 350 C.
  • the rate of growth of the crystal appears to increase as the average temperature in the chamber is increased but the temperature of the growing crystal should be maintained safely below 573 C., the inversion temperature for quartz, and safely within the mechanical limitations of the bomb .in which the growing takes place. It is preferable that the temperature in the vicinity of the crystal, or more preferably in the hottest part of the chamber, not exceed about 550 C. More practical operating temperatures are below 500 C., and preferably below 450C.
  • the density, or inversely the specific volume, of the aqueous medium is controlled by the degree to which thefree space in the growing chamber is filled with the aqueous solution prior to the sealing of the chamber. Filling about 33 percent of the free space in the chamber with liquid at room temperature will result in a specific volume, at the critical temperature of pure water, which is equal to the critical volume. Practical rates of growth can be achieevd by the present process only by using considerably higher degrees of fill, with correspondingly lower specific volume.
  • the free space of the chamber excluding the space occupied by nutrient, seed and supporting means, to at least 60 percent with the liquid aqueous growing medium at room temperature.
  • the upper limit to the degree of fill to be used is set only by the ability of the bomb to withstand the pressure which is generated. A fill of about 80 percent has been found very satisfactory but a fill of 90 percent will give faster results in a bomb designed to withstand the pressure.
  • the specific volume of the aqueous solution above the point where the vessel fills completely is about 1.67 times the specific volume of the liquid at the specific volumes above the point where the vessel fills completely are 1.25 and 1.11 times those at room temperature, respectively.
  • the temperature differential can be controlled with the apparatus shown in the drawing by varying the amount of insulation placed around the bombs in the furnace. Temperature differentials between the crystallization portion of the chamber and the nutrient mass of approximately 55 C. are typical in commercial operations. Differentials as low as about 15 C. and as high as 70 C. can be used satisfactorily.
  • the optimum temperature differential within the ranges set forth above may also be dependent upon other operating conditions, such as the particle size of the quartz nutrient. With the larger particle sizes, the best results are obtained with the greater temperature differentials. With smaller particle sizes, smaller temperature differentials give the best results.
  • the chamber 11 of the autoclave was charged with approximately 31,780 grams of nutrient quartz crystals of a size approximately one to two inches cubed.
  • An aqueous medium of 1.0 molar NaOH containing the addition as indicated in Fable I was added in an amount sulficient to fill 82 percent of the chamber at room temperature (excluding volume of nutrient, seeds and supporting means).
  • the seed crystals were in the form of basal plates approximately 0.05 inch in thickness.
  • the temperature of the crystallization portion of the chamber was 345 C. while the temperature of the nutrient seeds was 400 C.
  • the autoclave pressure under these conditions is approximately 22,000 p.s.i.
  • the growth rate was approximately 70 mils/day, total growth on each side of the seed plane.
  • the following specific embodiment illustrates the unusual crystal quality obtainable through the use of the invention. This run was made using a lower temperature differential between the seed and nutrient and a slightly smaller fill percentage both of which contribute to a slower growth rate and thus a higher quality product.
  • the hydrothermal solution was 0.1 M NaOH and 0.1 M LiNO and the degree of fill was 79 percent. This produces a pressure of the order of 15,500 p.s.i.
  • the temperature of the growth region was 355 C. and the nutrient zone temperature was 380 C.
  • the seeds were 2- cut as before.
  • the growth rate was about 40 mils/day.
  • the measured Q value for crystals produced according to this procedure ranged from 1,200,000 to over 2,000,000.
  • a method for synthesizing quartz crystals which comprises disposing a quartz crystal seed and a mass of nutrient SiO in an aqueous medium comprising sodium ions at least .2 molar has been inserted, lithium ions at least .02 molar and an anion selected from the group consisting of nitrate and nitrite, heating said medium to a temperature of at least 300 C. While under a pressure 5 exceeding the pressure present when the vessel is filled to at least 60 percent of its volume with said aqueous medium at room temperature and then heated to 300 C. and maintaining a temperature difierence between said seed and said nutrient mass of at least C. until a sub- 10 stantial increase in the size of said seed is obtained.
  • aqueous medium comprises Na CO 4.
  • anion is nitrate.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
US490018A 1965-09-24 1965-09-24 Synthetic quartz growth Expired - Lifetime US3356463A (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
US490018A US3356463A (en) 1965-09-24 1965-09-24 Synthetic quartz growth
IL26375A IL26375A (en) 1965-09-24 1966-08-23 Synthetic quartz growth
GB40112/66A GB1153802A (en) 1965-09-24 1966-09-08 Method for preparing improved Synthetic Quartz Crystals
BE687141D BE687141A (US07122603-20061017-C00045.png) 1965-09-24 1966-09-20
NL6613410A NL6613410A (US07122603-20061017-C00045.png) 1965-09-24 1966-09-22
DE1592308A DE1592308C3 (de) 1965-09-24 1966-09-22 Verfahren zur synthetischen Herstellung von Quarzkristallen
DK494766AA DK112518B (da) 1965-09-24 1966-09-23 Fremgangsmåde til fremstilling af syntetiske kvartskrystaller.
FR77519A FR1495138A (fr) 1965-09-24 1966-09-23 Procédé de synthèse de cristaux de quartz
SE12839/66A SE315270B (US07122603-20061017-C00045.png) 1965-09-24 1966-09-23

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US490018A US3356463A (en) 1965-09-24 1965-09-24 Synthetic quartz growth

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US3356463A true US3356463A (en) 1967-12-05

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US490018A Expired - Lifetime US3356463A (en) 1965-09-24 1965-09-24 Synthetic quartz growth

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US (1) US3356463A (US07122603-20061017-C00045.png)
BE (1) BE687141A (US07122603-20061017-C00045.png)
DE (1) DE1592308C3 (US07122603-20061017-C00045.png)
DK (1) DK112518B (US07122603-20061017-C00045.png)
GB (1) GB1153802A (US07122603-20061017-C00045.png)
IL (1) IL26375A (US07122603-20061017-C00045.png)
NL (1) NL6613410A (US07122603-20061017-C00045.png)
SE (1) SE315270B (US07122603-20061017-C00045.png)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3634044A (en) * 1970-01-14 1972-01-11 Texas Instruments Inc Growth of crystals at a uniform and constant rate
US4021294A (en) * 1974-01-18 1977-05-03 Valentin Evstafievich Khadzhi Process for producing amethyst crystals
US4024013A (en) * 1974-01-11 1977-05-17 Valentin Evstafievich Khadzhi Method of producing citrine crystals
US4529430A (en) * 1983-06-10 1985-07-16 Moskovsky Gosudarstvenny Universitet Imeni M.V. Lomonosova Process for producing fine-crystalline α-quartz
US4579622A (en) * 1983-10-17 1986-04-01 At&T Bell Laboratories Hydrothermal crystal growth processes
US4762588A (en) * 1985-11-12 1988-08-09 Seiko Instruments & Electronics Ltd. Method of manufacturing calcium carbonate single crystal
US4961823A (en) * 1985-11-12 1990-10-09 Shinichi Hirano Method of manufacturing calcium carbonate single crystal
US5135603A (en) * 1982-03-11 1992-08-04 The United States Of America As Represented By The United States Department Of Energy Quartz crystal growth
US20070283879A1 (en) * 2006-04-28 2007-12-13 Braun Minel J Thermally driven externally circulating hydrothermal crystallization vessel
US10358739B2 (en) 2016-12-15 2019-07-23 The United States Of America, As Represented By The Secretary Of The Air Force Heteroepitaxial hydrothermal crystal growth of zinc selenide

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2139204B (en) * 1983-05-06 1986-10-08 Univ Moskovsk Process for producing fine-crystalline-quartz

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB682203A (en) * 1949-05-21 1952-11-05 Brush Dev Co Process for growing a single crystal of quartz
US2785058A (en) * 1952-04-28 1957-03-12 Bell Telephone Labor Inc Method of growing quartz crystals

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB682203A (en) * 1949-05-21 1952-11-05 Brush Dev Co Process for growing a single crystal of quartz
US2785058A (en) * 1952-04-28 1957-03-12 Bell Telephone Labor Inc Method of growing quartz crystals

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3634044A (en) * 1970-01-14 1972-01-11 Texas Instruments Inc Growth of crystals at a uniform and constant rate
US4024013A (en) * 1974-01-11 1977-05-17 Valentin Evstafievich Khadzhi Method of producing citrine crystals
US4021294A (en) * 1974-01-18 1977-05-03 Valentin Evstafievich Khadzhi Process for producing amethyst crystals
US5135603A (en) * 1982-03-11 1992-08-04 The United States Of America As Represented By The United States Department Of Energy Quartz crystal growth
US4529430A (en) * 1983-06-10 1985-07-16 Moskovsky Gosudarstvenny Universitet Imeni M.V. Lomonosova Process for producing fine-crystalline α-quartz
US4579622A (en) * 1983-10-17 1986-04-01 At&T Bell Laboratories Hydrothermal crystal growth processes
US4762588A (en) * 1985-11-12 1988-08-09 Seiko Instruments & Electronics Ltd. Method of manufacturing calcium carbonate single crystal
US4961823A (en) * 1985-11-12 1990-10-09 Shinichi Hirano Method of manufacturing calcium carbonate single crystal
US20070283879A1 (en) * 2006-04-28 2007-12-13 Braun Minel J Thermally driven externally circulating hydrothermal crystallization vessel
US10358739B2 (en) 2016-12-15 2019-07-23 The United States Of America, As Represented By The Secretary Of The Air Force Heteroepitaxial hydrothermal crystal growth of zinc selenide

Also Published As

Publication number Publication date
NL6613410A (US07122603-20061017-C00045.png) 1967-03-28
DK112518B (da) 1968-12-23
IL26375A (en) 1970-08-19
DE1592308C3 (de) 1974-07-18
GB1153802A (en) 1969-05-29
SE315270B (US07122603-20061017-C00045.png) 1969-09-29
DE1592308A1 (de) 1970-12-10
DE1592308B2 (de) 1973-12-13
BE687141A (US07122603-20061017-C00045.png) 1967-03-01

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Effective date: 19831229