IL26375A - Synthetic quartz growth - Google Patents
Synthetic quartz growthInfo
- Publication number
- IL26375A IL26375A IL26375A IL2637566A IL26375A IL 26375 A IL26375 A IL 26375A IL 26375 A IL26375 A IL 26375A IL 2637566 A IL2637566 A IL 2637566A IL 26375 A IL26375 A IL 26375A
- Authority
- IL
- Israel
- Prior art keywords
- molar
- growth
- quartz
- temperature
- nutrient
- Prior art date
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims description 38
- 239000010453 quartz Substances 0.000 title claims description 33
- 239000013078 crystal Substances 0.000 claims description 44
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 27
- 235000015097 nutrients Nutrition 0.000 claims description 23
- 239000012736 aqueous medium Substances 0.000 claims description 10
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 5
- 229910001415 sodium ion Inorganic materials 0.000 claims description 5
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- IDNHOWMYUQKKTI-UHFFFAOYSA-M lithium nitrite Chemical compound [Li+].[O-]N=O IDNHOWMYUQKKTI-UHFFFAOYSA-M 0.000 claims description 3
- 239000002609 medium Substances 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims 2
- 239000000243 solution Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 239000004115 Sodium Silicate Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 6
- 229910052911 sodium silicate Inorganic materials 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 229910013553 LiNO Inorganic materials 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical class C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000012814 acoustic material Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000004933 hydrothermal crystal growth Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- -1 nitrate ions Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- 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)
Description
'niUJl ]71D Τ11ΠΙ"Ί 'Π PATENT ATTORNEYS ■ B IB 3 ' □ PATENTS AND DESIGNS ORDINANCE SPECIFICATION 8VNYMEYI0 QUARTZ GROWTH WESTERN ELECTRIC COMPANY, INCORPORATE!), A U.S.A. CORPORATION, BROADWAY, HEW YORK, M.Y.10007, U.S.A. do hereby declare the nature of this invention and in what manner the same is to be performed, to particularly described and ascertained in and by t follpwing statement :- This invention relates to improved synthetic quartz crystals and to methods for their preparation.
To satisfy the need for increasing quantities of quartz crystals for use in electrical devices such as piezoelectric resonators and transducers and to provide a dependable supply, various synthesis procedures have been extensively investigated and significant improvements in growth techniques have been developed. Thus, it has been possible over the past several years to synthesize quartz crystals which adequately perform the electrical functions which previously could be achieved only with natural quartz.
Recent advances in synthetic growth procedures have made possible extremely fast growth rates which may be as high as one-half inch per day. Commercial considerations often require rates in excess of 0.015 inch/day and faster rates are economically desirable. However, it is characteristic of crystals grown at these high rates that crystal imperfections tend to interfere with the high acoustic efficiency characteristic of natural quartz and obtainable in slow-grown synthetic quartz. Thus, it becomes highly desirable to find a synthetic growth mechanism which permits fast growth and still provides crystals of high resonator quality.
It has been found that a significant improvement in the acoustic quality of synthetically grown quartz crystals can be realized by growing the quartz crystal in a hydro-thermal solution containing lithium ions. While the mechanism is not fully understood this expedient produces crystals which characteristically exhibit twice the Q value of quartz grown in the conventional manner. This improved process for synthesizing quartz is described and claimed in Israeli Patent No.18,031 (Ballman et al Case 4-2-2).
It has been believed that the anion accompanying the desired lithium ion is inconsequential to the process. Hydrothermal solutions employing lithium carbonate are currently used in commercial production. However, all soluble lithium salts would be expected to be more or less equivalent in terms of their /Iffeet on the ultimate acoustical properties of the crystal.
In accordance with the present invention there is provided a method for synthesizing quartz crystals, which method comprises disposing a quartz crystal seed and a mass of nutrient S1O2 in an aqueous medium comprising sodium ions, lithium ions and a nitrate or nitrite anion in concentrations of at least 0.2 molar, 0.02 molar, and 0.02 molar, respectively, heating the said medium under pressure to a temperature of at least 300°C and maintaining a temperature difference between the seed and the nutrient mass of at least 15°C It has now been discovered that the anion in solution can be extremely significant. Specifically, it has been 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 1 preferably 1.0 molar soluble sodium salt such as sodium hydroxide, sodium carbonate, sodium silicate or mixtures thereof.
The invention will become more apparent with reference to the accompanying drawing in which the single figure is a perspective view, partly in section, of an autoclave used for the growth of quartz crystals.
Various crystal samples were prepared according to the standard commercial growth technique except that in each case a lithium salt was added to the hydrothermal growth solution. The acoustic absorption of the individual samples was measured by infra-red absorption technique. In this manner a survey was performed to evaluate the effect of the presence of various anions in the hydrothermal solution on the acoustic behaviour of the crystals formed.
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 U.S. Patent No.2, 785, 058 (Buehler Case 2). 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 rise 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. This action provides an effective seal for the growth chamber.
The chamber is initially temporarily sealed by means of the set screws 15 which compress a resilient washer $3 against the shank of the plunger.
For the growth procedure 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 per cent of the chamber at room temperature (excluding the volume of the nutrient, seeds and supporting means). The seed crystals 16 are suspended as shown. For the growth of the samples described herein a baffle 17 was interposed between the nutrient mass and the seed crystals so as to divide the chamber into essentially two thermal zones. This baffle maintains a reliable temperature differential between the nutrient crystals and the crystallization zone. This particular baffle had 4 per cent open area.
The quartz used as the nutrient should possess a particle size such as 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 the seed crystal. It has been found that with proper control o of the other conditions, sustained rapid growth may be obtained with a nutrient consisting of quartz particles of such size that the average particle diameter is. as large as about one-third the diameter of the growing chamber 11. The amount of nutrient, is not important as long as it is. at least the weight desired in the final crystals.
The seeds 16 may consist of any whole crystal, fra ment cut f n tur l e should be free of twinning if it is desired to produce an unt inned crystal.
Growth on the seed crystal has been obtained by the process of the present embodiment 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. However, in a reaction chamber in which a higher temperature differential can be readily maintained, it may be more advantageous to use sodium hydroxide (or sodium silicate) since the system is more stable with this compound so that there is a lesser tendency toward spurious seeding.
Growth can be obtained with other sodium salts, particularly salts of weak acids. Salts of sodium with organic acids which are stable against substantial decomposition at the temperatures and concentrations used may also be employed.
For reasonably rapid growth, 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 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 present process 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 450°C.
The density of the aqueous medium in which the quartz crystal is grown, and therefore the pressure existing in the bomb during the growing operation, exert a considerable influence upon the rate at which the quartz crystal is grown. The density, or inversely the specific volume, of the aqueous medium is controlled by the degree to whi»h the free space in the growing chamber is filled with the aqueous solution prior to the sealing of the chamber. Filling about 33 per cent of the free s ace in the chamber with li uid at room tem erature 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 achieved by the present process only by using considerably higher degrees of fill, with correspondingly lower specific volume.
To obtain a practical rate of growth, it is necessary to fill the free^ space of the chamber, excluding the space occupied by nutrient, seed and supporting means, to at least 60 per cent with the liquid aqueous growing medium at room temperature. As the degree of fill is increased, the growing rate increases markedly. 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 per cent has been found very satisfactory but a fill of 90 per cent will give faster results in a bomb designed to withstand the pressure.
With a liquid fill of about 60 per cent of the free space at room temperature, 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 room temperature. With fills of 80 per cent and 90 per cent, the specific volumes above the point where the vessel fills completely are 1.25 and 1.11 times those at room temperature, respectively.
It is important to the rate of growth of the crystal that the proper temperature differential be maintained thoughout the process, between the aqueous solvent leaving the mass of quartz nutrient and the aqueous solvent in the vicinity of the quartz seed crystal. With a very small temperature increases, the rate of growth increases but, if it becomes excessive, a degree of spurious seeding occurs on the walls of the bomb. In avoiding the possibility of spurious seeding,-it is necessary to avoid an excessive temperature differential not only between the nutrient mass and the seed crystal but also between the nutrient mass and any portion of the bomb.
As indicated above, 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 5°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 following description illustrates the specific manner in which the crystal samples were prepared.
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 Table I was added in an amount sufficient to fill 82 per cent of the chamber at room temperature (excluding volume 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 psi. The growth rate was approximately 70 mils/day, total growth on each side of the seed plane.
All of the samples were prepared in an essentially identical manner. The measurements of "Q" on each sample were made as previously indicated and the results are reported in the following table. The "Q" value is the reciprocal of the acoustic absorption at 5 mc, the standard figure of merit for acoustic materials.
' ' " TABLE I Additive Concentration. Q Value None 100,000-150,000 LiOH 0.1 molar Li2C05 0.1 molar LiB02 0.1 molar LiCl 0.1 molar 200,000-300,000 LiP 0.1 molar Li2S04 0.1 molar Li3P04 0.1 molar LiNO, 0.1 molar 350,000-500,000 3 LiN02 0.04 molar 400,000-560,000 LiN02 0.10 molar 690,000-800,000 LiNO 0.15 molar 620,000-760,000 The ranges indicate that several crystals in each category were measured giving different values. The range of concentration which give useful results and other experience indicates that these concentration effects are applicable to nitrate ions as well. Thus, a concentration range of 0.02 to 0.15 molar nitrate or nitrite is to be preferred although no particular advantage is seen in extending the concentration appreciably beyond 0.1 molar.
The following specific embodiment of the invention illustrates the unusual crystal quality obtainable. 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 LiN02 and the degree of fill was 79 per cent. This produces a pressure of the order of 15,500 psi. The temperature of the growth region was 355°C and the nutrient zone temperature was 380°C. The seeds were z-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.
Various additions , modifications and extensions o will become apparent to those skilled in the art. For instance, it is obvious that the nitrate or nitrite anion does not necessarily have to be added in association with lithium. Thus, sodium hydroxide, sodium nitrite and lithium carbonate can be dissolved in water to achieve an identical solution for the present purposes.
Claims (8)
1. . 1. A method for synthesizing quartz crystals, which method comprises disposing a quartz crystal seed and a mass of nutrient SiOg in an aqueous medium comprising sodium ions, lithium, ions and a nitrate or nitrite anion in coneen-trations of at least 0.2 molar, 0.02 molar, and 0.02 molar, respectively, heating the said medium under pressure to a temperature of at least 300°C and maintaining a temperature difference between the seed and the nutrient mass of at least 15°C
2. A method according to claim ,1, wherein the aqueous medium comprises NaOH or NaCO^.
3. A method according to claim 1, wherein the concentration of the nitrate or nitrite is within the range 0.02 to 0.15.
4. A method according to claim 3> wherein the aqueous medium contains lithium nitrate, or lithium nitrite.
5. A method according to claim 1, 2, 3 or 4, wherein the aqueous medium is heated to a temperature in the range 350°C to 573°C.
6. A method according to any one of the preceding claims, wherein the said temperature difference is in the range 15°C to 70°C.
7. A method of synthesizing quartz crystals, substantially as hereinbefore described with reference to the accompanying drawing.
8. Quartz crystals prepared by the method according to any one of the receding claims.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US490018A US3356463A (en) | 1965-09-24 | 1965-09-24 | Synthetic quartz growth |
Publications (1)
Publication Number | Publication Date |
---|---|
IL26375A true IL26375A (en) | 1970-08-19 |
Family
ID=23946271
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
IL26375A IL26375A (en) | 1965-09-24 | 1966-08-23 | Synthetic quartz growth |
Country Status (8)
Country | Link |
---|---|
US (1) | US3356463A (en) |
BE (1) | BE687141A (en) |
DE (1) | DE1592308C3 (en) |
DK (1) | DK112518B (en) |
GB (1) | GB1153802A (en) |
IL (1) | IL26375A (en) |
NL (1) | NL6613410A (en) |
SE (1) | SE315270B (en) |
Families Citing this family (11)
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 |
GB2139204B (en) * | 1983-05-06 | 1986-10-08 | Univ Moskovsk | Process for producing fine-crystalline-quartz |
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 |
US4961823A (en) * | 1985-11-12 | 1990-10-09 | Shinichi Hirano | Method of manufacturing calcium carbonate single crystal |
JPS62113798A (en) * | 1985-11-12 | 1987-05-25 | Shinichi Hirano | Production of 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 |
Family Cites Families (2)
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 |
-
1965
- 1965-09-24 US US490018A patent/US3356463A/en not_active Expired - Lifetime
-
1966
- 1966-08-23 IL IL26375A patent/IL26375A/en unknown
- 1966-09-08 GB GB40112/66A patent/GB1153802A/en not_active Expired
- 1966-09-20 BE BE687141D patent/BE687141A/xx unknown
- 1966-09-22 NL NL6613410A patent/NL6613410A/xx unknown
- 1966-09-22 DE DE1592308A patent/DE1592308C3/en not_active Expired
- 1966-09-23 DK DK494766AA patent/DK112518B/en unknown
- 1966-09-23 SE SE12839/66A patent/SE315270B/xx unknown
Also Published As
Publication number | Publication date |
---|---|
BE687141A (en) | 1967-03-01 |
SE315270B (en) | 1969-09-29 |
DE1592308A1 (en) | 1970-12-10 |
US3356463A (en) | 1967-12-05 |
DK112518B (en) | 1968-12-23 |
DE1592308B2 (en) | 1973-12-13 |
NL6613410A (en) | 1967-03-28 |
GB1153802A (en) | 1969-05-29 |
DE1592308C3 (en) | 1974-07-18 |
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