CN1052154A - The growth method of colour crystal - Google Patents
The growth method of colour crystal Download PDFInfo
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- CN1052154A CN1052154A CN 89106859 CN89106859A CN1052154A CN 1052154 A CN1052154 A CN 1052154A CN 89106859 CN89106859 CN 89106859 CN 89106859 A CN89106859 A CN 89106859A CN 1052154 A CN1052154 A CN 1052154A
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- crystal
- growth
- colour
- growth method
- autoclave
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Abstract
A kind of growth method of colour crystal belongs to artificial lens Hydrothermal Growth field.Adopting melting level quartz is raw material, uses K
2CO
3Make flux, other is a small amount of K that mixes
2Cr
2O
7Or Fe
2(SO
4)
3XH
2O or 2CoCO
33Co (OH)
2XH
2O, under certain temperature, pressure condition, with 0.2-0.8mm/ days yellow, green, the tea crystal of all kinds of speed growth, the colour crystal of the present invention's growth did not need irradiation for directly painted, can be used for jewellery, decorative lamp, senior eyeglass etc.Technology of the present invention is simple, and is easy to operate, is suitable for producing in batches, and product performance are good.
Description
The Hydrothermal Growth technical field that belongs to artificial lens.
Rock crystal is a kind of piezoelectric crystal material, at first obtains quartzy crystallite with the Hydrothermal Growth technology in 1851 by the match sodium illiteracy of France is special in the laboratory, and he has used broken natural quartz piece to make nutrilite, uses NaHCO
3Make solvent.After this Si Piziya (Spezia) has realized quartzy growth on seed wafer in 1908, proved the possibility of synthetic crystal, but because of it will place the top of growth container than the dissolve area of heat, and colder crystal growth district places the bottom of container, be unfavorable for convection current, crystalline growth velocity is extremely low, and synthetic quartzy in subsequently 30 years develops rapidly, (English) Richard adopts melting level quartz to make nutrilite, has grown gratifying crystal in sealing autoclave.The Bell Laboratory of the U.S. and the General Electric Corporation of Britain have finished the commercialization work of quartzy production in 1956, so far worldwide, the rock crystal growing technology does not all have big improvement.
Colour crystal and rock crystal growth method are basic identical, difference is, the former needs to add suitable " impurity " in solution makes quartzy painted, and the latter requires growing system purifying as much as possible, what deserves to be mentioned is Hao Erdeng (Holden) and Wilder people such as (wild), nineteen twenty has been determined the contribution of most of trace element to quartzy color.With a kind of crystal different colour centers is often arranged, can make crystal produce distinct colors, depend primarily on the valence state of element in growing system, physics, electrochemical conditions when diffusion in crystal and growth with a kind of element.This has brought many difficulties for the growth of colour crystal, and human K is once arranged
2CO
3Make solvent with KOH, use V
2O
5Grow yellow crystal (1) as doping agent, use K
2Cr
2O
7Grow dark green crystal (1) as doping agent; Make solvent with NaOH, mix Al
2O
3, LiNO
2Deng the growth through the painted yellow quartz of irradiation (2).The color brilliant technology of above-mentioned growth, some mixes the ion costliness, the growing crystal repeatability and the poor stability that have, what have then need become yellow quartz (fading under 400 ℃ of high temperature of this yellow quartz) through the irradiation after stain, and to producing in batches, it is all unfavorable to reduce cost.
In order to overcome the shortcoming of prior art, the present invention has designed the mature and stable colour crystal growth technique of a cover, can grow lucuriant in designly, and cost is low, the jewellery that purposes is wide, lamp decoration colour crystal.
Technology of the present invention relates to the Hydrothermal Growth of colour crystals such as Huang, green, tea, selecting the melting level quartzy is raw material, pressing autoclave volumetrical 1/3 drops into, place the high-temperature zone of no liner autoclave bottom, make seed crystal with the rock crystal sheet that 1-2mm is thick, seed orientation Z or AT or X, the cold zone that is placed on autoclave top (or claims the vitellarium, crystallizing field), make seed crystal if any the crystal cut of same color, effect is better.Use 1-8%K
2CO
3(top grade is pure) deionized water solution (is the weight percent of solution, down together), other adds the 0.01-0.5% doping agent, the dissolve area temperature is controlled at 350-390 ℃, the temperature of crystallizing field is controlled at 300-350 ℃, the baffle openings rate in two districts is 20%-5% in the autoclave, and the compactedness of solution is 80-90%, (is the percentage ratio that solution is filled behind the shared volume such as the interior free space volumes deduction of autoclave raw material, seed crystal, baffle plate, seed crystal frame.) pressure is generally 70-150MPa, crystal Z was generally 0.2-0.8mm/ days to the speed of growth, was good with 0.3-0.5mm/ days.For the crystal of different colours, the doping agent that only needs to add different ratios in solution gets final product.
1, yellow crystal, doping agent are K
2Cr
2O
7, other adds the H of 2-5%
2O
2Strong oxidizer, 3.5-4.5%H
2O
2For good, to stablize Cr
6+The ionic valence state.
2, prasioleta.Doping agent is Fe
2(SO
4)
3XH
2O is with 5-6% K
2CO
3For good.
3, citrite, doping agent are 2CoCO
33Co(OH)
2XH
2O is with 6-7% K
2CO
3For good.
The present invention adopts follow-on Bridgman seal autoclave; as shown in Figure 1; this still is the pressurized vessel that steel or special alloy are made, and intensity is able to take to give fixed pressure and temperature, internal diameter φ 22-240mm; interior is 360-4700mm deeply; inner product 145-210000ml, with the stove heating of electric furnace filament winding system, power is the accurate temperature controller temperature control of 1.2-18KVA DWT-702; for guaranteeing that autoclave inwall impurity does not enter crystal, must " plating " protective layer before the crystal of all kinds of growing first.
General operation process of the present invention is:
(1) autoclave " protective layer plating
Its technological process is: the temperature than actual growth colour crystal exceeds 5-6 ℃, and pressure exceeds 10-20MPa, and autoclave base is put the 1/5-1/10 of normal growth desired raw material, the NaOH of 4-5% or K
2CO
3Solution, 4-7%H
2O
2, put seed crystal frame and baffle plate in the still, do not put seed crystal, carry out the constant temperature of lower temperature difference, 20-30 ℃ of △ T ≈ needs 5-7 days during this period of time, and surplus material is poured out in blowing out then, cleans autoclave, and is stand-by.
(2) according to the crystal growth requirement of different colours, prepare raw material, hang up seed crystal on the seed crystal frame, solvent, doping agent, deionized water carry out weighing.
(3) dress still, sealing is put in the process furnace then and is heated up.
(4) constant temperature growth phase, requiring to heat up in 24 hours reaches the temperature of setting, keeps the temperature difference of setting then, △ T=30-50 ℃ growth, wherein, the yellow crystal growth temperature difference is good for 30-35 ℃, growth cycle 13-50 days.
(5) lower the temperature, open still and come out of the stove, take out crystal.
Description of drawings:
Fig. 1 is the growing apparatus synoptic diagram, wherein: 1, autoclave, 2, raw material, 3, baffle plate, 4, seed crystal, 5, sealing plug, 6, wear ring, 7, fastening nut.
The yellow crystal of Fig. 2, embodiment 1 growth.
The yellow crystal of Fig. 3, embodiment 2 growths.
The prasioleta of Fig. 4 embodiment 3 growths
The citrite of Fig. 5 embodiment 4 growths
Be most preferred embodiment of the present invention below:
Embodiment 1: the growth of yellow crystal
The quartzy material of melting level 45g, φ 22mm autoclave, the rock crystal sheet is made seed crystal, and degree of filling is F=87%, and the baffle openings rate is 20%, 4%K
2CO
3Deionized water solution, 0.05%K
2Cr
2O
7, 4%H
2O
2, above-mentioned batching is placed autoclave, sealing heats up, and the crystallizing field temperature is 310 ℃, and the dissolve area temperature is 340 ℃, 30 ℃ of the temperature difference, pressure 150MPa, growth cycle 13 days, crystal Z is 0.3mm/ days to the speed of growth, obtains yellow transparent crystal.
Embodiment 2: the growth of yellow crystal
As described in embodiment 1, difference is quartz raw material 5000g, φ 120mm autoclave, 5% K
2CO
3Solution, 0.07%K
2Cr
2O
7, degree of filling is 84%, 325 ℃ of crystallizing field temperature, dissolve area temperature are 360 ℃, and 35 ℃ of the temperature difference, the plate washer aperture opening ratio is 7.9%, growth cycle 50 days, Z is 0.5mm/ days to the speed of growth, crystalline size 170 * 65 * 28(mm).
Embodiment 3: the growth of prasioleta
As described in embodiment 1, difference is, 6% K
2CO
3Solution, doping agent are 0.5%Fe
2(SO
4)
3XH
2O does not add H
2O
2, degree of filling is 82%, 335 ℃ of crystallizing field temperature, and 370 ℃ of dissolve area temperature, 35 ℃ of the temperature difference, pressure is 110MPa, growth cycle 21 days, the speed of growth (Z) 0.4mm/ days.
Embodiment 4: the growth of citrite
As described in embodiment 3, difference is, 6.9% K
2CO
3Solution, doping agent are 0.1% 2CoCO
33Co(OH)
2XH
2O, degree of filling are 82%, and the crystallizing field temperature is 345 ℃, and the dissolve area temperature is 380 ℃, 35 ℃ of the temperature difference, and pressure 130MPa growth cycle 19 days, the speed of growth is 0.3mm/ days.
The invention has the advantages that, growth technique conditional stability, repeatability is good, and strong adaptability without the liner autoclave, is convenient to promote, and batch production, cost are low, and crystal property is stable. The colour crystal that this method grows is precious Gem Grade crystal, can be used to process multiple jewellery and ornament, and is lucuriant in design, graceful true to nature, wherein, yellow quartz belongs to directly painted, does not need irradiation, 400 ℃ lower colour-fast, is the ideal material of making lens, and yellow crystal is at K2Cr
2O
7Strong oxidizer H is arranged in the adulterant2O
2Grow successfully under the condition that exists, also belong to international initiative, also colour-fast under 400 ℃, prasioleta can be compared U.S. with " emerald ", enjoy favor in market, above-mentioned color brilliant growth successfully be the Crystal lamp market of becoming increasingly active, and jewellery market etc. provides the raw material that enriches, and certain facilitation has been played in the life that beautifies and enrich the people.
Reference
1, Tian Fu harvests technical chemistry magazine (Japan) Vol.68 NO.10 (1965) P1862
2、KVRT NASSAN Gems Made By Man CHILTON BOOK COMPANY Radnor Pennsylvania IS BNO-8019-6773-2 P116
Claims (10)
1, the growth method of colour crystal adopts the direct coloring process of Hydrothermal Growth, uses modified version Bridgman formula sealing autoclave, internal diameter φ 22-φ 240mm, interior dark 360-4700mm, volume 145-210000ml is a raw material with melting level quartz, be invested in the high-temperature digestion district, bottom of still by autoclave volumetrical 1/3, seed crystal is the thick rock crystal sheet of 1-2mm, and seed orientation is Z, or AT or X section hangs on the seed crystal frame, put the cold zone of autoclave internal upper part, the K of 1-8%
2CO
3Deionized water solution, compactedness 80-90%, the dissolve area temperature is controlled at 350-390 ℃, and the crystallizing field temperature is controlled at 300-350 ℃, and the plate washer aperture opening ratio is 20-5% between two districts, and growing period pressure is 70-150MPa, growth cycle is 13-15 days.Crystalline growth velocity Z is to being 0.2-0.8mm/ days,
Add doping agent concentration be 0.01-0.5%;
(1) yellow crystal, doping agent K
2Cr
2O
7, add the H of 2-5% again
2O
2
(2) prasioleta, doping agent Fe
2(SO
4)
3XH
2O.
(3) citrite, doping agent 2CoCO
33Co (OH)
2XH
2O.
2, colour crystal growth method as claimed in claim 1 is characterized in that be good with homochromy crystal as seed crystal.
3, colour crystal growth method as claimed in claim 1 is characterized in that used autoclave is no liner autoclave, must " plating " protective layer before the crystal of all kinds of growing first.
4, colour crystal growth method as claimed in claim 1 is characterized in that, growth yellow crystal H
2O
2Add-on is good with 3.5-4.5%.
5, colour crystal growth method as claimed in claim 1 is characterized in that, the Tc optimum value of yellow crystal is 310-325 ℃.
6, colour crystal growth method as claimed in claim 1 is characterized in that, the yellow crystal growth, and the temperature difference is good with 30-35 ℃.
7, colour crystal growth method as claimed in claim 1 is characterized in that, the growth of prasioleta, K
2CO
3The concentration of solution is best with 5-6%.
8, colour crystal growth method as claimed in claim 1 is characterized in that, the growth of citrite, K
2CO
3Strength of solution is best with 6-7%.
9, colour crystal growth method as claimed in claim 1 is characterized in that Huang, green, the citrite speed of growth were good with 0.3-0.5mm/ days.
10, colour crystal growth method as claimed in claim 1 is characterized in that green, citrite growth, and degree of filling is best with 82-83%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89106859 CN1016715B (en) | 1989-11-25 | 1989-11-25 | Growth method of colour crystal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89106859 CN1016715B (en) | 1989-11-25 | 1989-11-25 | Growth method of colour crystal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1052154A true CN1052154A (en) | 1991-06-12 |
| CN1016715B CN1016715B (en) | 1992-05-20 |
Family
ID=4856930
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 89106859 Expired CN1016715B (en) | 1989-11-25 | 1989-11-25 | Growth method of colour crystal |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1016715B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103710751A (en) * | 2014-01-09 | 2014-04-09 | 辽宁工业大学 | Electric smelting method-based preparation of color quartz crystals |
| CN103938264A (en) * | 2014-04-29 | 2014-07-23 | 三明市港乐水晶电子有限公司 | Method for growing optical crystal |
| CN104988575A (en) * | 2015-06-25 | 2015-10-21 | 北京石晶光电科技股份有限公司济源分公司 | Reaction kettle and technology used for growing yellow crystals |
-
1989
- 1989-11-25 CN CN 89106859 patent/CN1016715B/en not_active Expired
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103710751A (en) * | 2014-01-09 | 2014-04-09 | 辽宁工业大学 | Electric smelting method-based preparation of color quartz crystals |
| CN103710751B (en) * | 2014-01-09 | 2016-05-04 | 辽宁工业大学 | The electric smelting legal system of colored quartz crystal is standby |
| CN103938264A (en) * | 2014-04-29 | 2014-07-23 | 三明市港乐水晶电子有限公司 | Method for growing optical crystal |
| CN104988575A (en) * | 2015-06-25 | 2015-10-21 | 北京石晶光电科技股份有限公司济源分公司 | Reaction kettle and technology used for growing yellow crystals |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1016715B (en) | 1992-05-20 |
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