CN101407402A - Beryllium aluminate crystal substrate color changing gem, and preparation and growth apparatus thereof - Google Patents
Beryllium aluminate crystal substrate color changing gem, and preparation and growth apparatus thereof Download PDFInfo
- Publication number
- CN101407402A CN101407402A CNA2008101220291A CN200810122029A CN101407402A CN 101407402 A CN101407402 A CN 101407402A CN A2008101220291 A CNA2008101220291 A CN A2008101220291A CN 200810122029 A CN200810122029 A CN 200810122029A CN 101407402 A CN101407402 A CN 101407402A
- Authority
- CN
- China
- Prior art keywords
- beo
- crystal
- preparation
- gem
- powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000013078 crystal Substances 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000758 substrate Substances 0.000 title claims abstract description 15
- -1 Beryllium aluminate Chemical class 0.000 title claims abstract description 14
- 229910052790 beryllium Inorganic materials 0.000 title claims abstract description 14
- 239000010437 gem Substances 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 29
- 230000008859 change Effects 0.000 claims abstract description 8
- 230000003068 static effect Effects 0.000 claims abstract description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 26
- 239000000843 powder Substances 0.000 claims description 26
- 239000010439 graphite Substances 0.000 claims description 23
- 229910002804 graphite Inorganic materials 0.000 claims description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 13
- 238000009413 insulation Methods 0.000 claims description 11
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 11
- 229910052721 tungsten Inorganic materials 0.000 claims description 11
- 239000010937 tungsten Substances 0.000 claims description 11
- 238000005516 engineering process Methods 0.000 claims description 10
- 238000011081 inoculation Methods 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- 239000002019 doping agent Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000010431 corundum Substances 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- 238000005086 pumping Methods 0.000 claims description 4
- 238000010583 slow cooling Methods 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 239000000919 ceramic Substances 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 229910001602 chrysoberyl Inorganic materials 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 11
- 150000002500 ions Chemical class 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000010923 batch production Methods 0.000 abstract description 2
- 230000008901 benefit Effects 0.000 abstract description 2
- 230000002950 deficient Effects 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 230000007704 transition Effects 0.000 abstract 1
- 229910001751 gemstone Inorganic materials 0.000 description 26
- 241000282326 Felis catus Species 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 6
- NNBFNNNWANBMTI-UHFFFAOYSA-M brilliant green Chemical compound OS([O-])(=O)=O.C1=CC(N(CC)CC)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](CC)CC)C=C1 NNBFNNNWANBMTI-UHFFFAOYSA-M 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 239000000498 cooling water Substances 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 239000002932 luster Substances 0.000 description 2
- 230000009347 mechanical transmission Effects 0.000 description 2
- 238000005204 segregation Methods 0.000 description 2
- 241000579895 Chlorostilbon Species 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229910052876 emerald Inorganic materials 0.000 description 1
- 239000010976 emerald Substances 0.000 description 1
- 238000007716 flux method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000010977 jade Substances 0.000 description 1
- 239000000087 laser glass Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000010979 ruby Substances 0.000 description 1
- 229910001750 ruby Inorganic materials 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium atom Chemical compound [Tm] FRNOGLGSGLTDKL-UHFFFAOYSA-N 0.000 description 1
Images
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention discloses a beryllium aluminate crystal substrate phenomenal gem, a preparation method and a growth device thereof, which is characterized in that, in a special growth device, BeAl2O4 monocrystal substrate is proportionally blended with Cr<3+>, Fe<3+>, Ti<3+> or Ni<2+> three transition element ions, and a vertical static temperature gradient method is used for preparing the artificial phenomenal gem with strong color change effect. The invention aims at meeting the constant requirements of people on the color and hue of the gems of chrysopal group, wishing that more distinct variation can be obtained in the aspect of color change effect between red and green, and solving the civil batch production problem of the gem. The phenomenal gem which can generate broader color and hue has obvious color change effect between red and green. The preparation method has the advantages of obviously enhancing mass output rate, having relatively simple equipment, and overcoming the defective impact of mechanical drive and vibration on crystal growth, thus being beneficial to the scale production of high-quality gems.
Description
Technical field
The present invention relates to special glass, be specifically related to a kind of thulium adulterated germanate laser glass and preparation method thereof.
Background technology
Natural natural gemstone is of a great variety, comprises ruby, sapphire, emerald, jade ... or the like, these jewels have gorgeous color and luster, and hard quality is the jewel that people like.The crystal of chrysoberyl family particularly: three kinds of jewels of the purple emerald green alexandrite (Alexandrite) of chrysoberyl cat's eye (Chrysoberyl Cat ' s Eye), chrysoberyl (Chrysoberyl) and Alexandria are rare special jewels, cost an arm and a leg, be loved by the people, the commercial market amount is big, but these jewel natural resource seldom, can not satisfy the growing demand of people, the technology of the above-mentioned jewel of synthetic therefore occur.The technology that adopts mainly contains: liquation method, hydrothermal method, flame method and flux method etc., but the crystal blank that these methods obtain is too little, does not have actual decorative value.J.C.Walling etal (saw in the U.S. in 1980, " Tunable Alexandrite Lasers " IEEE Journal of Quantum Electronics, QE16 (12), (1980): 1302～1315) (see that a new people waits artificial lens journal 28 (2) (1999): 210-214) begin report crystal pulling method technology growth BeAl with Shanghai ray machine institute of the Chinese Academy of Sciences in 1999
2O
4Crystal.
Crystal pulling method is raw material to be put into iridium crucible be fused into melt, allows seed crystal contact bath surface under proper temperature, the lifting crystal growth that slowly makes progress then.Crystal diameter be limited to the crucible bore 1/3～1/2 but the crystal pulling method technology has only 1/4 raw material can be drawn as color and luster available crystal, and crystal pulling method equipment complexity, the technical requirements height, the output/output-input ratio that is used for producing such civilian jewel is low, is unfavorable for producing in batches.In addition, because adulterated ionic valence state can not get optimum control, crystal pulling method is difficult to produce chrysoberyl cat's eye and chrysoberyl.
The basal component of the chrysoberyl cat's eye of synthetic, chrysoberyl, the purple emerald green alexandrite of Alexandria is identical, i.e. Al
2O
3And BeO, be contained doping agent difference.Chrysoberyl cat's eye is at BeAl
2O
4Mix Fe in the crystal simultaneously
2O
3With TiO
2Chrysoberyl is at BeAl
2O
4In mix Fe
2O
3The purple emerald green alexandrite of Alexandria is at BeAl
2O
4Mix Cr in the monocrystalline
2O
3With V
2O
5
In patent documentation, put down in writing the technology of the above-mentioned three kinds of jewels of some newer synthetic in recent years, for example, Chinese patent notification number CN1033313C, November 20 1996 Granted publication day, denomination of invention " manufacture method of artificial cat's eye ", this method adopt the cat's eye jewel of the various colors of preparation such as concentric crucible method, toning process; Chinese patent notification number CN1062318C, February 21 calendar year 2001 Granted publication day, denomination of invention " growth method and the device thereof of chrysoberyl family non-functional jewel ", the growth method that this invention is adopted is the warm terraced method of rotation, growing apparatus is the rotation gradient furnace, can prepare chrysoberyl cat's eye respectively, chrysoberyl, the purple emerald green alexandrite of Alexandria, the process that is characterized in crystal growth is from the melt bottom upwards, crucible can rotate or move up and down, can replenish reinforced from the crucible top or replenish and add required impurity, its weak point is to produce the jewel that produces specific color, the jewel that obtains can not produce broad tone, effect is undesirable aspect red and green color changeable effect, simultaneously because the detrimentally affect that mechanical transmission and vibration bring crystal growth, such as in crystal, producing a large amount of colour bands, defectives such as striation have a strong impact on the crystalline quality.
Above-mentioned jewel synthetic technology can only be produced the jewel that produces specific color, and the jewel tone that obtains is single, and effect is undesirable aspect red and green color changeable effect.Along with improving constantly of people's life, the color and the tone of such high-grade jewel are had higher requirement, wish that jewel produces broad more color and tone, distinct more variation is being arranged aspect red and the green color changeable effect.This just requires at BeAl
2O
4Introduce multiple doping agent in the crystal growing process simultaneously, the various ionic valence states of strict control are to obtain the color changeable effect that the client needs.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art part, a kind of beryllium aluminate crystal substrate color changing gem is provided, its preparation method and growing apparatus, to satisfy the continuous requirement of people to the color and the tone of such high-grade jewel, wishing is having distinct more variation aspect red and the green color changeable effect; And solve the civilian batch process problem of such jewel.
The present invention solves the problems of the technologies described above the technical scheme that is adopted: a kind of beryllium aluminate crystal substrate color changing gem is characterized in that at BeAl
2O
4In the monocrystalline, mix Cr
2O
3, Fe
2O
3, Ti
2O
3Or three kinds of doping agents of NiO, its molar percentage is respectively:
Cr
2O
3 0～0.3％
Fe
2O
3 0～0.6％
Ti
2O
3Or NiO 0～0.2%.
Producing the preparation method that this kind jewel adopted is:
A kind of preparation method of beryllium aluminate crystal substrate color changing gem is characterized in that comprising the steps:
1., batching: composition of raw materials is calculated as follows respectively, according to actual doping content, takes by weighing the Al of corresponding weight respectively
2O
3Crystal block, BeO briquetting, Cr
2O
3Powder, Fe
2O
3Powder and Ti
2O
3Powder, all material purities are all greater than 99.99%:
(1-x-y-z)Al
2O
3+BeO+xCr
2O
3+yFe
2O
3+zTi
2O
3→BeAl
2-2x-2y-2zCr
2xFe
2yTi
2zO
4(1-u-v-w)Al
2O
3+BeO+uCr
2O
3+vFe
2O
3+wNiO→BeAl
2-2u-2v-wCr
2uFe
2vNi
wO
4-wO
2
Wherein: x=0～0.003, y=0～0.006, z=0～0.002, w=0～0.002;
2., reinforced and change material: adopt secondary material technology. first timeization material: a part of BeO, the Al that weigh up
2O
3Join the bottom with doping agent BeAl has been housed
2O
4In the tungsten crucible of crystal seed (c direction of principal axis), keep the relative Al of BeO
2O
3Excessive, after the shove charge, vacuumize, charge into the 0.4atm argon gas, the furnace temperature that slowly raises then is incubated 8 hours to 1800-1870 ℃, slowly cooling. the second time remaining all substances are packed in the crucible;
3., inoculation: the stove pumping high vacuum reaches 1.3*10
-3After handkerchief is above, charge into the argon gas of 0.4atm, slow elevated temperature, according to thermocouple signal, the control crystal seed is in the inoculation state, keeps stove under this state of temperature 4～10 hours;
4., crystal growth: the heating power with computer control stove, make its slow cooling, along with decrease of temperature, growth interface moves from lower to upper, carries out crystal growth.
5., cooling: after waiting crystallization to finish, can suitably accelerate cooling rate,, pour out crystal, remove the opaque resistates on top, obtain transparent crystals up to room temperature.
The 1. described BeO briquetting of above-mentioned steps is through 1.2*10 with the BeO powder
3MPa is pressed into briquetting, afterwards 1200 ℃ of sintering 8 hours.
2. described the feeding in raw material of above-mentioned steps is with BeO and Al
2O
3Two kinds of cross layered placements of composition, below BeO is put in, Cr
2O
3Powder, Fe
2O
3Powder and Ti
2O
3Powder evenly is put in every layer of raw material.
The 3. described inoculation state of above-mentioned steps is meant that the top crystal seed is in melted state, and the bottom still is a crystal, and this moment, top crystal seed and melt temperature were greater than 1870 ℃.
The 4. described slow cooling of above-mentioned steps is to lower the temperature with 1.5 ℃/h speed.
The 5. described cooling of above-mentioned steps is to cool off respectively one day with 3 ℃/h and 6 ℃/h, at last with 10 ℃/h speed cool to room temperature always.
The structural representation of the device that the present invention is used as shown in Figure 1.Its body of heater comprises and placing in the graphite heater 2, the ZrO that is supported by collet 6
2The tungsten crucible 3 that holds raw material and be stamped crucible cover plate 1 is arranged on the ceramic base 5, and the seed mixer 4 of placing crystal seed is arranged at the bottom of crucible 3, and graphite heater 2 passes through by Al
2O
3Graphite Electrodes 12 and electrode 10 that corundum post 9 supports link with external power, and the insulation of going up molybdenum sheet 17 is arranged above the graphite heater 2, and insulation molybdenum sheet 8 is down arranged below, are incubated molybdenum sheet 16 around having on every side, are incubated molybdenum sheet 16 logical Al all around
2O
3Corundum insulation layer 13 links with Graphite Electrodes 12, graphite fixed plate 14 is fixed together Graphite Electrodes 12 and graphite heater 2, press close to graphite heater 2 and tungsten crucible 3 bottoms temperature thermocouple 1 and following thermopair 11 are arranged, stainless steel water-cooled tube 7 passes down insulation molybdenum sheet 8 and links with collet 6, graphite heater 2, on be incubated molybdenum sheet 17, the wall thickness that is incubated molybdenum sheet 8 and insulation molybdenum sheet 16 down is adjustable.Graphite wall thickness by position about change heating element 2 cylinders can be regulated the heating power of position, top and the bottom, regulates the temperature of different sites up and down thereby reach; By regulating up and down and all around insulation molybdenum shield layer thickness adjustable space temperature distribution; Regulate the cooling water flow of bottom stainless steel waterpipe 7 and can regulate the distribution of thermograde.
Because crystal growth is to finish with strict vertical temperature gradient by the precision control of temperature, sees accompanying drawing 2, all devices all is in a kind of stationary state in process of growth, therefore claims vertical static temperature gradient method.
Advantage of the present invention; Cr
3+Ionic mixes and makes crystal show purple emerald green look; Fe
3+With Ti
3+Ion doping makes crystal show bright red, Ni
2+Ionic mixes and makes crystal show blueness.Cr
3+The segregation coefficient of ion in this crystal is 1.3, Fe
3+The ionic segregation coefficient is 1, Ti
3+With Ni
2+All less than 1.These ionic mix jointly and can make jewel produce broad more color and tone, and the jewel of acquisition has significantly red green color changeable effect, sees accompanying drawing 3.Also can adjust doping content according to the color and the tone of market demand.1. thermograde mainly by changing the graphite wall thickness of heating element cylinder in the stove of this method; 2. by regulating up and down and all around the insulation molybdenum shield number of plies and thickness; The means such as cooling water flow of 3. regulating the bottom stainless steel waterpipe realize that comparatively ideal vertical temperature gradient distributes, and sees accompanying drawing 2.This method can obviously improve the crystalline mass output rate, and equipment is simple relatively and high temperature resistant.Tungsten and molybdenum material and high purity graphite are at the high temperature that can bear under vacuum and the inert atmosphere more than 2300 ℃, the iraurite crucible that uses in the crystal pulling method, design to the temperature field brings very big adjusting space, overcome because action of high temperature makes iraurite crucible cracky, and oxidation and the loss and cause the unfavorable factors such as raising of cost in use of precious metal iraurite.Simultaneously owing to be stationary state, overcome since mechanical transmission to crystal growth bring such as in crystal, producing a large amount of colour band, striation, have a strong impact on undesirable elements such as crystalline quality, help the scale production of the above-mentioned jewel of fine.
Description of drawings
Fig. 1 is the structural representation of equipment therefor of the present invention;
Fig. 2 is the temperature gradient distribution curve (X-axis is a temperature, and Y-axis is a crucible length) of embodiment 1～3;
Fig. 3 (a) is the Cr of embodiment 1 preparation
3+, Fe
3+, Ti
3+Mix BeAl altogether
2O
4Jewel captured photochrome figure under sunlight:
Fig. 3 (b) is the Cr of embodiment 1 preparation
3+, Fe
3+, Ti
3+Mix BeAl altogether
2O
4Jewel captured photochrome figure under tungsten light.
Embodiment
Embodiment describes in further detail the present invention below in conjunction with accompanying drawing.
Embodiment 1
A, batching:,, carry out weighing according to actual doping content according to following reaction formula
(1-x-y-z)Al
2O
3+BeO+xCr
2O
3+yFe
2O
3+zTi
2O
3→BeAl
2-2x-2y-2zCr
2xFe
2yTi
2zO
4
Wherein: Cr
2O
3(x) be 0.15mol%, Fe
2O
3(y) be 0.15mol%, Ti
2O
3(z) adopt Al for the 0.1mol%. raw material
2O
3Crystal block, BeO briquetting, Cr
2O
3Powder, Fe
2O
3Powder and Ti
2O
3Powder. all material purities are all greater than 99.99%.
B, reinforced and change material: carry out the secondary material. first timeization material is BeO, the Al of 3/5 mole of part of the 2/3 mole of part that weighs up
2O
3, the Cr of half
2O
3Powder, Fe
2O
3Powder and Ti
2O
3Powder joins the bottom BeAl has been housed
2O
4In the tungsten crucible of crystal seed (c direction of principal axis). in mixture, keep the relative Al of BeO molar weight
2O
3Excessive. in crucible, BeO and Al
2O
3Two kinds of cross layered placements of composition are below BeO is put in, in case the light and come-up .Cr of BeO during fusion
2O
3Powder, Fe
2O
3Powder and Ti
2O
3Powder evenly is put in every layer of raw material. and after the shove charge, vacuumize, charge into the 0.4atm argon gas, slowly being warmed up to furnace temperature then is 1860 ℃, is incubated after 8 hours, slowly cooling. and second timeization material is remaining BeO, Al
2O
3With the other Cr of half
2O
3Powder, Fe
2O
3Powder and Ti
2O
3Powder joins in the crucible. with for the first time similar, and BeO and Al
2O
3Keep cross layered placement, during hotchpotch evenly is put in every layer.
C, inoculation: the stove pumping high vacuum reaches 1.3*10
-3After handkerchief is above, charge into the argon gas of 0.4atm, slowly elevated temperature according to following thermocouple signal 11, is regulated and the control furnace, makes crystal seed be in the inoculation state, and it is shown in Figure 2 that the temperature distribution of stove is seen, kept this state of temperature balance 6 hours;
D, crystal growth: with the power of computer control stove, make it slowly with the cooling of 1.5 ℃/h speed, along with decrease of temperature, growth interface moves from lower to upper, and crystal growth is progressively carried out;
E, cooling: lower the temperature after 7 days, crystalline growth finishes, and suitably accelerates speed of cooling, cools off respectively one day with 3 ℃/h and 6 ℃/h, at last with 10 ℃/h speed cool to room temperature always;
F, vacuumize and exit, open stove then, take out the crystalline crucible is housed. because slick crucible inner wall surface and crystal combination are not firm, beat crucible, crystal can come off from crucible, takes out crystal, removes the opaque resistates on top, obtains transparent crystals.
Embodiment 2:
A, batching:,, carry out weighing according to actual doping content according to following reaction formula
(1-u-v-w)Al
2O
3+BeO+uCr
2O
3+vFe
2O
3+wNiO→BeAl
2-2u-2v-wCr
2uFe
2vNi
wO
4-wO
2
Wherein: Cr
2O
3(x) be 0.15mol%, Fe
2O
3(y) be 0.1mol% for 0.15mol%, NiO.Raw material adopts Al
2O
3Crystal block, BeO briquetting, Cr
2O
3Powder, Fe
2O
3Powder and NiO powder.All material purities are all greater than 99.99%.
B, change material: take the secondary material. first timeization material is BeO, the Al of 1/2 mole of part of the 2/3 mole of part that weighs up
2O
3, the Cr of half
2O
3Powder, Fe
2O
3Powder and NiO powder join the bottom BeAl have been housed
2O
4In the tungsten crucible of crystal seed (c direction of principal axis). in mixture, keep the relative Al of BeO molar weight
2O
3Excessive. in crucible, BeO and Al
2O
3Two kinds of cross layered placements of composition are below BeO is put in, in case the light and come-up .Cr of BeO during fusion
2O
3Powder, Fe
2O
3Powder and NiO powder evenly are put in every layer of raw material. and after the shove charge, vacuumize, charge into the 0.4atm argon gas, slowly being warmed up to furnace temperature then is 1850 ℃, is incubated after 8 hours, slowly cooling. and second timeization material is remaining BeO, Al
2O
3With the other Cr of half
2O
3Powder, Fe
2O
3Powder and NiO powder join in the crucible. with for the first time similar, and BeO and Al
2O
3Keep cross layered placement, during hotchpotch evenly is put in every layer.
C, inoculation: the stove pumping high vacuum reaches 1.3*10
-3After handkerchief is above, charge into the argon gas of 0.4atm, slowly elevated temperature according to following thermocouple signal 11, is regulated and the control furnace, makes crystal seed be in the inoculation state, and it is shown in Figure 2 that the temperature distribution of stove is seen, kept this state of temperature balance 6 hours;
D, crystal growth: with the power of computer control stove, make it slowly with the cooling of 1.5 ℃/h speed, along with decrease of temperature, growth interface moves from lower to upper, and crystal growth is progressively carried out;
E, cooling: lower the temperature after 7 days, crystalline growth finishes, and suitably accelerates speed of cooling, cools off respectively one day with 3 ℃/h and 6 ℃/h, at last with 10 ℃/h speed cool to room temperature always;
F, vacuumize and exit, open stove then, take out the crystalline crucible is housed. because slick crucible inner wall surface and crystal combination are not firm, beat crucible, crystal can come off from crucible, just takes out crystal.Remove the opaque resistates on top, obtain transparent crystals.
Embodiment 3:
According to following reaction formula,, carry out weighing and batching according to actual doping content
(1-x-y-z)Al
2O
3+BeO+xCr
2O
3+yFe
2O
3+zTi
2O
3→BeAl
2-2x-2y-2zCr
2xFe
2yTi
2zO
4
Wherein: Cr
2O
3(x) be 0.2mol%, Fe
2O
3(y) be 0.5mol%, Ti
2O
3(z) be 0.2mol%.
Other technological processs are embodiment 1. roughly the same
Embodiment 4:
According to following reaction formula,, carry out weighing and batching according to actual doping content
(1-x-y-z)Al
2O
3+BeO+xCr
2O
3+yFe
2O
3+zTi
2O
3→BeAl
2-2x-2y-2zCr
2xFe
2yTi
2zO
4
Wherein: Cr
2O
3(x) be 0.1mol%, Fe
2O
3(y) be 0.1mol%, Ti
2O
3(z) be 0.05mol%.
Other technological processs are embodiment 1. roughly the same
Embodiment 5:
According to following reaction formula,, carry out weighing and batching according to actual doping content
(1-u-v-w)Al
2O
3+BeO+uCr
2O
3+vFe
2O
3+wNiO→BeAl
2-2u-2v-wCr
2uFe
2vNi
wO
4-wO
2
Wherein: Cr
2O
3(x) be 0.3mol%, Fe
2O
3(y) be 0.2mol% for 0.5mol%, NiO.
Other technological processs are embodiment 2. roughly the same
Embodiment 6:
According to following reaction formula,, carry out weighing and batching according to actual doping content
(1-u-v-w)Al
2O
3+BeO+uCr
2O
3+vFe
2O
3+wNiO→BeAl
2-2u-2v-wCr
2uFe
2vNi
wO
4-wO
2
Wherein: Cr
2O
3(x) be 0.1mol%, Fe
2O
3(y) be 0.1mol% for 0.1mol%, NiO.
Other technological processs are embodiment 2. roughly the same
Claims (8)
1. a beryllium aluminate crystal substrate color changing gem is characterized in that at BeAl
2O
4In the monocrystalline, be mixed with Cr
2O
3, Fe
2O
3, Ti
2O
3Or three kinds of doping agents of NiO, its molar percentage is respectively:
Cr
2O
3 0～0.3％
Fe
2O
3 0～0.6％
Ti
2O
3Or NiO 0～0.2%.
2. according to the preparation method of the beryllium aluminate crystal substrate color changing gem of claim 1, what it is characterized in that adopting in the crystalline process of growth is vertical static temperature gradient method, comprises the steps:
1., batching: composition of raw materials is calculated as follows respectively, according to actual doping content, takes by weighing the Al of corresponding weight respectively
2O
3Crystal block, BeO briquetting, Cr
2O
3Powder, Fe
2O
3Powder and Ti
2O
3Powder, all material purities are all greater than 99.99%:(1-x-y-z) Al
2O
3+ BeO+xCr
2O
3+ yFe
2O
3+ zTi
2O
3→ BeAl
2-2x-2y-2zCr
2xFe
2yTi
2zO
4(1-u-v-w) Al
2O
3+ BeO+uCr
2O
3+ vFe
2O
3+ wNiO → BeAl
2-2u-2v-wCr
2uFe
2vNi
wO
4-wO
2Wherein: x=0～0.003, y=0～0.006, z=0～0.002, w=0～0.002;
2., reinforced and change material: adopt secondary material technology. first timeization material: a part of BeO, the Al that weigh up
2O
3Join the bottom with doping agent BeAl has been housed
2O
4In the tungsten crucible of crystal seed (c direction of principal axis), keep the relative Al of BeO
2O
3Excessive, after the shove charge, vacuumize, charge into the 0.4atm argon gas, furnace temperature to 1800～1870 ℃ of slowly raising then are incubated 8 hours, slowly cooling. for the second time remaining all substances are packed in the crucible;
3., inoculation: the stove pumping high vacuum reaches 1.3*10
-3After handkerchief is above, charge into the argon gas of 0.4atm, slow elevated temperature, according to thermocouple signal, the control crystal seed is in the inoculation state, keeps stove under this state of temperature 4～10 hours;
4., crystal growth: the heating power with computer control stove, make its slow cooling, along with decrease of temperature, growth interface moves from lower to upper, carries out crystal growth;
5., cooling: after waiting crystallization to finish, can suitably accelerate cooling rate,, pour out crystal, remove the opaque resistates on top, obtain transparent crystals up to room temperature.
3. according to the preparation method of the beryllium aluminate crystal substrate color changing gem of claim 2, it is characterized in that the 1. described BeO briquetting of step is through 1.2*10 with the BeO powder
3MPa is pressed into briquetting, afterwards 1200 ℃ of sintering 8 hours.
4. according to the preparation method of the beryllium aluminate crystal substrate color changing gem of claim 2, it is characterized in that step 2. described reinforced be with BeO and Al
2O
3Two kinds of cross layered placements of composition, below BeO is put in, Cr
2O
3Powder, Fe
2O
3Powder and Ti
2O
3Powder evenly is put in every layer of raw material.
5. according to the preparation method of the beryllium aluminate crystal substrate color changing gem of claim 2, it is characterized in that the 3. described inoculation state of step is meant that the top crystal seed is in melted state, the bottom still is a crystal, and this moment, top crystal seed and melt temperature were greater than 1870 ℃.
6. according to the preparation method of the beryllium aluminate crystal substrate color changing gem of claim 2, it is characterized in that the 4. described slow cooling of step is to lower the temperature with 1.5 ℃/h speed.
7. according to the preparation method of the beryllium aluminate crystal substrate color changing gem of claim 2, it is characterized in that the 5. described cooling of step is to cool off respectively one day with 3 ℃/h and 6 ℃/h, at last with 10 ℃/h speed cool to room temperature always.
8, the used growing apparatus of the preparation method of the described beryllium aluminate crystal substrate color changing gem of claim 2, its body of heater comprise and placing in the graphite heater (2), the ZrO that is supported by collet (6)
2The tungsten crucible (3) that holds raw material and be stamped crucible cover plate (1) is arranged on the ceramic base (5), and the seed mixer (4) of placing crystal seed is arranged at the bottom of tungsten crucible (3), and graphite heater (2) passes through by Al
2O
3Graphite Electrodes (12) that corundum post (9) supports and electrode (10) link with external power, and the insulation of going up molybdenum sheet (17) is arranged above the graphite heater (2), and insulation molybdenum sheet (8) is down arranged below, are incubated molybdenum sheet (16) around having on every side, are incubated the logical Al of molybdenum sheet (16) all around
2O
3Corundum insulation layer (13) links with Graphite Electrodes (12), graphite fixed plate (14) is fixed together Graphite Electrodes (12) and graphite heater (2), press close to graphite heater (2) and tungsten crucible (3) bottom temperature thermocouple (15) and following thermopair (11) are arranged, stainless steel water-cooled tube (7) passes down insulation molybdenum sheet (8) and links with collet (6), it is characterized in that graphite heater (2), on be incubated molybdenum sheet (17), the wall thickness that is incubated molybdenum sheet (8) and is incubated molybdenum sheet (16) all around down is adjustable.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101220291A CN101407402B (en) | 2008-10-28 | 2008-10-28 | A kind of preparation method of beryllium aluminate crystal matrix color-changing gemstone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101220291A CN101407402B (en) | 2008-10-28 | 2008-10-28 | A kind of preparation method of beryllium aluminate crystal matrix color-changing gemstone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101407402A true CN101407402A (en) | 2009-04-15 |
| CN101407402B CN101407402B (en) | 2011-03-30 |
Family
ID=40570645
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008101220291A Expired - Fee Related CN101407402B (en) | 2008-10-28 | 2008-10-28 | A kind of preparation method of beryllium aluminate crystal matrix color-changing gemstone |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101407402B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108060456A (en) * | 2017-12-12 | 2018-05-22 | 中国科学院上海光学精密机械研究所 | The Bridgman-Stockbarger method of beryllium aluminate crystal |
-
2008
- 2008-10-28 CN CN2008101220291A patent/CN101407402B/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108060456A (en) * | 2017-12-12 | 2018-05-22 | 中国科学院上海光学精密机械研究所 | The Bridgman-Stockbarger method of beryllium aluminate crystal |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101407402B (en) | 2011-03-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103370452B (en) | Preparation of doped garnet structure single crystals with diameters of up to 500 mm | |
| Osiko et al. | Synthesis of refractory materials by skull melting technique | |
| CN106498488B (en) | A variety of doping CaF are grown simultaneously2The device of crystal and preparation method based on the device | |
| JP2011190127A (en) | Gallium oxide single crystal and method for producing the same | |
| CN102758249A (en) | Method for preparing colorless corundum monocrystal | |
| CN107699950A (en) | One kind mixes scandium terbium aluminium garnet magneto-optical crystal and preparation method thereof | |
| CN101054723A (en) | Method for growing R-surface sapphire crystal | |
| EP4194415A1 (en) | High-transparency fluorescent glass-ceramic, and preparation method therefor and application thereof | |
| CN104451564B (en) | A kind of method preparing siliceous target | |
| CN102061522B (en) | Two-step method for preparing large-sized Al2O3-based crystals | |
| CN107937983A (en) | A kind of sapphire material of multicomponent doping and its preparation method and application | |
| CN108203844A (en) | Tantalic acid magnesium serial crystal and preparation method thereof | |
| CN1225572C (en) | Integrated melt method for crystal growth | |
| CN111575795A (en) | Preparation method of blue morusite | |
| CN110067024B (en) | Photoelectric functional crystal M3RE(PO4)3And method for preparing the same | |
| CN108373261A (en) | Artificial color changing gem and preparation method thereof | |
| CN102260914A (en) | Growth method of large dimension LGS crystal | |
| JP5688589B2 (en) | Melt composition controlled unidirectionally solidified crystal growth apparatus and crystal growth method | |
| CN106987903B (en) | A kind of improved large scale synthetic sapphire production technology | |
| CN101407402A (en) | Beryllium aluminate crystal substrate color changing gem, and preparation and growth apparatus thereof | |
| JP2010143782A (en) | Melt composition control unidirectional solidification crystal growth apparatus and crystal growth method | |
| KR100753322B1 (en) | Method and apparatus for preparing crystal | |
| CN102383186B (en) | Method of growing Ca12Al14O33 single crystal in non-stoichiometric melt by pulling method | |
| CN206385277U (en) | A kind of silicon solar hypoxemia, low light attenuation monocrystal thermal-field | |
| JP2012101946A (en) | Quartz glass crucible and method for producing the same, and method for producing monocrystalline silicon |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110330 Termination date: 20131028 |