Patent ID: 11898268
Assignee: XINJIANG TECHNICAL INSTITUTE OF PHYSICS & CHEMISTRY. CHINESE ACADEMY OF SCIENCES
Field: Surface technology, coating (Chemistry)
Classification: CPC C  G | IPC C  G

Claim 0:
1. A preparation method of a calcium metaborate birefringent crystal having a chemical formula of CaB2O4 and a molecular weight of 125.70, and belonging to the orthorhombic crystal system and space group Pbcn with unit-cell parameters a=11.60(4)Å, b=4.28(8)Å, c=6.21(6)Å, and Z=4, wherein the calcium metaborate birefringent crystal is a negative biaxial crystal with a transmission range of 165-3400 nm and a birefringence between 0.09-0.36, wherein the preparation method is a melt method, a flux method, a Bridgman method or a heat exchange method;
the preparation of the calcium metaborate birefringent crystal using the melt method is specifically operated in the following steps:
a. mixing a calcium-containing compound and a boron-containing compound with a molar ratio of calcium to boron of 1:2 and grinding the same, then pre-sintering the mixture in a corundum crucible at a temperature of 300° C. for 4 hours, taking out and compacting the mixture, then raising the temperature to 900° C., keeping the temperature for 1-3 days to obtain polycrystalline powder of a calcium metaborate compound, and performing X-ray analysis on the powder, to obtain an X-ray spectrum consistent with that after a calcium metaborate single crystal is ground into powder; and then putting the obtained polycrystalline powder of the calcium metaborate compound into a platinum crucible, heating the powder to a temperature of 1160-1180° C., and keeping the temperature constant for 1-50 hours to obtain a mixed melt;
or directly mixing a calcium-containing compound and a boron-containing compound with a molar ratio of calcium to boron of 1:2, grinding the mixture and putting the same into a platinum crucible, slowly heating the mixture to a temperature of 1160-1180° C., and keeping the temperature constant for 10-50 hours to obtain a mixed melt;
wherein the calcium-containing compound is calcium oxide, calcium hydroxide, calcium carbonate, calcium nitrate, calcium acetate, calcium oxalate or calcium metaborate, and the boron-containing compound is boric acid, boron oxide or calcium metaborate;
b. preparing a calcium metaborate seed crystal: rapidly cooling the mixed melt obtained in step a by 5-10° C., keeping a corresponding temperature for 2-6 hours, repeating the process of cooling and heat preservation until a floating crystal appears on the liquid surface, then slowly cooling down at a rate of 0.1-5° C./d until crystallization is completed, and then cooling to the room temperature at a cooling rate of 20° C./h, to obtain a calcium metaborate seed crystal by spontaneous crystallization;
or immersing a platinum wire fixed at a lower end of a seed rod into the mixed melt obtained in step a, slowly cooling down at a rate of 1-5° C./h until a crystal appears on the platinum wire, then rotating the seed rod at a rotation rate of 0-30 r/min, slowly cooling down at a rate of 0.1-5° C./d while pulling the crystal up at a speed of 0-3 mm/h, and after the crystal is grown to a desired size, lifting the same off the liquid surface, and cooling to the room temperature at a cooling rate of 20° C./h, to obtain a calcium metaborate seed crystal; and
c. placing the crucible containing the mixed melt prepared in step a into a crystal growth furnace, fixing the seed crystal obtained in step b to a seed rod, cooling down to 1152-1158° C., lowering the seed crystal from the top of the crystal growth furnace into a hearth, first preheating the seed crystal for 10 minutes above the mixed melt, then lowering the seed crystal onto the surface of the melt or into the melt for meltback, keeping a constant temperature for 1-20 minutes, then rapidly cooling to 1145-1150° C., and slowly cooling at a rate of 0.1-5° C./d, rotating the seed rod at a rotation speed of 0-30r/min while pulling the crystal up at a speed of 0-3 mm/h, carrying out a necking and shouldering process to optimize the crystal quality, and after the crystal grows to a desired size, lifting the crystal off the liquid surface and cooling to the room temperature at a cooling rate of 5-20° C./h, and taking out the crystal from the hearth to obtain a centimeter-sized calcium metaborate birefringent crystal;
the preparation of the calcium metaborate birefringent crystal using the flux method is specifically operated in the following steps:
a. mixing a calcium-containing compound and a boron-containing compound with a molar ratio of calcium to boron of 1:2 and grinding the same, then pre-sintering the mixture in a corundum crucible at a temperature of 300° C. for 4 hours, taking out and compacting the mixture, then raising the temperature to 900° C., keeping the temperature for 1-3 days to obtain polycrystalline powder of a calcium metaborate compound, and performing X-ray analysis on the powder, to obtain an X-ray spectrum consistent with that after a calcium metaborate single crystal is ground into powder; and then mixing the obtained polycrystalline powder of the calcium metaborate compound and a flux and putting the mixture into a platinum crucible, heating the mixture to a temperature of 900-1160° C., and keeping the temperature constant for 1-50 hours to obtain a mixed solution containing the flux, wherein the molar ratio of the calcium metaborate compound to the flux is 1:0.01-4;
or directly weighing and mixing a calcium-containing compound, a boron-containing compound and a flux with a molar ratio of Ca:B:flux of 1:2:0.01-4, grinding the mixture and putting the same into a platinum crucible, slowly heating the mixture to a temperature of 900-1160° C., and keeping the temperature constant for 10-50 hours to obtain a mixed solution containing the flux;
wherein the calcium-containing compound is calcium oxide, calcium hydroxide, calcium carbonate, calcium nitrate, calcium acetate, calcium oxalate or calcium metaborate; the boron-containing compound is boric acid, boron oxide or calcium metaborate; the flux is boron oxide, boric acid, sodium carbonate, sodium hydroxide, sodium fluoride, sodium nitrate, lithium fluoride, lithium hydroxide, lithium carbonate, lithium nitrate, or a mixture of a lithium-containing compound and a boron-containing compound, or a mixture of a sodium-containing compound and a boron-containing compound; wherein the molar ratio of lithium to boron in the mixture of the lithium-containing compound and the boron-containing compound is Li:B of 1-3:1, and the molar ratio of sodium to boron in the mixture of the sodium-containing compound and the boron-containing compound is Na:B of 1-3:1;
b. preparing a calcium metaborate seed crystal: rapidly cooling the mixed solution containing the flux obtained in step a by 5-10° C., keeping a corresponding temperature for 2-6 hours, repeating the process of cooling and heat preservation until a floating crystal appears on the liquid surface, then slowly cooling down at a rate of 0.1-5° C./d until crystallization is completed, and then cooling to the room temperature at a cooling rate of 20° C./h, to obtain a calcium metaborate seed crystal by spontaneous crystallization;
or immersing a platinum wire fixed at a lower end of a seed rod into the mixed solution containing the flux obtained in step a, slowly cooling down at a rate of 1-5° C./h until a crystal appears on the platinum wire, then rotating the seed rod at a rotation rate of 0-30 r/min, slowly cooling down at a rate of 0.1-5° C./d, and after the crystal is grown to a desired size, lifting the same off the liquid surface, and cooling to the room temperature at a cooling rate of 20° C./h, to obtain a calcium metaborate seed crystal; and
c. placing the crucible containing the mixed solution prepared in step a into a crystal growth furnace, fixing the seed crystal obtained in step b to a seed rod, cooling down to 850-1150° C., lowering the seed crystal from the top of the crystal growth furnace into a hearth, first preheating the seed crystal for 10 minutes above the surface of the mixed solution, then lowering the seed crystal onto the surface of the liquid or into the liquid for meltback, keeping a constant temperature for 1-20 minutes, then rapidly cooling to 845-1145° C., and slowly cooling at a rate of 0.1-5° C./d, rotating the seed rod at a rotation speed of 0-30r/min while pulling the crystal up at a speed of 0-3 mm/h, and after the crystal grows to a desired size, lifting the crystal off the liquid surface and cooling to the room temperature at a cooling rate of 5-20° C./h, and taking out the crystal from the hearth to obtain a centimeter-sized calcium metaborate birefringent crystal;
the preparation of the calcium metaborate birefringent crystal using the Bridgman method is specifically operated in the following steps:
a. mixing a calcium-containing compound and a boron-containing compound with a molar ratio of calcium to boron of 1:2-2.1 and grinding the same, then pre-sintering the mixture in a corundum crucible at a temperature of 300° C. for 4 hours, taking out and compacting the mixture, then raising the temperature to 900° C., keeping the temperature for 2 days to obtain a mixed raw material for crystal growth; wherein the calcium-containing compound is calcium oxide, calcium hydroxide, calcium carbonate, calcium nitrate, calcium acetate, calcium oxalate or calcium metaborate, and the boron-containing compound is boric acid, boron oxide or calcium metaborate;
b. preparing a calcium metaborate seed crystal: putting the mixed raw material obtained in step a into a platinum crucible for a Bridgman method, placing the crucible into a temperature gradient furnace, and heating the same to a temperature of 1200° C. to completely melt the mixed raw material in the crucible, keeping the temperature constant for 10 hours, then lowering the crucible at a rate of 0.1-2 mm/h, so that the melt or solution in the crucible slowly crystallizes from bottom to top, and after the crystallization is completed, cooling to the room temperature at a cooling rate of 20° C./h to obtain a calcium metaborate seed crystal; and
c. putting the seed crystal into a seed well at the bottom of the platinum crucible for the Bridgman method, then putting the mixed raw material obtained in step a into the crucible, placing the crucible into a temperature gradient furnace, heating the same to a temperature of 1150-1180° C., keeping the temperature constant for 1-20 hours, to completely melt the mixed raw material in the crucible and keep the seed crystal at the bottom in a crystalline state, then lowering the crucible at a rate of 0.1-2 mm/h, so that the melt or solution in the crucible slowly crystallizes from bottom to top, and after the crystallization is completed, cooling to the room temperature at a cooling rate of 5-20° C./h to obtain a centimeter-sized calcium metaborate single crystal;
the preparation of the calcium metaborate birefringent crystal using the heat exchange method is specifically operated in the following steps:
a. mixing a calcium-containing compound and a boron-containing compound with a molar ratio of calcium to boron of 1:2-2.1 and grinding the same, then pre-sintering the mixture in a corundum crucible at a temperature of 300° C. for 4 hours, taking out and compacting the mixture, then raising the temperature to 900° C., keeping the temperature for 2 days to obtain a mixed raw material for crystal growth; wherein the calcium-containing compound is calcium oxide, calcium hydroxide, calcium carbonate, calcium nitrate, calcium acetate, calcium oxalate or calcium metaborate, and the boron-containing compound is boric acid, boron oxide or calcium metaborate;
b. preparing a calcium metaborate seed crystal: putting the mixed raw material obtained in step a into a platinum crucible for a heat exchange method, placing the crucible into a heat exchange furnace, heating the same to a temperature of 1200° C. to completely melt the mixed raw material in the crucible, keeping the temperature constant for 10 hours, then cooling down at a rate of 0.1-1° C./h, so that the melt or solution in the crucible slowly crystallizes from bottom to top, and after the crystallization is completed, cooling to the room temperature at a cooling rate of 20° C./h to obtain a calcium metaborate seed crystal; and
c. putting the seed crystal into a seed well at the bottom of the platinum crucible for the heat exchange method, then putting the mixed raw material obtained in step a into the crucible, heating the same to a temperature of 1150-1180° C., keeping the temperature constant for 1-20 hours, to completely melt the raw material in the crucible and keep the seed crystal at the bottom in a crystalline state, creating a temperature distribution in which the temperature falls from top to bottom through a heater, a reflective insulation screen and a seed rod cooling device, then cooling at a rate of 0.1-1° C./h so that the melt in the crucible slowly crystallizes from bottom to top, and after the crystallization is completed, cooling to the room temperature at a cooling rate of 5-20° C./h to obtain a centimeter-sized calcium metaborate single crystal.