LU503665B1 - Method for preparing titanium-doped and high-water single-crystal coulsonite under high-temperature and high-pressure condition - Google Patents
Method for preparing titanium-doped and high-water single-crystal coulsonite under high-temperature and high-pressure condition Download PDFInfo
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- LU503665B1 LU503665B1 LU503665A LU503665A LU503665B1 LU 503665 B1 LU503665 B1 LU 503665B1 LU 503665 A LU503665 A LU 503665A LU 503665 A LU503665 A LU 503665A LU 503665 B1 LU503665 B1 LU 503665B1
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- temperature
- coulsonite
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- 239000013078 crystal Substances 0.000 title claims abstract description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000000843 powder Substances 0.000 claims abstract description 54
- 239000007787 solid Substances 0.000 claims abstract description 43
- 229910052598 goethite Inorganic materials 0.000 claims abstract description 21
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 claims abstract description 21
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 20
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 19
- 229910021646 siderite Inorganic materials 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Natural products OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 12
- FSJSYDFBTIVUFD-XHTSQIMGSA-N (e)-4-hydroxypent-3-en-2-one;oxovanadium Chemical compound [V]=O.C\C(O)=C/C(C)=O.C\C(O)=C/C(C)=O FSJSYDFBTIVUFD-XHTSQIMGSA-N 0.000 claims abstract description 10
- 239000007858 starting material Substances 0.000 claims abstract description 8
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 40
- 229910002804 graphite Inorganic materials 0.000 claims description 40
- 239000010439 graphite Substances 0.000 claims description 40
- 238000003760 magnetic stirring Methods 0.000 claims description 26
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 22
- 239000011521 glass Substances 0.000 claims description 21
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 20
- 239000011812 mixed powder Substances 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 230000003247 decreasing effect Effects 0.000 claims description 12
- 239000003517 fume Substances 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- 229910052786 argon Inorganic materials 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 11
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 10
- 239000001569 carbon dioxide Substances 0.000 claims description 10
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- 239000010936 titanium Substances 0.000 claims description 10
- 229910001252 Pd alloy Inorganic materials 0.000 claims description 9
- BBKFSSMUWOMYPI-UHFFFAOYSA-N gold palladium Chemical compound [Pd].[Au] BBKFSSMUWOMYPI-UHFFFAOYSA-N 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- DECCZIUVGMLHKQ-UHFFFAOYSA-N rhenium tungsten Chemical compound [W].[Re] DECCZIUVGMLHKQ-UHFFFAOYSA-N 0.000 claims description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 7
- 239000010935 stainless steel Substances 0.000 claims description 7
- 229910001220 stainless steel Inorganic materials 0.000 claims description 7
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 claims description 7
- 229910052593 corundum Inorganic materials 0.000 claims description 6
- 239000010431 corundum Substances 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000004570 mortar (masonry) Substances 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- 238000005245 sintering Methods 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000007731 hot pressing Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- PXXKQOPKNFECSZ-UHFFFAOYSA-N platinum rhodium Chemical compound [Rh].[Pt] PXXKQOPKNFECSZ-UHFFFAOYSA-N 0.000 claims description 4
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 239000010432 diamond Substances 0.000 claims description 3
- 229910003460 diamond Inorganic materials 0.000 claims description 3
- 238000010791 quenching Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 229910000691 Re alloy Inorganic materials 0.000 claims description 2
- 238000005520 cutting process Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 10
- 238000006297 dehydration reaction Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229910052595 hematite Inorganic materials 0.000 description 5
- 239000011019 hematite Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229910000629 Rh alloy Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000001413 cellular effect Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910002588 FeOOH Inorganic materials 0.000 description 1
- 229910011011 Ti(OH)4 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229910052592 oxide mineral Inorganic materials 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 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
- 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
- C30B29/22—Complex oxides
- C30B29/30—Niobates; Vanadates; Tantalates
-
- 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
- C30B1/00—Single-crystal growth directly from the solid state
- C30B1/10—Single-crystal growth directly from the solid state by solid state reactions or multi-phase diffusion
-
- 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
- C30B1/00—Single-crystal growth directly from the solid state
- C30B1/12—Single-crystal growth directly from the solid state by pressure treatment during the growth
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
A method for preparing titanium-doped and high-water single-crystal coulsonite under a coulsonite sample using solid trigonal siderite crystals, solid bis(2,4-pentanedionato)vanadium(IV) oxide powder, liquid titanium(IV) isopropoxide, solid oxalic acid powder, solid α-phase goethite powder, solid titanium hydroxide powder and liquid dilute nitric acid as starting materials; preparing water-sourced discs from the α-phase goethite powder and the titanium hydroxide powder according to a weight ratio of 4:1; and placing the water-sourced discs at two ends of the cylindrical coulsonite sample, and then placing the cylindrical coulsonite sample with the water-sourced discs in an inner tube of a double-layer sample chamber for high-temperature and high-pressure reaction to obtain single-crystal coulsonite. The present invention solves the problem that there is no technique for preparing large-grained, titanium-doped and high-water single-crystal coulsonite under a high-temperature and high-pressure condition at present, and can obtain large-grained, titanium-doped and high-water single-crystal coulsonite experimental samples.
Description
METHOD FOR PREPARING TITANIUM-DOPED AND HIGH-WATER
SINGLE-CRYSTAL COULSONITE UNDER HIGH-TEMPERATURE AND
HIGH-PRESSURE CONDITION
[0001] 1. Technical Field
[0002] The present invention belongs to the technical field of single-crystal mineral sample synthesis, and particularly relates to a method for preparing titanium-doped and high-water single-crystal coulsonite under a high-temperature and high-pressure condition.
[0003] 2. Description of Related Art
[0004] As an important end-member component of the vanadium-containing ulvite sub-group, coulsonite contains oxides, the percentages of which may be expressed as:
FeO/(FeO+V203)=32.40% and Cr,03/(MgO+Cr203)=67.60%.
[0005] Coulsonite with a spinel structure does not contain hydrone or hydroxyl in its molecular structure, and is manifested as an obvious nominal unhydrous mineral. There has not been yet an effective method for synthesizing coulsonite so far. So, it becomes particularly urgent to effectively synthesize large-grained, titanium-doped and high-water single-crystal coulsonite to meet geoscientific research requirements of various high-temperature and high-pressure laboratory simulations, especially the requirement for studying the lattice preferred orientation and crystal axis anisotropy of single-crystal coulsonite under high pressure.
[0006] The technical issue to be settled by the present invention is to provide a 1 method for preparing titanium-doped and high-water single-crystal coulsonite under a LU503665 high-temperature and high-pressure condition, to solve the above-mentioned technical problems.
[0007] The technical solution of the present invention 1s as follows:
[0008] A method for preparing titanium-doped and high-water single-crystal coulsonite under a high-temperature and high-pressure condition, comprising: preparing a cylindrical coulsonite sample using solid trigonal siderite crystals, solid bis(2,4-pentanedionato)vanadium(IV) oxide powder, liquid titanium(IV) isopropoxide, solid oxalic acid powder, solid a-phase goethite powder, solid titanium hydroxide powder and liquid dilute nitric acid as starting materials; preparing water-sourced discs from the a-phase goethite powder and the titanium hydroxide powder according to a weight ratio of 4:1; and placing the water-sourced discs at two ends of the cylindrical coulsonite sample, and then placing the cylindrical coulsonite sample with the water-sourced discs in an inner tube of a double-layer sample chamber for high-temperature and high-pressure reaction to obtain single-crystal coulsonite.
[0009] Preferably, the solid transparent-semitransparent trigonal siderite crystals (purity > 99.99%), the solid bis(2,4-pentanedionato)vanadium(IV) oxide powder (purity > 99.99%), the liquid titanium(IV) isopropoxide (purity > 99.99%), the solid oxalic acid powder (purity > 99.99%), the solid a-phase goethite powder (purity > 99%), the solid titanium hydroxide powder (purity > 99%) and the liquid dilute nitric acid (concentration: 10%) are used.
[0010] Preferably, the cylindrical coulsonite sample is prepared by:
[0011] Step 1: measuring out 60 ml of dilute nitric acid with the concentration of 10%, and pouring it in a beaker with a notch;
[0012] Step 2: weighing out 5.0 g of trigonal siderite crystals, adding them into the beaker with the notch, and putting a magnetic stirring rotor in the beaker with the notch; 2
[0013] Step 3: covering a mouth of the beaker with watch-glass, placing the beaker
LU503665 on a high-temperature magnetic stirring heater coil in a fume hood, and reacting for 72 hrs at normal temperature and 700 rpm;
[0014] Step 4: measuring out 22.8874 g of solid bis(2,4-pentanedionato)vanadium(IV) oxide powder and 200 ml of liquid titanium(I'V) isopropoxide according to coulsonite Fe(V, T1)2O4 stoichiometry, and adding them into the beaker;
[0015] Step 5: covering the beaker with the watch-glass;
[0016] Step 6: placing the beaker on the high-temperature magnetic stirring heater coil in the fume hood, and stirring for 48 hrs at normal temperature and 800 rpm;
[0017] Step 7: weighing out 2 g of solid oxalic acid powder, and placing it in the beaker;
[0018] Step 8: placing the beaker on the high-temperature magnetic stirring heater coil in the fume hood again, covering the beaker with the watch-glass, and setting parameters of the high-temperature magnetic stirring heater coil to 80 °C and 1000 rpm for stirring for 36 hrs;
[0019] Step 9: removing the watch-glass from the beaker, and increasing the temperature of the high-temperature magnetic stirring heater coil to 110 °C until the mixed solution in the beaker is completely desiccated;
[0020] Step 10: taking the magnetic stirring rotor out of the beaker, stripping all sample powder adhering to a surface of the magnetic stirring rotor into the beaker, taking all mixed powder out of the beaker with a spoon, and placing it in a graphite crucible;
[0021] Step 11: increasing the temperature of the graphite crucible containing the mixed powder to 1150 °C at arate of 300 °C/h by means of a muffle furnace which is at normal pressure and high temperature, and maintaining the graphite crucible at this temperature for 5 hrs; 3
[0022] Step 12: cooling the mixed powder in the graphite crucible in the muffle
LU503665 furnace to room temperature at a rate of 200 °C/h;
[0023] Step 13: grinding the mixed powder in a corundum mortar for 1 h;
[0024] Step 14: cold-pressing the mixed powder into three ® 10.0 mm * 3.0 mm sample discs, and stacking the three sample discs at a bottom of the graphite crucible from bottom to top;
[0025] Step 15: hanging the graphite crucible, in which the three sample discs are stacked, in a middle of a high-temperature oxygen atmosphere furnace, connecting and fixing two ends of a platinum-rhodium metal wire of the graphite crucible to a vertical four-hole aluminum oxide tube, and fixing an upper end of the four-hole aluminum oxide tube to a middle of a circular cover capable of being pushed into and pulled out of a furnace body:
[0026] Step 16: placing a stainless steel container containing secondary deionized pure cold water on one side of the high-temperature oxygen atmosphere furnace;
[0027] Step 17: connecting a top of a furnace body of the high-temperature oxygen atmosphere furnace to an argon inert gas cylinder and a proportion-adjustable carbon monoxide and carbon dioxide cylinder;
[0028] Step 18: opening an argon inert gas valve to continuously inject argon for 30 min, and under the protection of the argon, calcinating the sample at high temperature to 800 °C at a heating rate of 400 °C/h;
[0029] Step 19: when the temperature in the furnace body reaches 800 °C, switching a carbon monoxide and carbon dioxide gas control valve to enable a volume ratio of carbon monoxide and carbon dioxide in the oxygen atmosphere furnace to reach 4:1;
[0030] Step 20: increasing the temperature of a sample chamber in the furnace body to 1600 °C at a rate of 200 °C/h to perform constant-temperature calcination for 15 min;
[0031] Step 21: after the sample is calcinated at 1600 °C for 15 min, pulling the 4 graphite crucible containing the sample, the four-hole aluminum oxide tube and the
LU503665 circular cover on the furnace body out of the furnace body, and then directly immersing then in the stainless steel container to quench the sample into coulsonite glass;
[0032] Step 22: taking the coulsonite glass out of the graphite crucible, grinding it into fine-grained and uniform-composition sample powder in the corundum mortar, and drying the glassy-state coulsonite powder in a vacuum drying oven at 200 °C for 12 hrs; and
[0033] Step 23: cold-pressing the glassy-state coulsonite powder into a ® 4.0 mm (diameter) * 4.0 mm (height) cylindrical coulsonite sample on a cold isostatic press by a tungsten carbide grinding tool.
[0034] Preferably, the water-sourced discs are prepared by:
[0035] Step 24: cold-pressing the a-phase goethite powder and the titanium hydroxide powder on a cold isostatic press by a tungsten carbide grinding tool according to the weight ratio of 4:1 to obtain two ® 4.0 mm (diameter) * 0.1 mm (height) water-sourced discs.
[0036] Preferably, placing the water-sourced discs at two ends of the cylindrical coulsonite sample and then placing the cylindrical coulsonite sample with the water-sourced discs in an inner tube of a double-layer sample chamber for high-temperature and high-pressure reaction to obtain single-crystal coulsonite comprise:
[0037] Step 25: sealing the cylindrical coulsonite sample and the two water-sourced discs in a double-layer experimental sample chamber with an inner tube being a graphite tube and an outer tube being a gold-palladium alloy tube, wherein during sealing, the two water-sourced discs are placed at two ends of the cylindrical coulsonite sample;
[0038] Step 26: placing the double-layer sample chamber in a typical Kawai-1000t 6-8 multi-anvil, large-volume, high-temperature and high-pressure apparatus, and increasing the pressure and temperature to 4.0 GPa and 1250 °C at a rate of 0.5 GPa/h and a rate of 10 °C/min respectively for hot-pressing sintering, and reacting at constant
LU503665 temperature and constant pressure for 72 hrs:
[0039] Step 27: decreasing the temperature in a sample cavity from 1250 °C to 800 °C at a rate of 3 °C/min, and maintaining the temperature for 1h; then, decreasing the temperature in the sample cavity from 800 °C to room temperature at a rate of 5 °C/min;
[0040] Step 28: when the temperature in the sample cavity is decreased to room temperature, decreasing the pressure in the sample cavity from 4.0 GPa to normal pressure at a rate of 0.5 GPa; and
[0041] Step 29: after the high-temperature and high-pressure reaction is finished, taking the sample out of the typical Kawai-1000t 6-8 multi-anvil, large-volume, high-temperature and high-pressure apparatus, removing the graphite tube and the gold-palladium alloy tube of the double-layer sample chamber outside the sample, cutting the cylindrical sample in the middle with a diamond wire cutter, and picking out single-crystal coulsonite under a 20-power Olympus microscope.
[0042] Preferably, during the high-temperature and high-pressure reaction, two sets of tungsten-rhenium thermocouples are used for temperature calibration; each of the two sets of tungsten-rhenium thermocouples is composed of two tungsten-rhenium alloy wires made of different materials, the chemical composition of which is W95%Re5% and
W74%Re26%; and the two sets of tungsten-rhenium thermocouples are symmetrically disposed at an upper end and a lower end of the double-layer sample chamber composed of a graphite tube and a gold-palladium alloy tube.
[0043] The present invention has the following beneficial effects:
[0044] The titanium-doped and high-water single-crystal coulsonite obtained through the method of the present invention is a pure substance and has good chemical stability. The method of the present invention has the remarkable advantages of a simple operation process and a short reaction time, and the obtained single-crystal coulsonite has 6 good physical and chemical properties such as high purity, large size and stable chemical
LU503665 properties. Most importantly, the synthesized coulsonite has a high titanium content (7500-8500 ppm wt%) and a high water content (300-400 ppm), and the titanium content and the water content can be controlled. The single-crystal coulsonite has a large particle size, provides an important experimental sample guarantee for exploring the lattice preferred orientation and crystal axis anisotropy of single-crystal minerals under high pressure, and breaks through the technical bottleneck of single-crystal coulsonite synthesis.
[0045] The present invention provides a method for preparing titanium-doped and high-water single-crystal coulsonite under a high-temperature and high-pressure condition, which specifically comprises:
[0046] Solid transparent-semitransparent trigonal siderite crystals (purity > 99.99%), solid bis(2,4-pentanedionato)vanadium(TV) oxide powder (purity > 99.99%), liquid titantum(IV) isopropoxide (purity > 99.99%), solid oxalic acid powder (purity > 99.99%), solid a-phase goethite powder (purity > 99%), the solid titanium hydroxide powder (purity > 99%) and liquid dilute nitric acid (concentration: 10%) are used as starting materials.
[0047] Step 1: a chemical fume hood is opened, a volumetric flask with a standard volume of 100 ml is selected to accurately measure out 60 ml of dilute nitric acid with the concentration of 10%, a glass pipette is placed in a 500 ml beaker with a notch, and the liquid diluted nitric acid is completely transferred into the beaker carefully through the pipette, wherein due to the fact that the beaker with the notch will not be completely sealed after the beaker is covered with watch-glass, the beaker with the notch is used as a reaction container to ensure that generated gas can be easily volatilized in the fume hood.
[0048] Step 2: 5.0 g of high-purity transparent-semitransparent trigonal siderite 7 crystals are accurately weighed out with a 10 ug high-precision analytical balance, and are
LU503665 carefully added into the beaker containing the dilute nitric acid solution with the concentration of 10%, and a magnetic stirring rotor is put in the beaker.
[0049] Step 3: a mouth of the beaker containing the dilute nitric acid solution with the trigonal siderite crystals is covered with watch-glass, and then the beaker is placed on a high-temperature magnetic stirring heater coil in the fume hood; in order to fully dissolve the starting material, namely the solid siderite crystals, in the dilute nitric acid solution and make the solid siderite crystals undergo hydrolysis reaction and acidification reaction, the reaction temperature is normal temperature, the rotational speed is 700 rpm, and the reaction time is 72 hrs.
[0050] Step 4: 22.8874 g of high-purity bis(2,4-pentanedionato)vanadium(IV) oxide powder and 200 ml of high-purity liquid titanium(IV) isopropoxide are accurately weighed out with the high-precision analytical balance according to coulsonite Fe(V,
Ti)2O4 stoichiometry, and are carefully added to the dilute nitric acid solution containing the siderite crystals.
[0051] Step 5: the beaker containing the dilute nitric acid solution with the solid siderite crystals, the solid bis(2,4-pentanedionato)vanadium(IV) oxide powder and the liquid titanium(IV) isopropoxide is covered with watch-glass to ensure that gas generated during reaction is volatilized via the notch of the beaker, and the starting material, namely the dilute nitric acid solution, in the beaker is prevented from splashing during the high-speed stirring process, which may otherwise raise a risk and compromise the synthesis accuracy of single-crystal coulsonite.
[0052] Step 6: the beaker containing the sealed dilute nitric acid solution and magnetic stirring rotor is placed on the high-temperature magnetic stirring heater coil in the fume hood, stirring is performed at normal temperature and 800 rpm for 48 hrs to enable the starting materials, namely the solid siderite crystals, the solid 8 bis(2,4-pentanedionato)vanadium(I'V) oxide powder and the liquid titanium(I'V)
LU503665 isopropoxide, to be completely dissolved in the dilute nitric acid solution without any residues, and volatile substances such as NH;+H:0, CHa, CoH, CO», and Hz can be volatilized more easily in the fume hood.
[0053] Step 7: 2 g of high-purity solid oxalic acid powder is accurately weighed out with the high-precision analytical balance, and is added to the diluted nitric acid solution containing the solid siderite crystals, the solid bis(2,4-pentanedionato)vanadium(IV) oxide powder and the liquid titanium(IV) isopropoxide, as an important metal-chelator.
[0054] Step 8: the beaker containing the mixed solution is placed on the high-temperature magnetic stirring heater coil in the fume hood again, and then the beaker is covered with the watch-glass; the parameters of the high-temperature magnetic stirring heater coil are set to 80 °C and 1000 rpm for stirring for 36 hrs to enable all the starting materials to form uniform colloidal sol under the combined action of dilute nitric acid and oxalic acid.
[0055] Step 9: the watch-glass is removed from the beaker, and the temperature of the high-temperature magnetic stirring heater coil is increased to 110 °C until the mixed solution in the beaker is completely desiccated.
[0056] Step 10: the magnetic stirring rotor is taken out of the beaker on the high-temperature magnetic stirring heater coil, all sample powder adhering to the surface of the magnetic stirring rotor is stripped into the beaker, and all mixed powder is carefully taken out of the beaker with a spoon and is placed in a graphite crucible.
[0057] Step 11: the temperature of the graphite crucible containing the mixed powder is increased to 1150 °C at a low heating rate of 300 °C/h by means of a muffle furnace which is at normal pressure and high temperature, and the graphite crucible is maintained at this temperature for 5 hrs. The high-temperature calcination rate is low, and the temperature maintaining time is long. 9
[0058] Step 12: the mixed powder in the graphite crucible in the muffle furnace is
LU503665 cooled to room temperature at a rate of 200 °C/h. Compared with the heating rate, a relatively low cooling rate is more beneficial to the formation of cellular loose sample powder. The mixed powder is taken out carefully.
[0059] Step 13: the cellular loose coulsonite sample powder is fully ground in a super-hard thickened corundum mortar for 1 h to obtain a fine-grained and uniform experimental powder sample.
[0060] Step 14: the fine-grained and uniform coulsonite powder sample is cold-pressed into three ® 10.0 mm * 3.0 mm sample discs by a high-precision tungsten carbide grinding tool (size: ® 10.0 mm * 10.0 mm) of a stainless steel press; the three sample discs are stacked from bottom to top and are then carefully placed at the bottom of the graphite crucible.
[0061] Step 15: two circular holes with a diameter of 1.0 mm are symmetrically drilled in the wall of the graphite crucible, in which the three sample discs are stacked, by means of a high-speed electric drill. A 0.5 mm platinum-rhodium alloy wire is made to penetrate through the two symmetrical 1.0 mm circular holes in the wall of the graphite crucible carefully to hang the graphite crucible in the middle of a high-temperature oxygen atmosphere furnace. Two ends of the platinum-rhodium alloy wire penetrating through the graphite crucible are connected and fixed to a vertical four-hole aluminum tube with a bore diameter of 0.6 mm, an outer diameter of 5.0 mm and a length of 40 mm. An upper end of the four-hole aluminum tube is fixed to the middle of a circular cover capable of being pushed into and pulled out of a furnace body at any time.
[0062] Step 16: a stainless steel container containing 3 L of secondary deionized pure cold water is placed on one side of the high-temperature oxygen atmosphere furnace in advance.
[0063] Step 17: the top of the furnace body of the high-temperature oxygen atmosphere furnace is connected to an argon inert gas cylinder and a proportion-adjustable
LU503665 carbon monoxide and carbon dioxide cylinder, the quantity of gas injected into a sample chamber is controlled through a barometer, and during the high-temperature calcination process, each gas can be switched and regulated in time through a valve.
[0064] Step 18: an argon inert gas valve is opened, and a pointer button controlled by the gas barometer is rotated to continuously inject argon for 30 min.
[0065] Step 19: when the temperature in the furnace body reaches 800 °C, a carbon monoxide and carbon dioxide gas control valve is switched quickly and the pointer button controlled by the gas barometer is rotated to enable the volume ratio of carbon monoxide and carbon dioxide in the oxygen atmosphere furnace to reach 4:1.
[0066] Step 20: when a mixed gas flow of the carbon monoxide and the carbon dioxide with the volume ratio of 4:1 in the sample chamber is stabilized, which takes about 3-5 min, the temperature of the sample chamber in the furnace body is increased to 1600 °C at arate of 200 °C/h to perform constant-temperature calcination for 15 min to melt the sample into glassy-state coulsonite.
[0067] Step 21: after the sample is calcinated at 1600 °C for 15 min, the graphite crucible containing the sample, the four-hole aluminum oxide tube and the circular cover on the furnace body are pulled out of the furnace body and then directly immersed in the stainless steel container containing 3L of secondary deionized pure cold water to quickly quench the sample into coulsonite glass.
[0068] Step 22: the coulsonite glass is taken out of the graphite crucible carefully, and is fully ground into fine-grained and uniform-composition sample powder in the corundum mortar. The glassy-state coulsonite powder is dried in a vacuum drying oven at 200 °C for 12 hrs.
[0069] Step 23: the coulsonite glass powder is cold-pressed on a cold isostatic press by a high-precision ® 4.0 mm (diameter) * 10.0 mm tungsten carbide grinding tool to 11 obtain a ® 4.0 mm (diameter) * 4.0 mm (height) cylindrical coulsonite sample.
LU503665
[0070] To obtain high-water coulsonite, the a-phase goethite powder (molecular formula: FeOOH) and the titanium hydroxide powder (molecular formula: Ti(OH)4), the weight ratio of which is 4:1, are used as a water source. The mixture of a-phase goethite and titanium hydroxide is used as the water source mainly for the following reasons: first, the a-phase goethite and the titanium hydroxide are both typical hydrous substances and have low dehydration temperature, some researchers believe that the high-purity a-phase goethite undergoes dehydration reaction at 270 °C to directly produce hematite and release a large amount of water at the same time, the other researchers hold that the a-phase goethite undergoes dehydration reaction at 238 °C to produce super-structural hematite [molecular formula: Fec-x3)(OH)xO(-x] and the super-structural hematite undergoes dehydration reaction at 800 °C to produce hematite and release a large amount of water at the same time, the high-purity titanium hydroxide, as a typical hydrous white powdery substance containing titanium, is an acid soluble and alkali-soluble amphoteric oxide, can be used as a mordant and an acetylene polymerization catalyst, and undergoes dehydration reaction to produce rutile (TiO) and release a large amount of water at the same time when the temperature is over 650 °C, and all these dehydration temperatures are within a relatively low temperature interval during the process of preparing titanium-doped single-crystal coulsonite under a high-temperature and high-pressure condition, which fully guarantees that the titanium-doped single-crystal coulsonite is in a water environment long enough, thus ensuring sufficient diffusion of lattice water of the sample and the formation of lattice sites; second, the a-phase goethite and titanium hydroxide are both ferrum-rich and titanium-rich substances, so the ferrum activity and the titanium activity of main lattice sites can be controlled in the process of preparing titanium-doped and high-water single-crystal coulsonite in a sample cavity; and finally, final products of thea-phase goethite and titanium hydroxide with the weight ratio of 4:1, which are used 12 for providing the water source and disposed at two ends of the sample, are oxides such as
LU503665 hematite and rutile, which will not chemically react with the sample, thus ensuring the purity of a prepared titanium-doped and high-water single-crystal coulsonite sample. In addition, by adjusting the weight ratio of the a-phase goethite and titanium hydroxide for providing the water source and the height of the corresponding water-source discs, the water content of the titanium-doped and high-water single-crystal coulsonite sample can be adjusted.
[0071] Step 24: the a-phase goethite powder and the titanium hydroxide powder are cold-pressed on a cold isostatic press by a high-precision ® 4.0 mm (diameter) * 10.0 mm tungsten carbide grinding tool according to the weight ratio of 4:1 to obtain two ® 4.0 mm (diameter) * 0.1 mm (height) water-sourced discs.
[0072] Step 25: the cylindrical coulsonite sample (size: ® 4.0 mm (diameter) * 4.0 mm (height)) and the two water-sourced discs (size: ® 4.0 mm (diameter) * 0.1 (height)) are sequentially sealed in a double-layer experimental sample chamber with an inner tube being a graphite tube (size: ® 4.4 mm (outer diameter) * 4.4 mm (height), 0.2 mm (wall thickness)) and an outer tube being a gold-palladium alloy tube (size: ® 4.6 mm (outer diameter) * 4.6 mm (height), 0.1 mm (wall thickness)). In the present invention, the titanium-doped singe-crystal coulsonite sample is placed in the middle of the inner graphite tube, the two water-sourced discs prepared from the a-phase goethite and the titanium hydroxide with the weight ratio of 4:1 are placed at two symmetrical ends of the inner graphite tube close to the sample.
[0073] Step 26: coulsonite is one of the important ferrum-rich and vanadium-rich oxide minerals in the lower crust and upper mantle of the earth and other terrestrial planets; in order to truly simulate the growth environment of coulsonite deep in the lower crust of the earth and other terrestrial planets and invert the temperature and pressure conditions for stable existence of the coulsonite phase, the double-layer sample chamber composed of 13 the graphite tube and the gold-palladium alloy tube is placed in a typical Kawai-1000t 6-8
LU503665 multi-anvil, large-volume, high-temperature and high-pressure apparatus, the pressure and temperature are increased to 4.0 GPa and 1250 °C at a rate of 0.5 GPa/h and a rate of 10 °C/min respectively for hot-pressing sintering, and the reaction time is 72 hrs.
[0074] The preparation process at the high pressure of 4.0 GPa and the sintering temperature of 1250 °C 1s designed based on the physical and chemical properties of coulsonite.
[0075] Step 27: after the reaction is performed at 4.0 GPa and 1250 °C for 72 hrs, the temperature in a sample cavity is decreased from 1250 °C to 800 °C at a rate of 3 °C/min, and the temperature 1s maintained at 800 °C for 1 h; then, the temperature in the sample cavity is decreased from 800 °C to room temperature at a rate of 5 °C/min.
[0076] Step 28: when the temperature in the sample cavity is decreased to room temperature, the pressure in the sample cavity 1s decreased from 4.0 GPa to normal pressure at a rate of 0.5 GPa. In addition, the process for preparing the titanium-doped and high-water single-crystal coulsonite sample through hot-pressing sintering is pure, and the introduction of all possible impurities from the sample or generated during high-pressure sample assembly is avoided.
[0077] Step 29: after the high-temperature and high-pressure reaction is completed, the sample is taken out of the typical Kawai-1000t 6-8 multi-anvil, large-volume, high-temperature and high-pressure apparatus. The graphite tube and the gold-palladium alloy tube of the double-layer sample chamber outside the sample are removed carefully, and the cylindrical sample is cut in the middle with a high-precision diamond wire cutter.
Single-crystal coulsonite is picked out under a 20-power high-precision Olympus microscope. 14
Claims (6)
1. À method for preparing titanium-doped and high-water single-crystal coulsonite under a high-temperature and high-pressure condition, comprising: preparing a cylindrical coulsonite sample using solid trigonal siderite crystals, solid bis(2,4-pentanedionato)vanadium(IV) oxide powder, liquid titanium(IV) isopropoxide, solid oxalic acid powder, solid a-phase goethite powder, solid titanium hydroxide powder and liquid dilute nitric acid as starting materials; preparing water-sourced discs from the a-phase goethite powder and the titanium hydroxide powder according to a weight ratio of 4:1; and placing the water-sourced discs at two ends of the cylindrical coulsonite sample, and then placing the cylindrical coulsonite sample with the water-sourced discs in an inner tube of a double-layer sample chamber for high-temperature and high-pressure reaction to obtain single-crystal coulsonite.
2. The method for preparing titanium-doped and high-water single-crystal coulsonite under a high-temperature and high-pressure condition according to Claim 1, wherein the solid transparent-semitransparent trigonal siderite crystals (purity > 99.99%), the solid bis(2,4-pentanedionato)vanadium(IV) oxide powder (purity > 99.99%), the liquid titanium(I'V) isopropoxide (purity > 99.99%), the solid oxalic acid powder (purity >
99.99%), the solid a-phase goethite powder (purity > 99%), the solid titanium hydroxide powder (purity > 99%) and the liquid dilute nitric acid (concentration: 10%) are used.
3. The method for preparing titanium-doped and high-water single-crystal coulsonite under a high-temperature and high-pressure condition according to Claim 1, wherein the cylindrical coulsonite sample is prepared by: Step 1: measuring out 60 ml of dilute nitric acid with the concentration of 10%, and pouring it in a beaker with a notch; Step 2: weighing out 5.0 g of trigonal siderite crystals, adding them into the beaker with the notch, and putting a magnetic stirring rotor in the beaker with the notch;
Step 3: covering a mouth of the beaker with watch-glass, placing the beaker on a LU503665 high-temperature magnetic stirring heater coil in a fume hood, and reacting for 72 hrs at normal temperature and 700 rpm;
Step 4: measuring out 22.8874 g of solid bis(2,4-pentanedionato)vanadium(IV) oxide powder and 200 ml of liquid titanium(IV) isopropoxide according to coulsonite Fe(V, Ti)2O4 stoichiometry, and adding them into the beaker;
Step 5: covering the beaker with the watch-glass;
Step 6: placing the beaker on the high-temperature magnetic stirring heater coil in the fume hood, and stirring for 48 hrs at normal temperature and 800 rpm;
Step 7: weighing out 2 g of solid oxalic acid powder, and placing it in the beaker;
Step 8: placing the beaker on the high-temperature magnetic stirring heater coil in the fume hood again, covering the beaker with the watch-glass, and setting parameters of the high-temperature magnetic stirring heater coil to 80 °C and 1000 rpm for stirring for 36 hrs;
Step 9: removing the watch-glass from the beaker, and increasing the temperature of the high-temperature magnetic stirring heater coil to 110 °C until the mixed solution in the beaker is completely desiccated;
Step 10: taking the magnetic stirring rotor out of the beaker, stripping all sample powder adhering to a surface of the magnetic stirring rotor into the beaker, taking all mixed powder out of the beaker with a spoon, and placing it in a graphite crucible;
Step 11: increasing the temperature of the graphite crucible containing the mixed powder to 1150 °C at a rate of 300 °C/h by means of a muffle furnace which is at normal pressure and high temperature, and maintaining the graphite crucible at this temperature for 5 hrs;
Step 12: cooling the mixed powder in the graphite crucible in the muffle furnace to room temperature at a rate of 200 °C/h;
16
Step 13: grinding the mixed powder in a corundum mortar for 1 h;
LU503665
Step 14: cold-pressing the mixed powder into three ® 10.0 mm * 3.0 mm sample discs, and stacking the three sample discs at a bottom of the graphite crucible from bottom to top;
Step 15: hanging the graphite crucible, in which the three sample discs are stacked, in a middle of a high-temperature oxygen atmosphere furnace, connecting and fixing two ends of a platinum-rhodium metal wire of the graphite crucible to a vertical four-hole aluminum oxide tube, and fixing an upper end of the four-hole aluminum oxide tube to a middle of a circular cover capable of being pushed into and pulled out of a furnace body;
Step 16: placing a stainless steel container containing secondary deionized pure cold water on one side of the high-temperature oxygen atmosphere furnace;
Step 17: connecting a top of a furnace body of the high-temperature oxygen atmosphere furnace to an argon inert gas cylinder and a proportion-adjustable carbon monoxide and carbon dioxide cylinder;
Step 18: opening an argon inert gas valve to continuously inject argon for 30 min, and under the protection of the argon, calcinating the sample at high temperature to 800 °C at a heating rate of 400 °C/h;
Step 19: when the temperature in the furnace body reaches 800 °C, switching a carbon monoxide and carbon dioxide gas control valve to enable a volume ratio of carbon monoxide and carbon dioxide in the oxygen atmosphere furnace to reach 4:1;
Step 20: increasing the temperature of a sample chamber in the furnace body to 1600 °C at a rate of 200 °C/h to perform constant-temperature calcination for 15 min;
Step 21: after the sample is calcinated at 1600 °C for 15 min, pulling the graphite crucible containing the sample, the four-hole aluminum oxide tube and the circular cover on the furnace body out of the furnace body, and then directly immersing then in the stainless steel container to quench the sample into coulsonite glass;
17
Step 22: taking the coulsonite glass out of the graphite crucible, grinding it into LU503665 fine-grained and uniform-composition sample powder in the corundum mortar, and drying the glassy-state coulsonite powder in a vacuum drying oven at 200 °C for 12 hrs; and Step 23: cold-pressing the glassy-state coulsonite powder into a ® 4.0 mm (diameter) *
4.0 mm (height) cylindrical coulsonite sample on a cold isostatic press by a tungsten carbide grinding tool.
4. The method for preparing titanium-doped and high-water single-crystal coulsonite under a high-temperature and high-pressure condition according to Claim 1, wherein the water-sourced discs are prepared by: Step 24: cold-pressing the a-phase goethite powder and the titanium hydroxide powder on a cold isostatic press by a tungsten carbide grinding tool according to the weight ratio of 4:1 to obtain two ® 4.0 mm (diameter) * 0.1 mm (height) water-sourced discs.
5. The method for preparing titanium-doped and high-water single-crystal coulsonite under a high-temperature and high-pressure condition according to Claim 1, wherein placing the water-sourced discs at two ends of the cylindrical coulsonite sample and then placing the cylindrical coulsonite sample with the water-sourced discs in an inner tube of a double-layer sample chamber for high-temperature and high-pressure reaction to obtain single-crystal coulsonite comprise: Step 25: sealing the cylindrical coulsonite sample and the two water-sourced discs in a double-layer experimental sample chamber with an inner tube being a graphite tube and an outer tube being a gold-palladium alloy tube, wherein during sealing, the two water-sourced discs are placed at two ends of the cylindrical coulsonite sample; Step 26: placing the double-layer sample chamber in a typical Kawai-1000t 6-8 multi-anvil, large-volume, high-temperature and high-pressure apparatus, and increasing the pressure and temperature to 4.0 GPa and 1250 °C at a rate of 0.5 GPa/h and a rate of °C/min respectively for hot-pressing sintering, and reacting at constant temperature and 18 constant pressure for 72 hrs; LU503665 Step 27: decreasing the temperature in a sample cavity from 1250 °C to 800 °C at a rate of 3 °C/min, and maintaining the temperature for 1h; then, decreasing the temperature in the sample cavity from 800 °C to room temperature at a rate of 5 °C/min: Step 28: when the temperature in the sample cavity 1s decreased to room temperature, decreasing the pressure in the sample cavity from 4.0 GPa to normal pressure at a rate of
0.5 GPa; and Step 29: after the high-temperature and high-pressure reaction is finished, taking the sample out of the typical Kawai-1000t 6-8 multi-anvil, large-volume, high-temperature and high-pressure apparatus, removing the graphite tube and the gold-palladium alloy tube of the double-layer sample chamber outside the sample, cutting the cylindrical sample in the middle with a diamond wire cutter, and picking out single-crystal coulsonite under a 20-power Olympus microscope.
6. The method for preparing titantum-doped and high-water single-crystal coulsonite under a high-temperature and high-pressure condition according to Claim 1, wherein during the high-temperature and high-pressure reaction, two sets of tungsten-rhenium thermocouples are used for temperature calibration; each of the two sets of tungsten-rhenium thermocouples is composed of two tungsten-rhenium alloy wires made of different materials, the chemical composition of which is W95%Re5% and W74%Re26%; and the two sets of tungsten-rhenium thermocouples are symmetrically disposed at an upper end and a lower end of the double-layer sample chamber composed of a graphite tube and a gold-palladium alloy tube. ABSTRACT OF THE DISCLOSURE A method for preparing titanium-doped and high-water single-crystal coulsonite under a 19
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