LU503613B1 - Method for preparing manganese-doped and high-water single-crystal trevorite under high-temperature and high-pressure condition - Google Patents
Method for preparing manganese-doped and high-water single-crystal trevorite under high-temperature and high-pressure condition Download PDFInfo
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- LU503613B1 LU503613B1 LU503613A LU503613A LU503613B1 LU 503613 B1 LU503613 B1 LU 503613B1 LU 503613 A LU503613 A LU 503613A LU 503613 A LU503613 A LU 503613A LU 503613 B1 LU503613 B1 LU 503613B1
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- temperature
- trevorite
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- 239000013078 crystal Substances 0.000 title claims abstract description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000000843 powder Substances 0.000 claims abstract description 97
- 239000007787 solid Substances 0.000 claims abstract description 71
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 28
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000001301 oxygen Substances 0.000 claims abstract description 23
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 23
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims abstract description 22
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Natural products OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229960002413 ferric citrate Drugs 0.000 claims abstract description 15
- SZINCDDYCOIOJQ-UHFFFAOYSA-L manganese(2+);octadecanoate Chemical compound [Mn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O SZINCDDYCOIOJQ-UHFFFAOYSA-L 0.000 claims abstract description 15
- 238000001354 calcination Methods 0.000 claims abstract description 14
- DGOBMKYRQHEFGQ-UHFFFAOYSA-L acid green 5 Chemical compound [Na+].[Na+].C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=2C=CC(=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S([O-])(=O)=O)=C1 DGOBMKYRQHEFGQ-UHFFFAOYSA-L 0.000 claims abstract description 12
- 229910010272 inorganic material Inorganic materials 0.000 claims abstract description 12
- -1 nickel carbonate inorganic compound Chemical class 0.000 claims abstract description 12
- 238000010791 quenching Methods 0.000 claims abstract description 11
- 238000007789 sealing Methods 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 239000007858 starting material Substances 0.000 claims abstract description 9
- 230000000171 quenching effect Effects 0.000 claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 64
- 229910002804 graphite Inorganic materials 0.000 claims description 64
- 239000010439 graphite Substances 0.000 claims description 64
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 34
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 32
- 238000003760 magnetic stirring Methods 0.000 claims description 25
- 239000011521 glass Substances 0.000 claims description 20
- 238000000227 grinding Methods 0.000 claims description 18
- 239000011812 mixed powder Substances 0.000 claims description 18
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 17
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 16
- 229910052786 argon Inorganic materials 0.000 claims description 16
- 239000001569 carbon dioxide Substances 0.000 claims description 16
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 16
- 230000003247 decreasing effect Effects 0.000 claims description 16
- 239000003517 fume Substances 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 13
- 229910001252 Pd alloy Inorganic materials 0.000 claims description 12
- BBKFSSMUWOMYPI-UHFFFAOYSA-N gold palladium Chemical compound [Pd].[Au] BBKFSSMUWOMYPI-UHFFFAOYSA-N 0.000 claims description 12
- DECCZIUVGMLHKQ-UHFFFAOYSA-N rhenium tungsten Chemical compound [W].[Re] DECCZIUVGMLHKQ-UHFFFAOYSA-N 0.000 claims description 12
- 239000010935 stainless steel Substances 0.000 claims description 12
- 229910001220 stainless steel Inorganic materials 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 10
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 10
- 238000003825 pressing Methods 0.000 claims description 9
- 229910000629 Rh alloy Inorganic materials 0.000 claims description 8
- 229910052593 corundum Inorganic materials 0.000 claims description 8
- 239000010431 corundum Substances 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 8
- 239000011572 manganese Substances 0.000 claims description 8
- 239000004570 mortar (masonry) Substances 0.000 claims description 8
- PXXKQOPKNFECSZ-UHFFFAOYSA-N platinum rhodium Chemical compound [Rh].[Pt] PXXKQOPKNFECSZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000007731 hot pressing Methods 0.000 claims description 4
- 230000000149 penetrating effect Effects 0.000 claims description 4
- 238000005245 sintering Methods 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 229910000691 Re alloy Inorganic materials 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 3
- 238000005553 drilling Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 239000003566 sealing material Substances 0.000 claims description 3
- 238000004088 simulation Methods 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000018044 dehydration Effects 0.000 description 5
- 238000006297 dehydration reaction Methods 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000001413 cellular effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 2
- 229910052592 oxide mineral Inorganic materials 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000009792 diffusion process Methods 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
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 1
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910021508 nickel(II) hydroxide Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 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
- C30B29/26—Complex oxides with formula BMe2O4, wherein B is Mg, Ni, Co, Al, Zn, or Cd and Me is Fe, Ga, Sc, Cr, Co, or Al
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
- B01J3/06—Processes using ultra-high pressure, e.g. for the formation of diamonds; Apparatus therefor, e.g. moulds or dies
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/10—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by application of pressure, e.g. hydrothermal processes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
A method for preparing manganese-doped and high-water single-crystal trevorite under a high-temperature and high-pressure condition comprises: preparing trevorite powder sample mixture discs using solid light-green basic nickel carbonate inorganic compound powder, solid transparent russet flaky ferric citrate (III) crystals, solid oxalic acid powder, solid pink manganese stearate powder, solid nickel hydroxide powder, solid natural manganite powder and liquid dilute nitric acid as starting materials; calcinating and quenching the trevorite powder sample mixture discs in a high-temperature oxygen atmosphere furnace to prepare a cylindrical trevorite sample; and placing water-sourced discs at two ends of the cylindrical trevorite sample and then sealing the cylindrical trevorite sample with the water-sourced discs for high-temperature and high-pressure reaction to obtain single-crystal trevorite. The method can effectively synthesize large-grained, manganese-doped and high-water single-crystal trevorite and can meet the geoscientific research requirements of various high-temperature and high-pressure laboratory simulations.
Description
METHOD FOR PREPARING MANGANESE-DOPED AND HIGH-WATER
LU503613
SINGLE-CRYSTAL TREVORITE 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 manganese-doped and high-water single-crystal trevorite under a high-temperature and high-pressure condition.
[0003] 2. Description of Related Art
[0004] Trevorite, the chemical formula of which is NiFe204, is an important oxide mineral rich in nickel and ferrum.
[0005] Trevorite 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 trevorite so far. So, it becomes particularly urgent to effectively synthesize large-grained, manganese-doped and high-water single-crystal trevorite 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 trevorite under high pressure.
[0006] The technical issue to be settled by the present invention is to provide a method for preparing manganese-doped and high-water single-crystal trevorite under a high-temperature and high-pressure condition, to solve the above-mentioned technical problems. 1
[0007] The technical solution of the present invention is as follows:
LU503613
[0008] A method for preparing manganese-doped and high-water single-crystal trevorite under a high-temperature and high-pressure condition, comprising: preparing trevorite powder sample mixture discs using solid light-green basic nickel carbonate inorganic compound powder, solid transparent russet flaky ferric citrate (III) crystals, solid oxalic acid powder, solid pink manganese stearate powder, solid nickel hydroxide powder, solid natural manganite powder and liquid dilute nitric acid as starting materials; calcinating and quenching the trevorite powder sample mixture discs in a high-temperature oxygen atmosphere furnace to prepare a cylindrical trevorite sample; and placing water-sourced discs at two ends of the cylindrical trevorite sample and then sealing the cylindrical trevorite sample with the water-sourced discs for high-temperature and high-pressure reaction to obtain single-crystal trevonite.
[0009] Preferably, the purity of the solid light-green basic nickel carbonate inorganic compound powder is over 99.99%, the purity of the solid transparent russet flaky ferric citrate (HT) crystals is over 99.99%, the purity of the solid oxalic acid powder is over 99.99%, the purity of the solid pink manganese stearate powder is over 99.99%, the purity of the solid nickel hydroxide powder is 99%, the purity of the solid natural manganite powder is over 99%, and the concentration of the liquid dilute nitric acid is 10%.
[0010] Preferably, the trevorite powder sample mixture discs are 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 light-green basic nickel carbonate inorganic compound powder, placing it in the beaker with the notch, and putting a magnetic stirring rotor in the beaker with the notch;
[0013] Step 3: covering a mouth of the beaker with watch-glass, placing the beaker on a high-temperature magnetic stirring heater coil in a fume hood, and reacting for 72 hrs 2 at normal temperature and 700 rpm;
LU503613
[0014] Step 4: measuring out 19.5343 g of solid ferric citrate (IIT) crystals and 60 mg of solid manganese stearate powder according to trevorite (N1, Mn)Fe204 stoichiometry, and adding them to the dilute nitric acid solution containing basic nickel carbonate;
[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 adding it into the beaker;
[0018] Step 8: placing the beaker on the high-temperature magnetic stirring heater coil in the fume hood, covering the beaker with the watch-glass, and stirring for 36 hrs at 80 °C and 1000 rpm;
[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 mixed powder out of the beaker, and placing it in a graphite crucible;
[0021] Step 11: placing the graphite crucible containing the mixed powder in a muffle furnace, then increasing the temperature of the graphite crucible to 1100 °C at a rate of 300 °C/h, and maintaining the graphite crucible at this temperature for 5 hrs;
[0022] Step 12: cooling the mixed powder to room temperature at a rate of 200 °C/h, and then taking out the mixed powder;
[0023] Step 13: grinding the mixed powder in a thickened corundum mortar for 1 h to obtain a trevorite powder sample mixture; and
[0024] Step 14: cold-pressing the trevorite powder sample mixture into three ® 10.0 3 mm * 3.0 mm sample discs by a tungsten carbide grinding tool of a stainless steel press.
LU503613
[0025] Preferably, calcinating and quenching the trevorite powder sample mixture discs in a high-temperature oxygen atmosphere furnace to prepare a cylindrical trevorite sample comprises:
[0026] Step 15: stacking the three sample discs at a bottom of the graphite crucible, and drilling symmetrical circular holes in a wall of the graphite crucible; enabling a platinum-rhodium alloy wire to penetrate through the two symmetrical circular holes in the wall of the graphite crucible to hang the graphite crucible in a middle of the high-temperature oxygen atmosphere furnace; connecting and fixing two ends of the platinum-rhodium alloy wire penetrating through the graphite crucible to a vertical four-hole aluminum oxide tube, and fixing an upper end of the four-hole aluminum oxide tube in a middle of a circular cover of a furnace body;
[0027] Step 16: placing a stainless steel container containing secondary deionized pure cold water on one side of the high-temperature oxygen atmosphere furnace;
[0028] Step 17: connecting a top of the 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;
[0029] Step 18: opening an argon inert gas valve to continuously inject argon for 30 min; under the protection of the argon, calcinating the sample at high temperature to 800 °C at a heating rate of 400 °C/h;
[0030] 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;
[0031] Step 20: when a mixed gas flow of the carbon monoxide and the carbon dioxide with the volume ratio of 4:1 in a sample chamber is stabilized, increasing the temperature of the sample chamber in the furnace body to 1450 °C at a rate of 200 °C/h to 4 perform constant-temperature calcination for 15 min;
LU503613
[0032] Step 21: after the sample 1s calcinated at 1450 °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 them in the stainless steel container containing the secondary deionized pure cold water to quench the sample into a glassy-state trevorite sample;
[0033] Step 22: taking the glassy-state trevorite sample out of the graphite crucible, and grinding it into fine-grained and uniform-composition glassy-state trevorite powder in the corundum mortar; drying the glassy-state trevorite powder in a vacuum drying oven at 200 °C for 12 hrs; and
[0034] Step 23: cold-pressing the glassy-state trevorite powder into a ® 4.0 mm (diameter) * 4.0 mm (height) cylindrical trevorite sample on a cold isostatic press by a tungsten carbide grinding tool.
[0035] Preferably, placing water-sourced discs at two ends of the cylindrical trevorite sample and then sealing the cylindrical trevorite sample with the water-sourced discs for high-temperature and high-pressure reaction to obtain single-crystal trevorite comprise:
[0036] Step 24: cold-pressing the nickel hydroxide powder and the natural manganite powder on a cold isostatic press by a tungsten carbide grinding tool according to a weight ratio of 4:1 to obtain two ® 4.0 mm (diameter) * 0.1 mm (height) water-sourced discs;
[0037] Step 25: sealing the cylindrical trevorite sample and the two water-sourced discs in the double-layer experimental sample chamber with an inner tube being a graphite tube, wherein the cylindrical trevorite sample is placed in a middle of the graphite inner tube, the two water-sourced discs are placed at two symmetrical ends of the graphite inner tube close to the sample, and an outer tube of the double-layer sample chamber uses gold-palladium alloy as sealing materials; LUS03643
[0038] Step 26: placing the double-layer sample chamber composed of the graphite tube and a gold-palladium alloy tube in a typical Kawai-1000t 6-8 multi-anvil, large-volume, high-temperature and high-pressure apparatus, and increasing the pressure and temperature to 3.0 GPa and 1100 °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 temperature and constant pressure for 72 hrs;
[0039] Step 27: after reacting at 3.0 GPa and 1100 °C for 72 hrs, decreasing the temperature in a sample cavity from 1100 °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 3.0 GPa to normal pressure at arate of 0.5 GPa; and
[0041] Step 29: after the high-temperature and high-pressure reaction is completed, 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, and cutting the cylindrical sample in the middle; picking out single-crystal trevorite under a 20-power high-precision Olympus microscope.
[0042] Preferably, during the high-temperature and high-pressure reaction, two sets of high-temperature 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 tungsten-rhenium thermocouples are symmetrically disposed at an upper end and a lower end of a sample chamber respectively. 6
[0043] A method for preparing manganese-doped and high-water single-crystal
LU503613 trevorite under a high-temperature and high-pressure condition, comprising: preparing trevorite powder sample mixture discs using solid light-green basic nickel carbonate inorganic compound powder, solid transparent russet flaky ferric citrate (III) crystals, solid oxalic acid powder, solid pink manganese stearate powder, solid nickel hydroxide powder, solid natural manganite powder and liquid dilute nitric acid as starting materials; calcinating and quenching the trevorite powder sample mixture discs in a high-temperature oxygen atmosphere furnace to prepare a cylindrical trevorite sample; and placing water-sourced discs at two ends of the cylindrical trevorite sample and then sealing the cylindrical trevorite sample with the water-sourced discs for high-temperature and high-pressure reaction to obtain single-crystal trevonite.
[0044] Preferably, the purity of the solid light-green basic nickel carbonate inorganic compound powder is over 99.99%, the purity of the solid transparent russet flaky ferric citrate (HT) crystals is over 99.99%, the purity of the solid oxalic acid powder is over 99.99%, the purity of the solid pink manganese stearate powder is over 99.99%, the purity of the solid nickel hydroxide powder is 99%, the purity of the solid natural manganite powder is over 99%, and the concentration of the liquid dilute nitric acid is 10%.
[0045] Preferably, the trevorite powder sample mixture discs are prepared by:
[0046] Step 1: measuring out 60 ml of dilute nitric acid with the concentration of 10%, and pouring it in a beaker with a notch;
[0047] Step 2: weighing out 5.0 g of light-green basic nickel carbonate inorganic compound powder, placing it in the beaker with the notch, and putting a magnetic stirring rotor in the beaker with the notch;
[0048] Step 3: covering a mouth of the beaker with watch-glass, placing the beaker on a high-temperature magnetic stirring heater coil in a fume hood, and reacting for 72 hrs at normal temperature and 700 rpm; 7
[0049] Step 4: measuring out 19.5343 g of solid ferric citrate (III) crystals and 60
LU503613 mg of solid manganese stearate powder according to trevorite (N1, Mn)Fe204 stoichiometry, and adding them to the dilute nitric acid solution containing basic nickel carbonate;
[0050] Step 5: covering the beaker with the watch-glass;
[0051] 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;
[0052] Step 7: weighing out 2 g of solid oxalic acid powder, and adding it into the beaker;
[0053] Step 8: placing the beaker on the high-temperature magnetic stirring heater coil in the fume hood, covering the beaker with the watch-glass, and stirring for 36 hrs at 80 °C and 1000 rpm;
[0054] 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;
[0055] Step 10: taking mixed powder out of the beaker, and placing it in a graphite crucible;
[0056] Step 11: placing the graphite crucible containing the mixed powder in a muffle furnace, then increasing the temperature of the graphite crucible to 1100 °C at a rate of 300 °C/h, and maintaining the graphite crucible at this temperature for 5 hrs;
[0057] Step 12: cooling the mixed powder to room temperature at a rate of 200 °C/h, and then taking out the mixed powder;
[0058] Step 13: grinding the mixed powder in a thickened corundum mortar for 1 h to obtain a trevorite powder sample mixture; and
[0059] Step 14: cold-pressing the trevorite powder sample mixture into three ® 10.0 mm * 3.0 mm sample discs by a tungsten carbide grinding tool of a stainless steel press. 8
[0060] Preferably, calcinating and quenching the trevorite powder sample mixture
LU503613 discs in a high-temperature oxygen atmosphere fumace to prepare a cylindrical trevorite sample comprises:
[0061] Step 15: stacking the three sample discs at a bottom of the graphite crucible, and drilling symmetrical circular holes in a wall of the graphite crucible; enabling a platinum-rhodium alloy wire to penetrate through the two symmetrical circular holes in the wall of the graphite crucible to hang the graphite crucible in a middle of the high-temperature oxygen atmosphere furnace; connecting and fixing two ends of the platinum-rhodium alloy wire penetrating through the graphite crucible to a vertical four-hole aluminum oxide tube, and fixing an upper end of the four-hole aluminum oxide tube in a middle of a circular cover of a furnace body;
[0062] Step 16: placing a stainless steel container containing secondary deionized pure cold water on one side of the high-temperature oxygen atmosphere furnace;
[0063] Step 17: connecting a top of the 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;
[0064] Step 18: opening an argon inert gas valve to continuously inject argon for 30 min; under the protection of the argon, calcinating the sample at high temperature to 800 °C at a heating rate of 400 °C/h;
[0065] 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;
[0066] Step 20: when a mixed gas flow of the carbon monoxide and the carbon dioxide with the volume ratio of 4:1 in a sample chamber is stabilized, increasing the temperature of the sample chamber in the furnace body to 1450 °C at a rate of 200 °C/h to perform constant-temperature calcination for 15 min; 9
[0067] Step 21: after the sample is calcinated at 1450 °C for 15 min, pulling the
LU503613 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 them in the stainless steel container containing the secondary deionized pure cold water to quench the sample into a glassy-state trevorite sample;
[0068] Step 22: taking the glassy-state trevorite sample out of the graphite crucible, and grinding it into fine-grained and uniform-composition glassy-state trevorite powder in the corundum mortar; drying the glassy-state trevorite powder in a vacuum drying oven at 200 °C for 12 hrs; and
[0069] Step 23: cold-pressing the glassy-state trevorite powder into a ® 4.0 mm (diameter) * 4.0 mm (height) cylindrical trevorite sample on a cold isostatic press by a tungsten carbide grinding tool.
[0070] Preferably, placing water-sourced discs at two ends of the cylindrical trevorite sample and then sealing the cylindrical trevorite sample with the water-sourced discs for high-temperature and high-pressure reaction to obtain single-crystal trevorite comprise:
[0071] Step 24: cold-pressing the nickel hydroxide powder and the natural manganite powder on a cold isostatic press by a tungsten carbide grinding tool according to a weight ratio of 4:1 to obtain two ® 4.0 mm (diameter) * 0.1 mm (height) water-sourced discs;
[0072] Step 25: sealing the cylindrical trevorite sample and the two water-sourced discs in the double-layer experimental sample chamber with an inner tube being a graphite tube, wherein the cylindrical trevorite sample is placed in a middle of the graphite inner tube, the two water-sourced discs are placed at two symmetrical ends of the graphite inner tube close to the sample, and an outer tube of the double-layer sample chamber uses gold-palladium alloy as sealing materials;
[0073] Step 26: placing the double-layer sample chamber composed of the graphite
LU503613 tube and a gold-palladium alloy tube in a typical Kawai-1000t 6-8 multi-anvil, large-volume, high-temperature and high-pressure apparatus, and increasing the pressure and temperature to 3.0 GPa and 1100 °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 temperature and constant pressure for 72 hrs;
[0074] Step 27: after reacting at 3.0 GPa and 1100 °C for 72 hrs, decreasing the temperature in a sample cavity from 1100 °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;
[0075] Step 28: when the temperature in the sample cavity is decreased to room temperature, decreasing the pressure in the sample cavity from 3.0 GPa to normal pressure at a rate of 0.5 GPa; and
[0076] Step 29: after the high-temperature and high-pressure reaction is completed, 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, and cutting the cylindrical sample in the middle; picking out single-crystal trevorite under a 20-power high-precision Olympus microscope.
[0077] Preferably, during the high-temperature and high-pressure reaction, two sets of high-temperature 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 tungsten-rhenium thermocouples are symmetrically disposed at an upper end and a lower end of a sample chamber respectively.
[0078] The present invention has the following beneficial effects: 11
[0079] The manganese-doped and high-water single-crystal trevorite obtained
LU503613 through the method of the present invention 1s 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 trevorite has good physical and chemical properties such as high purity, large size and stable chemical properties. Most importantly, the synthesized trevorite has a high manganese content (2000-3000 ppm wt%) and a high water content (300-600 ppm), and the manganese content and the water content can be controlled. The single-crystal trevorite 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 trevorite synthesis.
[0080] A method for preparing manganese-doped and high-water single-crystal trevorite under a high-temperature and high-pressure condition comprises the following steps:
[0081] Solid light-green basic nickel carbonate inorganic compound powder (purity: >99.99%), solid transparent russet flaky ferric citrate (III) crystals (purity: >99.99%), solid oxalic acid powder (purity: >99.99%), solid pink manganese stearate powder (purity: >99.99%), solid nickel hydroxide powder (purity: >99%), solid natural manganite powder (purity: >99%) and liquid dilute nitric acid (concentration: 10%) are used as starting materials.
[0082] 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 12 liquid diluted nitric acid is completely transferred into the beaker carefully through the
LU503613 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.
[0083] Step 2: 5.0 g of high-purity light-green basic nickel carbonate inorganic compound powder is accurately weighed out with a 10 ug high-precision analytical balance, and is 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.
[0084] Step 3: a mouth of the beaker containing the dilute nitric acid solution with the solid basic nickel carbonate powder 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 basic nickel carbonate powder, in the dilute nitric acid solution and make the solid basic nickel carbonate powder 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.
[0085] Step 4: 19.5343 g of high-purity solid ferric citrate (III) crystals and 60 mg of high-purity manganese stearate powder are accurately weighed out with the high-precision analytical balance according to trevorite (Ni, Mn)Fe204 stoichiometry, and are carefully added to the dilute nitric acid solution containing basic nickel carbonate.
[0086] Step 5: the beaker containing the dilute nitric acid solution with the solid basic nickel carbonate powder, the solid ferric citrate (III) crystals and the solid manganese stearate powder 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 trevorite. 13
[0087] Step 6: the beaker containing the sealed dilute nitric acid solution and
LU503613 magnetic stirring rotor 1s 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 material, namely the solid basic nickel carbonate powder, the solid ferric citrate (IIT) crystals and the solid manganese stearate powder, to be completely dissolved in the dilute nitric acid solution without any residues, and volatile substances such as NH3<H20, CH4, C2H2, CO2, CO and H2 can be volatilized more easily in the fume hood.
[0088] 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 basic nickel carbonate powder, the solid ferric citrate (III) crystals and the solid manganese stearate powder, as an important metal-chelator.
[0089] 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.
[0090] 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.
[0091] Step 10: the magnetic stirring rotor in the beaker on the high-temperature magnetic stirring heater coil is taken out, all sample powder adhering to the surface of the magnetic stirring rotor is stripped into the beaker, and all mixed powder in the beaker is carefully taken out with a spoon and is placed in a graphite crucible.
[0092] Step 11: the temperature of the graphite crucible containing the mixed 14 powder is increased to 1100 °C at a low heating rate of 300 °C/h by means of a muffle
LU503613 furnace which is at normal pressure and high temperature, and the graphite crucible 1s maintained at this temperature for 5 hrs. The high-temperature calcination rate 1s low, and the temperature maintaining time is long.
[0093] Step 12: The mixed powder in the graphite crucible in the muffle furnace is cooled to room temperature at a rate of 200 °C/h. Compared with the heating rate, a relatively low cooling rate is more beneficial for the formation of cellular loose sample powder can be formed more easily. The mixed powder is taken out carefully.
[0094] Step 13: the cellular loose trevorite 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.
[0095] Step 14: the fine-grained and uniform noble spinel 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.
[0096] 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.
[0097] Step 16: a stainless steel container containing 3 L of secondary deionized
LU503613 pure cold water is placed on one side of the high-temperature oxygen atmosphere furnace in advance.
[0098] Step 17: the top of the furnace body of the high-temperature oxygen atmosphere fumace is connected to an argon inert gas cylinder and a proportion-adjustable 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 is switched and regulated in time through a valve.
[0099] 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; under the protection of the argon, the sample is calcinated at high temperature to 800 °C at a heating rate of 400 °C/h.
[00100] 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.
[00101] 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 1450 °C at arate of 200 °C/h to perform constant-temperature calcination for 15 min to melt the sample into glassy-state trevorite.
[00102] Step 21: after the sample is calcinated at 1450 °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 trevorite glass. 16
[00103] Step 22: the quenched glassy-state trevorite is taken out of the graphite LU503613 crucible carefully, and is fully ground into fine-grained and uniform-composition sample powder in the corundum mortar. The glassy-state trevorite powder is dried in a vacuum drying oven at 200 °C for 12 hrs.
[00104] Step 23: the trevorite 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 obtain a ® 4.0 mm (diameter) * 4.0 mm (height) cylindrical trevorite sample.
[00105] To obtain high-water trevorite, nickel hydroxide powder (molecular formula:
Ni(OH)2) and natural manganite powder (molecular formula; Mn(OH)2), the weight ratio of which is 4:1, are used as a water source. The mixture of the nickel hydroxide and the manganite is used as the water source for the following reasons: first, the nickel hydroxide and the manganite are both typical hydrous substances and have low dehydration temperature, the dehydration temperature of nickel hydroxide is 230 °C, and the two dehydration temperatures of manganese hydroxide are 300 °C and 560 °C respectively, and all these dehydration temperatures are within a relatively low temperature interval during the process of preparing manganese-doped single-crystal trevorite under a high-temperature and high-pressure condition, which fully guarantees that the manganese-doped single-crystal trevorite 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 nickel hydroxide and the manganite are both nickel-rich and manganese-rich substances, so the nickel activity and the manganese activity can be controlled in the process of preparing manganese-doped and high-water single-crystal trevorite under a high-temperature and high-pressure condition in a sample cavity; and finally, dehydration products of the nickel hydroxide and the natural manganite with the weight ratio of 4:1, which are used for providing the water source and disposed at two ends of the sample, are nickel oxide, pyrolusite and manganic oxide, which will not chemically react with the 17 sample, thus ensuring the purity of a prepared manganese-doped and high-water
LU503613 single-crystal trevorite sample. In addition, by adjusting the weight ratio of the nickel hydroxide and the natural manganite for providing the water source and the height of the corresponding water-source discs, the water content of the manganese-doped and high-water single-crystal trevorite sample can be adjusted.
[00106] Step 24: the nickel hydroxide powder and the natural manganite 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.
[00107] Step 25: the cylindrical trevorite 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 manganese-doped trevorite sample is placed in the middle of the inner graphite tube, the two water-sourced discs prepared from the nickel hydroxide and the natural manganite with the weight ratio of 4:1 are placed at two symmetrical ends of the inner graphite tube close to the sample.
[00108] Step 26: trevorite is one of the important nickel-rich and ferrum-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 trevorite deep in the lower crust of the earth and other terrestrial planets and invert the temperature and pressure conditions for stable existence of the trevorite phase, the double-layer sample chamber composed of the graphite tube and the gold-palladium alloy tube is placed in a typical Kawai-1000t 6-8 multi-anvil, large-volume, high-temperature and high-pressure apparatus, the pressure and 18 temperature are increased to 3.0 GPa and 1100 °C at a rate of 0.5 GPa/h and a rate of 10
LU503613 °C/min respectively for hot-pressing sintering, and the reaction time is 72 hrs.
[00109] Step 27: after the reaction is performed at 3.0 GPa and 1100 °C for 72 hrs, the temperature in a sample cavity is decreased from 1100 °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.
[00110] Step 28: when the temperature in the sample cavity is decreased to room temperature, the pressure in the sample cavity 1s decreased from 3.0 GPa to normal pressure at a rate of 0.5 GPa.
[00111] 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 trevorite is picked out under a 20-power high-precision Olympus microscope. 19
Claims (6)
1. A method for preparing manganese-doped and high-water single-crystal trevorite under a high-temperature and high-pressure condition, comprising: preparing trevorite powder sample mixture discs using solid light-green basic nickel carbonate inorganic compound powder, solid transparent russet flaky ferric citrate (III) crystals, solid oxalic acid powder, solid pink manganese stearate powder, solid nickel hydroxide powder, solid natural manganite powder and liquid dilute nitric acid as starting materials; calcinating and quenching the trevorite powder sample mixture discs in a high-temperature oxygen atmosphere furnace to prepare a cylindrical trevorite sample; and placing water-sourced discs at two ends of the cylindrical trevorite sample and then sealing the cylindrical trevorite sample with the water-sourced discs for high-temperature and high-pressure reaction to obtain single-crystal trevorite.
2. The method for preparing manganese-doped and high-water single-crystal trevorite under a high-temperature and high-pressure condition according to Claim 1, wherein the purity of the solid light-green basic nickel carbonate inorganic compound powder is over
99.99%, the purity of the solid transparent russet flaky ferric citrate (III) crystals is over
99.99%, the purity of the solid oxalic acid powder is over 99.99%, the purity of the solid pink manganese stearate powder is over 99.99%, the purity of the solid nickel hydroxide powder is 99%, the purity of the solid natural manganite powder is over 99%, and the concentration of the liquid dilute nitric acid is 10%.
3. The method for preparing manganese-doped and high-water single-crystal trevorite under a high-temperature and high-pressure condition according to Claim 1, wherein the trevorite powder sample mixture discs are 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 light-green basic nickel carbonate inorganic compound powder, placing it in the beaker with the notch, and putting a magnetic stirring rotor in the LU503613 beaker with the notch;
Step 3: covering a mouth of the beaker with watch-glass, placing the beaker on a 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 19.5343 g of solid ferric citrate (III) crystals and 60 mg of solid manganese stearate powder according to trevorite (Ni, Mn)Fe204 stoichiometry, and adding them to the dilute nitric acid solution containing basic nickel carbonate;
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 adding it into the beaker;
Step 8: placing the beaker on the high-temperature magnetic stirring heater coil in the fume hood, covering the beaker with the watch-glass, and stirring for 36 hrs at 80 °C and 1000 rpm;
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 mixed powder out of the beaker, and placing it in a graphite crucible;
Step 11: placing the graphite crucible containing the mixed powder in a muffle furnace, then increasing the temperature of the graphite crucible to 1100 °C at a rate of 300 °C/h, and maintaining the graphite crucible at this temperature for 5 hrs;
Step 12: cooling the mixed powder to room temperature at a rate of 200 °C/h, and then taking out the mixed powder;
Step 13: grinding the mixed powder in a thickened corundum mortar for 1 h to obtain a trevorite powder sample mixture; and
21
Step 14: cold-pressing the trevorite powder sample mixture into three ® 10.0 mm * 3.0 LU503613 mm sample discs by a tungsten carbide grinding tool of a stainless steel press.
4. The method for preparing manganese-doped and high-water single-crystal trevorite under a high-temperature and high-pressure condition according to Claim 1, wherein calcinating and quenching the trevorite powder sample mixture discs in a high-temperature oxygen atmosphere furnace to prepare a cylindrical trevorite sample comprises: Step 15: stacking the three sample discs at a bottom of the graphite crucible, and drilling symmetrical circular holes in a wall of the graphite crucible; enabling a platinum-rhodium alloy wire to penetrate through the two symmetrical circular holes in the wall of the graphite crucible to hang the graphite crucible in a middle of the high-temperature oxygen atmosphere furnace; connecting and fixing two ends of the platinum-rhodium alloy wire penetrating through the graphite crucible to a vertical four-hole aluminum oxide tube, and fixing an upper end of the four-hole aluminum oxide tube in a middle of a circular cover 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 the 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; under the protection of the argon, calcinating the sample at high temperature to 800 °C ata 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; 22
Step 20: when a mixed gas flow of the carbon monoxide and the carbon dioxide with LU503613 the volume ratio of 4:1 in a sample chamber 1s stabilized, increasing the temperature of the sample chamber in the furnace body to 1450 °C at a rate of 200 °C/h to perform constant-temperature calcination for 15 min: Step 21: after the sample is calcinated at 1450 °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 them in the stainless steel container containing the secondary deionized pure cold water to quench the sample into a glassy -state trevorite sample: Step 22: taking the glassy-state trevorite sample out of the graphite crucible, and grinding it into fine-grained and uniform-composition glassy-state trevorite powder in the corundum mortar; drying the glassy-state trevorite powder in a vacuum drying oven at 200 °C for 12 hrs; and Step 23: cold-pressing the glassy-state trevorite powder into a ® 4.0 mm (diameter) *
4.0 mm (height) cylindrical trevorite sample on a cold isostatic press by a tungsten carbide grinding tool.
5. The method for preparing manganese-doped and high-water single-crystal trevorite under a high-temperature and high-pressure condition according to Claim 1, wherein placing water-sourced discs at two ends of the cylindrical trevorite sample and then sealing the cylindrical trevorite sample with the water-sourced discs for high-temperature and high-pressure reaction to obtain single-crystal trevorite comprise: Step 24: cold-pressing the nickel hydroxide powder and the natural manganite powder on a cold isostatic press by a tungsten carbide grinding tool according to a weight ratio of 4:1 to obtain two ® 4.0 mm (diameter) * 0.1 mm (height) water-sourced discs; Step 25: sealing the cylindrical trevorite sample and the two water-sourced discs in the double-layer experimental sample chamber with an inner tube being a graphite tube, 23 wherein the cylindrical trevorite sample is placed in a middle of the graphite inner tube, LU503613 the two water-sourced discs are placed at two symmetrical ends of the graphite inner tube close to the sample, and an outer tube of the double-layer sample chamber uses gold-palladium alloy as sealing materials; Step 26: placing the double-layer sample chamber composed of the graphite tube and a gold-palladium alloy tube in a typical Kawai-1000t 6-8 multi-anvil, large-volume, high-temperature and high-pressure apparatus, and increasing the pressure and temperature to 3.0 GPa and 1100 °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 temperature and constant pressure for 72 hrs; Step 27: after reacting at 3.0 GPa and 1100 °C for 72 hrs, decreasing the temperature in a sample cavity from 1100 °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 is decreased to room temperature, decreasing the pressure in the sample cavity from 3.0 GPa to normal pressure at a rate of
0.5 GPa; and Step 29: after the high-temperature and high-pressure reaction is completed, 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, and cutting the cylindrical sample in the middle; picking out single-crystal trevorite under a 20-power high-precision Olympus microscope.
6. The method for preparing manganese-doped and high-water single-crystal trevorite under a high-temperature and high-pressure condition according to Claim 1, wherein during the high-temperature and high-pressure reaction, two sets of high-temperature 24 tungsten-rhenium thermocouples are used for temperature calibration; each of the two sets LU503613 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 tungsten-rhenium thermocouples are symmetrically disposed at an upper end and a lower end of a sample chamber respectively.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211551729.9A CN115852469A (en) | 2022-12-05 | 2022-12-05 | Preparation method of manganese-doped and high-water-content nickel magnetite single crystal at high temperature and high pressure |
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| Publication Number | Publication Date |
|---|---|
| LU503613B1 true LU503613B1 (en) | 2023-09-14 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| LU503613A LU503613B1 (en) | 2022-12-05 | 2023-03-13 | Method for preparing manganese-doped and high-water single-crystal trevorite under high-temperature and high-pressure condition |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN115852469A (en) |
| LU (1) | LU503613B1 (en) |
| ZA (1) | ZA202302208B (en) |
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2022
- 2022-12-05 CN CN202211551729.9A patent/CN115852469A/en active Pending
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2023
- 2023-02-22 ZA ZA2023/02208A patent/ZA202302208B/en unknown
- 2023-03-13 LU LU503613A patent/LU503613B1/en active IP Right Grant
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| CN115852469A (en) | 2023-03-28 |
| ZA202302208B (en) | 2023-05-31 |
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