CN110592674A - Micron-sized Cr3C2Preparation method of whisker - Google Patents
Micron-sized Cr3C2Preparation method of whisker Download PDFInfo
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- CN110592674A CN110592674A CN201910993279.0A CN201910993279A CN110592674A CN 110592674 A CN110592674 A CN 110592674A CN 201910993279 A CN201910993279 A CN 201910993279A CN 110592674 A CN110592674 A CN 110592674A
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- 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
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- 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
- C30B29/36—Carbides
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- 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
- C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
- C30B29/62—Whiskers or needles
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- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention relates to micron-sized Cr3C2The preparation method of the whisker comprises the steps of mixing chromium oxide, carbon black, glucose, nickel powder, sodium chloride and potassium chloride according to a certain proportion, ball-milling to prepare a whisker growth precursor, calcining at high temperature under the protection of argon gas, and decarbonizing to obtain micron-sized Cr with high purity3C2A whisker. The invention has the following effects: the preparation process is simple to operate, green and environment-friendly, has no toxic substances, is wide in raw material source and low in price, and can realize batch production; micron-sized Cr3C2The generation rate of the crystal whisker is high, and no other chromium carbide crystal phase is generated; prepared micron-sized Cr3C2The shape of the whisker is in a short rod shape, the part of the whisker is in a bending shape, the diameter is about 1 to 2 mu m, the length is about 6 to 15 mu m, and the length-diameter ratioAbout 6 to about 10.
Description
Technical Field
The invention belongs to the technical field of whisker preparation, and particularly relates to micron-sized Cr3C2A preparation method of the whisker.
Background
The whisker is composed ofThe micro-nano short fiber formed by high-purity single crystal growth has the advantages of high strength, high modulus, high elongation and the like due to the highly oriented growth characteristics, and therefore, the micro-nano short fiber is usually used as a reinforcing and toughening phase of a composite material. Among the whiskers, Cr3C2The crystal whisker has the advantages of high melting point, high wear resistance, excellent oxidation resistance, excellent corrosion resistance and the like, so the crystal whisker has potential application space in the environment with severe working conditions and high requirement on safety coefficient in the aviation industry, the nuclear industry and the like. However, at present, Cr is considered at home and abroad3C2Whiskers are relatively poorly studied.
Conventional Cr is obtained by examining the literature3C2The preparation method of the crystal whisker is characterized in that ammonium dichromate is used as a chromium source, glucose is used as a carbon source, halide or iron, cobalt and nickel are used as catalysts, and the crystal whisker is prepared by calcining in an anaerobic environment. The method comprises the steps of prefabricating a whisker growth precursor in a heated aqueous solution by using ammonium dichromate and glucose, taking three metal powders of iron, cobalt and nickel as catalysts, and carrying out heat preservation for 2 hours at 800 ℃ under the condition of introducing argon gas to prepare Cr with the diameter of less than 50nm3C2A nanowhisker. Although the method can obtain the nano-grade crystal whisker, the preparation process has high toxicity, so that the method cannot meet the environmental protection requirement of China and is not beneficial to batch production. Therefore, Cr which is simple to operate, green and environment-friendly and has high generation rate is sought3C2The preparation method of the whisker is very important.
Disclosure of Invention
In order to solve the above problems, an object of the present invention is to provide micron-sized Cr3C2A preparation method of the whisker.
In order to achieve the purpose, the invention provides micron-sized Cr3C2The preparation method of the whisker comprises the following steps which are carried out in sequence:
(1) mixing chromic oxide, carbon black, glucose, nickel powder, sodium chloride and potassium chloride according to the molar ratio of 2-3:5-8:1-2:1.1-1.3:0.9-1.1:0.9-1.1, then placing the mixture into a planetary ball mill, and carrying out ball milling for 6-8h at the rotating speed of 250r/min to obtain a whisker growth precursor;
(2) placing the whisker growth precursor in a tube furnace, heating to 1100-1300 ℃ at the heating rate of 3-5 ℃/min under the protection of argon gas to carry out high-temperature calcination and carbon removal, keeping the temperature for 2-5h, cooling to 900 ℃ at the cooling rate of less than or equal to 5 ℃/min, and then cooling along with the furnace;
(3) heating the product obtained in the step (2) to 500 ℃ at a heating rate of 10 ℃/min in the air atmosphere, and preserving heat for 30min to obtain micron-sized Cr with higher purity3C2A whisker.
The chromium sesquioxide and the glucose in the step (1) are purchased from Tianjin Kemi Euro reagent Co.
The carbon black in the step (1) is purchased from Tianjin Rihua chemical engineering Co., Ltd, and the particle size is 0.28 μm.
The nickel powder in the step (1) is purchased from Beijing Xinglong source science and technology limited, and the particle size is 5-8 mu m.
The sodium chloride and the potassium chloride in the step (1) are purchased from Tianjin Tianmao chemical Co., Ltd and are analytically pure.
The invention provides micron-sized Cr3C2The preparation method of the whisker has the following beneficial effects:
1. the preparation process is simple to operate, green and environment-friendly, has no toxic substances, is wide in raw material source and low in price, and can realize batch production;
2. micron-sized Cr3C2The generation rate of the crystal whisker is high, and no other chromium carbide crystal phase is generated;
3. prepared Cr3C2The shape of the whisker is in a short rod shape, the part of the whisker is in a bending shape, the diameter is about 1-2 mu m, the length is about 6-15 mu m, and the length-diameter ratio is about 6-10.
Drawings
FIG. 1 is micron-sized Cr prepared in example 13C2XRD analysis pattern of whisker;
FIG. 2 is micron-sized Cr prepared in example 13C2Scanning electron microscope photographs of the whiskers;
FIG. 3 is micron-sized Cr prepared in example 13C2Of whiskersTransmission electron micrographs.
Detailed Description
The present invention is further illustrated by the following specific examples.
Example 1
The micron-sized Cr provided in this embodiment3C2The preparation method of the whisker comprises the following steps which are carried out in sequence:
(1) mixing chromic oxide, carbon black, glucose, nickel powder, sodium chloride and potassium chloride according to a molar ratio of 2:5:2:1.1:0.9:0.9, then placing the mixture into a planetary ball mill, and carrying out ball milling for 6 hours at a rotating speed of 250r/min to obtain a whisker growth precursor;
(2) placing the whisker growth precursor in a tubular furnace, heating to 1300 ℃ at the heating rate of 5 ℃/min under the protection of argon, preserving heat for 2h, cooling to 900 ℃ at the cooling rate of 5 ℃/min, and then cooling along with the furnace;
(3) heating the product obtained in the step (2) to 500 ℃ at a heating rate of 10 ℃/min in the air atmosphere, and preserving heat for 30min to obtain micron-sized Cr with higher purity3C2A whisker.
Example 2
The micron-sized Cr provided in this embodiment3C2The preparation method of the whisker comprises the following steps which are carried out in sequence:
(1) mixing chromic oxide, carbon black, glucose, nickel powder, sodium chloride and potassium chloride according to a molar ratio of 2.5:6.5:1.5:1.2:1:1, then placing the mixture into a planetary ball mill, and carrying out ball milling for 7 hours at a rotating speed of 250r/min to obtain a whisker growth precursor;
(2) placing the whisker growth precursor in a tubular furnace, heating to 1200 ℃ at a heating rate of 3 ℃/min under the protection of argon, preserving heat for 3h, cooling to 900 ℃ at a cooling rate of 5 ℃/min, and then cooling along with the furnace;
(3) and (3) heating the product obtained in the step (2) to 500 ℃ at the heating rate of 10 ℃/min in the air atmosphere, and preserving the temperature for 30min to obtain the micron Cr3C2 crystal whisker with higher purity.
Example 3
The micron-sized Cr provided in this embodiment3C2The preparation method of the whisker comprises the following steps which are carried out in sequence:
(1) mixing chromic oxide, carbon black, glucose, nickel powder, sodium chloride and potassium chloride according to a molar ratio of 3:8:2:1.3:1.1:1.1, then placing the mixture into a planetary ball mill, and carrying out ball milling for 8 hours at a rotating speed of 250r/min to obtain a whisker growth precursor;
(2) placing the precursor for whisker growth in a tube furnace, heating to 1100 ℃ at a heating rate of 3 ℃/min under the protection of argon, preserving heat for 5h, cooling to 900 ℃ at a cooling rate of 3 ℃/min, and then cooling along with the furnace;
(3) heating the product obtained in the step (2) to 500 ℃ at a heating rate of 10 ℃/min in the air atmosphere, and preserving heat for 30min to obtain micron-sized Cr with higher purity3C2A whisker.
The invention provides micron-sized Cr3C2The crystal whisker takes chromium oxide as a chromium source, carbon black and glucose as carbon sources, and nickel powder as a catalyst for crystal whisker growth. The nickel powder can reduce the gasification activation energy of the carbon black and is beneficial to the gasification of the carbon black; the sodium chloride and the potassium chloride are beneficial to reducing the melting point of the chromium sesquioxide and improving the solubility of the chromium source in a liquid phase environment at high temperature; the molten state (micro-droplets) of the nickel powder can also provide a liquid phase environment for the reaction between the chromium source and the carbon source, so that the solid phase reaction is converted into a solid-liquid reaction or a solid-liquid-gas reaction, the reaction and the radial growth of whiskers are facilitated, and the generation of large grains is avoided, thereby obtaining the micron-sized Cr with higher purity3C2A whisker.
To verify the micron-sized Cr provided in the above examples3C2The inventors of the present invention conducted the following experiments:
(1) and (3) analyzing the whisker components: micron-sized Cr prepared in the above examples was analyzed using XRD tester (D/Max 2500v/PC, Rigaku)3C2The XRD pattern of the composition of the whisker is shown in figure 1.
As can be seen from FIG. 1, the XRD pattern showed almost all of the crystal phases as Cr3C2(PDF-71-2287) without other crystal phases, which shows that the preparation method can prepare Cr with extremely high purity3C2A whisker.
(2) Analyzing the surface topography of the whisker: micron-sized Cr observation using a scanning electron microscope (Nanosem430, FEI)3C2The microscopic morphology of the whiskers is shown in figure 2.
As can be seen from FIG. 2, the micron-sized Cr3C2The shape of the whisker is in a short rod shape, the part of the whisker is in a bending shape, the diameter is about 1-2 mu m, the length is about 6-15 mu m, and the length-diameter ratio is about 6-10.
(3) Transmission electron microscopy analysis of whiskers: micron-sized Cr was analyzed using a transmission electron microscope (Tecnai G2F 20, FEI)3C2Crystal structure of whisker, FIG. 3 is micron-sized Cr3C2High power transmission pictures of whiskers. From FIG. 3, clear lattice fringes were observed, and the crystal planes having a measured interplanar spacing of 0.164nm were Cr3C2{214} crystal face, and the whisker is along [214]Is grown in the direction of the crystal phase.
Claims (3)
1. Micron-sized Cr3C2The preparation method of the crystal whisker is characterized in that: the preparation method comprises the following steps which are carried out in sequence:
(1) mixing chromic oxide, carbon black, glucose, nickel powder, sodium chloride and potassium chloride according to the molar ratio of 2-3:5-8:1-2:1.1-1.3:0.9-1.1:0.9-1.1, then placing the mixture into a planetary ball mill, and carrying out ball milling for 6-8h at the rotating speed of 250r/min to obtain a whisker growth precursor;
(2) placing the whisker growth precursor in a tube furnace, heating to 1100-1300 ℃ at the heating rate of 3-5 ℃/min under the protection of argon gas to carry out high-temperature calcination and carbon removal, keeping the temperature for 2-5h, cooling to 900 ℃ at the cooling rate of less than or equal to 5 ℃/min, and then cooling along with the furnace;
(3) heating the product obtained in the step (2) to 500 ℃ at a heating rate of 10 ℃/min in the air atmosphere, and preserving heat for 30min to obtain micron-sized Cr with higher purity3C2A whisker.
2. Micron-sized Cr according to claim 13C2The preparation method of the crystal whisker is characterized in that: the particle diameter of the carbon black in the step (1) is 0.28 μm.
3. Micron-sized Cr according to claim 13C2The preparation method of the crystal whisker is characterized in that: the particle size of the nickel powder in the step (1) is 5-8 μm.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56100125A (en) * | 1980-01-14 | 1981-08-11 | Sumitomo Electric Ind Ltd | Manufacture of silicon carbide whisker |
| CN1472136A (en) * | 2003-07-15 | 2004-02-04 | 中国科学院理化技术研究所 | Method for preparing silicon carbide |
| CN102051676A (en) * | 2010-10-29 | 2011-05-11 | 山东大学 | In-situ grown tantalum carbide whisker material and preparation method thereof |
| CN103849934A (en) * | 2014-03-28 | 2014-06-11 | 四川理工学院 | Preparation method of nano Cr3C2 crystal whisker |
| CN110042468A (en) * | 2019-04-08 | 2019-07-23 | 西北工业大学 | A kind of preparation method of micrometer silicon carbide zirconium whisker |
-
2019
- 2019-10-15 CN CN201910993279.0A patent/CN110592674A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56100125A (en) * | 1980-01-14 | 1981-08-11 | Sumitomo Electric Ind Ltd | Manufacture of silicon carbide whisker |
| CN1472136A (en) * | 2003-07-15 | 2004-02-04 | 中国科学院理化技术研究所 | Method for preparing silicon carbide |
| CN102051676A (en) * | 2010-10-29 | 2011-05-11 | 山东大学 | In-situ grown tantalum carbide whisker material and preparation method thereof |
| CN103849934A (en) * | 2014-03-28 | 2014-06-11 | 四川理工学院 | Preparation method of nano Cr3C2 crystal whisker |
| CN110042468A (en) * | 2019-04-08 | 2019-07-23 | 西北工业大学 | A kind of preparation method of micrometer silicon carbide zirconium whisker |
Non-Patent Citations (1)
| Title |
|---|
| YONGZHONG JIN等: "First synthesis of Cr3C2 nanowhiskers by low-temperature vaccum carburization from precursor", 《MATERIALS CHEMISTRY AND PHYSICS》 * |
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