CN114032607A - Method for preparing zirconium carbide whisker by adopting zirconium carbide seed crystal - Google Patents
Method for preparing zirconium carbide whisker by adopting zirconium carbide seed crystal Download PDFInfo
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- 229910026551 ZrC Inorganic materials 0.000 title claims abstract description 163
- OTCHGXYCWNXDOA-UHFFFAOYSA-N [C].[Zr] Chemical compound [C].[Zr] OTCHGXYCWNXDOA-UHFFFAOYSA-N 0.000 title claims abstract description 163
- 239000013078 crystal Substances 0.000 title claims abstract description 83
- 238000000034 method Methods 0.000 title claims abstract description 51
- 239000000843 powder Substances 0.000 claims abstract description 29
- 239000000376 reactant Substances 0.000 claims abstract description 24
- 238000006722 reduction reaction Methods 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 13
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 44
- 238000000498 ball milling Methods 0.000 claims description 31
- 239000002245 particle Substances 0.000 claims description 29
- 239000006229 carbon black Substances 0.000 claims description 24
- 239000011775 sodium fluoride Substances 0.000 claims description 22
- 235000013024 sodium fluoride Nutrition 0.000 claims description 22
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 18
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 18
- 238000007873 sieving Methods 0.000 claims description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 13
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 11
- 229910052726 zirconium Inorganic materials 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 238000012216 screening Methods 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical class [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical class [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical class Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- WHJFNYXPKGDKBB-UHFFFAOYSA-N hafnium;methane Chemical compound C.[Hf] WHJFNYXPKGDKBB-UHFFFAOYSA-N 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical class [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical class [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 4
- UNASZPQZIFZUSI-UHFFFAOYSA-N methylidyneniobium Chemical compound [Nb]#C UNASZPQZIFZUSI-UHFFFAOYSA-N 0.000 claims description 4
- NFFIWVVINABMKP-UHFFFAOYSA-N methylidynetantalum Chemical compound [Ta]#C NFFIWVVINABMKP-UHFFFAOYSA-N 0.000 claims description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical class [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 4
- 229910003468 tantalcarbide Inorganic materials 0.000 claims description 4
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical class [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical class [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- 239000001110 calcium chloride Chemical class 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 239000010955 niobium Substances 0.000 claims description 2
- 239000005416 organic matter Substances 0.000 claims description 2
- 229920000620 organic polymer Polymers 0.000 claims description 2
- 239000001103 potassium chloride Chemical class 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 239000011698 potassium fluoride Chemical class 0.000 claims description 2
- 235000003270 potassium fluoride Nutrition 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 239000011592 zinc chloride Chemical class 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 238000003763 carbonization Methods 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 23
- 229910052751 metal Inorganic materials 0.000 abstract description 21
- 239000002184 metal Substances 0.000 abstract description 21
- 239000000919 ceramic Substances 0.000 abstract description 9
- 239000011159 matrix material Substances 0.000 abstract description 9
- 239000002131 composite material Substances 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 239000007772 electrode material Substances 0.000 abstract description 3
- 239000011347 resin Substances 0.000 abstract description 3
- 229920005989 resin Polymers 0.000 abstract description 3
- 238000007796 conventional method Methods 0.000 abstract description 2
- 230000003014 reinforcing effect Effects 0.000 abstract description 2
- 238000009827 uniform distribution Methods 0.000 abstract description 2
- 239000012535 impurity Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000011812 mixed powder Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000009975 flexible effect Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000011302 mesophase pitch Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000004098 selected area electron diffraction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000011215 ultra-high-temperature ceramic Substances 0.000 description 1
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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
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention relates to a method for preparing zirconium carbide whiskers by using zirconium carbide seed crystals, and provides a method for growing zirconium carbide whiskers by using zirconium carbide seed crystals without using a metal catalyst in order to solve the problems that the top of the zirconium carbide whiskers prepared by the conventional method contains the metal catalyst, the size of the whiskers is uncontrollable, the morphology is poor and the like. The technical scheme of the invention is that zirconium carbide seed crystals and reactant powder are mixed, and the zirconium carbide whiskers are synthesized by carbothermic reduction reaction at high temperature, and the size and the content of the zirconium carbide seed crystals are changed to effectively regulate and control the size of the zirconium carbide whiskers. The zirconium carbide whisker prepared by the method has the beneficial effects of no metal catalyst, controllable size, upright appearance, standard quadrangular prism shape, uniform distribution and high purity. The zirconium carbide whisker prepared by the method can be used as a reinforcing phase of a ceramic matrix, a metal matrix and a resin matrix composite material, and can also be used in the fields of superhard ceramics, electrode materials, nuclear power materials and the like.
Description
Technical Field
The invention belongs to the technical field of preparation of new materials, and relates to a method for preparing zirconium carbide whiskers by adopting zirconium carbide seed crystals.
Background
The zirconium carbide (ZrC) ceramic is one of ultra-high temperature ceramic materials, and has the characteristics of high melting point (about 3540 ℃), high strength, high hardness, high modulus, good ablation resistance, good heat conduction and electrical conductivity and the like. The zirconium carbide ceramic has wide application prospect in the fields of thermal protection, thermal structure materials, super-hard ceramics, electrode materials, nuclear power materials and the like. The zirconium carbide whisker not only has excellent intrinsic performance of zirconium carbide ceramic, but also has ultrahigh strength close to the theoretical limit due to one-dimensional single crystal structure. The zirconium carbide whisker is an ideal composite material reinforcement, can be widely applied to ceramic matrix, metal matrix and resin matrix composite materials, and improves the mechanical property, the electric conductivity, the heat conductivity, the electromagnetic property and the like of the composite material. At present, the methods for preparing zirconium carbide whiskers mainly comprise a carbothermic method and a chemical vapor deposition method. Among the reported methods for preparing zirconium carbide whiskers, most methods introduce metal catalysts (Fe, Co, Ni (NO)3)2·6H2O、Ni(NO3)2Etc.) to realize one-dimensional growth of zirconium carbide, thereby preparing zirconium carbide whiskers having a one-dimensional single crystal structure.
Zirconium carbide whiskers are prepared by carbothermic reduction using zirconium oxide, carbon black, sodium fluoride as raw Materials and metal Ni particles as catalysts, as described in "Study on the synthesis and growth mechanisms of the reaction ZrC whiskers, Liang Xu, Chuanzhen Huang, Hanlian Liu, Bin Zou, Hongtao Zhu, Guolong Zhuao, Jun Wang. int. journal of Refractry Metals and Hard Materials,2014,42: 116-" cited. The crystal whisker prepared by the method has a single crystal structure, the top of the crystal whisker is provided with catalyst Ni particles, the length and diameter of the crystal whisker are small, the yield of the crystal whisker is low, and the size is difficult to control. The patent "a method for preparing zirconium carbide whisker by using chemical vapor deposition method (CN 111549378A)" discloses a method for preparing zirconium carbide whisker by using ZrCl4-CH4(C3H6)-H2Ar as reactant system and Ni (NO)3)2The zirconium carbide crystal whisker is prepared by a chemical vapor deposition method as a catalyst. The crystal whisker prepared by the method has high purity and good appearance, and a larger catalyst is also arranged at the top of the crystal whiskerNi particles. The documents "In-situ homology growth of ZrC nanowines on carbon cloth and the third effects on flexible properties of carbon/carbon composites, Ningning Yan, Xiaohong Shi, Kun Li, Qiangang Fu, Wei Xie, Honghui Zhang, Qiang Song. composites Part B,2018,154: 200-. The method adopts zirconium carbide precursor as zirconium source and carbon source, and adopts Ni (NO)3)2·6H2And O is used as a catalyst to prepare the zirconium carbide whisker. The crystal whisker prepared by the method has curled appearance and low yield, and the top of the crystal whisker still has catalyst Ni particles.
The above methods all realize the preparation of zirconium carbide whiskers by introducing a metal catalyst into a reactant system, but inevitably generate the key problem that the metal catalyst with low melting point is an impurity existing at the top of each whisker and has adverse effects on the service performance (such as mechanical property, electromagnetic property and the like) of the zirconium carbide whiskers. In order to ensure the service performance of the zirconium carbide whisker, the whisker product is usually required to be subjected to acid washing and other operations, the acid washing possibly causes certain damage to the zirconium carbide whisker to influence the quality, and the preparation steps of acid washing impurity removal are added, so that the process steps become more complicated and do not accord with the economic and efficient principle, and meanwhile, the acid washing solution can also cause adverse effects on the environment and does not accord with the environment-friendly principle. Therefore, the development of the method for preparing the zirconium carbide whisker by using the metal-free catalyst has important significance.
The patent "a method for preparing zirconium carbide whisker (CN 108560058B)" discloses a method for preparing zirconium carbide whisker by using mesophase pitch and zirconium tetrachloride as reactants and without a metal catalyst. The method is simple to operate and high in yield, but the zirconium tetrachloride is seriously volatilized at high temperature, and the reaction is difficult to control, so that the diameter of the whisker prepared by the method is not uniform, and the size of the whisker is uncontrollable.
In summary, no report is available on the preparation method of the zirconium carbide whisker, which can effectively control the size and the shape of the whisker, does not use a metal catalyst, and has simple process, low cost and high yield.
Disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides a method for preparing zirconium carbide whiskers by using zirconium carbide seed crystals, which overcomes the defects of metal catalyst, uncontrollable size, curved and irregular shape, poor uniformity, low purity and the like of the zirconium carbide whiskers prepared by the prior art, and prepares the zirconium carbide whiskers which are free of metal catalyst, controllable in size, upright in shape, in a standard quadrangular shape, uniform in distribution, high in purity and short in production period.
Technical scheme
A method for preparing zirconium carbide whiskers by adopting zirconium carbide seed crystals is characterized by comprising the following steps:
step 1, preparing raw materials for ball milling: mixing a system I comprising zirconium oxide, carbon black, sodium fluoride and zirconium carbide seed crystals in proportion, mixing a system II comprising polycarbozircoalkane, carbon black, sodium fluoride and zirconium carbide seed crystals in proportion, and performing ball milling to obtain uniformly mixed reactant precursor powder;
in the system, the molar ratio of zirconium oxide, carbon black, sodium fluoride and zirconium carbide seed crystals is 1: 3-8: 0.1-2: 0.1-1;
in the second system, the molar ratio of zirconium element, carbon black, sodium fluoride and zirconium carbide seed crystal in the polycarboziridine is 1: 2-6: 0.1-2: 0.1-1;
step 2: sieving the precursor powder to obtain powder with uniform particle size;
step 3, carbon thermal reduction: putting the powder obtained in the step 2 into a graphite crucible, and carrying out carbothermic reduction reaction in a tubular furnace to obtain zirconium carbide whiskers; reaction temperature: 1500 ℃, heat preservation time: 2-4 h, heating rate: 5K/min, atmosphere: argon, flow: 20-200 sccm;
step 4, ultrasonic and screening: putting the zirconium carbide whisker into deionized water, performing ultrasonic treatment for 4 hours, sieving, and drying to obtain pure zirconium carbide whisker.
In the step 1, the zirconium carbide seed crystal is single crystal zirconium carbide particles.
The polycarbozircoalkane is zirconium carbide organic matter precursor powder, and the ratio of zirconium element to carbon element in the polycarbozircoalkane is 1: 1.
And the sodium fluoride in the step 1 is replaced by one of inorganic salts of sodium chloride, potassium chloride, lithium chloride, magnesium chloride, zinc chloride, aluminum chloride, calcium chloride, lithium fluoride and potassium fluoride.
In the step 1, the size of the single crystal zirconium carbide particles is 10-1000 nm, the size of the zirconium oxide particles is 200nm, the size of the carbon black is 13nm, and the size of the sodium fluoride particles is 2-3 μm.
The ball material ratio of the ball milling mixed material in the step 1 is 3: 1.
In the step 1, the ball milling speed is 50-200 r/min.
The sieving in the step 2 adopts 100 meshes
The mesh number of the screen subjected to screening treatment in the step 4 is determined according to the length of the whisker, and the mesh size of the screen is smaller than the length of the whisker.
The preparation method for preparing the carbonized whisker is characterized in that: when the zirconium carbide seed crystal is replaced by a hafnium carbide seed crystal, a titanium carbide seed crystal, a tantalum carbide seed crystal or a niobium carbide seed crystal, zirconium oxide and polycarbozirane are replaced by oxides of Hf, Ti, Ta and Nb and corresponding organic polymers, and the hafnium carbide whisker, the titanium carbide whisker, the tantalum carbide whisker or the niobium carbide whisker is prepared.
Advantageous effects
The invention provides a method for preparing zirconium carbide whiskers by using zirconium carbide seed crystals, which aims to solve the problems that the top of the zirconium carbide whiskers prepared by the conventional method contains a metal catalyst, the size of the whiskers is uncontrollable, the morphology is poor and the like. The technical scheme of the invention is that zirconium carbide seed crystals and reactant powder are mixed, and the zirconium carbide whiskers are synthesized by carbothermic reduction reaction at high temperature, and the size and the content of the zirconium carbide seed crystals are changed to effectively regulate and control the size of the zirconium carbide whiskers. The zirconium carbide whisker prepared by the method has the beneficial effects of no metal catalyst, controllable size, upright appearance, standard quadrangular prism shape, uniform distribution and high purity. The zirconium carbide whisker prepared by the method can be used as a reinforcing phase of a ceramic matrix, a metal matrix and a resin matrix composite material, and can also be used in the fields of superhard ceramics, electrode materials, nuclear power materials and the like.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, zirconium carbide crystal seeds are adopted to replace a metal catalyst, and the anisotropic growth of zirconium carbide particles is realized by utilizing a V-S mechanism to prepare the zirconium carbide whisker, so that the zirconium carbide whisker does not contain metal catalyst impurities, and the adverse effect of the metal catalyst on the service performance of the zirconium carbide whisker is avoided.
(2) The zirconium carbide crystal whisker prepared by the method is quadrangular, grows vertically and has good appearance. The zirconium carbide crystal whisker has uniform size, the size of the zirconium carbide crystal whisker can be effectively controlled by changing the size and the content of the added zirconium carbide seed crystal, the diameter of the prepared zirconium carbide crystal whisker can be controlled within 100-5000 nm, and the length of the zirconium carbide crystal whisker can be controlled within the range of 1-1000 mu m.
(3) The purity of the zirconium carbide whisker prepared by the method is close to 100 percent, and the yield (n (Zr)ZrCw)/n(ZrZrO2) Defined as the ratio of the molar amount of zirconium element in the zirconium carbide whiskers to the molar amount of zirconium element in the zirconia raw material) up to 35%.
(4) The zirconium carbide whisker preparation method developed by the invention has the advantages of simple process, low equipment requirement, convenient operation and short production period, and is suitable for large-scale industrial production.
(5) The purification process of the whisker related by the invention is ultrasonic and sieving, the purification process is simple, and the whisker is not damaged.
Drawings
FIG. 1 is a process flow diagram of the present invention.
FIG. 2 is a TEM image of a zirconium carbide seed crystal of example 1 of the present invention.
Fig. 3 is a Scanning Electron Microscope (SEM) photograph of zirconium carbide whiskers prepared by other methods.
FIG. 4 is a Scanning Electron Microscope (SEM) photograph of zirconium carbide whiskers of example 1 of the present invention.
FIG. 5 is a selected area electron diffraction (TEM) photograph of zirconium carbide whiskers of example 1 of the present invention.
Figure 6 is an X-ray diffraction (XRD) pattern of zirconium carbide whisker according to example 1 of the present invention.
Detailed Description
The invention will now be further described with reference to the following examples and drawings:
the technical solutions in the embodiments of the present invention will be clearly described below, and it is obvious that the described embodiments are only some of the embodiments of the present invention. Based on the embodiments of the present invention, those skilled in the art can obtain other embodiments without creative efforts and without departing from the method provided by the present invention, which belong to the protection scope of the present invention.
In the example of preparing zirconium carbide whisker by using zirconium carbide seed crystal:
step 1, preparing raw materials for ball milling: mixing zirconium oxide, carbon black, sodium fluoride and zirconium carbide seed crystals according to a certain proportion, mixing polycarbozicloalkane, carbon black, sodium fluoride and zirconium carbide seed crystals according to a certain proportion, and performing ball milling to obtain reactant powder which is uniformly mixed.
Step 2, sieving: sieving the precursor powder obtained in the step 1 by a 100-mesh sieve to obtain powder with uniform particle size;
step 3, carbothermic reduction: and (3) putting the powder obtained in the step (2) into a graphite crucible, and carrying out carbothermic reduction reaction in a tubular furnace to obtain the zirconium carbide whisker. Reaction temperature: 1500 ℃, heat preservation time: 2-4 h, heating rate: 5K/min, atmosphere: argon, flow: 20-200 sccm;
step 4, ultrasonic and screening: putting the zirconium carbide whisker into deionized water, performing ultrasonic treatment for 4 hours, sieving, and drying to obtain pure zirconium carbide whisker.
In the step 1, the molar ratio of zirconium oxide, carbon black, sodium fluoride and zirconium carbide seed crystals is 1: 3-8: 0.1-2: 0.1-1, and the molar ratio of zirconium element, carbon black, sodium fluoride and zirconium carbide seed crystals in polycarbozirane is 1: 2-6: 0.1-2: 0.1-1.
In the step 1, the zirconium carbide seed crystal is single crystal zirconium carbide particles, and the particle size is 10-1000 nm. When the size of the seed crystal is small, the diameter of the prepared zirconium carbide whisker is small, and the length of the prepared zirconium carbide whisker is long; when the size of the seed crystal is larger, the diameter of the synthesized crystal whisker is larger and the length is shorter. When the size of the zirconium carbide seed crystal is not changed, the higher the adding amount of the seed crystal is, the smaller the diameter of the zirconium carbide whisker is, and the longer the length of the zirconium carbide whisker is; the lower the seed crystal adding amount is, the larger the diameter of the zirconium carbide whisker is and the shorter the length of the zirconium carbide whisker is. Namely, the size and the content of the added zirconium carbide seed crystal can be regulated and controlled to effectively control the size of the generated zirconium carbide whisker.
In the step 1, the size of zirconium oxide particles is about 200nm, the size of carbon black is about 13nm, and the size of sodium fluoride particles is about 2-3 μm. The polycarbozircoalkane is zirconium carbide organic precursor powder, and the ratio of zirconium element to carbon element in the polycarbozircoalkane is about 1: 1.
The ball material ratio of the ball milling mixed material in the step 1 is 3: 1.
In the step 1, the ball milling speed is 50-200 r/min.
The mesh number of the screen subjected to screening treatment in the step 4 is determined according to the length of the whisker, and the mesh size of the screen is smaller than the length of the whisker.
Example 1
Step 1, preparing raw materials for ball milling:
the reactant system (i) is prepared by mixing zirconium oxide: carbon black: sodium fluoride: 5g of ball-milling raw material is prepared from zirconium carbide seed crystals in a ratio of 1:5:0.6:0.1, ball milling is carried out according to a ball-to-material mass ratio of 3:1 and a rotating speed of 100r/min, and the ball-milling time is 4 hours. And obtaining reactant powder which is uniformly mixed. In this example, the zirconium carbide seed particles are about 20 nm.
Step 2, sieving:
and (3) sieving the reactant powder obtained in the step (1) by a 100-mesh sieve to obtain reactant mixed powder with uniform particle size.
Step 3, carbothermic reduction
Putting the powder obtained in the step 2 into a graphite crucible
The tube furnace of (2) is used for carrying out carbothermic reduction reaction. Reaction temperature: 1500 ℃, heat preservation time: 4h, heating rate: 5K/min, atmosphere: argon, gas flow: and (5) 50sccm, and preparing the zirconium carbide whisker by using a carbothermic reduction reaction.
And 4, putting the zirconium carbide whisker obtained in the step 3 into deionized water for ultrasonic treatment for 4 hours, and filtering to remove residual impurities such as zirconium oxide, carbon black and the like. And finally drying the purified zirconium carbide whisker. As shown in fig. 4, the zirconium carbide whisker prepared by the method has a quadrangular prism shape, a smooth surface and no impurities; FIG. 3 shows that zirconium carbide whiskers produced by other methods have a high amount of metal catalyst particle impurities at the top of the whiskers and a low degree of purity. Therefore, the zirconium carbide whisker prepared by the method has obvious purity advantage.
Example 2
Step 1, preparing raw materials for ball milling:
the reactant system (i) is prepared by mixing zirconium oxide: carbon black: sodium fluoride: 5g of ball-milling raw materials are prepared from zirconium carbide seed crystals in a ratio of 1:5:0.6:0.2, the ball-milling is carried out at a ball-milling mass ratio of 3:1 and a rotation speed of 100r/min, and the ball-milling time is 4 hours. And obtaining reactant powder which is uniformly mixed. In this example, the zirconium carbide seed particles are about 20 nm.
Step 2, sieving:
and (3) sieving the reactant powder obtained in the step (1) by a 100-mesh sieve to obtain reactant mixed powder with uniform particle size.
Step 3, carbothermic reduction
Putting the powder obtained in the step 2 into a graphite crucible
The tube furnace of (2) is used for carrying out carbothermic reduction reaction. Reaction temperature: 1500 ℃, heat preservation time: 4h, heating rate: 5K/min, atmosphere: argon, gas flow: and (5) 50sccm, and preparing the zirconium carbide whisker by using a carbothermic reduction reaction.
And 4, putting the zirconium carbide whisker obtained in the step 3 into deionized water for ultrasonic treatment for 4 hours, and filtering to remove residual impurities such as zirconium oxide, carbon black and the like. And finally drying the purified zirconium carbide whisker.
Example 3
Step 1, preparing raw materials for ball milling:
a reactant system is prepared by mixing zirconium element: carbon black: sodium fluoride: 5g of ball-milling raw materials are prepared from zirconium carbide seed crystals in a ratio of 1:3:0.4:0.1, the ball-milling is carried out at a ball-milling mass ratio of 3:1 and a rotation speed of 100r/min, and the ball-milling time is 4 hours. And obtaining reactant powder which is uniformly mixed. In this example, the zirconium carbide seed particles are about 20 nm.
Step 2, sieving:
and (3) sieving the reactant powder obtained in the step (1) by a 100-mesh sieve to obtain reactant mixed powder with uniform particle size.
Step 3, carbothermic reduction
Putting the powder obtained in the step 2 into a graphite crucible
The tube furnace of (2) is used for carrying out carbothermic reduction reaction. Reaction temperature: 1500 ℃, heat preservation time: 4h, heating rate: 5K/min, atmosphere: argon, gas flow: and (5) 50sccm, and preparing the zirconium carbide whisker by using a carbothermic reduction reaction.
And 4, putting the zirconium carbide whisker obtained in the step 3 into deionized water for ultrasonic treatment for 4 hours, and filtering to remove residual impurities such as zirconium oxide, carbon black and the like. And finally drying the purified zirconium carbide whisker.
Example 4
Step 1, preparing raw materials for ball milling:
a reactant system is prepared by mixing zirconium element: carbon black: sodium fluoride: 5g of ball-milling raw materials are prepared from zirconium carbide seed crystals in a ratio of 1:3:0.4:0.2, the ball-milling is carried out at a ball-milling mass ratio of 3:1 and a rotation speed of 100r/min, and the ball-milling time is 4 hours. And obtaining reactant powder which is uniformly mixed. In this example, the zirconium carbide seed particles are about 20 nm.
Step 2, sieving:
and (3) sieving the reactant powder obtained in the step (1) by a 100-mesh sieve to obtain reactant mixed powder with uniform particle size.
Step 3, carbothermic reduction
Putting the powder obtained in the step 2 into a graphite crucible
The tube furnace of (2) is used for carrying out carbothermic reduction reaction. Reaction temperature: 1500 ℃ heat preservationTime: 4h, heating rate: 5K/min, atmosphere: argon, gas flow: and (5) 50sccm, and preparing the zirconium carbide whisker by using a carbothermic reduction reaction.
And 4, putting the zirconium carbide whisker obtained in the step 3 into deionized water for ultrasonic treatment for 4 hours, and filtering to remove residual impurities such as zirconium oxide, carbon black and the like. And finally drying the purified zirconium carbide whisker.
Claims (10)
1. A method for preparing zirconium carbide whiskers by adopting zirconium carbide seed crystals is characterized by comprising the following steps:
step 1, preparing raw materials for ball milling: mixing a system I comprising zirconium oxide, carbon black, sodium fluoride and zirconium carbide seed crystals in proportion, mixing a system II comprising polycarbozircoalkane, carbon black, sodium fluoride and zirconium carbide seed crystals in proportion, and performing ball milling to obtain uniformly mixed reactant precursor powder;
in the system, the molar ratio of zirconium oxide, carbon black, sodium fluoride and zirconium carbide seed crystals is 1: 3-8: 0.1-2: 0.1-1;
in the second system, the molar ratio of zirconium element, carbon black, sodium fluoride and zirconium carbide seed crystal in the polycarboziridine is 1: 2-6: 0.1-2: 0.1-1;
step 2: sieving the precursor powder to obtain powder with uniform particle size;
step 3, carbon thermal reduction: putting the powder obtained in the step 2 into a graphite crucible, and carrying out carbothermic reduction reaction in a tubular furnace to obtain zirconium carbide whiskers; reaction temperature: 1500 ℃, heat preservation time: 2-4 h, heating rate: 5K/min, atmosphere: argon, flow: 20-200 sccm;
step 4, ultrasonic and screening: putting the zirconium carbide whisker into deionized water, performing ultrasonic treatment for 4 hours, sieving, and drying to obtain pure zirconium carbide whisker.
2. The method for preparing zirconium carbide whiskers by using zirconium carbide seed crystals as claimed in claim 1, wherein: in the step 1, the zirconium carbide seed crystal is single crystal zirconium carbide particles.
3. The method for preparing zirconium carbide whiskers by using zirconium carbide seed crystals as claimed in claim 1, wherein: the polycarbozircoalkane is zirconium carbide organic matter precursor powder, and the ratio of zirconium element to carbon element in the polycarbozircoalkane is 1: 1.
4. The method for preparing zirconium carbide whiskers by using zirconium carbide seed crystals as claimed in claim 1, wherein: and the sodium fluoride in the step 1 is replaced by one of inorganic salts of sodium chloride, potassium chloride, lithium chloride, magnesium chloride, zinc chloride, aluminum chloride, calcium chloride, lithium fluoride and potassium fluoride.
5. The method for preparing zirconium carbide whiskers by using zirconium carbide seed crystals as claimed in claim 1, wherein: in the step 1, the size of the single crystal zirconium carbide particles is 10-1000 nm, the size of the zirconium oxide particles is 200nm, the size of the carbon black is 13nm, and the size of the sodium fluoride particles is 2-3 μm.
6. The method for preparing zirconium carbide whiskers by using zirconium carbide seed crystals as claimed in claim 1, wherein: the ball material ratio of the ball milling mixed material in the step 1 is 3: 1.
7. The method for preparing zirconium carbide whiskers by using zirconium carbide seed crystals as claimed in claim 1, wherein: in the step 1, the ball milling speed is 50-200 r/min.
8. The method for preparing zirconium carbide whiskers by using zirconium carbide seed crystals as claimed in claim 1, wherein: the screening in the step 2 adopts a 100-mesh screen.
9. The method for preparing zirconium carbide whiskers by using zirconium carbide seed crystals as claimed in claim 1, wherein: the mesh number of the screen subjected to screening treatment in the step 4 is determined according to the length of the whisker, and the mesh size of the screen is smaller than the length of the whisker.
10. The preparation method of the carbonization whisker according to any one of claims 1 to 9, which is characterized by comprising the following steps: when the zirconium carbide seed crystal is replaced by a hafnium carbide seed crystal, a titanium carbide seed crystal, a tantalum carbide seed crystal or a niobium carbide seed crystal, zirconium oxide and polycarbozirane are replaced by oxides of Hf, Ti, Ta and Nb and corresponding organic polymers, and the hafnium carbide whisker, the titanium carbide whisker, the tantalum carbide whisker or the niobium carbide whisker is prepared.
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