CN110182841B - Low-temperature medium-current fluidization process for preparing TiOxCyNzSystem and method for coating powder - Google Patents

Low-temperature medium-current fluidization process for preparing TiOxCyNzSystem and method for coating powder Download PDF

Info

Publication number
CN110182841B
CN110182841B CN201811397716.4A CN201811397716A CN110182841B CN 110182841 B CN110182841 B CN 110182841B CN 201811397716 A CN201811397716 A CN 201811397716A CN 110182841 B CN110182841 B CN 110182841B
Authority
CN
China
Prior art keywords
powder
gas
pipeline
reactor
flow
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201811397716.4A
Other languages
Chinese (zh)
Other versions
CN110182841A (en
Inventor
朱庆山
向茂乔
宋淼
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Institute of Process Engineering of CAS
Original Assignee
Institute of Process Engineering of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Institute of Process Engineering of CAS filed Critical Institute of Process Engineering of CAS
Priority to CN201811397716.4A priority Critical patent/CN110182841B/en
Publication of CN110182841A publication Critical patent/CN110182841A/en
Application granted granted Critical
Publication of CN110182841B publication Critical patent/CN110182841B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/17—Metallic particles coated with metal
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
    • C01B21/076—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with titanium or zirconium or hafnium
    • C01B21/0763—Preparation from titanium, zirconium or hafnium halides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
    • C01B21/0821—Oxynitrides of metals, boron or silicon
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
    • C01B21/0828—Carbonitrides or oxycarbonitrides of metals, boron or silicon
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/90—Carbides
    • C01B32/914—Carbides of single elements
    • C01B32/921—Titanium carbide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Powder Metallurgy (AREA)

Abstract

The invention discloses a method for preparing TiO by a low-temperature dielectric-stabilized fluidization processxCyNzSystem and method for coating powder, TiCl with low cost4After continuous treatment, the precursor is reduced into a coating precursor, and then the precursor is subjected to reduction and/or nitridation and/or carbonization and/or oxidation reaction on the surface of powder in a medium-flow fluidized reactor, so that TiO is obtained by depositing on the surface of the powderxCyNzAnd coating the powder. The invention prepares TiOxCyNzThe coated powder has the following advantages: (1) breaks through the limit of HCl to the coated powder and the production equipment material in the traditional process, and obviously expands the preparation of TiO by vapor depositionxCyNzThe types of the coated powder are different, and the cost of the traditional process equipment is reduced; (2) breaks through the existing preparation of TiO by low-cost fluidized vapor depositionxCyNzThe lower limit of the temperature of the coated powder obviously reduces the preparation of TiOxCyNzThe temperature of the coated powder; (3) has economic process, environmental protection and good industrial prospect, and can produce various TiOxCyNzThe coated powder has good economic and social benefits.

Description

Low-temperature medium-current fluidization process for preparing TiOxCyNzSystem and method for coating powder
Technical Field
The invention belongs to the field of chemical industry and materials, and particularly relates to a method for preparing TiO by a low-temperature dielectric-stabilized fluidization processxCyNzA system and method for coating powder.
Background
The metal titanium powder has the characteristics of moderate melting point, good wettability, easy formation of reinforced interface and the like, and is widely used as a reinforcing agent and a metal binder in high-hardness materials such as hard alloy cutters, carbide cutters, nitride cutters, diamond cutters and the like. TiO 2xPowder and TiOxNzPowder bodyHas excellent photoelectric property, catalytic property, sterilization, corrosion resistance and other effects, and can be widely used as an additive in the fields of cosmetics, catalytic degradation, medical equipment, material protection and the like. TiCyNzThe powder has excellent conductivity and catalytic performance, high melting point, high hardness, corrosion resistance and other performances, and is commonly used as a reinforcing agent in the fields of high-performance steel, alloy and ceramics. For the materials of the additive, the binder and the reinforcing agent, the key for determining the accurate molding, strengthening, stability and reliability of the material is to obtain the micro-morphology with uniform components, uniform tissues and uniform structures. At present, the following three methods are mainly used for adding the additives, the binders and the reinforcing agents into the materials:
(1) the mechanical mixing method is to disperse the additives, the binding agent and the reinforcing agent in the matrix powder by a ball milling or stirring method. For example, Shin Yung C et al, university of Prime (Materials)&Design, 2018, 159(5):212-2、BN、ZrO2、Al2O3And Hydroxyapatite (HA) powder, and the like, and a modified material is obtained through a subsequent sintering process. Hussain et al (Materials Today, 2017,4(9):9982-6Al4V, 6061 aluminum alloy, Al-12Si alloy, Fe-based, 316 stainless steel, TC4 alloy, Si3N4And the performance of the material is improved in the powder. However, it is difficult to uniformly disperse the additives, binders and reinforcing agents in the matrix by mechanical ball-milling. The main reason is that the mechanical mixing process only has physical effect, and the difference of rotational inertia is caused by the difference of the density and the particle size of the powder, so that the local enrichment is realized and the uniform mixing is difficult to realize. In addition, the powder after ball milling and mixing needs to be further pressed and formed, and in the process of transferring and pressing the powder,sedimentation is caused by the difference of density and particle size, the uniformity of components and the uniformity of tissue structures of the same batch of materials are difficult to ensure, and the stability is poor. These current situations severely restrict the application of high quality reinforced materials.
(2) The physical coating method solves the problem of nonuniform raw material density and particle size difference in the mechanical ball milling process, and simultaneously forms stronger physical adsorption force between the substrate and the coating layer, for example, Wang Richu et al (Journal of the Minerals, Metals & Materials Society,2017,69(4): 756) of the university of south and middle schools, Xu Lei et al (Applied Surface Science, 2016 (390) (909: 916) of the university of Yanshan university), Chang et al (Diamond and Related Materials,2017, 77:72-78) of the university of Yanshan university), Xipen Xu et al (Applied Surface Science, 2016 (390) (909: 916), Xia Kagaku et al (Diamond and Related Materials,2017, 72-78) of the university of Huaqiao university (material Chemistry, 2018, 201154, 2017, 72-78), Xipen Xu et al (material Chemistry, 2017, 3632, 33, 38, 204, 154, 38, 7, 72-78, 154, 7, 33, 7.
(3) Chemical coating, i.e. depositing the coated material on the powder by chemical reaction deposition technique. The chemical coating method further overcomes the defects of the physical coating method, the coating layer and the powder interface have stronger chemical bonds and stronger binding force, the component segregation caused by poor coating binding force in the subsequent processing or transferring process can not occur, and meanwhile, the powder with very high uniformity can be obtained through a proper deposition process, so that the method is most suitable for large-scale production in industry. At present, the chemical coating method includes a molten salt chemical coating method, a chemical deposition coating method, and a fluidized vapor deposition method. For example, Zhang Hailong et al (Surface and Coatings Technology,2015,278: 163- & 170) of Beijing Technology university prepared titanium-coated diamond powder by a molten salt chemical coating method. However, the molten salt coating method has the main disadvantages of easy introduction of impurities, high energy consumption, high cost, difficult subsequent separation and difficult continuous operation.
For the chemical reaction coating method, the chemical reaction is carried out on the surface of the powder through the design of a raw material reaction system, so that a reaction product is deposited on the surface of the powder. For example, Xian Luo et al, at the university of northwest, by Ti-I2And TiCl4-H2System Ti-coated SiC (Applied Surface Science,2017, 406: 62-68; Materials Chemistry and Physics,2016,184:189-196) was prepared in a tube furnace at about 950 ℃. ShiroShimada et al (Journal of Materials Chemistry,2002,12:361-4To prepare TiO from an aqueous or organic solution of2Coated Si3N4Powder, TiO2Coated SiO2Powder, followed by NH at elevated temperature of about 1000 ℃3Or N2，H2Reduction preparation of TiN coated Si3N4Powder, TiON coated Si3N4SiO coated with TiN powder2Powder, TiON coated SiO2Powder and TiN-coated Al2O3And (3) powder. Furthermore, Hideaki et al (Journal of Materials Science,1988,23: 43-47; Journal of Materials Science,1989,24:3643-4-N2-H2The system adopts a rotary rolling process to prepare TiN coated Ti powder, TiN coated C powder and TiN coated Fe powder at the temperature of about 1100 ℃. The main problems of such chemical deposition coating methods are that the deposition temperature is very high, the matrix powder needs to have a very high melting point, and the powder types are severely limited. In addition, although the preparation process is simple, the preparation efficiency is low, the preparation method is only suitable for laboratory preparation, and the continuous and batch preparation is difficult to realizeAnd (4) production.
Fluidized vapor deposition techniques, i.e., leaving the powder in a flowing state and preparing the coated powder based on chemical vapor deposition. The process can fundamentally solve the problem of uneven coating, and can realize continuous and batch production in industry. For example, Keiichi et al (Journal of Materials Science,1993,28: 3168) 3172, European patent EP0443659B1, US4623400 based on TiCl4-NH3And TiCl4-N2-H2The system adopts a fluidized bed process to prepare TiN coated Al at about 1000 DEG C2O3Powder and SiC powder coated with TiN. However, the deposition temperature of the reaction system is very high and exceeds the heat treatment temperature or powder bleeding temperature of most metal powder, so that the application range of the process is very limited. To reduce the deposition temperature, Bernard et al (Surface and Coatings Technology,1991,49:228-4-NH3Optimization of the system to Ti-HCl-NH3System and by adding catalyst, the temperature of Ti and TiN coating was reduced to about 650 ℃. However, this process has three problems: first, the minimum coating temperature is still high; secondly, the whole system is exposed in a large amount of HCl atmosphere, and the powder to be coated has the characteristic of HCl corrosion resistance; thirdly, the requirement on industrial equipment is high, and reaction equipment needs to have extremely high HCl corrosion resistance, so that the equipment cost is high. These three problems severely limit their practical application in industry. To overcome the limitations caused by HCl and to further lower the temperature, Arjen Didden et al (Journal of nanoparticie Research, 2016,18:35), recently at Dutch Industrial university, employed fluidized bed technology based on an organic titanium source (TDMAT) -NH3System, TiN coated SiO prepared at about 250 ℃2The particle greatly improves the conductivity of the powder. Although the process significantly reduces the minimum cladding temperature, the cost of the organic titanium source of the process is very high, and the process is flammable, explosive and toxic, and the industrial large-scale application of the process is limited from both an economic perspective and an environmental perspective.
In summary, how to reduce the temperature of preparing Ti-based coating powder by fluidized vapor deposition and widen the powder variety under the conditions of low cost and environmental protection is still a problem to be solved in the industry at present.
Disclosure of Invention
Aiming at the problems, the invention provides a low-temperature dielectric-stabilized fluidization process for preparing TiOxCyNzThe system and the method for coating the powder develop a novel medium-current stabilization process, and can produce TiO in batches at low temperature and with low cost and environmental protectionxCyNzAnd coating the powder.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention prepares TiOxCyNzThe system for coating powder comprises: a reducing agent bin 1, an inert powder bin 2 and TiCl4The device comprises an air inlet device 3, a first medium stable flow reactor 4, a purifier 5, a sublimator 6, a second medium stable flow reactor 7, a matrix powder bin 8, a first storage bin 9, a powder separating device 10, a second storage bin 11, a cleaning device 12, a product bin 13, a powder recovery bin 14 and a cold flow reflux device 15;
the discharge hole of the reducing agent bin 1 is connected with the feed hole of the first flow stabilization reactor 4 through a pipeline and a material valve; the discharge hole of the inert powder bin 2 is connected with the feed inlet of the first medium stable flow reactor 4 through a pipeline and a material valve;
the TiCl4The air inlet of the air inlet device 3 is connected with the hydrogen and inert gas pipeline through a pipeline and an air valve; the TiCl4The gas outlet of the gas inlet device 3 is connected with the gas inlet at the bottom of the first medium flow stabilizing reactor 4 through a pipeline and a gas valve; the TiCl4Air inlet of air inlet device 3 and TiCl4The air outlet of the air inlet device 3 is connected with an air valve through a pipeline; the TiCl4The feed inlet of the air inlet device 3 is connected with the discharge outlet of the cold flow reflux device 15 through a pipeline and a material valve;
the gas inlet of the first flow stabilization reactor 4 is connected with inert gas through a pipeline and a gas valve; the discharge hole of the first flow stabilization reactor 4 is connected with the feed hole of the purifier 5 through a pipeline and a material valve; the gas outlet of the first medium-flow stable reactor 4 is connected with the gas inlet of the cold-flow reflux device 15 through a pipeline and a gas valve;
the gas inlet of the purifier 5 is connected with inert gas through a pipeline and a gas valve; the air outlet of the purifier 5 is connected with the air inlet of the cold flow reflux device 15 through a pipeline and an air valve; the discharge hole of the purifier 5 is connected with the feed hole of the sublimator 6 through a pipeline and a material valve; the discharge hole of the purifier 5 is connected with the feed hole of the second medium flow stabilizing reactor 7 through a pipeline and a material valve;
the gas inlet of the sublimator 6 is connected with inert gas through a pipeline and a gas valve; the discharge hole of the sublimator 6 is connected with the feed hole of the first flow stabilization reactor 4 through a pipeline and a material valve; the gas outlet of the sublimator 6 is connected with the gas inlet of the second flow stabilization reactor 7 through a pipeline and a gas valve; the gas inlet of the second flow stabilization reactor 7 is connected with the inert gas, the nitrogen source gas, the carbon source gas and the oxygen gas through pipelines and gas valves; the gas outlet of the second medium-flow stable reactor 7 is connected with the gas inlet of the cold-flow reflux device 15 through a pipeline;
the discharge hole of the matrix powder bin 8 is connected with the feed inlet of the second medium-stabilized flow reactor 7 through a pipeline and a material valve; the discharge hole of the second flow stabilization reactor 7 is connected with the feed hole of the first storage bin 9 through a pipeline and a material valve; the discharge hole of the first storage bin 9 is connected with the feed inlet of the powder separating device 10 through a pipeline and a material valve; the discharge hole of the first storage bin 9 is connected with the feed inlet of the cleaning device 12 through a pipeline and a material valve; the discharge hole of the powder separating device 10 is connected with the feed inlets of the second storage bin 11 and the powder recovery bin 14 through pipelines and material valves; the discharge hole of the second storage bin 11 is connected with the feed inlet of the cleaning device 12 through a pipeline and a material valve; the discharge hole of the cleaning device 12 is connected with the feed inlet of the product bin 13 through a pipeline and a material valve; the discharge hole of the powder recovery bin 14 is connected with the feed inlet of the first flow stabilization reactor 4 through a pipeline and a material valve.
The invention prepares TiO based on the systemxCyNzThe powder coating method comprises the following steps:
the reducing agent in the reducing agent bin 1 and the inert powder in the inert powder bin 2 enter the first medium-stabilized flow reactor 4; the matrix powder in the matrix powder bin 8 enters the second medium-current stabilized flow reactor 7 through a pipeline and a material valve; the inert gas enters the TiCl4A gas inlet device 3, the first flow stabilization reactor 4 and the second flow stabilization reactor 7; the TiCl4TiCl in the gas inlet means 34The inert gas and the hydrogen are loaded into the first flow stabilization reactor 4 for reaction; the material in the first flow stabilization reactor 4 enters the purifier 5; the material in the purifier 5 enters the sublimator 6 and/or the second flow stabilization reactor 7 after purification; the material is gasified in the sublimer 6 and carried into the second flow stabilization reactor 7 by inert gas; the residue in the sublimator 6 enters the first flow stabilization reactor 4 through a pipeline and a material valve to realize the reutilization of the titanium source; the inert gas and one or more of carbon source gas, nitrogen source gas and oxygen are mixed and enter a second flow stabilization reactor 7 to react with the material, and the reacted material enters a first storage bin 9; the material in the first storage bin 9 enters the powder separating device 10 or enters the cleaning device 12; the powder in the powder separation device 10 is separated to obtain coated powder and residual materials, wherein the coated powder enters the second storage bin 11, and the residual materials enter the powder recovery bin 14 and return to the first metastable reactor 4 through a pipeline and a material valve to realize the reutilization of the titanium source; the coated powder in the second storage bin 11 enters the cleaning device 12, and the coated powder in the cleaning device 12 is cleaned and dried and then enters the product bin 13 to obtain a coated product.
Preferably, the TiO isxCyNzX is more than or equal to 0 and less than or equal to 2, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, and x + y + z is more than or equal to 0 and less than or equal to 3 in the coated powder.
Preferably, the reducing agent in the reducing agent bin 1 is any one or a combination of any two or more of aluminum, titanium, manganese, iron and copper.
Preferably, the inert powder in the inert powder bin 2 is any one or a combination of any two or more of inert metal elemental powder, inert non-metal elemental powder, oxide powder and non-metal oxide powder, which have a melting point higher than 1200 ℃, such as one or more of molybdenum, carbon, zirconium oxide, titanium nitride and titanium carbide.
Preferably, the inert powder is contained in the first metastable reactor 4, the mass ratio of the mass of the reducing agent to the mass of the inert powder is greater than or equal to zero, and the sum of the molar quantity of the reducing agent and the molar quantity of the hydrogen and the TiCl in the first metastable reactor 44The molar ratio is more than zero, the operation gas velocity is more than or equal to 0.5 time of the minimum fluidization gas velocity, the reaction temperature is more than 400 ℃, and the time is more than or equal to 10 min.
Preferably, the temperature of the purifier 5 ranges from room temperature to 700 ℃, the inert gas flow rate is greater than or equal to 0.1 times the minimum fluidizing gas flow rate or the vacuum pressure is less than or equal to 1000 Pa.
Preferably, the temperature of the sublimator 6 is equal to or higher than 500 ℃, and the inert gas velocity is equal to or higher than 0.1 times the minimum fluidization gas velocity.
Preferably, in the second flow stabilization reactor 7, the operation gas velocity is greater than zero but less than the turbulent flow gas velocity, the temperature is greater than or equal to 250 ℃, and the time is greater than 10 min.
Preferably, the matrix powder in the matrix powder bin 8 is inert powder with a melting point higher than 250 ℃, and the inert powder is selected from one or more of inert metal simple substance powder, alloy powder, non-metal simple substance powder, oxide ceramic powder and non-oxide ceramic powder.
The invention adopts TiCl with low cost4After continuous treatment, the precursor is reduced into a coating precursor, and then the precursor is subjected to reduction and/or nitridation and/or carbonization and/or oxidation reaction on the surface of powder in a medium-flow fluidized reactor, so that TiO is obtained by depositing on the surface of the powderxCyNzAnd coating the powder.
Compared with the prior art, the invention has the following advantages:
(1) breaks through the limitation of HCl to the types of the coated powder and the materials of production equipment in the traditional process, and obviously widens the preparation of TiO by vapor depositionxCyNzThe types of the coated powder are different, and the cost of the traditional process equipment is reduced;
(2) breaks through the existing preparation of TiO by low-cost fluidized vapor depositionxCyNzThe lower limit of the temperature of the coated powder obviously reduces the preparation of TiOxCyNzThe temperature of the coated powder;
(3) has economic process, environmental protection and good industrial prospect, and can produce various TiOxCyNzAnd coating the powder.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention.
FIG. 1 shows the preparation of TiO by the low-temperature dielectric-stabilized fluidization process of the inventionxCyNzA schematic configuration of the coated powder system;
FIG. 2 is an SEM image of Ti-coated silica powder;
FIG. 3 is an SEM image of TiN-coated aluminum powder;
FIG. 4 is an SEM image of TiON-coated titanium nitride powder;
FIG. 5 is an SEM image of TiC-coated zirconium dioxide powder;
FIG. 6 is an SEM image of TiOCN-coated zirconium dioxide powder;
reference numerals:
a reducing agent bin 1, an inert powder bin 2 and TiCl4The device comprises an air inlet device 3, a first medium stable flow reactor 4, a purifier 5, a sublimator 6, a second medium stable flow reactor 7, a matrix powder bin 8, a first storage bin 9, a powder separating device 10, a second storage bin 11, a cleaning device 12, a product bin 13, a powder recovery bin 14 and a cold flow reflux device 15.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. It should be noted that the examples are only for illustrating the technical solutions of the present invention, and not for limiting the same.
Example 1
Referring to FIG. 1, this example illustrates the preparation of TiO by the low temperature dielectric fluidizationxCyNzThe powder coating system comprises a reducing agent bin 1, an inert powder bin 2 and TiCl4The device comprises an air inlet device 3, a first medium stable flow reactor 4, a purifier 5, a sublimator 6, a second medium stable flow reactor 7, a matrix powder bin 8, a first storage bin 9, a powder separating device 10, a second storage bin 11, a cleaning device 12, a product bin 13, a powder recovery bin 14 and a cold flow reflux device 15;
the discharge hole of the reducing agent bin 1 is connected with the feed hole of the first flow stabilization reactor 4 through a pipeline and a material valve; the discharge hole of the inert powder bin 2 is connected with the feed inlet of the first medium stable flow reactor 4 through a pipeline and a material valve;
the TiCl4The air inlet of the air inlet device 3 is connected with the hydrogen and inert gas pipeline through a pipeline and an air valve; the TiCl4The gas outlet of the gas inlet device 3 is connected with the gas inlet at the bottom of the first medium flow stabilizing reactor 4 through a pipeline and a gas valve; the TiCl4Air inlet of air inlet device 3 and TiCl4The air outlet of the air inlet device 3 is connected with an air valve through a pipeline; the TiCl4The feed inlet of the air inlet device 3 is connected with the discharge outlet of the cold flow reflux device 15 through a pipeline and a material valve;
the gas inlet of the first flow stabilization reactor 4 is connected with inert gas through a pipeline and a gas valve; the discharge hole of the first flow stabilization reactor 4 is connected with the feed hole of the purifier 5 through a pipeline and a material valve; the gas outlet of the first medium-flow stable reactor 4 is connected with the gas inlet of the cold-flow reflux device 15 through a pipeline and a gas valve;
the gas inlet of the purifier 5 is connected with inert gas through a pipeline and a gas valve; the air outlet of the purifier 5 is connected with the air inlet of the cold flow reflux device 15 through a pipeline and an air valve; the discharge hole of the purifier 5 is connected with the feed hole of the sublimator 6 through a pipeline and a material valve; the discharge hole of the purifier 5 is connected with the feed hole of the second medium flow stabilizing reactor 7 through a pipeline and a material valve;
the gas inlet of the sublimator 6 is connected with inert gas through a pipeline and a gas valve; the discharge hole of the sublimator 6 is connected with the feed hole of the first flow stabilization reactor 4 through a pipeline and a material valve; the gas outlet of the sublimator 6 is connected with the gas inlet of the second flow stabilization reactor 7 through a pipeline and a gas valve; the gas inlet of the second flow stabilization reactor 7 is connected with the inert gas, the nitrogen source gas, the carbon source gas and the oxygen gas through pipelines and gas valves; the gas outlet of the second medium-flow stable reactor 7 is connected with the gas inlet of the cold-flow reflux device 15 through a pipeline;
the discharge hole of the matrix powder bin 8 is connected with the feed inlet of the second medium-stabilized flow reactor 7 through a pipeline and a material valve; the discharge hole of the second flow stabilization reactor 7 is connected with the feed hole of the first storage bin 9 through a pipeline and a material valve; the discharge hole of the first storage bin 9 is connected with the feed inlet of the powder separating device 10 through a pipeline and a material valve; the discharge hole of the first storage bin 9 is connected with the feed inlet of the cleaning device 12 through a pipeline and a material valve; the discharge hole of the powder separating device 10 is connected with the feed inlets of the second storage bin 11 and the powder recovery bin 14 through pipelines and material valves; the discharge hole of the second storage bin 11 is connected with the feed inlet of the cleaning device 12 through a pipeline and a material valve; the discharge hole of the cleaning device 12 is connected with the feed inlet of the product bin 13 through a pipeline and a material valve; the discharge hole of the powder recovery bin 14 is connected with the feed inlet of the first flow stabilization reactor 4 through a pipeline and a material valve.
Example 2
In this example, the low temperature dielectric stabilized fluidization process of the system in the above example 1 is utilized to prepare TiOxCyNzThe powder coating method specifically comprises the following steps:
the reducing agent in the reducing agent bin 1 and the inert powder in the inert powder bin 2 enter the first medium-stabilized flow reactor 4; the matrix powder in the matrix powder bin 8 enters the second medium-current stabilized flow reactor 7 through a pipeline and a material valve; the inert gas enters the TiCl4A gas inlet device 3, the first flow stabilization reactor 4 and the second flow stabilization reactor 7; the TiCl4TiCl in the gas inlet means 34The inert gas and the hydrogen are loaded into the first flow stabilization reactor 4 for reaction; the material in the first flow stabilization reactor 4 enters the purifier 5; the material in the purifier 5 enters the sublimator 6 and/or the second flow stabilization reactor 7 after purification; the material is gasified in the sublimer 6 and carried into the second flow stabilization reactor 7 by inert gas; the residue in the sublimator 6 enters the first flow stabilization reactor 4 through a pipeline and a material valve to realize the reutilization of the titanium source; the inert gas and one or more of carbon source gas, nitrogen source gas and oxygen are mixed and enter a second flow stabilization reactor 7 to react with the material, and the reacted material enters a first storage bin 9; the material in the first storage bin 9 enters the powder separating device 10 or enters the cleaning device 12; the powder in the powder separation device 10 is separated to obtain coated powder and residual materials, wherein the coated powder enters the second storage bin 11, and the residual materials enter the powder recovery bin 14 and return to the first metastable reactor 4 through a pipeline and a material valve to realize the reutilization of the titanium source; the coated powder in the second storage bin 11 enters the cleaning device 12, and the coated powder in the cleaning device 12 is cleaned and dried and then enters the product bin 13 to obtain a coated product.
Example 3
In this embodiment, on the basis of the above embodiment 2, the inert powder in the inert powder bin 2 is silicon oxide powder; the above-mentionedThe powder in the matrix powder bin 8 is silicon oxide powder; the TiCl4The carrier gas in the gas inlet means 3 is H2And mixed gas of Ar, H2Flow rate ratio to Ar of 5; h in the first flow stabilization reactor 42With TiCl4The molar ratio of (a) to (b) is 2, the temperature in the first flow stabilization reactor 4 is 800 ℃, the reaction time is 60min, and the gas velocity is 2 times of the minimum fluidization gas velocity; the temperature in the purifier 5 is 480 ℃, the pressure is the standard atmospheric pressure, the argon gas velocity is 0.2 times of the minimum fluidization gas velocity, and the purification time is 30 min; the volume ratio of the inert powder to the matrix powder in the second flow stabilization reactor 7 is 2, the temperature of the second flow stabilization reactor 7 is 300 ℃, the argon gas velocity is 0.5 times of the minimum fluidization gas velocity, and the material enters the first storage bin 9 after the coating time is 60 min; materials are screened and separated in the powder separating device 10, and the coated powder enters the cleaning device 12, is subjected to ultrasonic cleaning and drying by industrial alcohol and then enters the product bin 13 to obtain Ti-coated silicon dioxide powder; FIG. 2 is an SEM image of a Ti-coated silica powder, from which it can be seen that nano Ti particles are uniformly coated on the silica powder.
Example 4
In this embodiment, on the basis of the above embodiment 2, the reducing agent in the reducing agent bin 1 is coarse titanium sponge powder; the powder in the matrix powder bin 8 is aluminum powder; the TiCl4The carrier gas in the gas inlet means 3 is H2And mixed gas of Ar, H2Flow rate ratio to Ar 0.5; h in the first flow stabilization reactor 42With TiCl4The molar ratio of (a) to (b) is 0.2, the temperature in the first flow stabilization reactor 4 is 500 ℃, the reaction time is 60min, and the gas velocity is 1 time of the minimum fluidization gas velocity; the temperature in the purifier 5 is 480 ℃, the pressure is the standard atmospheric pressure, and the argon gas velocity is 0.2 times of the minimum fluidization gas velocity; the temperature in the sublimator 6 is 800 ℃, the argon gas velocity is 0.8 times of the minimum fluidization gas velocity, and the reaction time is 180 min; in the second flow stabilization reactor 7, the volume ratio of the reducing agent and the inert powder to the matrix powder is zero, the temperature in the second flow stabilization reactor 7 is 580 ℃, and the nitrogen source gas NH is3And the gas velocity is 2 times of the minimum fluidization gas velocity, the coating time is 180min, and after the coating is finished, the material enters the first storage bin 9 and enters the cleaning device 12 to be cleaned by deionized water, and after the drying, the material enters the product bin 13 to obtain TiN coated powder. FIG. 3 is an SEM image of the aluminum powder coated with TiN, from which it can be seen that nodular TiN particles are grown on the surface of the aluminum powder.
Example 5
In this embodiment, on the basis of the above embodiment 2, the reducing agent in the reducing agent bin 1 is aluminum powder, and the inert powder in the inert powder bin 2 is silicon carbide powder; the powder in the matrix powder bin 8 is titanium nitride powder; the TiCl4The carrier gas in the gas inlet means 3 is H2(ii) a H in the first flow stabilization reactor 42With TiCl4Is 0.5, the reducing agent and TiCl4The molar ratio of (a) to (b) is 1.5, the temperature in the first flow stabilization reactor 4 is 400 ℃, the reaction time is 30min, and the gas velocity is 2 times of the minimum fluidization gas velocity; the temperature in the purifier 5 is 150 ℃, the pressure is the standard atmospheric pressure, the argon gas velocity is 0.8 times of the minimum fluidization gas velocity, and the purification time is 10 min; the temperature in the sublimator 6 is 650 ℃, the argon gas velocity is 2 times of the minimum fluidization gas velocity, and the reaction time is 120 min; the temperature in the second flow stabilization reactor 7 is 490 ℃, and the nitrogen source gas NH3The oxygen is industrial pure oxygen, oxygen and NH3The flow rate ratio of (1) is 0.001, the gas velocity is 0.8 times of the minimum fluidization gas velocity, the coating time is 120min, and after the coating is finished, the material enters the first storage bin 9 and enters the cleaning device 12 to be cleaned by deionized water, and after being dried, the material enters the product bin 13 to obtain the TiON coated titanium nitride powder. FIG. 4 is an SEM image of TiON-coated titanium nitride powder, from which it can be seen that TiON of about 10nm is uniformly coated on the surface of titanium nitride particles.
Example 6
In this embodiment, on the basis of embodiment 2, the reducing agent in the reducing agent bin 1 is 100-mesh iron powder and 100-mesh manganese powder; inert powder is not added into the inert powder bin 2; the powder in the base body powder bin 8 is 500-mesh zirconium oxide powder; what is needed isTiCl as described above4The carrier gas in the gas inlet device 3 is Ar and H2Gas, the sum of the molar amounts of the iron powder and the manganese powder in the first dielectric stabilized flow reactor 4 and TiCl4The molar ratio of (a) is 1, the temperature in the first flow stabilization reactor 4 is 600 ℃, the reaction time is 60min, and the fluidizing gas velocity is 1 time of the minimum fluidizing gas velocity; the temperature in the purifier 5 is 280 ℃, the argon gas velocity is 0.8 times of the minimum fluidization gas velocity, and the purification time is 30 min; the temperature in the sublimator 6 is 750 ℃, the argon gas velocity is 1 time of the minimum fluidization gas velocity, and the reaction time is 120 min; the temperature in the second flow stabilization reactor 7 is 590 ℃, and the carbon source gas CH4And the gas velocity is 1.2 times of the minimum fluidization gas velocity, the coating time is 120min, and after the coating is finished, the material enters the storage bin 9 and enters the cleaning device 12 to be cleaned by deionized water, and after the drying, the material enters the product bin 13 to obtain TiC coated zirconium dioxide powder. Fig. 5 is an SEM image of the TiC-coated zirconia powder, and it can be seen that the flaky nano TiC grows uniformly on the surface of the powder.
Example 7
In the embodiment, on the basis of the embodiment 2, the reducing agent in the reducing agent bin 1 is copper powder with 100 meshes; the inert powder bin 2 is filled with carbon powder; the powder in the base body powder bin 8 is 500-mesh zirconium oxide powder; the TiCl4The carrier gas in the gas inlet device 3 is Ar and H2Gas, the molar amount of copper powder and TiCl in said first metastable reactor 44The molar ratio of (A) to (B) is 0.5, the temperature is 550 ℃, the reaction time is 60min, and the fluidizing gas velocity is 1 time of the minimum fluidizing gas velocity; the temperature in the purifier 5 is 380 ℃, the argon gas speed is 0.5 time of the minimum fluidization gas speed, and the purification time is 30 min; the temperature in the sublimator 6 is 750 ℃, the argon gas velocity is 1 time of the minimum fluidization gas velocity, and the reaction time is 120 min; the temperature in the second flow stabilization reactor 7 is 550 ℃, and the carbon source gas is CH4The nitrogen source gas is NH3The oxygen is technically pure oxygen CH4And NH3At a flow ratio of 1/1, oxygen to NH3The flow rate ratio of (A) is 0.001, the operation gas velocity is 1.8 times of the minimum fluidization gas velocity, the coating time is 80min, and the material is coated after the coating is finishedAnd the zirconium dioxide powder enters the storage bin 9, enters the cleaning device 12, is cleaned by deionized water, and enters the product bin 13 after being dried to obtain the TiOCN coated zirconium dioxide powder. FIG. 6 is an SEM image of TiOCN-coated zirconium dioxide powder, from which it can be seen that about 3 μm of TiOCN is uniformly grown on the surface of the powder.
The method can be realized by upper and lower limit values and interval values of intervals of process parameters (such as temperature, time and the like), and embodiments are not listed.
Conventional technical knowledge in the art can be used for the details which are not described in the present invention.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and are not limited. Although the present invention has been described in detail with reference to the embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (10)

1. Low-temperature medium-current fluidization process for preparing TiOxCyNzA system for coating a powder, the system comprising: a reducing agent bin (1), an inert powder bin (2) and TiCl4The device comprises an air inlet device (3), a first medium stable flow reactor (4), a purifier (5), a sublimator (6), a second medium stable flow reactor (7), a matrix powder bin (8), a first storage bin (9), a powder separating device (10), a second storage bin (11), a cleaning device (12), a product bin (13), a powder recovery bin (14) and a cold flow reflux device (15);
the discharge hole of the reducing agent bin (1) is connected with the feed inlet of the first medium-stable flow reactor (4) through a pipeline and a material valve; the discharge hole of the inert powder bin (2) is connected with the feed inlet of the first medium stable flow reactor (4) through a pipeline and a material valve;
the TiCl4The gas inlet of the gas inlet device (3) is connected with the hydrogen and inert gas pipeline through a pipeline and a gas valve; the TiCl4The air outlet of the air inlet device (3) is opposite to the first dielectric constant flowThe air inlet at the bottom of the reactor (4) is connected with an air valve through a pipeline; the TiCl4An air inlet of an air inlet device (3) and the TiCl4The air outlet of the air inlet device (3) is connected with an air valve through a pipeline; the TiCl4A feed inlet of the air inlet device (3) is connected with a discharge outlet of the cold flow reflux device (15) through a pipeline and a material valve;
the gas inlet of the first flow stabilization reactor (4) is connected with inert gas through a pipeline and a gas valve; the discharge hole of the first flow stabilization reactor (4) is connected with the feed hole of the purifier (5) through a pipeline and a material valve; the gas outlet of the first medium-flow stable reactor (4) is connected with the gas inlet of the cold-flow reflux device (15) through a pipeline and a gas valve;
the gas inlet of the purifier (5) is connected with inert gas through a pipeline and a gas valve; the air outlet of the purifier (5) is connected with the air inlet of the cold flow reflux device (15) through a pipeline and an air valve; the discharge hole of the purifier (5) is connected with the feed hole of the sublimator (6) through a pipeline and a material valve; the discharge hole of the purifier (5) is connected with the feed hole of the second medium flow stabilizing reactor (7) through a pipeline and a material valve;
the gas inlet of the sublimator (6) is connected with inert gas through a pipeline and a gas valve; the discharge hole of the sublimator (6) is connected with the feed hole of the first medium stable flow reactor (4) through a pipeline and a material valve; the gas outlet of the sublimator (6) is connected with the gas inlet of the second flow stabilization reactor (7) through a pipeline and a gas valve; the gas inlet of the second medium flow stable reactor (7) is connected with the inert gas, the nitrogen source gas, the carbon source gas and the oxygen through pipelines and gas valves; the gas outlet of the second medium-flow stable reactor (7) is connected with the gas inlet of the cold-flow reflux device (15) through a pipeline;
the discharge hole of the matrix powder bin (8) is connected with the feed inlet of the second medium-stability reactor (7) through a pipeline and a material valve; the discharge hole of the second flow stabilization reactor (7) is connected with the feed hole of the first storage bin (9) through a pipeline and a material valve; the discharge hole of the first storage bin (9) is connected with the feed inlet of the powder separating device (10) through a pipeline and a material valve; the discharge hole of the first storage bin (9) is connected with the feed inlet of the cleaning device (12) through a pipeline and a material valve; the discharge hole of the powder separating device (10) is connected with the feed inlets of the second storage bin (11) and the powder recovery bin (14) through a pipeline and a material valve; the discharge hole of the second storage bin (11) is connected with the feed inlet of the cleaning device (12) through a pipeline and a material valve; the discharge hole of the cleaning device (12) is connected with the feed inlet of the product bin (13) through a pipeline and a material valve; and the discharge hole of the powder recovery bin (14) is connected with the feed inlet of the first medium-stability flow reactor (4) through a pipeline and a material valve.
2. Preparation of TiO on the basis of the system according to claim 1xCyNzA method of coating a powder, the method comprising the steps of:
the reducing agent in the reducing agent bin (1) and the inert powder in the inert powder bin (2) enter the first flow stabilization reactor (4); the matrix powder in the matrix powder bin (8) enters the second medium-current stabilized flow reactor (7) through a pipeline and a material valve; the inert gas enters the TiCl4A gas inlet device (3), the first flow stabilization reactor (4) and the second flow stabilization reactor (7); the TiCl4TiCl in the gas inlet device (3)4Carrying the inert gas and hydrogen into the first flow stabilization reactor (4) for reaction; the material in the first flow stabilization reactor (4) enters the purifier (5); the material in the purifier (5) enters the sublimator (6) and/or the second flow stabilization reactor (7) after purification; the material is gasified in the sublimer (6) and is loaded into the second flow stabilization reactor (7) by inert gas; the residue in the sublimator (6) enters the first flow stabilization reactor (4) through a pipeline and a material valve to realize the reutilization of the titanium source; the inert gas and one or more of carbon source gas, nitrogen source gas and oxygen are mixed and enter a second flow stabilization reactor (7) to react with the materials, and the reacted materials enter a first storage bin (9); the material in the first storage bin (9) enters the powder-a body separating device (10) or into the cleaning device (12); the powder in the powder separation device (10) is separated to obtain coated powder and residual materials, wherein the coated powder enters the second storage bin (11), and the residual materials enter the powder recovery bin (14) and return to the first flow stabilization reactor (4) through a pipeline and a material valve to realize the reutilization of the titanium source; and the coating powder in the second storage bin (11) enters the cleaning device (12), and the coating powder in the cleaning device (12) is cleaned and dried and then enters the product bin (13) to obtain a coating product.
3. The method for preparing TiO according to claim 2xCyNzMethod for coating powder, characterized in that the TiO isxCyNzX is more than or equal to 0 and less than or equal to 2, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, and x + y + z is more than or equal to 0 and less than or equal to 3 in the coated powder.
4. The method for preparing TiO according to claim 2xCyNzThe powder coating method is characterized in that the reducing agent in the reducing agent bin (1) is any one or the combination of any two or more of aluminum, titanium, manganese, iron and copper.
5. The method for preparing TiO according to claim 2xCyNzThe powder coating method is characterized in that the inert powder in the inert powder bin (2) is any one or the combination of any two or more of inert metal simple substance powder, inert nonmetal simple substance powder and oxide powder.
6. The method for preparing TiO according to claim 2xCyNzThe powder coating method is characterized in that the mass ratio of the reducing agent to the inert powder in the first dielectric stabilized flow reactor (4) is more than or equal to zero, and the sum of the molar quantity of the reducing agent and the molar quantity of the hydrogen and TiCl4The molar ratio is more than zero, the operation gas velocity is more than or equal to 0.5 time of the minimum fluidization gas velocity, the reaction temperature is more than 400 ℃, and the time is more than or equal to 10 min.
7. The method for preparing TiO according to claim 2xCyNzThe powder coating method is characterized in that the temperature of the purifier (5) ranges from room temperature to 700 ℃, and the gas velocity of the inert gas is more than or equal to 0.1 time of the minimum fluidization gas velocity.
8. The method for preparing TiO according to claim 2xCyNzThe method for coating the powder is characterized in that the temperature of the sublimator (6) is more than or equal to 500 ℃, and the gas velocity of the inert gas is more than or equal to 0.1 time of the minimum fluidization gas velocity.
9. The method for preparing TiO according to claim 2xCyNzThe method for coating the powder is characterized in that in the second medium flow stabilizing reactor (7), the operation gas velocity is larger than zero but smaller than the turbulent flow gas velocity, the temperature is larger than or equal to 250 ℃, and the time is longer than 10 min.
10. The method for preparing TiO according to claim 2xCyNzThe powder coating method is characterized in that the matrix powder in the matrix powder bin (8) is inert powder with the melting point higher than 250 ℃, and the inert powder is selected from one or more of inert metal simple substance powder, alloy powder, nonmetal simple substance powder, oxide ceramic powder and non-oxide ceramic powder.
CN201811397716.4A 2018-11-22 2018-11-22 Low-temperature medium-current fluidization process for preparing TiOxCyNzSystem and method for coating powder Active CN110182841B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811397716.4A CN110182841B (en) 2018-11-22 2018-11-22 Low-temperature medium-current fluidization process for preparing TiOxCyNzSystem and method for coating powder

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811397716.4A CN110182841B (en) 2018-11-22 2018-11-22 Low-temperature medium-current fluidization process for preparing TiOxCyNzSystem and method for coating powder

Publications (2)

Publication Number Publication Date
CN110182841A CN110182841A (en) 2019-08-30
CN110182841B true CN110182841B (en) 2020-06-16

Family

ID=67713914

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811397716.4A Active CN110182841B (en) 2018-11-22 2018-11-22 Low-temperature medium-current fluidization process for preparing TiOxCyNzSystem and method for coating powder

Country Status (1)

Country Link
CN (1) CN110182841B (en)

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60149773A (en) * 1984-01-13 1985-08-07 Mitsui Eng & Shipbuild Co Ltd Formation of cvd film
US4555416A (en) * 1984-08-27 1985-11-26 Ball Corporation Spray apparatus with self cleaning nozzle
KR100629172B1 (en) * 2004-11-08 2006-09-27 삼성전자주식회사 Apparatus for forming a layer
CN101289174B (en) * 2008-06-18 2010-07-07 浙江大学 Method for preparing TiN nano-powders
CN108689726B (en) * 2018-05-25 2020-08-18 中国科学院过程工程研究所 Preparation method of nickel-coated ceramic composite powder

Also Published As

Publication number Publication date
CN110182841A (en) 2019-08-30

Similar Documents

Publication Publication Date Title
KR101410154B1 (en) Polycrystalline abrasive compacts
JPH07232965A (en) Preparation of sintered body and coating article of metal and ceramic
CN106431498B (en) A method of preparing graphite/carbon SiClx densified composite
CN111099596B (en) Simple method for coating high-hydrophobicity boron nitride nanosheet thin layer on surface of silicon dioxide aerogel particle
CN113443928B (en) Preparation method of zirconium and/or tungsten-based multiphase ceramic coating
CN109971982B (en) Preparation method of in-situ authigenic ceramic phase reinforced titanium-based composite material and product
CN110155966A (en) A kind of preparation system and preparation method of TiN, TiC, TiCN powder
CN110182841B (en) Low-temperature medium-current fluidization process for preparing TiOxCyNzSystem and method for coating powder
CN116462517B (en) Method for preparing silicon nitride coating on graphite substrate by molten salt method
KR100596676B1 (en) Massive synthesis method of single-walled carbon nanotubes using the vapor phase growth
CN101475151A (en) Preparation of conductive titanium nitride/silicon nitride nano composite material
CN110158051B (en) Low-temperature medium-steady flow process for preparing TiOxCyNzSystem and method for coating and composite coating thereof
CN110155965B (en) System and method for producing TiN, TiC and TiCN powder
KR20060112546A (en) A production process of fe nano powder with silica coating by chemical vapor condensation
Mao et al. Controllable Preparation and Forming Mechanism of Bamboo-Shaped SiC Nanowires Reinforced SiC Dense Coating
CN1202044C (en) Method for preparing composite powder of ceramics with bionics structure
Hu et al. Effects of deposition temperature on microstructures and ablative properties of SiC coatings prepared by CVD from methylsilane
CN111170317B (en) Preparation method of graphene modified diamond/copper composite material
JP2015507593A (en) An improved method for synthesizing carbon nanotubes on multiple supports
Li et al. Silicon assistant carbothermal reduction for SiC powders
CN113929099A (en) Preparation method of superfine tungsten carbide powder
CN1057515C (en) Method for deoxidisation and reinforcement of solid organic procursor of silicon nitride material
CN111620340A (en) Method for in-situ growth of TiC nanotube
Xie et al. Dense TiN‐Ni cermets with improved sinterability, microstructure, and mechanical properties using Ni‐coated TiN powders
CN110923493A (en) Preparation process of hole structure SiC/Al composite material

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant