CN107721429B - Zirconium carbide-silicon carbide composite powder material and preparation method thereof - Google Patents
Zirconium carbide-silicon carbide composite powder material and preparation method thereof Download PDFInfo
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Abstract
The application discloses a zirconium carbide-silicon carbide composite powder material, wherein the molar ratio of components in the zirconium carbide-silicon carbide composite powder material satisfies ZrC: 1 of SiC: 0.1-1: 10; the preparation process is simple, the cost is low, and the process is easy to control; the obtained zirconium carbide-silicon carbide composite powder material has the advantages of submicron grade, uniform components and high purity.
Description
Technical Field
The application relates to a zirconium carbide-silicon carbide composite powder material and a preparation method thereof, belonging to the field of inorganic non-metallic materials.
Background
The carbide ceramic is an excellent structural ceramic material, can still maintain good mechanical properties under extreme conditions of high temperature, corrosion, irradiation and the like, and can be applied to the fields of aerospace, nuclear reactor, hard alloy processing, high-temperature structural parts and the like. The single-phase carbide has low fracture toughness and poor high-temperature oxidation resistance, and the application of the single-phase carbide is greatly limited. In recent years, based on the characteristics of two-phase materials, the performance addition and complementation of composite materials are realized, and the method becomes a research hotspot. The zirconium carbide-silicon carbide composite material can integrate excellent high temperature resistance and radiation resistance of ZrC and high temperature oxidation resistance of SiC, and the mechanical property of the composite material can be further improved by regulating and controlling the growth of crystal grains through two-phase compounding. The sintering activity of the carbide is poor due to the characteristics of strong covalent bond, low self-diffusion coefficient and the like of the carbide. The zirconium carbide-silicon carbide superfine composite powder has high surface activity, can effectively reduce sintering temperature and promote densification, simultaneously realizes uniform distribution of two phases, obtains a composite material with excellent microstructure and performance, and has obtained extensive attention of researchers.
The existing method for preparing the composite ceramic powder mainly comprises the following steps: (1) the solid phase mixing method is to directly grind and mix the carbide through mechanical mixing, or to mechanically mix the corresponding oxide/metal simple substance and the carbon simple substance raw material and then perform high temperature solid phase reaction, for example, in patent CN 103288454A, zirconium salt, silicon powder and phenolic resin are ball-milled and mixed, and heat treatment is performed at 1500-1800 ℃, so as to prepare the zirconium carbide-silicon carbide composite powder with the particle size of about 50 μm. The method is simple, but the two-phase components are difficult to be uniformly mixed, the reaction temperature is high, the obtained powder is easy to agglomerate and agglomerate, and the morphology and the particle size distribution are difficult to control. (2) A liquid-phase precursor method for preparing carbide composite material includes dissolving organic zirconium and organic silane compound in organic solvent, polymerizing, high-temp cracking, dissolving zirconocene dichloride, halogenated silane monomer and catalyst in organic solvent, filtering, concentrating, and high-temp ceramizing at 2500 deg.C. The method has the advantages of uniform mixing, high raw material cost, easy environmental pollution of a large amount of organic solvents, non-independence of a silicon source and a carbon source, and difficult adjustment of the Zr/Si ratio of the compound, thereby easily causing carbon residue. (3) The sol-gel method adopts metal alkoxide, adds surfactant and the like, slowly hydrolyzes to form uniform gel, and obtains the nano-scale powder material after heat treatment. For example, Tao Cai and the like adopt zirconium tetrabutoxide and polymethyl silicon acetylene silane as raw materials to obtain gel, and then react at 1700 ℃ to obtain zirconium carbide-silicon carbide composite powder with the particle size of 100-300 nm and uniformly distributed components. The method has the advantages of complex raw material components, high cost, long aging time and difficult process control, and limits the industrial large-scale application of the method.
Disclosure of Invention
According to one aspect of the application, a zirconium carbide-silicon carbide composite powder material is provided, which has the advantages of submicron size, uniform particle size distribution, high crystallization purity, no impurity phase and small particle agglomeration.
The molar ratio of the components in the zirconium carbide-silicon carbide composite powder material meets the requirements of ZrC: 1 of SiC: 0.1-1: 10.
preferably, the particle size of the zirconium carbide-silicon carbide composite powder material is 100 nm-1 μm.
Preferably, the particle size of the zirconium carbide-silicon carbide composite powder material is 200 nm-500 nm.
In another aspect of the present application, a method for preparing the zirconium carbide-silicon carbide composite powder material is provided, which at least comprises the following steps:
(1) carrying out hydrothermal reaction on a mixed solution containing a zirconium source, a carbon source and a silicon source to obtain a hydrothermal precursor;
(2) calcining the precursor obtained in the step (1) in an inert gas atmosphere to obtain a pyrolysis precursor with the components of zirconia-silica-carbon;
(3) and (3) carrying out a carbonization-reduction reaction on the pyrolysis precursor in the step (2) in an inert gas atmosphere to obtain the zirconium carbide-silicon carbide composite powder material.
Preferably, the zirconium source in step (1) is selected from at least one of zirconium oxychloride, zirconyl nitrate, zirconium sulfate;
the carbon source is selected from at least one of carbohydrates;
the silicon source is at least one selected from methyltrimethoxysilane, hexamethyldisiloxane, ethyl orthosilicate, gamma-glycidoxypropyltrimethoxysilane and gamma-aminopropyltriethoxysilane.
Preferably, the carbon source is selected from at least one of glucose, fructose, sucrose, lactose, soluble starch.
Preferably, the molar ratio of the zirconium source to the silicon source in the mixed solution in the step (1) is 1: 0.1-1: 10; the ratio of the sum of the moles of the zirconium source and the silicon source to the moles of the carbon source is 1: 2.5-1: 5.
preferably, the ratio of the sum of the moles of the zirconium source and the silicon source to the moles of the carbon source in the mixed solution is 1: 2.5-1: 4.5.
preferably, the upper limit of the molar ratio of the zirconium source to the silicon source in the mixed solution in the step (1) is selected from 1: 0.2, 1: 0.3, 1: 0.4, 1: 0.5, 1: 0.6, 1: 0.7, 1: 0.8, 1: 0.9, 1: 2. 1: 3. 1: 4. 1: 5. 1: 6. 1: 7. 1: 8 or 1: 9.
preferably, the lower limit of the molar ratio of the zirconium source to the silicon source in the mixed solution in the step (1) is selected from 1: 0.2, 1: 0.3, 1: 0.4, 1: 0.5, 1: 0.6, 1: 0.7, 1: 0.8, 1: 0.9, 1: 2. 1: 3. 1: 4. 1: 5. 1: 6. 1: 7. 1: 8 or 1: 9.
preferably, the upper limit of the ratio of the sum of the moles of the zirconium source and the silicon source to the moles of the carbon source in the mixed solution in the step (1) is selected from 1: 2.8, 1: 3. 1: 3.5, 1: 4. 1: 4.5 or 1: 4.8.
preferably, the lower limit of the ratio of the sum of the moles of the zirconium source and the silicon source to the moles of the carbon source in the mixed solution in the step (1) is selected from 1: 2.8, 1: 3. 1: 3.5, 1: 4. 1: 4.5 or 1: 4.8.
wherein the number of moles of the zirconium source is based on the number of moles of a zirconium element in the zirconium source; the mole number of the silicon source is calculated by the mole number of silicon element in the silicon source; the moles of the carbon source are based on the moles of carbon in the carbon source.
Preferably, the total molar concentration of the zirconium element and the silicon element in the mixed solution is 0.1-1.0 mol/L.
Preferably, the total molar concentration of the zirconium element and the silicon element in the mixed solution is 0.2-0.8 mol/L.
Preferably, the conditions of the hydrothermal reaction in step (1) are: reacting at 120-240 ℃ for 24-72 hours.
Preferably, the conditions of the hydrothermal reaction in step (1) are: reacting at 140-220 ℃ for 24-72 hours.
Preferably, after the hydrothermal reaction in step (1) is finished, the product is washed and dried to obtain the hydrothermal precursor.
Preferably, the washing is carried out for several times by using deionized water until the pH value is detected to be neutral; the drying mode is vacuum drying and freeze drying at 80-110 ℃, and the drying time is 6-12 hours.
Preferably, the hydrothermal precursor obtained in step (1) is a homogeneous precursor solidified by coordination polymerization and carbonized to some extent by carbohydrate.
Preferably, the calcining condition in the step (2) is that calcining is carried out for 1.5-2.5 hours at 800-1000 ℃.
Preferably, a pyrolysis precursor is obtained after the calcination in the step (2), and the product is ground to obtain powder.
Preferably, the inert gas atmosphere in step (2) is independently selected from at least one of nitrogen, argon, helium, neon and xenon; the inert gas atmosphere in the step (3) is independently selected from at least one of argon, helium, neon and xenon.
Preferably, the conditions of the carbonization-reduction reaction in step (3) are: reacting for 2-8 hours at 1400-1600 ℃, wherein the heating rate is 3-10 ℃/min, and the flow of the inactive gas is 100-400 mL/min.
Preferably, the flow rate of the inactive gas is 100-200 mL/min.
Preferably, the powder obtained in the step (2) is subjected to a carbothermic reduction reaction to obtain the zirconium carbide-silicon carbide superfine composite powder.
As a preferred embodiment, the method for preparing the zirconium carbide-silicon carbide composite material at least comprises the following steps: the preparation method comprises the steps of taking zirconium salt as a zirconium source, Tetraethoxysilane (TEOS) as a silicon source and carbohydrate rich in hydroxyl as a carbon source material, dissolving the raw materials in deionized water according to a proportion, stirring to dissolve the raw materials to uniformly mix the raw materials, placing the mixed solution in a reactor to carry out hydrothermal treatment, washing and drying a hydrothermal product to obtain a homogeneous hydrothermal precursor which is subjected to coordination polymerization curing and has carbohydrate carbonization to a certain degree. Calcining the obtained precursor in an inactive atmosphere to obtain a pyrolysis precursor, taking out the pyrolysis precursor and grinding the pyrolysis precursor into powder, carrying out carbothermic reduction reaction on the corresponding powder at 1400-1600 ℃ in an argon atmosphere, wherein carbon in the precursor is uniformly coated on the surfaces of zirconium and silicon particles, so that the segregation and agglomeration of the raw materials in the drying and reaction processes are avoided, and the submicron-grade high-purity zirconium carbide-silicon carbide superfine composite powder with uniform components can be obtained.
The method has the advantages of low cost, simple synthesis process, easy control of the process and industrial production prospect.
The beneficial effects that this application can produce include:
1) the zirconium carbide-silicon carbide composite powder material provided by the application has the advantages of submicron size, uniform particle size distribution, high crystallization purity, no impurity phase and small particle agglomeration.
2) According to the method provided by the application, inorganic zirconium salt is used as a zirconium source material, soluble carbohydrate is used as a carbon source material, and pure water is used as a medium, so that organic solvent is avoided, and reaction pollutants are not generated; the raw material has good solubility, is convenient to prepare high-concentration homogeneous water-based slurry, has high yield, and the proportion of two phases can be adjusted at will; the raw materials have wide sources, low price and low production cost.
3) The method provided by the application does not need to use special equipment and process, and has the advantages of simple process and easiness in process control.
4) In the method provided by the application, the hydrothermal reaction has a special high-temperature and high-pressure environment, and under the condition of no additive, the coordination polymerization and solidification of carbohydrate molecules rich in hydroxyl and zirconium and silicon atoms can be effectively promoted, meanwhile, the carbonization of the carbohydrate is realized, and a precursor with zirconium, silicon and carbon elements uniformly mixed at a molecular level is obtained; the technical method can avoid the loss of carbon components caused by the foaming in the processes of heating dehydration and thermal decomposition of carbohydrates, and ensures that the components (zirconium and silicon) in the formula are as follows: the (carbon) proportion is not changed accurately; the carbon obtained by hydrothermal carbonization in the precursor has great reaction activity, can effectively improve the carbothermic reduction reaction rate and reduce the reaction temperature, and can be uniformly and tightly coated on the surfaces of zirconium and silicon component particles, thereby avoiding segregation and agglomeration in the reaction process and obtaining the zirconium carbide-silicon carbide composite powder with excellent performance.
Drawings
Fig. 1 is a TEM image of a zirconium carbide-silicon carbide pyrolysis precursor prepared in example 1.
FIG. 2 is an SEM photograph of a zirconium carbide-silicon carbide composite powder prepared in example 1.
Fig. 3 is an XRD spectrum of the zirconium carbide-silicon carbide composite powder prepared in example 1.
FIG. 4 is an EDS analysis chart of the zirconium carbide-silicon carbide composite powder prepared in example 1; in the figure, (a) is a scanning view of the Si element surface of the powder, (b) is a scanning view of the Zr element surface of the powder, and (c) is a view of the element content.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The raw materials in the examples of the present application were all purchased commercially, unless otherwise specified.
The analysis method in the examples of the present application is as follows:
XRD spectrum analysis was carried out using an X-ray diffractometer (Miniflex-600, Rigaku Japan).
SEM analysis and EDS elemental analysis were performed using a field emission scanning electron microscope (SU8010, Hitachi Japan).
TEM analysis was performed using transmission scanning electron microscopy (Tecnai F20, FEI USA).
EXAMPLE 1 preparation of zirconium carbide-silicon carbide composite powder Material 1#
Zirconium oxychloride (ZrOCl)2·8H2O), Tetraethoxysilane (TEOS) and glucose are respectively added into 100ml of deionized water and stirred to be dissolved so as to be uniformly mixed; wherein Zr: the molar ratio of Si elements is 1: 1; the element proportion of (Zr + Si) is 1: 2.5; the total molar concentration of the (Zr + Si) elements in the solution was 0.2 mol/L. Placing the solution in a reactor, and carrying out hydrothermal reaction treatment at the reaction temperature of 220 ℃ for 24 hours; washing the hydrothermal product with deionized water until the pH value is neutral, and vacuum-drying at 80 ℃ for 12h to obtain a homogeneous hydrothermal precursor which is subjected to coordination polymerization and solidification and has a certain degree of carbohydrate carbonization; calcining the obtained precursor for 2 hours at 900 ℃ in a nitrogen atmosphere to obtain a pyrolysis precursor, taking out and grinding the precursor into powder, and carrying out carbothermic reduction reaction on the corresponding powder at 1600 ℃ in an argon atmosphere, wherein the flow of argon is 100 mL/min; the heating rate is 3 ℃/min, and the temperature is kept for 2 hours, thus obtaining the zirconium carbide-silicon carbide composite powder material which is marked as # 1.
EXAMPLE 2 preparation of zirconium carbide-silicon carbide composite powder Material No. 2
Zirconium nitrate (Zr (NO)3)4·5H2O), Tetraethoxysilane (TEOS) and sucrose are respectively added into 100ml of deionized water and stirred to be dissolved so as to be uniformly mixed; wherein, Zr: the molar ratio of Si elements is 1: 2; the element proportion of (Zr + Si) is 1: 3.5; the total molar concentration of the (Zr + Si) elements in the solution was 0.5 mol/L. Placing the solution in a reactor, and carrying out hydrothermal reaction treatment at the reaction temperature of 200 ℃ for 36 hours; washing the hydrothermal product by deionized water until the pH value is neutral, and vacuum-drying at 100 ℃ for 10 hours to obtain a homogeneous hydrothermal precursor which is subjected to coordination polymerization and solidification and has a certain degree of carbohydrate carbonization; calcining the precursor at 900 ℃ for 2 hours in nitrogen atmosphere to obtain a pyrolytic precursorTaking out the powder after the reaction, grinding the powder into powder, and carrying out carbothermic reduction reaction on the corresponding powder at 1500 ℃ in an argon atmosphere, wherein the argon flow is 200 mL/min; the heating rate is 5 ℃/min, and the temperature is kept for 4 hours, thus obtaining the zirconium carbide-silicon carbide composite powder material which is marked as 2 #.
EXAMPLE 3 preparation of zirconium carbide-silicon carbide composite powder Material No. 3
Zirconium sulfate (Zr (SO)4)2·4H2O), Tetraethoxysilane (TEOS) and soluble starch are respectively added into 100ml of deionized water, and are stirred and dissolved to be uniformly mixed, wherein the ratio of Zr: the molar ratio of Si element is 2: 1; the element proportion of (Zr + Si) is 1: 4.5; the total molar concentration of the (Zr + Si) elements in the solution was 0.8 mol/L. Placing the solution in a reactor, and carrying out hydrothermal reaction treatment at the reaction temperature of 180 ℃ for 48 hours; washing the hydrothermal product with deionized water until the pH value is neutral, and freeze-drying for 8 hours to obtain a homogeneous hydrothermal precursor which is subjected to coordination polymerization and solidification and has certain carbohydrate degree carbonization; calcining the obtained precursor for 2 hours at 900 ℃ in a nitrogen atmosphere to obtain a pyrolysis precursor, taking out and grinding the precursor into powder, and carrying out carbothermic reduction reaction on the corresponding powder at 1500 ℃ in an argon atmosphere, wherein the flow of argon is 200 mL/min; the heating rate is 10 ℃/min, and the temperature is kept for 4 hours, thus obtaining the zirconium carbide-silicon carbide composite powder material which is marked as 3 #.
EXAMPLE 4 preparation of zirconium carbide-silicon carbide composite powder Material No. 4
Zirconium sulfate (Zr (SO)4)2·4H2O), Tetraethoxysilane (TEOS) and fructose are respectively added into 100ml of deionized water, and are stirred and dissolved to be uniformly mixed, wherein the ratio of Zr: the molar ratio of Si element is 1: 2; the ratio of (Zr + Si) to (C) elements is 1:3, and the total molar concentration of the (Zr + Si) elements in the solution is 0.6 mol/L. Placing the solution in a reactor, and carrying out hydrothermal reaction treatment at the reaction temperature of 140 ℃ for 72 hours; washing the hydrothermal product by deionized water until the pH value is neutral, and freeze-drying for 12 hours to obtain a homogeneous hydrothermal precursor which is subjected to coordination polymerization and solidification and has a certain degree of carbohydrate carbonization; calcining the precursor at 900 ℃ in nitrogen atmosphere for 2 hours to obtain a pyrolysis precursor, taking out the pyrolysis precursor and grinding the pyrolysis precursor into powder, and feeding the corresponding powder at 1400 ℃ in argon atmosphereCarrying out carbothermic reduction reaction, wherein the flow rate of argon is 100 mL/min; the heating rate is 10 ℃/min, and the heat preservation is carried out for 8 hours, thus obtaining the zirconium carbide-silicon carbide composite powder material.
Example 5 topography characterization
TEM characterization was performed on the zirconium carbide-silicon carbide pyrolysis precursors in examples 1 to 4. As shown typically in fig. 1, the precursor corresponds to the zirconium carbide-silicon carbide pyrolysis precursor obtained in example 1. From the figure it follows that: the amorphous carbon matrix in the prepared pyrolysis precursor is tightly wrapped on the surfaces of zirconium and silicon component particles, so that the mass transfer distance is effectively shortened, the agglomeration of crystal grains is inhibited, and the pyrolysis precursor has a positive effect on reducing the carbothermic reaction temperature and the particle size. The test results for the zirconium carbide-silicon carbide pyrolysis precursor calcination in examples 2-4 were similar to those of example 1.
In addition, SEM topography analysis was performed on samples # 1 to # 4, which typically corresponds to # 1 as shown in FIG. 2. The ZrC-SiC complex phase material prepared is ultrafine powder, has the average grain diameter of 200-500 nm, and has the advantages of complete crystallization, narrow grain size distribution range and better dispersibility. The test results of # 2 to # 4 are similar to the test results of # 1.
Example 6 phase analysis
Phase analysis was performed on samples # 1 to # 4, typically as shown in figure 3, which corresponds to # 1. The figure shows that the prepared composite powder has high crystallinity, only contains ZrC and SiC phases, does not contain the mixed peaks of zirconia and silica, and shows that the product has high purity. The test results of # 2 to # 4 are similar to the test results of # 1.
Example 7 elemental analysis
Elemental analysis was performed on samples # 1 to # 4, which typically corresponds to # 1 as shown in FIG. 4; wherein, the figure (a) is a scanning diagram of the Si element surface of the powder, (b) is a scanning diagram of the Zr element surface of the powder, and (c) is a diagram of the element content. It can be seen from the figure that the zirconium and silicon elements in the sample are uniformly distributed, and the composite effect is good. The test results of # 2 to # 4 are similar to the test results of # 1.
In summary, the preparation methods of embodiments 1 to 4 have the advantages of high product quality, simple process, low cost, and the like, and are helpful for realizing the wide application of the zirconium carbide-silicon carbide composite material in various fields.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (11)
1. The preparation method of the zirconium carbide-silicon carbide composite powder material is characterized by at least comprising the following steps:
(1) carrying out hydrothermal reaction on a mixed solution containing a zirconium source, a carbon source and a silicon source to obtain a hydrothermal precursor;
(2) calcining the precursor obtained in the step (1) in an inert gas atmosphere to obtain a pyrolysis precursor with the components of zirconia-silica-carbon;
(3) carrying out a carbonization-reduction reaction on the pyrolysis precursor in the step (2) in an inert gas atmosphere to obtain the zirconium carbide-silicon carbide composite powder material;
wherein the content of the first and second substances,
the hydrothermal precursor is a homogeneous precursor which is subjected to coordination polymerization curing and carbohydrate carbonization to a certain degree;
the molar ratio of the components in the zirconium carbide-silicon carbide composite powder material meets the requirements of ZrC: 1 of SiC: 0.1-1: 10;
the hydrothermal reaction conditions in the step (1) are as follows: reacting for 24-72 hours at 120-240 ℃;
calcining at 800-1000 ℃ for 1.5-2.5 hours under the calcining condition in the step (2);
the conditions of the carbonization-reduction reaction in the step (3) are as follows: reacting for 2-8 hours at 1400-1600 ℃, wherein the heating rate is 3-10 ℃/min, and the flow of the inactive gas is 100-400 mL/min.
2. The method according to claim 1, wherein the particle size of the zirconium carbide-silicon carbide composite powder material is 100nm to 1 μm.
3. The method according to claim 1, wherein the particle size of the zirconium carbide-silicon carbide composite powder material is 200nm to 500 nm.
4. The method according to claim 1, wherein the zirconium source in step (1) is selected from at least one of zirconium oxychloride, zirconyl nitrate, zirconium nitrate, and zirconium sulfate;
the carbon source is at least one selected from glucose, fructose, sucrose, lactose and soluble starch;
the silicon source is at least one selected from methyltrimethoxysilane, hexamethyldisiloxane, ethyl orthosilicate, gamma-glycidoxypropyltrimethoxysilane and gamma-aminopropyltriethoxysilane.
5. The method according to claim 1, wherein the molar ratio of the zirconium source to the silicon source in the mixed solution in step (1) is 1: 0.1-1: 10;
the ratio of the sum of the moles of the zirconium source and the silicon source to the moles of the carbon source is 1: 2-1: 5;
wherein the moles of the zirconium source are based on the moles of the zirconium element in the zirconium source; the mole number of the silicon source is calculated by the mole number of silicon element in the silicon source; the moles of the carbon source are based on the moles of carbon in the carbon source.
6. The method according to claim 5, wherein the ratio of the sum of the moles of the zirconium source and the silicon source to the moles of the carbon source is 1: 2.5-1: 4.5.
7. the method according to claim 1 or 4, wherein the total molar concentration of the zirconium element and the silicon element in the mixed solution is 0.1 to 1.0 mol/L.
8. The method according to claim 7, wherein the total molar concentration of the zirconium element and the silicon element in the mixed solution is 0.2 to 0.8 mol/L.
9. The preparation method according to claim 1, wherein the hydrothermal reaction in step (1) is carried out under the following conditions: reacting at 140-220 ℃ for 24-72 hours.
10. The method according to claim 1, wherein the inert gas atmosphere in the step (2) is independently selected from at least one of nitrogen, argon, helium, neon, and xenon;
the inert gas atmosphere in the step (3) is independently selected from at least one of argon, helium, neon and xenon.
11. The method according to claim 1, wherein the flow rate of the inert gas is 100 to 200 mL/min.
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| CN105418071B (en) * | 2015-07-28 | 2018-01-16 | 山东合创明业精细陶瓷有限公司 | The synthetic method of high pure and ultra-fine ZrC SiC composite granules |
| CN108483447B (en) * | 2018-04-28 | 2019-10-22 | 北京科技大学 | A kind of preparation method of micro/nano level spherical carbide silicon materials |
| CN109265190B (en) * | 2018-10-15 | 2021-07-23 | 陕西科技大学 | Preparation method of silicon carbide whisker-alumina submicron particle multi-scale modified ZrC-SiC complex phase ceramic powder |
| CN110590368A (en) * | 2019-10-25 | 2019-12-20 | 中南大学 | Preparation method of ZrC-SiC mixed nano powder |
| CN111187075A (en) * | 2020-02-18 | 2020-05-22 | 陕西科技大学 | Precursor conversion method preparation process of self-dispersion superfine ZrC-SiC ceramic composite powder |
| CN112479711A (en) * | 2020-12-17 | 2021-03-12 | 西安理工大学 | Preparation method of zirconium carbide/hafnium carbide nano composite particles |
| CN115676830A (en) * | 2022-09-14 | 2023-02-03 | 淮北师范大学 | Preparation method of zirconium carbide powder |
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| CN105418071B (en) * | 2015-07-28 | 2018-01-16 | 山东合创明业精细陶瓷有限公司 | The synthetic method of high pure and ultra-fine ZrC SiC composite granules |
| CN106629732B (en) * | 2016-11-08 | 2018-10-19 | 西安科技大学 | A kind of preparation method of nanometer of ZrC-SiC composite granule |
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