CN107721429A - Zirconium carbide silicon carbide composite powder body material and preparation method thereof - Google Patents

Zirconium carbide silicon carbide composite powder body material and preparation method thereof Download PDF

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CN107721429A
CN107721429A CN201711126902.XA CN201711126902A CN107721429A CN 107721429 A CN107721429 A CN 107721429A CN 201711126902 A CN201711126902 A CN 201711126902A CN 107721429 A CN107721429 A CN 107721429A
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zirconium
source
silicon
composite powder
molal quantity
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CN107721429B (en
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许文涛
周有福
王志光
卢帅
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Fujian Institute of Research on the Structure of Matter of CAS
Institute of Modern Physics of CAS
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Fujian Institute of Research on the Structure of Matter of CAS
Institute of Modern Physics of CAS
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
    • C04B35/5607—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on refractory metal carbides
    • C04B35/5622—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on refractory metal carbides based on zirconium or hafnium carbides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
    • C04B35/565—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide
    • C04B35/571—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide obtained from Si-containing polymer precursors or organosilicon monomers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures

Abstract

This application discloses a kind of zirconium carbide silicon carbide composite powder body material, the mol ratio of component meets ZrC in the zirconium carbide silicon carbide composite powder body material：SiC=1：0.1~1：10；Its preparation technology is simple, and cost is low, process is easily controllable；Obtained zirconium carbide silicon carbide composite powder body material has the advantages of uniform submicron order, composition, high-purity.

Description

Zirconium carbide-silicon carbide composite powder material and preparation method thereof
Technical field
The application is related to a kind of Zirconium carbide-silicon carbide composite powder material and preparation method thereof, belongs to inorganic non-metallic material Material field.
Background technology
Carbide ceramics is excellent structural ceramic material, under the extreme conditions such as high temperature, burn into irradiation, remains to keep Good mechanical properties, it can be applied to the fields such as Aero-Space, core heap reactor, hard alloy processing, thermal structure part.Single-phase Carbide fracture toughness is low, high temperature oxidation resistance is poor, greatly limit its application.In recent years, based on two phase material feature, realize Composite property add and with complementation, turn into study hotspot.Zirconium carbide-composite material of silicon carbide can integrate excellent resistance to of ZrC The high-temperature oxidation resistance of high temperature, anti-radiation performance and SiC, it is compound by two-phase, adjusting seed size growth, it can further improve The mechanical performance of composite.Due to the strong covalent bond of carbide, the characteristic such as low self-diffusion coefficient, its sintering activity is poor.Carbonization Zirconium-silicon carbide super composite granule has high surface, can effectively reduce sintering temperature and promote to be densified, while realize two Mutually it is uniformly distributed, obtains the composite of microstructure and excellent performance, has obtained the extensive concern of researcher.
The method for preparing composite ceramic material at present mainly has following methods：(1) mixing oxides method, will by mechanical batch mixing The direct ground and mixed of carbide, or corresponding oxide/metal simple-substance and high temperature solid-state after carbon simple substance raw material machinery batch mixing is anti- Should, as the A of patent CN 103288454 by zirconates, silica flour, phenolic resin ball milling mix, be heat-treated at 1500~1800 DEG C, Prepare the Zirconium carbide-silicon carbide composite powder of about 50 μm of particle diameter.This method is simple, but two phase constituents are difficult to be well mixed, reaction Temperature is high, and the powder of acquisition is easily reunited caking, and its pattern, size distribution are difficult to control.(2) liquid phase precursor process, with organic Zirconium, organic silane compound are dissolved in organic solvent, and after polymerisation, Pintsch process prepares carbide composite material, such as patent CN Bis cyclopentadienyl zirconium dichloride, halogenated silanes monomer, catalyst etc. are dissolved in organic solvent by 105237773 A, after filtering and concentrating, at 2500 DEG C Ceramic under high temperature.This method batch mixing is uniform, but cost of material is high, while a large amount of organic solvents easily pollute environment, and silicon source It is not independent with carbon source, it is not easy to adjust compound Zr/Si ratios and easily cause carbon residual.(3) sol-gel process, using metal Alkoxide, surfactant etc. is added, slowly hydrolysis, forms homogeneous gel, nanoscale powder body material can be obtained after heat treatment.Such as After Tao Cai etc. use four butanol zirconiums, poly- methyl silico acetylene base silane to obtain gel for raw material, 1700 DEG C of reactions, particle diameter is obtained 100~300nm, the Zirconium carbide-silicon carbide composite powder of distributed components.The material composition of this method is complicated, cost is high, and Digestion time is long, the difficult control of process, limits it and industrializes large-scale application.
The content of the invention
According to the one side of the application, there is provided a kind of Zirconium carbide-silicon carbide composite powder material, the scantling reach To submicron order, particle diameter distribution is uniform, crystallization purity is high, small without dephasign, particle agglomeration.
The mol ratio of component meets ZrC in the Zirconium carbide-silicon carbide composite powder material：SiC=1：0.1~1：10.
Preferably, the particle diameter of the Zirconium carbide-silicon carbide composite powder material is 100nm~1 μm.
Preferably, the particle diameter of the Zirconium carbide-silicon carbide composite powder material is 200nm~500nm.
The another aspect of the application, there is provided the method for preparing described Zirconium carbide-silicon carbide composite powder material, at least Comprise the steps of：
(1) by containing zirconium source, carbon source, silicon source mixed solution, carry out hydro-thermal reaction, obtain hydro-thermal presoma；
(2) under non-active gas atmosphere, the presoma obtained in step (1) is calcined, obtains composition as oxidation The Means of Pyrolyzed Precursor of zirconium-oxidation silico-carbo；
(3) by the Means of Pyrolyzed Precursor of step (2) under atmosphere of inert gases, carbonizing reduction reaction is carried out, obtains the carbon Change zirconium-silicon carbide composite powder body material.
Preferably, zirconium source described in step (1) is at least one in basic zirconium chloride, zirconyl nitrate, zirconium nitrate, zirconium sulfate Kind；
The carbon source is selected from least one of carbohydrate；
The silicon source is selected from MTMS, HMDO, tetraethyl orthosilicate, γ-glycidol ether At least one of oxygen propyl trimethoxy silicane, gamma-aminopropyl-triethoxy-silane.
Preferably, the carbon source is selected from least one of glucose, fructose, sucrose, lactose, soluble starch.
Preferably, the mol ratio of zirconium source and silicon source is 1 in mixed solution described in step (1)：0.1~1：10；Zirconium source with The ratio between the molal quantity sum of silicon source and the molal quantity of carbon source are 1：2.5~1：5.
Preferably, the ratio between molal quantity of molal quantity sum and carbon source of zirconium source and silicon source is 1 in the mixed solution：2.5 ~1：4.5.
Preferably, the mol ratio upper limit of zirconium source and silicon source is selected from 1 in mixed solution described in step (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 mole ratio limit of zirconium source and silicon source is selected from 1 in mixed solution described in step (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, described in step (1) in mixed solution the molal quantity sum and carbon source of zirconium source and silicon source molal quantity it 1 is selected from than the upper limit：2.8、1：3、1：3.5、1：4、1：4.5 or 1：4.8.
Preferably, described in step (1) in mixed solution the molal quantity sum and carbon source of zirconium source and silicon source molal quantity it 1 is selected from than lower limit：2.8、1：3、1：3.5、1：4、1：4.5 or 1：4.8.
Wherein, the molal quantity in above-mentioned zirconium source is in terms of the molal quantity of zr element in zirconium source；The molal quantity of silicon source is with silicon in silicon source The molal quantity meter of element；The molal quantity of carbon source is in terms of the molal quantity of carbon in carbon source.
Preferably, the total mol concentration of zr element and element silicon is 0.1~1.0mol/L in the mixed solution.
Preferably, the total mol concentration of zr element and element silicon is 0.2~0.8mol/L in the mixed solution.
Preferably, the condition of hydro-thermal reaction is described in step (1)：120~240 DEG C are reacted 24~72 hours.
Preferably, the condition of hydro-thermal reaction is described in step (1)：140~220 DEG C are reacted 24~72 hours.
Preferably, hydro-thermal reaction is washed after terminating to product in step (1), is dried, is obtained hydro-thermal presoma.
Preferably, the washing is washed with deionized several times to adopt, and neutrality is detected as to pH value；Drying mode be 80~ 110 DEG C of vacuum drying freeze-dryings, drying time are 6~12 hours.
Preferably, gained hydro-thermal presoma is that coordination polymerization solidifies and has carbohydrate carbonization to a certain degree in step (1) Homogeneous presoma.
Preferably, the condition calcined described in step (2) is 800~1000 DEG C and calcined 1.5~2.5 hours.
Preferably, calcining obtains Means of Pyrolyzed Precursor after terminating in step (2), and product is ground, obtains powder.
Preferably, non-active gas atmosphere described in step (2) is independently selected from nitrogen, argon gas, helium, neon, xenon At least one of；Atmosphere of inert gases described in step (3) in argon gas, helium, neon, xenon at least one Kind.
Preferably, the condition of the reaction of carbonizing reduction described in step (3) is：1400~1600 DEG C are reacted 2~8 hours, are risen Warm speed is 3~10 DEG C/min, and the flow of non-active gas is 100~400mL/min.
Preferably, the flow of the non-active gas is 100~200mL/min.
Preferably, the powder obtained in step (2) carries out carbothermic reduction reaction, and it is compound to obtain zirconium carbide-silicon carbide super Powder.
Mode is preferably carried out as one kind, the method for preparing described zirconium carbide-composite material of silicon carbide, is comprised at least Following steps：Using zirconates as zirconium source, tetraethyl orthosilicate (TEOS) is silicon source, and the carbohydrate rich in hydroxyl is carbon source material Material, in proportion by dissolution of raw material in deionized water, stirring and dissolving makes it well mixed, and mixed solution, which is placed in reactor, enters water-filling Heat treatment, hydrothermal product is scrubbed, dries, and obtains the homogeneous hydro-thermal that coordination polymerization solidifies and has carbohydrate carbonization to a certain degree Presoma.Gained presoma is calcined in inert atmosphere, takes out and pulverizes after acquisition Means of Pyrolyzed Precursor, corresponding powder exists 1400-1600 DEG C carries out carbothermic reduction reaction in argon atmosphere, and carbon is uniformly wrapped on zirconium, silicon grain surface in presoma, avoids Raw material dry and course of reaction in segregation and reunion, can obtain that submicron order, composition be uniform, high-purity zirconium carbide-carbon SiClx ultrathin composite powder.
Method cost in the application is low, synthesis technique is simple, process is easily controllable and has industrialization production prospect.
Beneficial effect caused by the application energy includes：
1) Zirconium carbide-silicon carbide composite powder material provided herein, it is equal that size reaches submicron order, particle diameter distribution It is even, crystallization purity is high, small without dephasign, particle agglomeration.
2) method provided herein, using inorganic zirconium salts as zirconium source material, using soluble-carbohydrate as Carbon source material, pure water are medium, avoid using organic solvent, do not produce reaction contaminant；Dissolution of raw material degree is good, is easy to prepare High concentration homogeneous aqueous slurries, yield is higher, and two-phase proportion can be adjusted arbitrarily；Raw material sources are extensive, cheap, production cost It is low.
3) method provided herein, it is not necessary to use special equipment and technique, have that technique is simple, process is easy to The advantages of control.
4) in method provided herein, the environment of the peculiar HTHP of hydro-thermal reaction, under the conditions of additive is not required to, It is can effectively facilitating the carbohydrate molecule rich in hydroxyl to solidify with zirconium, silicon atom coordination polymerization, while realize carbon water The carbonization of compound, obtain zirconium, silicon, carbon molecular level mixed uniformly presoma；The technical method can avoid Carbon component is lost in caused by foaming in carbohydrate thermal dehydration and thermal decomposition process, ensures in formula (zirconium+silicon)：(carbon) Ratio is accurately constant；The carbon reaction work that hydrothermal carbonization obtains in presoma is very big, can effectively improve carbothermic reduction reaction speed simultaneously Reduce reaction temperature, and can uniformly and intimately be coated on zirconium, silicon components particle surface, avoid segregation in course of reaction with Reunite, obtain the Zirconium carbide-silicon carbide composite powder of excellent performance.
Brief description of the drawings
Fig. 1 is the TEM figures for zirconium carbide-carborundum Means of Pyrolyzed Precursor that embodiment 1 is prepared.
Fig. 2 is the Zirconium carbide-silicon carbide composite powder SEM figures that embodiment 1 is prepared.
Fig. 3 is the Zirconium carbide-silicon carbide composite powder XRD spectrums that embodiment 1 is prepared.
Fig. 4 is the Zirconium carbide-silicon carbide composite powder EDS analysis charts that embodiment 1 is prepared；Wherein, it is powder to scheme (a) Si element Surface scan figures, figure (b) is powder Zr element Surface scan figures, and figure (c) is constituent content figure.
Embodiment
The application is described in detail with reference to embodiment, but the application is not limited to these embodiments.
Unless otherwise instructed, the raw material in embodiments herein is bought by commercial sources.
Analysis method is as follows in embodiments herein：
XRD spectrum analyses are carried out using X-ray diffractometer (Miniflex-600, Rigaku Japan).
Sem analysis and EDS elementary analyses are carried out using field emission scanning electron microscope (SU8010, Hitachi Japan).
Using carrying out tem analysis on transmission scanning electron microscope (Tecnai F20, FEI USA).
Embodiment 1 prepares Zirconium carbide-silicon carbide composite powder material 1#
By zirconium oxychloride (ZrOCl2·8H2O), tetraethyl orthosilicate (TEOS), glucose are separately added into 100ml deionized waters In, stirring and dissolving makes it well mixed；Wherein Zr：Si elemental mole ratios example is 1：1；(Zr+Si):(C) element ratio is 1： 2.5；(Zr+Si) element total mol concentration is 0.2mol/L in solution.Above solution is placed in reactor, carries out hydro-thermal reaction Processing, 220 DEG C of reaction temperature, 24 hours reaction time；It is neutral, 80 DEG C of vacuum that hydrothermal product is washed to pH value through deionized water 12h is dried, obtains the homogeneous hydro-thermal presoma that coordination polymerization solidifies and has carbohydrate carbonization to a certain degree；By gained forerunner Body is 900 DEG C in nitrogen atmosphere, and calcining obtains taking out after Means of Pyrolyzed Precursor pulverizing for 2 hours, and corresponding powder is in argon atmosphere In 1600 DEG C progress carbothermic reduction reactions, argon flow amount 100mL/min；Heating rate is 3 DEG C/min, is incubated 2 hours, produces The Zirconium carbide-silicon carbide composite powder material, labeled as 1#.
Embodiment 2 prepares Zirconium carbide-silicon carbide composite powder material 2#
By zirconium nitrate (Zr (NO3)4·5H2O), tetraethyl orthosilicate (TEOS), sucrose are separately added into 100ml deionized waters, Stirring and dissolving makes it well mixed；Wherein, Zr：Si elemental mole ratios example is 1：2；(Zr+Si):(C) element ratio is 1：3.5； (Zr+Si) element total mol concentration is 0.5mol/L in solution.Above solution is placed in reactor, carried out at hydro-thermal reaction Reason, 200 DEG C of reaction temperature, 36 hours reaction time；It is neutral, 100 DEG C of vacuum that hydrothermal product is washed to pH value through deionized water Dry 10 hours, obtain the homogeneous hydro-thermal presoma that coordination polymerization solidifies and has carbohydrate carbonization to a certain degree；By gained Presoma is 900 DEG C in nitrogen atmosphere, and calcining obtains taking out after Means of Pyrolyzed Precursor pulverizing for 2 hours, and corresponding powder is in argon gas 1500 DEG C of progress carbothermic reduction reactions, argon flow amount 200mL/min in atmosphere；Heating rate is 5 DEG C/min, is incubated 4 hours, The Zirconium carbide-silicon carbide composite powder material is produced, labeled as 2#.
Embodiment 3 prepares Zirconium carbide-silicon carbide composite powder material 3#
By zirconium sulfate (Zr (SO4)2·4H2O), tetraethyl orthosilicate (TEOS), soluble starch be separately added into 100ml go from In sub- water, stirring and dissolving makes it well mixed, wherein Zr：Si elemental mole ratios example is 2:1；(Zr+Si):(C) element ratio is 1：4.5；(Zr+Si) element total mol concentration is 0.8mol/L in solution.Above solution is placed in reactor, it is anti-to carry out hydro-thermal It should handle, 180 DEG C of reaction temperature, 48 hours reaction time；Hydrothermal product is washed to pH value through deionized water and done for neutral, freezing Dry 8 hours, obtain the homogeneous hydro-thermal presoma that coordination polymerization solidifies and has certain journey carbohydrate degree carbonization；By gained forerunner Body is 900 DEG C in nitrogen atmosphere, and calcining obtains taking out after Means of Pyrolyzed Precursor pulverizing for 2 hours, and corresponding powder is in argon atmosphere In 1500 DEG C progress carbothermic reduction reactions, argon flow amount 200mL/min；Heating rate is 10 DEG C/min, is incubated 4 hours, i.e., The Zirconium carbide-silicon carbide composite powder material is obtained, labeled as 3#.
Embodiment 4 prepares Zirconium carbide-silicon carbide composite powder material 4#
By zirconium sulfate (Zr (SO4)2·4H2O), tetraethyl orthosilicate (TEOS), fructose are separately added into 100ml deionized waters, Stirring and dissolving makes it well mixed, wherein Zr：Si elemental mole ratios example is 1:2；(Zr+Si):(C) element ratio is 1:3, solution In (Zr+Si) element total mol concentration be 0.6mol/L.Above solution is placed in reactor, carries out hydro-thermal reaction processing, instead Answer 140 DEG C of temperature, 72 hours reaction time；Hydrothermal product is washed to pH value through deionized water to be neutrality, is freeze-dried 12 hours, Obtain the homogeneous hydro-thermal presoma that coordination polymerization solidifies and has carbohydrate carbonization to a certain degree；By gained presoma in nitrogen 900 DEG C in atmosphere, calcining obtains taking out after Means of Pyrolyzed Precursor pulverizing for 2 hours, and corresponding powder is 1400 DEG C in argon atmosphere Carry out carbothermic reduction reaction, argon flow amount 100mL/min；Heating rate is 10 DEG C/min, is incubated 8 hours, produces the carbon Change zirconium-silicon carbide composite powder body material.
The morphology characterization of embodiment 5
TEM signs are carried out to the zirconium carbide in 1~embodiment of embodiment 4-carborundum Means of Pyrolyzed Precursor.Wherein, typically As shown in figure 1, zirconium carbide-carborundum the Means of Pyrolyzed Precursor obtained in its corresponding embodiment 1.It can be drawn from figure：It is prepared Means of Pyrolyzed Precursor in amorphous carbon substrate tight in zirconium, silicon components particle surface, effectively shorten mass transfer distance and press down Crystal grain reunion has been made, has been played the role of to reduction carbon-thermal reduction temperature and particle size positive.In 2~embodiment of embodiment 4 The test result that zirconium carbide-carborundum Means of Pyrolyzed Precursor is forged is similar with the test result of embodiment 1.
In addition, SEM morphology analysis is carried out to sample 1#~4#, it is typical as shown in Fig. 2 its corresponding 1#.Can be with from figure It is superfine powder to find out prepared ZrC-SiC composite diphase materials, and average grain diameter crystallizes complete, granularity point in 200~500nm Cloth narrow range, dispersiveness are preferably.2#~4# test result is similar with 1# test result.
The material phase analysis of embodiment 6
Material phase analysis is carried out to sample 1#~4#, it is typical as shown in figure 3, its corresponding 1#.As can be seen from the figure it is made Standby composite granule crystallinity is high, and comprises only ZrC and SiC thing phases, without zirconium oxide and silica miscellaneous peak, illustrates product purity It is high.2#~4# test result is similar with 1# test result.
The elementary analysis of embodiment 7
Elementary analysis is carried out to sample 1#~4#, it is typical as shown in figure 4, its corresponding 1#；Wherein, (a) figure is powder Si Element Surface scan figure, (b) figure are powder Zr element Surface scan figures, and (c) figure is constituent content figure.As can be seen from the figure in sample Middle zirconium, element silicon are evenly distributed, and composite effect is good.2#~4# test result is similar with 1# test result.
To sum up, it is excellent to have that product quality is high, process is simple, cost is low etc. for the preparation method in 1~embodiment of embodiment 4 Point, help to realize extensive use of the zirconium carbide-composite material of silicon carbide in each field.
It is described above, only it is several embodiments of the application, any type of limitation is not done to the application, although this Shen Please with preferred embodiment disclose as above, but and be not used to limit the application, any person skilled in the art, do not taking off In the range of technical scheme, make a little variation using the technology contents of the disclosure above or modification is equal to Case study on implementation is imitated, is belonged in the range of technical scheme.

Claims (10)

  1. A kind of 1. Zirconium carbide-silicon carbide composite powder material, it is characterised in that the Zirconium carbide-silicon carbide composite powder material The mol ratio of middle component meets ZrC：SiC=1：0.1~1：10.
  2. 2. Zirconium carbide-silicon carbide composite powder material according to claim 1, it is characterised in that the zirconium carbide-carbonization The particle diameter of silicon composite powder material is 100nm~1 μm；
    Preferably, the particle diameter of the Zirconium carbide-silicon carbide composite powder material is 200nm~500nm.
  3. 3. prepare the method for the Zirconium carbide-silicon carbide composite powder material described in claim 1 or 2, it is characterised in that at least wrap Containing following steps：
    (1) by containing zirconium source, carbon source, silicon source mixed solution, carry out hydro-thermal reaction, obtain hydro-thermal presoma；
    (2) under non-active gas atmosphere, the presoma obtained in step (1) is calcined, it is zirconium oxide-oxygen to obtain composition Change the Means of Pyrolyzed Precursor of silico-carbo；
    (3) by the Means of Pyrolyzed Precursor of step (2) under atmosphere of inert gases, carry out carbonizing reduction reaction, obtain the zirconium carbide- Silicon carbide composite powder body material.
  4. 4. according to the method for claim 3, it is characterised in that zirconium source described in step (1) is selected from basic zirconium chloride, Nitric Acid Oxidation At least one of zirconium, zirconium nitrate, zirconium sulfate；
    The carbon source is selected from least one of carbohydrate；
    The silicon source is selected from MTMS, HMDO, tetraethyl orthosilicate, γ-glycidyl ether oxygen third At least one of base trimethoxy silane, gamma-aminopropyl-triethoxy-silane；
    Preferably, the carbon source is selected from least one of glucose, fructose, sucrose, lactose, soluble starch.
  5. 5. according to the method for claim 3, it is characterised in that zirconium source and silicon source in mixed solution described in step (1) Mol ratio is 1：0.1~1：10；
    The ratio between molal quantity of molal quantity sum and carbon source of zirconium source and silicon source is 1：2~1：5；
    Preferably, the ratio between molal quantity of molal quantity sum and carbon source of zirconium source and silicon source is 1：2.5~1：4.5；
    Wherein, the molal quantity in zirconium source is in terms of the molal quantity of zr element in zirconium source；The molal quantity of silicon source is rubbed with element silicon in silicon source That number meter；The molal quantity of carbon source is in terms of the molal quantity of carbon in carbon source.
  6. 6. the method according to claim 3 or 5, it is characterised in that zr element and element silicon is total in the mixed solution Molar concentration is 0.1~1.0mol/L；
    Preferably, the total mol concentration of zr element and element silicon is 0.2~0.8mol/L in the mixed solution.
  7. 7. according to the method for claim 3, it is characterised in that the condition of hydro-thermal reaction is described in step (1)：120~ 240 DEG C are reacted 24~72 hours；
    Preferably, the condition of hydro-thermal reaction is described in step (1)：140~220 DEG C are reacted 24~72 hours.
  8. 8. according to the method for claim 3, it is characterised in that the condition calcined described in step (2) is 800~1000 DEG C Calcining 1.5~2.5 hours.
  9. 9. according to the method for claim 3, it is characterised in that non-active gas atmosphere is independently selected described in step (2) From at least one of nitrogen, argon gas, helium, neon, xenon；
    Atmosphere of inert gases is independently selected from least one of argon gas, helium, neon, xenon described in step (3).
  10. 10. according to the method for claim 3, it is characterised in that carbonizing reduction described in step (3) reaction condition be： 1400~1600 DEG C are reacted 2~8 hours, and heating rate is 3~10 DEG C/min, and the flow of non-active gas is 100~400mL/ min；
    Preferably, the flow of the non-active gas is 100~200mL/min.
CN201711126902.XA 2017-11-15 2017-11-15 Zirconium carbide-silicon carbide composite powder material and preparation method thereof Active CN107721429B (en)

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CN108483447A (en) * 2018-04-28 2018-09-04 北京科技大学 A kind of preparation method of micro/nano level spherical carbide silicon materials
CN109265190A (en) * 2018-10-15 2019-01-25 陕西科技大学 A kind of preparation method of the multiple dimensioned modified ZrC-SiC multiphase ceramic powder of silicon carbide whisker-aluminium oxide submicron particles
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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US20180186700A1 (en) * 2015-07-28 2018-07-05 Shandong Ul Traming Fine Ceramics Co., Ltd. Method for synthesizing high-purity ultrafine ZrC-SiC composite powder
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CN109265190A (en) * 2018-10-15 2019-01-25 陕西科技大学 A kind of preparation method of the multiple dimensioned modified ZrC-SiC multiphase ceramic powder of silicon carbide whisker-aluminium oxide submicron particles
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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