CN102924083B - Method for preparing zirconium carbide ceramic powder - Google Patents
Method for preparing zirconium carbide ceramic powder Download PDFInfo
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Abstract
The invention relates to a method for preparing the zirconium carbide ceramic powder. The method is characterized by comprising material selection: selecting normal propyl alcohol zirconium, cane sugar, thinner normal propyl alcohol and chelating agent acetic acids according to a mass ratio of the normal propyl alcohol zirconium and the cane sugar in a range from (12:3.6) to (12:4.6) and a volume ratio of the normal propyl alcohol zirconium, thinner normal propyl alcohol and the chelating agent acetic acids in a range from (8:32:2) to (8:64:3); and selecting solvent acetic acids according to a proportion of the cane sugar and the chelating agent acetic acids of (7-8)g:50mL; dry gel powder preparation; precursor powder preparation; and precursor powder heat treatment to obatin zirconium carbide ceramic powder. According to the method, the problem that the oxygen content in the zirconium carbide powder is generally high is effectively solved, and the zirconium carbide powder of high purity and fine crystal particles is obtained; and an independent graphite mould exists, so that synthesis of zirconium carbide powder and preparation of other materials in a hot-pressing mold can be performed simultaneously, heat supply is achieved, and the energy consumption is greatly decreased.
Description
Technical field
The present invention relates to a kind of preparation method of zirconium carbide ceramics powder.
Background technology
Zirconium carbide (ZrC) is the study hotspot of non-oxide ceramic material in recent years.ZrC belongs to transition metal carbide, has the premium properties such as high rigidity, strong wear resistance, low-thermal-expansion rate, high heat conductance, high conductivity.Compared with other transition metal carbides such as silicon carbide, ZrC has more excellent chemical physical property.Zirconium carbide ceramic powder is a kind of extremely important Novel engineering ceramic raw material, and the feature of its excellence makes it on Wimet, have very large application space, can improve Wimet intensity, erosion resistance etc.Zirconium carbide is the raw material of production atomic level zirconium sponge, can be used as the additive of high grade refractory.Zirconium carbide has high strength and hardness; Secondly, for the neutron of 2200m/s, the absorption cross section of pure zirconium is 0.18 ± 0.02mb, and the absorption cross section of carbon is 3.2mb, and therefore ZrC thermal neutron absorption cross section is little; Moreover the spread coefficient of 137Cs in 1600,1800 DEG C time in ZrC coating is than low two orders of magnitude in SiC coating, and therefore ZrC radiation resistance is good, can do the material on high temperature gas cooled reactor coated fuel particles blocking layer.
Zirconium carbide is the non-stoichiometric carbide of one and the ZrC of transition element Zr and C formation
x(0.5≤x≤l), this is because NaCl type crystal structure is a kind of metastable structure, and ZrC is very easily oxidized, and its oxidizing temperature is about 300 DEG C.O atom can replace the position of C atom thus form ZrCxOy compound.Therefore, zirconium carbide is widely used as the protecting materials of the oxidation-resistance of enhanced carbon fiber.Due to the special purpose of zirconium carbide, the performance of people to Zirconium carbide powder it is also proposed corresponding requirement: purity is high, and oxygen level is low and crystal grain is tiny.
The traditional synthesis of zirconium carbide ceramic powder is: low temperature synthesis method, combustion synthesis method, carbothermic method, sol-gel method etc.Although the zirconium carbide powder particle diameter synthesized by these techniques can reach tens to hundreds of nanometer, due to the impact of the factor such as technique and raw material, and intermediate product ZrCxOy changes into ZrC difficulty, the problem that therefore ubiquity purity is not high.At present, Chinese scholars sol-gel method prepares high-purity, ultra-fine zirconium carbide powder.Mickael Doll ' e, Dominique Gosset etc., with zirconium-n-propylate, acetic acid and sucrose for zirconium source and carbon source obtain presoma.It heat-treated at 1400 ~ 1800 DEG C, obtain the ZrC that particle diameter is 90 ~ 150nm, oxygen level is between 3at. ~ 8at.%.Yongjie Yan etc., with ZrOCl
28H
2o, resol are respectively zirconium source and carbon source obtains presoma.Presoma 1400 DEG C insulation 1h is heat-treated, obtains the ZrC that median size is 200nm, but to be only the theoretical carbon content of 10.67%(in conjunction with the content of carbon be 11.64%).If adopt traditional heat treatment mode visible, required generated time is long, and energy consumption is large, and cost is higher.And oxygen level is usually higher or on the low side compared with theoretical value in conjunction with carbon in products therefrom.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of zirconium carbide ceramics powder, the method low cost, energy-conservation, the zirconium carbide ceramics powder oxygen level adopting the method to obtain is low and crystal grain is tiny.
To achieve these goals, the technical solution used in the present invention is: a kind of preparation method of zirconium carbide ceramics powder, it is characterized in that it comprises the steps:
1) the choosing of raw material: by the amount (mol ratio) of zirconium-n-propylate and sucrose than being 12:3.6 ~ 12:4.6 [i.e. 12:(3.6 ~ 4.6)], the volume ratio of zirconium-n-propylate, thinner n-propyl alcohol, sequestrant acetic acid is 8:32:2 ~ 8:64:3, chooses zirconium-n-propylate, sucrose, thinner n-propyl alcohol, sequestrant acetic acid; By proportioning=(7 ~ 8) g:50mL of sucrose and solvent acetic acid, choose solvent acetic acid;
2) preparation of dry gel powder:
Sucrose being dissolved in temperature is in the solvent acetic acid of 75 ~ 90 DEG C, and gained solution is cooled to room temperature, obtains carbon source solution (using as carbon source); The n-propyl alcohol getting thinner n-propyl alcohol cumulative volume 25 ~ 50% mixes with zirconium-n-propylate in the thermostat water bath being placed on 25 ~ 30 DEG C and stirs, and adds sequestrant acetic acid, stirs and makes it mix, obtain zirconium-n-propylate mixed solution; The n-propyl alcohol of remainder is mixed with carbon source solution, obtains carbon source mixing solutions; Then carbon source mixing solutions is added drop-wise in the zirconium-n-propylate mixed solution of high-speed stirring, at 25 ~ 30 DEG C, stirs 1 ~ 3 day, mix, generate good three-dimensional space network structure, after ageing in 1 ~ 4 day, obtain wine-colored gel; Gel is placed in 80 ~ 150 DEG C of loft drier inner drying 24 ~ 48h, after dry grinding 1h ~ 2h, obtains dry gel powder;
3) preparation of precursor:
Dry gel powder is heat-treated under the condition of argon shield, with the temperature rise rate of 3 ~ 5 DEG C/min, at 600 ~ 700 DEG C of temperature, be incubated 30 ~ 60min(fully decompose and get rid of organism), carry out dry grinding 0.5 ~ 1h after cooling, obtain zirconium carbide precursor;
4) thermal treatment of precursor:
10 ~ 15g zirconium carbide precursor is placed in (the internal diameter ∮ 40mm being covered with graphite paper, external diameter is ∮ 50mm) in independent graphite jig, cover graphite cover (this mould also can be applicable in the powder synthesis of discharge plasma SPS), graphite jig is placed on the ring-shaped jacket of hot pressing die (once can put 4 graphite jigs at the most, as Fig. 1), put into hot pressing furnace and pass to argon shield, the temperature of reaction (wherein best synthesis temperature scope is 1650 ~ 1750 DEG C) of 1550 ~ 1800 DEG C is heated to the speed of 5 DEG C ~ 10 DEG C/min, under temperature of reaction (synthesis temperature), soaking time is: 25 ~ 60 minutes (best soaking time is 30 ~ 50 minutes), obtain the zirconium carbide ceramics powder of size of microcrystal within the scope of 150 ~ 500nm.
Graphite jig is only placed on the ring-shaped jacket of hot pressing die, the preparation of Zirconium carbide powder can be carried out with the preparation of some materials (in the preparation process of other material, need ensure that the gas that nothing and zirconium carbide precursor and final product zirconium carbide react is released) simultaneously.Specifically see embodiment 1 and 4.
Described zirconium-n-propylate, sucrose, thinner n-propyl alcohol, sequestrant acetic acid, solvent acetic acid containing H
2it is anhydrous system that O amount is all less than 0.05wt%(system, and namely selected organic reagent is containing H
2o ﹤ 0.05wt%).
High-speed stirring described in step 1) refers to rotating speed 1100 ~ 1300r/min.
In step 4), carbothermic reduction reaction device is independently graphite jig, forms the structure being similar to single carbon tube furnace.
In step 4) obtain zirconium carbide ceramics powder oxygen level be 0.3wt% ~ 1.2wt%, between size of microcrystal 150 ~ 500nm.
The present invention all adopts anhydrous organic solvent as raw material, avoids the problem causing because of the existence of large quantity of moisture synthesizing and follow-up sintering temperature raises; And with the dilution of appropriate n-propyl alcohol, solve the problem of the rapid gel of thickness because of zirconium-n-propylate, extend the time that colloidal sol exists to a certain extent, add the homogeneity of collosol and gel.Specifically see comparison example.
The present invention adopts in hot pressing furnace and places independently graphite jig, carries out carbothermic reduction reaction under precursor being put into the condition of independently graphite jig.It is reduction reaction that zirconium carbide synthesizes the solid state reaction related to, independently graphite jig forms the structure being similar to single carbon tube furnace, for reaction provides stronger reducing atmosphere, facilitate the formation of zirconium carbide, significantly reduce the content of oxygen in final product, its content successfully can be controlled at about 0.3wt%, utilize its reducing atmosphere to restrained effectively growing up of crystal simultaneously, solve oxygen level along with temperature raise, holding time and reduce but crystal along with temperature raise, holding time and this contradiction of growing up.On the other hand, put because independently mould is only placed in the outer of hot pressing die, and the preparation of other powder and block in without hindrance hot pressing die, thus can carry out with the preparation of some other materials (needing in the preparation process of other material to ensure that the gas that nothing and presoma and final product zirconium carbide react is released) simultaneously, reach the effect of heat supply, in addition the synthesis temperature of pure phase zirconium carbide is high, needs a large amount of energy to be provided with the carrying out of carbothermic reduction-thermo-negative reaction.So present method greatly reduces loss, reach energy-conservation effect.And compared with the technology preparing zirconium carbide with discharge plasma, hot pressing furnace has more ubiquity and economy.
The invention has the beneficial effects as follows: be respectively zirconium source, carbon source with zirconium-n-propylate, sucrose, and using acetic acid as sequestrant, n-propyl alcohol is thinner, adopts sol-gel process to prepare the precursor of applicable Fast back-projection algorithm.In precursor heat treatment step, because independently graphite jig exists, the synthesis of zirconium carbide powder can be carried out with the preparation of some materials in hot pressing simultaneously, reaches the effect of heat supply, greatly reduces loss, reach energy-conservation effect; And the similar single small-sized carbon tube furnace of graphite jig, for system provides reducing atmosphere, efficiently solve the general higher problem of oxygen level in Zirconium carbide powder.Obtain the zirconium carbide ceramics powder that purity is high, crystal grain is tiny (median size is less than 500nm).Be single zirconium carbide thing phase by X-ray diffraction analysis, in product, oxygen level is 0.3wt% ~ 1.2wt%, and free carbon content is between 0.5wt% ~ 2wt%; Uniform crystal particles is tiny, and median size is less than 500nm.
This zirconium carbide ceramics powder is not only applicable to the protecting materials preparing enhanced carbon fiber resistance of oxidation, is more suitable for the material on forth generation Nuclear power plants coated fuel particles blocking layer.
Accompanying drawing explanation
Fig. 1 is the hot-press equipment mould device figure that the present invention prepares zirconium carbide ceramics powder.
Fig. 2 is the XRD spectra of zirconium carbide ceramics powder prepared by the present invention, and spectral line a, spectral line b, spectral line c, spectral line d are the spectral line of embodiment 1, embodiment 2, embodiment 3, zirconium carbide ceramics powder prepared by embodiment 4 respectively.
Fig. 3 is the SEM photo of the zirconium carbide ceramics powder that in the present invention prepared by embodiment 1.
Fig. 4 is the SEM photo of the zirconium carbide ceramics powder that in the present invention prepared by embodiment 2.
Fig. 5 is the SEM photo of the zirconium carbide ceramics powder that in the present invention prepared by embodiment 3.
Fig. 6 is the SEM photo of the zirconium carbide ceramics powder that in the present invention prepared by embodiment 4.
Fig. 7 is the SEM photo of zirconium carbide ceramics block prepared by comparison example simultaneous test.
Fig. 8 is zirconium carbide ceramics block SEM photo prepared by comparison example.
Embodiment
In order to understand the present invention better, illustrate content of the present invention further below in conjunction with embodiment, but content of the present invention is not only confined to the following examples.
Embodiment 1:
(1) 8g sucrose being dissolved in temperature is that in the 50mL solvent acetic acid of 85 DEG C, gained solution is cooled to room temperature, obtains carbon source solution (using as carbon source); After the thinner n-propyl alcohol of the zirconium-n-propylate 24mL of 8mL is diluted, be positioned in the thermostat water bath of 25 DEG C and stir 20 minutes, add the sequestrant acetic acid of 3mL in this mixed solution, and stir and make it mix in 15 minutes, obtain zirconium-n-propylate mixed solution; Measure carbon source solution by zirconium-n-propylate and the amount of sucrose than for 12:4.4, and obtain carbon source mixing solutions with the n-propyl alcohol dilution of 40mL; Then carbon source mixing solutions is added drop-wise in the zirconium-n-propylate mixed solution of high-speed stirring, at 25 DEG C, stirs 2 days, mix, after ageing in 1 day, obtain wine-colored gel, dry 48h in the loft drier of 150 DEG C, after dry grinding 1h, obtains dry gel powder subsequently.
(2) dry gel powder is heat-treated under argon shield condition in tube furnace, with the temperature rise rate of 5 DEG C/min, at the temperature of 700 DEG C, be incubated 30min, after cooling, after dry grinding 1h, obtain zirconium carbide precursor;
(3) get 12g zirconium carbide precursor and be placed in graphite jig (the internal diameter ∮ 40mm being covered with graphite paper, external diameter is ∮ 50mm), cover graphite cover, graphite jig is placed on the ring-shaped jacket of hot pressing die (once can put 4 graphite jigs at the most, as Fig. 1), prepare TiB in hot pressing die simultaneously
2-carbon composite is [by the powder (TiB mixed by a certain percentage
2powder, Graphite Powder 99) put into hot pressing graphite jig, be placed in hot-pressed sintering furnace, and keep 30MPa axle pressure to having sintered].Be filled with argon gas as protective atmosphere in preparation process, be heated to 1800 DEG C with the speed of 8 DEG C/min, and cool to room temperature with the furnace after being incubated 25 minutes at such a temperature, obtain loose black powder (i.e. zirconium carbide ceramics powder) and TiB
2-carbon composite.
Adopting XRD to detect its thing phase composite is single-phase zirconium carbide, and do not find zirconium white phase (see Fig. 2 spectral line a), sem analysis display powder particle particle diameter is all less than 500nm(and sees Fig. 3), median size is that 356.8nm(Zeta PALS laser fineness gage measures).The purity of the zirconium carbide in product is 97wt% ~ 98wt%, and wherein oxygen level is 0.62wt%(TC-600 oxygen-nitrogen analyzer), be respectively the CS-444 model carbon and sulfur analytical instrument of LECD company of 11.01wt% and the 1.31wt%(U.S. in conjunction with carbon and free carbon content).Gained TiB
2the relative density of-carbon composite is: 96.13%, and resistivity is: 33.52 μ Ω cm, bending strength is: 198.15MPa, and fracture toughness property is: 3.40MPam
1/2.
Embodiment 2:
(1) 7.5g sucrose being dissolved in temperature is that in the 50mL solvent acetic acid of 75 DEG C, gained solution is cooled to room temperature, obtains carbon source solution (using as carbon source); After the thinner n-propyl alcohol of the zirconium-n-propylate 16mL of 8mL is diluted, be positioned in the thermostat water bath of 30 DEG C and stir 20 minutes, add the sequestrant acetic acid of 2mL in this mixed solution, and stir and make it mix in 15 minutes, obtain zirconium-n-propylate mixed solution.Measure carbon source solution by zirconium-n-propylate and the amount of sucrose than for 12:4, and obtain carbon source mixing solutions with the n-propyl alcohol dilution of 16mL; Then carbon source mixing solutions is added drop-wise in the zirconium-n-propylate mixed solution of high-speed stirring, at 25 DEG C, stirs 2 days, mix, after ageing in 3 days, obtain wine-colored gel, dry 48h in the loft drier of 80 DEG C, after dry grinding 2h, obtains dry gel powder subsequently.
(2) dry gel powder is heat-treated under argon shield condition in tube furnace, with the temperature rise rate of 5 DEG C/min, at the temperature of 650 DEG C, be incubated 30min, after cooling, after dry grinding 0.5h, obtain zirconium carbide precursor;
(3) get 12g zirconium carbide precursor and be placed in graphite jig (the internal diameter ∮ 40mm being covered with graphite paper, external diameter is ∮ 50mm), cover graphite cover, graphite jig is placed on the ring-shaped jacket of hot pressing die, put into hot pressing furnace and pass to argon shield, 1650 DEG C are heated to the speed of 10 DEG C/min, and cool to room temperature with the furnace after being incubated 30 minutes at such a temperature, obtain loose black powder (i.e. zirconium carbide ceramics powder), adopting XRD to detect its thing phase composite is single-phase zirconium carbide, do not find zirconium white phase (see Fig. 2 spectral line b), sem analysis display powder particle particle diameter is all less than 500nm(and sees Fig. 4), median size is that 156.4nm(Zeta PALS laser fineness gage measures).The purity of the zirconium carbide in product is 97wt% ~ 98wt%, and wherein oxygen level is 1.01wt%(TC-600 oxygen-nitrogen analyzer), be respectively the CS-444 model carbon and sulfur analytical instrument of LECD company of 10.45wt% and the 0.84wt%(U.S. in conjunction with carbon and free carbon content).
Embodiment 3:
(1) 7g sucrose being dissolved in temperature is that in the 50mL solvent acetic acid of 80 DEG C, gained solution is cooled to room temperature, obtains carbon source solution (using as carbon source); After the thinner n-propyl alcohol of the zirconium-n-propylate 8mL of 8mL is diluted, be positioned in the thermostat water bath of 25 DEG C and stir 20 minutes, add the sequestrant acetic acid of 2mL in this mixed solution, and stir and make it mix in 15 minutes, obtain zirconium-n-propylate mixed solution.Measure carbon source solution by zirconium-n-propylate and the amount of sucrose than for 12:4.6, and obtain carbon source mixing solutions with the n-propyl alcohol dilution of 24mL; Then carbon source mixing solutions is added drop-wise in the zirconium-n-propylate mixed solution of high-speed stirring, at 30 DEG C, stirs 1 day, mix, after ageing in 2 days, obtain wine-colored gel, dry 48h in the loft drier of 80 DEG C, after dry grinding 1h, obtains dry gel powder subsequently.
(2) dry gel powder is heat-treated under argon shield condition in tube furnace, with the temperature rise rate of 5 DEG C/min, at the temperature of 600 DEG C, be incubated 60min, fully get rid of organism, after cooling, after dry grinding 1h, obtain zirconium carbide precursor;
(3) get 10g zirconium carbide precursor and be placed in the graphite jig (internal diameter ∮ 40mm, external diameter is ∮ 50mm) being covered with graphite paper, cover graphite cover, graphite jig is placed on the ring-shaped jacket of hot pressing die.Put into hot pressing furnace and pass to argon shield; 1550 DEG C are heated to the speed of 5 DEG C/min; and cool to room temperature with the furnace after being incubated 50 minutes at such a temperature; obtain loose black powder (i.e. zirconium carbide ceramics powder); adopting XRD to detect its thing phase composite is single-phase zirconium carbide; do not find zirconium white phase (see Fig. 2 spectral line c), sem analysis display powder particle particle diameter is all less than 500nm(and sees Fig. 5), median size is that 330.4nm(Zeta PALS laser fineness gage measures).The purity of the zirconium carbide in product is 95wt% ~ 96wt%, and wherein oxygen level is 1.17wt%(TC-600 oxygen-nitrogen analyzer), be respectively the CS-444 model carbon and sulfur analytical instrument of LECD company of 10.72wt% and the 2.00wt%(U.S. in conjunction with carbon and free carbon content).
Embodiment 4:
(1) 7g sucrose being dissolved in temperature is that in the 50mL solvent acetic acid of 90 DEG C, gained solution is cooled to room temperature, obtains carbon source solution (using as carbon source); After the thinner n-propyl alcohol of the zirconium-n-propylate 16mL of 8mL is diluted, be positioned in the thermostat water bath of 27 DEG C and stir 20 minutes, add the sequestrant acetic acid of 2.5mL in this mixed solution, and stir and make it mix in 15 minutes, obtain zirconium-n-propylate mixed solution.Measure carbon source solution by zirconium-n-propylate and the amount of sucrose than for 12:3.6, and obtain carbon source mixing solutions with the n-propyl alcohol dilution of 48mL; Then carbon source mixing solutions is added drop-wise in the zirconium-n-propylate mixed solution of high-speed stirring, at 27 DEG C, stirs 3 days, mix, after ageing in 4 days, obtain wine-colored gel, dry 24h in the loft drier of 110 DEG C, after dry grinding 2h, obtains dry gel powder subsequently.
(2) dry gel powder is heat-treated under argon shield condition in tube furnace, with the temperature rise rate of 3 DEG C/min, at the temperature of 650 DEG C, be incubated 45min, fully get rid of organism, after cooling, after dry grinding 1h, obtain zirconium carbide precursor;
(3) get 15g zirconium carbide precursor and be placed in the graphite jig (internal diameter ∮ 40mm, external diameter is ∮ 50mm) being covered with graphite paper, cover graphite cover, graphite jig is placed on the ring-shaped jacket of hot pressing die.Prepare TiB in hot pressing die simultaneously
2-carbon composite is [by the powder (TiB mixed
2powder, Graphite Powder 99) put into graphite jig, be placed in hot-pressed sintering furnace, and keep 30MPa axle pressure to having sintered].Be filled with argon gas as protective atmosphere in preparation process, be heated to 1750 DEG C with the speed of 5 DEG C/min, and cool to room temperature with the furnace after being incubated 60 minutes at such a temperature, obtain loose black powder (i.e. zirconium carbide ceramics powder) and TiB
2-carbon composite.
Adopting XRD to detect its thing phase composite is single-phase zirconium carbide, does not find zirconium white phase (see Fig. 2 spectral line d), and sem analysis display powder particle particle diameter is all less than 500nm(and sees Fig. 6), median size is that 426.2nm(Zeta PALS laser fineness gage measures).The purity of the zirconium carbide in product is 98wt% ~ 99wt%, and wherein oxygen level is 0.30wt%(TC-600 oxygen-nitrogen analyzer), be respectively the CS-444 model carbon and sulfur analytical instrument of LECD company of 10.02wt% and the 0.27wt%(U.S. in conjunction with carbon and free carbon content).TiB
2the relative density of-carbon composite is: 96.45%, and resistivity is: 34.42 μ Ω cm, bending strength is: 197.37MPa, and fracture toughness property is: 3.36MPam
1/2.
Comparison example (this embodiment is comparison example, namely has aqueous systems and anhydrous system to contrast):
Prepare zirconium carbide powder according to embodiment 2, difference is in the preparation of dry gel powder, and additionally in the carbon source of the H2O of dropping 2mL after dilution, sol system is become aqueous systems.Other step is in strict accordance with the processing condition preparation described in embodiment 2.Subsequently the 2g zirconium carbide powder of gained is put into block sintering graphite mould, be placed in discharge plasma (SPS) sintering oven, and keep 30MPa axle pressure to having sintered.Be filled with argon gas in preparation process as protective atmosphere, be heated to 1850 DEG C with the speed of 100 DEG C/min, and cool to room temperature with the furnace after being incubated 5 minutes at such a temperature, obtain zirconium carbide ceramics block.Fig. 7 is shown in by its profile scanning picture; Simultaneously, be convenient to compare, sintered by same sintering process by zirconium carbide powder prepared in embodiment 2, (namely 2g powder puts into block sintering graphite mould, be placed in discharge plasma (SPS) sintering oven, and keep 30MPa axle pressure to having sintered.Be filled with argon gas as protective atmosphere in preparation process, be heated to 1850 DEG C with the speed of 100 DEG C/min, and cool to room temperature with the furnace after being incubated 5 minutes at such a temperature) obtain zirconium carbide ceramics block.Fig. 8 is shown in by its profile scanning picture.From section picture analyzing, when sol gel precursor is anhydrous system, the powder sintered activity of gained is high, and the block prepared under same technique is more closely knit, and crystal grain is tiny.
The bound of each raw material of the present invention, interval value, and the bound of processing parameter (as temperature, time etc.), interval value can realize the present invention, do not enumerate embodiment at this.
Claims (5)
1. a preparation method for zirconium carbide ceramics powder, is characterized in that it comprises the steps:
1) the choosing of raw material: by the amount of zirconium-n-propylate and sucrose than being 12:3.6 ~ 12:4.6, the volume ratio of zirconium-n-propylate, thinner n-propyl alcohol, sequestrant acetic acid is 8:32:2 ~ 8:64:3, chooses zirconium-n-propylate, sucrose, thinner n-propyl alcohol, sequestrant acetic acid; By proportioning=(7 ~ 8) g:50mL of sucrose and solvent acetic acid, choose solvent acetic acid;
2) preparation of dry gel powder:
Sucrose being dissolved in temperature is in the solvent acetic acid of 75 ~ 90 DEG C, and gained solution is cooled to room temperature, obtains carbon source solution; The n-propyl alcohol getting thinner n-propyl alcohol cumulative volume 25 ~ 50% mixes with zirconium-n-propylate in the thermostat water bath being placed on 25 ~ 30 DEG C and stirs, and adds sequestrant acetic acid, stirs and makes it mix, obtain zirconium-n-propylate mixed solution; The n-propyl alcohol of remainder is mixed with carbon source solution, obtains carbon source mixing solutions; Then carbon source mixing solutions is added drop-wise in the zirconium-n-propylate mixed solution of high-speed stirring, at 25 ~ 30 DEG C, stirs 1 ~ 3 day, mix, after ageing in 1 ~ 4 day, obtain wine-colored gel; Gel is placed in 80 ~ 150 DEG C of loft drier inner drying 24 ~ 48h, after dry grinding 1h ~ 2h, obtains dry gel powder;
3) preparation of precursor:
Dry gel powder is heat-treated under the condition of argon shield, with the temperature rise rate of 3 ~ 5 DEG C/min, is incubated 30 ~ 60min, carries out dry grinding 0.5 ~ 1h, obtain zirconium carbide precursor after cooling at 600 ~ 700 DEG C of temperature;
4) thermal treatment of precursor:
Zirconium carbide precursor is placed in the independent graphite jig being covered with graphite paper; cover graphite cover; graphite jig is placed on the ring-shaped jacket of hot pressing die; put into hot pressing furnace and pass to argon shield; the temperature of reaction of 1550 ~ 1800 DEG C is heated to the speed of 5 DEG C ~ 10 DEG C/min; soaking time is at the reaction temperatures: 25 ~ 60 minutes, obtains zirconium carbide ceramics powder.
2. the preparation method of a kind of zirconium carbide ceramics powder according to claim 1, is characterized in that: in step 1), described zirconium-n-propylate, sucrose, thinner n-propyl alcohol, sequestrant acetic acid, solvent acetic acid containing H
2o amount is all less than 0.05wt%.
3. the preparation method of a kind of zirconium carbide ceramics powder according to claim 1, it is characterized in that: in step 4), independently graphite jig is placed on the ring-shaped jacket of hot pressing die.
4. the preparation method of a kind of zirconium carbide ceramics powder according to claim 1, is characterized in that: in step 4), and range of reaction temperature is 1650 ~ 1750 DEG C; Soaking time is 30 ~ 50 minutes.
5. the preparation method of a kind of zirconium carbide ceramics powder according to claim 1, is characterized in that: in step 4), and the size of microcrystal of the zirconium carbide ceramics powder of acquisition is within the scope of 150 ~ 500nm.
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| CN103806267B (en) * | 2013-12-21 | 2016-03-23 | 中国科学院上海硅酸盐研究所 | A kind of method preparing zirconium carbide ceramics interface phase at carbon fiber surface |
| CN105481366A (en) * | 2014-09-15 | 2016-04-13 | 中国科学院上海硅酸盐研究所 | Preparation method of carbide ceramics nanometer powder |
| CN108046805B (en) * | 2017-12-16 | 2021-02-12 | 西安理工大学 | Preparation method of high-porosity open-pore zirconium carbide porous ceramic |
| CN111548162B (en) * | 2020-04-17 | 2022-06-07 | 西安理工大学 | Method for preparing ZrC ceramic by compression molding of precursor |
| CN112409020B (en) * | 2020-10-30 | 2022-05-20 | 江苏材睿科技有限公司 | High-temperature-resistant and antioxidant coating on surface of graphite material and preparation method thereof |
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| CN101844766A (en) * | 2010-06-12 | 2010-09-29 | 武汉理工大学 | Method for rapidly preparing zirconium carbide ceramics powder |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101844766A (en) * | 2010-06-12 | 2010-09-29 | 武汉理工大学 | Method for rapidly preparing zirconium carbide ceramics powder |
Non-Patent Citations (2)
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| ZrC陶瓷的性能、制备及应用;宋瑞颖 等;《硬质合金》;20090630;第26卷(第2期);134-140 * |
| 解晶晶 等."ZrC粉体的制备方法研究".《复合材料:创新与可持续发展(上册)》.2010, * |
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