CN106977221B - A kind of SiCw-ZrB2- ZrC ceramic composite powder and preparation method thereof - Google Patents

A kind of SiCw-ZrB2- ZrC ceramic composite powder and preparation method thereof Download PDF

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CN106977221B
CN106977221B CN201710157781.9A CN201710157781A CN106977221B CN 106977221 B CN106977221 B CN 106977221B CN 201710157781 A CN201710157781 A CN 201710157781A CN 106977221 B CN106977221 B CN 106977221B
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刘长青
李旭
张露月
伍媛婷
王秀峰
刘虎林
张新孟
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Shaanxi University of Science and Technology
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Abstract

A kind of SiCw‑ZrB2- ZrC ceramic composite powder, by SiC whisker and ZrB2- ZrC ceramic matrix composition, SiC whisker are dispersed in ZrB2Around-ZrC ceramic matrix or homoepitaxial is in ZrB2- ZrC ceramic matrix surface, the present invention also provides preparation SiCw‑ZrB2The method of-ZrC ceramic composite powder, first the ceramic forerunner polymer of synthesis boracic, silicon, zirconium；Then the dry, ball milling by precursor polymer, obtains presoma powder；Finally presoma powder is fitted into graphite crucible, carries out Pintsch process, SiC whisker ZrB of the present invention under protection of argon gas2- ZrC ceramic matrix synchronous growth in situ in presoma cracking process obtains, eliminate the pre-synthesis and mixed process of whisker, the preparation of the synthesis of whisker, introducing and material powder is combined into one, preparation process is simple, production cost is low, and obtained composite granule pattern is uniform, whisker is evenly dispersed, of uniform size, good interface compatibility.

Description

A kind of SiCw-ZrB2- ZrC ceramic composite powder and preparation method thereof
Technical field
The invention belongs to technical field of ceramic material, in particular to a kind of SiCw-ZrB2- ZrC ceramic composite powder and its system Preparation Method.
Background technique
ZrB2The superhigh temperature ceramics such as-ZrC have high temperature resistant, anticorrosive and conservation rate with higher under high temperature environment Etc. excellent characteristics, increasingly important role is played in aerospace and Defence business.Intrinsic for improvement ceramic material Brittleness problems, the ceramic composite for designing and preparing the enhancing of second phase such as particle, whisker, fiber is superhigh temperature ceramics development Inexorable trend.Wherein, SiC whisker (SiCw) be widely used in recent years as effective enhancing, toughening material.Mesh Before, Whisker-reinforced ceramic based composites are substantially all the side for being limited to pass through high temperature sintering using additional whisker mixed raw material powder Prepared by method, this method is difficult to overcome the problems, such as there are still following: (1) whisker and ceramic material powder are difficult to be uniformly mixed, and lead Material property is caused to show inhomogeneities；(2) treatment process of material powder can generate harm to human health, for example, whisker Sucking can cause the health problems such as cancer；(3) complex technical process, production cost are high.Therefore, the original of whisker is realized Position growth solves the problems, such as that it is introduced and dispersing uniformity, inexpensive, the quick preparation process for developing high-quality feedstocks powder are The emphasis of ceramic field research.
Summary of the invention
In order to overcome the disadvantages of the above prior art, the purpose of the present invention is to provide a kind of SiCw-ZrB2- ZrC ceramics Composite granule and preparation method thereof utilizes the synchronous growth in situ SiC whisker of presoma transformation technology and ZrB2- ZrC ceramics, solve The introducing and dispersing uniformity problem of SiC whisker in the preparation process of Whisker-reinforced ceramic based composites, by the conjunction of whisker At, introduce and the preparation of material powder is combined into one, simplify production technology, improve preparation speed, reduce and be prepared into This.
To achieve the goals above, the technical solution adopted by the present invention is that:
A kind of SiCw-ZrB2- ZrC ceramic composite powder, by SiC whisker and ZrB2- ZrC ceramic matrix composition, SiC whisker It is dispersed in ZrB2Around-ZrC ceramic matrix or homoepitaxial is in ZrB2- ZrC ceramic matrix surface.
The SiC whisker and ZrB2The percent by volume of-ZrC ceramic matrix is between 1:15 to 1:5.
The present invention also provides prepare the SiCw-ZrB2The method of-ZrC ceramic composite powder, includes the following steps:
Step 1, the ceramic forerunner polymer of boracic, silicon, zirconium is synthesized；
Step 2, the dry, ball milling by the precursor polymer, obtains presoma powder；
Step 3, the presoma powder is fitted into graphite crucible, carries out Pintsch process under protection of argon gas.
In the precursor polymer that the step 1 synthesizes: the mass fraction of boron is greater than 10%, and the mass fraction of silicon is greater than 15%, the mass fraction of zirconium is greater than 10%.
The synthetic method of the step 1 ceramic forerunner polymer can refer to patent 201310388263.X, basic step It is as follows:
1) phenol, formaldehyde and the hydroxide of metering ratio are added in the three-necked flask equipped with blender, condensation reflux unit Sodium solution, warming while stirring react 0.5-1.5h to 60-75 DEG C；
2) mass fraction is pressed are as follows: 5-30 parts of ethyl alcohol, 5-15 parts of acetylacetone,2,4-pentanedione, 1-15 parts of zirconium oxychloride, 1-10 parts of hydrogen peroxide Prepare zirconyl chloride solution；
3) 1-15 parts of ethyl orthosilicate is added drop-wise in the configured zirconyl chloride solution of step 2, is stirred evenly, prepared Zirconium oxychloride teos solution；
4) temperature of oil bath is adjusted to 80-95 DEG C, and the side Bian Shengwen is stirred, while the positive silicic acid of prepared zirconium oxychloride is added dropwise Ethyl ester solution, the pH value for controlling solution is 7-9, when temperature reaches 80-95 DEG C, isothermal reaction 0.5-1.5h；
5) 1-10 parts of boric acid are dissolved in 6-60ml boiling ethyl alcohol, prepare boric acid solution；
6) temperature of oil bath is adjusted to 100-110 DEG C, and the side Bian Shengwen is stirred, while prepared boric acid solution is added dropwise, and is controlled The pH value of solution processed is 7-9；
7) when temperature reaches 100-110 DEG C, after keeping the temperature 0.5-2h, discharging；
8) product that upper step obtains is put into vacuum oven 40-80 DEG C of heat preservation 3-5h to get to before boron zirconium silicon ceramics Drive body polymer.
The step 2 is dry, ball milling parameter request: 60-90 DEG C at a temperature of, it is 5-8 hours dry；Zirconium oxide is Ball-milling medium, rotational speed of ball-mill 150-250r/min, dry ball milling 4-8h.
The step 3 Pintsch process mode is as follows: composite granule is wrapped up with graphite paper, is put by argon atmosphere protection It is placed in graphite crucible, cracking temperature is 1600-1900 DEG C, soaking time 60-120min, then furnace cooling.
Compared with prior art, a kind of SiC proposed by the present inventionw-ZrB2The master of the preparation method of-ZrC ceramic composite powder Advantage is wanted to be: SiC whisker ZrB2- ZrC ceramic matrix synchronous growth in situ in presoma cracking process obtains, and eliminates crystalline substance The pre-synthesis and mixed process of palpus, the preparation of the synthesis of whisker, introducing and material powder is combined into one, preparation process letter List, production cost are low, and obtained composite granule pattern is uniform, whisker is evenly dispersed, of uniform size, interface compatibility is good It is good.
Detailed description of the invention
Fig. 1 is the SiC prepared in specific embodiment 1w-ZrB2The microscopic appearance figure of-ZrC ceramic composite powder；Wherein, (a) The SEM of composite granule schemes；(b)ZrB2The SEM of-ZrC ceramics schemes；(c) the SEM figure of SiC whisker；(d) the EDS figure of SiC whisker.
Fig. 2 is the SiC prepared in specific embodiment 2w-ZrB2The microscopic appearance figure of-ZrC ceramic composite powder；Wherein, (a) The SEM of composite granule schemes；(b)ZrB2The SEM of-ZrC ceramics schemes；(c) the SEM figure of SiC whisker；(d) the EDS figure of SiC whisker.
Specific embodiment
The embodiment that the present invention will be described in detail with reference to the accompanying drawings and examples.Technical solution of the present invention be not limited to Lower listed specific embodiment, further includes any combination between each specific embodiment.
Embodiment 1
A kind of SiCw-ZrB2The preparation method of-ZrC ceramic composite powder is realized according to the following steps:
One, the ceramic forerunner polymer of boracic, silicon, zirconium, boron source mass fraction about 15%, silicon source mass fraction are synthesized About 20%, zirconium source mass fraction is not less than 20%.The specific method is as follows:
(1) phenol, formaldehyde and the hydroxide of metering ratio are added in the three-necked flask equipped with blender, condensation reflux unit Sodium solution, warming while stirring react 1h to 70 DEG C；
(2) mass fraction is pressed are as follows: 5 parts of 20 parts of ethyl alcohol, 5 parts of acetylacetone,2,4-pentanedione, 8 parts of zirconium oxychloride, hydrogen peroxide preparation oxychlorination Zirconium solution；
(3) 8 parts of ethyl orthosilicates are added drop-wise in the configured zirconyl chloride solution of step 2, are stirred evenly, prepare oxygen chlorine Change zirconium teos solution；
(4) temperature of oil bath is adjusted to 90 DEG C, and the side Bian Shengwen is stirred, while the positive silicic acid second of prepared zirconium oxychloride is added dropwise Ester solution, the pH value for controlling solution is 8, when temperature reaches 90 DEG C, isothermal reaction 1.5h；
(5) 5 parts of boric acid are dissolved in 30ml boiling ethyl alcohol, prepare boric acid solution；
(6) temperature of oil bath is adjusted to 107 DEG C, and the side Bian Shengwen is stirred, while prepared boric acid solution is added dropwise, and is controlled molten The pH value of liquid is 8；
(7) when temperature reaches 107 DEG C, after keeping the temperature 1h, discharging；
(8) product that upper step obtains 60 DEG C of heat preservations 4 in vacuum oven are put into gather to get to boron zirconium silicon ceramic forerunner Close object.
Two, by precursor polymer, dry 6 hours, ball milling obtain presoma powder at 80 DEG C；
Three, presoma powder is fitted into graphite crucible, carries out 1800 DEG C of Pintsch process, heating rate under protection of argon gas For 10 DEG C/min, 2 hours are kept the temperature.
The microscopic appearance of the prepared composite granule come out of the present embodiment is as shown in Figure 1.Fig. 1 (a) is prepared comes out SiCw-ZrB2The shape appearance figure of-ZrC ceramic composite powder；Fig. 1 (b) is ZrB2The microscopic appearance figure of-ZrC ceramic matrix；Fig. 1 (c) For the microscopic appearance figure of SiC whisker；Fig. 1 (d) is the energy spectrum diagram of SiC whisker.As seen from the figure, ZrB2Uniformly divide with ZrC ceramic phase Portion, prepared SiC whisker purity is higher, size uniformity, while SiC whisker is evenly dispersed in ZrB2- ZrC ceramic matrix Around.Thus, using the technique can growth in situ go out SiC whisker, and be evenly dispersed in matrix, to solve SiC The problem that the synthesis and introducing of whisker and whisker dispersing uniformity are difficult to control.
Embodiment 2
A kind of SiCw-ZrB2The preparation method of-ZrC ceramic composite powder is realized according to the following steps:
One, the ceramic forerunner polymer of boracic, silicon, zirconium, boron source mass fraction about 25%, silicon source mass fraction are synthesized About 30%, zirconium source mass fraction is not less than 20%.The specific method is as follows:
(1) phenol, formaldehyde and the hydroxide of metering ratio are added in the three-necked flask equipped with blender, condensation reflux unit Sodium solution, warming while stirring react 1h to 70 DEG C；
(2) mass fraction is pressed are as follows: 5 parts of 18 parts of ethyl alcohol, 5 parts of acetylacetone,2,4-pentanedione, 6 parts of zirconium oxychloride, hydrogen peroxide preparation oxychlorination Zirconium solution；
(3) 10 parts of ethyl orthosilicates are added drop-wise in the configured zirconyl chloride solution of step 2, are stirred evenly, prepare oxygen Zirconium chloride teos solution；
(4) temperature of oil bath is adjusted to 90 DEG C, and the side Bian Shengwen is stirred, while the positive silicic acid second of prepared zirconium oxychloride is added dropwise Ester solution, the pH value for controlling solution is 8, when temperature reaches 90 DEG C, isothermal reaction 1.5h；
(5) 8 parts of boric acid are dissolved in 40ml boiling ethyl alcohol, prepare boric acid solution；
(6) temperature of oil bath is adjusted to 107 DEG C, and the side Bian Shengwen is stirred, while prepared boric acid solution is added dropwise, and is controlled molten The pH value of liquid is 8；
(7) when temperature reaches 107 DEG C, after keeping the temperature 1h, discharging；
(8) product that upper step obtains 60 DEG C of heat preservations 4 in vacuum oven are put into gather to get to boron zirconium silicon ceramic forerunner Close object.
Two, by precursor polymer, dry 8 hours, ball milling obtain presoma powder at 70 DEG C；
Three, presoma powder is fitted into graphite crucible, carries out 1900 DEG C of Pintsch process, heating rate under protection of argon gas For 10 DEG C/min, 2 hours are kept the temperature.
The microscopic appearance of the prepared composite granule come out of the present embodiment is as shown in Figure 2.Fig. 2 (a) is prepared comes out SiCw-ZrB2The shape appearance figure of-ZrC ceramic composite powder；Fig. 2 (b) is ZrB2The microscopic appearance figure of-ZrC ceramic matrix；Fig. 2 (c) For the microscopic appearance figure of SiC whisker；Fig. 2 (d) is the energy spectrum diagram of SiC whisker.As seen from the figure, ZrB2Uniformly divide with ZrC ceramic phase Cloth, prepared SiC whisker purity is higher, size uniformity, at the same SiC whisker even compact be grown in bar matrix surface, Form a kind of thin and continuous network-like pattern.When treatment temperature is 1900 DEG C, SiO2It reacts with bar matrix carbon, greatly The gaseous state SiO and CO of amount are quickly generated, and a large amount of SiC whisker nucleating point is just generated around carbon base body before abundant diffusion. Simultaneously at higher temperature, the growth rate of ceramic phase is accelerated, thus the diameter of whisker becomes smaller and homoepitaxial is in bar matrix Surface.
It can be seen that the present invention can be realized the SiC whisker and ZrB of different-shape2The growth in situ of-ZrC ceramics, thus The introducing of SiC whisker and dispersing uniformity in the preparation process of Whisker-reinforced ceramic based composites are solved the problems, such as, by whisker Synthesis, introducing and the preparation of material powder are combined into one, and realize SiCw-ZrB2- ZrC ceramic composite powder it is simple, inexpensive Preparation.

Claims (4)

1. a kind of SiCw-ZrB2The preparation method of-ZrC ceramic composite powder, the SiCw-ZrB2- ZrC ceramic composite powder by SiC whisker and ZrB2- ZrC ceramic matrix composition, SiC whisker are dispersed in ZrB2Around-ZrC ceramic matrix or homoepitaxial In ZrB2- ZrC ceramic matrix surface, which is characterized in that preparation method includes the following steps:
Step 1, the ceramic forerunner polymer of boracic, silicon, zirconium is synthesized, in which: the mass fraction of boron is greater than 10%, the quality of silicon Score is greater than 15%, and the mass fraction of zirconium is greater than 10%, and synthetic method is as follows:
1) phenol, formaldehyde and sodium hydroxide that metering ratio is added in the three-necked flask equipped with blender, condensation reflux unit are molten Liquid, warming while stirring react 0.5-1.5h to 60-75 DEG C；
2) mass fraction is pressed are as follows: 5-30 parts of ethyl alcohol, 5-15 parts of acetylacetone,2,4-pentanedione, 1-15 parts of zirconium oxychloride, 1-10 parts of hydrogen peroxide preparations Zirconyl chloride solution；
3) 1-15 parts of ethyl orthosilicate is added drop-wise in the configured zirconyl chloride solution of step 2, is stirred evenly, prepare oxygen chlorine Change zirconium teos solution；
4) temperature of oil bath is adjusted to 80-95 DEG C, and the side Bian Shengwen is stirred, while prepared zirconium oxychloride ethyl orthosilicate is added dropwise Solution, the pH value for controlling solution is 7-9, when temperature reaches 80-95 DEG C, isothermal reaction 0.5-1.5h；
5) 1-10 parts of boric acid are dissolved in 6-60ml boiling ethyl alcohol, prepare boric acid solution；
6) temperature of oil bath is adjusted to 100-110 DEG C, and the side Bian Shengwen is stirred, while prepared boric acid solution is added dropwise, and is controlled molten The pH value of liquid is 7-9；
7) when temperature reaches 100-110 DEG C, after keeping the temperature 0.5-2h, discharging；
8) product that upper step obtains is put into vacuum oven 40-80 DEG C of heat preservation 3-5h to get to boron zirconium silicon ceramic forerunner Polymer；
Step 2, the dry, ball milling by the precursor polymer, obtains presoma powder；
Step 3, the presoma powder is fitted into graphite crucible, carries out Pintsch process under protection of argon gas.
2. SiC according to claim 1w-ZrB2The preparation method of-ZrC ceramic composite powder, which is characterized in that the step 2 dry, ball milling parameter requests: 60-90 DEG C at a temperature of, it is 5-8 hours dry；Zirconium oxide is ball-milling medium, rotational speed of ball-mill For 150-250r/min, dry ball milling 4-8h.
3. SiC according to claim 1w-ZrB2The preparation method of-ZrC ceramic composite powder, which is characterized in that the step 3 Pintsch process modes are as follows: composite granule is wrapped up with graphite paper, is placed in graphite crucible, splits by argon atmosphere protection Solving temperature is 1600-1900 DEG C, soaking time 60-120min, then furnace cooling.
4. SiC according to claim 1w-ZrB2The preparation method of-ZrC ceramic composite powder, which is characterized in that the SiC Whisker and ZrB2The percent by volume of-ZrC ceramic matrix is between 1:15 to 1:5.
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