CN104649676A - Preparation method of zirconium diboride ceramic precursor - Google Patents
Preparation method of zirconium diboride ceramic precursor Download PDFInfo
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- CN104649676A CN104649676A CN201410711543.4A CN201410711543A CN104649676A CN 104649676 A CN104649676 A CN 104649676A CN 201410711543 A CN201410711543 A CN 201410711543A CN 104649676 A CN104649676 A CN 104649676A
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Abstract
The invention relates to the technical field of material chemistry, and in particular relates to a preparation method of a zirconium diboride ceramic precursor. The preparation method of the zirconium diboride ceramic precursor comprises the following steps: 1 preparing raw materials; 2 synthesizing a zirconium-containing polymer PZS; and 3 preparing a ZrB2 ceramic precursor. Zirconium oxychloride, acetylacetone and ortho-hydroxybenzyl alcohol are subjected to condensation polymerization in an alkaline condition to prepare the zirconium-containing polymer, and the polymer is mixed with boric acid in a solution to obtain the ZrB2 ceramic precursor. The ceramic precursor prepared by the method can form a homogeneous steeping liquor, has relatively high ceramic conversion rate, meets the requirements of a PIP technology, and has a wide application prospect in construction of a ZrB2 ceramic-modified C/C composite material.
Description
Technical field
The present invention relates to material chemistry technical field, be specifically related to a kind of preparation method of zirconium diboride ceramics presoma.
Background technology
In recent years, the carbon/carbon compound material of refractory metal carbon/boride ceramics modification is subject to extensive concern because having numerous excellent properties such as low density, Gao Biqiang, Gao Bimo, anti-yaw damper, anti-thermal shock, particularly its outstanding high temperature oxidation resistance, makes such matrix material on hypersonic aircraft, demonstrate tempting application prospect.At present, this carbon ceramic composite material is mainly through polymer infiltration and pyrolysis) technique builds, namely first the low density carbon fiber preform of porous is immersed in refractory metal carbon/boride ceramics precursor solution, presoma macromole is made to enter precast body matrix by molecular diffusion and osmosis, then under high temperature action, there is cracking, generate corresponding ceramic powder, thus form the ceramic modified C/C matrix material of MX.In this process, the selection of ceramic forerunner is most important with preparation.In general, selected ceramic forerunner must have certain solubleness, to form homogeneous phase steeping fluid, thus after ensureing cracking, ceramic composition is uniformly dispersed in matrices of composite material; In addition, ceramic forerunner also must possess higher ceramic conversion rate.Such as,
Acetic acid zirconium and resol are mixed to form ZrC ceramic forerunner, the C/C matrix material that a kind of ZrC that utilized PIP technique to prepare is ceramic modified; About ZrB
2the research rarely seen report so far of ceramic modified C/C matrix material.
At present, ZrB
2the preparation method of ceramic forerunner mainly contains sol-gel method, the diketonate of zirconium and boric acid and the blended reaction method of resol and boron-containing polymer and zirconium white blending method.ZrB prepared by aforesaid method
2ceramic forerunner all can not form homogeneous phase steeping fluid, cannot meet PIP technique and prepare ZrB
2the requirement of ceramic modified C/C matrix material, therefore develops a kind of new method to prepare ZrB
2ceramic forerunner seems particularly necessary and important.
Summary of the invention
The present invention is intended to the preparation method proposing a kind of zirconium diboride ceramics presoma.
Technical program of the present invention lies in:
A preparation method for zirconium diboride ceramics presoma, adopts following steps:
Step 1: raw material:
Eight water zirconium oxychlorides, diathesin, methyl ethyl diketone and boric acid;
Step 2: the synthesis containing zirconium polymer PZS:
By methyl ethyl diketone (2g, 0.02mol), diathesin, triethylamine (2.02g, 0.02mol) mix with methyl alcohol (25mL), then in normal temperature, drop in the there-necked flask that zirconium oxychloride (3.22 g, 0.01mol) methanol solution (50mL) is housed again;
After dropwising, stirring reaction 6h at normal temperatures; Reaction solution dissolved through rotary evaporation, tetrahydrofuran (THF) successively, filters, filtrate is concentrated, normal hexane precipitation, be deposited in room temperature in vacuo drying and other steps, obtain flaxen containing zirconium polymer powder;
Step 3:ZrB
2the preparation of ceramic forerunner:
First, acetone (95g) will be dissolved in containing zirconium polymer PZS (5g) and form solution I;
Boric acid (5g) is dissolved in ethanol (95g) and forms solution II;
Solution I is mixed with solution II, after solvent being volatilized completely at 40 ~ 50 DEG C of temperature, can ZrB be obtained
2ceramic forerunner.
Preferably, by prepared ZrB
2ceramic forerunner puts into pyrolyzer, is cured successively under an argon atmosphere and cracking, obtains ZrB
2ceramic powder.
More preferably, described by ZrB
2ceramic forerunner obtains ZrB
2in the solidification of ceramic powder and cracking, temperature variation is: room temperature-150 DEG C/2h-170 DEG C/2h-200 DEG C/2h; Cracking temperature 200 DEG C, temperature rise rate is 2 DEG C/min.
Technique effect of the present invention is:
There is polycondensation and can generate a kind of containing zirconium polymer in zirconium oxychloride of the present invention and methyl ethyl diketone and diathesin, this polymkeric substance and boric acid are blended in the solution, can obtain ZrB in the basic conditions
2ceramic forerunner.The ceramic forerunner adopting the method to prepare can form the steeping fluid of homogeneous phase, has higher ceramic conversion rate, meets the requirement of PIP technique, at structure ZrB
2ceramic modified C/C matrix material aspect has broad application prospects.
Embodiment
A preparation method for zirconium diboride ceramics presoma, adopts following steps:
Step 1: raw material:
Eight water zirconium oxychlorides, diathesin, methyl ethyl diketone and boric acid;
Step 2: the synthesis containing zirconium polymer PZS:
By methyl ethyl diketone (2g, 0.02mol), diathesin, triethylamine (2.02g, 0.02mol) mix with methyl alcohol (25mL), then in normal temperature, drop in the there-necked flask that zirconium oxychloride (3.22 g, 0.01mol) methanol solution (50mL) is housed again;
After dropwising, stirring reaction 6h at normal temperatures; Reaction solution dissolved through rotary evaporation, tetrahydrofuran (THF) successively, filters, filtrate is concentrated, normal hexane precipitation, be deposited in room temperature in vacuo drying and other steps, obtain flaxen containing zirconium polymer powder;
Step 3:ZrB
2the preparation of ceramic forerunner:
First, acetone (95g) will be dissolved in containing zirconium polymer PZS (5g) and form solution I;
Boric acid (5g) is dissolved in ethanol (95g) and forms solution II;
Solution I is mixed with solution II, after solvent being volatilized completely at 40 ~ 50 DEG C of temperature, can ZrB be obtained
2ceramic forerunner.
Prepared ZrB
2ceramic forerunner puts into pyrolyzer, is cured successively under an argon atmosphere and cracking, obtains ZrB
2ceramic powder.Wherein, room temperature-150 DEG C/2h-170 DEG C/2h-200 DEG C/2h; Cracking temperature 200 DEG C, temperature rise rate is 2 DEG C/min.
Claims (3)
1. a preparation method for zirconium diboride ceramics presoma, is characterized in that: adopt following steps:
Step 1: raw material:
Eight water zirconium oxychlorides, diathesin, methyl ethyl diketone and boric acid;
Step 2: the synthesis containing zirconium polymer PZS:
By methyl ethyl diketone (2g, 0.02mol), diathesin, triethylamine (2.02g, 0.02mol) mix with methyl alcohol (25mL), then in normal temperature, drop in the there-necked flask that zirconium oxychloride (3.22 g, 0.01mol) methanol solution (50mL) is housed again;
After dropwising, stirring reaction 6h at normal temperatures; Reaction solution dissolved through rotary evaporation, tetrahydrofuran (THF) successively, filters, filtrate is concentrated, normal hexane precipitation, be deposited in room temperature in vacuo drying and other steps, obtain flaxen containing zirconium polymer powder;
Step 3:ZrB
2the preparation of ceramic forerunner:
First, acetone (95g) will be dissolved in containing zirconium polymer PZS (5g) and form solution I;
Boric acid (5g) is dissolved in ethanol (95g) and forms solution II;
Solution I is mixed with solution II, after solvent being volatilized completely at 40 ~ 50 DEG C of temperature, can ZrB be obtained
2ceramic forerunner.
2. as the preparation method of a claim 1 zirconium diboride ceramics presoma, it is characterized in that: by prepared ZrB
2ceramic forerunner puts into pyrolyzer, is cured successively under an argon atmosphere and cracking, obtains ZrB
2ceramic powder.
3. as the preparation method of a claim 1 zirconium diboride ceramics presoma, it is characterized in that: described by ZrB
2ceramic forerunner obtains ZrB
2in the solidification of ceramic powder and cracking, temperature variation is: room temperature-150 DEG C/2h-170 DEG C/2h-200 DEG C/2h; Cracking temperature 200 DEG C, temperature rise rate is 2 DEG C/min.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410711543.4A CN104649676A (en) | 2014-12-01 | 2014-12-01 | Preparation method of zirconium diboride ceramic precursor |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107867826A (en) * | 2017-11-23 | 2018-04-03 | 苏州科茂电子材料科技有限公司 | A kind of preparation method of refractory ceramics dielectric material |
| CN109852950A (en) * | 2019-02-28 | 2019-06-07 | 常州西夏墅东方工具有限公司 | A kind of preparation method of high mating type corrosion resistant metal ceramic coating material |
| CN109988505A (en) * | 2019-02-25 | 2019-07-09 | 常州金艺广告传媒有限公司 | A kind of preparation method of high temperature resistant type infrared low-emissivity coating material |
-
2014
- 2014-12-01 CN CN201410711543.4A patent/CN104649676A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107867826A (en) * | 2017-11-23 | 2018-04-03 | 苏州科茂电子材料科技有限公司 | A kind of preparation method of refractory ceramics dielectric material |
| CN109988505A (en) * | 2019-02-25 | 2019-07-09 | 常州金艺广告传媒有限公司 | A kind of preparation method of high temperature resistant type infrared low-emissivity coating material |
| CN109852950A (en) * | 2019-02-28 | 2019-06-07 | 常州西夏墅东方工具有限公司 | A kind of preparation method of high mating type corrosion resistant metal ceramic coating material |
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