CN101205065A - Method for preparing boron-carbon-zirconium material by liquid phase process - Google Patents
Method for preparing boron-carbon-zirconium material by liquid phase process Download PDFInfo
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- CN101205065A CN101205065A CNA200710171688XA CN200710171688A CN101205065A CN 101205065 A CN101205065 A CN 101205065A CN A200710171688X A CNA200710171688X A CN A200710171688XA CN 200710171688 A CN200710171688 A CN 200710171688A CN 101205065 A CN101205065 A CN 101205065A
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Abstract
The invention relates to a method for preparing boron carbon zirconium materials by liquid phase method, which belongs to the field of structural ceramics. By using carbothermal reduction as the basic principle and adopting zirconium oxychloride, boric acid and phenolic resin as the main materials, the method comprises the steps as follows: the phenolic resin is mixed with zirconia sol which is formed by titration of ammonia; then gel is formed by the titration of the ammonia; finally ball milling is carried out; after drying, screening and heat treatment, the ultrafine boron carbon zirconium materials can be obtained. The boron carbon zirconium materials which are prepared by the invention, with product granularity smaller than 200nm and excellent molding and sintering performance, can be applied to fields such as electron materials and refractory materials.
Description
Technical field
The present invention relates to a kind of method of preparing boron-carbon-zirconium material by liquid phase process, belong to the structural ceramics field.
Background technology
ZrB
2All has high-melting-point with ZrC, high-modulus, high rigidity, high thermal conductivity and specific conductivity, no phase transformation and good thermal shock resistance, especially ZrB
2Have overall characteristics such as the chemical bond of extra-heavy, low saturated vapor pressure and the low elevated temperature heat coefficient of expansion, therefore zirconium boride 99.5004323A8ure-zirconium carbide and complex phase ceramic thereof become the potential candidate material that thermal structure is used, and are expected to be applied in fields such as matrix material, refractory materials, electrode materialss.
At present, industrial preparation ZrB
2Adopt solid phase method and vapor phase process with the ZrC powder, because its raw material adopts micron-sized powder, the diameter of particle of preparation is bigger more, and sintering activity is poor.And the super-refinement of powder can improve motivating force in the sintering process, improves microtexture, improve mechanical property, so the preparation of ultrathin composite powder is subjected to paying attention to widely.
Liquid phase method particularly sol-gel method forms unbodied metastable phase in preparation process, reaction contact area is big, is the common method that low temperature prepares superfine powder, is commonly used to prepare oxide powder, film and fiber and other glass and equates.But it is at present less to the liquid phase method preparation research of carbide, boride.(Preiss H et al.J Mater Sci., 1998,33 (19): 4697-4706) alkoxide sol-gel method of employing titanium and zirconium is prepared fiber and the film of TiC and ZrC to Preiss etc.(Sacks.et al.J.Mat.Sci., 2004,39 (9): 6057-6066) utilize the source of the alkoxide of zirconium and hafnium as Zr, polyalcohols is prepared the ZrC powder as the source of C to Sacks etc., and particle diameter is at 50～130nm.The liquid phase method research of boride powder seldom only has (Chen LY, Gu YL, et al.J alloy compd, 2004,368 (1-2): 353-356, Scripta Mater., 2004,50 (7): 959-961) utilize hydrothermal method, with ZrCl such as Chen and Gu at present
4, HfCl
4And NaBH
4Be reactant, prepare ZrB at 500～700 ℃
2And HfB
2Nano-powder, but output is little, only as laboratory study.
Zirconium boride 99.5004323A8ure, zirconium carbide ceramics have very strong covalent linkage characteristic, and industrialization synthetic powder sintering specific activity is relatively poor, normal pressure-sintered difficulty; Simple powder direct mixing method is adopted in the preparation of complex phase ceramic at present, and the phase homogeneity is poor; Though alkoxide sol-gel method is successfully prepared the ZrC powder, itself exists shortcoming.Alkoxide is relatively more expensive, and a small amount of toxicity is arranged, and there is certain cracking carbon amount in this under high temperature inert atmosphere, so C/Zr, and C/B/Zr is difficult for determining.
Summary of the invention
The boron carbon zirconium powder body particle diameter that the method that the object of the present invention is to provide a kind of liquid phase method to prepare ultra-fine boron carbon zirconium powder body solves industrial preparation is big, sintering difficulty, complex phase ceramic shortcoming mutually pockety.
The present invention is achieved in that
At first zirconium oxychloride is dissolved in the mixing solutions that the second alcohol and water is made into, the concentration of zirconium oxychloride is about 0.2～1mol/L, and the volume ratio of second alcohol and water is 3: 1～5: 1.By zirconium boride 99.5004323A8ure: zirconium carbide=(100～0): (0～100) adds an amount of boric acid or does not join in the mixing solutions, add polyoxyethylene glycol as dispersion agent, concentration is 0.5～2wt%, weak ammonia titration with 20～50vol% concentration, regulating pH is 3～5 o'clock, the phenol resin solution that adds 10～80vol% then, form binary colloidal sol, continue with 20～50vol% concentration ammonia water titration, until forming gel, then with gel drying, oven dry then, grind, sieve precursor powder, obtained boron carbon zirconium powder body in 0.5～3 hour in vacuum or inert atmosphere, heat-treating under 1300～1600 ℃ at last
The preparation method of boron carbon zirconium powder body provided by the invention, its advantage is conspicuous:
(1) adopt industrial comparative maturity, the inorganic salt zirconium oxychloride that cost is lower, boric acid and resol are as the synthetic raw material, and it is relatively more expensive to have overcome traditional alkoxide sol-gel method, and C/Zr is difficult for determining, and the shortcoming of toxic side effect.
(2) preparation temperature is lower, and speed of response is fast, and oxygen level is low, and product granularity is little, and size distribution is even.(seeing accompanying drawing 2 for details)
(3) processability of powder is good, the sintering character excellence.(seeing embodiment for details)
Description of drawings
Fig. 1: liquid phase method prepares the schema of boron carbon zirconium and composite granule thereof
Fig. 2: 1500 ℃ of calcining 1h obtain ZrB
2The XRD figure of powder
Fig. 3: 1500 ℃ of calcining 1h obtain the XRD figure (wherein the ZrC theoretical content is 50wt% in the composite granule) of composite granule.
Fig. 4: 1400 ℃ of calcining 1h obtain the XRD figure of ZrC powder
Fig. 5: the ZrB of 1500 ℃ of calcining 1h preparation
2The SEM photo of powder (as can be seen from the figure, powder has certain reunion, and median size is below 200nm).
Embodiment
Embodiment 1:
It is 4: 1 mixing solutions that the 32.25g zirconium oxychloride is dissolved in 500ml ethanol and water volume ratio, stirs and makes its dissolving.Add 12.36g boric acid and mix, and add the 3.60g polyoxyethylene glycol, drip the weak ammonia of 25vol% then, regulate about pH to 3, form zirconia sol as dispersion agent.Add 20g resol (remaining carbon is about 50%, and concentration is 50vol%) and be made into mixed sols.Continue dropping ammonia, make its cohesion.Gel is transferred to ball grinder, is ball milling bulbec mill 24h with the zirconium white, and drying is 12 hours under 80 ℃, obtains the powder presoma.Calcining obtained ZrB in 1 hour under 1500 ℃
2Powder.Obviously find out ZrB in the XRD figure
2There are not other intermediate phase in phase.It is comparatively even that (see figure 2) finds out that from the SEM photo powder disperses, and median size is about 50～200nm.(see figure 5)
Embodiment 2:
It is 4: 1 mixing solutions that the 41.16g zirconium oxychloride is dissolved in 500ml ethanol and water volume ratio, stirs and makes its dissolving.Add 12.36g boric acid and mix, and add the 4.80g polyoxyethylene glycol, drip the weak ammonia of 25vol% then, regulate about pH to 3, form zirconia sol as dispersion agent.Add 23.28g resol (remaining carbon is about 50%, and concentration is 50vol%) and be made into mixed sols.Continue dropping ammonia, make its cohesion.Gel is transferred to ball grinder, is ball milling bulbec mill 24h with the zirconium white, and drying is 12 hours under 80 ℃, obtains the powder presoma.Calcining obtained ZrB in 1 hour under 1500 ℃
2-ZrC composite granule, the ZrC theoretical content is 20wt% in the composite granule, obviously finds out ZrB in the XRD figure
2Exist mutually with ZrC, do not have other intermediate phase.(see figure 3)
Embodiment 3:
It is 4: 1 mixing solutions that the 49.99g zirconium oxychloride is dissolved in 500ml ethanol and water volume ratio, stirs and makes its dissolving.Add 12.36g boric acid and mix, and add the 4.90g polyoxyethylene glycol, drip the weak ammonia of 25vol% then, regulate about pH to 3, form zirconia sol as dispersion agent.Add 26.55g resol (remaining carbon is about 50%, and concentration is 50vol%) and be made into mixed sols.Continue dropping ammonia, make its cohesion.Gel is transferred to ball grinder, is ball milling bulbec mill 24h with the zirconium white, and drying is 12 hours under 80 ℃, obtains the powder presoma.Calcining obtained ZrB in 1 hour under 1500 ℃
2-ZrC composite granule, the ZrC theoretical content is 50wt% in the composite granule.
Embodiment 4:
It is 4: 1 mixing solutions that the 58.81g zirconium oxychloride is dissolved in 500ml ethanol and water volume ratio, stirs and makes its dissolving.Add 12.36g boric acid and mix, and add the 5.40g polyoxyethylene glycol, drip the weak ammonia of 25vol% then, regulate about pH to 3, form zirconia sol as dispersion agent.Add 29.83g resol (remaining carbon is about 50%, and concentration is 50vol%) and be made into mixed sols.Continue dropping ammonia, make its cohesion.Gel is transferred to ball grinder, is ball milling bulbec mill 24h with the zirconium white, and drying is 12 hours under 80 ℃, obtains the powder presoma.Calcining obtained ZrB in 1 hour under 1500 ℃
2-ZrC composite granule, the ZrC theoretical content is 80wt% in the composite granule.
Embodiment 5:
It is 4: 1 mixing solutions that the 32.25g zirconium oxychloride is dissolved in 500ml ethanol and water volume ratio, stirs and makes its dissolving, and add the 3.60g polyoxyethylene glycol as dispersion agent, drips the weak ammonia of 25vol% then, regulates about pH to 3, forms zirconia sol.Add 12g resol (remaining carbon is about 50%, and concentration is 50vol%) and be made into mixed sols.Continue dropping ammonia, make its cohesion.Gel is transferred to ball grinder, is ball milling bulbec mill 24h with the zirconium white, and drying is 12 hours under 80 ℃, obtains the powder presoma.Calcining obtained the ZrC powder in 1 hour under 1400 ℃.Obviously find out the ZrC phase in the XRD figure, do not have other intermediate phase.(see figure 4)
Claims (5)
1. the method for a preparing boron-carbon-zirconium material by liquid phase process comprises the steps:
(1) zirconium oxychloride is dissolved in the mixing solutions that the second alcohol and water is made into, by zirconium boride 99.5004323A8ure: zirconium carbide=(100～0): (0～100) adds or does not add boric acid, and adds ethylene glycol as dispersion agent;
(2) add the weak ammonia titration, regulate the pH value;
(3) add resol and form binary colloidal sol;
(4) continue the weak ammonia titration, up to forming the binary gel;
(5) gel is through super-dry, and oven dry is ground, and sieving obtains precursor powder;
(6) obtained boron carbon zirconium powder body in 0.5～3 hour in vacuum or inert atmosphere, heat-treating under 1300～1600 ℃.
2. press the method for the described a kind of preparing boron-carbon-zirconium material by liquid phase process of claim 1, the concentration that it is characterized in that zirconium oxychloride in the step (1) is at 0.2～1mol/L, the volume ratio of second alcohol and water is 3: 1～5: 1 in the mixing solutions, and the concentration of polyoxyethylene glycol is 0.5～2wt%.
3. as the method for claim 2 or 3 described a kind of preparing boron-carbon-zirconium material by liquid phase process, the concentration that it is characterized in that weak ammonia in the step (2) is at 20～50vol%, and the pH value is controlled at 3～5.
4. as the method for a kind of preparing boron-carbon-zirconium material by liquid phase process as described in claim 2 or 3, it is characterized in that the concentration of resol in the step (3) is 10～80vol%.
5. as the method for a kind of preparing boron-carbon-zirconium material by liquid phase process as described in the claim 4, the concentration that it is characterized in that described resol is 50vol%.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102285661A (en) * | 2011-05-25 | 2011-12-21 | 山东理工大学 | Preparation method of tungsten boride powder |
| CN101486577B (en) * | 2009-02-24 | 2012-03-28 | 武汉理工大学 | Preparation of nano zirconium diboride ceramic powder |
| CN102515164A (en) * | 2011-11-30 | 2012-06-27 | 北京科技大学 | Preparation method of zirconium carbide ceramic powder |
| CN102530942A (en) * | 2010-12-08 | 2012-07-04 | 中国科学院金属研究所 | Preparation method for synthesizing zirconium carbide powder material by utilizing zirconium-containing organic matter precursor |
| CN102887524A (en) * | 2012-10-09 | 2013-01-23 | 天津大学 | Method for preparing nano-zirconium boride (ZrB2) powder by liquid-phase chemical technology |
| CN103435766A (en) * | 2013-08-30 | 2013-12-11 | 西北工业大学 | Boron-zirconium-silicon ternary modified phenolic resin and preparation method thereof |
| CN104030689A (en) * | 2014-06-25 | 2014-09-10 | 中国人民解放军国防科学技术大学 | Preparation method of boride ultrahigh-temperature ceramic |
| CN104086180A (en) * | 2014-06-25 | 2014-10-08 | 中国人民解放军国防科学技术大学 | Preparation method and application of boride ceramic precursor |
| CN105110347A (en) * | 2015-08-11 | 2015-12-02 | 中国核动力研究设计院 | Preparation method for nuclear grade concentrated 10B zirconium diboride powder and target |
| CN108975919A (en) * | 2018-09-19 | 2018-12-11 | 陕西科技大学 | A kind of liquid phase method prepares the technique of spherical ultra-fine zirconium boride powder and the zirconium boride powder of preparation |
| CN111517799A (en) * | 2020-04-20 | 2020-08-11 | 中国科学院合肥物质科学研究院 | Method for preparing zirconium boride powder with assistance of alcohol solvent |
| CN112062577A (en) * | 2020-09-06 | 2020-12-11 | 西北工业大学 | Method for preparing boride ultrahigh-temperature ceramic powder by hydrothermal method-assisted molten salt growth method |
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- 2007-12-03 CN CNA200710171688XA patent/CN101205065A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101486577B (en) * | 2009-02-24 | 2012-03-28 | 武汉理工大学 | Preparation of nano zirconium diboride ceramic powder |
| CN102530942A (en) * | 2010-12-08 | 2012-07-04 | 中国科学院金属研究所 | Preparation method for synthesizing zirconium carbide powder material by utilizing zirconium-containing organic matter precursor |
| CN102285661B (en) * | 2011-05-25 | 2013-02-13 | 山东理工大学 | Preparation method of tungsten boride powder |
| CN102285661A (en) * | 2011-05-25 | 2011-12-21 | 山东理工大学 | Preparation method of tungsten boride powder |
| CN102515164A (en) * | 2011-11-30 | 2012-06-27 | 北京科技大学 | Preparation method of zirconium carbide ceramic powder |
| CN102515164B (en) * | 2011-11-30 | 2013-08-28 | 北京科技大学 | Preparation method of zirconium carbide ceramic powder |
| CN102887524A (en) * | 2012-10-09 | 2013-01-23 | 天津大学 | Method for preparing nano-zirconium boride (ZrB2) powder by liquid-phase chemical technology |
| CN103435766B (en) * | 2013-08-30 | 2015-06-24 | 西北工业大学 | Boron-zirconium-silicon ternary modified phenolic resin and preparation method thereof |
| CN103435766A (en) * | 2013-08-30 | 2013-12-11 | 西北工业大学 | Boron-zirconium-silicon ternary modified phenolic resin and preparation method thereof |
| CN104030689A (en) * | 2014-06-25 | 2014-09-10 | 中国人民解放军国防科学技术大学 | Preparation method of boride ultrahigh-temperature ceramic |
| CN104086180A (en) * | 2014-06-25 | 2014-10-08 | 中国人民解放军国防科学技术大学 | Preparation method and application of boride ceramic precursor |
| CN104086180B (en) * | 2014-06-25 | 2016-03-30 | 中国人民解放军国防科学技术大学 | A kind of boride ceramics raw powder's production technology |
| CN104030689B (en) * | 2014-06-25 | 2016-03-30 | 中国人民解放军国防科学技术大学 | A kind of preparation method of boride ultra-temperature pottery |
| CN105110347A (en) * | 2015-08-11 | 2015-12-02 | 中国核动力研究设计院 | Preparation method for nuclear grade concentrated 10B zirconium diboride powder and target |
| CN108975919A (en) * | 2018-09-19 | 2018-12-11 | 陕西科技大学 | A kind of liquid phase method prepares the technique of spherical ultra-fine zirconium boride powder and the zirconium boride powder of preparation |
| CN111517799A (en) * | 2020-04-20 | 2020-08-11 | 中国科学院合肥物质科学研究院 | Method for preparing zirconium boride powder with assistance of alcohol solvent |
| CN112062577A (en) * | 2020-09-06 | 2020-12-11 | 西北工业大学 | Method for preparing boride ultrahigh-temperature ceramic powder by hydrothermal method-assisted molten salt growth method |
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