CN102126861B - In-situ self-toughening ZrB2-based composite ceramic material and preparation method thereof - Google Patents
In-situ self-toughening ZrB2-based composite ceramic material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an in-situ self-toughening ZrB2-based composite ceramic material and a preparation method thereof. The method comprises the following step of: subjecting zirconium powder with the purity of not lower than 98 percent, boron powder (or boron carbide powder), silicon powder and molybdenum powder to reaction, hot pressing and sintering at the temperature of between 1,600 DEG C and 1,900 DEG C for 0.5-2 hours according to the reaction equation of Zr+2xSi+xMo+2B=ZrB2+xMoSi2 for generating ZrB2-MoSi2, wherein x is more than or equal to 0.08 and less than or equal to 1, and the reaction equation of 2Zr+(1+2x)Si+xMo+B4C=2ZeB2+xMoSi2+SiC for generating ZrB2-MoSi2-SiC, wherein x is more than or equal to 0.2 and less than or equal to 2. By adopting the method, a material with the relative density of greater than 98 percent can be prepared at low temperature. ZrB2 crystal grains generated in the microscopic structure of the material by an in-situ reaction grow in a stick form, so that the toughness of the material is remarkably enhanced.
Description
Technical field
The present invention relates to in-situ self-toughening ZrB
2Base complex phase ceramic material and preparation method thereof belongs to non-oxidized substance base ceramic material field.
Background technology
Because ZrB
2Have high fusing point and strong covalent linkage, self-diffusion coefficient is low, is difficult to obtain fine and close material.Usually adopt hot pressed sintering in 1900-2200 ℃ of temperature range, pressure is higher than 20MPa even reaches under the condition of 50MPa and is prepared.The people such as Bellosi are to ZrB
2/ HfB
2Sintering behavior be studied, studies show that MoSi
2Introducing can reduce most effectively sintering temperature even realize pressureless sintering, and prepared ZrB
2-MoSi
2Material still can keep excellent mechanical property (D.Sciti, S.Guicciardi, and A.Bellosi, " Properties of a Pressureless-SinteredZrB at 1500 ℃
2-MoSi
2Ceramic Composite, " J.Am.Ceram.Soc., 89[7] (2006) 2320).The different Mo Si that the people such as Guo also prepare hot pressed sintering thereupon
2The ZrB of content
2-MoSi
2And ZrB
2-MoSi
2-SiC diphase ceramic material is studied (S-Q.Guo, T.Nishimura, T.Mizuguchi, and Y.Kagawa, " Mechanical properties of hot-pressedZrB
2-MoSi
2-SiC composites, " J.Eur.Ceram.Soc., 28 (2008) 1891).
But, because MoSi
2Toughness is lower, and the toughness of resulting materials is not high (generally at 2.5MPam
1/2About), thereby be restricted using.
The present invention utilizes reactive hot press sintering, with cheap raw material, according to reaction Zr+2xSi+xMo+2B=ZrB
2+ xMoSi
2, perhaps Zr+ (1+2x) Si+xMo+B
4C=2ZrB
2+ xMoSi
2+ SiC by changing the value of x, obtains the controlled ZrB of component
2-MoSi
2Diphase ceramic material.
Summary of the invention
The purpose of this invention is to provide a kind of in-situ self-toughening ZrB
2Base complex phase ceramic material and preparation method thereof.
The objective of the invention is to implement by following manner.Namely adopting purity to be not less than 98% zirconium powder, boron powder or boron carbide powder, silica flour, molybdenum powder is raw material, by the method for hot pressure reaction sintering, prepares relative density greater than 98% body material under 1600-1900 ℃ temperature.ZrB in this material microstructure
2Crystal grain presents bar-shaped growth, and toughness of material is at 4-5MPam
1/2Between.
Specific implementation method:
(1) is not less than 98% zirconium powder, purity take purity and is not less than that 98% boron powder, purity are not less than 98% silica flour, purity is not less than 98% molybdenum powder as raw material, according to generating ZrB
2-MoSi
2Reaction equation Zr+2xSi+xMo+2B=ZrB
2+ xMoSi
2, 0.08≤x≤3 preparation raw material, take acetone as solvent, the preparation solid content be 20～60 ball milling 5-24 hours, the powder that obtains mixing behind the gained slurry drying.
Perhaps be not less than 98% zirconium powder, purity take purity and be not less than that 98% boron powder, purity are not less than 98% silica flour, purity is not less than 98% molybdenum powder as raw material, according to generating ZrB
2-MoSi
2The reaction equation 2Zr+ of-SiC (1+2x) Si+xMo+B
4C=2ZrB
2+ xMoSi
2+ SiC, 0.2≤x≤18 preparation raw material, the preparation solid content is the slurry of 10～70wt%, ball milling 5-24 hour, the powder that obtains mixing behind the gained slurry drying take acetone as solvent.
Preferred described zirconium powder particle diameter≤28 μ m; Described boron carbide powder particle diameter≤2 μ m; Described boron powder footpath≤1 μ m; Described silica flour particle diameter≤50 μ m; Described molybdenum powder particle diameter≤75 μ m;
(2) powder that mixes is placed in the graphite jig of inner wall surface coating B N, 1600-1900 ℃ is carried out reaction sintering in vacuum or argon gas atmosphere,
Temperature rise rate is 10-100 ℃/min during preferred sintering, and further preferred temperature applies the pressure of 20-30MPa, heat-insulation pressure keeping 0.5-2hr when rising to 1600-1900 ℃.
The material ZrB of the present invention's preparation
2Crystal grain presents bar-shaped growth, and toughness of material is at 4-5MPam
1/2Between.
Advantage of the present invention is:
(1) cost of material is cheap, and is not high to purity requirement,, preparation technology is simple, realizes easily.
(2) prepared material component is adjustable, uniform microstructure.
(3) ZrB in the material microstructure
2Crystal grain presents bar-shaped growth, and toughness of material is at 4-5MPam
1/2Between, excellent property.
Embodiment
Embodiment 1
Be raw material with zirconium powder (≤28 μ m, 98%), boron powder (≤1 μ m, 99%), silica flour (≤50 μ m, 99%), molybdenum powder (≤75 μ m, 99%).Design ZrB
2-MoSi
2Middle MoSi
2Volumn concentration is 20, i.e. equation Zr+2xSi+xMo+2B=ZrB is answered in negate
2+ xMoSi
2In x=0.190013 batching, the preparation solid content with 550 rev/mins speed, is used ZrO as the slurry of 10wt% take acetone as solvent
2The powder that ball planetary ball mill 8 hours, gained slurry obtain mixing after drying by rotary evaporation.The powder that mixes is placed in the graphite jig of inner wall surface coating BN, carries out in a vacuum reaction sintering, temperature rise rate is 10 ℃/min during sintering, is warming up to the pressure of 1600 ℃ of after-applied 20-30MPa, heat-insulation pressure keeping 0.5hr.Material density reaches 99.2%.The microstructure of material as shown in Figure 1.The fracture toughness property of material is 4.9MPam
1/2
Embodiment 2
Be raw material with zirconium powder (≤28 μ m, 98%), boron carbide powder (≤2 μ m, 99%), silica flour (≤50 μ m, 99%), molybdenum powder (≤75 μ m, 99%).Design ZrB
2-MoSi
2MoSi among the-SiC
2Volumn concentration is 20, i.e. reaction equation Zr+ (1+2x) Si+xMo+B
4C=2ZrB
2+ xMoSi
2X=0.508135 among the+SiC, this moment, the volumn concentration of SiC also was 20, and the preparation solid content is the slurry of 40wt% take acetone as solvent, and according to the method preparation pottery of embodiment 1, sintering temperature is 1900 ℃, and material density reaches 98.9%.The microstructure of material as shown in Figure 2.The fracture toughness property of material is 4.4MPam
1/2
Embodiment 3
Be raw material with zirconium powder (≤28 μ m, 98%), boron powder (≤1m, 99%), silica flour (≤50 μ m, 99%), molybdenum powder (≤75 μ m, 99%).Design ZrB
2-MoSi
2Middle MoSi
2Volumn concentration is 20, i.e. reaction equation Zr+2xSi+xMo+2B=ZrB
2+ xMoSi
2In x=0.190013, the preparation solid content is the slurry of 30wt% take acetone as solvent, ball milling method adopts the roll-type ball milling.According to the method preparation pottery of embodiment 1, sintering temperature is 1650 ℃, and material density is greater than 98%.The microstructure of material as shown in Figure 3.
Embodiment 4
Be raw material with zirconium powder (≤28 μ m, 98%), boron carbide powder (≤2 μ m, 99%), silica flour (≤50 μ m, 99%), molybdenum powder (≤75 μ m, 99%).Design ZrB
2-MoSi
2MoSi among the-SiC
2Volumn concentration is 20, i.e. reaction equation Zr+ (1+2x) Si+xMo+B
4C=2ZrB
2+ xMoSi
2X=0.508135 among the+SiC, this moment, the volumn concentration of SiC also was 20, and the preparation solid content is the slurry of 70wt% take acetone as solvent, and ball milling method adopts the roll-type ball milling.According to the method preparation pottery of embodiment 1, sintering temperature is 1850 ℃, and material density reaches 99.1%.The microstructure of material as shown in Figure 4.
Embodiment 5
Be raw material with zirconium powder (≤28 μ m, 98%), boron powder (≤1 μ m, 99%), silica flour (≤50 μ m, 99%), molybdenum powder (≤75 μ m, 99%).Design ZrB
2-MoSi
2Middle MoSi
2Volumn concentration is 50, i.e. reaction equation Zr+2xSi+xMo+2B=ZrB
2+ xMoSi
2In x=0.760053, the preparation solid content is the slurry of 60wt% take acetone as solvent, ball milling method adopts the roll-type ball milling.According to the method preparation pottery of embodiment 1, sintering temperature is 1650 ℃, and material density is greater than 98%.
Description of drawings
The preparation of 1800 ℃ of reactive hot press sinterings of Fig. 1 ZrB
2-20vol%MoSi
2The microstructure of stupalith.
The preparation of 1900 ℃ of reactive hot press sinterings of Fig. 2 ZrB
2-20vol%MoSi
2The microstructure of-20vol%SiC stupalith.
The preparation of 1650 ℃ of reactive hot press sinterings of Fig. 3 ZrB
2-20vol%MoSi
2The microstructure of stupalith.
The preparation of 1850 ℃ of reactive hot press sinterings of Fig. 4 ZrB
2-20vol%MoSi
2The microstructure of-20vol%SiC stupalith.
Claims (9)
1. in-situ self-toughening ZrB
2Base complex phase ceramic material preparation method is characterized in that comprising the steps:
(1) is not less than 98% zirconium powder, purity take purity and is not less than that 98% boron powder, purity are not less than 98% silica flour, purity is not less than 98% molybdenum powder as raw material, according to generating ZrB
2-MoSi
2Reaction equation Zr+2xSi+xMo+2B=ZrB
2+ xMoSi
2, 0.08≤x≤3 preparation raw material, take acetone as solvent, the preparation solid content is the slurry of 20～60wt%, ball milling 5-24 hour, the powder that obtains mixing behind the gained slurry drying;
(2) powder that mixes is placed in the graphite jig of inner wall surface coating BN, 1600-1900 ℃ is carried out reaction sintering in vacuum or argon gas atmosphere.
2. by method claimed in claim 1, temperature rise rate is 10-100 ℃/min when it is characterized in that sintering.
3. by method claimed in claim 1, it is characterized in that temperature applies the pressure of 20-30MPa, heat-insulation pressure keeping 0.5-2hr when rising to 1600-1900 ℃.
4. by method claimed in claim 1, it is characterized in that described zirconium powder particle diameter≤28 μ m; Described boron powder footpath≤1 μ m; Described silica flour particle diameter≤50 μ m; Described molybdenum powder particle diameter≤75 μ m.
5. in-situ self-toughening ZrB
2Base complex phase ceramic material preparation method is characterized in that comprising the steps:
(1) is not less than 98% zirconium powder, purity take purity and is not less than that 98% boron carbide powder, purity are not less than 98% silica flour, purity is not less than 98% molybdenum powder as raw material, according to generating ZrB
2-MoSi
2The reaction equation 2Zr+ of-SiC (1+2x) Si+xMo+B
4C=2ZrB
2+ xMoSi
2+ SiC, 0.2≤x≤18 preparation raw material, the preparation solid content is the slurry of 10～70wt%, ball milling 5-24 hour, the powder that obtains mixing behind the gained slurry drying take acetone as solvent;
(2) powder that mixes is placed in the graphite jig of inner wall surface coating BN, 1600-1900 ℃ is carried out reaction sintering in vacuum or argon gas atmosphere.
6. by method claimed in claim 5, temperature rise rate is 10-100 ℃/min when it is characterized in that sintering.
7. by method claimed in claim 5, it is characterized in that temperature applies the pressure of 20-30MPa, heat-insulation pressure keeping 0.5-2hr when rising to 1600-1900 ℃.
8. by method claimed in claim 5, it is characterized in that described zirconium powder particle diameter≤28 μ m; Described boron carbide powder particle diameter≤2 μ m; Described silica flour particle diameter≤50 μ m; Described molybdenum powder particle diameter≤75 μ m.
9. by claim 1 or 2 described in-situ self-toughening ZrB
2The material of base complex phase ceramic material preparation method preparation, ZrB
2Crystal grain presents bar-shaped growth, and toughness of material is at 4-5MPam
1/2Between.
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|---|---|---|---|---|
| CN106478110A (en) * | 2016-10-12 | 2017-03-08 | 黑龙江科技大学 | A kind of ZrB2The preparation method of SiC composite ceramicses |
| CN107746263A (en) * | 2017-11-15 | 2018-03-02 | 石婷 | A kind of Compound Ceramic Evaporator and its manufacture method |
| CN109534825B (en) * | 2019-01-16 | 2021-06-01 | 电子科技大学 | ZrB coated with in-situ synthesized inert glass phase2And method for preparing the same |
| CN111548164B (en) * | 2020-05-19 | 2021-06-29 | 中钢集团洛阳耐火材料研究院有限公司 | Continuous self-toughening nitride-bonded silicon carbide refractory material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1125211A (en) * | 1995-09-07 | 1996-06-26 | 华东理工大学 | Large block body tight nanometer ceramic material and its preparation method |
| CN101104561A (en) * | 2007-03-16 | 2008-01-16 | 中国科学院上海硅酸盐研究所 | In-situ reaction preparation method for zirconium diboride base composite phase ceramic |
| CN101531519A (en) * | 2008-03-12 | 2009-09-16 | 李琎 | Composite high-temperature molybdenum disilicide-base material and preparation method thereof |
-
2010
- 2010-01-14 CN CN 201010022825 patent/CN102126861B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1125211A (en) * | 1995-09-07 | 1996-06-26 | 华东理工大学 | Large block body tight nanometer ceramic material and its preparation method |
| CN101104561A (en) * | 2007-03-16 | 2008-01-16 | 中国科学院上海硅酸盐研究所 | In-situ reaction preparation method for zirconium diboride base composite phase ceramic |
| CN101531519A (en) * | 2008-03-12 | 2009-09-16 | 李琎 | Composite high-temperature molybdenum disilicide-base material and preparation method thereof |
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