CN101913876A - Method for preparing zirconium boride-tungsten titanium carbide self-lubricating composite ceramic material - Google Patents
Method for preparing zirconium boride-tungsten titanium carbide self-lubricating composite ceramic material Download PDFInfo
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Abstract
The invention relates to a method for preparing a zirconium boride-tungsten titanium carbide self-lubricating composite ceramic material. The material is prepared by adding (W, Ti) C solid solution and ZrO2 powder into a ZrB2 matrix, taking MgO as a sintering aid and performing hot pressing sintering on the materials under the vacuum environment. Matrix phase ZrB2 and enhanced phase (W, Ti) C form a good framework structure by introducing (W, Ti) C solid solution; and the ZrO2 is added so as to improve the toughness of the composite ceramic material by means of the phase change characteristic. The sintering temperature of the ZrB2 is reduced by adding the MgO sintering aid, so that a material with higher compactness is obtained. Self-lubricating function of the zirconium boride-tungsten titanium carbide self-lubricating composite ceramic material can be realized by using the chemical reaction of the composite material under the action of high temperature friction. The method has the characteristics of high hardness, high bending strength, high fracture toughness and the like and is suitable for preparing metal cutting tools, modules, nozzles and the like.
Description
One, technical field
The invention belongs to the engineering materials technical field, particularly a kind of preparation method of zirconium boride-tungsten titanium carbide self-lubricating composite ceramic material.
Two, background technology
ZrB
2Be the C32 metalloid structural compounds of hexagonal system, it has high-melting-point, high rigidity, high stability and favorable conductive, thermal conductivity and resistance to chemical corrosion, therefore at refractory materials, nozzle, cutting tool and die industry very big development prospect is arranged.In addition, ZrB
2Have good neutron controllability, can be used for nuclear industry.But because ZrB
2Stupalith self sintering densification is difficulty, bending strength, drawbacks limit that fracture toughness property is lower its range of application, usually lost efficacy because of damaged.In order to improve ZrB
2The mechanical property of pottery, Melendez-Martinez has developed ZrB
2/ Ni composite ceramic material, fracture toughness property can reach 2.8~3.5MPam
1/2, bending strength can reach 351~371MPa, but still can not satisfy a lot of engineering demands (Journal of the European Ceramic Society, 2002,22:2543-2549).Monteverde studies show that: at ZrB
2Add the performance that SiC can improve (1200 ℃~1600 ℃) under its ultrahigh-temperature in the stupalith, but the fracture toughness property under the normal temperature is still lower, only is 3.3~4.0MPam
1/2(Materials Science and Engineering A, 2008,485:415-421).ZrB
2Belong to the boracic series ceramic, can generate the oxide compound lubricant film of the boron that is dissolved with other element under friction high temperature (800 ℃~1000 ℃) drives, can realize self-lubricating, be a kind of good self-lubricating material (Acta Materialia, 2007,55:5999-6010).Yet the defective that fracture toughness property is lower has limited ZrB significantly
2The application of stupalith in actual production.Studies show that recently: (W, Ti) adding of C can effectively improve the bending strength and the fracture toughness property of composite ceramic material, obviously improves its mechanical property.Al
2O
3/ (fracture toughness property and bending strength reach 6.55MPa.m respectively for W, Ti) C matrix material
1/2And 840MPa, with respect to Al
2O
3One-component ceramic, its fracture toughness property and bending strength have improved 91.5% and 124.5% (Chinese mechanical engineering, 2009, (22): 2751-2754) respectively.Therefore, at ZrB
2(W, Ti) the mutually compound further comprehensive mechanical property of betterment works stupalith of C enlarges its range of application in introducing in the ceramic matrix.
Three, summary of the invention
The objective of the invention is to overcome above-mentioned the deficiencies in the prior art, a kind of preparation method with zirconium boride-tungsten titanium carbide self-lubricating composite ceramic material of high strength, high tenacity is provided.
The present invention realizes in the following manner.
A kind of zirconium boride-tungsten titanium carbide self-lubricating composite ceramic material preparation method of the present invention, this material mainly comprises ZrB
2, (W, Ti) C and ZrO
2, it is characterized in that preparing by the following method:
(1) first ball-milling technology: earlier respectively with ZrB
2Raw material and (W, Ti) the C raw material is medium wet ball-milling 100 hours with the dehydrated alcohol, is sieving behind the dry 24h with vacuum drying oven down at 150 ℃ then, obtains uniform refinement powder;
(2) batching, stirring and secondary ball milling technology: with the ZrB of first refinement
2As body material, (W, Ti) C is a strengthening phase, ZrO
2Be toughness reinforcing phase, add the MgO sintering agent; The volume percent of each component is: ZrB
245.2~82.1%, (W, Ti) C 10.0~50.0%, ZrO
23.8~6.9%, MgO 1.0%; It is in the beaker of medium that the mixing raw material that configures is poured into the dehydrated alcohol, ultra-sonic oscillation stirred 30 minutes, compound is medium wet ball-milling 200 hours with the dehydrated alcohol, sieves behind the dry 24h with vacuum drying oven down at 150 ℃, obtains being suitable for the even refinement composite powder of agglomerating;
(3) hot pressed sintering: with the composite powder that mixes dress as in the high-strength graphite mould, hot pressed sintering under vacuum environment then, sintering range is 1700~1800 ℃, pressure is 30MPa, soaking time is 30~35 minutes.
By above step, the zirconium boride 99.5004323A8ure-tungsten carbide composite ceramic material that can make even particle size distribution, hardness height, have high-flexural strength and fracture toughness property.(W, Ti) C sosoloid can make matrix phase ZrB in introducing
2(W Ti)/C interts mutually, parcel, forms skeleton structure preferably, thereby improves the bending strength and the fracture toughness property of matrix material with wild phase; Add ZrO
2Mainly be to utilize its phase-change characteristic to realize strengthening and toughening mechanism of, improve ZrB to reach
2The toughness of pottery; Add the MgO sintering agent and reduce ZrB
2Sintering temperature, thereby obtain material with higher compactness.Utilize the chemical reaction of zirconium boride-tungsten titanium carbide self-lubricating composite ceramic material under the high temperature friction effect, generate reaction film, can realize the self-lubricating function of this matrix material with lubrication at material surface.Zirconium boride-tungsten titanium carbide self-lubricating composite ceramic material is suitable for making metal cutting tool, mould and the nozzle etc. that high temperature and wear resistance are had relatively high expectations.
Four, embodiment
Provide embodiments of the invention below.
Embodiment one: earlier respectively with ZrB
2Raw material is with (W, Ti) the C raw material is medium difference wet ball-milling 100 hours with the dehydrated alcohol, is sieving behind the dry 24h with vacuum drying oven down at 150 ℃ then, obtains uniform refinement powder.ZrB with first refinement
2As body material, (W, Ti) C is a strengthening phase, ZrO
2Be toughness reinforcing phase, add the MgO sintering agent; The volume percent of each component is: ZrB
263.0%, (W, Ti) C 30.5%, ZrO
25.5%, MgO 1.0%.It is in the beaker of medium that the mixing raw material that configures is poured into the dehydrated alcohol, and ultra-sonic oscillation stirred 30 minutes, prevents the material reunion.Compound is medium wet ball-milling 200 hours with the dehydrated alcohol, sieves behind the dry 24h with vacuum drying oven down at 150 ℃, obtains being suitable for the composite powder of the even refinement of agglomerating.The compound material powder that mixes is adorned as in the high-strength graphite mould, adopted vacuum environment and hot-pressing sintering technique, sintering temperature is 1800 ℃, and pressure is 30MPa, and soaking time is 35 minutes.
Embodiment two: earlier respectively with ZrB
2Raw material is with (W, Ti) the C raw material is medium difference wet ball-milling 100 hours with the dehydrated alcohol, is sieving behind the dry 24h with vacuum drying oven down at 150 ℃ then, obtains uniform refinement powder.ZrB with first refinement
2As body material, (W, Ti) C is a strengthening phase, ZrO
2Be toughness reinforcing phase, add the MgO sintering agent; The volume percent of each component is: ZrB
254.4%, (W, Ti) C 40.0%, ZrO
24.5%, MgO 1.0%.It is in the beaker of medium that the mixing raw material that configures is poured into the dehydrated alcohol, and ultra-sonic oscillation stirred 30 minutes, prevents the material reunion.Compound is medium wet ball-milling 200 hours with the dehydrated alcohol, sieves behind the dry 24h with vacuum drying oven down at 150 ℃, obtains being suitable for the composite powder of the even refinement of agglomerating.The compound material powder that mixes is adorned as in the high-strength graphite mould, adopted vacuum environment and hot-pressing sintering technique, sintering temperature is 1750 ℃, and pressure is 30MPa, and soaking time is 32 minutes.
Embodiment three: earlier respectively with ZrB
2Raw material is with (W, Ti) the C raw material is medium difference wet ball-milling 100 hours with the dehydrated alcohol, is sieving behind the dry 24h with vacuum drying oven down at 150 ℃ then, obtains uniform refinement powder.ZrB with first refinement
2As body material, (W, Ti) C is a strengthening phase, ZrO
2Be toughness reinforcing phase, add the MgO sintering agent; The volume percent of each component is: ZrB
245.2%, (W, Ti) C 50.0%, ZrO
23.8%, MgO 1.0%.It is in the beaker of medium that the mixing raw material that configures is poured into the dehydrated alcohol, and ultra-sonic oscillation stirred 30 minutes, prevents the material reunion.Compound is medium wet ball-milling 200 hours with the dehydrated alcohol, sieves behind the dry 24h with vacuum drying oven down at 150 ℃, obtains being suitable for the composite powder of the even refinement of agglomerating.The compound material powder that mixes is adorned as in the high-strength graphite mould, adopted vacuum environment and hot-pressing sintering technique, sintering temperature is 1700 ℃, and pressure is 30MPa, and soaking time is 30 minutes.
Adopt the zirconium boride-tungsten titanium carbide self-lubricating composite ceramic material of above-mentioned prepared have granularity tiny and be evenly distributed, characteristics such as high rigidity, high-flexural strength and high-fracture toughness.Utilize the chemical reaction of zirconium boride-tungsten titanium carbide self-lubricating composite ceramic material under the high temperature friction effect, generate reaction film, can realize the self-lubricating function of this matrix material with lubrication at material surface.This material closes metal cutting tool, mould and the nozzle etc. of high temperature and wear resistance being had relatively high expectations in making.
Claims (1)
1. the preparation method of a zirconium boride-tungsten titanium carbide self-lubricating composite ceramic material, this material mainly comprises ZrB
2, (W, Ti) C and ZrO
2, it is characterized in that preparing by the following method:
(1) first ball-milling technology: earlier respectively with ZrB
2Raw material and (W, Ti) the C raw material is medium wet ball-milling 100 hours with the dehydrated alcohol, is sieving behind the dry 24h with vacuum drying oven down at 150 ℃ then, obtains uniform refinement powder;
(2) batching, stirring and secondary ball milling technology: with the ZrB of first refinement
2As body material, (W, Ti) C is a strengthening phase, ZrO
2Be toughness reinforcing phase, add the MgO sintering agent; The volume percent of each component is: ZrB
245.2~82.1%, (W, Ti) C 10.0~50.0%, ZrO
23.8~6.9%, MgO 1.0%.It is in the beaker of medium that the mixing raw material that configures is poured into the dehydrated alcohol, and ultra-sonic oscillation stirred 30 minutes; Compound is medium wet ball-milling 200 hours with the dehydrated alcohol, sieves behind the dry 24h with vacuum drying oven down at 150 ℃, obtains being suitable for the even refinement composite powder of agglomerating;
(3) hot pressed sintering: with the composite powder that mixes dress as in the high-strength graphite mould, hot pressed sintering under vacuum environment then, sintering range is 1700~1800 ℃, pressure is 30MPa, soaking time is 30~35 minutes.
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Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
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CN103553626A (en) * | 2013-09-27 | 2014-02-05 | 大连理工大学 | High density ceramic matrix composite material, preparation method and application thereof |
CN104355624A (en) * | 2014-10-29 | 2015-02-18 | 安徽省皖捷液压科技有限公司 | Multi-functional ceramic nozzle prepared from fluorite slag and preparation method thereof |
CN104387080A (en) * | 2014-11-11 | 2015-03-04 | 合肥皖为电气设备工程有限责任公司 | Zirconium boride ceramic applied to cutters and preparation method of zirconium boride ceramic |
CN104387062A (en) * | 2014-11-07 | 2015-03-04 | 合肥大安印刷有限责任公司 | Heat-resisting cutting tool ceramic and preparation method thereof |
CN104860680A (en) * | 2015-06-17 | 2015-08-26 | 洛阳理工学院 | Wide-adaptability dual-mechanism self-lubricating bearing material and preparation method thereof |
CN104909761A (en) * | 2015-06-17 | 2015-09-16 | 洛阳理工学院 | Preparation method of self-lubricating cutter material capable of adapting to high temperature and low temperature |
CN104909760A (en) * | 2015-06-17 | 2015-09-16 | 洛阳理工学院 | Preparation method of self-lubricating ZrB2-ZrO2-CaF2 ceramic material |
CN106316398A (en) * | 2016-08-17 | 2017-01-11 | 齐鲁工业大学 | Tungsten titanium carbide-based ceramic tool material added with cubic boron nitride and preparation method of material |
CN108191249A (en) * | 2018-02-28 | 2018-06-22 | 宁波革创新材料科技有限公司 | A kind of strength energy-saving foam glass and preparation method thereof |
CN114773038A (en) * | 2022-05-10 | 2022-07-22 | 燕山大学 | Ceramic cutter integrating temperature sensing and cutting functions, and preparation method and application thereof |
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JPH05330926A (en) * | 1992-06-02 | 1993-12-14 | Toray Ind Inc | Boride-based composite ceramic sintered compact |
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CN101747047A (en) * | 2009-10-21 | 2010-06-23 | 哈尔滨工业大学 | Method for improving heat shock resistance and strength of ZrB2-SiC superhigh temperature ceramic material |
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JPH05330926A (en) * | 1992-06-02 | 1993-12-14 | Toray Ind Inc | Boride-based composite ceramic sintered compact |
CN101279840A (en) * | 2008-05-13 | 2008-10-08 | 山东大学 | Preparation of aluminum oxide-tungsten carbide nanometer composite ceramic material |
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Cited By (13)
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CN103553626A (en) * | 2013-09-27 | 2014-02-05 | 大连理工大学 | High density ceramic matrix composite material, preparation method and application thereof |
CN103553626B (en) * | 2013-09-27 | 2015-12-09 | 大连理工大学 | A kind of high-compactness ceramic matric composite and its preparation method and application |
CN104355624A (en) * | 2014-10-29 | 2015-02-18 | 安徽省皖捷液压科技有限公司 | Multi-functional ceramic nozzle prepared from fluorite slag and preparation method thereof |
CN104387062A (en) * | 2014-11-07 | 2015-03-04 | 合肥大安印刷有限责任公司 | Heat-resisting cutting tool ceramic and preparation method thereof |
CN104387080A (en) * | 2014-11-11 | 2015-03-04 | 合肥皖为电气设备工程有限责任公司 | Zirconium boride ceramic applied to cutters and preparation method of zirconium boride ceramic |
CN104909760A (en) * | 2015-06-17 | 2015-09-16 | 洛阳理工学院 | Preparation method of self-lubricating ZrB2-ZrO2-CaF2 ceramic material |
CN104909761A (en) * | 2015-06-17 | 2015-09-16 | 洛阳理工学院 | Preparation method of self-lubricating cutter material capable of adapting to high temperature and low temperature |
CN104860680A (en) * | 2015-06-17 | 2015-08-26 | 洛阳理工学院 | Wide-adaptability dual-mechanism self-lubricating bearing material and preparation method thereof |
CN104860680B (en) * | 2015-06-17 | 2017-02-22 | 洛阳理工学院 | Wide-adaptability dual-mechanism self-lubricating bearing material and preparation method thereof |
CN104909760B (en) * | 2015-06-17 | 2017-05-24 | 洛阳理工学院 | Preparation method of self-lubricating ZrB2-ZrO2-CaF2 ceramic material |
CN106316398A (en) * | 2016-08-17 | 2017-01-11 | 齐鲁工业大学 | Tungsten titanium carbide-based ceramic tool material added with cubic boron nitride and preparation method of material |
CN108191249A (en) * | 2018-02-28 | 2018-06-22 | 宁波革创新材料科技有限公司 | A kind of strength energy-saving foam glass and preparation method thereof |
CN114773038A (en) * | 2022-05-10 | 2022-07-22 | 燕山大学 | Ceramic cutter integrating temperature sensing and cutting functions, and preparation method and application thereof |
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