CN110256081A - A kind of boron carbide base composite ceramic material and its preparation process - Google Patents

A kind of boron carbide base composite ceramic material and its preparation process Download PDF

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CN110256081A
CN110256081A CN201910552810.0A CN201910552810A CN110256081A CN 110256081 A CN110256081 A CN 110256081A CN 201910552810 A CN201910552810 A CN 201910552810A CN 110256081 A CN110256081 A CN 110256081A
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sic
composite ceramic
ceramic material
graphite
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钟志宏
王睿
魏仁伟
吴玉程
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Hefei University of Technology
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Hefei University of Technology
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Abstract

The invention discloses a kind of boron carbide base composite ceramic material and its preparation processes, and the composite ceramic material is by B4C、Ti3SiC2And Si is prepared through vacuum hot-pressed sintered technology, raw material is Ti by the proportion of percentage by volume3SiC2Powder 9.4-25%, Si powder 6.3-16.7%, surplus B4C powder.The present invention utilizes B4C and Ti3SiC2And to generate crystal grain tiny and in B for Si reaction in-situ4Be evenly distributed TiB in C matrix2With SiC Strengthening and Toughening phase, B is effectively inhibited4C crystal grain is grown up, and has the characteristics that consistency is high, conductivity is good, comprehensive mechanical property is excellent, practical value with higher.

Description

A kind of boron carbide base composite ceramic material and its preparation process
Technical field
The present invention relates to a kind of B4C based composite ceramic material and its preparation process, belong to B4The reaction of C base composite ceramic is burnt Knot field.
Background technique
Boron carbide (B4C) ceramics are very attractive high temperature function-structural materials, have excellent chemically and physically property Can, such as good chemical stability, high rigidity, low-density, high-melting-point and good wearability.Therefore, B4C is extensive It is applied in field, such as bulletproof armour, refractory material, abrasive coating, electronics.Further, since boron has good neutron Absorbability, B4C also has a wide range of applications in nuclear reactor as neutron-absorbing material and shielding material.B4The sintering of C ceramics Property and the big problem of the brittleness that machining property is poor and its is intrinsic, limit B4The practical application of C ceramics, it is therefore desirable to send out Open up B4C base composite ceramic or composite material.B4The wide application prospect of C and its composite material promotes the hair of ceramic sintering technology Exhibition, while B has been widened in the development of ceramic material sintering technology of preparing again4The application field of C.Therefore, B is studied4C and its composite wood The sintering preparation process of material has great importance.
B4C agglutinating property difference is attributed to high covalent bond and low diffusion mobility, and machining property difference is attributed to its high rigidity And low conductivity.B4The big reason of C brittleness of ceramics is the highly sensitive of On Crack Propagation.Therefore, B is reduced4The sintering temperature of C ceramics It spends (~2200 DEG C), improves its fracture toughness and improve most important for its machining property is applied to.Carbon, aluminium, silicon, Aluminium oxide is usually directed into as sintering aid, to reduce sintering temperature.However, the addition of these sintering aids does not make B4The fracture toughness of C ceramics significantly improves.Promoting B4While C densified sintering product, the performance for generating some Dispersed precipitates is excellent Different ceramic phase has very important effect to its comprehensive mechanical property is improved.For example, in B4Silicon carbide (SiC) is added in C Afterwards, its oxidation resistance and fracture toughness can be greatly improved；And in B4Titanium diboride (TiB is added in C2) that its fracture can be improved is tough Property and improve machining property.Therefore, a kind of new sintering aid is found, at a relatively low sintering temperature, is realized high-densit The B of degree, high conductivity, excellent comprehensive mechanical property4The sintering of C base composite ceramic, has important practical significance.
Summary of the invention
In order to avoid the shortcomings of the prior art, the present invention is intended to provide a kind of high-compactness, high conductivity, The good B of comprehensive mechanical property4C based composite ceramic material and its preparation process.
The present invention is to realize goal of the invention, is adopted the following technical scheme that
The invention discloses a kind of boron carbide base composite ceramic materials, it is characterized in that: the composite ceramic material be by B4C、Ti3SiC2And Si is prepared through vacuum hot-pressed sintered technology.Further, the raw material of the composite ceramic material presses body The proportion of product percentage is Ti3SiC2Powder 9.4-25%, Si powder 6.3-16.7%, surplus B4C powder.
The preparation process of boron carbide base composite ceramic material of the present invention, includes the following steps:
Step 1: the preparation of reaction-sintered mixed-powder
Amount weighs B according to the ratio4C powder, Ti3SiC2Powder and Si powder, are poured into the ball grinder of planetary ball mill, with no watery wine Essence is ball-milling medium, is milled to and is mixed thoroughly, then is placed in a vacuum drying oven dry to get reaction-sintered mixed-powder；
Step 2: reaction in-situ hot pressed sintering
Prepare what a graphite jig, two matched graphite pressure heads, two Graphite pads, graphite paper in advance；By graphite The square that paper determines the circular graphitic paper of two diameters size identical as graphite jig internal diameter and one can cover graphite jig inner wall Shape graphite paper；Rectangle graphite paper is attached to graphite jig inner wall, and according to graphite pressure head/Graphite pad/graphite paper/reaction-sintered Mixed-powder/graphite paper/Graphite pad/graphite pressure head sequence is assembled；The graphite jig that assembly is completed is put into very again In empty hot-pressed sintering furnace, 10 are evacuated to sintering furnace at room temperature-1Pa is hereinafter, being warming up to 1850-1950 DEG C of sintering temperature and protecting Warm 30-60min, on-load pressure 30-50MPa cool down after heat preservation, are depressured to get B4C based composite ceramic material.
Further: the B4The granularity of C powder is 0.5-5 μm, and purity is not less than 96%；The Ti3SiC2The granularity of powder is 0.5-10 μm, purity is not less than 98%: the granularity of the Si powder is 0.5-20 μm, and purity is not less than 98%.
Further, in step 1, the revolving speed of the planetary ball mill is 150-250rpm, and ball grinder material is nylon, mill Ball material is agate, Ball-milling Time 6-10h.
Further, in step 1, the temperature of the drying is 40-60 DEG C, time 8-12h.
Further, in step 2, during hot pressed sintering, heating rate is 5-15 DEG C/min, rate of pressure rise 20- 30MPa/h。
Further, in step 2, the mode of the cooling is furnace cooling, or first with the cooling speed of 10 DEG C/min Rate is down to 1000 DEG C, then furnace cooling again.Wherein the effect of second of cooling method is preferable, and slower cooling velocity can prevent Cooling is too fast and generates biggish residual stress, to improve B4The mechanical property of C base composite ceramic.
Further, in step 2, the mode of the decompression is to be down to 0MPa with the rate of pressure reduction of 30MPa/h.
The present invention utilizes reaction in-situ hot-pressing sintering technique (sintering temperature: 1850-1950 DEG C；Soaking time: 30- 60min；Pressure: 30-50MPa) preparation B4C base composite ceramic.Sintering temperature be 1850 DEG C, soaking time 30min, pressure For 30MPa, 25%Ti is added3SiC2When with 16.7%Si, the preferable B of performance is obtained4C base composite ceramic, it is microhardness, curved Qu Qiangdu and fracture toughness are respectively 34.4GPa, 516.7MPa, 7.8MPam1/2, practical value with higher.In addition, system The open porosity of standby composite ceramics is lower, and can be added with the spark cutting that common linear cutting equipment carries out complicated shape Work.
Compared with prior art, the beneficial effects of the present invention are embodied in:
1, the present invention explores Ti3SiC2, Si and B4C powder mixture ratio and hot-pressing sintering technique parameter, relatively low At a temperature of, high-compactness B is obtained by mixed-powder reaction in-situ4C base composite ceramic.Ti3SiC2B is effectively reduced with Si4C The sintering temperature of ceramics, solves B4The high problem of C ceramic sintering temperature.
2, the present invention utilizes B4C and Ti3SiC2And Si reaction in-situ generates TiB2With SiC Strengthening and Toughening phase, B is obtained4C-TiB2- SiC three-phase composite ceramics.Keeping B4Under the premise of C ceramic high intensity and high rigidity, pass through the TiB of reaction in-situ generation2With SiC is tiny with crystal grain and in B4The characteristics of being evenly distributed in C matrix can effectively inhibit B4C crystal grain is grown up, and ceramics are improved The fracture toughness of composite material makes the B of preparation4C base composite ceramic has excellent comprehensive mechanical property.
3, in the present invention, since reaction in-situ generates more TiB2Strengthening and Toughening phase, B4C-TiB2- SiC three-phase composite pottery Porcelain conductivity with higher can carry out spark cutting processing, solve B4C ceramics cannot carry out electrical spark working with wire cutting The problem of work.
Detailed description of the invention
Fig. 1 is pure B4The Ti of C and addition different volumes score3SiC2With the B of Si preparation4The microstructure of C base composite ceramic Photo, in which: pure B prepared by (a) corresponding comparative example 14C ceramic material；(b) B prepared by corresponding embodiment 14C base is compound Ceramic material, 9.4%Ti3SiC2+ 6.3%Si powder；(c) B prepared by corresponding embodiment 24C based composite ceramic material, 17.6%Ti3SiC2+ 11.8%Si；(d) B prepared by corresponding embodiment 34C based composite ceramic material, 25%Ti3SiC2+ 16.7%Si, illustration are its partial enlarged view.Ti is added as can be seen from Figure 13SiC2After Si, microstructure is refined, and is caused Density is improved.
Fig. 2 is addition different volumes score Ti3SiC2With the B of Si preparation4The density and open porosity of C base composite ceramic.From Fig. 2 can be seen that with Ti3SiC2With the increase of Si volume fraction, density is continuously improved, and open porosity constantly reduces.
Fig. 3 is addition different volumes score Ti3SiC2With the B of Si preparation4The mechanical property of C base composite ceramic, (a) are dimension Family name's hardness, (b) are bending strength, (c) is fracture toughness.From figure 3, it can be seen that the Vickers hardness of material, bending strength and disconnected Toughness is split with Ti3SiC2Increase with Si volume fraction and improve.
Specific embodiment
Below in conjunction with specific embodiment to technical solution of the present invention explanation for further analysis.
In following embodiments, B used4The granularity of C powder is 0.8 μm, purity 96%, Ti used3SiC2The granularity of powder is 0.5 μm, purity 98%, the granularity of Si powder used is 0.5 μm, purity 99%.
Comparative example 1
The present embodiment hot pressed sintering prepares pure B4The sintering process of C ceramic material is as follows:
Prepare the graphite jig of what a internal diameter 50mm, two matched graphite pressure heads, two Graphite pads, graphite in advance Paper；By graphite paper determine two diameter 50mm circular graphitic paper and one just cover graphite jig inner wall rectangle graphite Paper；Rectangle graphite paper is attached to graphite jig inner wall, and according to graphite pressure head/Graphite pad/graphite paper/boron carbide powder/stone The sequence of black paper/Graphite pad/graphite pressure head is assembled；
The graphite jig that assembly is completed is put into vacuum sintering funace, 10 are evacuated to sintering furnace at room temperature-1Pa Hereinafter, vacuum sintering furnace is warming up to 1850 DEG C (heating rates be 10 DEG C/min), on-load pressure is that (rate of pressure rise is 30MPa 30MPa/h), in 1850 DEG C of heat preservation 30min, 1000 DEG C, then furnace cooling are down to the rate of temperature fall of 10 DEG C/min later, and 0MPa is down to the rate of pressure reduction of 30MPa/h.
After tested, pure B obtained by the present embodiment4The open porosity of C ceramic material, microhardness, bending strength and fracture are tough Property is respectively 17.66%, 8.2GPa, 198.4MPa and 2.1MPam1/2。
Embodiment 1
The present embodiment prepares B by reaction in-situ hot pressed sintering4The sintering process of C based composite ceramic material is as follows:
Step 1: the preparation of reaction-sintered mixed-powder
According to percentage by volume, 84.3%B is weighed4C powder, 9.4%Ti3SiC2Powder and 6.3%Si powder, by three kinds Powder pours into ball grinder, and using absolute alcohol as ball-milling medium, ball milling 8h is subsequently placed at vacuum oven to being mixed thoroughly In 50 DEG C of dry 12h to get reaction-sintered mixed-powder；
Step 2: reaction in-situ hot pressed sintering
Prepare the graphite jig of what a internal diameter 50mm, two matched graphite pressure heads, two Graphite pads, graphite in advance Paper；By graphite paper determine two diameter 50mm circular graphitic paper and one just cover graphite jig inner wall rectangle graphite Paper；Rectangle graphite paper is attached to graphite jig inner wall, and according to graphite pressure head/Graphite pad/graphite paper/reaction-sintered mixed powder End/graphite paper/Graphite pad/graphite pressure head sequence is assembled；
The graphite jig that assembly is completed is put into vacuum sintering funace, 10 are evacuated to sintering furnace at room temperature-1Pa Hereinafter, vacuum sintering furnace is warming up to 1950 DEG C (heating rates be 10 DEG C/min), on-load pressure is that (rate of pressure rise is 30MPa 30MPa/h), in 1950 DEG C of heat preservation 60min, 1000 DEG C, then furnace cooling are down to the rate of temperature fall of 10 DEG C/min later, and 0MPa is down to the rate of pressure reduction of 30MPa/h.
After tested, B obtained by the present embodiment4The open porosity of C based composite ceramic material, microhardness, bending strength and disconnected Splitting toughness is respectively 9.3%, 26.1GPa, 378.3MPa and 4.5MPam1/2。
Embodiment 2
The present embodiment prepares B by reaction in-situ hot pressed sintering4The sintering process of C based composite ceramic material is as follows:
Step 1: the preparation of reaction-sintered mixed-powder
According to percentage by volume, 70.5%B is weighed4C powder, 17.6%Ti3SiC2Powder and 11.8%Si powder, by three Kind powder pours into ball grinder, and using absolute alcohol as ball-milling medium, ball milling 8h is subsequently placed at vacuum drying to being mixed thoroughly 50 DEG C of dry 12h are in case to get reaction-sintered mixed-powder；
Step 2: reaction in-situ hot pressed sintering
Prepare the graphite jig of what a internal diameter 50mm, two matched graphite pressure heads, two Graphite pads, graphite in advance Paper；By graphite paper determine two diameter 50mm circular graphitic paper and one just cover graphite jig inner wall rectangle graphite Paper；Rectangle graphite paper is attached to graphite jig inner wall, and according to graphite pressure head/Graphite pad/graphite paper/mixed powder to be sintered End/graphite paper/Graphite pad/graphite pressure head sequence is assembled；
The graphite jig that assembly is completed is put into vacuum sintering funace, 10 are evacuated to sintering furnace at room temperature-1Pa Hereinafter, vacuum sintering furnace is warming up to 1900 DEG C (heating rates be 10 DEG C/min), on-load pressure is that (rate of pressure rise is 30MPa 30MPa/h), in 1900 DEG C of heat preservation 60min, 1000 DEG C, then furnace cooling are down to the rate of temperature fall of 10 DEG C/min later, and 0MPa is down to the rate of pressure reduction of 30MPa/h.
After tested, B obtained by the present embodiment4The open porosity of C based composite ceramic material, microhardness, bending strength and disconnected Splitting toughness is respectively 3.2%, 31.3GPa, 472.1MPa and 7.1MPam1/2。
Embodiment 3
The present embodiment prepares B by reaction in-situ hot pressed sintering4The sintering process of C based composite ceramic material is as follows:
Step 1: the preparation of reaction-sintered mixed-powder
According to percentage by volume, 58.3%B is weighed4C powder, 25%Ti3SiC2Powder and 16.7%Si powder, by three kinds Powder pours into ball grinder, and using absolute alcohol as ball-milling medium, ball milling 8h is subsequently placed at vacuum oven to being mixed thoroughly In 50 DEG C of dry 12h to get reaction-sintered mixed-powder；
Step 2: reaction in-situ hot pressed sintering
Prepare the graphite jig of what a internal diameter 50mm, two matched graphite pressure heads, two Graphite pads, graphite in advance Paper；By graphite paper determine two diameter 50mm circular graphitic paper and one just cover graphite jig inner wall rectangle graphite Paper；Rectangle graphite paper is attached to graphite jig inner wall, and according to graphite pressure head/Graphite pad/graphite paper/mixed powder to be sintered End/graphite paper/Graphite pad/graphite pressure head sequence is assembled；
The graphite jig that assembly is completed is put into vacuum sintering funace, 10 are evacuated to sintering furnace at room temperature-1Pa Hereinafter, vacuum sintering furnace is warming up to 1850 DEG C (heating rates be 10 DEG C/min), on-load pressure is that (rate of pressure rise is 30MPa 30MPa/h), in 1850 DEG C of heat preservation 30min, 1000 DEG C, then furnace cooling are down to the rate of temperature fall of 10 DEG C/min later, and 0MPa is down to the rate of pressure reduction of 30MPa/h.
After tested, B obtained by the present embodiment4The open porosity of C based composite ceramic material, microhardness, bending strength and disconnected Splitting toughness is respectively 1.0%, 34.4GPa, 516.7MPa and 7.8MPam1/2。
Embodiment 4
The present embodiment prepares B by reaction in-situ hot pressed sintering4The sintering process of C based composite ceramic material is as follows:
Step 1: the preparation of reaction-sintered mixed-powder
According to percentage by volume, 70.5%B is weighed4C powder, 17.6%Ti3SiC2Powder and 11.8%Si powder, by three Kind powder pours into ball grinder, and using absolute alcohol as ball-milling medium, ball milling 8h is subsequently placed at vacuum drying to being mixed thoroughly 50 DEG C of dry 12h are in case to get reaction-sintered mixed-powder；
Step 2: reaction in-situ hot pressed sintering
Prepare the graphite jig of what a internal diameter 50mm, two matched graphite pressure heads, two Graphite pads, graphite in advance Paper；By graphite paper determine two diameter 50mm circular graphitic paper and one just cover graphite jig inner wall rectangle graphite Paper；Rectangle graphite paper is attached to graphite jig inner wall, and according to graphite pressure head/Graphite pad/graphite paper/mixed powder to be sintered End/graphite paper/Graphite pad/graphite pressure head sequence is assembled；
The graphite jig that assembly is completed is put into vacuum sintering funace, 10 are evacuated to sintering furnace at room temperature-1Pa Hereinafter, vacuum sintering furnace is warming up to 1850 DEG C (heating rates be 10 DEG C/min), on-load pressure is that (rate of pressure rise is 30MPa 30MPa/h), in 1850 DEG C of heat preservation 30min, 1000 DEG C, then furnace cooling are down to the rate of temperature fall of 10 DEG C/min later, and 0MPa is down to the rate of pressure reduction of 30MPa/h.
After tested, B obtained by the present embodiment4The open porosity of C based composite ceramic material, microhardness, bending strength and disconnected Splitting toughness is respectively 7.6%, 25.6GPa, 401MPa and 5.9MPam1/2。
Each embodiment result is summarized:
The present invention utilizes B4C and Ti3SiC2And Si reaction in-situ generates TiB2And SiC, obtain high-compactness, resultant force Learn function admirable, can linear cutter B4C-TiB2- SiC three-phase composite ceramics.Ti3SiC2B is being effectively reduced with Si4C ceramics Sintering temperature and improve material density while, pass through reaction in-situ generate TiB2Mutually there is crystal grain with SiC Strengthening and Toughening It is tiny and in B4The characteristics of being evenly distributed in C matrix effectively inhibits B4The crystal grain of C grows up, improves the comprehensive mechanical property of material Energy.In addition, B4C-TiB2- SiC three-phase composite ceramics conductivity with higher, can carry out Wire-cut Electrical Discharge Machining.Preferred Add 25%Ti3SiC2When powder and 16.7%Si powder, 1850 DEG C of hot pressed sintering temperature, sintering pressure 30MPa, soaking time When 30min, the consistency and comprehensive mechanical property of composite ceramics are higher.It is excellent, high that the present invention can prepare comprehensive mechanical property The B of conductivity4C based composite ceramic material, solves B4One technical problem of the preparation of C base composite ceramic and application.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.

Claims (9)

1. a kind of boron carbide base composite ceramic material, it is characterised in that: the composite ceramic material is by B4C、Ti3SiC2And Si It is prepared through vacuum hot-pressed sintered technology.
2. boron carbide base composite ceramic material according to claim 1, it is characterised in that: the original of the composite ceramic material Material is Ti by the proportion of percentage by volume3SiC2Powder 9.4-25%, Si powder 6.3-16.7%, surplus B4C powder.
3. a kind of preparation process of boron carbide base composite ceramic material as claimed in claim 1 or 2, which is characterized in that including as follows Step:
Step 1: the preparation of reaction-sintered mixed-powder
Amount weighs B according to the ratio4C powder, Ti3SiC2Powder and Si powder, are poured into the ball grinder of planetary ball mill, are with absolute alcohol Ball-milling medium is milled to and is mixed thoroughly, then is placed in a vacuum drying oven dry to get reaction-sintered mixed-powder；
Step 2: reaction in-situ hot pressed sintering
The reaction-sintered mixed-powder is assembled in graphite jig, then the graphite jig that assembly is completed is put into vacuum hotpressing In sintering furnace, 10 are evacuated to sintering furnace at room temperature-1Pa is hereinafter, being warming up to 1850-1950 DEG C of sintering temperature and keeping the temperature 30- 60min, on-load pressure 30-50MPa cool down after heat preservation, are depressured to get B4C based composite ceramic material.
4. according to the method described in claim 3, it is characterized by: the B4The granularity of C powder is 0.5-5 μm, and purity is not less than 96%；The Ti3SiC2The granularity of powder is 0.5-10 μm, and purity is not less than 98%: the granularity of the Si powder is 0.5-20 μm, pure Degree is not less than 98%.
5. according to the method described in claim 3, it is characterized by: the revolving speed of the planetary ball mill is 150- in step 1 250rpm, ball grinder material are nylon, and Material quality of grinding balls is agate, Ball-milling Time 6-10h.
6. according to the method described in claim 3, it is characterized by: the temperature of the drying is 40-60 DEG C, time in step 1 For 8-12h.
7. according to the method described in claim 3, it is characterized by: in step 2, during hot pressed sintering, heating rate 5- 15 DEG C/min, rate of pressure rise 20-30MPa/h.
8. according to the method described in claim 3, it is characterized by: the mode of the cooling is furnace cooling in step 2, or Person is first to be down to 1000 DEG C, then furnace cooling again with the rate of temperature fall of 10 DEG C/min.
9. according to the method described in claim 3, it is characterized by: the mode of the decompression is with 30MPa/h in step 2 Rate of pressure reduction is down to 0MPa.
CN201910552810.0A 2019-06-25 2019-06-25 A kind of boron carbide base composite ceramic material and its preparation process Pending CN110256081A (en)

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Application publication date: 20190920