CN104529456B - Preparation method for B4C-HfB2 high-temperature eutectic in-situ composite ceramic - Google Patents
Preparation method for B4C-HfB2 high-temperature eutectic in-situ composite ceramic Download PDFInfo
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Abstract
The invention discloses a preparation method for B4C-HfB2 high-temperature eutectic in-situ composite ceramic. According to the invention, the proportion of boron carbide and hafnium boride is changed so as to prepare a uniformly distributed eutectic structure, wherein the molar content of hafnium boride is 10% to 50%. The preparation method comprises the following concrete steps: uniformly mixing boron carbide powder and hafnium boride powder, then pressing the mixed powder into a flake with a diameter of 10 mm at room temperature via cold isostatic pressing and preparing a B4C-HfB2 eutectic composite material by using an arc melting method. Compared with a traditional solid phase sintering method, the preparation method provided by the invention has the following advantages: the method is simple, a preparation cycle is short, and the prepared B4C-HfB2 composite ceramic has high density and more excellent high temperature performance. In addition, the composite ceramic has performance advantages of both HfB2 and B4C and can be used as an ultra-high temperature ceramic material.
Description
Technical field
The present invention relates to superhigh temperature ceramic material and its preparing technical field, particularly a kind of B4C-HfB2Binary eutectic is certainly
Raw composite ceramics and preparation method thereof.
Background technology
HfB2Belong to transition metal boride, used as superhigh temperature ceramic material, which has high-melting-point (3250 DEG C), height hard
The features such as degree, conductive and good heat conductivity, relatively good high-temperature oxidation resistance and shock resistance, these excellent properties make which
Can be used as high-temperature structural material, such as：The thermal protection system of high temperature electrode, burner hearth element, rocket engine and supersonic vehicle
System etc..But, single hafnium boride material is difficult densified sintering product, and self-strength and toughness is not relatively high, limits which in harshness
Application under environment.
At present, it is to improve this present situation, can be by traditional solid-phase sintering method, B4C as a kind of sintering aid, to carry
The reports such as high its consistency, Harlan J.Brown-Shaklee are due to B4C can be anti-at high temperature with transition metal oxide
Metal boride should be generated, its particle surface oxide impurity is reduced so that the consistency of hafnium boride material is improved, and grinds
B/C atomic ratios have been studied carefully to hot pressed sintering HfB2-BxThe impact of C ceramic denses degree and hot property.
In addition, Frederic Monteverde etc. think B4C can also suppress in addition to playing a part of sintering aid
The growth of hafnium boride crystal grain, obtains thinner grain structure.
But, using traditional solid-phase sintering method, required sintering temperature is higher, and manufacturing cycle is longer.It is even more important
, the B prepared by arc melting method4C-HfB2Eutectic ceramic, compared with conventional method, connection circle between phase and phase
Face is that melt-growth is composited, and boundary conformability is good, very clean, and bond strength is high, and eutectic structure is tiny, and presents
Interlaced tridimensional network so that B4C-HfB2Eutectic ceramic obtains more excellent high-temperature behavior.
The content of the invention
The technical problem to be solved is：For existing boron carbide and hafnium boride composite ceramic material and its biography
The not enough and defect of system solid-phase sintering method, there is provided a kind of preparation method is simple, short preparation period, and it is fine and close to effectively improve which
The method of degree, makes the B for preparing4C-HfB2The performance of the spontaneous composite ceramics of high temperature eutectic is produced near or above conventional method
Product.
The present invention solves its technical problem and adopts following technical scheme：
The B that the present invention is provided4C-HfB2The preparation method of the spontaneous composite ceramics of high temperature eutectic, specifically：By boron carbide powder
Be respectively 50%-90% and 10%-50% dispensings with hafnium boride massage your content, the dispensing Jing after ball milling mixing is uniform
Isostatic cool pressing slabbing under room temperature, then sample Flashmelt in the environment of argon gas, Ran Housui are made by arc-melting furnace electric discharge
In arc-melting furnace, copper coin cools down rapidly acquisition B4C-HfB2The spontaneous composite ceramics of high temperature eutectic.
The purity of the boron carbide powder is 98%, and particle diameter is 1-10 μm.
The purity of the boronation hafnium powder is 99%.
The ball mill mixing technique, uses ball grinder, the zirconia ball of polyethylene, ball milling 1h.
The sheet is isostatic cool pressing at room temperature into a diameter of 10mm, the cylinder of a height of 5mm.
In the arc-melting furnace, power output of the argon pressure control in 60kPa, Flashmelt is 20%-40%,
Electric current is 120-250A.
The cooling procedure is carried out on copper coin in arc-melting furnace, and hydraulic pressure during rapid cooling is 0.06-
0.07MPa。
B prepared by the said method that the present invention is provided4C-HfB2The spontaneous composite ceramics of high temperature eutectic, which is making superhigh temperature
Application in ceramic article.
It is of the invention compared with traditional solid-phase sintering method, with following major advantage：
1. preparation method is simple, and required manufacturing cycle is shorter.
2. B prepared by4C-HfB2Eutectic composite ceramics linkage interface between phase and phase is that melt-growth is composited,
Boundary conformability is good, and boundary is very clean, and bond strength is high.
3. B prepared by4C-HfB2Eutectic composite ceramics eutectic structure is tiny, and interlaced three-dimensional netted knot is presented
Structure, even structure.
4. B prepared by4C-HfB2Eutectic composite ceramics consistency is high, with more excellent mechanical performance and thermally-stabilised
Property.
Description of the drawings
Fig. 1 is B of the present invention4C powder and HfB2Powder of the powder Jing after ball mill is well mixed at room temperature isostatic cool pressing into
Sheet, then in arc-melting furnace Flashmelt, cooling obtained in sample XRD spectrum.
Fig. 2 is B of the present invention4C powder and 50 (mol%) HfB2Powder of the powder Jing after ball mill is well mixed is at room temperature
Isostatic cool pressing slabbing, then in arc-melting furnace Flashmelt, cooling obtained in sample BSE collection of illustrative plates.
Fig. 3 is B of the present invention4C powder and 35 (mol%) HfB2Powder of the powder Jing after ball mill is well mixed is at room temperature
Isostatic cool pressing slabbing, then in arc-melting furnace Flashmelt, cooling obtained in sample BSE collection of illustrative plates.
Fig. 4 is B of the present invention4C powder and 22 (mol%) HfB2Powder of the powder Jing after ball mill is well mixed is at room temperature
Isostatic cool pressing slabbing, then in arc-melting furnace Flashmelt, cooling obtained in sample BSE collection of illustrative plates.
Fig. 5 is B of the present invention4C powder and 10 (mol%) HfB2Powder of the powder Jing after ball mill is well mixed is at room temperature
Isostatic cool pressing slabbing, then in arc-melting furnace Flashmelt, cooling obtained in sample BSE collection of illustrative plates.
Specific embodiment
With reference to specific case study on implementation and accompanying drawing, the invention will be further described, but does not limit the present invention.
Embodiment 1
The implementation case is a kind of B4C-HfB2The preparation method of the spontaneous composite ceramics of high temperature eutectic.
The method is：Using commercially available high-purity B4C and HfB2Powder, by mol ratio, wherein B4C powder mole contains
Measure as 50%, HfB2Molar content be 50%, using the ball grinder of polyethylene, zirconia ball is on high energy ball mill with 300
Rev/min rotating speed ball milling 1h obtain needed for powder, the then isostatic cool pressing at room temperature of the powder by ball milling mixing after uniform
Into a diameter of 10mm, high is about the sheet of 5mm, is put in arc-melting furnace, under the ar gas environment of 60kPa, by electric arc
Electric discharge, make sample Flashmelt, power output is 20-40%, and electric current is 120-250A, after with arc-melting furnace copper coin it is fast
Speed is cooled to room temperature, and hydraulic pressure is 0.06-0.07MPa.
After testing, referring to Fig. 1 and Fig. 2, the B4C-HfB2The XRD of the spontaneous composite ceramics of high temperature eutectic shows only B4C and
HfB2Diffraction maximum, have no other materials and generate.And back scattering figure also indicates that only two-phase, i.e., black is mutually B4C, Bai Xiangwei HfB2,
In addition to it is observed that the binary eutectic of distribution uniform is organized, bar-shaped HfB is also grown in a large number2Phase structure.
Embodiment 2
The implementation case is a kind of B4C-HfB2The preparation method of the spontaneous composite ceramics of high temperature eutectic.
The method is：Using commercially available high-purity B4C and HfB2Powder, by mol ratio, wherein B4C powder mole contains
Measure as 65%, HfB2Molar content be 35%, using the ball grinder of polyethylene, zirconia ball is on high energy ball mill with 300
Rev/min rotating speed ball milling 1h obtain needed for powder, the then isostatic cool pressing at room temperature of the powder by ball milling mixing after uniform
Into a diameter of 10mm, high is about the sheet of 5mm, is put in arc-melting furnace, under the ar gas environment of 60kPa, by electric arc
Electric discharge, make sample Flashmelt, power output is 20-40%, and electric current is 120-250A, after with arc-melting furnace copper coin it is fast
Speed is cooled to room temperature, and hydraulic pressure is 0.06-0.07MPa.
After testing, referring to Fig. 1 and Fig. 3, the B4C-HfB2The XRD of the spontaneous composite ceramics of high temperature eutectic shows only B4C and
HfB2Diffraction maximum, have no other materials and generate.And back scattering figure also indicates that only two-phase, i.e., black is mutually B4C, Bai Xiangwei HfB2,
In addition to it is observed that the binary eutectic of distribution uniform is organized, bar-shaped HfB is also grown on a small quantity2Phase structure.
Embodiment 3
The present embodiment is a kind of B4C-HfB2The preparation method of the spontaneous composite ceramics of high temperature eutectic.
The method is：Using commercially available high-purity B4C and HfB2Powder, by mol ratio, wherein B4C powder mole contains
Measure as 78%, HfB2Molar content be 22%, using the ball grinder of polyethylene, zirconia ball is on high energy ball mill with 300
Rev/min rotating speed ball milling 1h obtain needed for powder, the then isostatic cool pressing at room temperature of the powder by ball milling mixing after uniform
Into a diameter of 10mm, high is about the sheet of 5mm, is put in arc-melting furnace, under the ar gas environment of 60kPa, by electric arc
Electric discharge, make sample Flashmelt, power output is 20-40%, and electric current is 120-250A, after with arc-melting furnace copper coin it is fast
Speed is cooled to room temperature, and hydraulic pressure is 0.06-0.07MPa.
After testing, referring to Fig. 1 and Fig. 4, the B4C-HfB2The XRD of the spontaneous composite ceramics of high temperature eutectic shows only B4C and
HfB2Diffraction maximum, have no other materials and generate.And back scattering figure also indicates that only two-phase, i.e., black is mutually B4C, Bai Xiangwei HfB2,
And it is observed that the binary eutectic structure of distribution uniform.
Embodiment 4
The implementation case is a kind of B4C-HfB2The preparation method of the spontaneous composite ceramics of high temperature eutectic.
The method is：Using commercially available high-purity B4C and HfB2Powder, by mol ratio, wherein B4C powder mole contains
Measure as 90%, HfB2Molar content be 10%, using the ball grinder of polyethylene, zirconia ball is on high energy ball mill with 300
Rev/min rotating speed ball milling 1h obtain needed for powder, the then isostatic cool pressing at room temperature of the powder by ball milling mixing after uniform
Into a diameter of 10mm, high is about the sheet of 5mm, is put in arc-melting furnace, under the ar gas environment of 60kPa, by electric arc
Electric discharge, make sample Flashmelt, power output is 20-40%, and electric current is 120-250A, after with arc-melting furnace copper coin it is fast
Speed is cooled to room temperature, and hydraulic pressure is 0.06-0.07MPa.
After testing, referring to Fig. 1 and Fig. 5, the B4C-HfB2The XRD of the spontaneous composite ceramics of high temperature eutectic shows only B4C and
HfB2Diffraction maximum, have no other materials and generate.And back scattering figure also indicates that only two-phase, i.e., black is mutually B4C, Bai Xiangwei HfB2,
In addition to it is observed that the binary eutectic of distribution uniform is organized, also a large amount of B4The phase structure of C.
The high energy ball mill referred in above-described embodiment can adopt Retsch PM100.
Claims (4)
1. a kind of B4C-HfB2The preparation method of the spontaneous composite ceramics of high temperature eutectic, is characterized in that boron carbide powder and hafnium boride
Massage that content is respectively 50%-90% and 10%-50% dispensings, and the dispensing is cold at room temperature Jing after ball milling mixing is uniform
Isostatic pressed slabbing, then sample Flashmelt in the environment of argon gas is made by arc-melting furnace electric discharge, it is molten then as electric arc
In furnace, copper coin cools down rapidly acquisition B4C-HfB2The spontaneous composite ceramics of high temperature eutectic；
The ball mill mixing technique, uses ball grinder, the zirconia ball of polyethylene, ball milling 1h；
The sheet is isostatic cool pressing at room temperature into a diameter of 10mm, the cylinder of a height of 5mm；
In arc-melting furnace, power output of the argon pressure control in 60kPa, Flashmelt is 20%-40%, and electric current is
120-250A；
The cooling procedure is carried out on copper coin in arc-melting furnace, and hydraulic pressure during rapid cooling is 0.06-0.07MPa.
2. B according to claim 14C-HfB2The preparation method of the spontaneous composite ceramics of high temperature eutectic, it is characterised in that described
The purity of boron carbide powder is 98%, and particle diameter is 1-10 μm.
3. B according to claim 14C-HfB2The preparation method of the spontaneous composite ceramics of high temperature eutectic, it is characterised in that described
The purity of boronation hafnium powder is 99%.
4. the B that in claims 1 to 3 prepared by any claim methods described4C-HfB2The spontaneous composite ceramics of high temperature eutectic, its
Application in superhigh temperature ceramics articles for use are made.
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| CN110627504A (en) * | 2019-09-26 | 2019-12-31 | 宁波东联密封件有限公司 | Pressureless sintering preparation method of boron carbide composite material |
| CN113716965A (en) * | 2021-08-19 | 2021-11-30 | 中山市气相科技有限公司 | Binary eutectic target material and preparation method thereof |
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| CN101767996B (en) * | 2008-12-31 | 2013-01-16 | 中国科学院上海硅酸盐研究所 | Texturing boride-based ceramics and preparing method thereof |
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