CN101870586A - Amorphous and nanocrystalline Si-B-C-N ceramic composite material and preparation method thereof - Google Patents
Amorphous and nanocrystalline Si-B-C-N ceramic composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an amorphous and nanocrystalline Si-B-C-N ceramic composite material and a preparation method thereof, relating to an Si-B-C-N ceramic composite material and a preparation method thereof. The invention solves the problems of poor performance, complicated preparation process and high cost of the traditional Si-B-C-N ceramic composite material. The composite material is made of silicon powder, graphite and hexagonal boron nitride. One method comprises the steps of weighting raw materials, ball milling and mixing the raw materials, and then sintering the raw materials to obtain the composite material. Another method comprises the following steps of: after weighing the raw materials, ball milling silicon powder and one part of graphite; adding the weighed hexagonal boron nitride and residual graphite and continuously ball milling; and then sintering the mixture to obtain the composite material. The Si-B-C-N ceramic composite material has the advantages of favorable performance, simple preparation process and low cost.
Description
Technical field
The present invention relates to Si-B-C-N ceramic composite material and preparation method thereof.
Background technology
Si-B-C-N ceramic composite material is a kind of novel high temperature thermal protection struc ture material, though from being synthesized to first now the only year surplus in the of 10, because of it has that density is low, intensity is high, Young's modulus is low, good in oxidation resistance, thermal expansivity is low and superior performance such as stable use temperature height has attracted a lot of researchists' concern.But in research in the past, numerous research reports and patent lay particular emphasis on the at first synthetic organic precursor method of utilization, generate inorganic powder in slow cracking then, last refabrication stupalith, these patents are respectively US2005/0026769A1, WO9606813-A, DE4447534-A1, DE19741458-A1, DE19741459-A1, DE19741460-A1.Utilize this route synthetic non-crystalline silicon B-C-N ceramic composite material to have higher performance, but have following shortcoming: 1, organic precursor prepares the step complexity of non-crystalline silicon B-C-N ceramic composite material, technology is restive, synthetic environment is strict, each step behind raw material preservation, building-up process and synthetic organic precursor method all needs to operate under the environment of height anhydrous and oxygen-free, and building-up process is slow; 2, it is low to utilize organic precursor to prepare non-crystalline silicon B-C-N ceramic composite material productive rate, and the single resultant quantity is few, and the solid by-product of the generation in part organic synthesis process is not easy to remove; 3, cleavage method prepares and requires rate of cleavage only to be 1 ℃/minute in the Si-B-C-N ceramic process, and the cracking temperature height need reach about 1400 ℃, and each cracked amount is few, and to require be to operate under high-purity protection of inert gas, and control is difficulty comparatively; 4, the Si-B-C-N ceramic that adopts cleavage method to obtain can't be realized densification, is porous material, can not effectively satisfy actual service requirements; 5. the cost of material of organic synthesis is higher.These shortcomings have limited the large-scale application of Si-B-C-N ceramic composite material aspect engineering greatly." in-situ synthesis of SiC-BN composite ceramics " that researchists such as GuojunZhang propose is a kind of matrix material of crystalline state, and its preparation is simple, but the more amorphous Si-B-C-N ceramic composite material of its performance has big gap, poor-performing.
Summary of the invention
The objective of the invention is in order to solve existing Si-B-C-N ceramic composite material poor performance, complicated process of preparation, problem that cost is high, and amorphous and nanocrystalline Si-B-C-N ceramic composite material and preparation method thereof are provided.
Amorphous of the present invention and nanocrystalline Si-B-C-N ceramic composite material are that the ratio of 2:3:1 is that 99% ~ 99.9% silica flour, purity are that 99% ~ 99.9% graphite and purity are that 99% ~ 99.9% hexagonal boron nitride is made by purity according to the Si:C:B mol ratio, and wherein silica flour, graphite and hexagonal boron nitride particle diameter are 1 ~ 20 μ m.
The preparation method of amorphous of the present invention and nanocrystalline Si-B-C-N ceramic composite material carries out according to following steps: one, according to the Si:C:B mol ratio be the ratio of 2:3:1 to take by weighing purity be that 99% ~ 99.9% silica flour, purity are that 99% ~ 99.9% graphite and purity are 99% ~ 99.9% hexagonal boron nitride, wherein silica flour, graphite and hexagonal boron nitride particle diameter are 1 ~ 20 μ m; Two, the raw material that step 1 is taken by weighing is put into and carry out ball milling in the ball mill under argon shield, and ball material mass ratio is 5 ~ 100:1, and ball radius is 3 ~ 10mm, and the ball milling time is 1 ~ 50 hour, promptly obtains the nanocrystalline composite powder of non-crystalline state parcel; Three, the nanocrystalline composite powder of non-crystalline state parcel that obtains of step 2 carries out discharge plasma sintering or hot pressed sintering, has promptly obtained amorphous and nanocrystalline Si-B-C-N ceramic composite material.Amorphous that this method prepares and nanocrystalline Si-B-C-N ceramic composite material are after testing as can be known, the bending strength of amorphous of the present invention and nanocrystalline Si-B-C-N ceramic composite material is 310 ~ 319MPa, Young's modulus is 134 ~ 138GPa, hardness is 3.9 ~ 4.3GPa, and fracture toughness property is 3.31MPam
1/2About, the insulation in 1200 ℃ dry air of amorphous of the present invention and nanocrystalline Si-B-C-N ceramic composite material 85 hours, the matrix material oxidation weight gain is less than 0.8mg/cm
2, oxidated layer thickness＜10 μ m of this moment, (absolute humidity is 0.816g/cm at 1050 ℃ damp atmospheres
3) in the insulation 85 hours, the matrix material oxidation weight gain is less than 0.6mg/cm
2Oxidated layer thickness＜the amorphous that 21 μ m(the present invention prepare of this moment and the granular size of nanocrystalline Si-B-C-N ceramic composite material are 2 ~ 50nm), be respectively 286 ~ 289MPa and 224 ~ 228MPa 1000 ℃ and 1400 ℃ of airborne bending strengths, amorphous of the present invention and nanocrystalline Si-B-C-N ceramic composite material have excellent high-temperature oxidation resistance and resistance to elevated temperatures.
The another kind of preparation method of amorphous of the present invention and nanocrystalline Si-B-C-N ceramic composite material carries out according to following steps: one, according to the Si:C:B mol ratio be the ratio of 2:3:1 to take by weighing purity be that 99% ~ 99.9% silica flour, purity are that 99% ~ 99.9% graphite and purity are 99% ~ 99.9% hexagonal boron nitride, wherein silica flour, graphite and hexagonal boron nitride particle diameter are 1 ~ 20 μ m; Two, under argon shield, carry out ball milling after whole silica flours that step 1 taken by weighing and 2/3 graphite mix and obtain mixture, ball material mass ratio is 5 ~ 100:1, ball radius is 3 ~ 10mm, the ball milling time is 1 ~ 20 hour, the graphite of hexagonal boron nitride that step 1 takes by weighing and residue 1/3 joins and carries out ball milling in the mixture, and ball material mass ratio is 5 ~ 100:1, and ball radius is 3 ~ 10mm, the ball milling time is 1 ~ 30 hour, promptly obtains the nanocrystalline composite powder of non-crystalline state parcel; Three, the nanocrystalline composite powder of non-crystalline state parcel that obtains of step 2 carries out discharge plasma sintering or hot pressed sintering, has promptly obtained amorphous and nanocrystalline Si-B-C-N ceramic composite material.The bending strength of amorphous that this method prepares and nanocrystalline Si-B-C-N ceramic composite material can reach 420 ~ 511MPa, and Young's modulus is 130 ~ 158GPa, and hardness is 3.8 ~ 6GPa, and fracture toughness property is 4 ~ 6MPam
1/2Amorphous that present embodiment prepares and nanocrystalline Si-B-C-N ceramic composite material have excellent high-temperature oxidation resistance, and insulation is 85 hours in 1200 ℃ dry air, and the matrix material oxidation weight gain is less than 0.7mg/cm
2, the oxidated layer thickness＜amorphous that 8 μ m(the present invention prepare of this moment and the granular size of nanocrystalline Si-B-C-N ceramic composite material are 2 ~ 50nm); (absolute humidity is 0.816g/cm at 1050 ℃ damp atmospheres
3) in the insulation 85 hours, the matrix material oxidation weight gain is less than 1.7mg/cm
2, oxidated layer thickness＜22 μ m of this moment.Amorphous that present embodiment prepares and nanocrystalline Si-B-C-N ceramic composite material are respectively 370 ~ 380MPa and 357 ~ 360MPa 1000 ℃ and 1400 ℃ of airborne bending strengths, and amorphous that present embodiment prepares and nanocrystalline Si-B-C-N ceramic composite material resistance to elevated temperatures are good.
Employed raw material raw material obtained easily during amorphous of the present invention and nanocrystalline Si-B-C-N ceramic composite material prepared, cheap, simple to operate in preparation process, preparation cycle is short, preparation condition is required low, the preparation cost of amorphous of the present invention and nanocrystalline Si-B-C-N ceramic composite material is low; Si-B-C-N ceramic composite material performance of the present invention is good, is suitable for making space flight solar heat protection kernel component.
Description of drawings
Amorphous that Fig. 1 prepares for embodiment 17 and nanocrystalline Si-B-C-N ceramic composite material organize Electronic Speculum figure; The Electronic Speculum figure of the composite powder that the non-crystalline state parcel that Fig. 2 obtains for step 2 in the embodiment 38 is nanocrystalline, wherein a represents the Electronic Speculum figure of the composite powder that the non-crystalline state parcel is nanocrystalline, b represents the local Electronic Speculum figure that amplifies; 3C-SiC and BCN Electronic Speculum figure mutually in the weave construction of amorphous that Fig. 3 prepares for embodiment 39 and nanocrystalline Si-B-C-N ceramic composite material; The accumulation area Electronic Speculum figure of nano-crystalline and amorphous attitude tissue in the weave construction of amorphous that Fig. 4 prepares for embodiment 39 and nanocrystalline Si-B-C-N ceramic composite material; Amorphous that Fig. 5 prepares for embodiment 39 and nanocrystalline Si-B-C-N ceramic composite material are through surface grinding machine, cylindrical grinder and drilling machine processed ceramics exemplar figure.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: present embodiment amorphous and nanocrystalline Si-B-C-N ceramic composite material are that the ratio of 2:3:1 is that 99% ~ 99.9% silica flour, purity are that 99% ~ 99.9% graphite and purity are that 99% ~ 99.9% hexagonal boron nitride is made by purity according to the Si:C:B mol ratio, and wherein silica flour, graphite and hexagonal boron nitride particle diameter are 1 ~ 20 μ m.
The crystal formation of the silica flour in the present embodiment is a cubical, can buy from the market to obtain.
Embodiment two: the preparation method of present embodiment amorphous and nanocrystalline Si-B-C-N ceramic composite material carries out according to following steps: one, according to the Si:C:B mol ratio be the ratio of 2:3:1 to take by weighing purity be that 99% ~ 99.9% silica flour, purity are that 99% ~ 99.9% graphite and purity are 99% ~ 99.9% hexagonal boron nitride, wherein silica flour, graphite and hexagonal boron nitride particle diameter are 1 ~ 20 μ m; Two, the raw material that step 1 is taken by weighing is put into and carry out ball milling in the ball mill under argon shield, and ball material mass ratio is 5 ~ 100:1, and ball radius is 3 ~ 10mm, and the ball milling time is 1 ~ 50 hour, promptly obtains the nanocrystalline composite powder of non-crystalline state parcel; Three, the nanocrystalline composite powder of non-crystalline state parcel that obtains of step 2 carries out discharge plasma sintering or hot pressed sintering, has promptly obtained amorphous and nanocrystalline Si-B-C-N ceramic composite material.
The ball mill kind is oscillatory type ball mill or the high planetary ball mill of rotating speed in the present embodiment step 1.
The non-crystalline state that obtains in the present embodiment step 2 is wrapped up nanocrystalline composite powder in the scope of 2.4nm, there are four kinds of elements of Si-B-C-N simultaneously, and these four kinds of elements have formed the bonding of various ways such as B-C-N, Si-C, C-C, B-N, C-B, and silica flour, graphite and hexagonal boron nitride are through having reached compound on the nanoscale in this explanation present embodiment behind the ball milling.
The molar percentage of N element is 5% ~ 45% in amorphous that present embodiment prepares and the nanocrystalline Si-B-C-N ceramic composite material, the B element molar percentage be 5% ~ 45%.
Amorphous that present embodiment prepares and nanocrystalline Si-B-C-N ceramic composite material are after testing as can be known, the bending strength of the amorphous of present embodiment and nanocrystalline Si-B-C-N ceramic composite material is 310 ~ 319MPa, Young's modulus is 134 ~ 138GPa, hardness is 3.9 ~ 4.3GPa, and fracture toughness property is 3.31MPam
1/2About, the insulation in 1200 ℃ dry air of present embodiment amorphous and nanocrystalline Si-B-C-N ceramic composite material 85 hours, the matrix material oxidation weight gain is less than 0.8mg/cm
2, oxidated layer thickness＜10 μ m of this moment, (absolute humidity is 0.816g/cm at 1050 ℃ damp atmospheres
3) in the insulation 85 hours, the matrix material oxidation weight gain is less than 0.6mg/cm
2Oxidated layer thickness＜21 μ m of this moment, be respectively 286 ~ 289MPa and 224 ~ 228MPa 1000 ℃ and 1400 ℃ of airborne bending strengths, compare with room temperature strength and to have descended 8.2% and 28.0% respectively, the amorphous of present embodiment and nanocrystalline Si-B-C-N ceramic composite material have excellent high-temperature oxidation resistance and resistance to elevated temperatures.
Embodiment three: what present embodiment and embodiment two were different is: ball material mass ratio is 10 ~ 90:1 in the step 2, and ball radius is 5 ~ 8mm, and the ball milling time is 15 ~ 35 hours.Other steps and parameter are identical with embodiment two.
Embodiment four: what present embodiment and embodiment two were different is: ball material mass ratio is 50:1 in the step 2, and ball radius is 6mm, and the ball milling time is 20 hours.Other steps and parameter are identical with embodiment two.
Embodiment five: what present embodiment and embodiment two were different is: ball material mass ratio is 10:1 in the step 2, and ball radius is 8mm, and the ball milling time is 35 hours.Other steps and parameter are identical with embodiment two.
Embodiment six: what present embodiment and embodiment two were different is: ball material mass ratio is 90:1 in the step 2, and ball radius is 5mm, and the ball milling time is 15 hours.Other steps and parameter are identical with embodiment two.
Embodiment seven: what present embodiment was different with one of embodiment two to six is: the sintering condition of discharge plasma sintering is in the step 3: sintering temperature is 1400 ~ 2000 ℃, pressure is 5 ~ 50MPa, sintering atmosphere is vacuum or nitrogen, and the sintered heat insulating time is 1 ~ 20 minute.Other steps and parameter are identical with one of embodiment two to six.
Embodiment eight: what present embodiment was different with one of embodiment two to six is: the sintering condition of discharge plasma sintering is in the step 3: sintering temperature is 1600 ~ 1800 ℃, and pressure is 15 ~ 35MPa, and the sintered heat insulating time is 8 ~ 15 minutes.Other steps and parameter are identical with one of embodiment two to six.
Embodiment nine: what present embodiment was different with one of embodiment two to six is: the sintering condition of discharge plasma sintering is in the step 3: sintering temperature is 1700 ℃, and pressure is 20MPa, and the sintered heat insulating time is 12 minutes.Other steps and parameter are identical with one of embodiment two to six.
Embodiment ten: what present embodiment was different with one of embodiment two to six is: the sintering condition of discharge plasma sintering is in the step 3: sintering temperature is 1800 ℃, and pressure is 15MPa, and the sintered heat insulating time is 15 minutes.Other steps and parameter are identical with one of embodiment two to six.
Embodiment 11: what present embodiment was different with one of embodiment two to six is: the sintering condition of discharge plasma sintering is in the step 3: sintering temperature is 1600 ℃, and pressure is 35MPa, and the sintered heat insulating time is 8 minutes.Other steps and parameter are identical with one of embodiment two to six.
Embodiment 12: what present embodiment was different with one of embodiment two to 11 is: the sintering condition of hot pressed sintering is in the step 3: sintering temperature is 1400 ~ 2000 ℃, pressure is 5 ~ 50MPa, sintering atmosphere is vacuum or nitrogen, and the sintered heat insulating time is 10 ~ 60 minutes.Other steps and parameter are identical with one of embodiment two to 11.
Embodiment 13: what present embodiment was different with one of embodiment two to 11 is: the sintering condition of hot pressed sintering is in the step 3: sintering temperature is 1600 ~ 1800 ℃, and pressure is 15 ~ 35MPa, and the sintered heat insulating time is 20 ~ 50 minutes.Other steps and parameter are identical with one of embodiment two to 11.
Embodiment 14: what present embodiment was different with one of embodiment two to 11 is: the sintering condition of hot pressed sintering is in the step 3: sintering temperature is 1700 ℃, and pressure is 20MPa, and the sintered heat insulating time is 30 minutes.Other steps and parameter are identical with one of embodiment two to 11.
Embodiment 15: what present embodiment was different with one of embodiment two to 11 is: the sintering condition of hot pressed sintering is in the step 3: sintering temperature is 1800 ℃, and pressure is 15MPa, and the sintered heat insulating time is 50 minutes.Other steps and parameter are identical with one of embodiment two to 11.
Embodiment 16: what present embodiment was different with one of embodiment two to 11 is: the sintering condition of hot pressed sintering is in the step 3: sintering temperature is 1600 ℃, and pressure is 35MPa, and the sintered heat insulating time is 20 minutes.Other steps and parameter are identical with one of embodiment two to 11.
Embodiment 17: the preparation method of present embodiment amorphous and nanocrystalline Si-B-C-N ceramic composite material carries out according to following steps: one, according to the Si:C:B mol ratio be the ratio of 2:3:1 to take by weighing purity be that 99.9% silica flour, purity are that 99.9% graphite and purity are 99.9% hexagonal boron nitride, wherein silica flour, graphite and hexagonal boron nitride particle diameter are 1 ~ 20 μ m; Two, the raw material that step 1 is taken by weighing is put into and carry out ball milling in the ball mill under argon shield, and ball material mass ratio is 20:1, and ball radius is 8mm, and the ball milling time is 20 hours, promptly obtains the nanocrystalline composite powder of non-crystalline state parcel; Three, the nanocrystalline composite powder of non-crystalline state parcel that obtains of step 2 carries out hot pressed sintering, has promptly obtained amorphous and nanocrystalline Si-B-C-N ceramic composite material.
The ball mill kind is oscillatory type ball mill or the high planetary ball mill of rotating speed in the present embodiment step 1.
The non-crystalline state that obtains in the present embodiment step 2 is wrapped up nanocrystalline composite powder in the scope of 2.4nm, there are four kinds of elements of Si-B-C-N simultaneously, and these four kinds of elements have formed the bonding of various ways such as B-C-N, Si-C, C-C, B-N, C-B, and silica flour, graphite and hexagonal boron nitride are through having reached compound on the nanoscale in this explanation present embodiment behind the ball milling.
The sintering condition of hot pressed sintering is in the present embodiment step 3: sintering temperature is 1900 ℃, and pressure is 30MPa, and the sintered heat insulating time is 30 minutes.
Amorphous that present embodiment obtains and nanocrystalline Si-B-C-N ceramic composite material be organized as 6H-SiC, 3C-SiC and BCN mutually, wherein, the SiC grain-size differs less, and grain-size is all less than 1 μ m, and BCN is distributed in (as shown in Figure 1) around the SiC crystal grain mutually.The bending strength of amorphous that present embodiment obtains and nanocrystalline Si-B-C-N ceramic composite material is 312.9MPa, and Young's modulus is 136.3GPa, and hardness is 4.17GPa, and fracture toughness property is 3.31MPam
1/2Amorphous that present embodiment obtains and nanocrystalline Si-B-C-N ceramic composite material have excellent high-temperature oxidation resistance, and insulation is 85 hours in 1200 ℃ dry air, and the matrix material oxidation weight gain is less than 0.8mg/cm
2, oxidated layer thickness＜10 μ m of this moment; (absolute humidity is 0.816g/cm at 1050 ℃ damp atmospheres
3) in the insulation 85 hours, the matrix material oxidation weight gain is less than 0.6mg/cm
2, oxidated layer thickness＜21 μ m of this moment.Amorphous that present embodiment obtains and nanocrystalline Si-B-C-N ceramic composite material have excellent hot strength, be respectively 287.3MPa and 225.3MPa 1000 ℃ and 1400 ℃ of airborne bending strengths, compare with room temperature strength and descended 8.2% and 28.0% respectively.
Embodiment 18: the another kind of preparation method of present embodiment amorphous and nanocrystalline Si-B-C-N ceramic composite material carries out according to following steps: one, according to the Si:C:B mol ratio be the ratio of 2:3:1 to take by weighing purity be that 99% ~ 99.9% silica flour, purity are that 99% ~ 99.9% graphite and purity are 99% ~ 99.9% hexagonal boron nitride, wherein silica flour, graphite and hexagonal boron nitride particle diameter are 1 ~ 20 μ m; Two, under argon shield, carry out ball milling after whole silica flours that step 1 taken by weighing and 2/3 graphite mix and obtain mixture, ball material mass ratio is 5 ~ 100:1, ball radius is 3 ~ 10mm, the ball milling time is 1 ~ 20 hour, the graphite of hexagonal boron nitride that step 1 takes by weighing and residue 1/3 joins and carries out ball milling in the mixture, and ball material mass ratio is 5 ~ 100:1, and ball radius is 3 ~ 10mm, the ball milling time is 1 ~ 30 hour, promptly obtains the nanocrystalline composite powder of non-crystalline state parcel; Three, the nanocrystalline composite powder of non-crystalline state parcel that obtains of step 2 carries out discharge plasma sintering or hot pressed sintering, has promptly obtained amorphous and nanocrystalline Si-B-C-N ceramic composite material.
The ball mill kind is oscillatory type ball mill or the high planetary ball mill of rotating speed in the present embodiment step 1.
The non-crystalline state that obtains in the present embodiment step 2 is wrapped up nanocrystalline composite powder in the scope of 2.4nm, there are four kinds of elements of Si-B-C-N simultaneously, and these four kinds of elements have formed the bonding of various ways such as B-C-N, Si-C, C-C, B-N, C-B, and silica flour, graphite and hexagonal boron nitride are through having reached compound on the nanoscale in this explanation present embodiment behind the ball milling.
The molar percentage of N element is 5% ~ 45% in amorphous that present embodiment prepares and the nanocrystalline Si-B-C-N ceramic composite material, the B element molar percentage be 5% ~ 45%.
Nitrogen, the total molar content of boron are 10% ~ 90% in amorphous that present embodiment prepares and the nanocrystalline Si-B-C-N ceramic composite material.
Embodiment 19: what present embodiment and embodiment 18 were different is: when graphite and silica flour ball milling, ball material mass ratio is 10 ~ 90:1 in the step 2, and ball radius is 5 ~ 8mm, and the ball milling time is 15 ~ 35 hours.Other steps and parameter are identical with embodiment 18.
Embodiment 20: what present embodiment and embodiment 18 were different is: when graphite and silica flour ball milling, ball material mass ratio is 50:1 in the step 2, and ball radius is 5 ~ 8mm, and the ball milling time is 15 ~ 35 hours.Other steps and parameter are identical with embodiment 18.
Embodiment 21: what present embodiment and embodiment 18 were different is: when graphite and silica flour ball milling, ball material mass ratio is 90:1 in the step 2, and ball radius is 5mm, and the ball milling time is 15 hours.Other steps and parameter are identical with embodiment 18.
Embodiment 22: what present embodiment and embodiment 18 were different is: when graphite and silica flour ball milling, ball material mass ratio is 10:1 in the step 2, and ball radius is 8mm, and the ball milling time is 35 hours.Other steps and parameter are identical with embodiment 18.
Embodiment 23: what present embodiment was different with one of embodiment 18 to 22 is: in the step 2 when hexagonal boron nitride and remaining graphite ball milling, ball material mass ratio is 10:1 ~ 90:1, ball radius is 5 ~ 8mm, and the ball milling time is 5 ~ 25 hours.Other steps and parameter are identical with one of embodiment 18 to 22.
Embodiment 24: what present embodiment was different with one of embodiment 18 to 22 is: when hexagonal boron nitride and remaining graphite ball milling, ball material mass ratio is 50:1 in the step 2, and ball radius is 6mm, and the ball milling time is 20 hours.Other steps and parameter are identical with one of embodiment 18 to 22.
Embodiment 25: what present embodiment was different with one of embodiment 18 to 22 is: in the step 2 when hexagonal boron nitride and remaining graphite ball milling, ball material mass ratio is 10:1 ~ 90:1, ball radius is 5 ~ 8mm, and the ball milling time is 5 ~ 25 hours.Other steps and parameter are identical with one of embodiment 18 to 22.
Embodiment 26: what present embodiment was different with one of embodiment 18 to 22 is: when hexagonal boron nitride and remaining graphite ball milling, ball material mass ratio is 50:1 in the step 2, and ball radius is 6mm, and the ball milling time is 15 hours.Other steps and parameter are identical with one of embodiment 18 to 22.
Embodiment 27: what present embodiment was different with one of embodiment 18 to 22 is: when hexagonal boron nitride and remaining graphite ball milling, ball material mass ratio is 90:1 in the step 2, and ball radius is 5mm, and the ball milling time is 25 hours.Other steps and parameter are identical with one of embodiment 18 to 22.
Embodiment 28: what present embodiment was different with one of embodiment 18 to 27 is: the sintering condition of discharge plasma sintering is in the step 3: sintering temperature is 1400 ~ 2000 ℃, pressure is 5 ~ 50MPa, sintering atmosphere is vacuum or nitrogen, and the sintered heat insulating time is 1 ~ 20 minute.Other steps and parameter are identical with one of embodiment 18 to 27.
Embodiment 29: what present embodiment was different with one of embodiment 18 to 27 is: the sintering condition of discharge plasma sintering is in the step 3: sintering temperature is 1600 ~ 1800 ℃, pressure is 15 ~ 35MPa, and the sintered heat insulating time is 8 ~ 15 minutes.Other steps and parameter are identical with one of embodiment 18 to 27.
Embodiment 30: what present embodiment was different with one of embodiment 18 to 27 is: the sintering condition of discharge plasma sintering is in the step 3: sintering temperature is 1700 ℃, and pressure is 20MPa, and the sintered heat insulating time is 12 minutes.Other steps and parameter are identical with one of embodiment 18 to 27.
The embodiment hentriaconta-: what present embodiment was different with one of embodiment 18 to 30 is: the sintering condition of discharge plasma sintering is in the step 3: sintering temperature is 1800 ℃, and pressure is 15MPa, and the sintered heat insulating time is 15 minutes.Other steps and parameter are identical with one of embodiment 18 to 30.
Embodiment 32: what present embodiment was different with one of embodiment 18 to 30 is: the sintering condition of discharge plasma sintering is in the step 3: sintering temperature is 1600 ℃, and pressure is 35MPa, and the sintered heat insulating time is 8 minutes.Other steps and parameter are identical with one of embodiment 18 to 30.
Embodiment 33: what present embodiment was different with one of embodiment 18 to 18 to 32 is: the sintering condition of hot pressed sintering is in the step 3: sintering temperature is 1400 ~ 2000 ℃, pressure is 5 ~ 50MPa, sintering atmosphere is vacuum or nitrogen, and the sintered heat insulating time is 10 ~ 60 minutes.Other steps and parameter are identical with one of embodiment 18 to 18 to 32.
Embodiment 34: what present embodiment was different with one of embodiment 18 to 32 is: the sintering condition of hot pressed sintering is in the step 3: sintering temperature is 1600 ~ 1800 ℃, pressure is 15 ~ 35MPa, and the sintered heat insulating time is 20 ~ 50 minutes.Other steps and parameter are identical with one of embodiment 18 to 32.
Embodiment 35: what present embodiment was different with one of embodiment 18 to 32 is: the sintering condition of hot pressed sintering is in the step 3: sintering temperature is 1700 ℃, and pressure is 20MPa, and the sintered heat insulating time is 30 minutes.Other steps and parameter are identical with one of embodiment 18 to 32.
Embodiment 36: what present embodiment was different with one of embodiment 18 to 32 is: the sintering condition of hot pressed sintering is in the step 3: sintering temperature is 1800 ℃, and pressure is 15MPa, and the sintered heat insulating time is 50 minutes.Other steps and parameter are identical with one of embodiment 18 to 32.
Embodiment 37: what present embodiment was different with one of embodiment 18 to 32 is: the sintering condition of hot pressed sintering is in the step 3: sintering temperature is 1600 ℃, and pressure is 35MPa, and the sintered heat insulating time is 20 minutes.Other steps and parameter are identical with one of embodiment 18 to 32.
Embodiment 38: the another kind of preparation method of present embodiment amorphous and nanocrystalline Si-B-C-N ceramic composite material carries out according to following steps: be that the ratio of 2:3:1 claims that purity is that 99.9% silica flour, purity are that 99.9% graphite and purity are 99.9% hexagonal boron nitride according to the Si:C:B mol ratio one,, wherein silica flour, graphite and hexagonal boron nitride particle diameter are 1 ~ 20 μ m; Two, under argon shield, carry out ball milling after whole silica flours that step 1 taken by weighing and 2/3 graphite mix and obtain mixture, ball material mass ratio is 20:1, ball radius is 8mm, the ball milling time is 15 hours, the graphite of hexagonal boron nitride that step 1 takes by weighing and residue 1/3 joins and carries out ball milling in the mixture, and ball material mass ratio is 20:1, and ball radius is 8mm, the ball milling time is 5 hours, promptly obtains the nanocrystalline composite powder of non-crystalline state parcel; Three, the nanocrystalline composite powder of non-crystalline state parcel that obtains of step 2 carries out hot pressed sintering, has promptly obtained amorphous and nanocrystalline Si-B-C-N ceramic composite material.
The ball mill kind is oscillatory type ball mill or the high planetary ball mill of rotating speed in the present embodiment step 1.
Ball-milling medium is ZrO in the present embodiment step 2
2
Nitrogen, the total molar content of boron are 60% in amorphous that present embodiment prepares and the nanocrystalline Si-B-C-N ceramic composite material.
The non-crystalline state that obtains in the present embodiment step 2 is wrapped up nanocrystalline composite powder in the scope of 2.4nm, there are four kinds of elements of Si-B-C-N simultaneously, and these four kinds of elements have formed the bonding of various ways such as B-C-N, Si-C, C-C, B-N, C-B, and silica flour, graphite and hexagonal boron nitride have reached compound (as shown in Figure 2) on the nanoscale through behind the ball milling in this explanation present embodiment.
The sintering condition of hot pressed sintering is in the present embodiment step 3: sintering temperature is 1900 ℃, and pressure is 30MPa, and the sintered heat insulating time is 30 minutes, nitrogen protection, and pressure is a normal atmosphere.
Nitrogen, the total molar content of boron are 70% in amorphous that present embodiment prepares and the nanocrystalline Si-B-C-N ceramic composite material.
The bending strength of amorphous that present embodiment prepares and nanocrystalline Si-B-C-N ceramic composite material can reach 423.4MPa, and Young's modulus is 134.1GPa, and hardness is 3.89GPa, and fracture toughness property is 4.22MPam
1/2Amorphous that present embodiment prepares and nanocrystalline Si-B-C-N ceramic composite material have excellent high-temperature oxidation resistance, and insulation is 85 hours in 1200 ℃ dry air, and the matrix material oxidation weight gain is less than 0.65mg/cm
2, oxidated layer thickness＜8 μ m of this moment; (absolute humidity is 0.816g/cm at 1050 ℃ damp atmospheres
3) in the insulation 85 hours, the matrix material oxidation weight gain is less than 1.6mg/cm
2, oxidated layer thickness＜22 μ m of this moment.Amorphous that present embodiment prepares and nanocrystalline Si-B-C-N ceramic composite material are respectively 375.4MPa and 358.7MPa 1000 ℃ and 1400 ℃ of airborne bending strengths, compare with room temperature strength and to have descended 11.3% and 19.7% respectively, amorphous that present embodiment prepares and nanocrystalline Si-B-C-N ceramic composite material resistance to elevated temperatures are good.
Si-B-C-N ceramic powder not obviously difference on the microtexture pattern that embodiment 17 and embodiment 38 these two kinds of different methods obtain, but by finding behind the analysis means analysis such as solid-state nuclear magnetic resonance, both have obvious difference on the residual degree of nanocrystalline content and primitive cube silica flour, details sees Table 1, data from 1 adopt the original simple substance silica flour of the composite ceramic powder noresidue that the method for embodiment 38 obtains as can be seen.
The relative content of elemental silicon, SiC crystal and amorphous SiC in the table 1 Si-B-C-N ceramic powder
| Sample | Si, % | 6H-SiC, % | 3C-SiC, % | Amorphous SiC, |
| Embodiment | ||||
| 17 | 8.3 | 25.3 | 39.8 | 26.6 |
| Embodiment 38 | 0 | 19.1 | 36.6 | 44.3 |
Embodiment 39: what present embodiment and embodiment 38 were different is to adopt the method for plasma discharging to carry out sintering in the step 3; sintering condition is that sintering temperature is 1800 ℃; pressure is 40MPa; the sintered heat insulating time is 3 minutes; nitrogen protection, pressure are a normal atmosphere.Other steps and parameter are identical with embodiment 38.
The ball mill kind is oscillatory type ball mill or the high planetary ball mill of rotating speed in the present embodiment step 1.
Ball-milling medium is ZrO in the present embodiment step 2
2
Nitrogen, the total molar content of boron are 10% ~ 90% in amorphous that present embodiment prepares and the nanocrystalline Si-B-C-N ceramic composite material.
The non-crystalline state that obtains in the present embodiment step 2 is wrapped up nanocrystalline composite powder in the scope of 2.4nm, there are four kinds of elements of Si-B-C-N simultaneously, and these four kinds of elements have formed the bonding of various ways such as B-C-N, Si-C, C-C, B-N, C-B, and silica flour, graphite and hexagonal boron nitride are through having reached compound on the nanoscale in this explanation present embodiment behind the ball milling.
Nitrogen, the total molar content of boron are 60% in amorphous that present embodiment prepares and the nanocrystalline Si-B-C-N ceramic composite material.
The weave construction of amorphous that present embodiment prepares and nanocrystalline Si-B-C-N ceramic composite material is mainly 3C-SiC and BCN (as shown in Figure 3) mutually, the accumulation area (as shown in Figure 4) that also contains part nano-crystalline and amorphous attitude tissue simultaneously, amorphous that present embodiment prepares and nanocrystalline Si-B-C-N ceramic composite material etc. axle shape crystal be the 3C-SiC crystal, its most crystalline sizes are about 400nm, have a large amount of lattice defects such as twin in the SiC crystal, the flaky BCN crystal of layer mainly is distributed in the SiC crystal edge.The bending strength of amorphous that present embodiment prepares and nanocrystalline Si-B-C-N ceramic composite material can reach 511MPa, and Young's modulus is 157.3GPa, and hardness is 5.92GPa, and fracture toughness property is 5.64MPam
1/2Amorphous that present embodiment prepares and nanocrystalline Si-B-C-N ceramic composite material have excellent elevated temperature heat physicals, and the room temperature thermal diffusivity is 16.7mm
2/ s, the thermal diffusivity in the time of 1800 ℃ has only 4.23mm
2/ s; The mean thermal expansion coefficients of this stupalith (room temperature ~ 1600 ℃) is 3.98 * 10
-6/ ℃.Amorphous that present embodiment prepares and nanocrystalline Si-B-C-N ceramic composite material are incubated 85 hours in 1200 ℃ dry air, the matrix material oxidation weight gain is less than 0.5mg/cm
2(absolute humidity is 0.816g/cm at 1050 ℃ damp atmospheres
3) in the insulation 85 hours, the matrix material oxidation weight gain is less than 2.8mg/cm
2, the antioxidant property of amorphous that present embodiment prepares and nanocrystalline Si-B-C-N ceramic composite material is good.
The Si-B-C-N ceramic composite material that the present invention obtains not only has good mechanical, electricity, heat physical properties, also has good processability simultaneously, can adopt conventional car, mill, processing means such as mill processes, Fig. 5 successively passes through surface grinding machine, cylindrical grinder and drilling machine processed ceramics exemplar for Si-B-C-N ceramic composite material.
Claims (9)
1. amorphous and nanocrystalline Si-B-C-N ceramic composite material, it is characterized in that amorphous and nanocrystalline Si-B-C-N ceramic composite material are that the ratio of 2:3:1 is that 99% ~ 99.9% silica flour, purity are that 99% ~ 99.9% graphite and purity are that 99% ~ 99.9% hexagonal boron nitride is made by purity according to the Si:C:B mol ratio, wherein silica flour, graphite and hexagonal boron nitride particle diameter are 1 ~ 20 μ m.
2. the preparation method of amorphous as claimed in claim 1 and nanocrystalline Si-B-C-N ceramic composite material, the preparation method who it is characterized in that amorphous and nanocrystalline Si-B-C-N ceramic composite material carries out according to following steps: one, according to the Si:C:B mol ratio be the ratio of 2:3:1 to take by weighing purity be that 99% ~ 99.9% silica flour, purity are that 99% ~ 99.9% graphite and purity are 99% ~ 99.9% hexagonal boron nitride, wherein silica flour, graphite and hexagonal boron nitride particle diameter are 1 ~ 20 μ m; Two, the raw material that step 1 is taken by weighing is put into and carry out ball milling in the ball mill under argon shield, and ball material mass ratio is 5 ~ 100:1, and ball radius is 3 ~ 10mm, and the ball milling time is 1 ~ 50 hour, promptly obtains the nanocrystalline composite powder of non-crystalline state parcel; Three, the nanocrystalline composite powder of non-crystalline state parcel that obtains of step 2 carries out discharge plasma sintering or hot pressed sintering, has promptly obtained amorphous and nanocrystalline Si-B-C-N ceramic composite material.
3. the preparation method of amorphous according to claim 2 and nanocrystalline Si-B-C-N ceramic composite material is characterized in that ball material mass ratio is 10 ~ 90:1 in the step 2, and ball radius is 5 ~ 8mm, and the ball milling time is 15 ~ 35 hours.
4. according to the preparation method of claim 2 or 3 described amorphous and nanocrystalline Si-B-C-N ceramic composite material, the sintering condition that it is characterized in that discharge plasma sintering in the step 3 is: sintering temperature is 1400 ~ 2000 ℃, pressure is 5 ~ 50MPa, sintering atmosphere is vacuum or nitrogen, and the sintered heat insulating time is 1 ~ 20 minute.
5. according to the preparation method of claim 2 or 3 described amorphous and nanocrystalline Si-B-C-N ceramic composite material, the sintering condition that it is characterized in that hot pressed sintering in the step 3 is: sintering temperature is 1400 ~ 2000 ℃, pressure is 5 ~ 50MPa, sintering atmosphere is vacuum or nitrogen, and the sintered heat insulating time is 10 ~ 60 minutes.
6. the preparation method of amorphous as claimed in claim 1 and nanocrystalline Si-B-C-N ceramic composite material, the preparation method who it is characterized in that amorphous and nanocrystalline Si-B-C-N ceramic composite material carries out according to following steps: one, according to the Si:C:B mol ratio be the ratio of 2:3:1 to take by weighing purity be that 99% ~ 99.9% silica flour, purity are that 99% ~ 99.9% graphite and purity are 99% ~ 99.9% hexagonal boron nitride, wherein silica flour, graphite and hexagonal boron nitride particle diameter are 1 ~ 20 μ m; Two, under argon shield, carry out ball milling after whole silica flours that step 1 taken by weighing and 2/3 graphite mix and obtain mixture, ball material mass ratio is 5 ~ 100:1, ball radius is 3 ~ 10mm, the ball milling time is 1 ~ 20 hour, the graphite of hexagonal boron nitride that step 1 takes by weighing and residue 1/3 joins and carries out ball milling in the mixture, and ball material mass ratio is 5 ~ 100:1, and ball radius is 3 ~ 10mm, the ball milling time is 1 ~ 30 hour, promptly obtains the nanocrystalline composite powder of non-crystalline state parcel; Three, the nanocrystalline composite powder of non-crystalline state parcel that obtains of step 2 carries out discharge plasma sintering or hot pressed sintering, has promptly obtained amorphous and nanocrystalline Si-B-C-N ceramic composite material.
7. the preparation method of amorphous according to claim 6 and nanocrystalline Si-B-C-N ceramic composite material is characterized in that ball material mass ratio is 10 ~ 90:1 in the step 2, and ball radius is 5 ~ 8mm, and the ball milling time is 15 ~ 35 hours.
8. according to the preparation method of claim 6 or 7 described amorphous and nanocrystalline Si-B-C-N ceramic composite material, the sintering condition that it is characterized in that discharge plasma sintering in the step 3 is: sintering temperature is 1400 ~ 2000 ℃, pressure is 5 ~ 50MPa, sintering atmosphere is vacuum or nitrogen, and the sintered heat insulating time is 1 ~ 20 minute.
9. according to the preparation method of claim 6 or 7 described amorphous and nanocrystalline Si-B-C-N ceramic composite material, the sintering condition that it is characterized in that hot pressed sintering in the step 3 is: sintering temperature is 1400 ~ 2000 ℃, pressure is 5 ~ 50MPa, sintering atmosphere is vacuum or nitrogen, and the sintered heat insulating time is 10 ~ 60 minutes.
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