CN110342936A - One kind is with CeO2Modified B4The fast preparation method of C ceramic block - Google Patents

One kind is with CeO2Modified B4The fast preparation method of C ceramic block Download PDF

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CN110342936A
CN110342936A CN201910599395.4A CN201910599395A CN110342936A CN 110342936 A CN110342936 A CN 110342936A CN 201910599395 A CN201910599395 A CN 201910599395A CN 110342936 A CN110342936 A CN 110342936A
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powder
ceo
ball
ceramic block
modified
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CN110342936B (en
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程兴旺
张朝晖
宋奇
尹仕攀
胡正阳
王浩
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Beijing University of Technology
Beijing Institute of Technology BIT
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Beijing University of Technology
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Abstract

The present invention relates to one kind with CeO2Modified B4The fast preparation method of C ceramic block belongs to armor facing field of material preparation.The preparation method is that: by B4C、Ti3SiC2, Si and CeO2Sphere of powder mill, which is uniformly mixed, obtains mixed-powder；Discharge plasma sintering system sintered compound powder is used again, obtains the B4C ceramic block.The electric field of discharge plasma sintering can clean and activate during the sintering process the particle surface of the mixed-powder, carry out mixed-powder densification process at a relatively low sintering temperature, greatly shorten sintering time, the B being sintered4C ceramic block consistency may be up to 99.9%, and have the generation of the second phase, and comprehensive mechanical property is good, and bending strength reaches as high as 497.6MPa, can be applied to protective materials field.

Description

One kind is with CeO2Modified B4The fast preparation method of C ceramic block
Technical field
The present invention relates to one kind with CeO2Modified B4The fast preparation method of C ceramic block, specifically, being related to one kind With Ti3SiC2, Si and CeO2For the B of sintering aid4The fast preparation method of C ceramic block belongs to armor facing material preparation neck Domain.
Background technique
Boron carbide (B4C) there are many excellent physics, chemistry and mechanical properties, such as: high hardness (35GPa~ 45GPa, the hard material of third, hardness are only second to diamond and c-BN in the world), lower density (2.52g/cm3), it is higher molten Point (2450 DEG C), good chemical stability, good inoxidizability and corrosion resistance, high temperature thermoelectric and high neutron absorption Scattering section etc..B4The lattice structure of C is rhombohedral structure, and lattice structure belongs to n5 3d-R3mDot matrix group, and mutually with covalent Bond is closed.Due to these characteristics, B4The purposes of C is extremely extensive, is almost related to each department and the modern technologies of national economy Every field, apply such as lightweight armor, wear-resistant material and in terms of.
But due to B4High-melting-point, strong covalent bond structure (covalent bond ratio is 90% or more), the oxide on surface of C is rich Oxygen layer (B2O3) and low self-diffusion coefficient these characteristics, result in B4C has poor sintering character, is sintered B4Needed for C Sintering temperature it is very high.Pure B4Even if C is sintered at a high temperature of close to fusing point, material transport also seldom occurs, is difficult Obtain the B of consistency4C sintered body, and high temperature is easy to appear the phenomenon that abnormal grain! growth and surface are melted, and can generate to performance Detrimental effect.Using conventional sintering means, such as pressureless sintering, hot pressed sintering and microwave sintering, it is more difficult to obtain high-densit The B of degree4C ceramic block, required sintering condition (sintering time of high sintering temperature, length) is for the B of acquisition4C ceramic block Performance adversely affect；Even if there is the addition of sintering aid, sintering temperature is still higher, and sintering time is equally also longer.
The prior art studies have shown that pressureless sintering (2300 DEG C~2375 DEG C) more difficult acquisition under higher sintering temperature Complete fully dense sintered product obtains fine and close B even if sintering aid is added4C ceramics are also required to the high temperature higher than 2000 DEG C, Such as Roy etc. has only prepared the B that consistency is 93% at 2300 DEG C~2375 DEG C4C ceramics；No pressure such as M.Mashhadi The method of sintering has obtained finer and close B at 2050 DEG C~2150 DEG C by the Al of addition 0%~5% as sintering aid4C Ceramics.Although hot pressed sintering etc. can obtain dense sintering product, sintering required temperature is high (>=2100 DEG C), and the time is long (>=1h), such as D.Jianxin et al. is not under conditions of adding sintering aid, it is obtained at 2100 DEG C using hot pressed sintering means The B that consistency is 98.5%4C ceramics；H.W.Kim et al. passes through addition 0%~10% using the means of hot pressed sintering Al2O3As sintering aid, it is 2000 DEG C in sintering temperature, almost fine and close B has been obtained under conditions of sintering time 1h4C pottery Porcelain.
Therefore how in the interior B for obtaining high-compactness of low-temperature short-time4C sintered body is that current scholars are of concern Problem and B4C ceramic field has a particularly significant problem to be solved.
Summary of the invention
In view of this, the object of the present invention is to provide one kind with CeO2Modified B4The fast preparation method of C ceramic block, The method uses discharge plasma sintering technique, and adds Ti3SiC2Powder, Si powder and CeO2Powder, the quality of three kinds of powders The 1%~10% of the total powder quality of the sum of score Zhan is used as sintering aid, to realize B during the sintering process4C ceramic block Low temperature quickly controllable low cost preparation；The method can reduce B4C ceramic sintering temperature (≤1900 DEG C), greatly shortens sintering Time (≤30min) improves consistency, improves material comprehensive mechanical property, is ceramic material in the following composite protective material Ideal chose.
The purpose of the present invention is realized by the following technical scheme.
One kind is with CeO2Modified B4The fast preparation method of C ceramic block, the method comprises the following steps:
(1) by B4C powder, Ti3SiC2Powder, Si powder and CeO2Powder is added in ball grinder, is uniformly mixed and obtains mixing mud, ball Mill, it is dry, obtain mixed-powder；
It is matched according to following equation (1), Ti3SiC2The ratio between amount of substance of powder and Si powder is 2:5,
3B4C+2Ti3SiC2+5Si→6TiB2+7SiC (1)；
Ti3SiC2Powder and Si powder quality sum and B4The mass ratio of C silty amount is 1:(11.25~495), preferably Ti3SiC2 Powder and Si powder quality sum and B4The mass ratio of C silty amount is 1:(11.25~95)；
CeO2Powder and B4The mass ratio of C powder is 1:(11.25~495), preferably CeO2Powder and B4The mass ratio of C powder is 1: (11.25~95)；
Ti3SiC2Powder and Si powder quality sum and CeO2The mass ratio of silty amount is 1:(0.25~4)；
It is preferred that B4Partial size≤10 μm of C powder；It is preferred that Ti3SiC2The partial size of powder≤200 mesh；It is preferred that partial size≤10 μm of Si powder； It is preferred that CeO2Partial size≤10 μm of powder；
It is preferred that ball milling parameter are as follows: ball-milling medium is dehydrated alcohol；Ratio of grinding media to material is (1~5): 1；Drum's speed of rotation is 100r/ Min~500r/min, Ball-milling Time are 0.5h~6h；
It is preferred that abrading-ball is (0.1~10) by mass ratio: 1 big agate ball and small agate ball form, the diameter of big agate ball For 10mm~30mm, the diameter of small agate ball is 1mm~5mm；
It is preferred that the drying process are as follows:
Mixing mud after the completion of ball milling is first carried out to the dry 0.2h~2.5h of revolving evaporation in vacuo at 60 DEG C~80 DEG C, After to ball-milling medium volatilization, dry 0.5h~1h at 30 DEG C~80 DEG C；
It is preferred that the vacuum drying uses vacuum rotary evaporator, revolving speed is 20r/min~100r/min；
(2) mixed-powder is sintered using discharge plasma sintering system, is obtained of the present invention One kind is with CeO2Modified B4C ceramic block.
Wherein, sintering process are as follows:
In initial depression < 15Pa, initial pressure is under 0.2MPa~1MPa, with the heating of 100 DEG C/min~200/min Rate heats up；When temperature rises to 700 DEG C~900 DEG C, adjusting heating rate is 70 DEG C/min~150 DEG C/min；Work as temperature When degree rises to 1400 DEG C~1850 DEG C and vacuum degree < 15Pa, adjusting heating rate is 30/min~50 DEG C/min, and adds simultaneously Pressure rises to 1450 DEG C~1900 DEG C, after pressure reaches 50MPa~100MPa to temperature, and heat-insulation pressure keeping 1min~15min obtains this Described one kind of invention is with CeO2Modified B4C ceramic block；Then it keeps pressure constant, cools to 900 DEG C with the furnace hereinafter, unloading Except pressure, 100 DEG C or less taking-ups are cooled to the furnace, clean, it is dry.
Beneficial effect
1. the present invention provides one kind with CeO2Modified B4The fast preparation method of C ceramic block, the method are selected B4C powder, Ti3SiC2Powder, Si powder and CeO2The mixed-powder of powder is raw material, is sintered using discharge plasma sintering system, electricity Field can clean and activate during the sintering process the particle surface of the mixed-powder, make mixed-powder densification process lower (1450 DEG C~1900 DEG C) are carried out under sintering temperature, substantially reduce sintering time (≤30min), the B being sintered4C ceramics Block consistency may be up to 99.9%, and have the generation of the second phase, and comprehensive mechanical property is good, can be applied to protective materials neck Domain；
2. the present invention provides one kind with CeO2Modified B4The fast preparation method of C ceramic block, what the method was added A small amount of Ti3SiC2Powder, Si powder and CeO2Powder is as sintering aid；Ti3SiC2Powder and Si powder and excessive B4The reaction of C powder, generation Second phase TiB2And TiC is advantageous to the performance of ceramics, CeO2Powder and excessive B4The reaction of C powder, generates second containing rare earth element Phase makes the B obtained using the method4C ceramic block bending strength may be up to 497.6MPa, and fracture toughness is reachable 4.90MPa·m0.5；
3. the present invention provides one kind with CeO2Modified B4The fast preparation method of C ceramic block, the method are simply easy Operation, short preparation period is practical, is conducive to industrialized production.
Detailed description of the invention
Fig. 1 is one kind made from Examples 1 to 3 with CeO2Modified B4The fine and close angle value of C ceramic block.
Fig. 2 is one kind made from Examples 1 to 3 with CeO2Modified B4The Fracture Toughness of C ceramic block.
Fig. 3 is one kind made from Examples 1 to 3 with CeO2Modified B4The bending strength value of C ceramic block.
Specific embodiment
Detailed elaboration is made to the present invention in the following with reference to the drawings and specific embodiments.
B described in following embodiment4C powder is purchased from Shanghai Xian Xin new material Science and Technology Ltd., and average grain diameter is 10 μm, Purity is 99.9%.
The Ti3SiC2Powder is purchased from Shanghai Xian Xin new material Science and Technology Ltd., and average grain diameter is 200 mesh, and purity is 99.9%；
The Si powder is purchased from Aladdin biochemical technology limited liability company, and average grain diameter is 10 μm, purity 99.9%.
The CeO2Powder is purchased from Aladdin biochemical technology limited liability company, and average grain diameter is 10 μm, purity 99.9%.
The dehydrated alcohol is produced by Tong Guang fine chemistry industry company, Beijing.
The actual density is according in national standard GB-T 25995-2010 " fine ceramics density and apparent porosity test method " Defined method carries out.
The calculation formula of the consistency D are as follows: D=ρIt is practical/ρIt is theoretical× 100%, wherein ρIt is practicalIndicate actual density, ρIt is theoreticalTable Show theoretical density.
The fracture toughness test carries out on universal testing machine (instron 5985), using the method for single side notched beam Fracture toughness is surveyed, each sample testing five times is averaged the actual crack toughness value as sample.
The bending strength test carries out on universal testing machine (instron 5985), using 3 points of curved method lateral bendings Qu Qiangdu, each sample testing five times are averaged the actual flexion intensity value as sample.
Embodiment 1
One kind is with CeO2Modified B4The fast preparation method of C ceramic block, the method comprises the following steps:
(1) by 90g B4C powder, 5.888g Ti3SiC2Powder, 2.112g Si powder and 2g CeO2Ball is added in the mixed-powder of powder In the ball grinder of grinding machine, and abrading-ball and excessive dehydrated alcohol is added by ratio of grinding media to material 1:1；Under the revolving speed of 150r/min, ball milling 3h is uniformly mixed and obtains mixing mud；The mixing mud is poured into vacuum rotary evaporator, is 40r/min, water in revolving speed Bath temperature turns to steam 2.5h under the conditions of being 60 DEG C, after volatilizing to ball-milling medium, obtains mixed-powder precursor；Before mixed-powder Body is put into electric heating constant-temperature blowing drying box, and dry 1h, obtains mixed-powder at 30 DEG C.
Wherein, abrading-ball is made of mass ratio for the big agate ball of 0.1:1 and small agate ball, and the diameter of big agate ball is 10mm, the diameter of small agate ball are 1mm.
(2) 100g mixed-powder is put into the cylindrical graphite mold that internal diameter is 25mm, then described in being wrapped up with asbestic blanket Graphite jig is put into discharge plasma sintering system (SPS-3.20-MV, SUMITOMO CHEMICAL coal mining industry Co., Ltd.), setting Initial depression is 2Pa, initial pressure 0.2MPa in the furnace chamber of discharge plasma sintering system, with the heating of 100 DEG C/min Rate heats up, and when temperature rises to 700 DEG C, adjusting heating rate is 70 DEG C/min；When temperature rises to 1400 DEG C and vacuum When degree is 5Pa, adjusting heating rate is 30 DEG C/min, and is pressurizeed simultaneously, rises to 1450 DEG C, after pressure reaches 100MPa to temperature, Heat-insulation pressure keeping 10min；Then it first keeps pressure constant, cools to 800 DEG C with the furnace, removal pressure, then cool to 70 DEG C with the furnace, it obtains To one kind of the present invention with CeO2Modified B4C ceramic block takes out, and first uses deionized water, cleans institute using ethyl alcohol afterwards The surface of ceramic block is stated, sample is made after dry.
One kind is made with CeO in the present embodiment2Modified B4The sample of C ceramic block is tested, and obtains test result such as Shown in Fig. 1~3, specific data are as follows:
1) B4The consistency of C ceramic block is 97.7%；
2) B4The fracture toughness of C ceramic block is 4.90MPam0.5；
3) B4The bending strength of C ceramic block is 497.6MPa.
Embodiment 2
One kind is with CeO2Modified B4The fast preparation method of C ceramic block, the method comprises the following steps:
(1) by 92.5g B4C powder, 1.104g Ti3SiC2Powder, 0.396g Si powder and 6g CeO2The mixed-powder of powder is added In the ball grinder of ball mill, and abrading-ball and excessive dehydrated alcohol is added by ratio of grinding media to material 3:1；Under the revolving speed of 300r/min, ball 2h is ground, is uniformly mixed and obtains mixing mud；The mixing mud is poured into vacuum rotary evaporator, revolving speed be 70r/min, Bath temperature turns to steam 1h under the conditions of being 70 DEG C, after volatilizing to ball-milling medium, obtains mixed-powder precursor；Before mixed-powder Body is put into electric heating constant-temperature blowing drying box, and dry 0.7h, obtains mixed-powder at 50 DEG C.
Wherein, abrading-ball is made of mass ratio for the big agate ball of 1:1 and small agate ball, and the diameter of big agate ball is 10mm, The diameter of small agate ball is 5mm.
(2) 100g mixed-powder is put into the cylindrical graphite mold that internal diameter is 25mm, then described in being wrapped up with asbestic blanket Graphite jig is put into discharge plasma sintering system (SPS-3.20-MV, SUMITOMO CHEMICAL coal mining industry Co., Ltd.), setting Initial depression is 5Pa, initial pressure 0.5MPa in the furnace chamber of discharge plasma sintering system, with the heating of 150 DEG C/min Rate heats up, and when temperature rises to 800 DEG C, adjusting heating rate is 100 DEG C/min；When temperature rises to 1600 DEG C and vacuum When degree is 10Pa, adjusting heating rate is 40 DEG C/min, and is pressurizeed simultaneously, rises to 1650 DEG C, after pressure reaches 80MPa to temperature, Heat-insulation pressure keeping 15min；Then it first keeps pressure constant, cools to 850 DEG C with the furnace, removal pressure, then cool to 80 DEG C with the furnace, it obtains To one kind of the present invention with CeO2Modified B4C ceramic block takes out, and first uses deionized water, cleans institute using ethyl alcohol afterwards The surface of ceramic block is stated, sample is made after dry.
One kind is made with CeO in the present embodiment2Modified B4The sample of C ceramic block is tested, and obtains test result such as Shown in Fig. 1~3, specific data are as follows:
1) B4The consistency of C ceramic block is 98.6%；
2) B4The fracture toughness of C ceramic block is 4.79MPam0.5；
3) B4The bending strength of C ceramic block is 485.8MPa.
Embodiment 3
One kind is with CeO2Modified B4The fast preparation method of C ceramic block, the method comprises the following steps:
(1) by 95g B4C powder, 2.944g Ti3SiC2Powder, 1.056g Si powder and 1g CeO2Ball is added in the mixed-powder of powder In the ball grinder of grinding machine, and abrading-ball and excessive dehydrated alcohol is added by ratio of grinding media to material 5:1；Under the revolving speed of 500r/min, ball milling 0.5h is uniformly mixed and obtains mixing mud；The mixing mud is poured into vacuum rotary evaporator, is 100r/ in revolving speed Min, bath temperature turn to steam 0.2h under the conditions of being 80 DEG C, after volatilizing to ball-milling medium, obtain mixed-powder precursor；It will mixing Powder precursor is put into electric heating constant-temperature blowing drying box, and dry 0.5h, obtains mixed-powder at 80 DEG C.
Wherein, abrading-ball is made of mass ratio for the big agate ball of 10:1 and small agate ball, and the diameter of big agate ball is 30mm, The diameter of small agate ball is 5mm.
(2) 100g mixed-powder is put into the cylindrical graphite mold that internal diameter is 25mm, then described in being wrapped up with asbestic blanket Graphite jig is put into discharge plasma sintering system (SPS-3.20-MV, SUMITOMO CHEMICAL coal mining industry Co., Ltd.), setting Initial depression is 10Pa, initial pressure 1MPa in the furnace chamber of discharge plasma sintering system, with the heating speed of 200 DEG C/min Rate heats up, and when temperature rises to 900 DEG C, adjusting heating rate is 150 DEG C/min；When temperature rises to 1850 DEG C and vacuum degree When for 14Pa, adjusting heating rate is 50 DEG C/min, and is pressurizeed simultaneously, rises to 1900 DEG C, after pressure reaches 50MPa to temperature, protects Warm pressure maintaining 3min；Then it first keeps pressure constant, cools to 890 DEG C with the furnace, removal pressure, then cool to 90 DEG C with the furnace, it obtains One kind of the present invention is with CeO2Modified B4C ceramic block takes out, and first uses deionized water, afterwards using described in ethyl alcohol cleaning Sample is made after dry in the surface of ceramic block.
One kind is made with CeO in the present embodiment2Modified B4The sample of C ceramic block is tested, and obtains test result such as Shown in Fig. 1~3, specific data are as follows:
1) B4The consistency of C ceramic block is 99.9%；
2) B4The fracture toughness of C ceramic block is 4.65MPam0.5；
3) B4The bending strength of C ceramic block is 477.2MPa.
The present invention includes but is not limited to above embodiments, it is all carried out under the principle of spirit of that invention it is any equivalent Replacement or local improvement, all will be regarded as within protection scope of the present invention.

Claims (10)

1. one kind is with CeO2Modified B4The fast preparation method of C ceramic block, it is characterised in that: the method comprises the following steps:
(1) by B4C powder, Ti3SiC2Powder, Si powder and CeO2Powder is added in ball grinder, is uniformly mixed and obtains mixing mud, and ball milling is done It is dry, obtain mixed-powder；
Wherein, Ti3SiC2The ratio between amount of substance of powder and Si powder is 2:5；Ti3SiC2Powder and Si powder quality sum and B4C silty amount Mass ratio be 1:(11.25~495)；CeO2Powder and B4The mass ratio of C powder is 1:(11.25~495)；Ti3SiC2Powder and Si powder Quality sum and CeO2The mass ratio of silty amount is 1:(0.25~4)；
(2) mixed-powder is sintered using discharge plasma sintering system, obtains one kind with CeO2Modified B4C ceramic block.
2. one kind according to claim 1 is with CeO2Modified B4The fast preparation method of C ceramic block, it is characterised in that: In step (1): Ti3SiC2Powder and Si powder quality sum and B4The mass ratio of C silty amount is 1:(11.25~95).
3. one kind according to claim 1 is with CeO2Modified B4The fast preparation method of C ceramic block, it is characterised in that: In step (1): CeO2Powder and B4The mass ratio of C powder is 1:(11.25~95).
4. one kind according to claim 1 is with CeO2Modified B4The fast preparation method of C ceramic block, it is characterised in that: In step (1): Ti3SiC2Powder and Si powder quality sum and B4The mass ratio of C silty amount is 1:(11.25~95), CeO2Powder and B4C The mass ratio of powder is 1:(11.25~95).
5. one kind according to claim 1 is with CeO2Modified B4The fast preparation method of C ceramic block, it is characterised in that: In step (1): B4Partial size≤10 μm of C powder；Ti3SiC2The partial size of powder≤200 mesh；Partial size≤10 μm of Si powder；CeO2The grain of powder Diameter≤10 μm.
6. one kind according to claim 1 is with CeO2Modified B4The fast preparation method of C ceramic block, it is characterised in that: In step (1): ball milling parameter are as follows: ball-milling medium is dehydrated alcohol；Ratio of grinding media to material is (1~5): 1；Drum's speed of rotation is 100r/min ~500r/min, Ball-milling Time are 0.5h~6h；Abrading-ball is (0.1~10): 1 big agate ball and small agate ball group by mass ratio At the diameter of big agate ball is 10mm~30mm, and the diameter of small agate ball is 1mm~5mm.
7. one kind according to claim 1 is with CeO2Modified B4The fast preparation method of C ceramic block, it is characterised in that: In step (1): the drying process are as follows: it is true that the mixing mud after the completion of ball milling is first carried out to revolving evaporation at 60 DEG C~80 DEG C Dry 0.2h~the 2.5h of sky, after volatilizing to ball-milling medium, dry 0.5h~1h at 30 DEG C~80 DEG C.
8. one kind according to claim 7 is with CeO2Modified B4The fast preparation method of C ceramic block, it is characterised in that: In step (1): the vacuum drying uses vacuum rotary evaporator, and revolving speed is 20r/min~100r/min.
9. one kind according to claim 1 is with CeO2Modified B4The fast preparation method of C ceramic block, it is characterised in that: In step (1): Ti3SiC2Powder and Si powder quality sum and B4The mass ratio of C silty amount is 1:(11.25~95)；CeO2Powder and B4C The mass ratio of powder is 1:(11.25~95)；
B4Partial size≤10 μm of C powder；Ti3SiC2The partial size of powder≤200 mesh；Partial size≤10 μm of Si powder；CeO2The partial size of powder≤10 μ m；
Ball milling parameter are as follows: ball-milling medium is dehydrated alcohol；Ratio of grinding media to material is (1~5): 1；Drum's speed of rotation be 100r/min~ 500r/min, Ball-milling Time are 0.5h~6h；Abrading-ball is (0.1~10): 1 big agate ball and small agate ball group by mass ratio At the diameter of big agate ball is 10mm~30mm, and the diameter of small agate ball is 1mm~5mm；
The drying process are as follows: it is dry that the mixing mud after the completion of ball milling is first carried out to revolving evaporation in vacuo at 60 DEG C~80 DEG C 0.2h~2.5h, after volatilizing to ball-milling medium, dry 0.5h~1h at 30 DEG C~80 DEG C；
The vacuum drying uses vacuum rotary evaporator, and revolving speed is 20r/min~100r/min.
10. one kind described according to claim 1~any one of 9 is with CeO2Modified B4The quick preparation side of C ceramic block Method, it is characterised in that: in step (2): sintering process are as follows: in initial depression < 15Pa, initial pressure is 0.2MPa~1MPa Under, it is heated up with 100 DEG C/min~200 DEG C/min heating rate；When temperature rises to 700 DEG C~900 DEG C, heating is adjusted Rate is 70 DEG C/min~150 DEG C/min；When temperature rises to 1400 DEG C~1850 DEG C and vacuum degree < 15Pa, heating speed is adjusted Rate is 30 DEG C/min~50 DEG C/min, and is pressurizeed simultaneously, rises to 1450 DEG C~1900 DEG C to temperature, pressure up to 50MPa~ After 100MPa, heat-insulation pressure keeping 1min~15min obtains one kind with CeO2Modified B4C ceramic block.
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