CN101456737B - Boron carbide base composite ceramic and preparation method thereof - Google Patents
Boron carbide base composite ceramic and preparation method thereof Download PDFInfo
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- CN101456737B CN101456737B CN2009100208117A CN200910020811A CN101456737B CN 101456737 B CN101456737 B CN 101456737B CN 2009100208117 A CN2009100208117 A CN 2009100208117A CN 200910020811 A CN200910020811 A CN 200910020811A CN 101456737 B CN101456737 B CN 101456737B
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Abstract
The invention discloses a boron carbide based composite ceramic and a preparation method thereof. The boron carbide based composite ceramic comprises the following compositions by weight percentage: 45 to 50 percent of boron carbide powder, 5 to 8 percent of phenolic resin, and 42 to 50 percent of metallic silicon. After the compositions are weighed, the phenolic resin is dissolved by alcohol first, and the boron carbide powder is added for mechanical ball milling to be mixed evenly; a granulator is used for granulation, and a green body with a shape of the needed product is obtained through compression molding; the compressed green body is placed into a baking oven for drying solidification; the weighed metallic silicon is added into a graphite crucible, the solidified green body is placed on the metallic silicon and is placed into a high-temperature vacuum sintering furnace for sintering along with the crucible, the sintering temperature is between 1,550 and 1,700 DEG C, and the green body is cooled with the furnace after the thermal insulation for 1 to 3 hours to obtain the boron carbide based composite ceramic. The phenolic resin plays a role in an adhesive and a carbon source during the preparation of the composite ceramic, and can also play a role in providing the green body with excessive air holes during the sintering, so that the infiltrability of silicon is improved.
Description
Technical field
The present invention relates to a kind of composite ceramics and preparation method thereof, particularly a kind of boron carbide base composite ceramic and preparation method thereof.
Background technology
Norbide covalent linkage content is very high, and specific surface area is little, and its room temperature hardness only is lower than diamond and cubic boron nitride, and approaching stable hot hardness is that other material is incomparable.Because the crystal boundary diffusion of norbide own is very slow, make therefore not have and press the temperature of normal sintering very high that its specific density generally is no more than 90%.In order to reduce the sintering temperature of norbide, the research worker adds metal or other potteries like aluminium, SP 1, aluminum oxide, wolfram varbide and titanium carbide or the like in boron carbide material, and has obtained some and made progress, but the too high problem of sintering temperature is still unresolved.Common sintering method has following several kinds at present:
1) normal pressure-sintered method, the general normal pressure-sintered slow factor of the crystal boundary diffusion of norbide that is limited to own need be at 2200 ℃～2400 ℃ following sintering, and can only reach 75～80% density.
2) hot pressing sintering method, hot pressed sintering are in inert atmosphere (or vacuum), to carry out, and general hot pressing temperature is 2200 ℃～2300 ℃; Pressure is 20MPa～40MPa, and soaking time 0.5h～2h is not if goods are strict with chemical ingredients; Can suitably add some additives; Acceleration of sintering reduces sintering temperature, obtains the higher norbide of density.The preparation of present boron carbide ceramics is main with pressure sintering, like Deng Jianxin etc.-" B
4C/SiC
wThe preparation of ceramic sand jet and the research of erosive wear mechanism thereof " (silicate circular, 2004,3,18～20), under 2000～2150 ℃ high temperature, prepared silicon carbide whisker enhanced norbide blast tube.Chinese patent CN1803714 discloses and in norbide, has added silicon carbide whisker, silica flour, boride etc., hot pressed sintering then.
The HIP sintering method is under 1700 ℃ of high temperature, through rare gas element such as Ar or N
2Transmit pressure; With the powder in the jacket or a kind of technology of green compact isostatic pressing agglomerating of pressing in advance, can't scale operation because its cost is too high, application (Xiao Hanning etc.-" high performance structure ceramic and application thereof " only arranged in the laboratory at present; Beijing chemical industry press, 2006).
3) activated sintering method through physics or chemical process, reduces the sintering temperature of boron carbide material, and the method for accelerating sintering process raising sintering character all belongs to activated sintering.As king zero gloomy etc.-" B
4The carbon dope activated sintering of C " (Materials Science and Engineering of Powder Metallurgy, 1997, vol.2, No.4 P260-265), adds carbon in the norbide sintering process, improve the density of sintered article.
4) reaction sintering is with B
4The C powder directly uses the bonding back of caking agent 1500～2200 ℃ of following siliconisings, because norbide meeting and pasc reaction, generation has B
4C, the matrix material of SiC and Si.Referring to USP Patent NO.3765300 (Taloy etl.Dense Carbide Composite For Armor andAbrasives, 1973)
More than four kinds of preparing methods, it is higher all can to obtain density, mechanical property is boron carbide material preferably; As HIP sintering and the hot pressing sintering method that present production boron carbide ceramics mainly adopts, the former since the goods cost is too high can't large-scale production, the pressure sintering cost is relatively low; But the product properties poor stability, foreign matter content is high, and mechanical property is unstable; And these two kinds of methods all have the big problem of goods sintering front and back linear shrinkage, cause being difficult to prepare the goods of change in shape.
Summary of the invention
The purpose of this invention is to provide that low, the clean forming property of a kind of sintering temperature is good, the boron carbide base composite ceramic with better mechanical property and the preparation method that can prepare the goods of complicated shape.
For reaching above purpose, the present invention takes following technical scheme to be achieved:
A kind of boron carbide base composite ceramic, percentage ratio comprises following component: boron carbide powder 45%～50%, resol 5%～8%, Pure Silicon Metal 42%～50% by weight.
The B of said boron carbide powder
4C content＞98%, powder particle size d
50＜5 μ m.
Said Pure Silicon Metal is that particle diameter is the technical grade silicon grain of 5mm, and the impurity mass percent is less than 3%.
Said resol is 2130 resins, and solid content is about 86%
A kind of preparation method of above-mentioned boron carbide base composite ceramic comprises the steps:
(1) percentage ratio by weight: boron carbide powder 45%～50%, resol 5%～8%, Pure Silicon Metal 42%～50% weighing, dissolve resol with alcohol earlier, and add the norbide powder, mechanical ball milling mixes:
(2) with the above-mentioned norbide powder that mixes, use the tablets press granulation, cross 120～400 mesh sieves:
(3) with above-mentioned granulation material, the green compact of the required article shape of compression molding, forming pressure is 60～140MPa:
(4), put into baking oven for drying solidification with compressed green body:
(5) Pure Silicon Metal of adding step (1) amount of weighing up in the plumbago crucible, the green compact with after solidifying are placed on the Pure Silicon Metal; Put into high-temperature vacuum sintering oven sintering together with crucible; 1550～1700 ℃ of sintering temperatures are incubated furnace cooling after 1～3 hour, promptly make boron carbide base composite ceramic.
In the aforesaid method, step (1) is said dissolves resol with alcohol, and the weight ratio of resol and alcohol is 1: 1-1.5.The processing parameter of said step (4) dry solidification is room temperature to 60 ℃ 2h, 60 ℃～80 ℃ 4h, 80 ℃～100 ℃ 4h, 100 ℃～140 ℃ 8h.
The present invention is matrix with the norbide, and resol is as caking agent and carbon source, and the method generation silit through reaction sintering couples together boron carbide particles.Simultaneously owing to there is the reaction (B of silicon-carbon reaction and silicon and norbide
4C+Si-B
xSi
y+ SiC, B
4C+Si-B
12(C, Si, B)
3+ SiC), can further reduce sintering temperature, obtain being close to fine and close fully sintered compact; The silit that generates in the reaction sintering process can also improve the antioxidant property of material, and the density of carbofrax material is relatively low simultaneously, so its density influence to goods is little.Prepared boron carbide base composite ceramic material has the advantages that density is low, hardness is high, intensity is high, Young's modulus is high, and the staple of sintered compact is norbide, silit, borosilicate carbon ternary phase, residual silicon and a spot of silicon boride.Compared with prior art, because the advantage of the dead size moulding that had of reaction sintering technology itself, can conveniently prepare the goods of complicated shape.The composite ceramic material of the present invention's preparation, density is lower than 2.8g/cm
3, Vickers' hardness is greater than 2700, and bending strength is greater than 300MPa, and Young's modulus is greater than 310GPa.Boron carbide base composite ceramic of the present invention can be widely used in the structured material under high-temperature atmosphere and the aggressive atmosphere, armoring bullet resistant material, antiradiation material, the control of atomic reactor and shielding material etc.
Description of drawings
Fig. 1 is the metallographic structure figure that the embodiment of the invention 2 is formed.
Fig. 2 is the XRD figure spectrum that the embodiment of the invention 5 is formed.
Embodiment
Below in conjunction with specific embodiment the present invention is done further detailed description.
A kind of boron carbide base composite ceramic, embodiment is formed as shown in table 1, in the embodiment shown in the table 1 1～5.The percentage composition of the norbide phase of the goods that obtained is generally 70～85%, if less than 70%, norbide content is very few in the sintered compact, and the hardness of material is lower behind the sintering, the sintered compact mechanical properties decrease.If greater than 85%, impermeable phenomenon appears in sintered compact easily.
The percentage composition of resol is preferably in 5～10% in the green compact.If less than 5%, the intensity of green compact is low excessively, and the adhesiveproperties of powder is relatively poor, and processability is relatively poor.If surpass 10%, the pore that forms after the resol cracking is more, and residual silicon amount improves, the corresponding decline of the mechanical property of material and high-temperature behavior.
The composition of table 1 boron carbide base composite ceramic of the present invention and sintering process condition
For metallic silicon power, add-on is preferably in 42%～47% generally 40%～50%.If less than 40%, possibly appear in the siliconising process green compact pore and fill not exclusively, cause product properties to reduce.If surpass 50%, silica flour is too much, can condensation silicon occur at product surface, is unfavorable for the surface property of goods, and causes the waste of raw material.
The preparation method of the boron carbide base composite ceramic that table 1 embodiment forms adds the absolute ethyl alcohol dilution with resol earlier, and norbide, resol are carried out wet mixing by forming to be respectively charged into shown in the table 1 in the ball mill, obtains uniform mixed powder.Then each is formed mixed powder and carry out granulation, cross 120 mesh sieves, 200 mesh sieves, 400 mesh sieves after the granulation, obtain the different granulation material of forming; Put into the green compact sample that the metal die press forming obtains embodiment 1-5; Forming pressure is controlled at 60～140Mpa according to the products thickness difference: the green compact sample of embodiment 1-5 is all through room temperature to 60 ℃ 2h, 60 ℃～80 ℃ 4h, 80 ℃～100 ℃ 4h; 100 ℃～140 ℃ 8h dry solidifications; Put it into respectively at last in the plumbago crucible, put in advance in the crucible by the silica flour of the proportion of composing amount of weighing up separately, the heat-up rate with 10 ℃/min under vacuum condition is heated to 1550-1750 ℃; Be incubated 1～3 hour (table 1) and accomplish siliconising technology, promptly obtain the sintered compact of embodiment 1-5 behind the furnace cooling.
Sintering temperature under the vacuum condition of the present invention can cause the perviousness of silicon too poor if be lower than 1500 ℃, can't realize infiltrating; If surpass 1750 ℃, too high temperature can cause surperficial desiliconization, may make the matrix material density reduce mechanical properties decrease.Under comparatively high temps, form borosilicate carbon ternary phase simultaneously, cause material mechanical performance to reduce because norbide and silicon can react.Heat-up rate is preferably in 10-50 ℃/min, is lower than 10 ℃/min, can increase sintering time, reduces production efficiency.Be higher than 50 ℃/min, may cause blank cracking.Soaking time was less than 1 hour, and the infiltration process can not thoroughly be accomplished.Be higher than 3 hours, on the one hand, may cause surperficial desiliconization, reduce the performance of material; Reduce production efficiency on the other hand, cause energy dissipation.Therefore soaking time is preferably in 1-3 hour.
Embodiment 1-5 boron carbide base composite ceramic sintered compact sample by aforesaid method obtains is measured the three-point bending strength under the room temperature.Archimedes's drainage is measured the ventilate rate.The observation by light microscope metallographic structure, and carry out microhardness testing with the Vickers' hardness appearance.Sem is observed microstructure on sample section.The results of property of these apparent porosities, sintered compact hardness and physical strength is as shown in table 2.
Can find out sintering in 1550-1700 ℃ TR by table 2, this matrix material is to show very high flexural strength at 88% o'clock at green compact norbide percentage composition, reaches as high as 328MPa (embodiment 2), and hardness can reach 3107HV, and density is about 2.75g/cm
3
Visible from Fig. 1, embodiment 2 material structures that obtain have only ternary phase seldom to form than homogeneous, and are less to the mechanical property influence of material.
Can see that from Fig. 2 the phase composite of embodiment 5 materials is B
4C, SiC, Si, B
12(C, Si, B)
3, when silicone content more also the silicon boride phase can occur.
The performance of table 2 boron carbide base composite ceramic of the present invention
| Ventilate rate (%) | Bending strength | Hardness (HV) | Density | |
| Embodiment 1 | 0.21 | 303 | 3067 | 2.757 |
| Embodiment 2 | 0.15 | 328 | 3107 | 2.746 |
| |
0.36 | 297 | 3024 | 2.771 |
| Embodiment 4 | 0.51 | 319 | 2907 | 2.742 |
| Embodiment 5 | 0.19 | 273 | 2814 | 2.536 |
Claims (3)
1. the preparation method of a boron carbide base composite ceramic is characterized in that, comprises the steps:
(1) percentage ratio by weight: boron carbide powder 45%～50%, resol 5%～8%, Pure Silicon Metal 42%～50% weighing, dissolve resol with alcohol earlier, and add the norbide powder, mechanical ball milling mixes:
(2) with the above-mentioned norbide powder that mixes, use the tablets press granulation, cross 120～400 mesh sieves:
(3) with above-mentioned granulation material, the green compact of the required article shape of compression molding, forming pressure is 60～140MPa:
(4), put into baking oven for drying solidification with compressed green body:
(5) Pure Silicon Metal of adding step (1) amount of weighing up in the plumbago crucible, the green compact with after solidifying are placed on the Pure Silicon Metal; Put into high-temperature vacuum sintering oven sintering together with crucible; 1550～1700 ℃ of sintering temperatures are incubated furnace cooling after 1～3 hour, promptly make boron carbide base composite ceramic.
2. the preparation method of boron carbide base composite ceramic as claimed in claim 1 is characterized in that, step (1) is said dissolves resol with alcohol, and the weight ratio of resol and alcohol is 1: 1-1.5.
3. the preparation method of boron carbide base composite ceramic as claimed in claim 1 is characterized in that, the processing parameter of said step (4) dry solidification is room temperature to 60 ℃ 2h, 60 ℃～80 ℃ 4h, 80 ℃～100 ℃ 4h, 100 ℃～140 ℃ 8h.
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| CN101967059B (en) * | 2010-09-17 | 2013-06-05 | 西安交通大学 | Method for preparing silicon carbide bullet-proof ceramics |
| FR2991981A1 (en) * | 2012-06-15 | 2013-12-20 | Saint Gobain Ct Recherches | SILICON CARBIDE PRODUCT FOR SHIELDING |
| CN105622102B (en) * | 2015-12-18 | 2018-01-09 | 中国科学院上海硅酸盐研究所 | Class boron carbide phase silicon carbide or class boron carbide phase silicon carbide boron carbide diphase ceramic material and preparation method thereof |
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| DE102018208427B4 (en) * | 2018-05-28 | 2022-03-17 | Brembo Sgl Carbon Ceramic Brakes Gmbh | Process for manufacturing a component, the component itself and its use |
| CN110304923B (en) * | 2019-07-04 | 2021-11-23 | 东北大学 | Preparation method of boron carbide-based ceramic composite material based on particle grading |
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| CN114409406A (en) * | 2020-10-28 | 2022-04-29 | 中国科学院理化技术研究所 | B12(C,Si,B)3Preparation method of-SiC two-phase ceramic |
| CN113105243A (en) * | 2021-04-28 | 2021-07-13 | 西安石油大学 | B with silicon carbide and silicon coating on surface4C/graphite composite material and preparation method thereof |
| CN113233899A (en) * | 2021-06-09 | 2021-08-10 | 西安石油大学 | B4B4C-SiC-Si composite material generated by siliconizing reaction of C/graphite preform and preparation method thereof |
| CN113620714A (en) * | 2021-07-22 | 2021-11-09 | 安徽应流久源核能新材料科技有限公司 | Preparation method of boron carbide-graphite shielding body |
| CN115010496B (en) * | 2022-07-04 | 2023-07-11 | 东北大学 | B with controllable performance 4 Preparation method of C-diamond composite material |
| CN115259859B (en) * | 2022-09-30 | 2022-12-27 | 潍坊衡益复合装甲研究院有限公司 | Boron carbide bulletproof ceramic material and preparation method thereof |
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