CN1022478C - Reinforcing of carbon-ceramics composite material with flexibilizer for coystal whiskers - Google Patents

Reinforcing of carbon-ceramics composite material with flexibilizer for coystal whiskers Download PDF

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CN1022478C
CN1022478C CN 91101684 CN91101684A CN1022478C CN 1022478 C CN1022478 C CN 1022478C CN 91101684 CN91101684 CN 91101684 CN 91101684 A CN91101684 A CN 91101684A CN 1022478 C CN1022478 C CN 1022478C
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silicon carbide
carbon
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CN1065058A (en
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田杰谟
童晓华
董利民
王振文
王玲玲
张宝清
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Tsinghua University
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Abstract

The present invention relates to a composite material of crystal whisker toughened and reinforced carbon ceramics, which belongs to the field of ceramics. The present invention comprises the contents that a certain number of silicon carbide whiskers are added to carbon powder and silicon carbide powder, and a reasonable material prescription and a technology are used for preparing a carbon ceramic material with high strength, large toughness, good wear resistance, good high-temperature resistance, good thermal-shock resistance, good oxidation resistance and good conductivity. The material is convenient for machine processing and electric processing and can be used for manufacturing conductive arc-striking nozzles, welding-wire nozzles and other structural components with high strength, wear resistance and conductivity.

Description

Reinforcing of carbon-ceramics composite material with flexibilizer for coystal whiskers
The present invention relates to the development of novel carbon ceramic material, belong to the stupalith field.
Carbon ceramics is an importance of high-performance ceramics material, and in the eighties, countries such as Japan and West Germany have all carried out the development of carbon ceramic material.Having reported with silicon carbide, graphite and carbon as European patent EP 0145496 is main raw material, has made carbon ceramic material at 1900~2300 ℃ of following sintering after adding a certain amount of norbide, aluminum oxide or beryllium oxide additive and polyvinyl alcohol binding agent, mixing, isostatic pressing.Reason owing to material prescription and technology, performances such as this carbon ceramic material intensity and toughness are low, do not satisfy the needs of Engineering Reliability, influenced the application of carbon ceramic material, therefore, the development high strength, toughness is big, wear-resisting, anti-thermal shock, oxidation-resistance and the high carbon ceramic material of resistivity seem extremely important.
The objective of the invention is in carbon and silicon carbide mixed matrix.Add silicon carbide whisker, and adopt rational material prescription and technology, prepare high strength, wear-resisting, high temperature resistant, anti-thermal shock, toughness is high and carbon ceramic material anti-oxidant, good conductivity, this material is applicable to makes various intensity height, wear-resisting, high temperature resistant, anti-thermal shock, oxidation-resistance and the good structure unit of conduction.
Content of the present invention: in carbon and silicon carbide powder, add a certain amount of silicon carbide whisker, to improve the intensity and the toughness of material; Add a certain amount of norbide, tantalum carbide or titanium carbide or titanium nitride additive, to improve the wear-resisting and oxidation-resistance and the electroconductibility of material, adopt that substep mixes, hot-pressing sintering technique makes the fine and close carbon ceramic material that has high strength, high tenacity, wear-resisting, high temperature resistant, anti-thermal shock, oxidation-resistance and conduct electricity very well, this material is convenient to machining and electromachining, can make high strength, big, wear-resisting, high temperature resistant, anti-oxidant, the anti-thermal shock of toughness, structure units such as conduction striking nozzle that conducts electricity very well and welding wire nozzle.
Main points of the present invention are as follows:
1. material prescription
In carbon content is weight percentage the silicon carbide powder mixed matrix of 10~50% carbon and 10~50%, the adding weight percent is 10~50% silicon carbide whisker, the diameter of silicon carbide whisker is 0.1~1 micron, and length is less than 5 microns, and short whisker is distributed in and plays dispersion-strengthened action in the matrix grain; Play toughening effect and long whisker is distributed in the crystal boundary of matrix grain, thereby improved the intensity and the toughness of material.Add weight percent and be 5~20% norbides and weight percent and be 3~10% tantalum carbides or titanium carbide or titanium nitride additive to improve the compactness and the wear-resisting and electroconductibility of material; Because following chemical reaction has at high temperature taken place behind the adding additive:
Figure 91101684_IMG2
Figure 91101684_IMG3
Because of B 2O 3+ SiO 2The laminated film that forms is distributed in sample surfaces and prevents the further oxidation of material, makes material have high antioxidant property and thermal shock resistance.The variation range of proportioning sees Table 1 in the prescription.
The variation range of proportioning in table 1 formula for raw stock
Material prescription weight percent granular size
Carbon 10~50% granularities≤6 μ m
Silicon carbide 10~50% granularities≤2 μ m
Silicon carbide whisker 10~50% diameters 0.1~1 μ m length≤5 μ m
Norbide 5~20% granularities<2 μ m
Tantalum carbide or titanium carbide 3~10% granularities<2 μ m
2. the processing of whisker: silicon carbide whisker is put in ethanol or other polar solvents, uses ultra-sonic oscillation, makes the whisker any surface finish and removes micro mist in the whisker, has increased the consistency and the binding ability of whisker and matrix like this.
3. technology: in order to make the material densification, the present invention adopts the substep mixing and ball milling, the technology of pre-molding hot pressed sintering under argon gas, promptly at first with carbon, silicon carbide, norbide, tantalum carbide or titanium carbide or titanium nitride and ethanol or other polar solvent mixing and ball milling 10~20 hours, add the silicon carbide whisker of having handled again and carry out the second step mixing and ball milling, after the oven dry, in graphite mo(u)ld, carry out coldmoulding, hot pressed sintering under argon gas then, hot pressing temperature is 1950 ℃~2150 ℃, 150~300 kilograms/square centimeter of pressure (15~30MPa), sintering time 0.5~1.5 hour.
4. the present invention's characteristics of having high strength, high tenacity, wear-resisting, high temperature resistant, anti-thermal shock, oxidation-resistance and conducting electricity very well are convenient to machining and electromachining, can be processed into the structure unit of conduction striking nozzle and welding wire nozzle and other wear-resistant conductives.
The invention has the advantages that the intensity height, toughness is big, wear-resisting, high temperature resistant and anti-thermal shock, antioxygen and conduct electricity very well.Be convenient to machining and electromachining.
The The performance test results of material sees Table 2.(table is seen the literary composition back)
Bending strength of the present invention and toughness are 4~6 times of high-strength graphite.
Table 3 has provided the comparison (table see literary composition back) of the present invention with external same type of material performance
Embodiment:
Example 1 is placed on the silicon carbide whisker of 15 grams in the ethanol, uses ultra-sonic oscillation 1 hour, and the oven dry back is standby.
The norbide that divides another name 5 grams, 3 gram tantalum carbides and 27 gram carbon dusts (coke powder), 50 gram carborundum powders, ball milling is 12 hours in containing ethanol agate glass mortar, added above-mentioned silicon carbide whisker 15 gram ball millings again 2 hours, to expect oven dry then, under the pressure of 15~20MPa, in graphite mo(u)ld, after the moulding, be put in the hot pressing furnace again, at 2050 ℃ under 15~30MPa pressure, sintering 0.5~1 hour, the material bending strength that obtains is 420MPa, tough factor 5MPam 1/2
Example 2 preparation technologies are with example 1, and raw-material prescription is as follows
Silicon carbide whisker 15 grams, 50 gram carbon; 5 gram norbides; 27 gram silicon carbide; The tantalum carbide of 3 grams.The material of preparing, bending strength is 250MPa, and toughness is 6MPam 1/2
Table 2 material properties test result
The anti-oxidant operating resistance rate of density of material hardness bending strength tough factor (Kic) thermal shock resistance
(g/cm 3)(HRA)(MPa)(MPam 1/2) △ T(℃) temperature upper limit (℃) (Ω M)
2.7-3.1 84-90 250-450 4-8 600 800 5×10 -5
Table 3 the present invention and the comparison of same type of material performance abroad
Phosphorus content bending strength tough factor (Kic)
(percentage by weight) be (MPam (MPa)1/2
The external the present invention of the present invention is external
10%    450    194.16    4.50    4.18
20% 400 values of not providing 5.0 2.48
50% 260 value of not providing 6.0 values of not providing
Annotate: the data that refer to European patent EP 0145496 report abroad.

Claims (3)

1, a kind of reinforcing of carbon-ceramics composite material with flexibilizer for coystal whiskers, it is characterized in that this material is that carbon and the silicon carbide powder of 10-50% is mixed matrix with the weight percent, the silicon carbide whisker that adds weight percent 10-50% adds tantalum carbide or titanium carbide additive that norbide that weight percent is 5-20% and weight percent are 3-10% again.
2, according to the described carbon ceramic composite materials of claim 1, the diameter that it is characterized in that described silicon carbide whisker is the 0.1-1 micron, and length is less than or equal to 5 microns.
3, the method for the carbon ceramic composite materials of the described crystal whisker toughened reinforcement of preparation claim 1 is characterized in that its preparation process:
(1) be 10-50% with weight percent, diameter is the 0.1-1 micron, and length is less than or equal to 5 microns silicon carbide whisker and is put in the polar solvent, handles with ultra-sonic oscillation;
(2) be 10-50% with weight percent again, it is 10-50% that granularity is less than or equal to 6 microns carbon and weight percent, mixed matrix and weight percent that granularity is less than or equal to 2 microns silicon carbide powder are 5-20%, granularity is 3-10% less than 2 microns norbide and weight percent, granularity was less than 2 microns carbonization or titanium carbide additive in polar solvent for example in the ethanol mixing and ball milling 10-20 hour, reenter the silicon carbide whisker of having handled described in (1) and carry out the second step mixing and ball milling, oven dry;
(3) mixture after the above-mentioned oven dry is carrying out coldmoulding, hot pressed sintering under argon gas then, and hot pressing temperature is 1950 ℃-2150 ℃, pressure is 150-300 kilogram/square centimeter, sintering time 0.5-1.5 hour.
CN 91101684 1991-03-21 1991-03-21 Reinforcing of carbon-ceramics composite material with flexibilizer for coystal whiskers Expired - Fee Related CN1022478C (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1041290C (en) * 1996-04-12 1998-12-23 清华大学 Welding electrode of carbon ceramic composite materials

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100341618C (en) * 2005-07-29 2007-10-10 中国科学院长春应用化学研究所 Carbon-ceramic utilized absorption material
CN101164996B (en) * 2006-10-16 2010-09-01 宁波大学 Silicon carbide ceramic containing silicon carbide whisker and rod-like aluminum oxide embedded particles
CN101172877B (en) * 2006-10-16 2010-06-16 宁波大学 Process for manufacturing multicomponent combination toughness reinforcing silicon carbide ceramic including crystal whisker and fibre
CN101289319B (en) * 2008-06-03 2010-06-30 浙江东新密封有限公司 Reaction sintering silicon carbide ceramic and production method thereof
CN105367111B (en) * 2015-11-09 2018-10-16 嘉兴皓特特种陶瓷有限公司 A kind of graphite/carbon SiClx composite material and preparation method
CN110563464A (en) * 2019-09-29 2019-12-13 威海恒科精工有限公司 High-temperature-resistant and oxidation-resistant graphite mold and preparation method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1041290C (en) * 1996-04-12 1998-12-23 清华大学 Welding electrode of carbon ceramic composite materials

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