CN103553627B - A kind of ceramic matric composite and its preparation method and application - Google Patents
A kind of ceramic matric composite and its preparation method and application Download PDFInfo
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- CN103553627B CN103553627B CN201310460525.9A CN201310460525A CN103553627B CN 103553627 B CN103553627 B CN 103553627B CN 201310460525 A CN201310460525 A CN 201310460525A CN 103553627 B CN103553627 B CN 103553627B
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Abstract
The invention discloses a kind of ceramic matric composite and its preparation method and application, belong to ultra-temperature ceramic-based composite material technical field, relate to a kind of preparation method with higher-strength, higher toughness, high-compactness, fine grained texture's material.Using zirconium diboride powder as matrix phase; Using zirconium disilicide powder as sintering aid, make the optimal sintering temperature of material in the present invention, sintering pressure, sintering time all lower than existing hot pressing and sintering technique requirement; Using multi-walled carbon nano-tubes as the additive improving material inside organization structure, significantly reduce the grain-size of material, the fracture toughness property of material is risen to 6.98MPa ﹒ m
1/2.The present invention adopts two step hot pressing and sintering techniques, prepares the zirconium diboride ceramics based composites with higher-density and mechanical property with feature that is quick, low temperature, facilitates its follow-up large-scale production preparation and fiber reinforced technology.
Description
Technical field
The invention belongs to ultra-temperature ceramic-based composite material technical field, relate to a kind of zirconium diboride ceramics based composites and preparation method thereof with higher-strength, higher toughness, be related specifically to the two step hot-pressing sintering methods of zirconium diboride based composites that low temperature, fast preparation have high-compactness, fine grained texture.
Background technology
In field of aerospace technology, " baffle " problem (flight velocity >1 Mach) that compressibility due to air is brought is solved, the Bellx-1 plan that National Advisory Committee for Aeronautics (NACA) starts makes aircraft speed exceed mach one becomes possibility, this and the thermally protective materials arisen at the historic moment are undivided, and traditional thermally protective materials can meet the requirement of supersonic flight substantially.But the birth of hypersonic aircraft (flight velocity >5 Mach) theory makes thermally protective materials traditional at present can not meet the flight environment of vehicle of its harshness.The difficult problem that the Aerodynamic Heating that hypersonic flight causes brings is called as " thermal boundary ".But, overcome " thermal boundary " not a duck soup, the hypersonic research team of NASA (NASA) Langley Research Center, when running into unprecedented Aerodynamic Heating and ultrahigh-temperature thermally protective materials problem, thinks that " heat " is the biggest obstacle of hypersonic flight.The prerequisite overcoming " thermal boundary " prepares advanced thermally protective materials, to be applicable to hypersonic aircraft high speed, long Aerodynamic Heating time, the requirement that can be recycled.So, have high-melting-point, high strength, high tenacity, high-compactness ultrahigh-temperature thermally protective materials become aerospace field be badly in need of the advanced material with strategic meaning.
Zirconium diboride (ZrB
2) there is high-melting-point (3250 DEG C), high strength (400MPa ~ 500MPa), good thermal conductivity (1.03 × 10
7Ω
-1m
-1), good electric conductivity (70Wm
-1k
-1), lower density (6.085g/cm
3), above advantage makes one of zirconium diboride advanced thermally protective materials being considered to most prospect.But the characteristics such as strong covalent bond and low self-diffusion rate reduce its coking property, cause the processing condition sintering zirconium diboride ceramics based composites very harsh.Processing condition needed for its hot pressing and sintering technique are generally: sintering temperature (1850 ~ 2300 DEG C), sintering pressure (30 ~ 60MPa), sintering time (1 ~ 2h).Which results in that its preparation cost is high, preparation cycle is long, bring difficulty to follow-up large-scale production zirconium diboride ceramics based composites.
In addition, the Fracture Toughness with the zirconium diboride of hard crisp characteristic is 2.1 ~ 3.5MPam
1/2, it can cause catastrophic destruction to the sensitivity characteristic of crackle and brittle failure mode, becomes the major cause that restriction zirconium diboride ceramics based composites is widely used in thermally protective materials field.High sintering temperature in the past and long sintering time make that the zirconium diboride material grains prepared is coarse, grain-size is comparatively large, cannot realize thin brilliant malleableize.The effect of being carried out self toughening zirconium diboride ceramics based composites by the interlocking structure preparing bar-like grains is unsatisfactory, still shows as brittle failure mode.Now generally believe that the method for toughening of most prospect adopts silicon carbide fiber or carbon fiber-reinforced zirconium diboride ceramics based composites, but toughening effect is critical constraints also, wherein most important reason is exactly when sintering temperature is higher than 1700 DEG C, decomposition breakoff phenomenon as the silicon carbide fiber of toughness reinforcing phase or carbon fiber is very serious, does not reach the toughening effect of expection.In sum, fast, low temperature (<1700 DEG C) preparation has high tenacity, the sintering process of fine grained texture's zirconium diboride ceramics based composites is very important.
Summary of the invention
The object of this invention is to provide a kind of fast, low-temperature growth has the sintering method of high-compactness, high tenacity, fine grained texture's zirconium diboride ceramics based composites, so that its follow-up large-scale production and fiber reinforced.Present invention also offers the application of this ceramic matric composite.
In order to achieve the above object, the invention provides a kind of ceramic matric composite, using zirconium diboride as matrix phase; Using zirconium disilicide as sintering aid; Using the matrix material that multi-walled carbon nano-tubes is mixed as the additive improving material inside organization structure; Wherein, the situation of raw material is:
The mass percent of described zirconium diboride is: 70 ~ 90%; Purity 99.5 ~ 99.9%, median size are 1 ~ 3 μm.
The mass percent of described zirconium disilicide is: 10 ~ 20%; Purity 99.5 ~ 99.9%, median size are 1 ~ 2 μm.
The mass percent of described multi-walled carbon nano-tubes is: 0 ~ 10%; Purity 97.5 ~ 99.9%, external diameter 20 ~ 40nm, length 5 ~ 15 μm.
The matrix material degree of compactness of preparation is 90.83% ~ 99.85%, flexural strength is 304 ~ 497MPa, fracture toughness property is 4.02 ~ 6.98MPam
1/2.In matrix material, zirconium diboride grain-size optimum is 0.3 ~ 0.6 μm.
Present invention also offers the application of a kind of above-mentioned ceramic matric composite as thermally protective materials; zirconium diboride-zirconium disilicide-carbon nanotube ceramic matric composite is as the thermofin bearing high-temperature component; as protective cover for thermocouple; the sprue gate of smelting metal equipment, electrode, hypersonic vehicle fuselage material, especially wing nose nose cone and engine mouth etc.
Present invention also offers a kind of preparation method of above-mentioned ceramic matric composite, comprise the steps:
Step1, dispersion grinding: get purity 99.5 ~ 99.9%, zirconium disilicide powder quality per-cent 10 ~ 20% that zirconium diboride powder quality per-cent 70 ~ 90% that median size is 1 ~ 3 μm, purity 99.5 ~ 99.9%, median size are 1 ~ 2 μm, and purity 97.5 ~ 99.9%, external diameter 20 ~ 40nm, length 5 ~ 15 μm multi-walled carbon nano-tubes mass percent 0 ~ 10%, add dehydrated alcohol and carry out concussion dispersion, then carry out using described dehydrated alcohol as medium grinding and disperseing.Wherein, ultrasonic oscillation dispersing mode is selected in concussion dispersion, and because carbon nanotube is easily reunited, the Main Function of ultrasonic oscillation allows carbon nanotube dispersed come, as long as carbon nanotube can be enable to spread out, additive method also can use.
The material slurry vaporize draw that Step2, Step1 obtain;
Step3, the dry powder mortar grinder of bulk that will extract, sieve through 200 order material screens after terminating;
Step4, load in mould carry out two step pressure sintering hot pressed sinterings by sieving the powder got, be specially:
First, with the temperature rise rate of 3 ~ 5 DEG C/min, sintering temperature is risen to 1250 DEG C from room temperature, heat-insulation pressure keeping 10 ~ 15min, sintering pressure is 10 ~ 30MPa; Then, rise to 1450 ~ 1650 DEG C with the temperature rise rate of 10 ~ 15 DEG C/min, heat-insulation pressure keeping 5 ~ 10min, sintering pressure 10 ~ 30MPa.Whole sintering process is high vacuum environment (<0.1Pa).Herein, sintering pressure refers to powder in sintering process, and the pressure head of hot pressing furnace acts on the pressure of powder, is 30MPa; Sintering atmosphere is high vacuum environment <0.1Pa, refers to powder when sintering, the air pressure both in furnace chamber.
Under optimal way, in Step1, zirconium diboride powder quality per-cent is 75%, and zirconium disilicide powder is 20%, and multi-walled carbon nano-tubes is 5%.If especially zirconium disilicide is less than 20%, then the relative density of final material is lower, as 85%ZrB in Examples below 2
2+ 10%ZrSi
2the test result of+5%CNTs/1550 DEG C is: density 95.01%, 75%ZrB in embodiment 8
2+ 20%ZrSi
2the test result of+5%CNTs/1550 DEG C is: density 99.75%.And if the massfraction adding multi-walled carbon nano-tubes is less than 5%, then the crystal grain having large-size occurs, as 78%ZrB in Examples below 10
2+ 20%ZrSi
2the test result of+2%CNTs/1550 DEG C is: grain-size 0.3 ~ 2 μm, if the massfraction of multi-walled carbon nano-tubes is too many, then can affect the relative density of final material, as 70%ZrB in embodiment 11
2+ 20%ZrSi
2the test result of+10%CNTs/1550 DEG C is: density 91.28%.
Under optimal way, in Step4, first, with the ramp to 1250 DEG C of 5 DEG C/min, heat-insulation pressure keeping 10min, sintering pressure 30MPa; Then, with the ramp to 1550 DEG C of 15 DEG C/min, heat-insulation pressure keeping 5min, sintering pressure 30MPa.Wherein, second step sintering temperature elects 1550 DEG C as optimum, if sintering temperature is too low, then can reduce the relative density of material, as 75%ZrB in Examples below 7
2+ 20%ZrSi
2the test result of+5%CNTs/1450 DEG C is: density 98.62%.If sintering temperature is too high, then there will be large size crystal grain in material, as 75%ZrB in Examples below 9
2+ 20%ZrSi
2the test result of+5%CNTs/1650 DEG C is: grain-size 0.3 ~ 2 μm.
In addition, in two step hot pressed sinterings, if sintering process is: first, with the ramp to 1250 DEG C of 3 DEG C/min, heat-insulation pressure keeping 15min, sintering pressure 30MPa; Then, with the ramp to 1550 DEG C of 10 DEG C/min, heat-insulation pressure keeping 10min, sintering pressure 30MPa.Then can, due to the overlong time stopped at comparatively high sintering temperature (1550 DEG C), make material grains start to grow up, and it be longer to sinter preparation cycle, causes the wasting of resources, as Examples below 12.If sintering process is: first, with the ramp to 1250 DEG C of 5 DEG C/min, heat-insulation pressure keeping 10min, sintering pressure 10MPa; Then, with the ramp to 1550 DEG C of 15 DEG C/min, heat-insulation pressure keeping 5min, sintering pressure 10MPa.Then can be too low and reduce the density of material, as Examples below 13 due to sintering pressure.
In addition, in Step1, during described ultrasonic oscillation dispersion, dehydrated alcohol is added; The speed setting of ball mill is 160 ~ 200rpm, Ball-milling Time 12 ~ 48h, and is filled with protection of inert gas to the ball grinder that material is housed, and adds dehydrated alcohol as medium during ball milling.Under optimal way, the speed setting of described ball mill is 180rpm, Ball-milling Time is 24h.
Select rotatory evaporator to extract in Step2, the condition that described rotary evaporation extracts is: bath temperature 40 ~ 45 DEG C, and the protection of omnidistance use ar gas environment.
The invention belongs to ultra-temperature ceramic-based composite material technical field, relate to a kind of zirconium diboride ceramics based composites and preparation method thereof with higher-strength, higher toughness, high-compactness, fine grained texture.With zirconium diboride powder (ZrB
2) as matrix phase; With zirconium disilicide powder (ZrSi
2) as sintering aid, make the optimal sintering temperature of material in the present invention (1550 DEG C), sintering pressure (30MPa), sintering time (15min) all lower than existing hot pressing and sintering technique requirement; Using multi-walled carbon nano-tubes (Multi-walledCNTs) as the additive improving material inside organization structure, significantly reduce the grain-size (0.3 ~ 0.6 μm) of material, the fracture toughness property of material is risen to 6.98MPa ﹒ m
1/2.The present invention adopts two step hot pressing and sintering techniques, prepares the zirconium diboride ceramics based composites with higher-density and mechanical property with feature that is quick, low temperature, facilitates its follow-up large-scale production preparation and fiber reinforced technology.
Effect of the present invention and benefit achieve low temperature, fast preparation to have the zirconium diboride ceramics based composites of high-compactness and fine crystalline structure, specific as follows:
1., using zirconium disilicide as sintering aid, improve the degree of compactness of material.Therefore, the relative density of zirconium diboride ceramics based composites that sinters of the present invention is all more than 90%.
2., with purity 99.5 ~ 99.9%, median size is that the zirconium diboride (ZrB2) of 1 ~ 3 μm is as matrix phase; Be that the zirconium disilicide (ZrSi2) of 1 ~ 2 μm is as sintering aid using purity 99.5 ~ 99.9%, median size; By adopting zirconium disilicide as sintering aid, make sintering temperature, sintering pressure and sintering time all lower than existing heat pressing process requirement, corresponding mechanism is: zirconium disilicide powder is when sintering, the stable liquid film of one deck can be formed at powder particle surface, this liquid film can infiltrate the crystal grain boundary of zirconium diboride and zirconium disilicide, promote the slippage between two kinds of crystal grain, die locations optimizes arrangement again, promote tap density, and then accelerate the closely knit speed of material, the final sintered compacting degree of lifting material.In addition; (confirm through a large amount of embodiment when hot pressing temperature reaches more than 1000 DEG C; when sintering temperature be 1250 DEG C, sintering pressure be 30MPa time closely knit speed maximum); zirconium disilicide crystal grain can be tending towards softening relative to zirconium diboride crystal grain; under the driving of sintering pressure, zirconium disilicide crystal grain produces viscous deformation; fill up zirconium diboride crystal grain space, be beneficial to the lifting of densify degree.Therefore, the relative density of zirconium diboride ceramics based composites that sinters of the present invention is all more than 90%.Using the multi-walled carbon nano-tubes (Multi-walledCNTs) of purity 97.5 ~ 99.9%, external diameter 20 ~ 40nm, length 5 ~ 15 μm as the additive improving material inside organization.The multi-walled carbon nano-tubes added plays the effect of crystal grain thinning in sintering process, mechanism is: when hot pressed sintering, and multi-walled carbon nano-tubes and zirconium disilicide generation chemical reaction generate the zirconium carbide (ZrC) and silicon carbide (SiC) crystal grain that are of a size of 30 ~ 60nm.These two kinds of nanoscale uniform crystal particles are distributed in around zirconium diboride crystal grain, zirconium diboride crystal grain can be stoped to grow up in sintering process, thus serve the effect of crystal grain thinning, result in the increase of the interfacial phase of material internal, cause crackle to deflect in material internal communication process, serve significant toughening effect.
3., owing to the addition of zirconium disilicide as sintering aid, the sintering temperature (1550 DEG C) of optimum of the present invention, sintering pressure (30MPa), sintering time (15min) are all lower than the processing requirement of existing hot pressed sintering zirconium diboride ceramics based composites: sintering temperature (1850 ~ 2300 DEG C), sintering pressure (30 ~ 60MPa), sintering time (1 ~ 2h).And then decrease preparation cost and preparation cycle, facilitate follow-up mass production zirconium diboride ceramics based composites and fiber reinforced.
4. the zirconium diboride crystal grain optimal size of hot pressed sintering of the present invention is 0.3 ~ 0.6 μm, is all less than the grain-size adopting zirconium diboride matrix material prepared by hot pressing and sintering technique both at home and abroad.By the test to degree of compactness, flexural strength, fracture toughness property, (flexural strength is 350 ~ 565MPa, fracture toughness property is 2.4 ~ 3.5MPam to record material of the present invention and existing zirconium diboride ceramics based composites
1/2) compare, the flexural strength of material of the present invention declines to some extent, but fracture toughness property significantly improves, and reduces the susceptibility of zirconium diboride ceramics based composites to crackle significantly.
Embodiment
The present invention is with zirconium diboride (ZrB
2) as matrix phase; With zirconium disilicide (ZrSi
2) as sintering aid; Using multi-walled carbon nano-tubes (Multi-walledCNTs) as the additive improving material inside organization structure, prepare zirconium diboride-zirconium disilicide-carbon nanotube ceramic matric composite, prepared zirconium diboride ceramics based composites degree of compactness is 90.83% ~ 99.85%, flexural strength is 304 ~ 497MPa, fracture toughness property is 4.02 ~ 6.98MPam
1/2; Detailed process is as follows:
Preparation process:
A) first material good for proportioning is carried out ultrasonic oscillation dispersion, then adopt planetary ball mill to carry out ball milling; By a large amount of embodiment, wherein zirconium diboride powder volume number 70 ~ 90%, show that optimum is 75%.Zirconium disilicide powder quality per-cent 10 ~ 20%, by taking this ratio, can make the degree of compactness preparing material all more than 90%, and there is higher flexural strength, show that optimum is 20% by a large amount of embodiment.Multi-walled carbon nano-tubes mass percent is 0 ~ 10%, and the carbon nanotube of contrast different content on the impact of material inside organization structure, and makes the degree of compactness of material all more than 90%, and its optimum is 5%.Dehydrated alcohol is added to strengthen dispersion effect when ultrasonic oscillation disperses.The speed setting of ball mill is 160 ~ 200rpm, and optimum is 180rpm; Ball-milling Time is 12 ~ 48h, and optimum is 24h.If rotational speed of ball-mill is excessively slow, the time is too short, then the bad dispersibility of carbon nanotube in material, the homogeneity of material microstructure and the stability of mechanical property are prepared in impact; If ball milling speed is too fast, overlong time, then stick together effect because powder produces cold welding, make the powder particle particle diameter after ball milling comparatively large on the contrary, be unfavorable for follow-up hot pressed sintering.Protection of inert gas is filled with to the ball grinder that material is housed, adds dehydrated alcohol during ball milling equally as medium to strengthen dispersion effect.
B), after zirconium diboride powder, zirconium disilicide powder and the abundant ball milling of multi-walled carbon nano-tubes, the material slurry mixed is extracted through rotatory evaporator; Rotatory evaporator extraction conditions is: bath temperature 40 ~ 45 DEG C, and the protection of omnidistance use ar gas environment.By taking argon shield environment, the possibility that powder contacts with oxygen in air when extracting can being reduced, ensure that the high purity extracting superfine powder, being beneficial to powder sintered closely knit.
C): by the dry powder mortar grinder of bulk extracted, filter through 200 order material screens after terminating, make powder dispersion more even.After sieve takes into, rapidly powder is loaded mould, to reduce the time that the ultrafine powder that extracts contacts with air.
D): the mould that powder is housed is placed in hot pressing furnace, two-step sintering method is taked to sinter.The first step: sintering temperature is risen to 1250 DEG C from room temperature with the temperature rise rate of 3 ~ 5 DEG C/min, optimum is 5 DEG C/min; Sintering pressure is 10 ~ 30MPa, and optimum is 30MPa, and at 1250 DEG C of insulation 10 ~ 15min, optimum is 10min.Second step: the temperature (1450 ~ 1650 DEG C) sintering temperature risen to needed for final sintering from 1250 DEG C with the speed of 10 ~ 15 DEG C/min, optimum temperature rise rate is 15 DEG C/min, and optimum sintering temperature is 1550 DEG C; Sintering pressure is 10 ~ 30MPa, and optimum is 30MPa; Insulation 5 ~ 10min, optimum is 5min.The feature of two-step sintering is: the first step, slower temperature rise rate, lower sintering temperature, longer soaking time; Second step, very fast temperature rise rate, comparatively high sintering temperature, shorter soaking time.Adopt two-step sintering can reduce the grain-size of material.Its reason is: powder completes most closely knit retraction strokes in the first step, and because the sintering temperature (1250 DEG C) of the first step is lower, powder particle size can not increase in this temperature.In order to continue the degree of compactness promoting material, making it close to theoretical degree of compactness, needing to complete in second step.Higher sintering temperature (1450 ~ 1650 DEG C) also can increase the possibility that material grains increases simultaneously, takes to be rapidly heated and short period of time Insulation can ensure that the grain-size of material can not increase.Sintering vacuum tightness is less than 0.1Pa, if vacuum tightness is too high, then raw material powder can be caused to be oxidized, be unfavorable for the mechanical property of powder densification and material.
In following embodiment, material therefor is commercially available material.
Embodiment 1:
1) be the proportioning of 85% zirconium diboride, 10% zirconium disilicide, 5% multi-walled carbon nano-tubes by mass percentage, in precision be 0.0001mg analytical balance on take 20.0000g zirconium diboride powder (purity 99.5%, median size 2 μm), 2.3529g zirconium disilicide powder (purity 99.5%, median size 1 μm), 1.1765g multi-walled carbon nano-tubes (purity be 97.5%, external diameter 20 ~ 40nm, length 5 ~ 15 μm).
2) the above-mentioned zirconium diboride taken is put into together with zirconium disilicide powder beaker and carry out ultrasonic oscillation dispersion 30min, and add ethanol solution as dispersion medium.
3) weighted multi-walled carbon nano-tubes is put into beaker and carry out ultrasonic oscillation dispersion 30min, and add ethanol solution as dispersion medium.
4) disperseed by ultrasonic oscillation complete zirconium diboride to put into beaker together with zirconium disilicide powder, multi-walled carbon nano-tubes slurry and carry out ultrasonic oscillation dispersion 30min, dehydrated alcohol is dispersion medium.
5) ultrasonic wave disperseed the mixed slurry of rear three kinds of raw materials to put into the ball grinder being filled with argon shield and carry out ground and mixed, add dehydrated alcohol as dispersion medium simultaneously, the speed setting of ball mill is 180rpm, and Ball-milling Time is 24h.
6) extracted through rotatory evaporator under ar gas environment protection by material slurry good for ball milling, extraction conditions is: bath temperature 45 DEG C.
7) dry for the bulk extracted powder is taken out, with mortar grinder, and filter through 200 order material screens, raw material powder is uniformly dispersed.
8), after sieve takes into, rapidly raw material powder is loaded mould two step hot pressed sinterings under vacuum, the first step: sintering temperature is risen to 1250 DEG C from room temperature with the temperature rise rate of 5 DEG C/min, sintering pressure is 30MPa, and at 1250 DEG C of insulation 10min.Second step: sintering temperature is risen to 1450 DEG C from 1250 DEG C with the speed of 15 DEG C/min, sintering pressure is 30MPa, insulation 5min.
Embodiment 2:
It is 1550 DEG C that the present embodiment sintering parameter different from embodiment 1 resets second step sintering temperature, and other are identical with embodiment 1.
Embodiment 3:
It is 1650 DEG C that the present embodiment sintering parameter different from embodiment 1 resets second step sintering temperature, and other are identical with embodiment 1.
Embodiment 4:
What the present embodiment was different from embodiment 1 takes 20.0000g zirconium diboride powder (80%), 3.7500g zirconium disilicide powder (15%), 1.2500g multi-walled carbon nano-tubes (5%), and other are identical with embodiment 1.
Embodiment 5.
It is 1550 DEG C that the present embodiment sintering parameter different from embodiment 1 resets second step sintering temperature, and other are identical with embodiment 1.
Embodiment 6.
It is 1650 DEG C that the present embodiment sintering parameter different from embodiment 1 resets second step sintering temperature, and other are identical with embodiment 1.
Embodiment 7.
What the present embodiment was different from embodiment 1 takes 20.0000g zirconium diboride powder (75%), 5.3333g zirconium disilicide powder (20%), 1.3333g multi-walled carbon nano-tubes (5%), and other are identical with embodiment 1.
Embodiment 8.
It is 1550 DEG C that the present embodiment sintering parameter different from embodiment 1 resets second step sintering temperature, and other are identical with embodiment 1.
Embodiment 9.
It is 1650 DEG C that the present embodiment sintering parameter different from embodiment 1 resets second step sintering temperature, and other are identical with embodiment 1.
Embodiment 10.
What the present embodiment was different from embodiment 1 takes 20.0000g zirconium diboride powder (78%), 5.1282g zirconium disilicide powder (20%), 0.5128g multi-walled carbon nano-tubes (2%), and other are identical with embodiment 2.
Embodiment 11.
What the present embodiment was different from embodiment 1 takes 20.0000g zirconium diboride powder (70%), 5.7143g zirconium disilicide powder (20%), 2.8571g multi-walled carbon nano-tubes (10%), and other are identical with embodiment 2.
Embodiment 12.
The present embodiment sintering parameter different from embodiment 7 is reset in two step hot pressed sinterings, the first step: sintering temperature is risen to 1250 DEG C from room temperature with the temperature rise rate of 3 DEG C/min, and sintering pressure is 30MPa, and at 1250 DEG C of insulation 15min.Second step: sintering temperature is risen to 1550 DEG C from 1250 DEG C with the speed of 10 DEG C/min, sintering pressure is 30MPa, and insulation 10min, other are identical with embodiment 2.
Embodiment 13.
The present embodiment sintering parameter different from embodiment 7 is reset to two step hot pressed sinterings, the first step: with the temperature rise rate of 5 DEG C/min, sintering temperature is risen to 1250 DEG C from room temperature, sintering pressure is 10MPa, and at 1250 DEG C of insulation 10min.Second step: sintering temperature is risen to 1550 DEG C from 1250 DEG C with the speed of 15 DEG C/min, sintering pressure is 10MPa, and insulation 5min, other are identical with embodiment 2.
The performance test of material:
1) cutting of test bars: the test bars sample of hot pressed sintering being cut into two kinds of sizes, dimensional parameters is A:25mm × 2mm × 1.5mm, B:25mm × 4mm (2mm breach dark/0.1mm breach is wide) × 4mm.A specification test bars is used for testing flexural strength and density, B specification test fracture toughness property.
2) polishing of test bars: two of well cutting kinds of size battens are carried out grinding and polishing on accurate polished machine, adopts diamond suspension polishing liquid to be polished to 0.3 μm of grade.
3) measurement of grain-size: the polished surface of sample is carried out electronic scanning microscopic examination (SEM), material grains size is measured.
4) density is measured: adopt Archimedes drainage, is put into by A specification batten good for polishing after the beaker filling deionized water infiltrates 1 hour, calculates the relative density of batten.
5) Mechanics Performance Testing: the flexural strength (according to ASTM-C1161-02C testing standard) and the fracture toughness property (according to ASTM-C1421-10 testing standard) that adopt three-point bend test batten.Load loading rate during test flexural strength is 0.2mm/min, and span is 20mm; The load loading rate of fracture toughness property is 0.05mm/min, and span is 20mm; Each group batten tests 10 times, gets its mean value.
85%ZrB in embodiment 1
2+ 10%ZrSi
2the test result of+5%CNTs/1450 DEG C is: density 90.83%, grain-size 0.3 ~ 0.6 μm, flexural strength 347MPa, fracture toughness property 4.31MPam
1/2.
85%ZrB in embodiment 2
2+ 10%ZrSi
2the test result of+5%CNTs/1550 DEG C is: density 95.01%, grain-size 0.3 ~ 0.6 μm, flexural strength 483MPa, fracture toughness property 5.35MPam
1/2.
85%ZrB in embodiment 3
2+ 10%ZrSi
2the test result of+5%CNTs/1650 DEG C is: density 95.08%, grain-size 0.3 ~ 2 μm, flexural strength 395MPa, fracture toughness property 4.12MPam
1/2.
80%ZrB in embodiment 4
2+ 15%ZrSi
2the test result of+5%CNTs/1450 DEG C is: density 92.03%, grain-size 0.3 ~ 0.6 μm, flexural strength 416MPa, fracture toughness property 5.28MPam
1/2.
80%ZrB in embodiment 5
2+ 15%ZrSi
2the test result of+5%CNTs/1550 DEG C is: density 97.24%, grain-size 0.3 ~ 0.6 μm, flexural strength 475MPa, fracture toughness property 6.61MPam
1/2.
80%ZrB in embodiment 6
2+ 15%ZrSi
2the test result of+5%CNTs/1650 DEG C is: density 97.32%, grain-size 0.3 ~ 2 μm, flexural strength 403MPa, fracture toughness property 4.43MPam
1/2.
75%ZrB in embodiment 7
2+ 20%ZrSi
2the test result of+5%CNTs/1450 DEG C is: density 98.62%, grain-size 0.3 ~ 0.6 μm, flexural strength 463MPa, fracture toughness property 5.49MPam
1/2.
75%ZrB in embodiment 8
2+ 20%ZrSi
2the test result of+5%CNTs/1550 DEG C is: density 99.75%, grain-size 0.3 ~ 0.6 μm, flexural strength 497MPa, fracture toughness property 6.98MPam
1/2.
75%ZrB in embodiment 9
2+ 20%ZrSi
2the test result of+5%CNTs/1650 DEG C is: density 99.79%, grain-size 0.3 ~ 2 μm, flexural strength 419MPa, fracture toughness property 4.57MPam
1/2.
78%ZrB in embodiment 10
2+ 20%ZrSi
2the test result of+2%CNTs/1550 DEG C is: density 99.85%, grain-size 0.3 ~ 2 μm, flexural strength 426MPa, fracture toughness property 4.42MPam
1/2.
70%ZrB in embodiment 11
2+ 20%ZrSi
2the test result of+10%CNTs/1550 DEG C is: density 91.28%, grain-size 0.3 ~ 0.6 μm, flexural strength 304MPa, fracture toughness property 4.02MPam
1/2.
75%ZrB in embodiment 12
2+ 20%ZrSi
2the test result of+5%CNTs/1550 DEG C is: density 99.79%, grain-size 0.5 ~ 1 μm, flexural strength 492MPa, fracture toughness property 6.96MPam
1/2.
75%ZrB in embodiment 13
2+ 20%ZrSi
2the test result of+5%CNTs/1550 DEG C is: density 98.88%, grain-size 0.3 ~ 0.6 μm, flexural strength 457MPa, fracture toughness property 6.45MPam
1/2.
70%ZrB in embodiment 8
2+ 25%ZrSi
2the test result of+5%CNTs/1550 DEG C and existing zirconium diboride-aluminium nitride (AlN) ceramic matric composite comparison sheet:
Note: in pertinent literature, the preparation method of material is hot pressed sintering, the volume parts proportioning of composition is 95.4%ZrB
2+ 4.6%AlN
Other embodiments are not listed completely, preparation process and test result as can be seen from embodiment 1 ~ 13:
Its density of zirconium diboride ceramics based composites prepared through the inventive method, all higher than 90%, shows that the method can realize the preparation of high-compactness ultra-temperature ceramic-based composite material.
The best hot pressing temperature (1550 DEG C) of material of the present invention, hot pressing time (15min) are all less than the sintering parameter in current open report needed for material.Its flexural strength is 497MPa simultaneously, decline to some extent compared to the flexural strength in report, this is due to zirconium carbide (ZrC) and silicon carbide (SiC) nanocrystal of distributing around zirconium diboride crystal grain, result in a kind of relatively weak interface cohesion, reduce the flexural strength of material, but 497MPa (embodiment 8) can reach the service requirements under the hypersonic environment of space industry.
Simultaneously between its optimum grain-size 0.3 ~ 0.6 μm, compared to the grain-size 4.5 μm (average) in report, its grain refining is comparatively obvious, because of the toughening effect highly significant caused by grain refining, makes the Fracture Toughness of material of the present invention reach 6.98MPam
1/2(embodiment 8), more than the twice for material in document.
In sum, by there is higher-strength to low temperature, fast preparation, be achieved compared with the preparation technology of the zirconium diboride ceramics based composites of high-fracture toughness, high-compactness, fine grained texture, facilitate the further toughness reinforcing zirconium diboride ceramics base composite wood of follow-up employing fiber, and embodiment 8 is optimum.
The above; be only the present invention's preferably embodiment; but protection scope of the present invention is not limited thereto; anyly be familiar with those skilled in the art in the technical scope that the present invention discloses; be equal to according to technical scheme of the present invention and inventive concept thereof and replace or change, all should be encompassed within protection scope of the present invention.
Claims (6)
1. a preparation method for ceramic matric composite, is characterized in that, using zirconium diboride as matrix phase; Using zirconium disilicide as sintering aid; Using the matrix material that multi-walled carbon nano-tubes is mixed as the additive improving material inside organization structure;
Comprise the steps:
S1, dispersion grinding: get purity 99.5 ~ 99.9%, median size is the zirconium diboride powder of 1 ~ 3 μm, mass percent 70 ~ 90%; Get purity 99.5 ~ 99.9%, median size is the zirconium disilicide powder of 1 ~ 2 μm, mass percent 10 ~ 20%; And get the multi-walled carbon nano-tubes of purity 97.5 ~ 99.9%, external diameter 20 ~ 40nm, length 5 ~ 15 μm, mass percent 0 ~ 10%; Add dehydrated alcohol and carry out concussion dispersion, then carry out using described dehydrated alcohol as medium grinding and disperseing;
The material slurry vaporize draw that S2, S1 obtain;
S3, the dry powder mortar grinder of bulk that will extract, sieve through 100 ~ 200 order material screens after terminating;
S4, load in mould carry out two step pressure sintering hot pressed sinterings by sieving the powder got, be specially:
First, with the temperature rise rate of 3 ~ 5 DEG C/min, sintering temperature is risen to 1250 DEG C from room temperature, heat-insulation pressure keeping 10 ~ 15min, sintering pressure is 10 ~ 30MPa;
Then, rise to 1450 ~ 1650 DEG C with the temperature rise rate of 10 ~ 15 DEG C/min, heat-insulation pressure keeping 5 ~ 10min, sintering pressure 10 ~ 30MPa;
In addition, whole sintering process is in high vacuum environment, 0 ~ 0.1Pa;
After sintering, in matrix material, be of a size of zirconium carbide and the carborundum grain of 30 ~ 60nm, be evenly distributed on around zirconium diboride crystal grain.
2. the preparation method of ceramic matric composite according to claim 1, it is characterized in that, in S1, zirconium diboride powder quality per-cent is 75%, and zirconium disilicide powder is 20%, and multi-walled carbon nano-tubes is 5%.
3. the preparation method of ceramic matric composite according to claim 1, is characterized in that, in S4, first, with the ramp to 1250 DEG C of 5 DEG C/min, and heat-insulation pressure keeping 10min, sintering pressure 30MPa; Then, with the ramp to 1550 DEG C of 15 DEG C/min, heat-insulation pressure keeping 5min, sintering pressure 30MPa.
4. according to the preparation method of the arbitrary described ceramic matric composite of claim 1-3, it is characterized in that, in S1, described grinding adopts planetary ball mill; The speed setting of ball mill is 160 ~ 200rpm, Ball-milling Time 12 ~ 48h, and is filled with protection of inert gas to the ball grinder that material is housed.
5. the preparation method of ceramic matric composite according to claim 4, is characterized in that, the speed setting of described ball mill is 180rpm, Ball-milling Time is 24h.
6. the preparation method of ceramic matric composite according to claim 5, is characterized in that, select rotatory evaporator to extract in S2, and the condition that described rotary evaporation extracts is: bath temperature 40 ~ 45 DEG C, and omnidistancely uses ar gas environment protection.
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| CN107721433B (en) * | 2015-10-21 | 2021-03-12 | 哈尔滨工业大学 | Boron nitride complex phase ceramic and sintering method and application thereof |
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| CN106518120B (en) * | 2016-10-27 | 2019-06-11 | 哈尔滨工业大学 | A kind of preparation method and application of carbon fiber-carbon nanotube composite toughening ZrC ceramic composite |
| CN108299000A (en) * | 2018-03-30 | 2018-07-20 | 安徽工程大学 | A kind of high-densit ZrB of low temperature preparation2-ZrSi2-CfThe method of ultrahigh temperature ceramic composite |
| CN110640138B (en) * | 2019-09-11 | 2021-07-06 | 大连理工大学 | ZrNiSn-based Half-Heusler thermoelectric material and preparation method thereof and method for regulating and controlling inversion defects |
| CN113773090B (en) * | 2021-11-15 | 2022-02-18 | 长沙理工大学 | ZrB2Preparation method of-ZrC-SiC nano composite ceramic material |
| CN114133271A (en) * | 2021-12-28 | 2022-03-04 | 河南联合精密材料股份有限公司 | Diamond-silicon carbide composite ceramic and preparation method thereof |
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