CN1232805A - Preparation of silicon nitride-based composite material with superhigh tenacity - Google Patents
Preparation of silicon nitride-based composite material with superhigh tenacity Download PDFInfo
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- CN1232805A CN1232805A CN 99107783 CN99107783A CN1232805A CN 1232805 A CN1232805 A CN 1232805A CN 99107783 CN99107783 CN 99107783 CN 99107783 A CN99107783 A CN 99107783A CN 1232805 A CN1232805 A CN 1232805A
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- polyvinyl alcohol
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- 239000002131 composite material Substances 0.000 title claims abstract description 12
- 229910052581 Si3N4 Inorganic materials 0.000 title claims abstract description 9
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 title claims abstract description 8
- 238000002360 preparation method Methods 0.000 title claims description 14
- 239000000463 material Substances 0.000 claims abstract description 29
- 239000000314 lubricant Substances 0.000 claims abstract description 21
- 239000000919 ceramic Substances 0.000 claims abstract description 20
- 239000000758 substrate Substances 0.000 claims abstract description 16
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 7
- 239000010439 graphite Substances 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims abstract description 7
- 235000011187 glycerol Nutrition 0.000 claims abstract description 5
- 238000005245 sintering Methods 0.000 claims description 28
- 239000011159 matrix material Substances 0.000 claims description 27
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 24
- 239000011230 binding agent Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 23
- 239000004902 Softening Agent Substances 0.000 claims description 20
- 239000011812 mixed powder Substances 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000012153 distilled water Substances 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 17
- 239000000835 fiber Substances 0.000 claims description 14
- 238000001125 extrusion Methods 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- 238000009472 formulation Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- 238000005096 rolling process Methods 0.000 claims description 9
- 229920003023 plastic Polymers 0.000 claims description 8
- 239000004033 plastic Substances 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 7
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- 235000011194 food seasoning agent Nutrition 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 238000007766 curtain coating Methods 0.000 claims description 5
- 238000003618 dip coating Methods 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- 230000003750 conditioning effect Effects 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- 238000005266 casting Methods 0.000 claims description 2
- 239000003446 ligand Substances 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 239000003292 glue Substances 0.000 abstract 1
- 229940057995 liquid paraffin Drugs 0.000 abstract 1
- 239000004014 plasticizer Substances 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 6
- 208000037656 Respiratory Sounds Diseases 0.000 description 5
- 238000005452 bending Methods 0.000 description 5
- 230000001066 destructive effect Effects 0.000 description 5
- 230000003592 biomimetic effect Effects 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 3
- 241000446313 Lamella Species 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 2
- 235000017491 Bambusa tulda Nutrition 0.000 description 2
- 241001330002 Bambuseae Species 0.000 description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 2
- 239000011805 ball Substances 0.000 description 2
- 239000011425 bamboo Substances 0.000 description 2
- 239000012620 biological material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 210000001170 unmyelinated nerve fiber Anatomy 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 230000029663 wound healing Effects 0.000 description 1
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Abstract
The composite material includes substrate and boundary layer, the material for the substrate includes Si3N4, baking assistant and flexibilizer, and the material for the boundary layer is BN. The substrate material powder after being ball ground and mixed is compounded with PVA solution as adhesive, liquid paraffin as lubricant and glycerine as plasticizer. The ceramic blank with formed boundary layer is placed into graphite mold to exhaust glue and sintered so as to result in the silicon nitride-based composite material of the present invention. The composite material of the present invention has high tenacity, high temperature resistance and good mechanical impact resistance and other advantages.
Description
The present invention relates to a kind of preparation method of silicon nitride-based composite material with superhigh tenacity, belong to materials science field.
Plurality of advantages such as structural ceramic material is high-strength with it, height is hard, high temperature resistant, corrosion-resistant, light weight, be subjected to people's extensive attention and research in recent decades always, obtained certain application at aspects such as heat exchanger, cutting tool, wear parts, sealing elements, used more widely but the fragility of stupalith has but limited it.For this reason, people have proposed many toughness reinforcing methods, as macrofiber is toughness reinforcing, crystal whisker toughened, particle dispersion is toughness reinforcing and transformation toughening etc., though these method for toughening have all been obtained certain toughening effect to some extent, but the fragility of stupalith fundamentally is not resolved.
In recent years, Chinese scholars takes a hint from the structure of natural biomaterial (as pearl, shell, bamboo etc.).These natural biologic materials only pass through the accurate compound of simple component, just can obtain excellent specific properties such as compound complementation, functional adaptation and wound healing.For example bamboo wood is typical macrofiber reinforced composite, and it strengthens the distribution that the body fiber has different yardstick and lift angle, makes its stretch-proof, bending and compressive strength and modulus can bring into play maximum effect in the combination of materials of isodose.Same, in shell pearl layer, the content of aragonite is up to 99%, but by connecting by special laminate structure less than 1% the organic matter aragonite wafer with different size, formed the matrix material of laminate structure, its fracture toughness property but exceeds more than 3000 times than pure aragonite.If with reference to the constructional feature of these biomaterials, when material designed, scientifically the microtexture of control material was expected to prepare the biomimetic features material with good mechanical property.Reported that as people such as the U.S. W.J.Clegg people such as the ceramic layered material of SiC/C, H.Y.Liu have reported Si
3N
4The ceramic layered material of/BN, Baskaran etc. have prepared the stupalith of SiC/C fiber monolithic structure, by these biomimetic features designs, the fracture toughness property and the work of rupture of prepared stupalith all have increased significantly, fracture toughness property can improve several times, and work of rupture can improve tens of times and even hundreds of times.A common characteristic is exactly in the design and preparation of material, has introduced a kind of weak bonded interfacial phase, by the repeatedly deviation of interfacial phase to crackle, improves fracture toughness property and work of rupture.Yet in research in the past, because the introducing of weak interface phase, though improved the toughness and the work of rupture of stupalith significantly, decline has to a certain degree but appearred in its intensity.
The objective of the invention is to propose a kind of preparation method of silicon nitride-based composite material with superhigh tenacity, on the basis of former studies, except introducing the weak interface phase, the whisker and the matrix long column shape crystal grain of strengthening effect also in the matrix ceramic phase, have been introduced, and through technology controlling and process, make whisker and matrix long column shape crystal grain by the certain way oriented alignment, improved the fracture toughness property and the fracture function of material on the one hand significantly, also kept the intensity of matrix stupalith simultaneously.
The used raw material of the present invention is:
Matrix:
Si
3N
4 (50～80)％
Sintering agent (10～25) % [(0～10) %La
2O
3+ (0～10) %Y
2O
3+ (0～5) %Al
2O
3+ (0～5) %MgO]
Toughner (0～25) % SiC whisker+(0～10) % β-Si
3N
4Crystal seed
Interfacial layer:
BN (60～90)％
Interface conditioning agent (0～40) %Al
2O
3+ (0～20) %Si
3N
4
The preparation method of silicon nitride-based composite material with superhigh tenacity of the present invention comprises following each step:
(1) by matrix formulation weighing ligand material, putting into ball grinder, is abrading-ball with the agate ball, is medium with alcohol, 24 hours (material: ball: alcohol=1: (1～2): (1.2～2)) of ball mill mixing.Discharging after oven dry about 80 ℃, is crossed 50～100 mesh sieves, obtains the blended powder.
(2) compound concentration is 10～25% polyvinyl alcohol solution: get the polymerization degree and be 10～25 parts of 1400～2000 polyvinyl alcohol, be dissolved in 75～85 parts 80 ℃ the distilled water, and add 4～10% calcium chloride (CaCl
3) as stablizer, after stirring, constant temperature is 8～15 hours in 80 ℃ water-bath.
(3) moulding process: comprise the moulding of matrix lamella and the formation of interfacial layer, the matrix lamella is divided into the base substrate of fiber born of the same parents shape base substrate and laminate structure again.
For the base substrate with fiber cell structure, fibrous green compact obtain by extrusion forming.
The polyvinyl alcohol water solution that adds preparation in (3) in the mixed powder that in (2), obtains as binding agent, add whiteruss as lubricant, add glycerine as softening agent.Add-on is pressed mixed powder: binding agent: lubricant: softening agent=100: (25～75): (1～5): (1～5).Carry out the batch mixing pugging with roll forming machine or vacuum mixer, until obtaining the good plastic walk of plasticity, the walk water ratio is 10～25%.And with walk under sealed state old 12～24 hours.Then plastic walk is put into forcing machine, extrusion moulding, extrusion pressure is 15～50MPa, extrusion diameter 0.3～1.5mm.Hang the thread base substrate of extruding up seasoning.
For the base substrate of rhythmo structure, synusia shape base substrate can obtain by methods such as rolling or curtain coatings, and thickness is 0.03～1mm.
If adopt rolling method, the polyvinyl alcohol water solution that then adds preparation in (3) in the mixed powder that in (2), obtains as binding agent, add whiteruss as lubricant, adding glycerine as softening agent.Add-on is pressed mixed powder: binding agent: lubricant: softening agent=100: (25～75): (1～5): (1～5).Carry out repeat-rolling with roll forming machine, obtain the green compact thin slice of thickness by roughing earlier, pass through finish rolling again, roll into the thin slice of thickness less than 0.08～1mm less than 2mm.
If adopt casting method, then in mixed powder: polyvinyl alcohol solution: dispersion agent: lubricant: softening agent: distilled water=100: (40～75): (1～2): (1～5): (1～5): the ratio of (30～120), the mixed powder that obtains in (2) is put into ball grinder with poly (vinyl alcohol) binder and dispersion agent, lubricant, softening agent and distilled water, ball mill mixing, obtain slurry even, good fluidity, the viscosity controller of slurry is at 1～100Pas.Curtain coating speed is 0.1～1m/min, and thickness is 0.03～1mm.
By the above method of moulding moulding process, the SiC whisker and the β-Si that in raw material, add in advance
3N
4The column crystal seed forms has aligning of certain orientation degree.
(4) interfacial layer moulding
By (60～90) %BN+ (0～40) %Al
2O
3+ (0～20) %Si
3N
4Ratio, put into ball grinder, in the material: ball: alcohol: distilled water: polyvinyl alcohol solution=100: (150～200): (20～50): (20～100): the ratio of (10～40), BN is mixed with the interfacial layer conditioning agent, obtain uniform interfacial layer slurry.Adopt the BN interfacial layer of methods such as spraying, dip-coating or silk screen printing at fiber born of the same parents shape or lamellated ceramic body surface-coated (0.01～0.1) mm thickness.
Then that the ceramic body after the coating is parallel, lamination or arrange by certain mode is put into graphite jig.
(5) binder removal and sintering
To arrange good ceramic body under air atmosphere, heat up at a slow speed earlier (＜5 ℃/minute) be incubateds 2～4 hours and carry out the binder removal processing to 300～400 ℃, treat that organism drains fully after, the pressure that applies 5～10MPa is colded pressing.Place the hot-pressed sintering furnace hot pressed sintering of nitrogen atmosphere afterwards, temperature rise rate is (5～20) ℃/min, and sintering temperature is 1600～1850 ℃, soaking time 1～2 hour, and in sintering process, apply the pressure of 15～40MPa, be nitride silicon based composite material of the present invention.
By the reality of biomimetic features and above-mentioned preparation technology, prepare SiCw-Si respectively with fiber cell structure
3N
4/ BN matrix material and SiCw-Si with laminate structure
3N
4/ BN matrix material in this two classes material, includes the ceramic matrix phase and the low intensive interfacial phase of high-intensity densification.Wherein low intensive interfacial phase forms a large amount of mechanics weak interfaces in stupalith, can carry out repeatedly deviation, make the crack tip passivation, cause the bridge joint of the fine and close relative crackle of ceramic matrix and extract etc. crackle in stupalith stressed when cracking, thereby reduce stupalith greatly to the susceptibility of crackle and improve toughness.Simultaneously the high strength matrix mutually in introducing whisker, bridge joint that long column shape crystal grain plays whisker again, extract, the bridge joint of long column shape crystal grain, extract, pinning and to the multiple toughening mechanisms such as deflection of crackle, thereby formed the coordination plasticizing effect of the multistage toughening mechanisms of different scale, thereby improved the mechanical property of described stupalith significantly.Prepared this two class matrix materials all have mechanical property preferably: fracture toughness property＞20MPam
1/2, intensity is 500～700MPa, work of rupture＞4000J/m
2, and load one displacement curve of material demonstrates non-brittle destructive characteristic.
The prepared biomimetic features matrix material of the present invention has high tenacity, high temperature resistant, good advantages such as mechanical shock resistance, can be used for the surfacing of parts such as space shuttle, plate armour, transport pipe and the material of some structure component, have boundless application prospect.
Introduce embodiments of the invention below:
Embodiment one:
The body material formulation selection is 85%Si
3N
4+ 8%Y
2O
3+ 2.5%Al
2O
3+ 1.5%MgO+3% β-Si
3N
4Crystal seed.The interfacial layer formulation selection is 80%BN+20%Al
2O
3With the matrix material weighing, putting into ball grinder earlier, is abrading-ball with the agate ball, is medium with alcohol, 24 hours (material: ball: alcohol=1: 2: 1.5) of ball mill mixing.Discharging after oven dry about 80 ℃, is crossed 100 mesh sieves, obtains the blended powder.Get the polymerization degree and be 20 parts of 1788 polyvinyl alcohol, be dissolved in 80 parts 80 ℃ the distilled water, and add 7% calcium chloride (CaCl
2) as stablizer, after stirring, constant temperature is 10 hours in 80 ℃ water-bath.In mixed powder: binding agent: lubricant: softening agent=100: 40: 3: 3 ratio joins binding agent, lubricant and softening agent in the mixed powder, carry out the batch mixing pugging with roll forming machine, until obtaining the good plastic walk of plasticity, the walk water ratio is 20%.And with walk under sealed state old 24 hours.Then plastic walk is put into forcing machine, extrusion moulding, extrusion pressure is 20MPa, extrusion diameter 0.3mm.Hang the thread base substrate of extruding up seasoning.The interfacial layer raw material is put into ball grinder by above-mentioned prescription, and in expecting: ball: alcohol: distilled water: polyvinyl alcohol solution=100: 150: 30: 80: 20 ratio is carried out batch mixing, obtains uniform interfacial layer slurry.Adopt the BN interfacial layer of the method for dip-coating at base substrate fiber surface coating 0.03mm thickness.Then the ceramic body after the coating is arranged in parallel, puts into graphite jig.To arrange good ceramic body under air atmosphere, the speed with 2 ℃/min is warming up to 320 ℃ at a slow speed earlier, be incubated 4 hours and carry out binder removal to handle, treat that organism drains fully after, the pressure that applies 8MPa is colded pressing.Place the hot-pressed sintering furnace hot pressed sintering of nitrogen atmosphere afterwards, temperature rise rate is 10 ℃/min, and sintering temperature is 1800 ℃, soaking time 1.5 hours, and in sintering process, apply the pressure of 22MPa.Contain β-Si thereby prepare
3N
4The Si of crystal seed
3N
4The matrix material of/BN fiber cell structure presents to a certain degree oriented alignment by the formed long column shape crystal grain of crystal seed along fiber direction.Through measuring, its bending strength is 530MPa, and fracture toughness property is 17.2MPam
1/2, work of rupture is 4000J/m
2, its load one inflection curves presents non-linear destructive characteristic.
Embodiment two:
The body material formulation selection is 60%Si
3N
4+ 11.3%La
2O
3+ 7.8%Y
2O
3+ 0.9%Al
2O
3+ 20%SiC whisker.The interfacial layer formulation selection is 85%BN+15%Si
3N
4With the matrix material weighing, putting into ball grinder earlier, is abrading-ball with the agate ball, is medium with alcohol, 24 hours (material: ball: alcohol=1: 2: 1.8) of ball mill mixing.Discharging after oven dry about 80 ℃, is crossed 60 mesh sieves, obtains the blended powder.Get the polymerization degree and be 18 parts of 1650 polyvinyl alcohol, be dissolved in 82 parts 80 ℃ the distilled water, and add 6% calcium chloride (CaCl
2) as stablizer, after stirring, constant temperature is 12 hours in 80 ℃ water-bath, obtains concentration and be 18% polyvinyl alcohol solution.In mixed powder: binding agent: lubricant: softening agent=100: 45: 3: 3 ratio joins binding agent, lubricant and softening agent in the mixed powder, carry out the batch mixing pugging with roll forming machine, until obtaining the good plastic walk of plasticity, the walk water ratio is 21.5%.And with walk under sealed state old 12 hours.Then plastic walk is put into forcing machine, extrusion moulding, extrusion pressure is 14MPa, extrusion diameter 0.5mm.Hang the thread base substrate of extruding up seasoning.The interfacial layer raw material is put into ball grinder by above-mentioned prescription, and in expecting: ball: alcohol: distilled water: polyvinyl alcohol solution=100: 120: 30: 90: 30 ratio is carried out batch mixing, obtains uniform interfacial layer slurry.Adopt the BN interfacial layer of the method for dip-coating at base substrate fiber surface coating 0.025mm thickness.Then the ceramic body after the coating is arranged in parallel, puts into graphite jig.To arrange good ceramic body under air atmosphere, the speed with 3 ℃/min is warming up to 350 ℃ at a slow speed earlier, be incubated 2 hours and carry out binder removal to handle, treat that organism drains fully after, the pressure that applies 10MPa is colded pressing.Place the hot-pressed sintering furnace hot pressed sintering of nitrogen atmosphere afterwards, temperature rise rate is 10 ℃/min, and sintering temperature is 1820 ℃, soaking time 1.5 hours, and in sintering process, apply the pressure of 20MPa.Thereby prepare the Si that contains the SiC whisker
3N
4The matrix material of-SiCw/BN fiber cell structure, and whisker presents oriented alignment preferably along fiber direction.Through measuring, its bending strength is 705MPa, and fracture toughness property is 20MPam
1/2, work of rupture is 4400J/m
2, its load one inflection curves presents non-linear destructive characteristic.
Embodiment three:
The body material formulation selection is 75%Si
3N
4+ 11.3%La
2O
3+ 7.8%Y
2O
3+ 0.9%Al
2O
3+ 15%SiC whisker.The interfacial layer formulation selection is 75%BN+25%Al
2O
3With the matrix material weighing, putting into ball grinder earlier, is abrading-ball with the agate ball, is medium with alcohol, 24 hours (material: ball: alcohol=1: 2: 1.5) of ball mill mixing.Graduate from old-type opera school, after oven dry about 80 ℃, cross 80 mesh sieves, obtain the blended powder.Get the polymerization degree and be 20 parts of 1800 polyvinyl alcohol, be dissolved in 80 parts 80 ℃ the distilled water, and add 9% calcium chloride (CaCl
2) as stablizer, after stirring, constant temperature is 8 hours in 80 ℃ water-bath, obtains concentration and be 20% polyvinyl alcohol solution.In mixed powder: binding agent: lubricant: softening agent=100: 35: 3: 1 ratio joins binding agent, lubricant and softening agent in the mixed powder, carry out repeat-rolling with roll forming machine, earlier obtain the green compact thin slice that thickness is 0.8mm by roughing, pass through finish rolling again, roll into the thin slice of thickness, seasoning less than 0.15mm.The interfacial layer raw material is put into ball grinder by above-mentioned prescription, and in expecting: ball: alcohol: distilled water: polyvinyl alcohol solution=100: 120: 40: 80: 25 ratio is carried out batch mixing, obtains uniform interfacial layer slurry.Adopt the BN interfacial layer of the method for spraying at base substrate fiber surface coating 0.04mm thickness.With the ceramic body stacked arrangement after the coating, put into graphite jig then.To arrange good ceramic body under air atmosphere, the speed with 3 ℃/min is warming up to 380 ℃ at a slow speed earlier, be incubated 2.5 hours and carry out binder removal to handle, treat that organism drains fully after, the pressure that applies 12MPa is colded pressing.Place the hot-pressed sintering furnace hot pressed sintering of nitrogen atmosphere afterwards, temperature rise rate is 10 ℃/min, and sintering temperature is 1780 ℃, soaking time 1 hour, and in sintering process, apply the pressure of 25MPa.Thereby prepare the Si that contains the SiC whisker
3N
4The matrix material of-SiCw/BN laminate structure, whisker presents one dimension oriented alignment preferably in the synusia direction.Through measuring, its bending strength is 740MPa, and fracture toughness property is 28.4MPam
1/2, work of rupture is 5700J/m
2, its load-deformation curve presents non-linear destructive characteristic.
Embodiment four:
The body material formulation selection is 67%Si
3N
4+ 10%Y
2O
3+ 3%MgO+20%SiC whisker.The interfacial layer formulation selection is 90%BN+10%Si
3N
4With the matrix material weighing, putting into ball grinder earlier, is abrading-ball with the agate ball, is medium with alcohol, 24 hours (material: ball: alcohol=1: 1.5: 1.2) of ball mill mixing.Discharging after oven dry about 80 ℃, is crossed 60 mesh sieves, obtains the blended powder.Get the polymerization degree and be 15 parts of 1700 polyvinyl alcohol, be dissolved in 85 parts 80 ℃ the distilled water, and add 6% calcium chloride (CaCl
2) as stablizer, after stirring, constant temperature is 15 hours in 80 ℃ water-bath, obtains concentration and be 15% polyvinyl alcohol solution.In mixed powder: polyvinyl alcohol solution: dispersion agent: lubricant: softening agent: distilled water=100: 55: 1: 3: 2: 80 ratio, mixed powder is put into ball grinder with tackiness agent, dispersion agent, lubricant, softening agent and distilled water, ball mill mixing, obtain even, mobile slurry, the viscosity controller of slurry is at 0.5Pas.Under the curtain coating speed of 1m/min, curtain coating goes out the matrix lamella that thickness is 0.09mm, seasoning.The interfacial layer raw material is put into ball grinder by above-mentioned prescription, and in expecting: ball: alcohol: distilled water: polyvinyl alcohol solution=100: 150: 30: 75: 30 ratio is carried out batch mixing, obtains uniform interfacial layer slurry.Adopt the BN interfacial layer of the method for dip-coating at base substrate fiber surface coating 0.03mm thickness.With the ceramic body stacked arrangement after the coating, put into graphite jig then.To arrange good ceramic body under air atmosphere, the speed with 2 ℃/min is warming up to 350 ℃ at a slow speed earlier, be incubated 3 hours and carry out binder removal to handle, treat that organism drains fully after, the pressure that applies 15MPa is colded pressing.Place the hot-pressed sintering furnace hot pressed sintering of nitrogen atmosphere afterwards, temperature rise rate is 10 ℃/min, and sintering temperature is 1800 ℃, soaking time 1.5 hours, and in sintering process, apply the pressure of 25MPa.Thereby prepare the Si that contains the SiC whisker
3N
4The matrix material of-SiCw/BN laminate structure, whisker presents one dimension oriented alignment preferably in the synusia direction.Through measuring, its bending strength is 710MPa, and fracture toughness property is 29MPam
1/2, work of rupture is 6500J/m
2, its load-deformation curve presents non-linear destructive characteristic.
Claims (1)
1, a kind of preparation method of silicon nitride-based composite material with superhigh tenacity is characterized in that, this preparation method comprises following each step:
(1) by matrix formulation weighing ligand material, the proportioning of matrix is:
Si
3N
4 (50～80)％
Sintering agent (10～25) % [(0～10) %La
2O
3+ (0～10) %Y
2O
3+ (0～5) %Al
2O
3+ (0～5) %MgO]
Toughner (0～25) % SiC whisker+(0～10) % β-Si
3N
4Crystal seed
Putting into ball grinder, is abrading-ball with the agate ball, is medium with alcohol, ball mill mixing 20～26 hours, and its ratio is: material: ball: alcohol=1: (1～2): (1.2～2), discharging after oven dry about 80 ℃, is crossed 50～100 mesh sieves, obtains the blended powder;
(2) preparation 10～25% polyvinyl alcohol solution: get the polymerization degree and be 10～25 parts of 1400～2000 polyvinyl alcohol, be dissolved in 75～85 parts 80 ℃ the distilled water, and add 4～10% calcium chloride as stablizer, after stirring, constant temperature is 8～15 hours in 80 ℃ water-bath;
The polyvinyl alcohol water solution that adds above-mentioned second step preparation in the mixed powder that the above-mentioned the first step obtains is as binding agent, add whiteruss as lubricant, add glycerine as softening agent, add-on is pressed mixed powder: binding agent: lubricant: softening agent=100: (25～75): (1～5): (1～5), carry out the batch mixing pugging with roll forming machine or vacuum mixer, until obtaining the good plastic walk of plasticity, the walk water ratio is 10～25%, and with walk under sealed state old 12～24 hours, then plastic walk is put into forcing machine, extrusion moulding, extrusion pressure is 15～50MPa, extrusion diameter 0.3～1.5mm, hang the thread base substrate of extruding up seasoning;
Or adopt rolling method adds above-mentioned second step preparation in the mixed powder that the above-mentioned the first step obtains polyvinyl alcohol water solution as binding agent, add whiteruss as lubricant, add glycerine as softening agent, add-on is pressed mixed powder: binding agent: lubricant: softening agent=100: (25～75): (1～5): (1～5), carry out repeat-rolling with roll forming machine, earlier obtain the green compact thin slice of thickness less than 2mm by roughing, pass through finish rolling again, roll into the thin slice of thickness less than 0.08～1mm;
Or employing casting method, the mixed powder that the first step obtains is put into ball grinder with poly (vinyl alcohol) binder and dispersion agent, lubricant, softening agent and distilled water, its ratio is: polyvinyl alcohol solution: dispersion agent: lubricant: softening agent: distilled water=100: (40～75): (1～2): (1～5): (1～5): the ratio of (30～120), ball mill mixing, obtain slurry even, good fluidity, the viscosity controller of slurry is at 1～100Pa-s, curtain coating speed is 0.1～1m/min, and thickness is 0.03～1mm;
(4) interfacial layer moulding
By (60～90) %BN+ (0～40) %Al
2O
3+ (0～20) %Si
3N
4Ratio, put into ball grinder, in expecting: ball: alcohol: distilled water: polyvinyl alcohol solution=100: (150～200): (20～50): (20～100): the ratio of (10～40), BN is mixed with the interfacial layer conditioning agent, obtain uniform interfacial layer slurry, adopt spraying, dip-coating or method for printing screen at the fiber born of the same parents shape of above-mentioned the 3rd step acquisition or the BN interfacial layer of lamellated ceramic body surface-coated (0.01～0.1) mm thickness; Then the ceramic body after the coating is put into graphite jig;
(5) binder removal and sintering
To arrange good ceramic body under air atmosphere, speed with 2～5 ℃ of per minutes is warming up to 300～400 ℃ earlier, be incubated 2～4 hours and carry out the binder removal processing, after treating that organism drains fully, the pressure that applies 5～10MPa is colded pressing, place the hot-pressed sintering furnace hot pressed sintering of nitrogen atmosphere afterwards, temperature rise rate is 5～20 ℃/minute, sintering temperature is 1600～1850 ℃, soaking time 1～2 hour, and in sintering process, apply the pressure of 15～40MPa, be silicon nitride-based composite material with superhigh tenacity of the present invention.
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