CN103833403A - Preparation method of silicon carbide whisker toughened boron carbide (B4C) ceramic composite material and product thereof - Google Patents
Preparation method of silicon carbide whisker toughened boron carbide (B4C) ceramic composite material and product thereof Download PDFInfo
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- CN103833403A CN103833403A CN201410075504.XA CN201410075504A CN103833403A CN 103833403 A CN103833403 A CN 103833403A CN 201410075504 A CN201410075504 A CN 201410075504A CN 103833403 A CN103833403 A CN 103833403A
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Abstract
The invention discloses a preparation method of a silicon carbide whisker toughened boron carbide (B4C) ceramic composite material and a product thereof. According to the method, a B4C blank is prepared by adopting a low-temperature reaction sintering and cold isostatic pressing combined method, so that the sintering temperature is lowered, and the relative density of a pressed blank is increased; through adopting a whisker toughening method, the crack propagation resistance is improved, and the fracture toughness of B4C ceramics is improved.
Description
Technical field
The invention belongs to field of inorganic nonmetallic material, relate to the preparation technology of matrix material, especially a kind of preparation method of silicon carbide toughened boron carbide ceramics matrix material.
Background technology
B
4c is widely used because having a series of premium propertiess such as high rigidity, high-melting-point, low density, high-wearing feature, high absorption neutron, but also there are two fatal weakness in it: the one, and sintering difficulty, because boron in boron carbide ceramics and carbon are with stronger covalent bonds (composition of covalent linkage is up to 93.9%); The 2nd, the low (KIC<2.2MPam of fracture toughness property
1/2), two above defects are greatly limited the application of boron carbide ceramics.
At present to B
4it is SiCw that C pottery carries out the maximum of toughness reinforcing use.At B
4in C pottery, add SiCw, preparation SiCw/B
4c matrix material.The unsticking of SiCw meeting generation whisker in ceramic breaking-down process is extracted, crack deflection, and this has all consumed energy, has strengthened fracture toughness and the intensity of material.For B
4c Sintering Problem, general sintering method is summed up and is mainly contained normal pressure-sintered, hot pressed sintering, high temperature isostatic pressing sintering etc.But the density of normal pressure-sintered material is lower, be difficult to reach necessary requirement; Hot pressed sintering, high temperature isostatic pressing sintering can make high-compactness and high performance stupalith, but sintering temperature is high, high and wayward to equipment requirements.
Current B
4there is sintering temperature high (2000 ~ 2300 ℃), problem that cost is large in C ceramic product preparation technology, high temperature sintering causes whisker damage toward contact meeting, and the product size that adopts this technique to prepare is restricted, can only do the simple goods of shape.
The present invention has overcome above-mentioned defect.
Summary of the invention
The object of the invention is to overcome above-mentioned the deficiencies in the prior art, a kind of SiCw/B for preparing at a lower temperature high-compactness, high fracture toughness is provided
4c ceramic composite.
The present invention addresses the aforementioned drawbacks taked technical scheme: adopt low temperature reaction sintering to prepare B in conjunction with the method for isostatic cool pressing
4c base substrate, reduces sintering temperature, improves pressed compact relative density; On the other hand, by adopting crystal whisker toughened method, increase crack growth resistance, improve B
4c Ceramic Fracture toughness.
Technical scheme of the present invention realizes by following processing step:
(1) by mass percentage the boron carbide particles of the SiCw of the carbon black of 5 ~ 8wt%, 15 ~ 20wt%, 70 ~ 80wt % is joined in ball grinder, add again paraffin, the 0.5 ~ 1wt.% Tetramethylammonium hydroxide of 1.5 ~ 2wt.%, using the dehydrated alcohol of 1.5 ~ 2 times of powder quality as ball-milling medium ball milling 24 hours, obtain slurry;
(2) above-mentioned gained ball milling material is poured in pallet and be placed in baking oven 40 ~ 60 ℃ dry, when drying in the time that powder humidity is 2% ~ 3% left and right, powder is taken out, 60 orders sieve, extracting screen underflow packs in mould, on hydropress, carry out pre-molding with 60 ~ 100MPa pressure, obtain the biscuit with certain density;
(3) biscuit of step (2) institute precompressed is carried out to isostatic cool pressing processing, concrete technology is for to be wrapped in biscuit in rubber die sleeve, and again suppresses 5 ~ 10 minutes with the pressure of 180 ~ 200MPa in cold isostatic press;
(4) green compact after the compacting of step 3 isostatic cool pressing are heat-treated, concrete technology is: biscuit is positioned in mobile hydrogen push boat type reduction furnace, at three temperature, be incubated, the setting range of three temperature is respectively 350 ~ 400 ℃, 450 ~ 600 ℃, 650 ~ 800 ℃, push away boat speed and be made as 15 ~ 20 points/boat, be incubated respectively 25 ~ 35min, after binder removal, obtain porous blank;
(5) porous blank step 4 being obtained is placed in plumbago crucible, and on blank, placing theory needs powdery or the buik silicon of 2 times of silicon amounts (theory needs silicon msi=base substrate porosity × blank apparent volume × ρ si), 10
-2~ 10
-3under the vacuum environment of Pa, at 1450 ℃ ~ 1600 ℃ temperature, be incubated 30 ~ 90min, after furnace cooling, can obtain the SiC of high-compactness, high fracture toughness
w/ B
4c ceramic composite.
In above-mentioned steps (1), the granularity of norbide powder is 3.5 ~ 12.8 μ m.
Length-to-diameter ratio >=20 of silicon carbide whisker in above-mentioned steps (1).
The amount of dehydrated alcohol is powder quality in above-mentioned steps (1) 1.5 ~ 2 times.
The amount of the silicon of placing on blank in above-mentioned steps (5) is powdery or the buik silicon that theory needs 2 times of silicon amounts, and it is to be multiplied by silicon density after base substrate porosity is multiplied by blank apparent volume that theory needs silicon silicon amount again.
With respect to prior art, the present invention has the following advantages:
1. preparation technology proposed by the invention obtains SiCw/B under lesser temps (1450～1600 ℃)
4c matrix material, has reduced sintering temperature, has significantly reduced preparation cost.
2. the material density of gained of the present invention is up to 96% ~ 98%, and this result has still reached quite high fine and close effect aspect Whisker-Reinforced Ceramics.
3. the fracture toughness of materials that prepared by the present invention is high, and SiCw is from B
4the energy that consumes a part of extraneous load while extracting in C matrix, makes B
4the fracture toughness property of C reaches 4.9 ~ 6.3MPam
1/2.The material fracture toughness that this method obtains on basis at low temperature, is cheaply not less than some high temperature hot pressing techniques.
Accompanying drawing explanation
Fig. 1,2 is respectively the microscopic appearance figure of boron carbide powder, silicon carbide whisker.
Fig. 3 is the metallographic structure photo of the complex phase ceramic prepared of the present invention.
After Fig. 4 is the complex phase ceramic fracture prepared of the present invention, the shape appearance figure that the silicon carbide whisker unsticking of observing at its section is extracted.
Embodiment
The toughness reinforcing B of a kind of SiCw
4the preparation method of C ceramic composite, it comprises the following steps:
(1) by mass percentage by 5% carbon black, 15%SiCw, 78% boron carbide particles, join in ball grinder, add again 1.5% paraffin, 0.5% Tetramethylammonium hydroxide, using the dehydrated alcohol of powder quality 160% as ball-milling medium ball milling 24 hours, obtain slurry.
(2) then ball milling material is poured in pallet and be placed in baking oven 60 ℃ dry, when drying in the time that powder humidity is 3% left and right, powder is taken out, 60 orders sieve, and extracting screen underflow packs in mould, on hydropress, carry out pre-molding with 60MPa pressure, obtain the biscuit with certain density.
(3) biscuit of above-mentioned institute precompressed is wrapped in rubber die sleeve, and the pressure with 180MPa is suppressed again in cold isostatic press.
(4) green compact after isostatic cool pressing compacting are positioned in mobile hydrogen push boat type reduction furnace, are incubated 30min respectively at 380 ℃, 550 ℃, 700 ℃ three temperature, binder removal obtains porous blank.
(5) by blank as for plumbago crucible, on blank, place the silicon of 30g block, 10
-3under the vacuum environment of Pa, in 1550 ℃ of insulation 30min, after furnace cooling, can obtain the SiCw/B of high-compactness, high fracture toughness
4c stupalith.
Embodiment 2
The toughness reinforcing B of a kind of SiCw
4the preparation method of C ceramic composite, it comprises the following steps:
(1) by mass percentage by 8% carbon black, 19%SiCw, 70% boron carbide particles, join in ball grinder, then add 2% paraffin, 1% Tetramethylammonium hydroxide, using powder quality 200% dehydrated alcohol as ball-milling medium ball milling 24 hours, obtain slurry.
(2) then ball milling material is poured in pallet and be placed in baking oven 50 ℃ dry, when drying in the time that powder humidity is 2% left and right, powder is taken out, 60 orders sieve, and extracting screen underflow packs in mould, on hydropress, carry out pre-molding with 90MPa pressure, obtain the biscuit with certain density.
(3) biscuit of above-mentioned institute precompressed is wrapped in rubber die sleeve, and the pressure with 200MPa is suppressed again in cold isostatic press.
(4) green compact after isostatic cool pressing compacting are positioned in mobile hydrogen push boat type reduction furnace, are incubated 35min respectively at 400 ℃, 600 ℃, 800 ℃ three temperature, binder removal obtains porous blank.
Blank, as for plumbago crucible, is placed to 32g silica flour, 10 on blank
-3under the vacuum environment of Pa, in 1480 ℃ of insulation 60min, after furnace cooling, can obtain the SiCw/B of high-compactness, high fracture toughness
4c stupalith.
Claims (6)
1. the toughness reinforcing norbide (B of a silicon carbide whisker (SiCw)
4c) preparation method of ceramic composite, is characterized in that:
Step 1, by mass percentage by the B of the SiCw of the carbon black of 5 ~ 8wt%, 15 ~ 20wt%, 70 ~ 80wt%
4c particle joins in ball grinder, then adds paraffin, the 0.5 ~ 1wt% Tetramethylammonium hydroxide of 1.5% ~ 2 wt%, using dehydrated alcohol as ball-milling medium ball milling 24 hours, obtains slurry;
Step 2, above-mentioned steps one gained slurry being poured in pallet and be placed in baking oven is dry at 40 ~ 60 ℃ in temperature, when drying in the time that powder humidity is 2% ~ 3% left and right, powder is taken out, 60 orders sieve, extracting screen underflow packs in mould, on hydropress, carry out pre-molding with 60 ~ 100MPa pressure, obtain the biscuit with certain density;
Step 3, carries out isostatic cool pressing processing by the biscuit of two precompressed of above-mentioned steps, is wrapped in rubber die sleeve, and again suppresses 5 ~ 10 minutes with the pressure of 180 ~ 200MPa in cold isostatic press by biscuit;
Step 4, green compact after isostatic cool pressing compacting are heat-treated, concrete technique is: biscuit is positioned in mobile hydrogen push boat type reduction furnace, at three temperature, be incubated, the setting range of three temperature is respectively 350 ~ 400 ℃, 450 ~ 600 ℃, 650 ~ 800 ℃, push away boat speed and be made as 15 ~ 20 points/boat, be incubated respectively 25 ~ 35min, after binder removal, obtain porous blank;
Step 5, is placed in plumbago crucible by gained porous blank in step 4, places appropriate powdery or buik silicon, 10 on blank
-2~ 10
-3under the vacuum environment of Pa, at 1450 ℃ ~ 1600 ℃ temperature, be incubated 30 ~ 90min, after furnace cooling, can obtain the SiCw/B of high-compactness, high fracture toughness
4c ceramic composite.
2. the preparation method of the toughness reinforcing boron carbide ceramics matrix material of silicon carbide whisker according to claim 1, is characterized in that:
In step 1, the granularity of norbide powder is 3.5 ~ 12.8 μ m.
3. the preparation method of the toughness reinforcing boron carbide ceramics matrix material of silicon carbide whisker according to claim 1, is characterized in that:
Length-to-diameter ratio >=20 of silicon carbide whisker in step 1.
4. the preparation method of the toughness reinforcing boron carbide ceramics matrix material of silicon carbide whisker according to claim 1, is characterized in that:
In step 1, the amount of dehydrated alcohol is powder quality 1.5 ~ 2 times.
5. the preparation method of the toughness reinforcing boron carbide ceramics matrix material of silicon carbide whisker according to claim 1, is characterized in that:
The amount of the silicon of placing on blank in step 5 is powdery or the buik silicon that theory needs 2 times of silicon amounts, and it is to be multiplied by silicon density after base substrate porosity is multiplied by blank apparent volume that theory needs silicon silicon amount again.
6. according to the toughness reinforcing norbide (B of the preparation-obtained silicon carbide whisker of method described in claim 1 (SiCw)
4c) ceramic composite.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104591738A (en) * | 2015-02-04 | 2015-05-06 | 中国科学院上海硅酸盐研究所 | High-toughness boron carbide ceramic and preparation method thereof |
| CN104909789A (en) * | 2015-05-20 | 2015-09-16 | 铜陵宏正网络科技有限公司 | Alumina-fiber-enhanced boron carbide ceramic-based composite material and preparation method thereof |
| WO2016037316A1 (en) * | 2014-09-09 | 2016-03-17 | 南京工业大学 | Preparation method of sic porous ceramic material and porous ceramic material manufactured by using same |
| CN106478103A (en) * | 2015-09-01 | 2017-03-08 | 常熟佳合高级陶瓷材料有限公司 | A kind of preparation method of silicon carbide/carbon boron composite ceramic material |
| CN106673661A (en) * | 2016-12-26 | 2017-05-17 | 上海工程技术大学 | Thick-plate silicon carbide ceramic material and preparation method and application thereof |
| CN108911773A (en) * | 2018-06-20 | 2018-11-30 | 浙江立泰复合材料股份有限公司 | A kind of preparation method of silicon carbide fibre enhancing boron carbide ceramics material |
| CN109020587A (en) * | 2018-07-23 | 2018-12-18 | 吉林长玉特陶新材料技术股份有限公司 | A kind of preparation method of boron nitride nano-tube toughening titanium carbide neutron-absorbing ceramics |
| CN113345615A (en) * | 2021-05-31 | 2021-09-03 | 中国工程物理研究院材料研究所 | Paraffin/boron carbide neutron protection composite material and preparation method thereof |
| CN115403386A (en) * | 2022-08-24 | 2022-11-29 | 佛山国防科技工业技术成果产业化应用推广中心 | Whisker-reinforced boron carbide composite ceramic and preparation method thereof |
| CN118005401A (en) * | 2024-02-05 | 2024-05-10 | 兰溪泛翌精细陶瓷有限公司 | Prestress reinforced composite ceramic and production process thereof |
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Cited By (14)
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|---|---|---|---|---|
| US10287214B2 (en) | 2014-09-09 | 2019-05-14 | Nanjing Tech University | Preparation method of SiC porous ceramic material and porous ceramic material manufactured by using same |
| WO2016037316A1 (en) * | 2014-09-09 | 2016-03-17 | 南京工业大学 | Preparation method of sic porous ceramic material and porous ceramic material manufactured by using same |
| EP3192786A4 (en) * | 2014-09-09 | 2018-05-16 | Nanjing University of Technology | Preparation method of sic porous ceramic material and porous ceramic material manufactured by using same |
| CN104591738A (en) * | 2015-02-04 | 2015-05-06 | 中国科学院上海硅酸盐研究所 | High-toughness boron carbide ceramic and preparation method thereof |
| CN104909789A (en) * | 2015-05-20 | 2015-09-16 | 铜陵宏正网络科技有限公司 | Alumina-fiber-enhanced boron carbide ceramic-based composite material and preparation method thereof |
| CN106478103A (en) * | 2015-09-01 | 2017-03-08 | 常熟佳合高级陶瓷材料有限公司 | A kind of preparation method of silicon carbide/carbon boron composite ceramic material |
| CN106673661A (en) * | 2016-12-26 | 2017-05-17 | 上海工程技术大学 | Thick-plate silicon carbide ceramic material and preparation method and application thereof |
| CN108911773A (en) * | 2018-06-20 | 2018-11-30 | 浙江立泰复合材料股份有限公司 | A kind of preparation method of silicon carbide fibre enhancing boron carbide ceramics material |
| CN109020587A (en) * | 2018-07-23 | 2018-12-18 | 吉林长玉特陶新材料技术股份有限公司 | A kind of preparation method of boron nitride nano-tube toughening titanium carbide neutron-absorbing ceramics |
| CN109020587B (en) * | 2018-07-23 | 2021-06-01 | 吉林长玉特陶新材料技术股份有限公司 | Preparation method of boron nitride nanotube toughened titanium carbide neutron absorption ceramic |
| CN113345615A (en) * | 2021-05-31 | 2021-09-03 | 中国工程物理研究院材料研究所 | Paraffin/boron carbide neutron protection composite material and preparation method thereof |
| CN113345615B (en) * | 2021-05-31 | 2022-12-27 | 中国工程物理研究院材料研究所 | Paraffin/boron carbide neutron protection composite material and preparation method thereof |
| CN115403386A (en) * | 2022-08-24 | 2022-11-29 | 佛山国防科技工业技术成果产业化应用推广中心 | Whisker-reinforced boron carbide composite ceramic and preparation method thereof |
| CN118005401A (en) * | 2024-02-05 | 2024-05-10 | 兰溪泛翌精细陶瓷有限公司 | Prestress reinforced composite ceramic and production process thereof |
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