CN100457409C - In situ inductive coagulating formative process for mullite-based ceramic by hydrolysis - Google Patents
In situ inductive coagulating formative process for mullite-based ceramic by hydrolysis Download PDFInfo
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- CN100457409C CN100457409C CNB2006100496962A CN200610049696A CN100457409C CN 100457409 C CN100457409 C CN 100457409C CN B2006100496962 A CNB2006100496962 A CN B2006100496962A CN 200610049696 A CN200610049696 A CN 200610049696A CN 100457409 C CN100457409 C CN 100457409C
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- 239000000919 ceramic Substances 0.000 title claims abstract description 67
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 229910052863 mullite Inorganic materials 0.000 title claims abstract description 65
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims description 24
- 230000008569 process Effects 0.000 title claims description 17
- 230000007062 hydrolysis Effects 0.000 title claims description 14
- 238000006460 hydrolysis reaction Methods 0.000 title claims description 14
- 230000001112 coagulating effect Effects 0.000 title 1
- 230000001939 inductive effect Effects 0.000 title 1
- 238000003756 stirring Methods 0.000 claims abstract description 31
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000005516 engineering process Methods 0.000 claims abstract description 21
- 239000002002 slurry Substances 0.000 claims description 48
- 239000000843 powder Substances 0.000 claims description 44
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 40
- 239000000758 substrate Substances 0.000 claims description 23
- 238000000465 moulding Methods 0.000 claims description 21
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 238000007596 consolidation process Methods 0.000 claims description 15
- 238000000498 ball milling Methods 0.000 claims description 13
- 239000002131 composite material Substances 0.000 claims description 13
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- 239000008187 granular material Substances 0.000 claims description 10
- 229920002545 silicone oil Polymers 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 239000004033 plastic Substances 0.000 claims description 9
- 229920003023 plastic Polymers 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 239000005543 nano-size silicon particle Substances 0.000 claims description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052851 sillimanite Inorganic materials 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 229910052845 zircon Inorganic materials 0.000 claims description 5
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims description 5
- 238000002347 injection Methods 0.000 claims description 4
- 239000007924 injection Substances 0.000 claims description 4
- 235000013312 flour Nutrition 0.000 claims description 3
- 238000001746 injection moulding Methods 0.000 claims description 3
- 239000004575 stone Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 2
- 239000011440 grout Substances 0.000 abstract 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract 1
- 239000003921 oil Substances 0.000 abstract 1
- 229910052710 silicon Inorganic materials 0.000 abstract 1
- 239000010703 silicon Substances 0.000 abstract 1
- 238000010583 slow cooling Methods 0.000 abstract 1
- 238000005245 sintering Methods 0.000 description 17
- 239000000463 material Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 239000003595 mist Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 238000007569 slipcasting Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 239000010431 corundum Substances 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 229910010293 ceramic material Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000003801 milling Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 230000001052 transient effect Effects 0.000 description 3
- KMWBBMXGHHLDKL-UHFFFAOYSA-N [AlH3].[Si] Chemical compound [AlH3].[Si] KMWBBMXGHHLDKL-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 235000015895 biscuits Nutrition 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
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- 238000011085 pressure filtration Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 1
- -1 aluminium silicon ion Chemical class 0.000 description 1
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
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- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 230000008676 import Effects 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
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Abstract
A technology for forming the mullite-based ceramic by hydrolytic reaction and induced in-situ solidifying includes such steps as adding formamide into the grout of mullite-based ceramic, stirring, pouring it in mould, covering a silicon oil on the surface of grout, solidifying at 50-80 deg.C for 10-60 min, slow cooling to 10-40 deg.C and demoulding.
Description
(1) technical field
The hydrolysis that the present invention relates to a kind of mullite-based ceramic is induced consolidation in-situ forming technology, belongs to the material engineering field.
(2) background technology
Mullite (3Al
2O
32SiO
2) have that load softening point height, creep-resistant property are good, characteristic such as chemical stability and good thermal stability, thermal conductivity and thermal coefficient of expansion are low, be a kind of important high-temperature structural material; Simultaneously, because good middle infrared transmission performance in its excellent dielectric properties and the hot environment, mullite also becomes very potential a kind of material in the applications such as electronic material, optical material.As high-temperature structural material or electronics and optical material, ceramic material property is not only relevant with the material composition, also depends on the moulding process of material to a great extent.Over past ten years, on traditional colloidal formation technology basis, people's multiple colloidal state in-situ consolidation forming technology that grows up gradually is used for the moulding of high-performance ceramic, and these methods can reduce the moulding volume defect effectively, improve the reliability of sintered body.In colloidal state consolidation in-situ forming technology, usually in technical process, introduce organic dispersing agent, organic monomer and crosslinking agent, natural gelatinous mass, organic substances such as protein, because these organic substances all have certain surface-active effect, in the pulp preparation process, will introduce well colloid bubble of a large amount of stability, slurry need be in the following stirring of condition of high vacuum degree before casting, the limit processing that outgases, could obtain the high-quality biscuit, this not only causes complex proceduresization, and bubble is difficult for thoroughly getting rid of, in base substrate, easily form defective, influence the reliability of ceramic component.
Because aluminium silicon ion diffusion coefficient is very little in the mullite, densified very high with the grain growth activation energy, reach 700kJmol
-1, therefore, the crystalline state mullite powder is difficult to sintering, realize densifiedly fully, and sintering temperature need reach more than 1700 ℃, perhaps adopts heat pressing process.Adopt the moulding of ultra-fine mullite powder and the sintering character of wet-chemical preparation also very poor, usually also need could obtain the mullite ceramic of height densification by means of isostatic compaction and hot pressed sintering or HIP sintering, study the ultra-fine mullite powder of hydrolytic precipitation method (Al as Guo Ruisong etc.
2O
3/ SiO
2=74/26, mass ratio) processability, with single shaft dry-pressing (250MPa), etc. static pressure (250MPa), first dry-pressing (100MPa) wait moulding process such as static pressure (250MPa), slip casting, press filtration, gel injection-moulding to prepare green compact again, microstructure, physical behaviors such as green density, microscopic appearance, gas cell distribution have been measured, show ultra-fine mullite powder compacting poor performance, dry-press process green compact relative volume density is the highest has only 38.6%; The wet moulding body is slightly high, and pressure filtration molding green compact relative volume density reaches 44.9%, gel casting forming green compact 42.1%; The moulding green compact are incubated 4h down at 1590 ℃, and the highest relative density of sintered density wet moulding body is 95.3% (pressure filtration molding base substrate), and gel casting forming blank sintering density is 94.1%, and the highest relative density of dry-press process body has only 76%, does not obtain sintering.Hrvoje Ivankovic etc. are with different raw material Al (NO
3)
39H
2O, γ-Al
2O
3And γ-AlOOH (boehmite) and TEOS (tetraethylorthosilicate), adopt the two-phase gel method to prepare and meet the two-phase gel that the mullite metering is formed, make mullite precursor powder through 700 ℃ of calcinings, forming method adopts after the 100MPa dry-pressing static pressure such as 200MPa again, formed body 1650 ℃ burn till 2 hours after relative volume density reach 98%.
To contain Al
2O
3And SiO
2Raw material prepare mullite ceramic as the initiation material reaction-sintered, can avoid mullite to be difficult to the shortcoming of sintering to a certain extent because under normal conditions, base substrate has reached very high density before mullitization.Simultaneously, because course of reaction and sintering process are integrated, can reduce cost.Earlier 1990s, M.D.Sacks etc. have developed a kind of transient state viscous sintering, and (Transient Viscous Sintering, the fine and close mullite ceramic of TVS) method preparation is by at ultra-fine α-Al
2O
3The powder surface utilizes the hydrolysis of TEOS to be coated with last layer amorphous Si O
2Coating is made composite granule, prepares green compact with injection forming then, utilizes unbodied SiO between 1100～1300 ℃
2It is densified that VISCOUS FLOW reaches, and in high temperature (1500～1600 ℃) heat treatment down, makes α-Al then
2O
3And SiO
2Reaction is converted into mullite, and silica alumina ratio is 74/26, and relative volume density can reach 98%, and crystallite dimension is 2-3 μ m.Adding mullite seed can be reduced to 1400 ℃ to the mullite formation temperature, simultaneously also refinement crystal grain.Compare with sol-gel technology, this method has some advantages: (1) has avoided the dry problem in the sol-gel process; (2) can obtain higher biscuit density; (3) the mullitization temperature is higher, can guarantee to make base substrate fully densified before the mullitization.The shortcoming of this method is: (1) TEOS cost is higher; (2) crystal seed is introduced after synthesizing in advance again, and the distributing homogeneity of crystal seed in base substrate is poor.
(3) summary of the invention
Be to solve deficiencies such as mullite ceramic material complex forming technology, cost height, gained even green body difference in the prior art, but but the invention provides that a kind of technology is simple, cost is low, the good original position of gained even green body forms the hydrolysis that nanometer coats micron composite structure, original position generates the mullite-based ceramic of mullite seed in sintering process and induces consolidation in-situ forming technology.
For reaching goal of the invention the technical solution used in the present invention be: a kind of hydrolysis of mullite-based ceramic is induced consolidation in-situ forming technology, described moulding process is as follows: adding volume toward the mullite-based ceramic slurry is the formamide of free water volume 0.2～2.0% in the slurry, back injection mould stirs, pulp surface behind injection molding covers one deck silicone oil, mould is incubated 10～60 minutes makes slurry curing under 50～80 ℃ of temperature, slowly cool to 10～40 ℃, the demoulding obtains described mullite ceramic base substrate.Described mold materials is non-porous material, comprises fine and close metal, plastics, glass or ceramic material etc.
The pH=1.5 of described mullite-based ceramic slurry～2.5, solid volume fraction 50～60%.
Described mullite-based ceramic slurry prepares as follows: add ceramic powder in the highly acid Ludox of pH=0.5～1.0, mass concentration 5～40%, the back ball milling that stirs disperseed 0.1～10 hour, promptly got described mullite-based ceramic slurry.
Described ceramic powder is one of following or two or more mixture wherein: 1. alumina powder, 2. sillimanite powder, 3. aquamaine stone flour, 4. zircon powder, 5. silicon carbide micro-powder.
Described highly acid Ludox is mixed by Ludox and strong acid solution and obtains.Described Ludox can be commercially available or homemade ammonia stabilized silica sol, low sodium type Ludox, acidic silicasol or modification sodium type Ludox.Described strong acid is one of following: 1. hydrochloric acid; 2. nitric acid.Can adopt concentrated hydrochloric acid or red fuming nitric acid (RFNA), also can will use behind concentrated hydrochloric acid or the red fuming nitric acid (RFNA) dilute with water.
Described ceramic powder can be the little composite granule of nano silicon coated aluminum oxide, also can be one or more the mixture in little composite granule of nano silicon coated aluminum oxide and alumina powder, sillimanite powder, aquamaine stone flour, zircon powder, the silicon carbide micro-powder.Described little composite granule can prepare as follows: add alumina powder in Ludox, be prepared into the Ludox dispersed alumina slurry that meets mullite chemistry metering composition, add the NH of preparation in advance
4Cl solution promotes slurry curing, obtains meeting the firming body that the metering of mullite chemistry is formed, and 100～110 ℃ of oven dry down, broken back ball-milling treatment 2h in planetary ball mill can obtain the little composite granule of nano silicon coated aluminum oxide with firming body.
Concrete, described moulding process is as follows: add concentrated hydrochloric acid in Ludox, regulate Ludox pH to 0.5, add alumina powder, ball milling is 0.1 hour after stirring, obtain the ceramic size of solid volume fraction 60%, add the formamide that accounts for the contained free water volume 0.2% of slurry while stirring, after stirring with slurry injected plastic mould, surface coverage one deck silicone oil, then mould was placed 20 minutes in being preheated to 80 ℃ baking oven, cooled off the demoulding after 30 minutes behind the slurry curing naturally, promptly get described ceramics materials based on mullite base substrate.
The hydrolysis of mullite-based ceramic of the present invention induces the beneficial effect of consolidation in-situ forming technology to be mainly reflected in:
The sol-gel destabilizing effect that the formation aluminium ion causes when (1) utilizing the Ludox of salic micro mist to disperse ceramic size pH value to adjust, regulate slurry pH value by formamide from hydrolysis, promote pulp gelization, because adopt inorganic sol to realize the slurry consolidation in-situ forming, technical process has no side effect;
(2) owing to do not have the organic substance with surface-active effect in the slurry, slurry need not the degassing and handles and can be injection molded, and technology is simple;
(3) silica sol gelization can form nanometer in ceramic powder particle surface original position and coat micron composite structure, can utilize the transient state viscous sintering theory of mullite-based ceramic, reduces sintering temperature;
(4) after the slurry consolidation in-situ forming, form aluminium silicon gel in base substrate, in the sintering process, but aluminium silicon gel forms mullite seed 1100～1250 ℃ of original positions, helps the sintering of mullite-based ceramic;
(5) utilize technology of the present invention; the ceramic component any surface finish of moulding; size is accurate; the inner good uniformity of base substrate, but original position forms nanometer coating micron composite structure in the body preparation process, but original position forms mullite seed in sintering process; reduced processing step; technical process does not have the noxious material introducing, thereby has reduced energy consumption and manufacturing cost, and is favourable to the protection environment.
(4) Figure of description
The complicated shape base substrate that Fig. 1 obtains for embodiment 1 moulding;
The base substrate micro-structure diagram of Fig. 2 for adopting technological forming of the present invention to obtain;
(5) specific embodiment
The present invention is described further below in conjunction with specific embodiment, but protection scope of the present invention is not limited in this:
Embodiment 1: the moulding of mullite-corundum complex phase ceramic base substrate
α-Al
2O
3Micro mist, day extraordinary alumina producer production in the Zhengzhou, Henan, d
50=1.68 μ m, d
90=6.31 μ m; Ludox is the ammonia stable type, and model is NS-10, pH=9.0, and mass concentration is 10%, density is 1.06g/cm
3, Shangyu, Zhejiang space reaches chemical industry Co., Ltd and produces.
In the 100ml Ludox, add concentrated hydrochloric acid, stir, regulate the pH to 0.5 of Ludox, add the 550g alumina powder then, after stirring, ball milling 0.1h in planetary ball mill, make solid volume fraction and be about 60% ceramic size, adding accounts for the formamide that contains free water volume 0.2% in the slurry, the slurry injected plastic mould after stirring while stirring then, add silicone oil and cover the pulp surface of injecting, mould after the slip casting is placed 20min in being preheated to 80 ℃ baking oven, slurry curing, the demoulding behind the cooling 30min naturally, obtain the complicated shape mullite/corundum complex phase ceramic base substrate of any surface finish, see Fig. 1.The ceramic body microstructure that obtains as shown in Figure 2, as seen, the billet surface of moulding is bright and clean, uniform microstructure does not exist and handles the visible pore cause owing to outgasing.
Embodiment 2: the moulding of mullite ceramic base substrate
Germany produces α-Al
2O
3Micro mist, d
50=1.06 μ m, d
90=4.31 μ m; Ludox is a modification sodium type, and model is the GS-40 type, pH=9.0, and mass concentration is 40%, density is 1.29g/cm
3, Shangyu, Zhejiang space reaches chemical industry Co., Ltd and produces.
The alumina powder that adds 663g in the 500ml Ludox is prepared into the Ludox dispersed alumina slurry that meets mullite chemistry metering composition, adds the NH of the 3.6mol/L of preparation in advance
4Cl promotes slurry curing, obtains meeting the firming body that the metering of mullite chemistry is formed, and 100～110 ℃ of oven dry down, broken back ball-milling treatment 2h in planetary ball mill obtains the little composite granule of nano silicon coated aluminum oxide with firming body.
In the 100ml Ludox, add red fuming nitric acid (RFNA), regulate about the pH to 1.0 of Ludox, add the alumina powder of 132.6g and the little composite granule of nano silicon coated aluminum oxide of 63.9g, after stirring, ball milling disperses 10h in the general milling machine, make solid volume fraction and be about 50% ceramic size, add while stirring then and account for the formamide that contains free water volume 1.0% in the slurry, slurry injected plastic mould after stirring, add silicone oil and cover pulp surface, the mould after the slip casting is placed 30min, slurry curing in being preheated to 60 ℃ baking oven, naturally the demoulding behind the cooling 60min obtains the complicated shape mullite ceramic base substrate of any surface finish.
Embodiment 3: the moulding of mullite ceramic base substrate
Used α-Al
2O
3Micro mist is identical with embodiment 2, and Ludox is the ammonia stable type, and model is the NS-30 type, and mass concentration is 30%, and pH=9.0, Shangyu, Zhejiang space reach chemical industry Co., Ltd and produce.The sillimanite powder, 325 orders are available from Changxing ceramic raw material company.
In the 100ml Ludox, add concentrated hydrochloric acid, regulate about the pH to 0.5 of Ludox, add the alumina powder of 155g and the sillimanite powder of 160g, after stirring, ball milling disperses 8h in the general milling machine, make solid volume fraction and be about 50% ceramic size, add while stirring then and account for the formamide that contains free water volume 1.0% in the slurry, slurry injected plastic mould after stirring, add silicone oil and cover pulp surface, the mould after the slip casting is placed 30min, slurry curing in being preheated to 60 ℃ baking oven, naturally the demoulding behind the cooling 60min obtains the complicated shape mullite ceramic base substrate of any surface finish.
Embodiment 4: the moulding of mullite/zirconia complex phase ceramic base substrate
Used α-Al
2O
3Micro mist is identical with embodiment 2, and Ludox is an acidic silicasol, and model is the HS-30 type, pH=3.5, and mass concentration is 30%, Shangyu, Zhejiang space reaches chemical industry Co., Ltd and produces.Import zircon powder, Australia produces, and 325 orders are available from Changxing ceramic raw material company.
The salpeter solution that in the 100ml Ludox, adds 1mol/L, regulate Ludox pH value to 0.6, add the alumina powder of 262.2g and the zircon powder of 203.6g, after stirring, ball milling 1h in planetary ball mill, make solid volume fraction and be about 55% ceramic size, add while stirring then and account for the formamide that contains free water volume 0.6% in the slurry, slurry injected plastic mould after stirring, add silicone oil and cover pulp surface, the mould after the slip casting is placed 30min, slurry curing in being preheated to 70 ℃ baking oven, naturally the demoulding behind the cooling 60min obtains the complicated shape mullite/zirconia complex phase ceramic base substrate of any surface finish.
Embodiment 5: corundum/mullite/carborundum composite-phase ceramic blank forming
Used α-Al
2O
3Micro mist is identical with embodiment 2, and Ludox is the ammonia stable type, and model is the NS-30 type, pH=9.0, and mass concentration is 30%, Shangyu, Zhejiang space reaches chemical industry Co., Ltd and produces.Superfine silicon carbide micro powder, Shandong produce, available from available from Changxing ceramic raw material company.
In the 100ml Ludox, add concentrated hydrochloric acid, regulate Ludox pH value to 0.6, add the alumina powder of 280.6g and the silicon carbide micro-powder of 50.5g, after stirring, ball milling 1h in planetary ball mill, make solid volume fraction and be about 55% ceramic size, add while stirring then and account for the formamide that contains free water volume 1.5% in the slurry, slurry injected plastic mould after stirring, add silicone oil and cover pulp surface, the mould after the slip casting is placed 30min, slurry curing in being preheated to 60 ℃ baking oven, naturally the demoulding behind the cooling 60min obtains the complicated shape corundum/mullite/carborundum composite-phase ceramic base substrate of any surface finish
Embodiment 6: mullite/carborundum composite-phase ceramic blank forming
Used α-Al
2O
3Micro mist is identical with embodiment 2 with Ludox, superfine silicon carbide micro powder, and produce in Shandong, available from available from Changxing ceramic raw material company.
The alumina powder that adds 663g in the 500ml Ludox is prepared into the Ludox dispersed alumina slurry that meets mullite chemistry metering composition, adds the NH of the 3.6mol/L of preparation in advance
4Cl promotes slurry curing, obtains meeting the firming body that the metering of mullite chemistry is formed, and 100～110 ℃ of oven dry down, broken back ball-milling treatment 2h in planetary ball mill obtains the little composite granule of nano silicon coated aluminum oxide with firming body.
In the 100ml Ludox, add red fuming nitric acid (RFNA), regulate about the pH to 0.8 of Ludox, the alumina powder that adds 132.6g, 45.6g the little composite granule of nano silicon coated aluminum oxide of silicon carbide micro-powder and 76.4g, after stirring, ball milling disperses 10h in the general milling machine, make solid volume fraction and be about 55% ceramic size, add while stirring then and account for the formamide that contains free water volume 1.2% in the slurry, slurry injected plastic mould after stirring, add silicone oil and cover pulp surface, mould after the slip casting is placed 30min in being preheated to 70 ℃ baking oven, slurry curing, naturally the demoulding behind the cooling 60min obtains the complicated shape mullite/carborundum composite-phase ceramic base substrate of any surface finish.
Claims (6)
1. the hydrolysis of a mullite-based ceramic is induced consolidation in-situ forming technology, it is characterized in that described moulding process is as follows: adding volume toward the mullite-based ceramic slurry is the formamide of free water volume 0.2～2.0% in the slurry, back injection mould stirs, pulp surface behind injection molding covers one deck silicone oil, mould is incubated 10～60 minutes makes slurry curing under 50～80 ℃ of temperature, slowly cool to 10～40 ℃, the demoulding obtains described mullite-based ceramic base substrate; Described mullite-based ceramic slurry pH=1.5～2.5, solid volume fraction is 50～60%.
2. the hydrolysis of mullite-based ceramic as claimed in claim 1 is induced consolidation in-situ forming technology, it is characterized in that described mullite-based ceramic slurry prepares as follows: in the highly acid Ludox of pH=0.5～1.0, mass concentration 5～40%, add ceramic powder, the back ball milling that stirs disperseed 0.1～10 hour, promptly get described mullite-based ceramic slurry, described strong acid is one of following: 1. hydrochloric acid; 2. nitric acid.
3. the hydrolysis of mullite-based ceramic as claimed in claim 2 is induced consolidation in-situ forming technology, it is characterized in that described ceramic powder is one of following or two or more mixture wherein: 1. alumina powder, 2. sillimanite powder, 3. aquamaine stone flour, 4. zircon powder, 5. silicon carbide micro-powder.
4. the hydrolysis of mullite-based ceramic as claimed in claim 2 is induced consolidation in-situ forming technology, it is characterized in that described highly acid Ludox is mixed by Ludox and strong acid solution to obtain.
5. the hydrolysis of mullite-based ceramic as claimed in claim 2 is induced consolidation in-situ forming technology, it is characterized in that described ceramic powder is the little composite granule of nano silicon coated aluminum oxide.
6. the hydrolysis of mullite-based ceramic as claimed in claim 2 is induced consolidation in-situ forming technology, it is characterized in that described moulding process is as follows: in Ludox, add concentrated hydrochloric acid, regulate Ludox pH to 0.5, add alumina powder, ball milling is 0.1 hour after stirring, obtain the ceramic size of solid volume fraction 60%, add the formamide that accounts for the contained free water volume 0.2% of slurry while stirring, after stirring with slurry injected plastic mould, surface coverage one deck silicone oil, then mould was placed 20 minutes in being preheated to 80 ℃ baking oven, cooled off the demoulding after 30 minutes behind the slurry curing naturally, promptly get described mullite-based ceramic base substrate.
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| DE2714139A1 (en) * | 1976-03-31 | 1977-10-20 | Atomic Energy Authority Uk | METHOD OF MANUFACTURING A REFRACTORY MATERIAL |
| AU2003266761A1 (en) * | 2003-10-10 | 2005-05-12 | Kolos, Elizabeth | Biomimetic ceramic fibre |
| JP2005345283A (en) * | 2004-06-03 | 2005-12-15 | Nec Corp | Poor transponder response removal system and method in ssr mode s aeronautical station |
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| DE2714139A1 (en) * | 1976-03-31 | 1977-10-20 | Atomic Energy Authority Uk | METHOD OF MANUFACTURING A REFRACTORY MATERIAL |
| AU2003266761A1 (en) * | 2003-10-10 | 2005-05-12 | Kolos, Elizabeth | Biomimetic ceramic fibre |
| JP2005345283A (en) * | 2004-06-03 | 2005-12-15 | Nec Corp | Poor transponder response removal system and method in ssr mode s aeronautical station |
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