CN1092167C - Colloidal shaping method of ceramics by chelating reaction to delay solidification - Google Patents
Colloidal shaping method of ceramics by chelating reaction to delay solidification Download PDFInfo
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- CN1092167C CN1092167C CN00124980A CN00124980A CN1092167C CN 1092167 C CN1092167 C CN 1092167C CN 00124980 A CN00124980 A CN 00124980A CN 00124980 A CN00124980 A CN 00124980A CN 1092167 C CN1092167 C CN 1092167C
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- sodium alginate
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- calcium salt
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- 239000000919 ceramic Substances 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 title abstract description 13
- 238000007711 solidification Methods 0.000 title abstract 2
- 230000008023 solidification Effects 0.000 title abstract 2
- 238000007493 shaping process Methods 0.000 title description 4
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000000661 sodium alginate Substances 0.000 claims abstract description 34
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 34
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 34
- 239000000725 suspension Substances 0.000 claims abstract description 27
- 159000000007 calcium salts Chemical class 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 15
- 238000000498 ball milling Methods 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001746 injection moulding Methods 0.000 claims abstract description 3
- 239000000138 intercalating agent Substances 0.000 claims description 14
- 241000270666 Testudines Species 0.000 claims description 12
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 claims description 7
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 7
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 7
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 7
- 239000001509 sodium citrate Substances 0.000 claims description 6
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000001506 calcium phosphate Substances 0.000 claims description 4
- 235000011010 calcium phosphates Nutrition 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 235000012204 lemonade/lime carbonate Nutrition 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 4
- 229940038773 trisodium citrate Drugs 0.000 claims description 4
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 abstract 2
- 239000001361 adipic acid Substances 0.000 abstract 1
- 235000011037 adipic acid Nutrition 0.000 abstract 1
- 239000002738 chelating agent Substances 0.000 abstract 1
- 230000009920 chelation Effects 0.000 abstract 1
- 239000000084 colloidal system Substances 0.000 abstract 1
- 238000004421 molding of ceramic Methods 0.000 abstract 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 15
- 238000000465 moulding Methods 0.000 description 10
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 9
- 229910001424 calcium ion Inorganic materials 0.000 description 9
- 235000006408 oxalic acid Nutrition 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 229910052581 Si3N4 Inorganic materials 0.000 description 5
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 235000019263 trisodium citrate Nutrition 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 229910010271 silicon carbide Inorganic materials 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical group [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000003701 mechanical milling Methods 0.000 description 2
- 150000002913 oxalic acids Chemical class 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 229910017083 AlN Inorganic materials 0.000 description 1
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006664 bond formation reaction Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000011224 oxide ceramic Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- SOBHUZYZLFQYFK-UHFFFAOYSA-K trisodium;hydroxy-[[phosphonatomethyl(phosphonomethyl)amino]methyl]phosphinate Chemical compound [Na+].[Na+].[Na+].OP(O)(=O)CN(CP(O)([O-])=O)CP([O-])([O-])=O SOBHUZYZLFQYFK-UHFFFAOYSA-K 0.000 description 1
- -1 vulcanite Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
Abstract
The present invention relates to a method for realizing controllable solidification ceramic colloid injection moulding by a chelation reaction. Firstly, a sodium alginate solution is prepared, then a ceramic powder material, calcium salt and a chelating agent are added in the sodium alginate solution, a mixture suspension body is in a ball way, the ball milling ceramic suspension body is defoamed by vacuum at the room temperature, the defoamed ceramic suspension body is added in a substance with strong acid performance, such as adipic acid or hydrochloric acid, the ceramic suspension body added with acid is immediately injected in a non-hole mould to be cooled and demoulded, and a ceramic component with a required shape can be obtained. The present invention is suitable for the molding of ceramic suspension bodies with different varieties, and a mould ceramic blank body has the advantages of smooth surfaces and high dimensional precision.
Description
The present invention relates to a kind of closing and react realization delay solidified colloidal shaping method of ceramics, belong to technical field of material by huge legendary turtle.
The high-performance ceramics material, as aluminum oxide, zirconium white, silicon nitride, aluminium nitride, silicon carbide etc. because of having high strength, high rigidity, a series of excellent mechanical property and chemical stability such as high temperature resistant, wear-resistant and anticorrosive; Therefore more and more many in modern science and technology and industrial circle (as aspects such as space flight, chemical industry, information electronics, life sciences) application.These materials are many to be used as a kind of structure unit, has various different shapeies, and requires size accurate, reaches near-net-shape.The ceramic component of traditional forming manufacture technique such as dry-pressing formed very difficult preparation complicated shape, and common injection forming is only limited to the thin-walled ceramic member, has density gradient for heavy wall ceramic molding inside, is easy to generate defective and cracking during sintering.Therefore, the precise forming of high-performance ceramics parts creates a gordian technique.
The object of the invention proposition is a kind of closes reaction realization delay solidified colloidal shaping method of ceramics by huge legendary turtle, and its ultimate principle is that the calcium ion chemical bonding formation gel macromole of using in sodium alginate and the calcium salt changes ceramic suspension body into the solid-state ceramic base substrate.And above-mentioned gel reaction can close with the huge legendary turtle of calcium salt and reacts by adding the calcium ion intercalating agent.Closing reaction when huge legendary turtle carries out when complete, sodium alginate is difficult to and calcium ion generation gel reaction, and when this huge legendary turtle was closed reaction by some acidic substance destruction, the calcium ion that huge legendary turtle is closed was released the ceramic body that becomes desired shape again with the ceramic suspension body in-situ solidifying of sodium alginate aqueous solution.
The huge legendary turtle that passes through that the present invention proposes is closed the ceramic colloidal casting that reaction realizes that curing is controlled, comprises following each step:
1) the preparation sodium alginate solution adds the solid powdery sodium alginate in the entry under the room temperature, till being stirred to sodium alginate and dissolving fully.The obtain solution ratio is: sodium alginate: water=0.5~2: 100 (in mass).
2) add ceramic powder, calcium salt and intercalating agent in the above-mentioned sodium alginate solution for preparing, mixing simultaneously stirs.Calcium salt mainly comprises: lime carbonate, calcium phosphate and secondary calcium phosphate.Intercalating agent comprises: trisodium citrate and Sodium hexametaphosphate 99.The volume ratio of sodium alginate aqueous solution and ceramic powder is 55~120: 100.The mass ratio of sodium alginate aqueous solution and intercalating agent and calcium salt is 100: 0.1~0.4: 0.1~0.3.
3) the compound suspensoid that second step is obtained is poured ball grinder into and is carried out ball milling, and the ball milling time is 48~72 hours.The one side ceramic powder is evenly dispersed in the solution gradually in the mechanical milling process; On the other hand, calcium ion generation huge legendary turtle is closed reaction in intercalating agent and the calcium salt, avoids calcium ion and sodium alginate reaction formation gel and suspensoid viscosity is increased.
4) ceramic suspension body behind the ball milling has better flowability, at room temperature carries out froth in vacuum 10~30 minutes, and vacuum tightness is 600~750mmHg.
5) add acid stronger material such as hexanodioic acid or hydrochloric acid in the ceramic suspension body after de-bubble, make its homodisperse by stirring.Acid is 0.5~1.0 (g) with the ratio of sodium alginate solution: 100 (ml).
6) ceramic suspension body after the adding acid injects non-punch die immediately.Moulding stock available metal, plastics, vulcanite, glass etc. are any.Behind the injection molding, the intravital acid that suspends in the mould will progressively cement out calcium ion from the huge legendary turtle compound, these calcium ions and sodium alginate generation chemical reaction form the gel macromole, and ceramic particle in the suspensoid and water molecules are all fixed, and make that the ceramic suspension body in-situ solidifying becomes ceramic body in the mould.After about 30~60 minutes, ceramic body has sufficient intensity, carries out the demoulding, can obtain the ceramic component of desired shape.
The method that the present invention proposes has following advantage:
1) moulding of suitable different types of ceramic suspension body;
2) ceramic component of plastic various complicated shape and size;
3) the ceramic body any surface finish of moulding, dimensional precision height;
4) the used sodium alginate of moulding separates son, and intercalating agent and calcium salt etc. are nontoxicity all, environmentally safe, and consumption is few, and cheap, be convenient to suitability for industrialized production.
Introduce embodiments of the invention below:
Embodiment 1: the moulding of high-purity alumina ceramic parts
Aluminum oxide is high-purity (99.97%) ceramics powder that u s company produces, and median size is 0.5 μ m.Sodium alginate is produced by Shanghai chemical reagent packing factory.Secondary calcium phosphate is that sharp fine chemicals company limited analytical reagent is covered in Beijing.The analytical reagent that Sodium hexametaphosphate 99 system is produced by Beijing chemical reagents corporation.The analytical reagent that oxalic acid is produced by Red Star chemical plant, Beijing.
Add 2 gram sodium alginate polymers and be stirred to dissolving fully in 200 ml waters, add 800 gram alumina-ceramic ultrafine powders then, the 0.5g Sodium hexametaphosphate 99 is that the secondary calcium phosphate of intercalating agent and 1 gram is the calcium salt solidifying agent.Mixing and ball milling 60 hours makes solid volume fraction and is about 50% ceramic suspension body, removes the bubble that may exist in the suspensoid then under vacuum condition.The oxalic acid that adds 1.5 grams is dispersed in the ceramic suspension body fully, subsequently above-mentioned ceramic suspension body is injected metal die.Approximately after half an hour, ceramic suspension body solidifies and forms solid-state base substrate in the die cavity, and reaches certain intensity, and can take out solidified ceramic component this moment from mould.
Experimental example 2: the moulding of homemade commercial alumina ceramic component
Aluminum oxide is the industrial powder that prosperous source, Henan Aluminum company limited produces, and averageparticle is about 2.8 μ m, and sodium alginate, secondary calcium phosphate, oxalic acid reagent are the same, but intercalating agent changes trisodium citrate into.
After adding 2.4 gram sodium alginate polymers are stirred to dissolving in 240 ml waters, add the above-mentioned homemade industrialization aluminium powder of 950 grams, 1.2 gram secondary calcium phosphates are the calcium salt solidifying agent, and 1.5 trisodium citrates that restrain are intercalating agent.By ball mill ball milling 72 hours, obtaining solid volume fraction was 52% ceramic suspension body, carries out froth in vacuum then.Add the oxalic acids of 1.8 grams again and be dispersed in the suspensoid, subsequently with in the above-mentioned ceramic suspension body injected plastic mould, but mould inner suspension body is cured as ceramic body and the demoulding and takes out after about 40 minutes.
Experimental example 3: the moulding of silicon nitride ceramic parts
Silicon nitride powder is that German STACK company produces, and median size is about 0.8um, uses sodium alginate gel polymer, the intercalating agent trisodium citrate.All the same, but calcium salt system sodium phosphate.
Add gram sodium alginate polymer in 300 ml waters, wait to stir dissolving fully after, add 1000 gram silicon nitride ceramics, 2 gram trisodium citrates and 1.5 gram calcium phosphate.Made the ceramic suspension body of good fluidity in 60 hours by ball milling, after froth in vacuum, after adding 2 gram oxalic acids and suspensoid uniform mixing again suspensoid is injected in the glass mold, suspensoid completely solidified and reach higher-strength after about 50 minutes, can in mould, take out, obtain any surface finish, the silicon nitride ceramics base substrate that shape is intact.
Experimental example 4: the moulding of silicon carbide ceramic components
Carborundum powder is produced by the magnificent grinding materials and grinding tool of Shandong Wei Chang factory, and median size is 1.48 μ m, and sodium alginate polymer and Sodium hexametaphosphate 99 are the same.But calcium salt adopts lime carbonate.
Add 2.5 gram sodium alginate polymers in 250 ml waters, be stirred to dissolving.Add 800 gram carborundum powders, the lime carbonate of 0.6 gram Sodium hexametaphosphate 99 and 0.8 gram.With above-mentioned compound ball milling 72 hours, obtain the low mobile ceramic suspension body that is easy to of viscosity, froth in vacuum adds 1 gram oxalic acid after 20 minutes, again suspensoid is injected metal die, static placement after 35 minutes suspensoid be solidified into base substrate, get final product the demoulding at this moment.
Experimental example 5: zirconium oxide ceramic component moulding
Zirconium white (ZrO
2) ceramic powder is by the production of the big high-performance ceramics in Beijing side company, median size is 0.8um, intercalating agent hexa metaphosphoric acid trisodium, and gel macromole sodium alginate is the same, and calcium salt adopts secondary calcium phosphate.
Add 1.5 gram sodium alginate polymers in 150 ml waters, be stirred to dissolving, add zirconia powder 850 grams then, 0.4 gram Sodium hexametaphosphate 99 and 0.6 gram secondary calcium phosphate.Said mixture is through ball milling after 54 hours, and froth in vacuum 15 minutes is so that some bubbles that produce in removing in mechanical milling process in the ceramic suspension body.Add about 1.2 grams of oxalic acid then and be used to eliminate huge legendary turtle and close reaction, discharge calcium ion.With being about in the ceramic suspension body injected plastic mould static placement 40 minutes.Mould inner suspension body changes the ceramic body with certain intensity into, but and the demoulding.The size shape of gained base substrate is intact.
Claims (1)
1, a kind of closing by huge legendary turtle reacted the ceramic colloidal injection moulding forming method of realizing that curing is controlled, it is characterized in that this method comprises following each step:
(1) preparation sodium alginate solution: under the room temperature solid powdery sodium alginate is added in the entry, till being stirred to sodium alginate and dissolving fully, the solution of preparation, its mass ratio is: sodium alginate: water=0.5~2: 100;
(2) in the above-mentioned sodium alginate solution for preparing, add ceramic powder, calcium salt and intercalating agent, mixing simultaneously stirs, wherein calcium salt is: any in lime carbonate, calcium phosphate or the secondary calcium phosphate, intercalating agent is: trisodium citrate or Sodium hexametaphosphate 99, the volume ratio of sodium alginate aqueous solution and ceramic powder is 55~120: 100, and the mass ratio of sodium alginate aqueous solution and intercalating agent and calcium salt is 100: 0.1~0.4: 0.1~0.3;
(3) the compound suspensoid that above-mentioned second step is obtained is poured ball grinder into and is carried out ball milling, and the ball milling time is 48~72 hours;
(4) ceramic suspension body behind the ball milling has better flowability, at room temperature carries out froth in vacuum 10~30 minutes, and vacuum tightness is 600~750mmHg;
(5) add hexanodioic acid or hydrochloric acid in the ceramic suspension body after de-bubble, make its homodisperse by stirring, acid is 0.5~1.0 (g) with the ratio of sodium alginate solution: 100 (ml);
(6) ceramic suspension body after the adding acid injects non-punch die immediately, and after 30~60 minutes, ceramic body has sufficient intensity, carries out the demoulding, is ceramic component of the present invention.
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CN102795864B (en) * | 2011-05-27 | 2014-09-17 | 清华大学 | Method for realizing direct solidification and molding of ceramic slurry through slowly releasing high-valent counter ions |
CN104844226B (en) * | 2015-01-05 | 2017-04-12 | 清华大学 | Method for curing of ceramic slurry by polyphosphate chelate controlled release of high valence counter ions |
Citations (5)
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CN1215711A (en) * | 1998-09-25 | 1999-05-05 | 清华大学 | Process for non-toxic gel moulding of precise ceramic component |
CN1218017A (en) * | 1998-10-30 | 1999-06-02 | 清华大学 | Method and apparatus for quick moulding ceramic parts |
CN1236761A (en) * | 1999-06-18 | 1999-12-01 | 清华大学 | Enzyme-catalytic high-molecular in-situ solidification process for shaping ceramic parts |
CN1246465A (en) * | 1999-08-27 | 2000-03-08 | 清华大学 | Quickly solidified doctor blading process for forming electronic ceramic substrate and ceramic sheet devices |
CN1263812A (en) * | 2000-03-10 | 2000-08-23 | 清华大学 | Continuous doctor-blading shaping method and equipment of water-base gel for raw thin wafer of ceramic device |
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Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
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CN1215711A (en) * | 1998-09-25 | 1999-05-05 | 清华大学 | Process for non-toxic gel moulding of precise ceramic component |
CN1218017A (en) * | 1998-10-30 | 1999-06-02 | 清华大学 | Method and apparatus for quick moulding ceramic parts |
CN1236761A (en) * | 1999-06-18 | 1999-12-01 | 清华大学 | Enzyme-catalytic high-molecular in-situ solidification process for shaping ceramic parts |
CN1246465A (en) * | 1999-08-27 | 2000-03-08 | 清华大学 | Quickly solidified doctor blading process for forming electronic ceramic substrate and ceramic sheet devices |
CN1263812A (en) * | 2000-03-10 | 2000-08-23 | 清华大学 | Continuous doctor-blading shaping method and equipment of water-base gel for raw thin wafer of ceramic device |
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