CN1236761A - Enzyme-catalytic high-molecular in-situ solidification process for shaping ceramic parts - Google Patents
Enzyme-catalytic high-molecular in-situ solidification process for shaping ceramic parts Download PDFInfo
- Publication number
- CN1236761A CN1236761A CN 99109165 CN99109165A CN1236761A CN 1236761 A CN1236761 A CN 1236761A CN 99109165 CN99109165 CN 99109165 CN 99109165 A CN99109165 A CN 99109165A CN 1236761 A CN1236761 A CN 1236761A
- Authority
- CN
- China
- Prior art keywords
- ceramic
- enzyme
- urea
- gelatin
- molecular
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Materials For Medical Uses (AREA)
- Immobilizing And Processing Of Enzymes And Microorganisms (AREA)
Abstract
An enzyme-catalytic high-molecular in-situ solidification process for shaping ceramic products includes such technological steps as preparing aqueous solution of gelatin, addition of ceramic powder and ceramic suspension disperser, ball grinding, vacuum debubbling, cooling, addition of urease solution, moulding, raising temp, holding the temp constant and demoulding. The obtained ceramic blank features high finishment and size accuracy and no poison.
Description
The present invention relates to a kind of method of enzyme-catalytic high-molecular in-situ coagulation forming of ceramic component, belong to technical field of material.
The high-performance ceramics material, as aluminum oxide, zirconium white, silicon 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.
In recent years, it was developed to utilize the ceramic suspension body original position to solidify the precision molding technology of realizing ceramic component, as directly solidifying injection forming (Direct coagulation casting) and gel casting forming (Gel-casting).Directly solidifying injection forming is the ion that produces by urine enzyme catalysis hydrolysis of urea, the pH value of ceramic suspension body is moved to about 9 by 4, the suspensoid particle relies on van der Waals' force and combination, the only suitable iso-electric point of this method is 9 Al2O3, and industrial Al2O3 and other the ceramic moulding lower for iso-electric point are very difficult.Gel-casting utilizes the three-dimensional network gel property that monomer polymerization reactions forms in the ceramic suspension body to mold ceramic component.But there is following shortcoming in this method moulding process in existing: 1) ceramic surface peels off because of oxygen inhibition produces; 2) employed monomer acryloyl has toxicity, and is unfavorable to environment and HUMAN HEALTH; 3) contain 3～4% organism in the ceramic molding, also need to carry out degreasing before the sintering, thereby increase production cycle and manufacturing cost.
The present invention seeks to propose a kind of method of enzyme-catalytic high-molecular in-situ coagulation forming of ceramic component, using the high molecular solution of Nantural non-toxic water soluble gelatine-gelation changes, at first polymer and urea are dissolved in the have certain temperature ceramic suspension body of (～40 ℃), after cooling, by introducing the urea decomposition in the urine enzyme catalysis slurry, impel gelatin molecule three-dimensional network gel structure to form, can make the ceramic size that injects behind the mould be solidified as the ceramic body of desired shape.
The method of the enzyme-catalytic high-molecular in-situ coagulation forming of ceramic component of the present invention comprises following each step:
1, preparation aqueous gelatin solution: gelatin polymer and urea, mix with water and be heated to about 30～40 ℃, till being stirred to gelatin simultaneously and dissolving fully, its ratio is, is benchmark with water, gelatin polymer 2～6wt%, urea 5～10wt%;
2, in above-mentioned aqueous gelatin solution, add ceramic powder and ceramic suspension body dispersion agent, its volume ratio is: aqueous gelatin solution: ceramic powder: dispersion agent=1: 0.8～1.2: 0.002～0.01, ceramic powder wherein is any in aluminum oxide, zirconium white, titanium oxide, silicon nitride, the silicon carbide, and dispersion agent wherein is any in polyacrylic acid, ammonium polyacrylate, ammonium polymethacrylate, the tetramethyl-oxyammonia;
3, the compound that second step is obtained carries out ball milling, and the time is 12～48 hours:
4, the ceramic size behind the ball milling has good fluidity, at room temperature carries out froth in vacuum 10～30 minutes, and vacuum tightness is 600～750mmHg;
5, the ceramic size after the de-bubble is cooled to 2～5 ℃, adds an amount of urine enzyme solution again, the proportionlity of urine enzyme add-on and urea generally is 5～20 units urine enzyme/every milligram of urea;
6, above-mentioned ceramic size injects non-punch die, and moulding stock is that metal, plastics, rubber, glass etc. are any.Make die temperature go back up to 20～30 ℃ then, and kept 0.1～2 hour, the length of soaking time can be decided according to the size of ceramic component, when piece volumes is big, soaking time prolongs, under this temperature, beginning catalyzing urea hydrolysis in the grinding tool in the slurry, because the decomposition of hydrogen bond blocker (urea), gelatin chains can produce hydrogen bond action each other and form three-dimensional net structure, make ceramic size original position in the mould be frozen into the ceramic body of desired shape, but the just demoulding after ceramic body has certain intensity.
Enzyme catalysis consolidation in-situ forming ceramic component novel process of the present invention has the following advantages:
1) moulding of suitable different types of ceramic size; 2) ceramic component of plastic different shape and size according to actual needs; 3) the ceramic body any surface finish of moulding, the dimensional precision height; 4) because ceramic size is that original position is solidified, do not have volumetric shrinkage, so it is good respectively to form distributing homogeneity in the base substrate, helps improving the stupalith reliability, all effective to various high-performance ceramics moulding; 5) the used material of moulding does not have any toxicity, and consumption few (0.5～1wt% is a benchmark with ceramic powder weight), and human body and environment are safe from harm.
Introduce embodiments of the invention below:
Embodiment 1: the moulding of alumina ceramic component
Aluminum oxide (Al
2O
3) be the industrial powder that prosperous source, Henan Aluminum company limited produces, purity is 99.7%.Median size is about 2.8 μ m.Gelatin by Shanghai chemical reagent packing factory produce, powdery is white in color.Urea is that the Beijing Chemical Plant produces, white crystals, and purity is 99%.The content of urine enzyme is 68unit/mg.
Add 5 gram gelatin and 25 gram urea in 250 ml waters, be heated to 45 ℃ and be stirred to dissolving.Add 1000 gram aluminum oxide powders and 5 gram ammonium polyacrylate dispersion agents then.Ball milling 24 hours makes solid volume fraction and is about 50% ceramic size.De-bubble under vacuum condition then (removing the bubble that may exist in the slurry).Ceramic size after the de-bubble is cooled to 3 ℃, adds 98mg urine enzyme dispersed with stirring again.Ceramic size injects metal die subsequently, after filling with mould is moved into 30 ℃ of constant temperature ovens, and through 30 minutes, the ceramic suspension body in the die cavity solidified and forms solid-state base substrate.This moment can be with solidified ceramic body taking-up in the mould.
(2) zirconium oxide ceramic component moulding
Zirconium white (ZrO
2) ceramic powder is by the big high-performance ceramics in Beijing side company production cerium and the stable ultrafine zirconia powder of yttrium, median size is 0.8 μ m, the dispersion agent ammonium polymethacrylate.Used gelatin, urea and urine enzyme are the same.
Add 4 gram gelatin and 20 gram urea in 200 ml waters, be heated to 45 ℃ and be stirred to dissolving.Add 1000 gram zirconia powders and 4 gram ammonium polymethacrylate dispersion agents then.Ball milling de-bubble under vacuum condition after 24 hours (removing the bubble that may exist in the slurry).Ceramic size after the de-bubble is cooled to 5 ℃, adds 85mg urine enzyme homodisperse again.Subsequently ceramic size is injected a glass mold and make die temperature rise to 28 ℃, the ceramic suspension body in the die cavity solidifies because of enzyme catalysis and forms solid-state base substrate.Get final product the demoulding after half an hour.
(3) moulding of silicon carbide ceramic components
The silicon carbide ceramics powder is by the magnificent grinding materials and grinding tool production of Shandong Wei Fang, and median size is 1.48 μ m.Used gelatin, urea and urine enzyme are the same, but ceramic dispersants employing Tetramethylammonium hydroxide,
In 300 ml waters, add 6 gram gelatin and 20 gram urea, be heated to 40 ℃ and be stirred to dissolving.Add 900 gram carborundum powders and 5 gram Tetramethylammonium hydroxide dispersion agents then.Ball milling is de-bubble under vacuum condition after 30 hours.Ceramic size after the de-bubble is cooled to 3 ℃, adds 90mg urine enzyme homodisperse again.Subsequently ceramic size injected plastic mould is risen to 30 ℃, the ceramic size in the die cavity solidified through 20 minutes and forms solid-state base substrate.Get final product the demoulding after a while half an hour.
(4) moulding of silicon nitride ceramic parts
Silicon nitride ceramic is produced by the big high-performance ceramics in Beijing side company, and median size is 2.2 μ m.Ceramics powder powder is a kind of ammonium salt of acroleic acid macromolecular.Used gelatin, urea and urine enzyme are the same.
In 300 ml waters, add 8 gram gelatin and 25 gram urea, be heated to 42 ℃ and be stirred to dissolving.The ammonium salt that adds 850 gram silicon nitride powders and 6 gram acroleic acid macromoleculars then.Ball milling is de-bubble under vacuum condition after 48 hours.Ceramic size after the de-bubble is cooled to 4 ℃, adds 100mg urine enzyme homodisperse again, and inject rubber mold.Rise to 30 ℃ again.Ceramic size in the die cavity solidified through 20 minutes and forms solid-state base substrate.Reach one and regularly (spend 40 minutes approximately) and get final product the demoulding Deng formed body intensity.
(5) titanium oxide ceramics parts-moulding
Titanium oxide (TiO
2) pottery is used for electronic industry.The median size of the titanium oxide powder of experiment usefulness is 0.4 μ m, the dispersion agent polyacrylate.Used gelatin, urea and urine enzyme are the same.
Add 3 gram gelatin and 10 gram urea in 100 ml waters, be heated to 45 ℃ and be stirred to dissolving.The dispersion agent that adds 800 gram titanium oxide powders and 4 gram polyacrylates then.Ball milling final vacuum de-bubble in 36 hours.Ceramic size is cooled to 5 ℃ again, adds 45mg urine enzyme homodisperse then.Subsequently ceramic size is injected a metal die and make die temperature rise to 30 ℃, the ceramic suspension body in the die cavity can be solidified into base substrate through 20 minutes approximately, but the demoulding after half an hour.
Claims (1)
1, a kind of method of enzyme-catalytic high-molecular in-situ coagulation forming of ceramic component is characterized in that, this method comprises following each step:
(1) preparation aqueous gelatin solution: gelatin polymer and urea, mix with water and be heated to about 30～40 ℃, till being stirred to gelatin simultaneously and dissolving fully, its ratio is, is benchmark with water, gelatin polymer 2～6wt%, urea 5～10wt%;
(2) in above-mentioned aqueous gelatin solution, add ceramic powder and ceramic suspension body dispersion agent, its volume ratio is: aqueous gelatin solution: ceramic powder: dispersion agent=1: 0.8～1.2: 0.002～0.01, ceramic powder wherein is any in aluminum oxide, zirconium white, titanium oxide, silicon nitride, the silicon carbide, and dispersion agent wherein is any in polyacrylic acid, ammonium polyacrylate, ammonium polymethacrylate, the tetramethyl-oxyammonia;
(3) compound that second step is obtained carries out ball milling, and the time is 12～48 hours;
(4) compound with the 3rd step at room temperature carried out froth in vacuum 10～30 minutes, and vacuum tightness is 600～750mmHg;
(5) ceramic size after the de-bubble is cooled to 2～5 ℃, adds an amount of urine enzyme solution again, the proportionlity of urine enzyme add-on and urea is 5～20 units urine enzyme/every milligram of urea;
(6) above-mentioned ceramic size is injected the non-hole that needs moulding, mould does not absorb water, moulding stock is any in metal, plastics, rubber, the glass, make die temperature go back up to 20～30 ℃ then, be incubated 0.1～2 hour, be ceramic component of the present invention after the demoulding.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99109165 CN1078574C (en) | 1999-06-18 | 1999-06-18 | Enzyme-catalytic high-molecular in-situ solidification process for shaping ceramic parts |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99109165 CN1078574C (en) | 1999-06-18 | 1999-06-18 | Enzyme-catalytic high-molecular in-situ solidification process for shaping ceramic parts |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1236761A true CN1236761A (en) | 1999-12-01 |
| CN1078574C CN1078574C (en) | 2002-01-30 |
Family
ID=5273725
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 99109165 Expired - Fee Related CN1078574C (en) | 1999-06-18 | 1999-06-18 | Enzyme-catalytic high-molecular in-situ solidification process for shaping ceramic parts |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1078574C (en) |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1092167C (en) * | 2000-09-29 | 2002-10-09 | 清华大学 | Colloidal shaping method of ceramics by chelating reaction to delay solidification |
| CN1092166C (en) * | 2000-05-19 | 2002-10-09 | 清华大学 | Spray initiation quick-hardening forming method of lamella ceramic device body and its equipment |
| CN1092168C (en) * | 2000-09-29 | 2002-10-09 | 清华大学 | Non-oxygen polymerization-inhibiting gel injection process for preparing ceramic parts |
| CN1120818C (en) * | 2000-12-29 | 2003-09-10 | 清华大学 | Process for preparing non-crack ceramic blank with electrolyte |
| CN1120819C (en) * | 2000-12-29 | 2003-09-10 | 清华大学 | Process for preparing non-crack ceramic blank |
| CN1293022C (en) * | 2005-03-02 | 2007-01-03 | 中国航空工业第一集团公司北京航空材料研究院 | Preparation method of honeycomb ceramic mud blank |
| CN100560536C (en) * | 2006-03-10 | 2009-11-18 | 中国科学院上海硅酸盐研究所 | The method of water-soluble epoxy resin in situ solidification for preparing ceramic blank |
| CN102010204A (en) * | 2010-10-22 | 2011-04-13 | 北方民族大学 | Colloidal forming process method for preparing silicon nitride bonded silicon carbide composite ceramic |
| CN101302117B (en) * | 2008-05-20 | 2011-05-11 | 中国航空工业第一集团公司北京航空材料研究院 | Preparation of ordered big hole porous ceramic film material |
| CN102748758A (en) * | 2012-07-23 | 2012-10-24 | 山西科德技术陶瓷有限公司 | Honeycomb ceramic |
| CN104291773A (en) * | 2014-09-29 | 2015-01-21 | 同济大学 | Preparation method of intense-radiation-resistant block material stable having low density and stability at superhigh temperature |
| EP2207499A4 (en) * | 2007-11-05 | 2016-03-23 | Glidewell James R Dental Ceramics Inc | Slip-casting method of fabricating zirconia blanks |
| US9790129B2 (en) | 2012-05-26 | 2017-10-17 | James R. Glidewell Dental Ceramics, Inc. | Method of fabricating high light transmission zirconia blanks for milling into natural appearance dental appliances |
| EP3171819A4 (en) * | 2014-07-24 | 2018-03-07 | John Fung | Dental prosthesis and moulding method |
| CN110937895A (en) * | 2019-12-26 | 2020-03-31 | 淄博奥诺新材料科技有限公司 | Preparation method of zirconia sheet ceramic |
| US11731312B2 (en) | 2020-01-29 | 2023-08-22 | James R. Glidewell Dental Ceramics, Inc. | Casting apparatus, cast zirconia ceramic bodies and methods for making the same |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1321090C (en) * | 2004-04-09 | 2007-06-13 | 中国航空工业第一集团公司北京航空材料研究院 | Enzymatic gel reacting synthetic method of composite ceramic powder |
-
1999
- 1999-06-18 CN CN 99109165 patent/CN1078574C/en not_active Expired - Fee Related
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1092166C (en) * | 2000-05-19 | 2002-10-09 | 清华大学 | Spray initiation quick-hardening forming method of lamella ceramic device body and its equipment |
| CN1092167C (en) * | 2000-09-29 | 2002-10-09 | 清华大学 | Colloidal shaping method of ceramics by chelating reaction to delay solidification |
| CN1092168C (en) * | 2000-09-29 | 2002-10-09 | 清华大学 | Non-oxygen polymerization-inhibiting gel injection process for preparing ceramic parts |
| CN1120818C (en) * | 2000-12-29 | 2003-09-10 | 清华大学 | Process for preparing non-crack ceramic blank with electrolyte |
| CN1120819C (en) * | 2000-12-29 | 2003-09-10 | 清华大学 | Process for preparing non-crack ceramic blank |
| CN1293022C (en) * | 2005-03-02 | 2007-01-03 | 中国航空工业第一集团公司北京航空材料研究院 | Preparation method of honeycomb ceramic mud blank |
| CN100560536C (en) * | 2006-03-10 | 2009-11-18 | 中国科学院上海硅酸盐研究所 | The method of water-soluble epoxy resin in situ solidification for preparing ceramic blank |
| EP2207499A4 (en) * | 2007-11-05 | 2016-03-23 | Glidewell James R Dental Ceramics Inc | Slip-casting method of fabricating zirconia blanks |
| CN101302117B (en) * | 2008-05-20 | 2011-05-11 | 中国航空工业第一集团公司北京航空材料研究院 | Preparation of ordered big hole porous ceramic film material |
| CN102010204B (en) * | 2010-10-22 | 2013-01-30 | 北方民族大学 | Colloidal forming process method for preparing silicon nitride bonded silicon carbide composite ceramic |
| CN102010204A (en) * | 2010-10-22 | 2011-04-13 | 北方民族大学 | Colloidal forming process method for preparing silicon nitride bonded silicon carbide composite ceramic |
| US9790129B2 (en) | 2012-05-26 | 2017-10-17 | James R. Glidewell Dental Ceramics, Inc. | Method of fabricating high light transmission zirconia blanks for milling into natural appearance dental appliances |
| CN102748758A (en) * | 2012-07-23 | 2012-10-24 | 山西科德技术陶瓷有限公司 | Honeycomb ceramic |
| EP3171819A4 (en) * | 2014-07-24 | 2018-03-07 | John Fung | Dental prosthesis and moulding method |
| US10646310B2 (en) | 2014-07-24 | 2020-05-12 | John Fung | Dental prosthesis and moulding method |
| CN104291773A (en) * | 2014-09-29 | 2015-01-21 | 同济大学 | Preparation method of intense-radiation-resistant block material stable having low density and stability at superhigh temperature |
| CN110937895A (en) * | 2019-12-26 | 2020-03-31 | 淄博奥诺新材料科技有限公司 | Preparation method of zirconia sheet ceramic |
| US11731312B2 (en) | 2020-01-29 | 2023-08-22 | James R. Glidewell Dental Ceramics, Inc. | Casting apparatus, cast zirconia ceramic bodies and methods for making the same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1078574C (en) | 2002-01-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1078574C (en) | Enzyme-catalytic high-molecular in-situ solidification process for shaping ceramic parts | |
| CN1065846C (en) | Process for non-toxic gel moulding of precise ceramic component | |
| CN1686945A (en) | Silica sol solidification method for forming ceramic component | |
| CN104844226B (en) | Method for curing of ceramic slurry by polyphosphate chelate controlled release of high valence counter ions | |
| CN101037342A (en) | Nitride aluminum hydrolyzing combined fire-resistant material | |
| CN1203830C (en) | Polycrystal zirconium oxide ceramic dental material and preparation thereof | |
| CN101200373A (en) | Preparation method of silicon carbide ceramic body for rubber mold | |
| HU212043B (en) | Moulding mass for producing inorganic sintered products and process for producing said products | |
| US5667548A (en) | Process for producing ceramic green compacts by double layer compression | |
| CN1490276A (en) | Material formula for precisive ceramic parts and injection moulding preparing method thereof | |
| CN1317234C (en) | Ceramic part gel injection moulding forming method realized by cellulose ether heat gel reaction | |
| KR20040074014A (en) | Y2O3 sinter and manufacturing method thereof | |
| CN101348376B (en) | Double-component monomer system for ceramic material gel pouring moulding and use method thereof | |
| CN1092168C (en) | Non-oxygen polymerization-inhibiting gel injection process for preparing ceramic parts | |
| CN101698607B (en) | Method for preparing alumina-based ceramic material by environmentally-friendly gelcasting | |
| CN102814498B (en) | Metal powder gel injection molding forming method | |
| CN1092167C (en) | Colloidal shaping method of ceramics by chelating reaction to delay solidification | |
| EP0420284B2 (en) | Preparation of zirconia sintered body | |
| CN1172876C (en) | Process for preparing ceramic sheet by water-base doctor blading method | |
| CN104744045A (en) | Method for preparing MgAlON transparent ceramic biscuit by direct coagulation casting | |
| CN1210134C (en) | Sizing material forming method of ceramic parts | |
| CN101224983A (en) | Gel casting method for pre-reduced hard magnetic ferrite ceramic parts | |
| CN1318348C (en) | Tech. for degassing-free gel injecting moulding shaping of mullite-base precision ceramic component | |
| CN1911619A (en) | Preparation method of strong magnetic-weak magnetic gradient material gel injection mould in pulse magnetic field | |
| CN112745120A (en) | Nano zirconia ceramic slurry for photocuring 3D printing dental crown and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |