CN1136163C - Water-base curtain coating process for preparing ceramic film - Google Patents
Water-base curtain coating process for preparing ceramic film Download PDFInfo
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- CN1136163C CN1136163C CNB991256972A CN99125697A CN1136163C CN 1136163 C CN1136163 C CN 1136163C CN B991256972 A CNB991256972 A CN B991256972A CN 99125697 A CN99125697 A CN 99125697A CN 1136163 C CN1136163 C CN 1136163C
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Abstract
The present invention relates to a method for preparing a ceramic film by a water base casting, which belongs to the preparation field of the ceramlc film. The present invention adopts water as a unique solvent in the casting technology, and adopts polyvinyl alcohol (PVA) and polyvinyl pyrrolidone (PVP) as an adhesive, and the addition of the PVP takes 10 to 30% of that of the total mass percentage of the PVA and the PVP. propanediol is used as a ductilimeter, and the quality ratio of the propanediol to the PVA is 1:4 to 1:1. The casting technology provided by the present invention is easy to realize, and the technological process is easy to control. The present invention not only is suitable for making films by oxide powder bodies represented by Al2O3, but also is suitable for making films with a casting method of non-oxide, such as SiC, Si3N4, TiC, etc.
Description
The present invention relates to adopt water as solvent, prepare the method for the thick ceramic membrane of 5-1000 μ m, belong to the preparation field of ceramic membrane by casting technique.
Curtain coating (doctor-blade process) is one of technology of preparation thin-film material, aspect the structure design of material and the functional development important application is being arranged also.Casting technique comprises two kinds of water base and non-aqueous tape-castings.Non-aqueous tape-casting technology is comparative maturity at present, and the diaphragm structure of preparation is even, the intensity height, and snappiness is good, is convenient to cutting and processing, uses for many years in industrial production.But the non-aqueous tape-casting process need use a large amount of deleterious organism as solvent, and the production cost height causes environmental pollution after the discharging, harmful HUMAN HEALTH.In contrast, water-based tape casting adopts water as solvent, and the organism consumption is few, and cost is low, pollutes for a short time, and Environmental compatibility is good, and is harmless to HUMAN HEALTH, is convenient to scale operation, and therefore, in recent years, people have carried out many researchs to water-based flow casting technique.But, can be in water dissolved organic polymer kind few, compare with organic solvent, the consistency of polymer and water is poor, in addition, the influence factor of this technology (kind of the pH value of solution, ionic strength, dispersion agent, binding agent, plastic agent and quantity etc.) is many, and the casting films rate of drying is slow, strong to the drying process dependency, the technological process further investigation of still needing.At present, the patent of water-based tape casting is few, and the binding agent of use mainly contains following three kinds: 1. carboxylic acid ester monomer, and as vinylformic acid etc.This monomer is beginning as the dispersion agent adding, and change condition after moulding makes it aggregate into polymer, as binding agent then.This method range of application is narrow, because different powders needs dissimilar dispersion agents, the molecular weight of dispersion agent too hour is difficult to form sterically hindered stable, and its dispersion effect also is affected.2. water soluble polyurethane resin.This arts demand adds the organic solvent with water compatible, and drying process also will be controlled.3. adopt polyacrylic acid to make binding agent, add the toughness that a spot of Polyvinylpyrolidone (PVP) improves casting films.Be mainly used in the moulding of aluminum oxide.4. adopt latex as binding agent.This technology is to be used for the moulding silicon carbide powder, the particle diameter of powder is bigger, maximum has 100 microns, by the grating between the powder, reduce the space between the ceramic particle, thereby reduce the consumption of binding agent, but the preparation process more complicated, slurry viscosity is also than higher (in example VI, viscosity is 2000cps).5. adopt polyvinyl alcohol (PVA) as binding agent.Up to the present, in the water-based flow casting technique, generally the binding agent of Shi Yonging is polyacrylic acid (PAA) and derivative thereof, and molecular weight is generally more than 200,000.Because the solution viscosity of PAA is low, so the content of binding agent can be increased to 18wt%, and the viscosity ratio of slurry is lower.Owing to use a large amount of organism, the solid content of ceramic particle is difficult to improve, and behind sintering, the organism in the casting films is difficult for getting rid of clean, and is not only unfavorable to sintering and densification in the future, and influences the ceramic performance behind the sintering.Simultaneously, casting films is relatively more responsive to drying conditions, and defectives such as pit, pore appear in film surface easily.
The object of the present invention is to provide a kind of water-based tape casting to prepare the method for ceramic membrane, comprise and select suitable binding agent and plastic agent, dual function by binding agent, make organic content reduction in the casting slurry, the viscosity of slurry reduces, and makes the drying of casting films insensitive to envrionment conditions, can (15-40 ℃) seasoning in than wide temperature range, the solid content of dry back casting films improves, carbon residual quantity minimizing in the pottery behind the sintering.
The present invention adopts water as solvent unique in the casting technique.Adopt two kinds of organism polymers as binding agent, i.e. polyvinyl alcohol (PVA) and Polyvinylpyrolidone (PVP) (PVP).The polymerization degree of PVA is between 1200-1700, and alcoholysis degree is between 50%--99%.The k value of PVP is K30 (the k value is for characterizing the parameter of PVP molecular weight).Selecting propylene glycol for use is plastic agent.Its casting technique comprises:
1. water and dispersant is even, and dispersion agent can be selected organism, the colloidal sol of suitable molecular weight and the salt that some are organic and inorganic for use.The powder adding is contained in the aqueous solution of dispersion agent, be mixed with slurry.
2. with the 1 slurry ball milling that obtains, the time is about 24 hours.
3. add binding agent and plastic agent, binding agent adds with the form of the aqueous solution, adds plastic agent then, and defoamer continued ball milling 12-24 hour, perhaps stirred 6 hours.
4. with the 3 slurry suction filtrations that obtain, vacuum outgas then.
5. 4 slurries that obtain are carried out curtain coating, obtain casting films.
6. 5 casting films that obtain are being opened wide drying in 15-40 ℃ of wide temperature range, general about 4-8 hour can be fully dry.
The present invention adopts two kinds of organism polymers as binding agent, PVA and PVP, and the adding of PVP has following effect: (1) PVP is a rigid structure, can improve the curtain coating film strength.(2) PVP can play the effect of binding agent and plastic agent simultaneously.The PVP water absorbability is strong, make dried casting films keep certain humidity, the existence of water can reduce the glass transition temperature of polyvinyl alcohol, simultaneously, because the existence of ketone group and pyrrole group also can be played the effect of plastic agent, therefore in the PVP molecule, the adding of PVP has reduced the consumption of plastic agent, thereby has reduced organic content in the slurry.(3) adding of PVP has reduced the viscosity of casting slurry, has also improved the moisture-absorption characteristics of the flowability and the casting films of casting slurry, and the homogeneity of the casting films that obtains is improved, and organic content reduces.(4) can make seasoning become possibility.Because the moisture-absorption characteristics of PVP has changed the moisture evaporation speed in the casting films drying process, has reduced the susceptibility of casting films to drying conditions, can realize that casting films is dry under field conditions (factors).
Below the present invention is elaborated.Binding agent and plastic agent that the present invention uses comprise three kinds of components: polyvinyl alcohol component (A) Polyvinylpyrolidone (PVP) component (B) and propylene glycol component (C).Component (A) mainly contains following two kinds of structures:
1,3-ethylene glycol structure 1 structure
The x span is 500-1000 in the formula.Above-mentioned two kinds of structures are represented the polyvinyl alcohol of complete alcoholysis.Because PVA obtains from the carboxylate methyl ester alcoholysis, the alcoholysis degree difference, the number of remaining carboxylate methyl ester is also variant among the then last PVA.For the polyvinyl alcohol of alcoholysis degree 50%, then there is half hydroxyl still to be carboxylate methyl ester in the said structure.
The structure of component (B) is as follows:
The k value of the Polyvinylpyrolidone (PVP) that the present invention selects for use is between 27-33.The mass percent that component (B) accounts for the total mass of component (A) and component (B) is 10-30%.Preferred scheme is 10-20%.Component (C) structure is as follows:
1, ammediol 1,2-propylene glycol
1, ammediol is main plasticity composition, and its quality accounts for 1, ammediol and 1, and the per-cent of the total mass of 2-propylene glycol can be between 50%-100%, and preferred percentage is between 80%-100%.The mass ratio of propylene glycol and PVA is 1: 4-1: between 1.Preferred ratio is 1: 2-1: 1.
Can there be three kinds usually as component of the present invention (A) (1) polyvinyl alcohol alcoholysis degree, promptly 78%, 88% and 98%, the alcoholysis degree scope of the PVA that the present invention adopts is between 50%--99%.The alcoholysis degree of preferred PVA is between 87-99%.(2) polymerization degree of polyvinyl alcohol is between 1000-2000.The preferred polymerization degree is between 1200-1700.Polyvinyl alcohol is very wide in industrial application, such as at papermaking, weaving, printing and medicine industry, its production technique is very ripe, and the product of different polymerization degree and alcoholysis degree can have been bought, cheap, its manufacture method is also well-known in the polyvinyl alcohol technical field.
Component (B) adds as binding agent.Its consumption accounts for the 10-30% of the total mass of polyvinyl alcohol and Polyvinylpyrolidone (PVP), because it is a rigid structure, for keeping the plasticity of film, preferred scheme is 10-20%.Component (B) also is a kind of common used in industry reagent, uses much in pharmaceutical industry, and its preparation method is also well-known in this field.
In the component (C), adopt 1, ammediol and 1, the mixture of 2-propylene glycol is as plastic agent.Corresponding with the structure of PVA, 1, ammediol is as main plasticity composition, and its quality accounts for 1, ammediol and 1, the preferred per-cent of the total mass of 2-propylene glycol is between 80%-100%.The preferred mass ratio of propylene glycol and PVA is 1: 2-1: 1.Improve the consumption of plastic agent and can avoid the surface of film that small pit is arranged, but too much plastic agent then can reduce film strength.The preparation method of propylene glycol is comparative maturity also.
Component (A) and the content of component (B) in slurry, different and variant with the volume content of the ceramic particle in the slurry.In slurry, when the volume content of ceramic particle was 30%, the volumn concentration of binding agent in slurry was between 5.52-7.37%, and the quality percentage composition is between 6.90-9.21%.
Adopt component (A) as binding agent fully, cooperate other plastic agent such as PEG, glycerine etc., also can obtain complete casting films.But, the casting films of this prepared, organic content height.Adopt component (B) as binding agent fully, can prepare complete casting films equally, still, also face same problem.If the organism that adds other in component (A) and component (B) if the three can be compatible, also can obtain casting films as binding agent, still, preferred composition of the present invention only is made up of component (A) and component (B).Generally, component (A) can not used but component (B) can be used as dispersion agent sometimes in the absorption of ceramic grain surface occurrence features, and this is as long as increase the amount of component (B).
Component (C) is to select for use according to the structure of component (A), and the plastic agent that adopts is glycerine and PEG usually.But meeting influence the viscosity of slurry after glycerine added, and also influential to the drying process of casting films.The consistency of PEG and component (A) is bad.Also can adopt ethylene glycol as plastic agent, still and 1, the 2-propylene glycol is compared, owing to lacked a methyl, its plasticization effect is not as 1, the 2-propylene glycol.In addition, ethers and polyethers organism, and amine organism as long as contain the group that can generate hydroxyl with PVA, can be used as plastic agent.But the organic plasticization effect of ethers and polyethers is not as component (C), and amine then will be considered the acid-basicity of slurry, and therefore, preferred plastic agent is component (C).
The casting technique that the present invention proposes is easy to realize that technological process also is easy to control.Be not only applicable to Al
2O
3Be the oxide powder of representative, and be applicable to SiC, Si
3N
4, the casting method preparation of non-oxidized substances such as TiC.Wherein the meta particle diameter of powder should be less than 3 microns.
The following stated embodiment describes this invention in detail.The application of wherein used dispersion agent separate case.
Embodiment 1
With 64 gram meta particle diameters is that 2 microns SiC joins 20ml and contains in the water of dispersion agent ball milling 24h.The PVA solution that adds 9wt%, the alcoholysis degree of PVA is 99%, add propylene glycol and PVP, wherein, the binding agent total mass is 6.17 grams, and the quality of PVP is 30% of a binding agent total mass, the quality of propylene glycol is 1/2 of PVA, 1, the quality of ammediol be propylene glycol total mass 50%, continued ball milling 24 hours.The slurry viscosity that obtains is between 350-600mPas.With the slurries filtration that obtains, vacuum outgas, curtain coating then, seasoning 4 hours.
Embodiment 2
With 64 gram meta particle diameters 0.6 micron Si
3N
4Join 20ml and contain in the water of dispersion agent ball milling 24h.The PVA solution that adds 9wt%, the alcoholysis degree of PVA is 99%, add propylene glycol and PVP, wherein, the binding agent total mass is 6.17 grams, and the quality of PVP is 30% of a binding agent total mass, the quality of propylene glycol is 1/2 of PVA, 1, the quality of ammediol be propylene glycol total mass 50%, continued ball milling 20 hours.The slurry viscosity that obtains is between 350-600mPas.With the slurries filtration that obtains, vacuum outgas, curtain coating then, seasoning 6 hours.
Embodiment 3
With 140 gram meta particle diameters is that 3 microns TiC joins 20ml and contains in the water of dispersion agent ball milling 24h.The PVA solution that adds 9wt%, the alcoholysis degree of PVA is 99%, add propylene glycol and PVP, wherein, the binding agent total mass is 8.74 grams, and the quality of PVP is 20% of a binding agent total mass, the quality of propylene glycol is 1/2 of PVA, 1, the quality of ammediol be propylene glycol total mass 100%, continued ball milling 18 hours.The slurry viscosity that obtains is between 300-600mPas.With the slurries filtration that obtains, vacuum outgas, curtain coating then, seasoning 7 hours.
Embodiment 4
With 80 gram meta particle diameters 0.4 micron Al
2O
3Join 20ml and contain in the water of dispersion agent ball milling 24h.The PVA solution that adds 9.5wt%, the alcoholysis degree of PVA is 50%, add propylene glycol and PVP, wherein, the binding agent total mass is 6.20 grams, and the quality of PVP is 20% of a binding agent total mass, the quality of propylene glycol is 1/2 of PVA, 1, the quality of ammediol be propylene glycol total mass 100%, continued ball milling 24 hours.The slurry viscosity that obtains is between 250-600mPas.All the other are with embodiment 1.
Embodiment 5
64 gram SiC are joined 20ml contain in the water of dispersion agent ball milling 24h.The PVA solution that adds 9.5wt%, the alcoholysis degree of PVA is 50%, add propylene glycol and PVP, wherein, the binding agent total mass is 4.58 grams, and the quality of PVP is 10% of a binding agent total mass, the quality and the PVA of propylene glycol are suitable, 1, the quality of ammediol be propylene glycol total mass 90%, continued ball milling 18 hours.The slurry viscosity that obtains is between 250-500mPas.All the other are with embodiment 1.
Embodiment 6
With 64 gram Si
3N
4Join 20ml and contain in the water of dispersion agent ball milling 24h.The PVA solution that adds 10wt%, the alcoholysis degree of PVA is 88-89%, add propylene glycol and PVP, wherein, wherein, the binding agent total mass is 4.58 grams, the quality of PVP is 10% of a binding agent total mass, and the quality and the PVA of propylene glycol are suitable, 1, the quality of ammediol be propylene glycol total mass 90%, continued ball milling 16 hours.The slurry viscosity that obtains is between 250-450mPas.All the other are with embodiment 2.
Embodiment 7
With 140 gram meta particle diameters is that 3 microns TiC joins 20ml and contains in the water of dispersion agent ball milling 24h.The PVA solution that adds 10wt%, the alcoholysis degree of PVA is 88-89%, add propylene glycol and PVP, wherein, wherein, the binding agent total mass is 4.58 grams, the quality of PVP is 10% of a binding agent total mass, and the quality and the PVA of propylene glycol are suitable, 1, the quality of ammediol be propylene glycol total mass 80%, stirred 6 hours.The slurry viscosity that obtains is between 250-400mPas.All the other are with embodiment 3.
Embodiment 8
With 80 gram Al
2O
3Join 20ml and contain in the water of dispersion agent ball milling 24h.The PVA solution that adds 10wt%, the alcoholysis degree of PVA is 88-89%, add propylene glycol and PVP, wherein, wherein, the binding agent total mass is 4.61 grams, the quality of PVP is 10% of a binding agent total mass, and the quality and the PVA of propylene glycol are suitable, 1, the quality of ammediol be propylene glycol total mass 80%, stirred 6 hours.The slurry viscosity that obtains is between 250-400mPas.All the other are with embodiment 4.
Claims (6)
1. a water-based tape casting prepares the method for ceramic membrane, comprises preparation, curtain coating, the drying of slurry, it is characterized in that:
(1) with water as the unique solvent in the casting technique;
(2) with the polymerization degree between 1200-1700, the polyvinyl alcohol of alcoholysis degree between 50%-99%, PVA and K value are the Polyvinylpyrolidone (PVP) of 27-33, and PVP two components are binding agent, and its add-on is: the mass percent that PVP accounts for the total mass of PVA and PVP is 10-30%;
(3) with the propylene glycol be plastic agent, 1, ammediol is main plasticity composition, 1, the quality of ammediol accounts for 1, and ammediol and 1, the per-cent of the total mass of 2-propylene glycol are between the 50%-100%;
(4) mass ratio of propylene glycol and PVA is 1: 4-1: between 1.
2. the method for preparing ceramic membrane according to the described water-based tape casting of claim 1 is characterized in that concrete technology is:
(1) water and dispersant is even, dispersion agent is selected organism, the colloidal sol of suitable molecular weight and the salt that some are organic and inorganic for use, powder is added contain in the aqueous solution of dispersion agent, is mixed with slurry;
(2) the slurry ball milling that step (1) is obtained, the time is about 24 hours;
(3) add binding agent and plastic agent, binding agent adds with the form of the aqueous solution, adds plastic agent then, and defoamer continued ball milling 12-24 hour, perhaps stirred 6 hours;
(4) the slurry suction filtration that step (3) is obtained, vacuum outgas then;
(5) slurry that step (4) is obtained carries out curtain coating, obtains casting films;
(6) casting films that step (5) is obtained is opened wide drying under room temperature in 15-40 ℃ of wide temperature range, and general about 4-8 hour can be fully dry.
3. the method for preparing ceramic membrane according to the described water-based tape casting of claim 1 is characterized in that the mass percent that described PVP accounts for the total mass of PVA and PVP is 10-20%.
4. prepare the method for ceramic membrane according to the described water-based tape casting of claim 1, it is characterized in that 1, the quality of ammediol accounts for 1, ammediol and 1, and the per-cent of the total mass of 2-propylene glycol is between 80%-100%.
5. prepare the method for ceramic membrane according to the described water-based tape casting of claim 1, the mass ratio that it is characterized in that propylene glycol and PVA is 1: 2-1: 1.
6. prepare the method for ceramic membrane according to the described water-based tape casting of claim 1, it is characterized in that being applicable to Al
2O
3Be the oxide powder of representative, and SiC, Si
3N
4, the water-based tape casting preparation of TiC non-oxidized substance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB991256972A CN1136163C (en) | 1999-12-22 | 1999-12-22 | Water-base curtain coating process for preparing ceramic film |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB991256972A CN1136163C (en) | 1999-12-22 | 1999-12-22 | Water-base curtain coating process for preparing ceramic film |
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| Publication Number | Publication Date |
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| CN1258657A CN1258657A (en) | 2000-07-05 |
| CN1136163C true CN1136163C (en) | 2004-01-28 |
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| CNB991256972A Expired - Fee Related CN1136163C (en) | 1999-12-22 | 1999-12-22 | Water-base curtain coating process for preparing ceramic film |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107602129A (en) * | 2017-10-12 | 2018-01-19 | 华中科技大学 | A kind of water-based tape casting preparation method of SiC |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101747025B (en) * | 2009-12-24 | 2013-03-27 | 中国科学院过程工程研究所 | Beta''-Al2O3 solid electrolyte precursor aqueous tape casting slurry and preparation method thereof |
| CN102180674B (en) * | 2011-01-31 | 2014-06-18 | 中国科学院上海硅酸盐研究所 | Preparation method of reaction-sintered SiC ceramic |
| CN104496267A (en) * | 2014-11-28 | 2015-04-08 | 景德镇陶瓷学院 | Flexible ceramic wallpaper and preparation method thereof |
| CN105272263B (en) * | 2015-10-09 | 2018-12-07 | 中国科学院上海硅酸盐研究所 | A kind of aqueous tape casting method preparing the carbon containing porous biscuit of silicon carbide reaction-sintered |
| CN106565280B (en) * | 2015-10-13 | 2019-09-13 | 中国科学院上海硅酸盐研究所 | A kind of CfThe preparation method of/SiC ceramic matrix composite material surface optical coating |
| CN111635215A (en) * | 2020-06-14 | 2020-09-08 | 佛山方竹科技有限公司 | Preparation process of ceramic sheet |
| CN114773067A (en) * | 2022-05-23 | 2022-07-22 | 江苏方大正塬生态环境科技有限公司 | GSPL-SNCS silicon nitride tape-casting slurry |
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1999
- 1999-12-22 CN CNB991256972A patent/CN1136163C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107602129A (en) * | 2017-10-12 | 2018-01-19 | 华中科技大学 | A kind of water-based tape casting preparation method of SiC |
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