CN1062122A - The production technique of blended metal oxide powder - Google Patents
The production technique of blended metal oxide powder Download PDFInfo
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- CN1062122A CN1062122A CN91111445A CN91111445A CN1062122A CN 1062122 A CN1062122 A CN 1062122A CN 91111445 A CN91111445 A CN 91111445A CN 91111445 A CN91111445 A CN 91111445A CN 1062122 A CN1062122 A CN 1062122A
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- alcoxides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/14—Methods for preparing oxides or hydroxides in general
- C01B13/32—Methods for preparing oxides or hydroxides in general by oxidation or hydrolysis of elements or compounds in the liquid or solid state or in non-aqueous solution, e.g. sol-gel process
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
- C01G23/006—Alkaline earth titanates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
- C01G25/006—Compounds containing, besides zirconium, two or more other elements, with the exception of oxygen or hydrogen
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
Abstract
The present invention is a kind of technology of producing mixed metal oxide powders, and in this technology, hydroxide metal, alcoxides and water are blended in a kind of common, contain in the organic solvent that dissolves organic salt.This technology is suitable for producing the barium titanate powder that is mixed with metal oxide that is used to make electronic component.
Description
The present invention relates to produce the production technique of blended metal oxide powder.
The production of known blended metal oxide powder is under certain condition, under the situation that the hydroxide metal is arranged alcoxides is hydrolyzed and carries out.For this reason, the technology of barium titanate powder that a kind of production has the tetragonal structure of uhligite is disclosed U.S. Pat-A-4636378(Hughes Aircraft Company), this technology is that titanium alkoxides is poured in a kind of aqueous barium hydroxide solution gradually, so that form the titanium oxide of hydration, mixture with reaction is heated to more than 100 ℃ in the autocrave that keeps certain pressure then, then after this mixture is cooled to envrionment temperature, under barometric point, moderately carry out reheat again, make its decomposition.
Known production process is very complicated, and needs expensive equipment.In addition, the powder that is obtained has uneven structure, just looks like by random grain formation, and has the different particle distribution of size.
Avoided the production technique of above-mentioned defective to be disclosed in European patent document EP-A-297646(SOLVAY ﹠amp; Cie) in.According to this technology, the hydrolysis of alcoxides is to carry out under the condition that has hydroxide metal and acidic organic compound, so that go out pulverous blended metal oxide at controlled condition sinking precipitation, and does not need the gelinite intermediate.
In above-mentioned known technology, the starting material of alcoxides are expensive.
At Japanese document JP-A-64003019(NIPPON GEMENT KK) in, the aqueous solution of the ethanolic soln of alcoxides and acetate metal, with the precipitate drying, calcination in oxidizing gas then.In this known technology, the composition that constitutes powder is that the step of branch several successive is separated out: what at first separate out is the hydrolyzate of alcoxides, it is just to produce in the solution mixing, and second kind of resolvent that precipitate is the acetoxyl metal, this resolvent produces in thereafter drying and calcination step.This operating procedure is unfavorable for producing uniform powder.
The present invention has overcome the shortcoming of disclosed technology among the Japanese document JP-A-64003019, and it provides a kind of new technology, uses organic metal-salt, as, acetoxyl metal etc., it is uniform making the mixed metal oxide powders of being produced.
Therefore, the present invention relates to produce the technology of blended metal oxide powder, it is that hydroxide metal, alcoxides and water are mixed in the common organic solvent; According to the present invention, before Jiang Shui mixed this mixture, organic salt was dissolved in the solvent.
Within the scope of the invention, the blended metal oxide powder is meant the powder of the oxide compound that includes different metal.Exactly, this mixed metal oxide is a sosoloid, that is, and and with the uniform mixture of molecule or ionic condition.
According to technology of the present invention, alcoxides is meant any compound with following feature, in this compound, metal links to each other with hydro carbons family by Sauerstoffatom, as, aromatic series or saturated or unsaturated straight line chain or cyclic aliphatics, it can not replaced, or partly replaced, or replaced fully.Contain aliphatic alcoxides and recommended especially, comprise saturated or be best by metathetical aliphatics, preferably, as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl and isobutyl base class.If necessary, the alcoxides that can or the mixture of alcoxides with dissociating.
Organic salt exactly, is a kind of organic acid metal-salt, and it must be dissolved in the organic solvent.For this reason, can consider from the salt that comprises the carboxylic acid that is less than 10 carbon atoms, to select the preferable alloy acetate.
According to technology of the present invention, must use an amount of water that is enough to make alcoxides generation hydrolysis.Yet in the alcoxides consumption of organic salt, the acid group of every mol organic salt must have greater than 1 molar alcoxides base.It is that the acid group of every mol organic salt is the value between 3 and 40 that for example corresponding amount can be selected the basic mole number of hydrocarbonylation Base Metal, and it is best selecting the numerical value between 5 to 20 for use.
According to technology of the present invention, alcoxides produces hydrolytic action when contacting with water.This hydrolytic action should be controlled with known mode, so that the blended metal oxide is separated out with Powdered, and a large amount of gels of the reaction mixture that does not cause by hydrolytic action.For this reason, suggestion makes the mixture of alcoxides, hydroxide metal, water and organic salt even as quickly as possible before nucleation begins in the common organic solvent.In order to produce this mixture, many kinds of working method are arranged.According to first kind of working method, hydroxide metal, alcoxides, organic salt and water are dissolved in organic solvent respectively, each organic solution that obtains is therefrom side by side poured into respectively in the reaction chamber.According to second kind of working method, produce earlier two kinds of different mixtures that give, a kind ofly comprise hydroxide metal and water, and another kind comprises alcoxides and organic salt, gives mixture with these two kinds then and mixes in reaction chamber.In these working method of the present invention, suggestion avoided having the existence of solid particles in organic solution before mixing.Can be with identical or different organic solvents for alcoxides, hydroxide metal, organic salt and water, still, the organic solvent of dissolving alcoxides must not have water.Under the situation of using different organic solvents, these solvents must be can blended, form the common organic solvent so that mix.Ethanol and their growth are fit to, particularly methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol.In solvent separately, alcoxides, hydroxide metal, organic salt and water-reducible optimum dilution degree depend on various factors, depend on the quality of used alcoxides and organic salt, service temperature and desired blended metal oxide powder especially; They must be measured in the laboratory of routine.For example,, before mixing, be no more than every liter 5 mol respectively, when being preferably in every liter 0.2 between 0.5, just can advantageously use alcohol solution at the composition of alcoxides, hydroxide metal, organic salt.Mixing can be carried out in atmospheric environment.Yet in order to prevent the carboniogenesis of hydroxide metal, suggestion is at no CO
2Ambient air in mix.In addition, for fear of the danger that alcoxides uncontrolledly decomposes, be preferably in the atmosphere of no moisture and operate.According to technology of the present invention, air, nitrogen, argon gas dry, anhydrous and that do not have a carbonic acid gas all are the examples of operable atmosphere.In order to ensure mixing, can adopt the process described in patent application GB-A-2168334 easily.
According to the special embodiment of technology of the present invention, the hydration of hydroxide metal can be utilized.The water of hydroxide metal generation hydration has constituted the water of the required at least a portion of alcoxides hydrolysis reaction.The hydroxide metal of best selected hydrated, its degree that hydrolytic action takes place are enough to provide all required water for the hydrolytic action of alcoxides.According to operation format of the present invention, the hydroxide metal can advantageously adopt the hydrated barta and/or the strontium hydroxide of hydrated.
According to an alternative embodiment of the invention, the acidic organic compound that preferably comprises 6 above carbon atoms in molecule dissolves in the common organic solvent.
According to embodiments of the invention, acidic organic compound is defined as a kind of organic acid or a kind of organic acid derivative.The organic acid derivative can have the characteristic of acid or not have the characteristic of acid, for example, is a kind of neutral substance.Special recommendation carboxylic acid saturated or that insatiable hunger is closed and their derivative.It is particularly advantageous being chosen in the acid or the sour derivative that contain 6 above carbon atoms in its molecule.Carboxylic acid includes at least 8 carbon atoms in molecule, verified have a special advantage, sad, the lauric acid of picture, palmitinic acid, different palmitinic acid (isopalmitic), oleic acid, stearic acid etc., but the carboxylic acid that contains 10 above carbon atoms in molecule is best.The example that can be used in the organic acid derivatives in the technology of the present invention is acid anhydride class, ester class and these sour salt.
In according to implementation of processes example of the present invention, acidity organises and thing is finished dissolving in the common organic solvent, and becomes evenly before the beginning nucleation.For this reason, suggestion is side by side poured the organic solution of other composition mixture in the mixing section, perhaps dissolves in wherein a kind of solution of these solution before the latter pours mixing section into.
Can see that acidic organic compound is to give by the cohesion that suppresses particle and spheric profile to come the effect of mixed metal oxide powders form with the latter.Usually, must just can act on the form of powder with the reaction of q.s, but should avoid exceeding threshold value, on threshold value, it is opposite to the effect of powder quality.In fact, the optimum amount of the acidic organic compound that is suitable for depends on many parameters, specifically comprise: selected acidic organic compound (mainly being the length of its carbochain), alcoxides, used hydroxide metal and organic salt, also comprise operational condition, and, every kind in particular cases, determine that optimum amount must depend on that the people is in desired powder morphology quality.Generally speaking, every mole of acidic organic compound that forms whole base metal oxide compound use 20～200g amount of mixed metal oxide to be prepared of suggestion.At acidic organic compound is when selecting from carboxylic acid, and the amount of 50～150g is preferred.
After hydrolysis reaction (and then mixing step) finishes, obtain the powder of particulate, it is made up of the complex compound and the organic residue of the metal oxide of noncrystalline state, and wherein hydration more or less takes place in the complex compound of this metal oxide.In fact, be the spheric particle substantially, its diameter is no more than 5 microns, and the powder that is generally 0.05～2 micron has just formed.This powder can arbitrarily carry out drying, heat-treat under suitable temperature, so that remove unnecessary water, organic solvent, if desired, also will remove acidic organic compound.In order to control porosity or it to be got rid of fully, thermal treatment can be regulated, and in addition, in order to make burning deposits yields crystallization, also can regulate.
Be particularly suitable for using the oxyhydroxide of the metal of from barium, strontium, boron, selenium, tellurium, selecting according to technology of the present invention, and from the periodic table of elements the selected metal of la family, as the oxyhydroxide of sodium, potassium, rubidium, cadmium.Alcoxides can be any alcoxides that can convert corresponding metal oxide or oxyhydroxide with hydrolytic action to.As unrestricted example, technology of the present invention can be used from Li, Na, K, Be, Mg, Ca, Sr, Ba, Ti, Zr, Nb, Ta, Mn, Fe, Co, Cu, Zn, Cd, Al, Ga, In, Si, Ge, Sn, Pb, As, Sb, Bi, Te, Y, La and rare earth, as the alcoxides (Ferro-electronics that selects among Nb, Sm, Eu and the Gd, Vol.49,1983, Pages 285-296: " ULtrafine Electroceramic Powder Preparation from Metal Alkoxides ").Organic salt can be selected from the above-mentioned metal-salt of mentioning that is used for alcoxides.
Be particularly suitable for producing the mixed metal oxide powders that is used for stupalith according to technology of the present invention, exactly, stupalith is nonmetal inorganic materials, this with the material use of powder as base material, need carry out pyroprocessing, as, melt or sintering processes (P.William Lee-" Ceramics "-1961-Reinhold Publishing Corp.-Page1; Kirk Othmer Encyclopedia of Chemical Technology-Third edition-Volume 5-1979, John Wiley﹠amp; Sons, USA-Page 234 to 236; " Ceramics, Scope ").
Constitute by spherical particle according to the blended metal oxide powder that technology of the present invention obtained.They are different from tiny particle distribution, in fact do not have cohesion and significant chemical uniformity, and surpass according to day presents JP-A-64003019(NIPPON CEMENTKK) powder that goes out of described explained hereafter.
According to technology of the present invention, can find, it provides valuable application scenario for the production of metal oxide powder, it can be used for the production with the insulating material in the capacitor arrangement of electronic component, particularly semiconductor element, PTC or the NTC thermistor and the application of sintering processing production.Therefore, technology of the present invention can be used to be mixed with the production of the barium titanate powder of metal oxide, and the metal in the metal oxide that is mixed is selected from calcium, magnesium, zirconium and silicon.And can produce the isolator that produces by metallurgy sintered operation.The another kind of technology of the present invention is used the production that relates to the barium titanate powder that is mixed with metal oxide, and the metal in these metal oxides is selected from calcium halophosphate activated by antimony andmanganese, calcium, silicon, lead and strontium, is applicable to the production of the PTC thermistor of making of metallurgy sintered mode.
Below will describe several embodiment and confirm technology of the present invention, these embodiment 1～6 carry out with reference to the accompanying drawings.Accompanying drawing 1-6 is the copy of six photos of the mixed metal oxide produced according to the present invention, is to see with 20,000 times electron emission microscope to find.
The first serial embodiment:
The embodiment 1～4 that describes below is particularly related to the operation of producing the used powder of non-conductive pottery.When these embodiment of explanation, use the following step.
Prepare following solution respectively
The solution that contains 0.08 mole barium monohydrate in every liter of formed organic solvent of mixture by the methyl alcohol of equal volume and Virahol,
Contain 0.08 mole different third oxygen titanium and 0.05 mole oleic solution in the formed organic solvent of mixture that every liter contains by the methyl alcohol of equal volume and Virahol,
The solution that 0.08 the Asia third oxygen zirconium is arranged in every liter of Virahol,
The solution that 0.02 mole lime acetate hydrate is arranged in every liter of methyl alcohol,
In every liter of formed organic solvent of mixture by the methyl alcohol of equal volume and Virahol
Have 0.01 mole the magnesium ethylate hydrate solution and
In every liter of Virahol 0.02 mole tetraethyl orthosilicate is arranged.
At first, with the different third oxygen titanium solution, calcium acetate solution, (if suitable) magnesium acetate and orthosilicic acid tetrem lipoprotein solution are poured in the reaction chamber in the environment that remains on the dry nitrogen atmosphere, respectively different third oxygen zirconium solution and barium hydroxide solution are side by side poured in this mixture then.The mixture of these solution is stirred at full tilt, so that before becoming nuclear reaction, produce uniform reaction mixture.Then with this reaction mixture timeliness 2 hours under 60 ℃ temperature, and be attended by the stirring of appropriateness.When completion of prescription, this reaction mixture is evaporated, like this; The exsiccant mixed metal oxide powders has just formed.Then, this exsiccant powder is carried out calcination handle, this processing is included in the moist nitrogen after the processing under 500 ℃ temperature, is then handling 2 hours under 860 ℃ temperature under the exsiccant air.When the calcination processing finishes, to collect powder, and measure particle size distribution with the MALVERN proofing unit, this MALVERN proofing unit is to carry out with the scattering testing method of Laser emission.On cumulative particle size distribution curve, can find following size of particles feature:
Diameter D(0.5), be equivalent to 50% particle weight (representing) with volume;
Diameter D(0.9), be equivalent to 90% particle weight (representing) with volume;
Diameter D(0.1), be equivalent to 10% particle weight (representing) with volume; And
Average deviation E is determined by the following relationship formula:
E＝ (D（0.9）-D（0.1）)/(D（0.5）)
The solution of hydrated barta, the different third oxygen titanium, third zirconium white and lime acetate is mixed with controllable certain proportion, obtain empirical formula
Ba
1.11Ca
0.1Zr
0.22TiO
3.65Product.
Fig. 1 shows the powder that is obtained when calcination processing finishes, it has following size of particles feature:
D（0.5）＝0.79μm
D（0.9）＝2.03μm
D（0.1）＝0.34μm
E＝2.2
Embodiment 2
The solution of hydrated barta, the different third oxygen titanium, third zirconium white and lime acetate is mixed with controllable certain proportion, obtain empirical formula
Ba
1.13Ca
0.1Zr
0.22TiO
3.67Product.
Fig. 2 has shown the powder that is obtained when the calcination processing finishes.
Embodiment 3
The solution of hydrated barta, the different third oxygen titanium, third zirconium white, magnesium acetate and lime acetate is mixed with controllable certain proportion, obtain empirical formula
Ba
1.077Ca
0.075Mg
0.008Zr
0.16TiO
3.48Product.
Fig. 3 has shown the powder that is obtained when calcination finishes, obtained following size of particles feature thus:
D（0.5）＝0.58μm
D（0.9）＝1.49μm
D（0.1）＝0.26μm
E＝2.1
Embodiment 4
The solution of hydrated barta, the different third oxygen titanium, third zirconium white, tetraethoxysilance, lime acetate and magnesium acetate is mixed with controllable certain proportion, obtains empirical formula:
Ba
1.066Ca
0.114Mg
0.005Zr
0.185TiSi
0.005O
3.565Product.
Fig. 4 has shown the powder that is obtained when calcining finishes, find to have following size of particles feature:
D（0.5）＝0.82μm
D（0.9）＝3.79μm
D（0.1）＝0.30μm
E＝4.2
Second series embodiment:
Embodiment 5 and 6 relates to the production of the powder that is used to make PTC type thermistor.
Embodiment 5
This embodiment relates to general empirical formula
Ba
0.9Ca
0.1Ti
1.01Sb
0.0034Mn
0.0008O
3.026The production of powder:
Following solution is poured in the reaction chamber:
259.9 the following solution of milliliter, this solution is every liter and contains
0.0619 different third titanium oxide of mole,
0.0614 the mole lime acetate and
0.0310 the mixture of oleic acid in equal-volume methyl alcohol and Virahol of mole;
3.08 the following solution of milliliter, this solution is every liter of methanol solution that contains 0.02 mole of acetic acid antimony;
With
1.45 the following solution of milliliter 5, this solution is every liter of methanol solution that contains 0.01 mole of acetic acid manganese.
The mixture of these solution is stirred evenly mixing, contain isopyknic methyl alcohol of 0.0816 moles of hydrogen barium oxide-hydrate with every liter then and the 200ml solution of isopropyl alcohol mixed solvent once is added in the said mixture.The mixture of these solution is stirred at full tilt, so that before nucleation begins, produce the mixture of homogeneous reaction.The mixture that will react timeliness 2 hours under 70 ℃ temperature then, and be accompanied by the stirring of appropriateness.When completion of prescription, the mixture of this reaction is carried out evaporation, has so just obtained the exsiccant mixed metal oxide powders.Then this exsiccant powder is carried out calcination processing, this calcination processing is included in and further is heated to 560 ℃ in the moist nitrogen and handled 3 and a half hours, then in the exsiccant air with 860 ℃ Temperature Treatment two hours.Collected powder is presented among Fig. 5 when calcining finishes.(Malvern Instruments Limited) carries out the mensuration of particle size distribution to be used in employed among the first serial embodiment " Master Sizer " device.With reference to the definition of the above-mentioned first serial embodiment, just can infer size of particles feature (0.5), D(0.9), D(0.1) and E:
D（0.5）＝0.48μm
D（0.9）＝0.93μm
D（0.1）＝0.25μm
E＝1.4
Embodiment 6
This embodiment relates to empirical formula
Ba
0.9Ca
0.1Ti
1.02Sb
0.0034Mn
0.0008O
3.046The production of powder.
Following ingredients is poured in the reaction chamber:
259.9 the following solution of milliliter, its every liter contains
0.0619 different third titanium oxide of mole,
0.00614 the mole lime acetate and
0.0310 the oleic acid of mole is in the mixed solvent of equal-volume methyl alcohol and Virahol
0.054 different third titanium oxide of milliliter,
Every liter of solution below 3.08 milliliters, its every liter antimony acetate that contains 0.02 mole, and be dissolved in the methyl alcohol
With
1.45 the following solution of milliliter, 0.01 mole manganous acetate also is dissolved in the methyl alcohol.
The mixture of these solution is stirred, once add the solution below 200 milliliters then in this mixture, every liter of this solution contains 0.0816 moles of hydrogen barium oxide-hydrate and is dissolved in the mixed solvent of equal-volume methyl alcohol and Virahol.The mixture of these solution is stirred at full tilt,,, and be accompanied by the stirring of appropriateness then with this reaction mixture timeliness 2 hours under 70 ℃ temperature before nucleation, to produce uniform reaction mixture.When completion of prescription, with this reaction mixture evaporation, the exsiccant mixed metal oxide powders has just formed like this.This powder is handled to carry out calcination under the condition described in the embodiment 5.Fig. 6 has shown powder collected when calcination processing finishes.The mensuration of particle size distribution is carried out according to the condition identical with embodiment 5, can obtain following size of particles characteristic thus:
D（0.5）＝0.49μm
D（0.9）＝0.95μm
D（0.1）＝0.25μm
E＝1.4
Claims (10)
1, a kind of technology of producing the blended metal oxide powder in this technology, is mixed hydroxide metal, alcoxides and water in common organic solution, it is characterized in that: before water was joined this mixture, organic salt dissolved in solvent.
2, according to the described technology of claim 1, it is characterized in that: organic salt is to select from the salt of content less than the carboxylic acid of 10 carbon atoms.
3, according to the described technology of claim 2, it is characterized in that: organic salt is selected from the acetate metal.
4, according to any one described technology in the claim 1 to 3, it is characterized in that: the acidic group of every mol organic salt must have greater than 1 molar alcoxides base in the consumption of organic salt and alcoxides.
5, according to any one described technology in the claim 1 to 4, it is characterized in that: the branch water of hydroxide metal and at least one portion is to use with the form of the hydroxide metal of hydration.
6, according to any described technology in the claim 1 to 5, it is characterized in that: common organic solution is a kind of ethanol or alcoholic acid mixture.
7, according to any described technology in the claim 1 to 6, it is characterized in that: the acidic organic compound that contains 6 above carbon atoms in its molecule dissolves in organic solvent.
8, according to the described technology of claim 7, it is characterized in that: acidic organic compound is by selecting in the carboxylic acid that contains 8 carbon atoms in its molecule at least and these the sour growths, and the acid consumption that based compound arranged is that whole metal oxide basis in every molar mixed metal oxide are 20～200g.
9, according to any described technology in the claim 1 to 8, it is characterized in that: before beginning into nuclear reaction, make mixture, so that it is even.
10, according to any described technology in the claim 1 to 9, it is characterized in that: the hydroxide metal is selected from hydrated barta and strontium hydroxide, alcoxides is by selecting in titanium alkoxides and the-oxyl zirconium, and organic salt is to select in the organic salt by calcium, magnesium, manganese and antimony.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| BE9001055A BE1004604A4 (en) | 1990-11-08 | 1990-11-08 | Manufacturing method of mixed metal oxide powder. |
| BE9001055 | 1990-11-08 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1062122A true CN1062122A (en) | 1992-06-24 |
Family
ID=3885004
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN91111445A Pending CN1062122A (en) | 1990-11-08 | 1991-11-08 | The production technique of blended metal oxide powder |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0556224A1 (en) |
| JP (1) | JPH06501445A (en) |
| KR (1) | KR930702222A (en) |
| CN (1) | CN1062122A (en) |
| AU (1) | AU8752391A (en) |
| BE (1) | BE1004604A4 (en) |
| PT (1) | PT99449A (en) |
| WO (1) | WO1992008672A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1063155C (en) * | 1997-02-05 | 2001-03-14 | 曾燮榕 | Technology for preparing hydrosol of superfine metal oxide powder |
| TWI645802B (en) * | 2012-04-13 | 2019-01-01 | 愛茉莉太平洋股份有限公司 | Cosmetic having screen and manufacturing method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001233604A (en) * | 2000-02-24 | 2001-08-28 | Kansai Research Institute | Application solution for forming thin oxide film, method for producing the same and method for producing thin oxide film |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2593166A1 (en) * | 1986-01-20 | 1987-07-24 | Solvay | PROCESS FOR PRODUCING A METAL OXIDE POWDER FOR CERAMIC MATERIALS AND ZIRCONIA POWDER OBTAINED THEREBY |
| FR2617151B1 (en) * | 1987-06-29 | 1990-10-12 | Solvay | PROCESS FOR THE MANUFACTURE OF MIXED METAL OXIDE POWDER, AND MIXED METAL OXIDE POWDERS |
| EP0297823B1 (en) * | 1987-07-02 | 1992-03-18 | Mitsui Petrochemical Industries, Ltd. | Process for producing barium titanates |
| KR920701048A (en) * | 1989-04-21 | 1992-08-11 | 원본미기재 | Thin-film ceramic manufacturing method by sol gel processing |
-
1990
- 1990-11-08 BE BE9001055A patent/BE1004604A4/en not_active IP Right Cessation
-
1991
- 1991-10-29 EP EP91918847A patent/EP0556224A1/en not_active Ceased
- 1991-10-29 JP JP3517113A patent/JPH06501445A/en active Pending
- 1991-10-29 AU AU87523/91A patent/AU8752391A/en not_active Abandoned
- 1991-10-29 WO PCT/EP1991/002065 patent/WO1992008672A1/en not_active Application Discontinuation
- 1991-10-29 KR KR1019930701379A patent/KR930702222A/en not_active Application Discontinuation
- 1991-11-07 PT PT99449A patent/PT99449A/en not_active Application Discontinuation
- 1991-11-08 CN CN91111445A patent/CN1062122A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1063155C (en) * | 1997-02-05 | 2001-03-14 | 曾燮榕 | Technology for preparing hydrosol of superfine metal oxide powder |
| TWI645802B (en) * | 2012-04-13 | 2019-01-01 | 愛茉莉太平洋股份有限公司 | Cosmetic having screen and manufacturing method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06501445A (en) | 1994-02-17 |
| KR930702222A (en) | 1993-09-08 |
| BE1004604A4 (en) | 1992-12-22 |
| WO1992008672A1 (en) | 1992-05-29 |
| PT99449A (en) | 1992-09-30 |
| EP0556224A1 (en) | 1993-08-25 |
| AU8752391A (en) | 1992-06-11 |
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