IE903320A1 - Macrocrystals of ó-alumina in the form of platelets and¹process for obtaining them - Google Patents
Macrocrystals of ó-alumina in the form of platelets and¹process for obtaining themInfo
- Publication number
- IE903320A1 IE903320A1 IE332090A IE332090A IE903320A1 IE 903320 A1 IE903320 A1 IE 903320A1 IE 332090 A IE332090 A IE 332090A IE 332090 A IE332090 A IE 332090A IE 903320 A1 IE903320 A1 IE 903320A1
- Authority
- IE
- Ireland
- Prior art keywords
- alumina
- flux
- macrocrystals
- process according
- diameter
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
- C30B29/20—Aluminium oxides
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B9/00—Single-crystal growth from melt solutions using molten solvents
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
- C01P2004/22—Particle morphology extending in two dimensions, e.g. plate-like with a polygonal circumferential shape
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/54—Particles characterised by their aspect ratio, i.e. the ratio of sizes in the longest to the shortest dimension
-
- 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
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Paper (AREA)
Abstract
Macrocrystals of alpha alumina in the form of monocrystalline hexagonal platelets. The invention also relates to a process for the manufacture of these macrocrystals by calcination of alumina, for example transition alumina, and in the presence of a fluorine-containing flux, at a relatively low temperature. The macrocrystals of alpha alumina can be employed as reinforcing materials.
Description
The invention relates to macrocrystals of aalumina or aluminium oxide or corundum, having the form of hexagonal platelets and to a process for the preparation of the said crystals from aluminium oxide or aluminium hydroxide.
The preparation of macrocrystals of alumina from aluminium hydroxide has already been described. Thus, in French Patent 2,441,594 macrocrystals of a-alumina are proposed which are in the form of hexagonal platelets having a particle size of from 16 to 250 μία and a diameter/thickness ratio of between 3/1 and 7/1, these macrocrystals being obtained by calcination of aluminium hydroxide at a temperature of between 1200"C and 1450°C in the presence of a mineralizing agent containing 0.001 to 0.5 % by weight of fluorinated compounds.
In German Patent Application DE-OS 2,623,482 it has been proposed to prepare primary crystals having an average size of between 16 and 25 μνα by calcination of aluminium hydroxide in the presence of at least one fluorinated salt and a vanadium salt. According to the abovementioned French patent (page 2, lines 19-22), raising the temperature or the use of other mineralizing agents has no or virtually no influence on the size and the shape of the crystals.
Moreover, Keiji DAIMON and Etsun KATO have proposed (Yogyo Kvokai Shi 94 [3] 1986 pp. 380-382 [7880]) the production of hexagonal platelets of o-alumina having a diameter of between 1.5 and 40 μία from hydrated aluminium sulphate in the presence of aluminium trifluoride.
In Japanese Patent Application No. 60/54916 it has been proposed to prepare platelets having an average diameter of 1.7 μτα. and a thickness of 0.18 μία from a mixture of hydrated aluminium sulphate and an alkali metal carbonate.
In Japanese Patent Application 60/38486 it has been proposed to prepare platelets having a thickness of less than 5 μία and a diameter (from the diameter/thickness ratio) of between 25 and 150 gm.
In Russian Patent 416313 it has been proposed to prepare hexagonal platelets of alumina which have a diameter of between 4 and 12 gm by thermal dissociation of an aluminium compound in the presence of hexagonal alumina seed at 1170°C.
Finally, in INTERCERAM No. 3, 1981 B.P. LOCSEL has proposed the preparation of α-alumina crystals having a diameter/thickness ratio of between 6 and 10 from bauxite having a low ferric oxide content, in the presence of aluminium trifluoride.
The invention relates to new macrocrystals of α-alumina having essentially the form of monocrystalline hexagonal platelets, the said platelets being characterized in that they have a diameter of between 2 and 20 μία., a thickness of between 0.1 and 2 μία and a diameter/thickness ratio of between 5 and 40.
Amongst these macrocrystals, the invention relates more particularly to macrocrystals of α-alumina in the form of hexagonal platelets having a diameter of between 2 and 18 μΐη, a thickness of between 0.1 and 1 μπι and a diameter/thickness ratio of between 5 and 40.
The invention also relates to a process for the 10 production of α-alumina in the form of essentially hexagonal platelets as defined above, this process being characterized in that it consists in carrying out the calcination of transition alumina or hydrated alumina in the presence of a flux which has a melting point of at most 800°C, contains chemically bonded fluorine and, in the molten state, dissolves the transition alumina or hydrated alumina.
The term transition alumina or hydrated alumina is used to indicate that this process applies to all types of aluminium oxide or aluminium hydroxide with the exception of a-alumina.
The flux, also termed mineralizing agent, having the characteristics defined above, essentially consists of one or more non-hydrolysable fluorinated compounds or a system comprising a phase consisting of the said non-hydrolysable, fluorinated compound or compounds and a phase consisting of a hydrolysable fluorinated compound, one of the said phases being dissolved in the other phase.
The systems comprising aluminium trifluoride and one or more alkali metal fluorides or alkaline earth metal fluorides, and in particular lithium fluoride, sodium fluoride, potassium fluoride or calcium fluoride, will be mentioned very particularly by way of illustration of the abovementioned fluxes. More specifically, the system AlF3-LiF in the form Li3AlF6 (lithium cryolite) or Li3Na3(AlFs)3 (cryolithionite) or 3AlFj,5LiF (lithium chiolite).
The fluxes used in the invention are in the form of powder, the particle size of which is preferably less than 1 mm (for at least 50 % by weight of the particles).
When carrying out the process according to the invention, at least 2 % and preferably 4 to 20 % by weight of flux are used relative to the weight of transition alumina or hydrated alumina employed.
The transition alumina or hydrated alumina can be chosen from a wide range of products and powders of various diameters and specific surface areas. The aluminas in which at least 50 % by weight of the particles have a diameter of less than 50 lm and preferably of less than 25 lm and yet more preferably of 1.5 lm will be used very particularly. Amongst these aluminas, preference will be given to the aluminas having a specific surface area equal to or larger than 100 m2/g (measured by the BET method) and preferably of κ u ti η ω ο .
MU - UtJ.u:*. cji OOCUJi PQuc between 100 and 400 m2/g.
Although dried aluminas may be used, preference will be given to the types which are non-dried or hydrated (AljOj, H20) , it being possible for the water content to reach 15 % of the weight of the alumina.
The calcination temperature can reach 1200’C or even higher. However, and this is a very particular valuable feature of the process according to the invention, the calcination can be carried out at a very much lower temperature, for example of between 900 and 1100°C.
In general, the mixture of transition alumina or hydrated alumina/flux, prepared by the customary techniques for powder mixtures, can be placed at ambient temperature in a heating chamber, the temperature being progressively raised to the abovementioned values. The temperature is advantageously raised in a rapid manner, that is to say of the order of lQOQ’C in 1 hour, this indication in no case limiting the field of the invention.
The calcination is advantageously carried out in an inert atmosphere, for example under a gentle stream of nitrogen. Once the calcination temperature has been reached, which temperature, as has been specified, can be between 900 and 1100C and more precisely around 1000*C, it is advantageous to maintain this temperature for a period which can range from half an hour to a few hours (for example up to 5 hours).
At the end of the calcination operation, the platelets can be chilled, or they can be allowed to cool naturally or in a refrigerated chamber, as desired.
The platelets collected essentially (> 95 % by weight) consist of α-alumina, which may be associated with the flux or with a product derived from the flux, such as AltLiOgF in the case of Li2AlF3. The flux or its derivative can be removed, for example by the action of a concentrated acid (H2SO* or HCl) under hot conditions (for example around 100’C).
The hexagonal platelets of α-alumina, which are the subject of the present invention, are suitable for numerous applications. They can be used, in particular, in the production of polishing products and as reinforcing materials for diverse materials, in particular ceramic matrices and metal and polymer matrices, on their own or in combination with fibres, particles or whiskers.
The following examples will enable the invention to be illustrated.
EXAMPLES 1 TQ 14 The equipment used consists of a furnace heated by a quartz tube in which a stream of nitrogen can be circulated and into which sintered aluminium crucibles containing the powder to be calcined are introduced.
The following aluminas are used (Dx - Υ pm indicates that X % of the particles (by weight) have a diameter smaller than Y lm): . P3s gamma-Al2O3 Dso = 1.1 im specific surface area = 172 m2/g . P2: gamma-Al2O3 Dso = 4.6 im specific surface area = 100 mJ/g . P,: Al2O3.H2O (boehmite) Dso = 25 lm D95 = 45 im specific surface area = 196m2/g . P4: gamma-Al2O3 D55 = 25 lm D37 = 45 lm specific surface area = 244 m2/g . P5: gamma-Al2O3 Di0 = 3.5 lm The following fluxes are used (D50 = lm having the meaning given above and D corresponding to all of the particles) in an amount of 5 % by weight relative to the weight of alumina (Px to P5): . FXJ Li3AlF6 (m.p. : 776‘C) D50 = 0.9 lm . F2: Li3AlF6 400 . F3: Li3AlF6 D > 630 lm . F4: Li3AlF6 160 < D <400 lm . Fs: LijNa3(AlF6)2 (m.p. : 710°C) . Fs: 3AlF3,5LiF The mixtures of aluminas and flux are prepared at ambient temperature and then placed in crucibles and the latter are introduced into the furnace, under a stream of nitrogen (10 1/h).
The temperature of the furnace is raised to X"C in the course of one hour (gradient) and then kept at this temperature for Z hours (plateau).
Cooling is carried out in the ambient air.
The product obtained is a white block which releases from the mould and deagglomerates easily. The average diameter d (in gm) and the average thickness e (in gm) of the platelets formed are measured.
The conditions and results are collated in the table which follows:
Claims (16)
1. Macrocrystals of α-alumina having essentially the form of monocrystalline hexagonal platelets, characterized in that the said platelets have a diameter of between 2 and 20 pm, a thickness of between 0·1 and 2 pm and a diameter/thickness ratio of between 5 and 40.
2. Macrocrystals according to Claim 1, characterized in that the hexagonal platelets have a diameter of between 2 and 18 pm and a thickness of between 0,1 and 1 pm.
3. Process for the production of macrocrystals according to either of Claims 1 and 2, from transition alumina or hydrated alumina and a flux, characterized in that the flux used has a melting point of at most 800’C, contains chemically bonded fluorine and, in the molten state, dissolves the transition alumina or hydrated alumina.
4. Process according to Claim 3, characterized in that the flux essentially consists of one or more nonhydrolysable fluorinated compounds or a system comprising a phase consisting of the said fluorinated compound or compounds and a second phase consisting of a hydrolysable fluorinated compound, one of the said phases being dissolved in the other phase.
5. Process according to Claim 4, characterized in that the flux consists of a system formed from aluminium trifluoride on the one hand and one or more alkali metal fluorides or alkaline earth metal fluorides on the other hand.
6. Process according to Claim 5, characterized in that the alkali metal fluoride or alkaline earth metal fluoride is chosen from lithium fluoride, sodium fluoride, potassium fluoride and calcium fluoride.
7. Process according to any one of Claims 4 to 6, characterized in that the flux consists of A1F 2 -LIF in the form Li 3 AlF s (lithium cryolite), Li 2 Na 2 (AlF s ) 2 (cryolithionite) or 3AlF 3 ,5Lif (lithium chiolite) .
8. Process according to any one of Claims 4 to 7, characterized in that the flux is used in an amount of at least 2 % and preferably of 4 to 20 % of flux relative to tha weight of transition alumina or hydrated alumina subjected to calcination.
9. Process according to any one of Claims 4 to 8, characterized in that the transition alumina or hydrated alumina consists of a powder in which at least 50 % (by weight) of the particles have a diameter of less than 50 μΐη, the said alumina having a specific surface area larger than 100 m 2 /g.
10. Process according to Claim 8, characterized in that the alumina contains up to 15 % by weight of water.
11. Process according to any one of Claims 4 to 10, characterized in that the calcination temperature is between 900 and 1100“C.
12. Use of the macrocrystals of «-alumina according to either of Claims 1 or 2 for making up polishing products or as reinforcing materials for matrices, in particular ceramic matrices, or metal or polymer matrices .
13. A macrocrystal of «-alumina according to Claim 1, substantially as hereinbefore described and exemplified.
14. A process for the production of a macrocrystal of «-alumina according to Claim 1, substantially as hereinbefore described and exemolified.
15. A macrocrystal of α-alumina according to Claim 1, whenever produced by a process claimed in a preceding claim.
16. Use according to Claim 12, substantially as hereinbefore described.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR8912402A FR2652075B1 (en) | 1989-09-21 | 1989-09-21 | ALPHA ALUMINA MACROCRYSTALS IN THE FORM OF PLATES AND PROCESS FOR OBTAINING SAME. |
Publications (1)
Publication Number | Publication Date |
---|---|
IE903320A1 true IE903320A1 (en) | 1991-04-10 |
Family
ID=9385725
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
IE332090A IE903320A1 (en) | 1989-09-21 | 1990-09-12 | Macrocrystals of ó-alumina in the form of platelets and¹process for obtaining them |
Country Status (15)
Country | Link |
---|---|
EP (1) | EP0425325B1 (en) |
JP (1) | JP2564205B2 (en) |
KR (1) | KR950003419B1 (en) |
CN (1) | CN1047576C (en) |
AT (1) | ATE98304T1 (en) |
AU (1) | AU627933B2 (en) |
CA (1) | CA2025037A1 (en) |
DD (1) | DD295885A5 (en) |
DE (1) | DE69005077T2 (en) |
DK (1) | DK0425325T3 (en) |
ES (1) | ES2060108T3 (en) |
FR (1) | FR2652075B1 (en) |
IE (1) | IE903320A1 (en) |
IL (1) | IL95719A0 (en) |
NO (1) | NO903690L (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2010108633A1 (en) | 2009-03-24 | 2010-09-30 | Clariant International Ltd | Laminates containing rigid, plate-shaped minerals |
Families Citing this family (29)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU639326B2 (en) * | 1990-05-23 | 1993-07-22 | Atochem | Ceramic preforms comprising monocrystalline hexagonal platelets of alpha-alumina, their production and applications thereof |
WO1993024681A1 (en) * | 1992-06-02 | 1993-12-09 | Sumitomo Chemical Company, Limited | α-ALUMINA |
CA2099734A1 (en) * | 1992-07-01 | 1994-01-02 | Akihiko Takahashi | Process for preparing polyhedral alpha-alumina particles |
RU2136596C1 (en) | 1993-11-25 | 1999-09-10 | Сумитомо Кемикал Компани, Лимитед | Method of preparing alpha-aluminum powder and alpha-aluminum powder |
FR2715169B1 (en) * | 1994-01-14 | 1996-04-05 | Atochem Elf Sa | Macrocrystals containing aluminum nitride in the form of platelets, their preparation process and their uses. |
JP3416855B2 (en) * | 1994-04-15 | 2003-06-16 | 株式会社フジミインコーポレーテッド | Polishing composition and polishing method |
AU699077B2 (en) * | 1995-02-21 | 1998-11-19 | Sumitomo Chemical Company, Limited | Alpha-alumina and method for producing the same |
FR2734812B1 (en) * | 1995-05-31 | 1997-07-04 | Atochem Elf Sa | PROCESS FOR THE PREPARATION OF CERAMIC DRILL PARTS COMPRISING SINGLE-CRYSTAL ALPHA ALUMINUM WAFERS |
TW460548B (en) * | 1998-12-23 | 2001-10-21 | Merck Patent Gmbh | Pigment mixture |
JP4270848B2 (en) * | 2002-11-08 | 2009-06-03 | 昭和電工株式会社 | Alumina particles and method for producing the same |
AU2003900030A0 (en) | 2003-01-07 | 2003-01-23 | Advanced Nano Technologies Pty Ltd | Process for the production of ultrafine plate-like alumina particles |
KR100555751B1 (en) | 2004-01-05 | 2006-03-03 | 삼성전자주식회사 | Process cartridge for image forming apparatus |
JP4841851B2 (en) * | 2005-03-02 | 2011-12-21 | 電気化学工業株式会社 | Alumina and production method thereof |
CN100348494C (en) * | 2005-08-26 | 2007-11-14 | 郑州大学 | High dispersibility alpha-Al2O3 nanometer powder preparation method |
JP5211467B2 (en) * | 2006-11-22 | 2013-06-12 | 日本軽金属株式会社 | Method for producing polyhedral α-alumina |
KR100803049B1 (en) * | 2007-08-31 | 2008-02-22 | (주)제이피에스 마이크로텍 | Manufacture method of flake aluminum oxide using microwave |
JPWO2013133300A1 (en) * | 2012-03-09 | 2015-07-30 | 旭硝子株式会社 | Glass ceramic body, laminate, portable electronic device casing, and portable electronic device |
JP5720848B2 (en) * | 2012-09-28 | 2015-05-20 | Dic株式会社 | Method for producing polyhedral α-alumina fine particles |
CN102924092A (en) * | 2012-10-24 | 2013-02-13 | 江苏大学 | Low-cost and pollution-free preparation method for highly dispersed flaky alumina |
JP6229661B2 (en) * | 2012-11-07 | 2017-11-15 | 旭硝子株式会社 | Glass ceramic substrate and casing for portable electronic device using the substrate |
JP6646864B2 (en) * | 2015-06-01 | 2020-02-14 | Dic株式会社 | Method for producing plate-like alumina particles |
CN104925843A (en) * | 2015-06-03 | 2015-09-23 | 清华大学 | Method for preparing laminar alpha-Al2O3 pearlescent pigment base material by use of compound aluminum salt |
CN108560052B (en) * | 2018-04-26 | 2020-05-01 | 闽江学院 | Preparation method and application of monocrystal hexagonal alumina |
US20220081310A1 (en) * | 2019-01-25 | 2022-03-17 | Dic Corporation | Tabular alumina particle and method for manufacturing tabular alumina particle |
JP6708281B2 (en) * | 2019-03-27 | 2020-06-10 | Dic株式会社 | Plate-shaped alumina particles |
EP4041828A1 (en) | 2019-10-09 | 2022-08-17 | DIC Corporation | Plate-like alumina particle and method for manufacturing plate-like alumina particle |
US20230096825A1 (en) * | 2019-10-09 | 2023-03-30 | Dic Corporation | Plate-like alumina particle and method for manufacturing plate-like alumina particle |
CN110938862A (en) * | 2019-12-23 | 2020-03-31 | 苏州纳迪微电子有限公司 | High-purity monocrystalline corundum powder and preparation method thereof |
CN114057505B (en) * | 2021-12-13 | 2023-02-28 | 西安邮电大学 | Preparation method of porous flaky alumina framework |
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GB935390A (en) * | 1960-12-20 | 1963-08-28 | Gen Electric Co Ltd | Improvements in or relating to the manufacture of corundum crystals |
JPS5215498A (en) * | 1975-07-28 | 1977-02-05 | Showa Denko Kk | Process for production of granular corrundum |
DE2623482C2 (en) * | 1976-05-26 | 1985-06-27 | Alcoa Chemie GmbH, 6700 Ludwigshafen | Process for the production of a crystalline aluminum oxide for polishing, lapping and grinding media |
DE2850064B1 (en) * | 1978-11-18 | 1980-05-08 | Giulini Chemie | Hexagonal tabular alpha alumina single crystals and process for their manufacture |
JPS5819640A (en) * | 1981-07-27 | 1983-02-04 | Matsushita Electric Ind Co Ltd | Temperature control device of air conditioners etc. |
JPS6033763A (en) * | 1983-08-05 | 1985-02-21 | Nippon Telegr & Teleph Corp <Ntt> | Speed selecting communication system |
JPS6054916A (en) * | 1983-09-06 | 1985-03-29 | 坂東 尚周 | Hexagonal flake a-al203 particle and manufacture |
JPS6433055A (en) * | 1987-07-27 | 1989-02-02 | Sumitomo Cement Co | Sintered body of alumina having high strength and its production |
US5009676A (en) * | 1989-04-28 | 1991-04-23 | Norton Company | Sintered sol gel alumina abrasive filaments |
JP3207739B2 (en) * | 1996-01-19 | 2001-09-10 | 松下電器産業株式会社 | Image playback device |
-
1989
- 1989-09-21 FR FR8912402A patent/FR2652075B1/en not_active Expired - Lifetime
-
1990
- 1990-08-22 NO NO90903690A patent/NO903690L/en unknown
- 1990-09-11 CA CA002025037A patent/CA2025037A1/en not_active Abandoned
- 1990-09-12 IE IE332090A patent/IE903320A1/en unknown
- 1990-09-17 DD DD90344059A patent/DD295885A5/en not_active IP Right Cessation
- 1990-09-18 KR KR1019900014770A patent/KR950003419B1/en not_active IP Right Cessation
- 1990-09-18 IL IL95719A patent/IL95719A0/en unknown
- 1990-09-19 JP JP2249896A patent/JP2564205B2/en not_active Expired - Fee Related
- 1990-09-20 DE DE69005077T patent/DE69005077T2/en not_active Expired - Fee Related
- 1990-09-20 EP EP90402599A patent/EP0425325B1/en not_active Expired - Lifetime
- 1990-09-20 AU AU62697/90A patent/AU627933B2/en not_active Ceased
- 1990-09-20 ES ES90402599T patent/ES2060108T3/en not_active Expired - Lifetime
- 1990-09-20 AT AT90402599T patent/ATE98304T1/en not_active IP Right Cessation
- 1990-09-20 DK DK90402599.6T patent/DK0425325T3/en active
- 1990-09-21 CN CN90107756A patent/CN1047576C/en not_active Expired - Fee Related
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2010108633A1 (en) | 2009-03-24 | 2010-09-30 | Clariant International Ltd | Laminates containing rigid, plate-shaped minerals |
DE102009014638A1 (en) | 2009-03-24 | 2010-09-30 | Clariant International Ltd. | Laminates containing hard, plate-shaped minerals |
Also Published As
Publication number | Publication date |
---|---|
CA2025037A1 (en) | 1991-03-22 |
EP0425325A1 (en) | 1991-05-02 |
NO903690L (en) | 1991-03-22 |
DD295885A5 (en) | 1991-11-14 |
KR910006145A (en) | 1991-04-27 |
ATE98304T1 (en) | 1993-12-15 |
DE69005077T2 (en) | 1994-05-26 |
CN1047576C (en) | 1999-12-22 |
JP2564205B2 (en) | 1996-12-18 |
FR2652075B1 (en) | 1991-12-06 |
IL95719A0 (en) | 1991-06-30 |
EP0425325B1 (en) | 1993-12-08 |
DE69005077D1 (en) | 1994-01-20 |
CN1050366A (en) | 1991-04-03 |
JPH03131517A (en) | 1991-06-05 |
AU627933B2 (en) | 1992-09-03 |
NO903690D0 (en) | 1990-08-22 |
DK0425325T3 (en) | 1994-02-14 |
ES2060108T3 (en) | 1994-11-16 |
AU6269790A (en) | 1991-04-11 |
FR2652075A1 (en) | 1991-03-22 |
KR950003419B1 (en) | 1995-04-12 |
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