NO313823B1 - FremgangsmÕte for fremstillling av polysilikatmikrogeler med lav konsentrasjon samt apparat for kontinuerlig produksjon av enstabil vandig polysilikatmikrogel - Google Patents
FremgangsmÕte for fremstillling av polysilikatmikrogeler med lav konsentrasjon samt apparat for kontinuerlig produksjon av enstabil vandig polysilikatmikrogel Download PDFInfo
- Publication number
- NO313823B1 NO313823B1 NO19944523A NO944523A NO313823B1 NO 313823 B1 NO313823 B1 NO 313823B1 NO 19944523 A NO19944523 A NO 19944523A NO 944523 A NO944523 A NO 944523A NO 313823 B1 NO313823 B1 NO 313823B1
- Authority
- NO
- Norway
- Prior art keywords
- silicate
- acid
- reservoir
- silica
- weight
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 19
- 238000010924 continuous production Methods 0.000 title claims description 5
- 230000008569 process Effects 0.000 title description 5
- 238000002360 preparation method Methods 0.000 title description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 111
- 239000002253 acid Substances 0.000 claims abstract description 60
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 51
- 239000000203 mixture Substances 0.000 claims abstract description 34
- 238000002156 mixing Methods 0.000 claims description 43
- 238000010790 dilution Methods 0.000 claims description 19
- 239000012895 dilution Substances 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 238000005086 pumping Methods 0.000 claims description 9
- 238000012546 transfer Methods 0.000 claims description 9
- 230000032683 aging Effects 0.000 claims description 7
- 230000001105 regulatory effect Effects 0.000 claims description 5
- 238000007865 diluting Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- 229910000619 316 stainless steel Inorganic materials 0.000 description 28
- 230000008878 coupling Effects 0.000 description 16
- 238000010168 coupling process Methods 0.000 description 16
- 238000005859 coupling reaction Methods 0.000 description 16
- 238000004519 manufacturing process Methods 0.000 description 16
- 241001469893 Oxyzygonectes dovii Species 0.000 description 12
- 238000012360 testing method Methods 0.000 description 9
- 239000007789 gas Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 230000008021 deposition Effects 0.000 description 5
- 238000011010 flushing procedure Methods 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 229910052681 coesite Inorganic materials 0.000 description 4
- 230000006835 compression Effects 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- 230000020477 pH reduction Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 238000011144 upstream manufacturing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000009972 noncorrosive effect Effects 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 238000001139 pH measurement Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
- C01B33/141—Preparation of hydrosols or aqueous dispersions
- C01B33/142—Preparation of hydrosols or aqueous dispersions by acidic treatment of silicates
- C01B33/143—Preparation of hydrosols or aqueous dispersions by acidic treatment of silicates of aqueous solutions of silicates
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
- Y10S516/922—Colloid systems having specified particle size, range, or distribution, e.g. bimodal particle distribution
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Silicon Compounds (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Silicon Polymers (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US07/887,793 US5279807A (en) | 1992-05-26 | 1992-05-26 | Method for preparing low-concentration polysilicate microgels |
PCT/US1993/004610 WO1993024409A1 (en) | 1992-05-26 | 1993-05-20 | Method for preparing low-concentration polysilicate microgels |
Publications (3)
Publication Number | Publication Date |
---|---|
NO944523L NO944523L (no) | 1994-11-25 |
NO944523D0 NO944523D0 (no) | 1994-11-25 |
NO313823B1 true NO313823B1 (no) | 2002-12-09 |
Family
ID=25391877
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
NO19944523A NO313823B1 (no) | 1992-05-26 | 1994-11-25 | FremgangsmÕte for fremstillling av polysilikatmikrogeler med lav konsentrasjon samt apparat for kontinuerlig produksjon av enstabil vandig polysilikatmikrogel |
Country Status (12)
Country | Link |
---|---|
US (2) | US5279807A (de) |
EP (1) | EP0642466B1 (de) |
JP (1) | JP2738981B2 (de) |
AT (1) | ATE135665T1 (de) |
AU (1) | AU661175B2 (de) |
BR (1) | BR9306543A (de) |
DE (1) | DE69301917T2 (de) |
DK (1) | DK0642466T3 (de) |
ES (1) | ES2086227T3 (de) |
GR (1) | GR3019596T3 (de) |
NO (1) | NO313823B1 (de) |
WO (1) | WO1993024409A1 (de) |
Families Citing this family (37)
Publication number | Priority date | Publication date | Assignee | Title |
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US5378399A (en) * | 1990-01-31 | 1995-01-03 | Industrial Progress, Inc. | Functional complex microgels with rapid formation kinetics |
US5503820A (en) * | 1992-05-26 | 1996-04-02 | E. I. Du Pont De Nemours And Company | Method for preparing low-concentration polysilicate microgels |
WO1998055398A1 (en) * | 1995-10-25 | 1998-12-10 | E.I. Du Pont De Nemours And Company | Improved method for preparing low-concentration polyaluminosilicate microgels |
US5980836A (en) * | 1992-05-26 | 1999-11-09 | E. I. Du Pont De Nemours And Company | Apparatus for preparing low-concentration polyaluminosilicate microgels |
US5707494A (en) * | 1994-03-14 | 1998-01-13 | E. I. Du Pont De Nemours And Company | Process for preparing water soluble polyaluminosilicates |
EP0810901B1 (de) * | 1995-02-24 | 2000-08-23 | Infineum USA L.P. | Additivmischsystem und verfahren |
US5846384A (en) * | 1995-06-15 | 1998-12-08 | Eka Chemicals Ab | Process for the production of paper |
SE9502522D0 (sv) * | 1995-07-07 | 1995-07-07 | Eka Nobel Ab | A process for the production of paper |
CA2236922A1 (en) * | 1995-11-08 | 1997-05-15 | Minerals Technologies Inc. | Synthetic mineral microparticles and retention aid and water treatment systems and methods using such particles |
GB9603909D0 (en) | 1996-02-23 | 1996-04-24 | Allied Colloids Ltd | Production of paper |
US5900116A (en) * | 1997-05-19 | 1999-05-04 | Sortwell & Co. | Method of making paper |
AU7387398A (en) | 1997-05-19 | 1998-12-11 | Sortwell & Co. | Method of water treatment using zeolite crystalloid coagulants |
AU739968B2 (en) * | 1997-06-04 | 2001-10-25 | E.I. Du Pont De Nemours And Company | Improved method for preparing low-concentration polyaluminosilicate microgels |
DE69841835D1 (de) | 1997-06-09 | 2010-09-23 | Akzo Nobel Nv | Polysilikat-Mikrogele |
CN1321887C (zh) | 1997-06-09 | 2007-06-20 | 阿克佐诺贝尔公司 | 聚硅酸盐微凝胶和二氧化硅基材料 |
KR100573343B1 (ko) * | 1997-06-13 | 2006-04-24 | 이 아이 듀폰 디 네모아 앤드 캄파니 | 저-농도 폴리알루미노실리케이트 마이크로겔의 개선된제조 방법 |
CO5070714A1 (es) | 1998-03-06 | 2001-08-28 | Nalco Chemical Co | Proceso para la preparacion de silice coloidal estable |
US6183650B1 (en) | 1998-05-04 | 2001-02-06 | Minerals Technologies Inc. | Synthetic mineral microparticles and retention aid and water treatment systems and methods using such particles |
US6060523A (en) * | 1998-07-20 | 2000-05-09 | E. I. Du Pont De Nemours And Company | Continuous process for preparing microgels |
US7169261B2 (en) | 1999-05-04 | 2007-01-30 | Akzo Nobel N.V. | Silica-based sols |
EP1619171B1 (de) * | 1999-05-04 | 2016-09-07 | Akzo Nobel N.V. | Sole auf der basis von kieselsäure |
KR100357638B1 (ko) * | 1999-08-31 | 2002-10-25 | 삼성전자 주식회사 | 실리카 솔의 초음파 분산 장치 |
US6274112B1 (en) * | 1999-12-08 | 2001-08-14 | E. I. Du Pont De Nemours And Company | Continuous production of silica-based microgels |
US7905653B2 (en) * | 2001-07-31 | 2011-03-15 | Mega Fluid Systems, Inc. | Method and apparatus for blending process materials |
CN100457620C (zh) * | 2002-01-28 | 2009-02-04 | 国家非金属矿深加工工程技术研究中心 | 天然硅酸镁铝凝胶的制备方法 |
US6883957B2 (en) * | 2002-05-08 | 2005-04-26 | Cytonome, Inc. | On chip dilution system |
US7732495B2 (en) * | 2004-04-07 | 2010-06-08 | Akzo Nobel N.V. | Silica-based sols and their production and use |
US7629392B2 (en) * | 2004-04-07 | 2009-12-08 | Akzo Nobel N.V. | Silica-based sols and their production and use |
EP1833760B1 (de) * | 2004-12-01 | 2012-04-11 | Ciba Specialty Chemicals Water Treatments Limited | Schnelles niederdruckverfahren zur herstellung von silikagelen und -mikrogelen |
DE102005018243A1 (de) * | 2005-04-19 | 2006-10-26 | Henkel Kgaa | Verfahren zur Erzeugung flüssiger Zubereitungen mit Festkörpergehalt |
CA2664490A1 (en) * | 2006-09-27 | 2008-04-03 | Ciba Holding Inc. | Siliceous composition and its use in papermaking |
US8409647B2 (en) * | 2008-08-12 | 2013-04-02 | E. I. Du Pont De Nemours And Company | Silica microgels for reducing chill haze |
US8609068B2 (en) | 2010-02-24 | 2013-12-17 | J.M. Huber Corporation | Continuous silica production process and silica product prepared from same |
WO2012018514A2 (en) | 2010-07-26 | 2012-02-09 | Sortwell & Co. | Method for dispersing and aggregating components of mineral slurries and high-molecular weight multivalent polymers for clay aggregation |
US9028605B2 (en) | 2011-02-25 | 2015-05-12 | J.M. Huber Corporation | Coating compositions comprising spheroid silica or silicate |
US8721896B2 (en) | 2012-01-25 | 2014-05-13 | Sortwell & Co. | Method for dispersing and aggregating components of mineral slurries and low molecular weight multivalent polymers for mineral aggregation |
CN108130801B (zh) * | 2013-12-18 | 2020-11-24 | 艺康美国股份有限公司 | 生产用于造纸的活化胶态二氧化硅的方法 |
Family Cites Families (26)
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CA584727A (en) * | 1959-10-06 | E. Armstrong James | Process and apparatus for making silica sol | |
US2234285A (en) * | 1937-04-02 | 1941-03-11 | William B Schworm | Treatment of natural waters |
US2217466A (en) * | 1937-09-17 | 1940-10-08 | City Of Chicago | Composition of matter for water treatment |
US2310009A (en) * | 1938-09-21 | 1943-02-02 | Philadelphia Quartz Co | Water purification |
US2444774A (en) * | 1943-11-03 | 1948-07-06 | Philadelphia Quartz Co | Purification of raw waters |
US2466842A (en) * | 1945-11-15 | 1949-04-12 | Davison Chemical Corp | Method for making silica hydrosol |
US2769785A (en) * | 1950-09-02 | 1956-11-06 | B I F Ind Inc | Continuous silica sol apparatus |
GB827586A (en) * | 1955-03-15 | 1960-02-10 | Water Res Ass | Improvements in or relating to the treatment of water |
GB1044019A (en) * | 1963-10-17 | 1966-09-28 | Permutit Co Ltd | Improvements relating to the production of silica sol |
GB1300946A (en) * | 1966-05-26 | 1972-12-29 | Peter Spence And Sons Ltd | Improvements in or relating to the preparation of active siliceous compounds and their use in the production of crystalline synthetic zeolites |
GB1386686A (en) * | 1972-09-13 | 1975-03-12 | Pfeiffer Vakuumtechnik | Production of casting resins |
DE2346347A1 (de) * | 1973-09-14 | 1975-03-27 | Demag Kunststofftech | Mischvorrichtung fuer die formgebende verarbeitung von sich aus mehreren, vorzugsweise fluessigen komponenten bildenden kunststoffen |
US4204977A (en) * | 1976-02-09 | 1980-05-27 | Olin Corporation | Polyurethane foam generating apparatus |
AU499635B2 (en) * | 1976-02-20 | 1979-04-26 | Thapa Chemical Industry Co Ltd | Material mixing apparatus |
DE2631588B2 (de) * | 1976-07-14 | 1979-06-07 | Elastogran Maschinenbau Gmbh & Co, 8021 Strasslach | Vorrichtung zur Herstellung von Kunststoffen, insbesondere Polyurethan, aus mindestens zwei reaktiven Komponenten |
US4213950A (en) * | 1978-12-22 | 1980-07-22 | E. I. Du Pont De Nemours And Company | Process for preparing amorphous particulate poly(alumino-silicate) |
DE3037898A1 (de) * | 1980-10-07 | 1982-05-06 | Bruker Analytische Meßtechnik GmbH, 7512 Rheinstetten | Mischkammer |
JPS5926911A (ja) * | 1982-08-04 | 1984-02-13 | Toyo Soda Mfg Co Ltd | 球状多孔性シリカゲルおよびその製造法 |
FR2567504B1 (fr) * | 1984-07-11 | 1989-12-29 | Rhone Poulenc Chim Base | Colloides de silice et silices spheriques et procedes pour leur obtiention |
DD270289A1 (de) * | 1986-02-21 | 1989-07-26 | Univ Schiller Jena | Verfahren zur herstellung von kieselgelen, vorzugsweise fuer chromatographische anwendungen |
DE3633343A1 (de) * | 1986-09-10 | 1988-03-17 | Bayer Ag | Verfahren und vorrichtung zum herstellen eines kunststoff, insbesondere schaumstoff bildenden, fliessfaehigen reaktionsgemisches aus mindestens zwei fliessfaehigen reaktionskomponenten im durchlauf |
US5176891A (en) * | 1988-01-13 | 1993-01-05 | Eka Chemicals, Inc. | Polyaluminosilicate process |
US4954220A (en) * | 1988-09-16 | 1990-09-04 | E. I. Du Pont De Nemours And Company | Polysilicate microgels as retention/drainage aids in papermaking |
DE68906623T2 (de) * | 1988-09-16 | 1993-11-11 | Du Pont | Polysilikatmikrogele als Rückhaltungs-/Entwässerungshilfsmittel bei der Papierherstellung. |
SE500387C2 (sv) * | 1989-11-09 | 1994-06-13 | Eka Nobel Ab | Silikasoler, förfarande för framställning av silikasoler samt användning av solerna i pappersframställning |
US5082633A (en) * | 1990-06-14 | 1992-01-21 | The Dow Chemical Company | Mix head for mixing reactive chemicals |
-
1992
- 1992-05-26 US US07/887,793 patent/US5279807A/en not_active Expired - Lifetime
-
1993
- 1993-05-20 DK DK93911324.7T patent/DK0642466T3/da active
- 1993-05-20 JP JP6500585A patent/JP2738981B2/ja not_active Expired - Lifetime
- 1993-05-20 AU AU42499/93A patent/AU661175B2/en not_active Expired
- 1993-05-20 EP EP93911324A patent/EP0642466B1/de not_active Expired - Lifetime
- 1993-05-20 AT AT93911324T patent/ATE135665T1/de active
- 1993-05-20 WO PCT/US1993/004610 patent/WO1993024409A1/en active IP Right Grant
- 1993-05-20 DE DE69301917T patent/DE69301917T2/de not_active Expired - Lifetime
- 1993-05-20 ES ES93911324T patent/ES2086227T3/es not_active Expired - Lifetime
- 1993-05-20 BR BR9306543A patent/BR9306543A/pt not_active IP Right Cessation
- 1993-07-23 US US08/093,157 patent/US5312595A/en not_active Expired - Lifetime
-
1994
- 1994-11-25 NO NO19944523A patent/NO313823B1/no not_active IP Right Cessation
-
1996
- 1996-04-09 GR GR960400990T patent/GR3019596T3/el unknown
Also Published As
Publication number | Publication date |
---|---|
ES2086227T3 (es) | 1996-06-16 |
EP0642466B1 (de) | 1996-03-20 |
NO944523L (no) | 1994-11-25 |
US5312595A (en) | 1994-05-17 |
AU661175B2 (en) | 1995-07-13 |
JP2738981B2 (ja) | 1998-04-08 |
ATE135665T1 (de) | 1996-04-15 |
AU4249993A (en) | 1993-12-30 |
JPH07507990A (ja) | 1995-09-07 |
DE69301917T2 (de) | 1996-09-05 |
NO944523D0 (no) | 1994-11-25 |
EP0642466A1 (de) | 1995-03-15 |
BR9306543A (pt) | 1998-09-15 |
DK0642466T3 (da) | 1996-04-15 |
GR3019596T3 (en) | 1996-07-31 |
DE69301917D1 (de) | 1996-04-25 |
WO1993024409A1 (en) | 1993-12-09 |
US5279807A (en) | 1994-01-18 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
MK1K | Patent expired |