EP0743352B1 - Schmiermittelzusammensetzung für die Anwendung auf Werkstücken bei der Heissumformung von Metallen - Google Patents
Schmiermittelzusammensetzung für die Anwendung auf Werkstücken bei der Heissumformung von Metallen Download PDFInfo
- Publication number
- EP0743352B1 EP0743352B1 EP96107611A EP96107611A EP0743352B1 EP 0743352 B1 EP0743352 B1 EP 0743352B1 EP 96107611 A EP96107611 A EP 96107611A EP 96107611 A EP96107611 A EP 96107611A EP 0743352 B1 EP0743352 B1 EP 0743352B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- lubricant composition
- water
- composition according
- weight
- sodium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/20—Metal working
- C10N2040/244—Metal working of specific metals
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/20—Metal working
- C10N2040/244—Metal working of specific metals
- C10N2040/245—Soft metals, e.g. aluminum
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/20—Metal working
- C10N2040/244—Metal working of specific metals
- C10N2040/246—Iron or steel
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/20—Metal working
- C10N2040/244—Metal working of specific metals
- C10N2040/247—Stainless steel
Definitions
- the invention relates to a new lubricant composition for use on workpieces in the hot forming of metals, in particular for use in the hot rolling of blocks and profiles or in the production of hollow blocks in so-called shaping bench systems. Due to the fact that the metals to be processed have a surface temperature of approx. 800 ° C to 1300 ° C, the focus in practice has so far been on the lubrication of the tools, which are more accessible to classic lubrication at temperatures of maximum 400 ° C are. Although it is disclosed in the prior art, for example in CH-PS 660 023, that workpieces with temperatures above 600 ° C.
- JP-A-5 516 897 discloses a high temperature lubricant for the hot forming of metals made from glass powder with a low melting point, graphite powder and alkali silicate as a binder.
- High temperature lubricant forms a lubricant film consisting of graphite dispersed in molten glass powder.
- the lubrication of the tools also has various difficulties afflicted. So is the application of the lubricant solely because of the geometry of the Tools often difficult or low tool temperatures around 100 ° C do not allow correct formation of a lubricant film. Because the tools are always with large amounts of cooling water are treated, are also large losses of lubricant the rule of what a waste water contamination and a appropriate treatment of the waste water entails. For good lubrication therefore relatively large amounts of lubricant required.
- a normal glass with an average grain diameter d 50 of ⁇ 100 ⁇ m and a softening range of approx. 700 ° C to 900 ° C is suitably used as the glass powder (CAS No. 65997-17-3).
- the glass powder is largely responsible for the excellent film properties of the lubricant. Due to its relatively high softening point, it is used in increasing quantities when the surface temperature of the workpiece exceeds the 1000 ° C limit.
- the glass frit is mainly used when the application temperatures are in the lower range from approx. 800 ° C. Then, due to the lower softening range of approx. 500 ° C to 700 ° C compared to glass powder, the film-forming properties of the glass frit come into full effect.
- the chemical frit of the glass frit is expediently an alkali-alkaline earth-alumo-boron silicate and is usually used in an average grain size d 50 of ⁇ 100 ⁇ m.
- glass powder and glass frit are available in any of the specified limits Mixing ratios can be used.
- graphite Another important component is graphite. Both synthetic graphite and natural graphite can be used.
- the average grain size d 50 of the graphite used is expediently less than 100 ⁇ m.
- the water-soluble alkali silicates play an essential role as binders.
- a mixture of the preferred alkali silicates mentioned in a ratio of sodium silicate: potassium silicate: lithium silicate of 12.3%: 67.5%: 20.7% is particularly preferably used.
- a water-soluble sodium metapolyphosphate acts as a lubricant component that suppresses foaming.
- This is expediently understood to mean a compound having the general formula (NaPO 3 ) n where n is less than 450. These compounds are also known under the name "hexametaphosphate” or "Graham's salt”.
- a water-insoluble sodium metapolyphosphate as a binder.
- Particularly suitable for this purpose are the compounds of the general formula (NaPO 3 ) n known under the name "Maddrell's salt", in which n is 40 to 70.
- a thickener expediently a polysaccharide or a polysaccharide derivative is critical to ensuring constant viscosity and Stability of the lubricant dispersion over a wide temperature range, as well as for the Prevention of sedimentation of the solids in the dispersion.
- a thickener expediently a polysaccharide or a polysaccharide derivative is critical to ensuring constant viscosity and Stability of the lubricant dispersion over a wide temperature range, as well as for the Prevention of sedimentation of the solids in the dispersion.
- Biopolysaccharides like xanthan gum, rhamsan gum or an alkyl cellulose like that Hydroxymethyl cellulose, application.
- alkali salts of the Add polyacrylic acid especially sodium polyacrylates.
- the lubricant composition expediently added a commercially available biocide.
- borax sodium tetraborate decahydrate
- the lubricant according to the invention is expediently used in the form of an aqueous dispersion with a solids content of preferably 20% to 50%. It is quite possible to vary the limits up and down.
- the dispersion can be produced in commercially available dispersing devices which enable high shear forces (cf., for example, EP-PS 218 989).
- the ready-to-use dispersion expediently has a viscosity in the range from 1000 MPas to 7000 MPas (Rheomat 15, 20 ° C., cell B, speed 5), but can be varied further by adding thickeners.
- the application of the lubricant dispersion can be done via known systems for spraying disperse systems (see e.g. EP-A 453 801).
- the lubricant composition disclosed above for Use on workpieces with surface temperatures from 800 ° C to 1300 ° C in the hot forming of metals, especially in the hot rolling of blocks and Profiles or used in the manufacture of hollow blocks in so-called push bench systems.
- the dispersion is applied to the workpiece immediately before the forming. Descaling the workpiece beforehand is an advantage but not essential. After the immediate evaporation of the water, a uniform, water-insoluble lubricating film on the workpiece surface from the subsequent forming process is not affected.
- Formulation 1 (suitable for workpieces with surface temperatures of 850 ° C - 1200 ° C).
- Formulation 2 (suitable for workpieces with surface temperatures of 1000 ° C - 1250 ° C)
- Formulation 3 (suitable for workpieces with surface temperatures of 1000 ° C - 1250 ° C)
- Formulation 4 (suitable for workpieces with surface temperatures of 850 ° C - 1250 ° C)
- Comparative formulation 1 (according to CH-PS 660 023, example 1)
- Comparative formulation 2 (according to CH-PS 670 106, example 2)
- Formulation Test result (class) 1 3 (from 850 ° C) 2nd 3 (from 1000 ° C) 3rd 3 (from 1000 ° C) 4th 3 (from 850 ° C) Comparison 1 1 Comparison 2 2nd
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Lubricants (AREA)
- Extrusion Of Metal (AREA)
- Mounting, Exchange, And Manufacturing Of Dies (AREA)
Description
Aufgrund der Tatsache, dass die zu verarbeitenden Metalle eine Oberflächentemperatur von ca. 800 °C bis 1300 °C aufweisen, hat man sich in der Praxis bisher auf die Schmierung der Werkzeuge konzentriert, die mit Temperaturen von maximal 400 °C der klassischen Schmierung besser zugänglich sind.
Obwohl im Stand der Technik z.B. in der CH-PS 660 023 offenbart wird, dass mit der dort genannten Schmiermitteldispersion auch Werkstücke mit Temperaturen über 600 °C behandelt werden können, zeigt der Praxisvergleich keine Ausbildung eines wirksamen haftenden Schmiermittelfilms bei Temperaturen im Bereich von 800 °C bis 1300 °C. Die fehlende Haftung wird im wesentlichen verursacht durch die sofortige Pyrolyse der organischen Bestandteile, die eine Haftung des Films verunmöglicht. Die Pyrolyse der organischen Bestandteile mit der damit verbundenen Rauchentwicklung ist zudem für das Arbeitsumfeld eine sehr unangenehme Begleiterscheinung. Eine Ausbildung eines Schmiermitttelfilms war im Praxistest auch bei den in Pulverform applizierten Schmiermittel/Beizmittel-Zusammensetzungen der CH-PS 670 106 nicht festzustellen. Alleine die gleichmässige Applikation eines Pulvergemisches bildet in diesem Fall ein beträchtliches Erschwernis.
- b) 10-25 Gew.-% natürlicher oder synthetischer Graphit
- c) 5-20 Gew.-% eines oder mehrerer Alkalisilikate der allgemeinen Formel Me2O n SiO2, worin Me Lithium, Kalium oder Natrium und n einen Zahlenwert zwischen 1 und 4 bedeutet.
- d) 1-6 Gew.-% eines wasserlöslichen Natriumpolymetaphosphates
- e) 0-3 Gew.-% eines wasserunlöslichen Natriumpolymetaphosphates
- f) 0,5-4 Gew.-% eines Verdickungsmittels
- g) 0-1 Gew.-% Borax
- d) 2-6 Gew.-% eines wasserlöslichen Natriumpolymetaphosphates
- e) 0-1 Gew.-% eines wasserunlöslichen Natriumpolymetaphosphates
- f) 3-4 Gew.-% eines Verdickungsmittels
- g) 0,2-0,7 Gew.-% Borax
Dann kommen, aufgrund des im Vergleich zum Glaspulver tieferen Erweichungsbereichs von ca. 500 °C bis 700 °C, die filmbildenden Eigenschaften der Glasfritte voll zum tragen. Die Glasfritte ist zweckmässig von seiner chemischen Zusammensetzung her ein Alkali-Erdalkali-Alumo-Bor-Silikat und wird üblicherweise in einer durchschnittlichen Korngrösse d50 von <100µm angewendet.
Zweckmässig ist die durchschnittliche Korngrösse d50 des verwendeten Graphits kleiner 100 µm. Von Vorteil wird ein Graphit mit hoher Kristallinität d. h. mit einer Kristallitlänge Lc von grösser 100 nm eingesetzt.
Besonders bevorzugt wird eine Mischung der genannten bevorzugten Alkalisilikate im Verhältnis Natriumsilikat:Kaliumsilikat:Lithiumsilikat von 12,3% : 67,5% : 20,7% verwendet.
Das erfindungsgemässe Schmiermittel wird zweckmässig in Form einer wässrigen Dispersion mit einem Feststoffanteil von vorzugsweise 20% bis 50% angewendet. Es ist durchaus möglich, die Grenzen nach oben und unten zu variieren. Die Herstellung der Dispersion kann in handelsüblichen Dispergiergeräten, die hohe Scherkräfte ermöglichen, erfolgen (vgl. z.B. EP-PS 218 989).
Die anwendungsbereite Dispersion weist zweckmässig eine Viskosität im Bereich von 1000 MPas bis 7000 MPas (Rheomat 15, 20 °C, Zelle B, Geschwindigkeit 5) auf, kann aber über den Zusatz von Verdickungsmittel weiter variiert werden.
- Dispersion: % Gehalt in Wasser 20%
- Viskosität: 1000-2000 MPas
- Dispersion: % Gehalt in Wasser 40%
- Viskosität: 1000 - 3000 MPas
- Dispersion: % Gehalt in Wasser 40%
- Viskosität: 2000 - 5000 MPas
- Dispersion: % Gehalt in Wasser 20%
- Viskosität: 2000 - 5000 MPas
Formulation | Testergebnis (Klasse) |
1 | 3 (ab 850 °C) |
2 | 3 (ab 1000 °C) |
3 | 3 (ab 1000 °C) |
4 | 3 (ab 850 °C) |
Vergleich 1 | 1 |
Vergleich 2 | 2 |
Claims (12)
- Schmiermittelzusammensetzung für die Anwendung auf Werkstücken bei der Heissumformung von Metallen bestehend ausa1) 0-80 Gew.-% eines Glaspulversa2) 0-50 Gew.-% einer Glasfritteb) 10-25 Gew.-% natürlicher oder synthetischer Graphitc) 5-20 Gew.-% eines oder mehrerer Alkalisilikate der allgemeinen Formel Me2O n SiO2, worin Me Lithium, Kalium oder Natrium und n einen Zahlenwert zwischen 1 und 4 bedeutet.d) 1-6 Gew.-% eines wasserlöslichen Natriumpolymetaphosphatese) 0-3 Gew.-% eines wasserunlöslichen Natriumpolymetaphosphatesf) 0,5-4 Gew.-% eines Verdickungsmittelsg) 0-1 Gew.-% Borax
- Schmiermittelzusammensetzung nach Patentanspruch 1, dadurch gekennzeichnet, dass ein Glaspulver eingesetzt wird, das einen durchschnittlichen Korndurchmesser d50 von <100µm und einen Erweichungsbereich von ca. 700 °C - 900 °C aufweist.
- Schmiermittelzusammensetzung nach Patentansprüchen 1 oder 2, dadurch gekennzeichnet, dass eine Glasfritte eingesetzt wird, die einen durchschnittlichen Korndurchmesser d50 von <100µm und einen Erweichungsbereich von ca. 500 °C - 700 °C aufweist.
- Schmiermittelzusammensetzung nach Patentansprüchen 1 - 3, dadurch gekennzeichnet, dass wasserlösliche Alkalisilikate, einzeln oder im Gemisch, der allgemeinen Formel Me2O n SiO2 verwendet werden, worin Me Lithium, Kalium oder Natrium und n einen Zahlenwert zwischen 1 und 4 bedeutet
- Schmiermittelzusammensetzung nach Patentansprüchen 1 - 4, dadurch gekennzeichnet. dass als wasserlösliches Natriumpolymetaphosphat ein Grahamsches Salz der allgemeinen Formel (NaPO3)n mit n kleiner 450 angewendet wird.
- Schmiermittelzusammensetzung nach Patentansprüchen 1 - 5, dadurch gekennzeichnet, dass als wasserunlösliches Natriumpolymetaphosphates ein Maddrellsches Salz der allgemeinen Formel (NaPO3)n mit n 40 bis 70 angewendet wird.
- Schmiermittelzusammensetzung nach Patentansprüchen 1 - 6, dadurch gekennzeichnet, dass als Verdickungsmittel ein Polysaccharid, ein Polysaccharidderivat oder ein Alkalisalz eines Polyacrylats verwendet wird.
- Schmiermittelzusammensetzung nach Patentansprüchen 1 - 7 in Form einer wässrigen Dispersion.
- Schmiermittelzusammensetzung nach Patentansprüchen 1 - 8 in Form einer wässrigen Dispersion mit einem Feststoffgehalt von 20% bis 50%.
- Schmiermittelzusammensetzung nach Patentansprüchen 1 - 9 zur Anwendung bei Werkstücken mit Oberflächentemperaturen ab 800 °C bestehend aus:a1) 0-20 Gew.-% eines Glaspulversa2) 30-50 Gew.-% einer Glasfritteb) 20-25 Gew.-% natürlicher oder synthetischer Graphitc) 7-20 Gew.-% eines oder mehrerer Alkalisilikate der allgemeinen Formel Me2O n SiO2, worin Me Lithium, Kalium oder Natrium und n einen Zahlenwert zwischen 1 und 4 bedeutet.d) 2-6 Gew.-% eines wasserlöslichen Natriumpolymetaphosphatese) 0-1 Gew.-% eines wasserunlöslichen Natrumpolymetaphosphatesf) 3-4 Gew.-% eines Verdickungsmittelsg) 0,2-0,7 Gew.-% Borax
- Schmiermittelzusammensetzung nach Patentansprüchen 1 - 9 zur Anwendung bei Werkstücken mit Oberflächentemperatur ab 1000 °C bestehend aus:a1) 45-70 Gew.-% eines Glaspulversa2) 0-20 Gew.-% einer Glasfritteb) 20-25 Gew.-% natürlicher oder synthetischer Graphitc) 7-20 Gew.-% eines oder mehrerer Alkalisililate der allgemeinen Formel Me2O n SiO2, worin Me Lithium, Kalium oder Natrium und n einen Zahlenwert zwischen 1 und 4 bedeutet.d) 1 - 2 Gew.% eines wasserlöslichen Natriumpolymetaphosphatese) 0 - 1 Gew.% eines wasserunlöslichen Natriumpolymetaphosphatesf) 1,5-2 Gew.-% eines Verdickungsmittelsg) 0-0,25 Gew.-% Borax
- Verwendung der Schmiermittelzusammensetzung gemäß Patentansprüchen 1 bis 11 zur direkten Schmierung von Werkstücken mit einer Oberflächentemperatur von ca. 800°C bis 1300°C bei der Heißumformung von Metallen.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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SI9630075T SI0743352T1 (en) | 1995-05-16 | 1996-05-13 | Lubricant composition suitable for application on metal workpieces during hot-forming |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH1416/95 | 1995-05-16 | ||
CH141695 | 1995-05-16 | ||
CH141695 | 1995-05-16 |
Publications (2)
Publication Number | Publication Date |
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EP0743352A1 EP0743352A1 (de) | 1996-11-20 |
EP0743352B1 true EP0743352B1 (de) | 1999-07-28 |
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Application Number | Title | Priority Date | Filing Date |
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EP96107611A Expired - Lifetime EP0743352B1 (de) | 1995-05-16 | 1996-05-13 | Schmiermittelzusammensetzung für die Anwendung auf Werkstücken bei der Heissumformung von Metallen |
Country Status (21)
Country | Link |
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US (1) | US5691282A (de) |
EP (1) | EP0743352B1 (de) |
JP (1) | JP2930003B2 (de) |
KR (1) | KR960041327A (de) |
CN (1) | CN1063479C (de) |
AR (1) | AR001910A1 (de) |
AT (1) | ATE182612T1 (de) |
BR (1) | BR9602185A (de) |
CA (1) | CA2174825A1 (de) |
CZ (1) | CZ140596A3 (de) |
DE (1) | DE59602520D1 (de) |
ES (1) | ES2136916T3 (de) |
HU (1) | HU219309B (de) |
NO (1) | NO962019L (de) |
RO (1) | RO116817B1 (de) |
RU (1) | RU2153525C2 (de) |
SI (1) | SI0743352T1 (de) |
SK (1) | SK61996A3 (de) |
TR (1) | TR199600394A2 (de) |
TW (1) | TW324739B (de) |
ZA (1) | ZA963198B (de) |
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US5242506A (en) * | 1990-10-19 | 1993-09-07 | United Technologies Corporation | Rheologically controlled glass lubricant for hot metal working |
JPH04239096A (ja) * | 1991-01-11 | 1992-08-26 | Nippon Parkerizing Co Ltd | 亜鉛めっき鋼板の潤滑前処理方法 |
US5273667A (en) * | 1991-09-12 | 1993-12-28 | Gill Colman A | Recovery and utilization of phosphate sludge |
CN1034668C (zh) * | 1992-11-20 | 1997-04-23 | 宝钢集团常州钢铁厂 | 热轧钢管芯轴的润滑剂 |
US5493886A (en) * | 1993-08-23 | 1996-02-27 | Cleveland State University | Elevated temperature metal forming lubrication method |
-
1996
- 1996-04-22 ZA ZA963198A patent/ZA963198B/xx unknown
- 1996-04-23 CA CA002174825A patent/CA2174825A1/en not_active Abandoned
- 1996-05-08 BR BR9602185A patent/BR9602185A/pt active Search and Examination
- 1996-05-09 JP JP8115070A patent/JP2930003B2/ja not_active Expired - Lifetime
- 1996-05-10 AR AR33646996A patent/AR001910A1/es unknown
- 1996-05-13 EP EP96107611A patent/EP0743352B1/de not_active Expired - Lifetime
- 1996-05-13 DE DE59602520T patent/DE59602520D1/de not_active Expired - Fee Related
- 1996-05-13 KR KR1019960015815A patent/KR960041327A/ko not_active Application Discontinuation
- 1996-05-13 ES ES96107611T patent/ES2136916T3/es not_active Expired - Lifetime
- 1996-05-13 SK SK619-96A patent/SK61996A3/sk unknown
- 1996-05-13 AT AT96107611T patent/ATE182612T1/de not_active IP Right Cessation
- 1996-05-13 RO RO96-00972A patent/RO116817B1/ro unknown
- 1996-05-13 SI SI9630075T patent/SI0743352T1/xx unknown
- 1996-05-14 TR TR96/00394A patent/TR199600394A2/xx unknown
- 1996-05-15 RU RU96109711/04A patent/RU2153525C2/ru active
- 1996-05-15 TW TW085105769A patent/TW324739B/zh active
- 1996-05-15 NO NO962019A patent/NO962019L/no not_active Application Discontinuation
- 1996-05-15 CZ CZ961405A patent/CZ140596A3/cs unknown
- 1996-05-16 US US08/648,958 patent/US5691282A/en not_active Expired - Fee Related
- 1996-05-16 HU HU9601314A patent/HU219309B/hu not_active IP Right Cessation
- 1996-05-16 CN CN96106237A patent/CN1063479C/zh not_active Expired - Fee Related
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US12054689B2 (en) | 2020-03-16 | 2024-08-06 | Chemische Fabrik Budenheim Kg | Composition for lubricating and/or descaling during hot working of metals |
Also Published As
Publication number | Publication date |
---|---|
BR9602185A (pt) | 1998-04-07 |
EP0743352A1 (de) | 1996-11-20 |
TR199600394A2 (tr) | 1996-12-21 |
JP2930003B2 (ja) | 1999-08-03 |
NO962019D0 (no) | 1996-05-15 |
ZA963198B (en) | 1996-10-25 |
RO116817B1 (ro) | 2001-06-29 |
KR960041327A (ko) | 1996-12-19 |
HUP9601314A2 (en) | 1997-02-28 |
CA2174825A1 (en) | 1996-11-17 |
AR001910A1 (es) | 1997-12-10 |
DE59602520D1 (de) | 1999-09-02 |
ATE182612T1 (de) | 1999-08-15 |
HU219309B (en) | 2001-03-28 |
ES2136916T3 (es) | 1999-12-01 |
MX9601821A (es) | 1997-07-31 |
JPH08311479A (ja) | 1996-11-26 |
CN1063479C (zh) | 2001-03-21 |
SI0743352T1 (en) | 1999-10-31 |
US5691282A (en) | 1997-11-25 |
RU2153525C2 (ru) | 2000-07-27 |
SK61996A3 (en) | 1997-07-09 |
HUP9601314A3 (en) | 1998-07-28 |
HU9601314D0 (en) | 1996-07-29 |
CZ140596A3 (en) | 1996-12-11 |
TW324739B (en) | 1998-01-11 |
NO962019L (no) | 1996-11-18 |
CN1143107A (zh) | 1997-02-19 |
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