EP0247582A1 - Verfahren zum Aufbringen einer Schutzschicht aus Kobalt-Chrom-Wolfram auf eine Turbinenschaufel aus einer Vanadium enthaltenden Titanlegierung sowie schutzbeschichtete Schaufel - Google Patents
Verfahren zum Aufbringen einer Schutzschicht aus Kobalt-Chrom-Wolfram auf eine Turbinenschaufel aus einer Vanadium enthaltenden Titanlegierung sowie schutzbeschichtete Schaufel Download PDFInfo
- Publication number
- EP0247582A1 EP0247582A1 EP87107674A EP87107674A EP0247582A1 EP 0247582 A1 EP0247582 A1 EP 0247582A1 EP 87107674 A EP87107674 A EP 87107674A EP 87107674 A EP87107674 A EP 87107674A EP 0247582 A1 EP0247582 A1 EP 0247582A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- vanadium
- chromium
- temperature
- blade
- powder
- 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.)
- Granted
Links
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C24/00—Coating starting from inorganic powder
- C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
- C23C24/10—Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the layer
- C23C24/103—Coating with metallic material, i.e. metals or metal alloys, optionally comprising hard particles, e.g. oxides, carbides or nitrides
- C23C24/106—Coating with metal alloys or metal elements only
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C24/00—Coating starting from inorganic powder
- C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/021—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material including at least one metal alloy layer
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01D—NON-POSITIVE DISPLACEMENT MACHINES OR ENGINES, e.g. STEAM TURBINES
- F01D5/00—Blades; Blade-carrying members; Heating, heat-insulating, cooling or antivibration means on the blades or the members
- F01D5/12—Blades
- F01D5/28—Selecting particular materials; Particular measures relating thereto; Measures against erosion or corrosion
- F01D5/288—Protective coatings for blades
-
- 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
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12458—All metal or with adjacent metals having composition, density, or hardness gradient
-
- 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
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12806—Refractory [Group IVB, VB, or VIB] metal-base component
- Y10T428/12812—Diverse refractory group metal-base components: alternative to or next to each other
Definitions
- the present invention relates to a method of applying a protective coating to a blade of titanium alloy comprising vanadium and to a blade thus coated.
- Titanium alloy blades have the advantage of having a high strength / density ratio and also remarkable mechanical resistance in the most corrosive environments.
- titanium alloy blades used in steam turbines especially when their peripheral speed is high, are quickly damaged by the water droplets that form in the steam.
- the titanium alloy vane comprising vanadium is characterized in that it comprises at its periphery a coating layer of cobalt-chromium-tungsten alloy at least 1 mm thick covering a vanadium sublayer of thickness between 0.5 and 1.5 mm.
- the process for installing this coating is as follows: the vanadium powder is deposited on the part of the blade to be coated, then the temperature of the powder is raised to a temperature slightly exceeding the melting point of vanadium.
- a powder of a cobalt-chromium-tungsten alloy is then deposited on the vanadium layer, and this powder is brought to a temperature above its melting temperature and below the melting temperature of vanadium.
- an induction heating with mobile inductor is preferably used.
- FIG. 1 represents a perspective of the dawn according to the invention.
- FIG. 2 represents a section of the dawn of FIG. 1.
- FIG. 3 represents a partial view of the section of FIG. 2.
- the steam turbine blade shown in FIG. 1 has a foot 1 and a twisted blade 2 comprising a leading edge 3 and a trailing edge 4. At the top of the blade, we deposited along the edge attack 3 on the upper side a protective coating layer 5. This coating layer extends over at least about a third of the width of the blade 2. Between the blade and the coating is a sub-layer of vanadium 6 ( fig. 2).
- the blade is made of titanium alloy comprising 6% aluminum and between 3.5 and 4.5% vanadium.
- the process for installing the protective covering is as follows:
- the surface to be coated with the blade receives a conventional preparation, then virtually pure vanadium powder (> 90%) of small particle size mixed with a binder is deposited on this surface.
- the quantity deposited is sufficient for the thickness of the final vanadium sublayer 6 to be greater than 1 mm.
- the blade is placed in a high-frequency induction furnace equipped with a movable inductor. The oven being empty or with an inert atmosphere, the atmosphere of the oven is preheated, then the vanadium layer is heated by spot of 30 mm in diameter while keeping the spot stationary from 20 to 75 seconds and we advance by 20 mm in 20 mm .
- the temperature is raised locally between 1950 ° C and 2000 ° C.
- the melting temperature of vanadium is 1900 ° C and that of the titanium alloy of the order of 2400 ° C. It follows that the vanadium is melted while the titanium alloy substrate is pasty, which is ideal for obtaining perfect bonding with low dilution of the vanadium in the substrate.
- the titanium alloy which comprises approximately 4% of vanadium can tolerate by dilution (see FIG. 3) a limited quantity of vanadium locally leading to a beta structure.
- the thickness of this layer 7 of alloy with diluted vanadium is very small (less than 1/10 mm).
- the temperature of the oven is brought down to ambient.
- a powder of cobalt-chromium-tungsten alloy combined with a binder is then deposited on the vanadium sublayer.
- This powder is deposited 3 or 4 mm from the edges of the vanadium sublayer so that there is never contact between the cobalt-chromium-tungsten alloy and the titanium alloy substrate.
- a second cycle is started in the oven under an inert atmosphere or under vacuum, by spot heating the alloy layer to a temperature of 50 ° C higher than the melting temperature of the cobalt-chromium-tungsten alloy (1200 ° C - 1500 ° C). This temperature being much lower than the melting point of vanadium, there will be a very low dilution (see Figure 3) of the cobalt-chromium-tungsten alloy in vanadium and the vanadium / substrate bond will be kept intact, layer 8 of vanadium with diluted cobalt-chromium-tungsten alloy being very low (less than 1/10 mm).
- the layer of alloy deposited will be approximately 1.5 mm thick.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Engineering & Computer Science (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Turbine Rotor Nozzle Sealing (AREA)
- Powder Metallurgy (AREA)
- Electroplating Methods And Accessories (AREA)
- Earth Drilling (AREA)
- Chemically Coating (AREA)
- Physical Vapour Deposition (AREA)
- Rotary Pumps (AREA)
- Structures Of Non-Positive Displacement Pumps (AREA)
- Materials For Medical Uses (AREA)
- Chemical Treatment Of Metals (AREA)
- Dental Preparations (AREA)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT87107674T ATE60630T1 (de) | 1986-05-28 | 1987-05-26 | Verfahren zum aufbringen einer schutzschicht aus kobalt-chrom-wolfram auf eine turbinenschaufel aus einer vanadium enthaltenden titanlegierung sowie schutzbeschichtete schaufel. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR8607662 | 1986-05-28 | ||
FR8607662A FR2599384B1 (fr) | 1986-05-28 | 1986-05-28 | Procede de pose d'un revetement protecteur cobalt-chrome-tungstene sur une aube en alliage de titane comportant du vanadium et aube ainsi revetue |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0247582A1 true EP0247582A1 (de) | 1987-12-02 |
EP0247582B1 EP0247582B1 (de) | 1991-01-30 |
Family
ID=9335747
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP87107674A Expired - Lifetime EP0247582B1 (de) | 1986-05-28 | 1987-05-26 | Verfahren zum Aufbringen einer Schutzschicht aus Kobalt-Chrom-Wolfram auf eine Turbinenschaufel aus einer Vanadium enthaltenden Titanlegierung sowie schutzbeschichtete Schaufel |
Country Status (11)
Country | Link |
---|---|
US (1) | US4839237A (de) |
EP (1) | EP0247582B1 (de) |
JP (1) | JPS62294185A (de) |
CN (1) | CN87104479A (de) |
AT (1) | ATE60630T1 (de) |
CS (1) | CS389187A2 (de) |
DE (1) | DE3767769D1 (de) |
ES (1) | ES2020224B3 (de) |
FR (1) | FR2599384B1 (de) |
GR (1) | GR3001774T3 (de) |
ZA (1) | ZA873836B (de) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4310896C1 (de) * | 1993-04-02 | 1994-03-24 | Thyssen Industrie | Verfahren zum Herstellen von verschleißfesten Kanten an Turbinenschaufeln |
EP0697503A1 (de) * | 1994-08-17 | 1996-02-21 | ABB Management AG | Verfahren zur Herstellung einer Turbinenschaufel aus einer (alpha-Beta)-Titan-Basislegierung |
EP0509758B1 (de) * | 1991-04-15 | 1998-12-02 | General Electric Company | Drehender Dichtungselement und Verfahren zur Herstellung |
Families Citing this family (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5077140A (en) * | 1990-04-17 | 1991-12-31 | General Electric Company | Coating systems for titanium oxidation protection |
FR2672906A1 (fr) * | 1991-02-19 | 1992-08-21 | Grumman Aerospace Corp | Revetement a barriere de diffusion pour alliages de titane. |
DE69321298T2 (de) * | 1992-06-05 | 1999-04-08 | Gec Alsthom Electromecanique S.A., Paris | Verfahren zur Herstellung eines Einsatzes auf einem zu beschichtenden Formkörper aus Stahl oder aus Titanlegierung |
US6045682A (en) * | 1998-03-24 | 2000-04-04 | Enthone-Omi, Inc. | Ductility agents for nickel-tungsten alloys |
US6254756B1 (en) * | 1999-08-11 | 2001-07-03 | General Electric Company | Preparation of components having a partial platinum coating thereon |
DE10001516B4 (de) * | 2000-01-15 | 2014-05-08 | Alstom Technology Ltd. | Zerstörungsfreies Verfahren zur Bestimmung der Schichtdicke einer metallischen Schutzschicht auf einem metallischen Grundmaterial |
EP1522375A1 (de) * | 2003-10-06 | 2005-04-13 | Siemens Aktiengesellschaft | Verfahren zur Herstellung eines Schichtsystems |
GB0412915D0 (en) * | 2004-06-10 | 2004-07-14 | Rolls Royce Plc | Method of making and joining an aerofoil and root |
GB0504576D0 (en) * | 2005-03-05 | 2005-04-13 | Alstom Technology Ltd | Turbine blades and methods for depositing an erosion resistant coating on the same |
CN100419219C (zh) * | 2006-12-22 | 2008-09-17 | 西安陕鼓动力股份有限公司 | 一种透平机械转子叶片的表面复合涂层及其制备方法 |
GB0906850D0 (en) * | 2009-04-22 | 2009-06-03 | Rolls Royce Plc | Method of manufacturing an aerofoil |
US20120021243A1 (en) * | 2010-07-23 | 2012-01-26 | General Electric Company | Components with bonded edges |
US9267218B2 (en) * | 2011-09-02 | 2016-02-23 | General Electric Company | Protective coating for titanium last stage buckets |
US9366144B2 (en) * | 2012-03-20 | 2016-06-14 | United Technologies Corporation | Trailing edge cooling |
PL224928B1 (pl) * | 2012-12-19 | 2017-02-28 | SYSTEM Spółka Akcyjna | Sposób napawania warstwy metalicznej na element metalowy |
CN103898502B (zh) * | 2014-04-10 | 2015-12-02 | 西安航空动力股份有限公司 | 涡轮叶片叶冠激光熔覆硬质合金涂层的方法 |
US9682449B2 (en) * | 2014-05-09 | 2017-06-20 | United Technologies Corporation | Repair material preform |
CN104043941B (zh) * | 2014-06-23 | 2017-02-15 | 河南伟彤科技股份有限公司 | 一种液压缸报废导向套内孔表面的再制造加工工艺 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1479855A (en) * | 1976-04-23 | 1977-07-13 | Statni Vyzkumny Ustav Material | Protective coating for titanium alloy blades for turbine and turbo-compressor rotors |
GB2005302A (en) * | 1977-10-04 | 1979-04-19 | Rolls Royce | Nickel-free cobalt alloy |
US4305998A (en) * | 1980-02-04 | 1981-12-15 | The United States Of America As Represented By The Secretary Of The Navy | Protective coating |
EP0094759A2 (de) * | 1982-05-03 | 1983-11-23 | Inductalloy Corporation | Vorrichtung und Verfahren zum Metallisieren von metallischen Gegenständen |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2612442A (en) * | 1949-05-19 | 1952-09-30 | Sintercast Corp America | Coated composite refractory body |
US2763919A (en) * | 1950-07-28 | 1956-09-25 | Thompson Prod Inc | Coated refractory body |
US2854739A (en) * | 1954-07-29 | 1958-10-07 | Thompson Prod Inc | Multiple coated molybdenum base article |
US3060557A (en) * | 1957-03-25 | 1962-10-30 | Armour Res Found | Metal cladding process and products resulting therefrom |
US3015880A (en) * | 1957-11-12 | 1962-01-09 | Power Jets Res & Dev Ltd | Corrosion resistant treatment of metal articles |
GB941089A (en) * | 1962-03-06 | 1963-11-06 | Coast Metals Inc | Application of cobalt-base alloys to metal parts |
US3471342A (en) * | 1966-07-29 | 1969-10-07 | Ibm | Wear-resistant titanium and titanium alloys and method for producing same |
US4137370A (en) * | 1977-08-16 | 1979-01-30 | The United States Of America As Represented By The Secretary Of The Air Force | Titanium and titanium alloys ion plated with noble metals and their alloys |
JPS60128256A (ja) * | 1983-12-14 | 1985-07-09 | Hitachi Ltd | 翼の表面硬化法 |
EP0188057A1 (de) * | 1984-11-19 | 1986-07-23 | Avco Corporation | Verschleissfeste Überzüge |
-
1986
- 1986-05-28 FR FR8607662A patent/FR2599384B1/fr not_active Expired
-
1987
- 1987-05-26 DE DE8787107674T patent/DE3767769D1/de not_active Expired - Fee Related
- 1987-05-26 JP JP62129589A patent/JPS62294185A/ja active Pending
- 1987-05-26 AT AT87107674T patent/ATE60630T1/de not_active IP Right Cessation
- 1987-05-26 ES ES87107674T patent/ES2020224B3/es not_active Expired - Lifetime
- 1987-05-26 EP EP87107674A patent/EP0247582B1/de not_active Expired - Lifetime
- 1987-05-27 ZA ZA873836A patent/ZA873836B/xx unknown
- 1987-05-28 CN CN198787104479A patent/CN87104479A/zh active Pending
- 1987-05-28 US US07/054,963 patent/US4839237A/en not_active Expired - Fee Related
- 1987-05-28 CS CS873891A patent/CS389187A2/cs unknown
-
1991
- 1991-04-11 GR GR91400480T patent/GR3001774T3/el unknown
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1479855A (en) * | 1976-04-23 | 1977-07-13 | Statni Vyzkumny Ustav Material | Protective coating for titanium alloy blades for turbine and turbo-compressor rotors |
GB2005302A (en) * | 1977-10-04 | 1979-04-19 | Rolls Royce | Nickel-free cobalt alloy |
US4305998A (en) * | 1980-02-04 | 1981-12-15 | The United States Of America As Represented By The Secretary Of The Navy | Protective coating |
EP0094759A2 (de) * | 1982-05-03 | 1983-11-23 | Inductalloy Corporation | Vorrichtung und Verfahren zum Metallisieren von metallischen Gegenständen |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0509758B1 (de) * | 1991-04-15 | 1998-12-02 | General Electric Company | Drehender Dichtungselement und Verfahren zur Herstellung |
DE4310896C1 (de) * | 1993-04-02 | 1994-03-24 | Thyssen Industrie | Verfahren zum Herstellen von verschleißfesten Kanten an Turbinenschaufeln |
EP0697503A1 (de) * | 1994-08-17 | 1996-02-21 | ABB Management AG | Verfahren zur Herstellung einer Turbinenschaufel aus einer (alpha-Beta)-Titan-Basislegierung |
Also Published As
Publication number | Publication date |
---|---|
FR2599384A1 (fr) | 1987-12-04 |
GR3001774T3 (en) | 1992-11-23 |
ZA873836B (en) | 1987-11-24 |
JPS62294185A (ja) | 1987-12-21 |
CS389187A2 (en) | 1991-02-12 |
EP0247582B1 (de) | 1991-01-30 |
FR2599384B1 (fr) | 1988-08-05 |
DE3767769D1 (de) | 1991-03-07 |
CN87104479A (zh) | 1988-02-03 |
ATE60630T1 (de) | 1991-02-15 |
US4839237A (en) | 1989-06-13 |
ES2020224B3 (es) | 1991-08-01 |
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