EP0256049B1 - Verfahren zur herstellung einer verschleissfesten, titankarbid enthaltenden schicht auf einem metallischen grundkörper - Google Patents
Verfahren zur herstellung einer verschleissfesten, titankarbid enthaltenden schicht auf einem metallischen grundkörper Download PDFInfo
- Publication number
- EP0256049B1 EP0256049B1 EP87900795A EP87900795A EP0256049B1 EP 0256049 B1 EP0256049 B1 EP 0256049B1 EP 87900795 A EP87900795 A EP 87900795A EP 87900795 A EP87900795 A EP 87900795A EP 0256049 B1 EP0256049 B1 EP 0256049B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- alloy
- weight
- percent
- heat treatment
- percentage
- 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
Links
- 238000000034 method Methods 0.000 title claims abstract description 25
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 title abstract description 7
- 238000000576 coating method Methods 0.000 title description 2
- 239000011248 coating agent Substances 0.000 title 1
- 239000002184 metal Substances 0.000 title 1
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 19
- 239000000956 alloy Substances 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 13
- 229910000531 Co alloy Inorganic materials 0.000 claims abstract description 5
- 229910000990 Ni alloy Inorganic materials 0.000 claims abstract description 5
- 229910000640 Fe alloy Inorganic materials 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims 2
- 238000010285 flame spraying Methods 0.000 abstract description 12
- 239000007921 spray Substances 0.000 abstract description 4
- 238000003754 machining Methods 0.000 abstract 2
- 239000010410 layer Substances 0.000 description 29
- 239000011159 matrix material Substances 0.000 description 8
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000012790 adhesive layer Substances 0.000 description 4
- 238000005422 blasting Methods 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 239000010431 corundum Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007750 plasma spraying Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000004563 wettable powder Substances 0.000 description 2
- 241000446313 Lamella Species 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910001566 austenite Inorganic materials 0.000 description 1
- 239000012084 conversion product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910000734 martensite Inorganic materials 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/06—Metallic material
-
- 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
- C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
-
- 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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
- C23C4/129—Flame spraying
-
- 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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/18—After-treatment
-
- 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
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/922—Static electricity metal bleed-off metallic stock
- Y10S428/9335—Product by special process
- Y10S428/937—Sprayed metal
-
- 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.]
- Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
- Y10T428/12576—Boride, carbide or nitride component
Definitions
- the present invention relates to a method for producing a wear-resistant layer on a metallic base body, in which a material in the form of sintered, agglomerated particles or alloy particles with a grain size of -150 / + 37 microns, which contain 10-50 weight percent TiC and im others consist of an Fe and / or Ni alloy or a Co alloy, is sprayed on by autogenous flame spraying in a thickness of at least 1 mm and the sprayed-on layer is then subjected to a heat treatment in the temperature range of 400-650 ° C, such that the layer after the heat treatment has a lamella structure with lamellae corresponding to the particle size.
- the publication DE -A- 2208070 describes a method in which a metallic base body is provided with a thin, wear-resistant layer of up to a maximum of about 0.635 mm thick, the spraying being carried out by plasma flame spraying and the material used having a grain size of, for example, the order of magnitude. 44 / + 88 ⁇ m.
- the layer is spray-quenched when sprayed on thanks to the cooling effect of the base body, and this results in a microstructure consisting of titanium carbide grains dispersed in a base material, the base material being formed by an austenite conversion product containing martensite. Even without further heat treatment, this leads to a relatively hard layer in which rounded titanium carbide grains are present as a result of the plasma spraying process.
- the layers that can be produced in this way are very limited in their thickness, preferably from 0.381 mm to 0.254 mm and 0.127 mm, since otherwise the structure mentioned would result in very high internal stresses.
- the small thickness corresponds to an equally limited lifespan.
- the mechanical machinability is also very limited and the elasticity of the layer is extremely low due to the small grain size of the spray material and the structure made up of the smallest lamellae.
- Wear-resistant coatings which were produced by flame spraying without melting and have a high hardness due to the incorporation of hard materials such as carbides, silicides, borides etc., or consist of hard alloys, show a strong sensitivity to crack formation due to the occurrence of internal stresses in the layer.
- the achievable layer thickness is very limited.
- the object of the invention is to provide a method for producing wear-resistant layers of great hardness, with the layers can be produced with a significantly longer life than that of the known layers and which also enables mechanical processing after spraying and is relatively problem-free with regard to internal stresses in the layer.
- the layer material is melted practically homogeneously in the autogenous flame during the spraying process, the titanium carbide being dissolved in the matrix alloy.
- the layer of austenitic character obtained in this way can be machined well.
- the titanium carbide is then separated out in a very fine-grained and evenly distributed manner.
- the layer has a lamellar structure with relatively large lamellae corresponding to the particle size, which results in greater elasticity of the layer. It should also be noted that the coefficient of expansion of the layer is very close to the coefficient of expansion of the matrix alloy.
- a wear-resistant layer of 1.8 mm thickness was then also applied to the adhesive layer by autogenous Flame spraying with the usual parameters, applied without subsequent melting, whereby the composition of the wettable powder, in percent by weight, and the grain size were as follows: 33.0 TiC with a matrix alloy of 0.9 C, 1.0 Cr, 0.3 Cu, 0.5 Mo, 1.9 Mn, 1.0 Si, 0.2 V, balance Fe. Grain size -150 / + 37 ⁇ m.
- the coated shaft was machined and brought to the finished size. It was then kept in a muffle furnace at 550 ° C. for five hours. The hardness of the coated shaft had a value of 420 Hv after the mechanical processing, and a hardness of 640 Hv was measured after the heat treatment.
- the sliding surface of 100 x 100 mm of a sliding plate of 50 mm thickness was coated in the following way. After preparing the sliding surface by blasting with corundum, the plate was preheated to 100 ° C. and then an adhesive layer of 0.1 mm thick was applied. A commercially available adhesive layer powder (Castolin 51000) was applied by autogenous flame spraying.
- a wear-resistant layer of 1.2 mm thickness was then also applied by autogenous flame spraying without subsequent melting, the composition of the wettable powder (grain size -150 / + 37 ⁇ m) in percent by weight being as follows: 32% TiC in a matrix alloy of 0.2 C, 0.5 Cr, 0.5 Cu, 6.0 Mo, 15.0 Ni, 0.7 Al, 9.0 Co, 0.7 Ti, 0.1 Nb, rest Fe.
- the coated surface was machined.
- the slide plate was then treated in a protective gas oven at 450 ° C. for four hours.
- the hardness of the sliding surface before the thermal treatment was 450 Hv
- the hardness measured after the heat treatment was 650 Hv.
- An axis of 40.0 mm in diameter was treated in the following manner to achieve high wear resistance.
- the axis was provided with a wear-resistant layer of 1.5 mm thickness by autogenous flame spraying under the usual working conditions, the composition of the spraying material in weight percent being chosen as follows: 33.0 TiC in a matrix alloy of 0.35 C, 2.0 Cr, 1.0 Cu, 2.0 Mo, balance Fe.
- the grain size was in the range -150 / + 37 ⁇ m.
- the surface was then machined and brought to the desired finished size by grinding, the surface layer retaining a thickness of 1 mm.
- the finished part was held in a muffle furnace at 500 ° C. for five hours.
- the hardness of the layer before the heat treatment was 400 Hv, after the heat treatment a hardness of 680 Hv was measured.
- a wear part with the dimensions 200 x 60 x 30 mm was coated on one of the areas of 200 x 60 mm in the following manner.
- the surface to be coated was prepared by blasting with corundum, on this surface a powdery spray material of grain size -150 / + 37 ⁇ m was made, in percent by weight, 16.5 TiC with a matrix alloy of 0.5 C, 14.0 Cr, 0 , 5 Cu, 14.0 Mo, 3.5 W, balance Ni applied by autogenous flame spraying without subsequent melting under normal conditions.
- the wear-resistant layer had a thickness of 2.2 mm and was then machined, the thickness of the layer being 2.0 mm was brought.
- the wearing part was then kept in a muffle furnace at 450 ° C. for five hours. The hardness was 380 Hv before the heat treatment and rose to 550 Hv after the heat treatment.
- Example 4 The procedure of Example 4 was repeated analogously with a spray material of the composition, in percent by weight, 20.0 TiC in a matrix alloy of 0.5 C, 14.0 Cr, 0.5 Cu, 14.0 Mo, 5.0 W, Rest Co. The hardness of the heat-treated part reached 530 Hv.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Coating By Spraying Or Casting (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH425/86A CH670103A5 (enrdf_load_stackoverflow) | 1986-02-04 | 1986-02-04 | |
| CH425/86 | 1986-02-04 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0256049A1 EP0256049A1 (de) | 1988-02-24 |
| EP0256049B1 true EP0256049B1 (de) | 1991-12-04 |
Family
ID=4186733
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP87900795A Expired - Lifetime EP0256049B1 (de) | 1986-02-04 | 1987-02-04 | Verfahren zur herstellung einer verschleissfesten, titankarbid enthaltenden schicht auf einem metallischen grundkörper |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4806394A (enrdf_load_stackoverflow) |
| EP (1) | EP0256049B1 (enrdf_load_stackoverflow) |
| CH (1) | CH670103A5 (enrdf_load_stackoverflow) |
| DE (1) | DE3774956D1 (enrdf_load_stackoverflow) |
| WO (1) | WO1987004732A1 (enrdf_load_stackoverflow) |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5035957A (en) * | 1981-11-27 | 1991-07-30 | Sri International | Coated metal product and precursor for forming same |
| JPH0778242B2 (ja) * | 1993-02-12 | 1995-08-23 | 日本ユテク株式会社 | 耐摩耗性複合金属部材の製造方法 |
| US6048586A (en) * | 1996-06-05 | 2000-04-11 | Caterpillar Inc. | Process for applying a functional gradient material coating to a component for improved performance |
| US6087022A (en) * | 1996-06-05 | 2000-07-11 | Caterpillar Inc. | Component having a functionally graded material coating for improved performance |
| DE19640788C1 (de) * | 1996-10-02 | 1997-11-20 | Fraunhofer Ges Forschung | Beschichtungspulver und Verfahren zu seiner Herstellung |
| DE19640787C1 (de) * | 1996-10-02 | 1998-04-16 | Fraunhofer Ges Forschung | Verschleißfeste Teile für Prozeßventile |
| US5798002A (en) * | 1996-12-02 | 1998-08-25 | Gugel; Saveliy M. | Method of and device for producing carbide and carbon solid solution containing surface layers |
| RU2004118415A (ru) * | 2001-12-04 | 2005-06-10 | Магото Интернешенел (Be) | Литая деталь с повышенной износостойкостью |
| JP2004359998A (ja) * | 2003-06-04 | 2004-12-24 | Hitachi Ltd | 化合物粒子分散合金層を有する金属部材の製造方法及び摺動部材 |
| EP1559806A1 (de) * | 2004-01-28 | 2005-08-03 | Ford Global Technologies, LLC, A subsidary of Ford Motor Company | Durch thermisches Spritzen aufgebrachte eisenhaltige Schicht einer Gleitfläche, insbesondere für Zylinderlaufflächen von Motorblöcken |
| WO2013101561A1 (en) | 2011-12-30 | 2013-07-04 | Scoperta, Inc. | Coating compositions |
| US20170043426A1 (en) * | 2014-04-30 | 2017-02-16 | Oerlikon Metco (Us) Inc. | Titanium carbide overlay and method of making |
| WO2016014851A1 (en) * | 2014-07-24 | 2016-01-28 | Scoperta, Inc. | Hardfacing alloys resistant to hot tearing and cracking |
| EP3344789B1 (en) | 2015-09-04 | 2025-02-12 | Oerlikon Metco (US) Inc. | Chromium free and low-chromium wear resistant alloys |
| US20210164081A1 (en) | 2018-03-29 | 2021-06-03 | Oerlikon Metco (Us) Inc. | Reduced carbides ferrous alloys |
| JP7641218B2 (ja) | 2018-10-26 | 2025-03-06 | エリコン メテコ（ユーエス）インコーポレイテッド | 耐食性かつ耐摩耗性のニッケル系合金 |
| US12227853B2 (en) | 2019-03-28 | 2025-02-18 | Oerlikon Metco (Us) Inc. | Thermal spray iron-based alloys for coating engine cylinder bores |
| AU2020269275B2 (en) | 2019-05-03 | 2025-05-22 | Oerlikon Metco (Us) Inc. | Powder feedstock for wear resistant bulk welding configured to optimize manufacturability |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3035144A1 (de) * | 1980-05-16 | 1981-11-26 | Metallurgical Industries, Inc., Tinton Falls, N.J. | Erosionsfeste auftraglegierung |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA659644A (en) * | 1963-03-19 | J. Dittrich Ferdinand | Production of carbide-containing sprayweld coatings | |
| FR1357986A (fr) * | 1963-05-21 | 1964-04-10 | Soudure Electr Autogene | Procédé d'application d'un recouvrement de matières sur une pièce par pulvérisation |
| US3617358A (en) * | 1967-09-29 | 1971-11-02 | Metco Inc | Flame spray powder and process |
| US3779720A (en) * | 1971-11-17 | 1973-12-18 | Chromalloy American Corp | Plasma sprayed titanium carbide tool steel coating |
| US3896244A (en) * | 1971-11-17 | 1975-07-22 | Chromalloy American Corp | Method of producing plasma sprayed titanium carbide tool steel coatings |
| US3941903A (en) * | 1972-11-17 | 1976-03-02 | Union Carbide Corporation | Wear-resistant bearing material and a process for making it |
| GB2050424B (en) * | 1979-05-09 | 1983-06-15 | Special Metals Corp | Nickel-cobalt-chromium base alloy |
| US4395279A (en) * | 1981-11-27 | 1983-07-26 | Gte Products Corporation | Plasma spray powder |
-
1986
- 1986-02-04 CH CH425/86A patent/CH670103A5/de not_active IP Right Cessation
-
1987
- 1987-02-04 US US07/112,832 patent/US4806394A/en not_active Expired - Fee Related
- 1987-02-04 WO PCT/CH1987/000016 patent/WO1987004732A1/de not_active Application Discontinuation
- 1987-02-04 DE DE8787900795T patent/DE3774956D1/de not_active Revoked
- 1987-02-04 EP EP87900795A patent/EP0256049B1/de not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3035144A1 (de) * | 1980-05-16 | 1981-11-26 | Metallurgical Industries, Inc., Tinton Falls, N.J. | Erosionsfeste auftraglegierung |
Non-Patent Citations (1)
| Title |
|---|
| Patent Abstracts of Japan, Vol. 9, No. 160 (C-289)(1883), 04 July 1985 & JP,A,6033364 (KOUEI SEIKOU K.K.) 20 February 1985 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CH670103A5 (enrdf_load_stackoverflow) | 1989-05-12 |
| EP0256049A1 (de) | 1988-02-24 |
| DE3774956D1 (de) | 1992-01-16 |
| US4806394A (en) | 1989-02-21 |
| WO1987004732A1 (fr) | 1987-08-13 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): DE FR GB |
|
| 17P | Request for examination filed |
Effective date: 19880125 |
|
| 17Q | First examination report despatched |
Effective date: 19890717 |
|
| GRAA | (expected) grant |
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