WO1990002218A1 - Plasma method for coating an object with a hardmetal - Google Patents
Plasma method for coating an object with a hardmetal Download PDFInfo
- Publication number
- WO1990002218A1 WO1990002218A1 PCT/EP1989/000967 EP8900967W WO9002218A1 WO 1990002218 A1 WO1990002218 A1 WO 1990002218A1 EP 8900967 W EP8900967 W EP 8900967W WO 9002218 A1 WO9002218 A1 WO 9002218A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- coating
- titanium nitride
- layer
- hardmetal
- base material
- Prior art date
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 15
- 239000011248 coating agent Substances 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 18
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000007797 corrosion Effects 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 4
- 229910001315 Tool steel Inorganic materials 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 29
- 235000019589 hardness Nutrition 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000007704 transition Effects 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
- 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
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
- C23C14/025—Metallic sublayers
Definitions
- the present invention relates to a method for coating a metallic object with a layer of a hard material by means of an arc plasma method.
- the preferred hard material is titanium nitride, which is formed in the reaction of metallic titanium which has been converted into the plasma state by an arc with nitrogen; the nitrogen is metered into a previously evacuated chamber which holds the objects to be coated (usually called “substrates"), in such a way that the reaction components are present in the correct stoichiometric ratio to one another.
- a method is e.g. B. is known from US-A-3 783 231.
- the titanium nitride layer reaches hardnesses of 2300 to 3000 HV, which is much higher than the typical values of 700 to 820 HV for tool steels.
- electroless nickel layers reach their maximum hardness of 1000 to 1100 HV by heat treatment for several hours, which is carried out at 400 ° C.
- the object of the present invention is to provide a coating process of the type mentioned at the outset, by means of which a metallic object which is particularly subject to wear later on can be provided with a hard, wear-resistant layer which, owing to its small thickness, should have a quasi-plastic behavior and which at the same time has one against most Corrosive substances occurring in practical operation have sufficient corrosion resistance.
- This object is achieved in that in a first step a nickel layer is deposited on the object in an electroless manner, and in a second step the hard material is deposited on the nickel layer.
- a combination layer is formed from two partial layers lying one on top of the other.
- the hard material layer should consist of titanium nitride.
- electrolessly deposited nickel layer also referred to as electroless nickel layer
- Hard material layer is protected from mechanical attack from the outside, the former need only be just so thick that a reliably pore-free layer is achieved.
- Preferred values for the layer thickness of nickel are approximately 20 ⁇ m and
- Titanium nitride 1 to 5 ⁇ ensure an optimal combination of the properties of the two sub-layers.
- Coating with the hard material at a temperature of about 400 ° C is annealed.
- the hardness of the electroless nickel layer achieved in this way is then in a middle range between the hardness of the base material and the hardness of the titanium nitride layer; the finely graduated transition achieved thereby improves the very good adhesive strength of the titanium nitride layer on the nickel layer with very extreme mechanical loads.
- nickel layer in the sense of this invention is also a nickel layer in the sense of this invention.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
- Physical Vapour Deposition (AREA)
Abstract
A titanium nitride (hardmetal) coating applied in particular on a tool (base material) for the purpose of reducing wear should not be thicker than 5 νm if it is to exhibit a quasi-plastic behaviour appropriate to the properties of the base material when mechanically stressed. However, this low coating thickness does not afford sufficient protection against corrosion to the base material because of the porosity of titanium nitride coating. To remedy this, the invention proposes that a nickel coating approximately 20 νm thick be first applied on the object to be coated with the hardmetal. The nickel coating ensures adequate protection against corrosion and is protected from mechanical damage by the hardmetal coating. The nickel coating is preferably annealed at approximately 400°C after application, in order to attain a hardness intermediate between that of the base material (approximately that of tool steel) and that of the titanium nitride coating.
Description
Verfahren zur Plasmabeschichtung von Gegenständen mit einem HartstoffProcess for plasma coating objects with a hard material
Die vorliegende Erfindung betrifft ein Verfahren zum Beschichten eines metallischen Gegenstandes mit einer Schicht aus einem Hartstoff mittels eines Lichtbogenplasmaverfahrens.The present invention relates to a method for coating a metallic object with a layer of a hard material by means of an arc plasma method.
Es ist bekannt, insbesondere metallische Gegenstände, wie spanende oder umformende Werkzeuge, mit einer verschleißhemmenden Schicht aus einem Hartstoff zu versehen. Als Hartstoff kommt bevorzugt in diesem Zusammenhang Titannitrid in Betracht, das bei der Reaktion von metallischem, durch einen Lichtbogen in den Plasmazustand überführte Titan mit Stickstoff entsteht; der Stickstoff wird dosiert in eine zuvor evakuierte, die zu beschichtenden Gegenstände (üblicherweise "Substrate" genannt) aufnehmende Kammer eingelassen, und zwar so, daß die Reaktionskomponenten im korrekten stöchiometrischen Verhältnis zueinander vorhanden sind. Ein solches Verfahren ist z. B. aus der US-A-3 783 231 bekannt. Die Titannitrid-Schicht erreicht Härten von 2300 bis 3000 HV, die also sehr viel höher liegen als die für Werkzeugstähle typischen Werte von 700 bis 820 HV.It is known to provide in particular metallic objects, such as cutting or forming tools, with a wear-resistant layer made of a hard material. In this context, the preferred hard material is titanium nitride, which is formed in the reaction of metallic titanium which has been converted into the plasma state by an arc with nitrogen; the nitrogen is metered into a previously evacuated chamber which holds the objects to be coated (usually called "substrates"), in such a way that the reaction components are present in the correct stoichiometric ratio to one another. Such a method is e.g. B. is known from US-A-3 783 231. The titanium nitride layer reaches hardnesses of 2300 to 3000 HV, which is much higher than the typical values of 700 to 820 HV for tool steels.
Die an sich zu erwartenden Probleme bei der Belastung von Verbundkörpern aus zwei Stoffen so unterschiedlicher Härte und Sprödigkeit (hier: metallischer Gegenstand und Titannitrid- Schicht) werden vermieden, wenn die Schichtdicke auf etwa 5 μm begrenzt wird. Dies reicht zur Erzielung der gewünschten Verschleißfestigkeit völlig aus. Eine solch dünne Schicht weist allerdings durchgehende Poren auf, durch die korrosive Medien das metallische Grundmaterial angreifen können. Die Titannitrid-Schicht selbst ist völlig korrosionsbeständig. Sie kann allenfalls in kochendem Königswasser aufgelöst werden.The problems to be expected when loading composite bodies made of two substances of such different hardness and brittleness (here: metallic object and titanium nitride layer) are avoided if the layer thickness is limited to approximately 5 μm. This is sufficient to achieve the desired wear resistance. However, such a thin layer has continuous pores through which corrosive media can attack the metallic base material. The titanium nitride layer itself is completely corrosion-resistant. At most, it can be dissolved in boiling aqua regia.
Es ist an sich bekannt, auf einem metallischen Gegenstand als Schutzschicht Nickel stromlos abzuscheiden. Als gut geeignet
hat sich eine Schutzschicht aus stromlos abgeschiedenem Nickel mit einem Nickelanteil von beispielsweise 92 % und einem Phosphorgehalt von 8 % erwiesen. Eine solche Schicht weist neben ihren günstigen korrosionshindernden Eigenschaften auch den für die Werkzeugherstellung wichtigen Vorteil derIt is known per se to deposit electroless nickel on a metallic object as a protective layer. As well suited a protective layer made of electrolessly deposited nickel with a nickel content of, for example, 92% and a phosphorus content of 8% has proven. In addition to its favorable corrosion-preventing properties, such a layer also has the important advantage of tool manufacture
Konturtreue auf. Wegen einer ins Einzelne gehenden Untersuchung der Eigenschaften dieser Schichten wird auf das Buch von Harald Simon/Martin Thoma: "Angewandte Oberflächentechnik für metallische Werkstoffe" Seiten 66 bis 75, München-Wien 1985 hingewiesen.Contour accuracy. For a detailed examination of the properties of these layers, reference is made to the book by Harald Simon / Martin Thoma: "Applied surface technology for metallic materials" pages 66 to 75, Munich-Vienna 1985.
Hieraus ist auch bekannt, daß Stromlos-Nickel-Schichten durch eine mehrstündige Wärmebehandlung, die bei 400 °C durchgeführt wird, ihre maximale Härte von 1000 bis 1100 HV erreichen.From this it is also known that electroless nickel layers reach their maximum hardness of 1000 to 1100 HV by heat treatment for several hours, which is carried out at 400 ° C.
Aufgabe der vorliegenden Erfindung ist die Angabe eines Beschichtungsverfahrens der eingangs genannten Art, mittels dessen ein insbesondere später verschleißbeanspruchter metallischer Gegenstand mit einer harten, verschleißhemmenden Schicht versehen werden kann, die ihrer geringen Dicke wegen ein quasi plastisches Verhalten zeigen soll und die gleichzeitig eine gegen die meisten im praktischen Betrieb vorkommenden korrosiven Stoffe ausreichende Korrosionsfestigkeit besitzt.The object of the present invention is to provide a coating process of the type mentioned at the outset, by means of which a metallic object which is particularly subject to wear later on can be provided with a hard, wear-resistant layer which, owing to its small thickness, should have a quasi-plastic behavior and which at the same time has one against most Corrosive substances occurring in practical operation have sufficient corrosion resistance.
Diese Aufgabe wird erfindungsgemäß dadurch gelöst, daß in einem ersten Schritt auf dem Gegenstand auf stromlosem Weg eine Nickelschicht abgeschieden wird, und in einem zweiten Schritt der Hartstoff auf der Nickelschicht niedergeschlagen wird. Es wird eine Kombinationsschicht aus zwei aufeinanderliegenden Teilschichten gebildet.This object is achieved in that in a first step a nickel layer is deposited on the object in an electroless manner, and in a second step the hard material is deposited on the nickel layer. A combination layer is formed from two partial layers lying one on top of the other.
Nach einer bevorzugten Ausführungsform der Erfindung soll die Hartstoffschicht aus Titannitrid bestehen.According to a preferred embodiment of the invention, the hard material layer should consist of titanium nitride.
Da die auf stromlosem Wege abgeschiedene Nickelschicht (auch
als Stromlos-Nickel-Schicht bezeichnet) durch dieSince the electrolessly deposited nickel layer (also referred to as electroless nickel layer) by the
Hartstoffschicht vor mechanischem Angriff von außen geschützt ist, braucht erstere nur gerade so dick zu sein, daß eine zuverlässig porenfreie Schicht erzielt wird. Bevorzugte Werte für die Schichtdicke von Nickel sind etwa 20 μm und vonHard material layer is protected from mechanical attack from the outside, the former need only be just so thick that a reliably pore-free layer is achieved. Preferred values for the layer thickness of nickel are approximately 20 μm and
Titannitrid 1 bis 5 μ . Diese Werte gewährleisten eine optimale Kombination der Eigenschaften der beiden Teilschichten.Titanium nitride 1 to 5 μ. These values ensure an optimal combination of the properties of the two sub-layers.
Eine bevorzugte Weiterbildung des Verfahrens zeichnet sich dadurch aus, daß die Stromlos-Nickel-Schicht vor demA preferred development of the method is characterized in that the electroless nickel layer before
Beschichten mit dem Hartstoff bei einer Temperatur von etwa 400 °C getempert wird. Die damit erzielte Härte der Stromlos-Nickel-Schicht liegt dann in einem mittleren Bereich zwischen der Härte des Grundmaterials und der Härte der Titannitrid-Schicht; der dadurch erzielte fein abgestufte Übergang verbessert die an sich sehr gute Haftfestigkeit der Titannitrid-Schicht auf der Nickelschicht bei recht extremen mechanischen Belastungen.Coating with the hard material at a temperature of about 400 ° C is annealed. The hardness of the electroless nickel layer achieved in this way is then in a middle range between the hardness of the base material and the hardness of the titanium nitride layer; the finely graduated transition achieved thereby improves the very good adhesive strength of the titanium nitride layer on the nickel layer with very extreme mechanical loads.
Als Nickelschicht im Sinne dieser Erfindung ist auch eineAs a nickel layer in the sense of this invention is also a
Schicht zu verstehen, die neben dem Hauptbestandteil Nickel (z.Understand layer, which in addition to the main component nickel (z.
B. 92 % ) geringe Beimengungen anderer Stoffe enthält (z. B. 8 % Phosphor) .
92%) contains small additions of other substances (e.g. 8% phosphorus).
Claims
1. Verfahren zum Beschichten eines metallischen Gegenstandes mit einer Schicht aus einem Hartstoff mittels eines Lichtbogenplasmaverfahrens, d a d u r c h g e k e n n z e i c h n e t, daß a) in einem ersten Schritt auf dem Gegenstand auf stromlosem Weg eine Nickelschicht abgeschieden wird und b) in einem zweiten Schritt der Hartstoff auf der Nickelschicht mittels Lichtbogenplasmaverfahrens niedergeschlagen wird.1. A method for coating a metallic object with a layer of a hard material by means of an arc plasma process, characterized in that a) in a first step a nickel layer is deposited on the object in an electroless manner and b) in a second step the hard material is deposited on the nickel layer Arc plasma process is suppressed.
2. Verfahren nach Anspruch 1, d a d u r c h g e k e n n z e i c h n e t, daß als Hartstoff Titannitrid vorgesehen ist.2. The method of claim 1, d a d u r c h g e k e n n z e i c h n e t that titanium nitride is provided as the hard material.
3. Verfahren nach Anspruch 2, d a d u r c h g e k e n n z e i c h n e t, daß die Nickelschicht eine Dicke von etwa 20 μm und die Titannitrid-Schicht eine Dicke von 1 bis 5 μm aufweist.3. The method of claim 2, d a d u r c h g e k e n n z e i c h n e t that the nickel layer has a thickness of about 20 microns and the titanium nitride layer has a thickness of 1 to 5 microns.
4. Verfahren nach Anspruch 1, 2 oder 3, d a d u r c h g e k e n n z e i c h n e t, daß die Nickelschicht vor dem Beschichten mit dem Hartstoff bei einer Temperatur von etwa 400 °C getempert wird. 4. The method of claim 1, 2 or 3, that the nickel layer is annealed at a temperature of about 400 ° C before coating with the hard material.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3829007.3 | 1988-08-26 | ||
| DE19883829007 DE3829007A1 (en) | 1988-08-26 | 1988-08-26 | METHOD FOR PLASMA COATING OBJECTS WITH A HARD MATERIAL |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1990002218A1 true WO1990002218A1 (en) | 1990-03-08 |
Family
ID=6361665
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP1989/000967 WO1990002218A1 (en) | 1988-08-26 | 1989-08-16 | Plasma method for coating an object with a hardmetal |
Country Status (3)
| Country | Link |
|---|---|
| DE (1) | DE3829007A1 (en) |
| ES (1) | ES2019152A6 (en) |
| WO (1) | WO1990002218A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0651071A1 (en) * | 1993-10-27 | 1995-05-03 | Degussa Aktiengesellschaft | Method for producing parts with wear-resistant coatings |
| WO1999054520A1 (en) * | 1998-04-22 | 1999-10-28 | Valmet Corporation | Parts of a paper/board or finishing machine that are subjected to intensive wear and method for manufacture of such parts |
| US6322671B1 (en) | 2000-01-04 | 2001-11-27 | Ionica, Llc | Method for formation of protective coatings with quasi-plasticity properties |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4217612A1 (en) * | 1992-05-27 | 1993-12-02 | Linde Ag | Surface protective layer and method for producing the same |
| JPH07102387A (en) * | 1993-10-01 | 1995-04-18 | Fuji Electric Co Ltd | Mechanical parts and film forming method thereof |
| EP0694629A3 (en) | 1994-07-27 | 1998-09-23 | Balzers Sa | Corrosion and wear resistant substrate, method of manufacture and vacuum processing installation |
| RU2230138C1 (en) * | 2003-01-08 | 2004-06-10 | Ивановский государственный химико-технологический университет | Electrolyte for nickel-plating of titanium and its alloys |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2000812A (en) * | 1977-06-10 | 1979-01-17 | Nishida N | Externally ornamental golden colour part |
| GB1540718A (en) * | 1975-03-21 | 1979-02-14 | Fulmer Res Inst Ltd | Hard coating and its method of formation |
| JPS59205476A (en) * | 1983-05-10 | 1984-11-21 | Chizuru Maekawa | Decorative article and surface treatment method thereof |
| JPS61119668A (en) * | 1984-11-16 | 1986-06-06 | Seiko Instr & Electronics Ltd | Manufacture of portable watch case made of zinc alloy |
| EP0188057A1 (en) * | 1984-11-19 | 1986-07-23 | Avco Corporation | Erosion resistant coatings |
| JPS61231163A (en) * | 1985-04-05 | 1986-10-15 | Citizen Watch Co Ltd | Personal ornament having colored surface |
| JPH01123062A (en) * | 1987-11-06 | 1989-05-16 | Citizen Watch Co Ltd | Ornament |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1542856A (en) * | 1975-11-14 | 1979-03-28 | Fulmer Res Inst Ltd | Coated die and a method for the production thereof |
-
1988
- 1988-08-26 DE DE19883829007 patent/DE3829007A1/en not_active Withdrawn
-
1989
- 1989-08-16 WO PCT/EP1989/000967 patent/WO1990002218A1/en unknown
- 1989-08-25 ES ES8902947A patent/ES2019152A6/en not_active Expired - Lifetime
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1540718A (en) * | 1975-03-21 | 1979-02-14 | Fulmer Res Inst Ltd | Hard coating and its method of formation |
| GB2000812A (en) * | 1977-06-10 | 1979-01-17 | Nishida N | Externally ornamental golden colour part |
| JPS59205476A (en) * | 1983-05-10 | 1984-11-21 | Chizuru Maekawa | Decorative article and surface treatment method thereof |
| JPS61119668A (en) * | 1984-11-16 | 1986-06-06 | Seiko Instr & Electronics Ltd | Manufacture of portable watch case made of zinc alloy |
| EP0188057A1 (en) * | 1984-11-19 | 1986-07-23 | Avco Corporation | Erosion resistant coatings |
| JPS61231163A (en) * | 1985-04-05 | 1986-10-15 | Citizen Watch Co Ltd | Personal ornament having colored surface |
| JPH01123062A (en) * | 1987-11-06 | 1989-05-16 | Citizen Watch Co Ltd | Ornament |
Non-Patent Citations (6)
| Title |
|---|
| CHEMICAL ABSTRACTS, Band 81, Nr. 13, 1974 (Columbus, Ohio, US), C.C. McCOMAS et al.: "Research for Engine Demonstration of Erosion-Resistant Coating Effectiveness", seite 230* Zusammenfassung Nr. 81313b, & U.S. NaT. Tech. Inform. Serv., AD Rep. 1974, No. 776416/0GA, 64 pp* * |
| PATENT ABSTRACTS OF JAPAN, Band 10, Nr. 310 (C-379) (2366), 22. Oktober 1986; & JP-A-61119668 (Seiko Instr. & Electronics Ltd) 6. Juni 1986 * |
| PATENT ABSTRACTS OF JAPAN, Band 11, Nr. 75 (C-408) (2522), 6. Marz 1987; & JP-A-61231163 (Citizen Watch Co. Ltd) 15. Oktober 1986, siehe Zusammenfassung * |
| PATENT ABSTRACTS OF JAPAN, Band 13, Nr. 367 (C-626) (3715), 15. August 1984; & JP-A-1123062 (Citizen Watch Co. Ltd) 16. Mai 1989 * |
| PATENT ABSTRACTS OF JAPAN, Band 5, Nr. 164 (C-76) (836), 21. Oktober 1981; & JP-A-5693875 (Hamasawa Kogyo K.K.) 29. Juli 1981 * |
| PATENT ABSTRACTS OF JAPAN, Band 9, Nr. 74 (C-273) (1797), 3. April 1985; & JP-A-59205476 (Chizuru Maekawa) 21. November 1984 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5494565A (en) * | 1993-01-27 | 1996-02-27 | Degussa Aktiengesellschaft | Method of producing workpieces of non-corrosion-resistant metals with wear-resistant coatings and articles |
| EP0651071A1 (en) * | 1993-10-27 | 1995-05-03 | Degussa Aktiengesellschaft | Method for producing parts with wear-resistant coatings |
| WO1999054520A1 (en) * | 1998-04-22 | 1999-10-28 | Valmet Corporation | Parts of a paper/board or finishing machine that are subjected to intensive wear and method for manufacture of such parts |
| US6322671B1 (en) | 2000-01-04 | 2001-11-27 | Ionica, Llc | Method for formation of protective coatings with quasi-plasticity properties |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3829007A1 (en) | 1990-03-01 |
| ES2019152A6 (en) | 1991-06-01 |
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