EP0651071B1 - Method for producing parts with wear-resistant coatings - Google Patents
Method for producing parts with wear-resistant coatings Download PDFInfo
- Publication number
- EP0651071B1 EP0651071B1 EP94116862A EP94116862A EP0651071B1 EP 0651071 B1 EP0651071 B1 EP 0651071B1 EP 94116862 A EP94116862 A EP 94116862A EP 94116862 A EP94116862 A EP 94116862A EP 0651071 B1 EP0651071 B1 EP 0651071B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- copper
- tin
- resistant
- layer
- wear
- 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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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
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with 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
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
- C23C28/3225—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only with at least one zinc-based 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
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
Description
Die Erfindung betrifft im Verfahren zur Herstellung von Werkstücken und Gegenständen aus nichtkorrosionsbeständigen Metallen und Metallegierungen, die mit verschleißfesten, nichtmetallischen Überzügen von Nitriden, Carbiden, Boriden, Oxiden oder Siliziden der Elemente der 4. bis 6. Nebengruppe des Periodensystems beschichtet sind, und bei denen zwischen der Werkstückoberfläche und dem Überzug eine korrosionsbeständige Zwischenschicht angeordnet ist.The invention relates to the process for the production of workpieces and objects made of non-corrosion-resistant metals and metal alloys which are coated with wear-resistant, non-metallic coatings of nitrides, carbides, borides, oxides or silicides of the elements of subgroup 4 to 6 of the periodic table, and in which a corrosion-resistant intermediate layer is arranged between the workpiece surface and the coating.
Für technische und dekorative Anwendungen werden zunehmend Werkstücke und Gegenstände aus Metallen und Metallegierungen, die wenig korrosionsbeständig sind, mit harten, verschleißfesten und zum Teil auch dekorativen Überzügen aus Nitriden, Carbiden, Boriden, Oxiden und Siliziden der Elemente der 4. bis 6. Nebengruppe des Periodensystems versehen, wie beispielsweise Titan, Zirkonium, Vanadium, Niob, Tantal, Chrom, Molybdän oder Wolfram. Das Aufbringen dieser Überzüge erfolgt nach dem sogenannten PVD-Verfahren (physical vapour deposition). Bevorzugt werden Schichten aus Titannitrid und Titancarbid.For technical and decorative applications, workpieces and objects made of metals and metal alloys, which are not very corrosion-resistant, with hard, wear-resistant and sometimes also decorative coatings made of nitrides, carbides, borides, oxides and silicides of the elements of the 4th to 6th subgroup of Periodic table, such as titanium, zirconium, vanadium, niobium, tantalum, chromium, molybdenum or tungsten. These coatings are applied using the so-called PVD process (physical vapor deposition). Layers of titanium nitride and titanium carbide are preferred.
Die so hergestellten Überzüge haben allerdings den Nachteil, daß sie spröde, porös und mikrorissig sind. Aufgrund ihres stengelartigen Wachstums weisen diese Schichten eine hohe sogenannte Pinhole-Dichte auf. Dadurch bieten sie keinen guten Korrosionsschutz für das darunterliegende Material, zumal diese Schichten sich elektrochemisch inert verhalten, so daß die unedleren Unterlagen korrosiv aufgelöst werden.However, the coatings produced in this way have the disadvantage that they are brittle, porous and micro-cracked. Because of their stalk-like growth, these layers have a high so-called pinhole density. As a result, they do not offer good corrosion protection for the underlying material, especially since these layers separate behave in an electrochemically inert manner so that the less noble substrates are dissolved in a corrosive manner.
Aus der DE-PS 38 09 139 ist es bekannt, zwischen der Werkstückeoberfläche und dem PVD-Überzug eine korrosionsbeständige, dichte Schicht aus einer Palladium-Nickellegierung anzuordnen. Diese Schicht verhindert einen Korrosionsangriff durch den porösen PVD-Überzug auf das nichtkorrosionsbeständige Unterlagenmaterial. Außerdem hat eine Palladiumnickelschicht den Vorteil, daß sie fast so edel wie die PVD-Schicht ist und daher auch elektrochemisch kaum angegriffen wird. Andererseits haben solche Schichten jedoch den Nachteil, daß sie Nickel enthalten, das als Auslöser von Allergien wirken kann. Auch das Palladium kann in machen Fällen Allergien auslösen. Für Gegenstände und Werkstücke, die mit der menschlichen Haut in Kontakt kommen können, ist man daher bestrebt, auf Nickel und wenn möglich auch auf Palladium als Legierungsbestandteile zu verzichten.From DE-PS 38 09 139 it is known to arrange a corrosion-resistant, dense layer of a palladium-nickel alloy between the workpiece surface and the PVD coating. This layer prevents corrosion attack by the porous PVD coating on the non-corrosion-resistant underlay material. In addition, a palladium-nickel layer has the advantage that it is almost as noble as the PVD layer and is therefore hardly attacked electrochemically. On the other hand, however, such layers have the disadvantage that they contain nickel, which can act as a trigger for allergies. Palladium can also cause allergies in some cases. For objects and workpieces that can come into contact with human skin, efforts are therefore made to avoid nickel and, if possible, palladium as alloy components.
In dem Dokument EP-A-0 571 796, veröffentlicht am 01.12.93 und mit dem Prioritätsdatum 27.05.92 werden metallische Werkstücke und ihre Herstellung beschrieben, die mit einer korrosionsbeständigen Unterschicht aus Kupfer-Zinn-Legierungen und einer verschleißfesten Oberschicht versehen sind, die aus Metallen, wie Chromstahl, Molybdän oder Mangan, oder Oxide, Carbide oder andere Hartstoffe enthaltenden Materialien besteht. Ihre Aufbringung erfolgt ausschließlich durch thermische Spritzverfahren, wie Flammspritzen.In the document EP-A-0 571 796, published on December 1, 1993 and with the priority date May 27, 1992, metallic workpieces and their production are described which are provided with a corrosion-resistant underlayer made of copper-tin alloys and a wear-resistant top layer which consists of metals such as chromium steel, molybdenum or manganese, or materials containing oxides, carbides or other hard materials. They are applied exclusively by thermal spray processes, such as flame spraying.
Die Verwendung von galvanisch aufgebrachten Kupfer-Zinn-Legierungen als korrosionsbeständige Überzüge ist auch aus "Ullmanns Encyklopädie der Technischen Chemie, 4. Auflage, Bd. 12, Seite 190 bis 194" bekannt.The use of electroplated copper-tin alloys as corrosion-resistant coatings is also known from "Ullmanns Encyklopadie der Technischen Chemie, 4th edition, vol. 12, pages 190 to 194".
Es war daher Aufgabe der vorliegenden Erfindung, ein Verfahren zur Herstellung von Werkstücken und Gegenständen aus nichtkorrosionsbeständigen Metallen und Metallegierungen zu entwickeln, die mit verschleißfesten, nichtmetallischen Überzügen von Nitriden, Carbiden, Boriden, Oxiden oder Siliziden der Elemente der 4. bis 6. Nebengruppe des Periodensystems beschichtet sind und bei denen zwischen der Werkstückoberfläche und dem Verschleißüberzug eine korrosionsbeständige Zwischenschicht angeordnet ist, wobei die Zwischenschicht nickel- und palladiumfrei sein sollte, eine der Verschleißschicht vergleichbares elektrochemisches Potential aufweisen und korrosionsbeständig sein sollte. Außerdem sollte diese Zwischenschicht aus galvanischen Bädern abscheidbar sein und einebnend wirken.It was therefore an object of the present invention to develop a process for the production of workpieces and objects made of non-corrosion-resistant metals and metal alloys which are coated with wear-resistant, non-metallic coatings of nitrides, carbides, borides, oxides or silicides of the elements of subgroup 4 to 6 Periodic table are coated and in which a corrosion-resistant intermediate layer is arranged between the workpiece surface and the wear coating, the intermediate layer should be free of nickel and palladium, have an electrochemical potential comparable to the wear layer and should be corrosion-resistant. In addition, this intermediate layer should be separable from galvanic baths and have a leveling effect.
Diese Aufgabe wird erfindungsgemäß dadurch gelöst, daß auf die Gegenstände zuerst galvanisch eine Zwischenschicht aus einer Kupfer-Zinnlegierung mit 45 bis 80 Gew. % Kupfer, 10 bis 55 Gew.% Zinn und 0 bis 15 Gew.% Zink und anschließend die Verschleißschicht mittels eines PVD-Verfahrens aufgebracht wird.This object is achieved according to the invention in that an intermediate layer of a copper-tin alloy with 45 to 80% by weight of copper, 10 to 55% by weight of tin and 0 to 15% by weight of zinc is first electroplated on the objects and then the wear layer is by means of a PVD process is applied.
Vorzugsweise bringt man als Zwischenschicht Legierungen auf, die aus 45 bis 65 Gew.% Kupfer und 35 bis 55 Gew.% Zinn, oder aus 50 bis 80 Gew.% Kupfer, 10 bis 35 Gew.% Zinn und 1 bis 15 Gew.% Zink bestehen.Alloys are preferably applied as the intermediate layer, which consist of 45 to 65% by weight of copper and 35 to 55% by weight of tin, or of 50 to 80% by weight of copper, 10 to 35% by weight of tin and 1 to 15% by weight. Zinc exist.
Diese Schichten sind sehr korrosionsbeständig und besitzen ein elektrochemisches Potential, das dem von Messing- und Bronzelegierungen nahekommt, die häufig als Unterlagewerkstoffe verwendet werden. Außerdem besitzen sie eine hohe Härte von etwa 600 HV und bieten daher einen guten Übergang zwischen den PVD-Schichten (1000-1500 HV) und dem Unterlagewerkstoff. Weichere Zwischenschichten, wie auch Palladium-Nickel, begünstigten ein Abplatzen der PVD-Schichten bei mechanischer Beanspruchung.These layers are very corrosion-resistant and have an electrochemical potential that comes close to that of brass and bronze alloys, which are often used as base materials. They also have a high hardness of around 600 HV and therefore offer a good transition between the PVD layers (1000-1500 HV) and the base material. Softer intermediate layers, like Palladium-nickel, too, promoted chipping of the PVD layers when subjected to mechanical stress.
Kupfer-Zinn-Legierungsschichten lassen sich preiswert auf praktisch allen Unterlagenwerkstoffen galvanisch abscheiden, wobei man auch bei komplizierten Geometrien geschlossene Schichten mit gleichmäßigen Schichtdicken erhält. Bewährt haben sich hierfür Bäder, wie sie in der DE-PS 33 39 541 beschrieben sind. Sie enthalten 1 bis 60 g/l Kupfer als Kupfercyanid, 7 bis 30 g/l Zinn in Form von Alkalistannat, 0,1 bis 100 g/l eines Komplexbildners, 1 bis 50 g/l freies Alkalicyanid, 1 bis 50 g/l Alkalihydroxid, bis zu 50 g/l Alkalicarbonat und 0,05 bis 5 g/l einer organischen Fettsäureverbindung oder eines Naphthols.Copper-tin alloy layers can be electroplated inexpensively on practically all base materials, whereby closed layers with uniform layer thicknesses are obtained even with complicated geometries. Baths such as those described in DE-PS 33 39 541 have proven successful. They contain 1 to 60 g / l copper as copper cyanide, 7 to 30 g / l tin in the form of alkali tannate, 0.1 to 100 g / l of a complexing agent, 1 to 50 g / l free alkali metal cyanide, 1 to 50 g / l Alkali hydroxide, up to 50 g / l alkali carbonate and 0.05 to 5 g / l of an organic fatty acid compound or a naphthol.
Beschichten lassen sich hiermit praktisch alle metallischen Werkstoffe, wie beispielsweise Aluminium, Kupfer, Stahl, Zink, Nickel, bzw. Aluminium-, Kupfer- und Nickellegierungen. Bevorzugst verwendet man als Unterlagewerkstoff Messing.Practically all metallic materials, such as aluminum, copper, steel, zinc, nickel, or aluminum, copper and nickel alloys can be coated with this. Brass is the preferred base material.
Die Zwischenschichten werden vorzugsweise mit einer Schichtdicke zwischen 0,1 und 10 µm aufgebracht.The intermediate layers are preferably applied with a layer thickness between 0.1 and 10 μm.
Neben der Sicherung des Korrosionsschutzes können die Kupfer-Zinn- oder Kupfer-Zinn-Zink-Schichten auch die Funktion der Einebnung und Glanzbildung übernehmen. Zur Erzielung der Einebnung und Glanzbildung wird dabei bevorzugt eine Kupfer-Zinn-Zink-Schicht eingesetzt. Üblicherweise werden zur Einebnung und Glanzbildung von Gestellware sonst saure Kupferelektrolyte verwendet. Bei Trommelware ist mit den sauren Kupferelektrolyten nur eine Einebnung aber keine Glanzbildung erzielbar. Mit einem Elektrolyten zur Abscheidung von Kupfer-Zinn-Zink-Schichten ist eine Einebnung und Glanzbildung sowohl bei Gestellware als auch bei Trommelware möglich.In addition to ensuring corrosion protection, the copper-tin or copper-tin-zinc layers can also take on the function of leveling and gloss formation. A copper-tin-zinc layer is preferably used to achieve leveling and gloss formation. Acidic copper electrolytes are usually used for leveling and glossing of rack goods. In the case of drumware, the acidic copper electrolytes can only level off but no gloss formation. With an electrolyte for the deposition of copper-tin-zinc layers, leveling and gloss formation are possible both for rack goods and for drum goods.
Zur Verbesserung der Anbindung der durch PVD-Verfahren aufgebrachten Hartstoffschicht an die Kupfer-Zinn- oder Kupfer-Zinn-Zink-Schicht können die Kupfer-Zinn- oder Kupfer-Zinn-Zink-Schichten galvanisch mit einer 0,1 µm dicken Goldschicht überzogen sein.To improve the connection of the hard material layer applied by the PVD process to the copper-tin or copper-tin-zinc layer, the copper-tin or copper-tin-zinc layers can be galvanically coated with a 0.1 μm thick gold layer .
Folgende Beispiele sollen das erfindungsgemäße Verfahren näher erläutern:
- 1. Polierte Stahlknöpfe werden wässrig alkalisch vorgereinigt, elektrolytisch entfettet, in einer Mineralsäure dekapiert und galvanisch mit einer Kupfer-Zinn-Schicht mit unterschiedlichen Schichtdicken (1 µm, 2 µm, 3 µm, 5 µm) beschichtet. Anschließend werden die Schichten mit dem Ferroxyl-Test, bzw. mit dem Dimetylglyoxim-Test auf Poren geprüft. Ab einer Schichtdicke von 3 µm rufen beide Lösungen keine Verfärbung der Oberflächen mehr hervor, d.h. sie weisen keine Poren nach. Zur Abscheidung der Kupfer-Zinnschichten (55 Cu, 45 Sn) werden galvanische Bäder eingesetzt, die 5 bis 10 g/l Kupfer als Kupferzyanid, 15 bis 30 g/l Zinn als Stannat 30 bis 50 g/l Kaliumyanid und 5 bis 25 g/l Kaliumhydroxid enthalten. Die Abscheidung erfolgte bei 50 bis 60°C mit Stromstärken von 2 bis 4 A/dm2.
- 2. Polierte Messingbleche werden wässrig alkalisch vorgereinigt, elektrolytisch entfettet, in einer Mineralsäure dekapiert und direkt mit einer 3 µm dicken Kupfer-Zinn-Schicht (gemäß Beispiel 1) galvanisch beschichtet. Anschließend werden die beschichteten Bleche einem Kesernich-Test (DIN 50018) von 5 Runden mit 0,2 1 SO2 unterzogen. Die Schichten zeigen sowohl auf der Oberfläche (REM-Aufnahme) als auch im Querschliff keinen Korrosionsangriff.
- 3. Messingbleche und Messinghülsen werden wässrig alkalisch vorgereinigt, elektrolytisch entfettet, in einer Mineralsäure dekapiert und zur Einebnung und Glanzbildung galvanisch mit einer 10 µm dicken Kupfer-Zinn-Zink-Schicht (60 Cu, 35 Sn, 5 Zn) überzogen. Auf diese Schicht wird eine 3 µm dicke Kupfer-Zinn-Schicht (55 Cn, 45 Sn) als funktionelle Korrosionsschutzschicht aufgebracht. Anschließend werden die beschichteten Bleche einem Kesternich-Test (DIN 50018) von 5 Runden mit 0,2 l SO2 wie im Beispiel 2 unterzogen. Die Schichten zeigen wie im Beispiel 2 keinen Korrosionsangriff.
- 1. Polished steel buttons are pre-cleaned with an alkaline water, electrolytically degreased, decapitated in a mineral acid and galvanically coated with a copper-tin layer with different layer thicknesses (1 µm, 2 µm, 3 µm, 5 µm). The layers are then checked for pores using the ferroxyl test or the dimethylglyoxime test. From a layer thickness of 3 µm, both solutions no longer cause discoloration of the surfaces, ie they have no pores. For the deposition of the copper-tin layers (55 Cu, 45 Sn) galvanic baths are used, the 5 to 10 g / l copper as copper cyanide, 15 to 30 g / l tin as stannate 30 to 50 g / l potassium cyanide and 5 to 25 g / l contain potassium hydroxide. The deposition took place at 50 to 60 ° C with currents of 2 to 4 A / dm 2 .
- 2. Polished brass sheets are pre-cleaned in aqueous alkaline solution, electrolytically degreased, picked up in a mineral acid and directly electroplated with a 3 µm thick copper-tin layer (according to Example 1). The coated sheets are then subjected to a Kesernich test (DIN 50018) of 5 rounds with 0.2 l SO2. The layers show no corrosion attack both on the surface (SEM image) and in the cross section.
- 3. Brass sheets and brass sleeves are pre-cleaned with alkaline water, electrolytically degreased, decapitated in a mineral acid and galvanically coated with a 10 µm thick copper-tin-zinc layer (60 Cu, 35 Sn, 5 Zn) for leveling and shining. A 3 µm thick copper-tin layer (55 Cn, 45 Sn) is applied to this layer as a functional corrosion protection layer. The coated sheets are then subjected to a Kesternich test (DIN 50018) of 5 rounds with 0.2 l of SO2 as in Example 2. As in Example 2, the layers show no corrosion attack.
Claims (4)
- Process for the production of workpieces and items made from non-corrosion-resistant metals and metal alloys which are coated with wear-resistant non-metallic coatings of nitrides, carbides, borides, oxides or silicides of elements from groups 4B to 6B of the Periodic System of Elements and in which a corrosion-resistant intermediate layer is located between the surface of the workpiece and the coating,
characterised in that
an intermediate layer of a copper/tin alloy with 45 to 80 wt.% of copper, 10 to 55 wt.% of tin and 0 to 15 wt.% of zinc is first electrodeposited onto the item and then the wear-resistant layer is applied by means of a PVD process. - Process according to Claim 1,
characterised in that
a copper/tin alloy with 45 to 65 wt.% of copper and 35 to 55 wt.% of tin is electrodeposited as the intermediate layer. - A process according to Claim 1,
characterised in that
an alloy of 50 to 80 wt.% of copper, 10 to 35 wt.% of tin and 1 to 15 wt.% of zinc is electrodeposited as the intermediate layer. - Process according to Claims 1 to 3,
characterised in that
titanium nitride or titanium carbide is applied as the wear-resistant layer.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4336664A DE4336664A1 (en) | 1993-10-27 | 1993-10-27 | Workpieces made of non-corrosion-resistant metals with coatings applied using the PVD process |
| DE4336664 | 1993-10-27 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0651071A1 EP0651071A1 (en) | 1995-05-03 |
| EP0651071B1 true EP0651071B1 (en) | 1997-07-30 |
Family
ID=6501152
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP94116862A Expired - Lifetime EP0651071B1 (en) | 1993-10-27 | 1994-10-26 | Method for producing parts with wear-resistant coatings |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US5494565A (en) |
| EP (1) | EP0651071B1 (en) |
| JP (1) | JP3347898B2 (en) |
| DE (2) | DE4336664A1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2531163T3 (en) * | 2002-10-11 | 2015-03-11 | Enthone | Procedure and electrolyte for galvanic deposition of bronzes |
| US7156904B2 (en) * | 2003-04-30 | 2007-01-02 | Mec Company Ltd. | Bonding layer forming solution, method of producing copper-to-resin bonding layer using the solution, and layered product obtained thereby |
| US7029761B2 (en) * | 2003-04-30 | 2006-04-18 | Mec Company Ltd. | Bonding layer for bonding resin on copper surface |
| US20060260948A2 (en) * | 2005-04-14 | 2006-11-23 | Enthone Inc. | Method for electrodeposition of bronzes |
| AT514818B1 (en) * | 2013-09-18 | 2015-10-15 | W Garhöfer Ges M B H Ing | Deposition of Cu, Sn, Zn coatings on metallic substrates |
| US9586381B1 (en) * | 2013-10-25 | 2017-03-07 | Steriplate, LLC | Metal plated object with biocidal properties |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0571796A1 (en) * | 1992-05-27 | 1993-12-01 | Linde Aktiengesellschaft | Surface protective coating and process for the manufacture thereof |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1970549A (en) * | 1932-10-18 | 1934-08-21 | City Auto Stamping Co | Process of electroplating bronze |
| US4036602A (en) * | 1975-11-26 | 1977-07-19 | Chromalloy American Corporation | Diffusion coating of magnesium in metal substrates |
| DE3339541C2 (en) * | 1983-11-02 | 1986-08-07 | Degussa Ag, 6000 Frankfurt | Alkaline-cyanide bath for the galvanic deposition of copper-tin alloy coatings |
| US4557980A (en) * | 1984-08-21 | 1985-12-10 | Martin Processing, Inc. | Radiation curable coating for film structure |
| JPS61119668A (en) * | 1984-11-16 | 1986-06-06 | Seiko Instr & Electronics Ltd | Manufacture of portable watch case made of zinc alloy |
| JPH0816262B2 (en) * | 1987-01-08 | 1996-02-21 | 住友電気工業株式会社 | Electrical wire |
| US5192410A (en) * | 1988-07-28 | 1993-03-09 | Nippon Steel Corporation | Process for manufacturing multi ceramic layer-coated metal plate |
| DE3829007A1 (en) * | 1988-08-26 | 1990-03-01 | Multi Arc Gmbh | METHOD FOR PLASMA COATING OBJECTS WITH A HARD MATERIAL |
| JPH03215658A (en) * | 1990-01-19 | 1991-09-20 | Citizen Watch Co Ltd | Structure of ornamental film |
| FR2688234B1 (en) * | 1992-03-03 | 1995-03-24 | Sarrel | PROCESS FOR PROTECTING A SILVER COVERED OR SILVER COVERED PIECE. |
-
1993
- 1993-10-27 DE DE4336664A patent/DE4336664A1/en not_active Ceased
-
1994
- 1994-10-17 US US08/323,928 patent/US5494565A/en not_active Expired - Fee Related
- 1994-10-26 EP EP94116862A patent/EP0651071B1/en not_active Expired - Lifetime
- 1994-10-26 DE DE59403544T patent/DE59403544D1/en not_active Expired - Fee Related
- 1994-10-27 JP JP26372594A patent/JP3347898B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0571796A1 (en) * | 1992-05-27 | 1993-12-01 | Linde Aktiengesellschaft | Surface protective coating and process for the manufacture thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| DE59403544D1 (en) | 1997-09-04 |
| EP0651071A1 (en) | 1995-05-03 |
| DE4336664A1 (en) | 1995-05-04 |
| JP3347898B2 (en) | 2002-11-20 |
| US5494565A (en) | 1996-02-27 |
| JPH07216560A (en) | 1995-08-15 |
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