EP0711848A1 - Process for copper electroless plating on iron or iron alloys surfaces - Google Patents
Process for copper electroless plating on iron or iron alloys surfaces Download PDFInfo
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- EP0711848A1 EP0711848A1 EP95116255A EP95116255A EP0711848A1 EP 0711848 A1 EP0711848 A1 EP 0711848A1 EP 95116255 A EP95116255 A EP 95116255A EP 95116255 A EP95116255 A EP 95116255A EP 0711848 A1 EP0711848 A1 EP 0711848A1
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- iron
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- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
Definitions
- the invention relates to a method for the currentless deposition of copper coatings on iron and iron alloy surfaces with the aid of solutions containing copper and hydrogen ions, and a solid concentrate for carrying out the method.
- the object of the invention is to provide a method for electroless deposition of copper coatings on iron and iron alloy surfaces, which does not have known, in particular the aforementioned disadvantages and is able to produce uniform and adherent coatings.
- the object is achieved in that the method of the type mentioned according to the invention is designed such that the surfaces are brought into contact with a solution which 5 to 30 g / l Cu as well 0.2 to 5 g / l Mg contains.
- a preferred embodiment of the invention provides for the surfaces to be brought into contact with a solution in which the weight ratio of Cu: Mg is in the range from (35 to 5): 1.
- a weight ratio in the above range leads to an optimal gloss of the coating produced.
- Another advantageous embodiment of the invention consists in bringing the iron or iron alloy surfaces into contact with a solution which additionally contains polyglycol and / or common salt.
- a solution which additionally contains polyglycol and / or common salt is additionally contained in a solution which additionally contains polyglycol and / or common salt.
- polyglycol makes it possible to improve the adhesive strength of the coating, by means of common salt to achieve a more uniform attack on the surface of the iron or iron alloy.
- the temperature of the solution should expediently be 20 to 65.degree.
- Part of the invention is a solid concentrate for preparing and supplementing the solution intended for carrying out the process, which is at least 85 wt .-% of CuSO4 ⁇ 5 H2O and MgSO4 (anhydrous) with a weight ratio of (35 to 5): 1 ( calculated as Cu: Mg).
- the solid concentrate additionally contains a maximum of 10% by weight of polyglycol and, according to a further advantageous embodiment, a maximum of 5% by weight of common salt.
- the iron or iron alloy surfaces are freed of impurities, in particular rust and scale. This is expediently done by pickling in mineral acid, preferably by pickling in hydrochloric acid or sulfuric acid. It is then rinsed with water.
- iron or iron alloy surfaces have additional dirt, it is advantageous to precede the pickling process with a cleaning stage.
- the copper coatings produced with the aid of the method according to the invention have considerable adhesive strength and have a high gloss.
- a further advantage of the process is that the iron rise in the copper plating solution is slowed down significantly, so that a larger throughput of iron or iron alloy surface is possible without influencing the iron concentration in the solution.
- the solid concentrate also forming part of the invention is characterized in that it itself long storage is easy to pour and therefore easy to handle.
- the effectiveness of the copper plating solution was kept at the aforementioned values by adding a solid concentrate which contained 90% by weight CuSO4 ⁇ 5 H2O, 8% by weight MgSO4 (anhydrous) and 2% by weight polyglycol, and by adding sulfuric acid .
- the steel wires treated by the process had a uniform, adhesive copper coating with a layer weight of 20 g / m2.
- the copper plating solution took up 18.5 g of iron per m2 of steel surface penetrated.
- the amount of iron dissolved was 22 g / m2. That is, without measures to reduce the iron content, the approximately 1.2 times the amount of steel wire could be provided with a copper coating without loss of quality when using the method according to the invention.
- the Cu: Mg weight ratio was 30.2: 1.
- the temperature of the solution was set to 60 ° C., the contact time was 30 seconds.
- the components of the solution were kept at the above-mentioned values by adding the above-mentioned concentrate and sulfuric acid.
- the steel wires were uniform Copper coating with very good adhesion and considerable gloss.
- the layer weight was 4 g / m2.
- the copper plating solution took up 3.7 g of iron per m2 of wire surface penetrated.
- the amount of iron dissolved in the solution was 4.4 g / m2.
- the process according to the invention therefore allowed an approximately 20% higher wire throughput without a deterioration in the quality of the copper coatings obtained.
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Abstract
Description
Die Erfindung betrifft ein Verfahren zur stromlosen Abscheidung von Kupferüberzügen auf Eisen- und Eisenlegierungsoberflächen mit Hilfe von Lösungen, die Kupfer- und Wasserstoffionen enthalten, sowie ein festes Konzentrat zur Durchführung des Verfahrens.The invention relates to a method for the currentless deposition of copper coatings on iron and iron alloy surfaces with the aid of solutions containing copper and hydrogen ions, and a solid concentrate for carrying out the method.
Es ist bekannt, die Kaltverformung von Eisen und Eisenlegierungen dadurch zu erleichtern, daß man auf das zu verformende Werkstück einen Kupferüberzug aufbringt. Derartige Überzüge können stromlos dadurch erzeugt werden, daß die Metalloberfläche mit einer wäßrigen, sauren, Kupferionen enthaltenden Lösung in Kontakt gebracht wird. Um gute und insbesondere haftfeste Überzüge zu erzielen, sind zahlreiche Vorschläge unterbreitet worden, die den Zusatz unterschiedlichster Modifizierungsmittel vorsehen.It is known to facilitate the cold forming of iron and iron alloys by applying a copper coating to the workpiece to be shaped. Such coatings can be produced without current by bringing the metal surface into contact with an aqueous, acidic solution containing copper ions. In order to achieve good and, in particular, adherent coatings, numerous proposals have been made which include the addition of a wide variety of modifiers.
Bei dem Verfahren der DE-C-714 437 gelangen Verkupferungslösungen zur Anwendung, die neben Kupfer-, Wasserstoff-, Chlorid-, Bromid- und/oder Fluoridionen starke organische Sparbeizen, die das Auflösen des Eisens verzögern, enthalten. Als brauchbare Sparbeizen sind Steinkohlenteerbasen, die aus tierischen Destillaten extrahierten Basen, Aldehydaminreaktionsprodukte, Aldehydketonreaktionsprodukte, zahlreiche Aminosäuren, Alkaloide und deren sulfurierte Derivate genannt.In the process of DE-C-714 437 coppering solutions are used which, in addition to copper, hydrogen, chloride, bromide and / or fluoride ions, contain strong organic savings which delay the dissolution of the iron. Coal tar bases, the bases extracted from animal distillates, aldehydamine reaction products, aldehyde ketone reaction products, numerous amino acids, alkaloids and their sulfurized derivatives are mentioned as useful savings.
Weiterhin ist es bekannt, stromlosen Verkupferungslösungen Polyhydroxythiole (US-A-2 410 844) und Glanzbildner bzw. Kornverfeinerungsmittel, wie Kondensationsprodukte von Fettalkoholen, Fettsäuren, Thallöl, Alkylphenolen, Fettaminen, substituierten Thioharnstoffen jeweils mit Ethylenoxid, sowie langkettige organische Amine, reduzierend wirkende Zucker, Abbauprodukte von Zucker (FR-A-1 257 758) zuzusetzen. Weiterhin ist es bekannt, zur stromlosen Herstellung von Kupferüberzügen auf Eisen- und Eisenlegierungen mit einer wäßrigen, sauren, Kupferionen, Chloridionen und organisches Modifizierungsmittel enthaltenden Lösung zu behandeln, wobei als organisches Modifizierungsmittel Acridin und/oder Acridinabkömmlinge eingesetzt werden (DE-B-16 21 291).Furthermore, it is known to use electroless copper plating solutions, polyhydroxy thiols (US Pat. No. 2,410,844) and brighteners or grain refining agents, such as condensation products of fatty alcohols, fatty acids, Thall oil, alkylphenols, fatty amines, substituted thioureas, each with ethylene oxide, as well as long-chain organic amines, reducing sugar, add sugar degradation products (FR-A-1 257 758). Furthermore, it is known for the electroless production of copper coatings on iron and iron alloys to be treated with an aqueous, acidic solution containing copper ions, chloride ions and organic modifiers, acridine and / or acridine derivatives being used as organic modifiers (DE-B-16 21 291).
Schließlich ist es bekannt, zur stromlosen Kupferabscheidung mit Lösungen zu arbeiten, die Kupfer-, Wasserstoff- und Fluoridionen enthalten und in denen in Abhängigkeit von der Temperatur sowohl die Fluoridkonzentration als auch die Wasserstoffionenkonzentration innerhalb bestimmter Koordinaten gewählt wird (DE-B-16 21 293).Finally, it is known to work for electroless copper deposition with solutions which contain copper, hydrogen and fluoride ions and in which, depending on the temperature, both the fluoride concentration and the hydrogen ion concentration are selected within certain coordinates (DE-B-16 21 293 ).
Trotz der Vielfalt der bekannten Verfahren zur stromlosen Kupferabscheidung treten in der Praxis jedoch immer wieder Probleme auf, indem es nicht oder nicht mit der erforderlichen Sicherheit gelingt, in gleicher Weise helle und haftfeste, gleichmäßig deckende und gut aussehende Kupferüberzüge zu erzeugen. Ein weiteres Problem liegt darin, daß die zur Herstellung der Verkupferungslösungen üblicherweise verwendeten festen Konzentrate eine geringe Rieselfähigkeit aufweisen und damit schwierig zu handhaben sind.Despite the variety of known methods for electroless copper deposition, problems always occur in practice in that it is not possible or not with the necessary certainty to produce bright and adherent, uniformly covering and good-looking copper coatings in the same way. Another problem lies in the fact that the solid concentrates usually used to prepare the copper plating solutions have a low flowability and are therefore difficult to handle.
Aufgabe der Erfindung ist es, ein Verfahren zur stromlosen Abscheidung von Kupferüberzügen auf Eisen- und Eisenlegierungsoberflächen bereitzustellen, das die bekannten, insbesondere vorgenannten Nachteile nicht aufweist und in der Lage ist, gleichmäßige und haftfeste Überzüge zu erzeugen.The object of the invention is to provide a method for electroless deposition of copper coatings on iron and iron alloy surfaces, which does not have known, in particular the aforementioned disadvantages and is able to produce uniform and adherent coatings.
Die Aufgabe wird gelöst, indem das Verfahren der eingangs genannten Art entsprechend der Erfindung derartig ausgestaltet wird, daß man die Oberflächen mit einer Lösung in Kontakt bringt, die
5 bis 30 g/l Cu sowie
0,2 bis 5 g/l Mg
enthält.The object is achieved in that the method of the type mentioned according to the invention is designed such that the surfaces are brought into contact with a solution which
5 to 30 g / l Cu as well
0.2 to 5 g / l Mg
contains.
Eine bevorzugte Ausgestaltung der Erfindung sieht vor, die Oberflächen mit einer Lösung in Kontakt zu bringen, in der das Gewichtsverhältnis von Cu : Mg im Bereich von (35 bis 5) : 1 liegt. Ein Gewichtsverhältnis im vorgenannten Bereich führt zu einem optimalen Glanz des erzeugten Überzuges.A preferred embodiment of the invention provides for the surfaces to be brought into contact with a solution in which the weight ratio of Cu: Mg is in the range from (35 to 5): 1. A weight ratio in the above range leads to an optimal gloss of the coating produced.
Eine weitere vorteilhafte Ausführungsform der Erfindung besteht darin, die Eisen- oder Eisenlegierungsoberflächen mit einer Lösung in Kontakt zu bringen, die zusätzlich Polyglykol und/oder Kochsalz enthält. Durch den Zusatz von Polyglykol läßt sich eine Verbesserung der Haftfestigkeit des Überzuges erzielen, durch den von Kochsalz eine Vergleichmäßigung des Angriffs auf die Eisen- oder Eisenlegierungsoberfläche erreichen.Another advantageous embodiment of the invention consists in bringing the iron or iron alloy surfaces into contact with a solution which additionally contains polyglycol and / or common salt. The addition of polyglycol makes it possible to improve the adhesive strength of the coating, by means of common salt to achieve a more uniform attack on the surface of the iron or iron alloy.
Weiterhin ist es vorteilhaft, für die Behandlung der Eisen- bzw. Eisenlegierungsoberflächen eine Dauer von 3 sec bis 15 min vorzusehen. Dabei sollte zweckmäßigerweise die Temperatur der Lösung 20 bis 65°C betragen.It is also advantageous to provide a duration of 3 seconds to 15 minutes for the treatment of the iron or iron alloy surfaces. The temperature of the solution should expediently be 20 to 65.degree.
Bestandteil der Erfindung ist ein festes Konzentrat zum Ansatz und zur Ergänzung der zur Durchführung des Verfahrens bestimmten Lösung, das zu mindestens 85 Gew.-% aus CuSO₄ · 5 H₂O und MgSO₄ (wasserfrei) mit einem Gewichtsverhältnis von (35 bis 5) : 1 (berechnet als Cu : Mg) besteht.Part of the invention is a solid concentrate for preparing and supplementing the solution intended for carrying out the process, which is at least 85 wt .-% of CuSO₄ · 5 H₂O and MgSO₄ (anhydrous) with a weight ratio of (35 to 5): 1 ( calculated as Cu: Mg).
Gemäß einer vorteilhaften Ausgestaltung enthält das feste Konzentrat zusätzlich maximal 10 Gew.-% Polyglykol und entsprechend einer weiteren vorteilhaften Ausführungsform maximal 5 Gew.-% Kochsalz.According to an advantageous embodiment, the solid concentrate additionally contains a maximum of 10% by weight of polyglycol and, according to a further advantageous embodiment, a maximum of 5% by weight of common salt.
Vor der Applikation der Verkupferungslösung werden die Eisen- oder Eisenlegierungsoberflächen von Verunreinigungen, insbesondere Rost und Zunder, befreit. Dies geschieht zweckmäßigerweise durch Beizen in Mineralsäure, vorzugsweise durch Beizen in Salzsäure oder Schwefelsäure. Anschließend wird mit Wasser gespült.Before the coppering solution is applied, the iron or iron alloy surfaces are freed of impurities, in particular rust and scale. This is expediently done by pickling in mineral acid, preferably by pickling in hydrochloric acid or sulfuric acid. It is then rinsed with water.
Sofern die Eisen- oder Eisenlegierungsoberflächen zusätzliche Verschmutzungen aufweisen, ist es vorteilhaft, dem Beizprozeß eine Reinigungsstufe vorzuschalten.If the iron or iron alloy surfaces have additional dirt, it is advantageous to precede the pickling process with a cleaning stage.
Die mit Hilfe des erfindungsgemäßen Verfahrens erzeugten Kupferüberzüge weisen eine beträchtliche Haftfestigkeit auf und besitzen einen starken Glanz. Ein weiterer Vorzug des Verfahrens ist, daß der Eisenanstieg in der Verkupferungslösung deutlich verlangsamt wird, so daß - ohne daß auf die Eisenkonzentration in der Lösung Einfluß genommen wird - ein größerer Durchsatz an Eisen- oder Eisenlegierungsoberfläche möglich ist.The copper coatings produced with the aid of the method according to the invention have considerable adhesive strength and have a high gloss. A further advantage of the process is that the iron rise in the copper plating solution is slowed down significantly, so that a larger throughput of iron or iron alloy surface is possible without influencing the iron concentration in the solution.
Das ebenfalls Gegenstand der Erfindung bildende feste Konzentrat zeichnet sich dadurch aus, daß es selbst nach langer Lagerung gut rieselfähig und mithin leicht handhabbar ist.The solid concentrate also forming part of the invention is characterized in that it itself long storage is easy to pour and therefore easy to handle.
Die Erfindung wird anhand der nachfolgenden Beispiele beispielsweise und näher erläutert.The invention is illustrated by the following examples, for example and in more detail.
In einer Drahtziehanlage wurden Stahldrähte mit Salzsäure gebeizt, in kaltem Wasser gespült und in eine Lösung getaucht, die mit
27 g/l CuSO₄ · 5 H₂O
2,4 g/l MgSO₄ (wasserfrei)
55 g/l H₂SO₄ (100 %ig) sowie
0,6 g/l Polyglykol
angesetzt worden war. Der Eintrag des Kupfersulfats, des Magnesiumsulfats und des Polyglykols erfolgte mit Hilfe eines vorgemischten Konzentrates. Es betrugen die Temperatur der Lösung 40°C und die Tauchdauer 10 min. Das Gewichtsverhältnis von Cu : Mg lag bei 14,2 : 1.In a wire drawing machine, steel wires were pickled with hydrochloric acid, rinsed in cold water and immersed in a solution containing the
27 g / l CuSO₄ · 5 H₂O
2.4 g / l MgSO₄ (anhydrous)
55 g / l H₂SO₄ (100%) and
0.6 g / l polyglycol
had been scheduled. The copper sulfate, the magnesium sulfate and the polyglycol were introduced with the aid of a premixed concentrate. The temperature of the solution was 40 ° C. and the immersion time was 10 minutes. The weight ratio of Cu: Mg was 14.2: 1.
Die Wirksamkeit der Verkupferungslösung wurde durch Zugabe eines festen Konzentrates, das 90 Gew.-% CuSO₄ · 5 H₂O, 8 Gew.-% MgSO₄ (wasserfrei) und 2 Gew.-% Polyglykol enthielt, sowie durch Zugabe von Schwefelsäure auf den vorgenannten Werten gehalten.The effectiveness of the copper plating solution was kept at the aforementioned values by adding a solid concentrate which contained 90% by weight CuSO₄ · 5 H₂O, 8% by weight MgSO₄ (anhydrous) and 2% by weight polyglycol, and by adding sulfuric acid .
Die nach dem Verfahren behandelten Stahldrähte wiesen einen gleichmäßigen, haftfesten Kupferüberzug mit einem Schichtgewicht von 20 g/m² auf. Die Verkupferungslösung nahm 18,5 g Eisen pro m² durchgesetzter Stahloberfläche auf.The steel wires treated by the process had a uniform, adhesive copper coating with a layer weight of 20 g / m². The copper plating solution took up 18.5 g of iron per m² of steel surface penetrated.
Wurde im Vergleich zum vorgenannten Verfahren eine Verkupferungslösung eingesetzt, die frei von Magnesium war, sonst jedoch die gleichen Gehalte an Kupfersulfat und Polyglykol enthielt und in gleicher Weise angewendet wurde, betrug die gelöste Eisenmenge 22 g/m². Das heißt, ohne Maßnahmen zur Verringerung des Eisengehaltes konnte bei Anwendung des erfindungsgemäßen Verfahrens die ca. 1,2-fache Stahldrahtmenge ohne Einbuße in der Qualität mit einem Kupferüberzug versehen werden.If, compared to the above-mentioned process, a copper solution was used which was free of magnesium, but otherwise contained the same copper sulfate and polyglycol contents and was used in the same way, the amount of iron dissolved was 22 g / m². That is, without measures to reduce the iron content, the approximately 1.2 times the amount of steel wire could be provided with a copper coating without loss of quality when using the method according to the invention.
Stahldrähte wurden mit Schwefelsäure gebeizt, mit kaltem Wasser gespült und im Durchzugverfahren mit einer Lösung in Kontakt gebracht, die durch Auflösen von 30 kg eines festen Konzentrates, bestehend aus 95 Gew.-% CuSO₄ · 5 H₂O, 4 Gew.-% MgSO₄ (wasserfrei) und 1 Gew.-% NaCl, sowie 55 kg Schwefelsäure (100 %ig) in 1000 l Wasser hergestellt worden war. Die Lösung enthielt - als Salz- bzw. Säuregehalt gerechnet -
28,5 g/l CuSO₄ · 5 H₂O
1,2 g/l MgSO₄ (wasserfrei)
0,3 g/l NaCl sowie
55 g/l H₂SO₄ (100 %ig).Steel wires were pickled with sulfuric acid, rinsed with cold water and brought into contact with a solution in a continuous process, which was dissolved by dissolving 30 kg of a solid concentrate consisting of 95 wt.% CuSO Cu. 5 H₂O, 4 wt ) and 1 wt .-% NaCl, and 55 kg of sulfuric acid (100%) had been prepared in 1000 l of water. The solution contained - calculated as salt or acid content -
28.5 g / l CuSO₄ · 5 H₂O
1.2 g / l MgSO₄ (anhydrous)
0.3 g / l NaCl as well
55 g / l H₂SO₄ (100%).
Das Gewichtsverhältnis Cu : Mg lag bei 30,2 : 1. Die Temperatur der Lösung war auf 60°C eingestellt, die Kontaktdauer betrug 30 sec.The Cu: Mg weight ratio was 30.2: 1. The temperature of the solution was set to 60 ° C., the contact time was 30 seconds.
Durch Zugabe des vorgenannten Konzentrates und von Schwefelsäure wurden die Bestandteile der Lösung auf den vorstehend genannten Werten gehalten. Auch in diesem Falle wiesen die Stahldrähte einen gleichmäßigen Kupferüberzug von sehr guter Haftung und beträchtlichem Glanz auf. Das Schichtgewicht lag bei 4 g/m². Die Verkupferungslösung nahm pro m² durchgesetzter Drahtoberfläche 3,7 g Eisen auf.The components of the solution were kept at the above-mentioned values by adding the above-mentioned concentrate and sulfuric acid. In this case too, the steel wires were uniform Copper coating with very good adhesion and considerable gloss. The layer weight was 4 g / m². The copper plating solution took up 3.7 g of iron per m² of wire surface penetrated.
Im Vergleich zu einer Lösung, die frei von Magnesium war, sonst aber die gleiche Beschaffenheit hatte und in gleicher Weise appliziert worden war, betrug die in Lösung gegangene Eisenmenge 4,4 g/m². Das erfindungsgemäße Verfahren gestattete mithin einen ca. 20 % höheren Drahtdurchsatz, ohne daß eine Verschlechterung in der Qualität der erhaltenen Kupferüberzüge auftrat.Compared to a solution that was free of magnesium, but otherwise had the same properties and was applied in the same way, the amount of iron dissolved in the solution was 4.4 g / m². The process according to the invention therefore allowed an approximately 20% higher wire throughput without a deterioration in the quality of the copper coatings obtained.
Claims (8)
5 bis 30 g/l Cu sowie
0,2 bis 5 g/l Mg
enthält.Process for the electroless deposition of copper coatings on iron or iron alloy surfaces with the aid of solutions containing copper and hydrogen ions, characterized in that the surfaces are brought into contact with a solution which
5 to 30 g / l Cu as well
0.2 to 5 g / l Mg
contains.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4440299 | 1994-11-11 | ||
| DE4440299A DE4440299A1 (en) | 1994-11-11 | 1994-11-11 | Process for the electroless deposition of copper coatings on iron and iron alloy surfaces |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0711848A1 true EP0711848A1 (en) | 1996-05-15 |
| EP0711848B1 EP0711848B1 (en) | 2003-02-12 |
Family
ID=6533057
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP95116255A Expired - Lifetime EP0711848B1 (en) | 1994-11-11 | 1995-10-16 | Process for copper electroless plating on iron or iron alloys surfaces |
Country Status (5)
| Country | Link |
|---|---|
| US (2) | US6261644B1 (en) |
| EP (1) | EP0711848B1 (en) |
| AT (1) | ATE232563T1 (en) |
| DE (2) | DE4440299A1 (en) |
| ES (1) | ES2192567T3 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002053801A2 (en) * | 2000-12-29 | 2002-07-11 | Chemetall Gmbh | Electroless copper plating of ferrous metal substrates |
| WO2012022660A1 (en) * | 2010-08-17 | 2012-02-23 | Chemetall Gmbh | Process for the electroless copper plating of metallic substrates |
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| DE10214859B4 (en) | 2002-04-04 | 2004-04-08 | Chemetall Gmbh | Process for coppering or bronzing an object and liquid mixtures therefor |
| US20050016658A1 (en) * | 2003-07-24 | 2005-01-27 | Thangavelu Asokan | Composite coatings for ground wall insulation in motors, method of manufacture thereof and articles derived therefrom |
| US20050019558A1 (en) * | 2003-07-24 | 2005-01-27 | Amitabh Verma | Coated ferromagnetic particles, method of manufacturing and composite magnetic articles derived therefrom |
| US7803457B2 (en) * | 2003-12-29 | 2010-09-28 | General Electric Company | Composite coatings for groundwall insulation, method of manufacture thereof and articles derived therefrom |
| DE102005038392B4 (en) * | 2005-08-09 | 2008-07-10 | Atotech Deutschland Gmbh | Method for producing pattern-forming copper structures on a carrier substrate |
| US7686875B2 (en) * | 2006-05-11 | 2010-03-30 | Lam Research Corporation | Electroless deposition from non-aqueous solutions |
| US8298325B2 (en) * | 2006-05-11 | 2012-10-30 | Lam Research Corporation | Electroless deposition from non-aqueous solutions |
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| JPS5627594B2 (en) * | 1975-03-14 | 1981-06-25 | ||
| US4297397A (en) * | 1976-01-22 | 1981-10-27 | Nathan Feldstein | Catalytic promoters in electroless plating catalysts in true solutions |
| US4563216A (en) * | 1984-06-15 | 1986-01-07 | Amchem Products, Inc. | Compositions and processes for coating ferrous surfaces with copper |
| US4684550A (en) * | 1986-04-25 | 1987-08-04 | Mine Safety Appliances Company | Electroless copper plating and bath therefor |
| US4762601A (en) * | 1986-11-10 | 1988-08-09 | Morton Thiokol, Inc. | Copper bath for electroless plating having excess counter-cation and process using same |
-
1994
- 1994-11-11 DE DE4440299A patent/DE4440299A1/en not_active Withdrawn
-
1995
- 1995-10-16 AT AT95116255T patent/ATE232563T1/en not_active IP Right Cessation
- 1995-10-16 EP EP95116255A patent/EP0711848B1/en not_active Expired - Lifetime
- 1995-10-16 ES ES95116255T patent/ES2192567T3/en not_active Expired - Lifetime
- 1995-10-16 DE DE59510554T patent/DE59510554D1/en not_active Expired - Lifetime
- 1995-11-06 US US08/554,288 patent/US6261644B1/en not_active Expired - Lifetime
-
1997
- 1997-02-18 US US08/802,029 patent/US5776231A/en not_active Expired - Lifetime
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE714437C (en) | 1938-03-23 | 1941-11-29 | American Chem Paint Co | Production of firmly adhering copper coatings on iron |
| US2410844A (en) | 1942-01-14 | 1946-11-12 | Du Pont | Metal plating process |
| FR1257758A (en) | 1960-02-24 | 1961-04-07 | Cie D Applic Chimiques A L Ind | Process for coating the surface of ferrous metals with a protective or decorative metal layer |
| US3460953A (en) * | 1966-05-27 | 1969-08-12 | Pennsalt Chemicals Corp | Process for depositing brasslike coatings and composition therefor |
| DE1621291B2 (en) | 1967-08-05 | 1971-02-11 | Metallgesellschaft Ag | Process for the electroless production of a copper coating on iron and iron alloys |
| DE1621293B2 (en) | 1967-11-28 | 1973-08-09 | Metallgesellschaft Ag, 6000 Frankfurt | PROCESS FOR ELECTRONIC DEPOSITION OF COPPER COATINGS ON STAINLESS STEELS BY CEMENTATION |
| FR2175729A1 (en) * | 1972-03-13 | 1973-10-26 | Parker Ste Continentale |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002053801A2 (en) * | 2000-12-29 | 2002-07-11 | Chemetall Gmbh | Electroless copper plating of ferrous metal substrates |
| WO2002053801A3 (en) * | 2000-12-29 | 2003-11-20 | Chemetall Gmbh | Electroless copper plating of ferrous metal substrates |
| WO2012022660A1 (en) * | 2010-08-17 | 2012-02-23 | Chemetall Gmbh | Process for the electroless copper plating of metallic substrates |
Also Published As
| Publication number | Publication date |
|---|---|
| ES2192567T3 (en) | 2003-10-16 |
| ATE232563T1 (en) | 2003-02-15 |
| EP0711848B1 (en) | 2003-02-12 |
| US6261644B1 (en) | 2001-07-17 |
| DE59510554D1 (en) | 2003-03-20 |
| DE4440299A1 (en) | 1996-05-15 |
| US5776231A (en) | 1998-07-07 |
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