WO2009059915A2 - Couche de nickel contenant de l'or - Google Patents

Couche de nickel contenant de l'or Download PDF

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Publication number
WO2009059915A2
WO2009059915A2 PCT/EP2008/064641 EP2008064641W WO2009059915A2 WO 2009059915 A2 WO2009059915 A2 WO 2009059915A2 EP 2008064641 W EP2008064641 W EP 2008064641W WO 2009059915 A2 WO2009059915 A2 WO 2009059915A2
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WO
WIPO (PCT)
Prior art keywords
nickel
gold
layer
layers
range
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.)
Ceased
Application number
PCT/EP2008/064641
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German (de)
English (en)
Other versions
WO2009059915A3 (fr
Inventor
Frank Brenner
Jürgen Sander
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nanogate Coating Systems GmbH
Original Assignee
Nanogate Coating Systems GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Nanogate Coating Systems GmbH filed Critical Nanogate Coating Systems GmbH
Priority to EP08846305A priority Critical patent/EP2212447A2/fr
Priority to CN200880114716A priority patent/CN101849035A/zh
Publication of WO2009059915A2 publication Critical patent/WO2009059915A2/fr
Publication of WO2009059915A3 publication Critical patent/WO2009059915A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • 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
    • C23C18/48—Coating with alloys
    • C23C18/50—Coating with alloys with alloys based on iron, cobalt or nickel
    • 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
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents

Definitions

  • the present invention relates to a chemical nickel bath containing gold ions, a process for producing a chemical nickel layer containing gold, the resulting nickel layer and their use.
  • electroless nickel is deposited as a wear or corrosion protection on metallic materials.
  • the difference to the galvanic nickel lies in the fact that no electrical current is used for the deposition.
  • conformal coatings are obtained in the case of chemical nickel plating, whose layer thickness, with a tolerance of ⁇ 2 ⁇ m to ⁇ 3 ⁇ m, can typically be in the range from 8 ⁇ m to 80 ⁇ m.
  • stresses in the layer must be expected. It is even possible to coat plastics such as polyamide.
  • Chemical nickel-phosphorus layers are known and found in many industrial applications: automotive, electronics, printing industry, chemical plant engineering, engineering, aerospace, oil and gas.
  • the main task of these coatings is to protect the substrate from corrosion and wear.
  • the chemically nickel layer can be combined with other coatings such as chrome coatings in the printing industry or gold coatings as a finish in electronics.
  • the chemical, electroless deposition is However, unlike the galvanic, current-carrying process of nickel deposition significantly slower. It is usually deposited 5 to 15 microns per hour. For high corrosion protection requirements usually layers of at least 25 to 30 microns are necessary. This results in relatively high costs in the application of such layers - on the one hand by the raw material nickel and on the other hand by the long process times for deposition.
  • the corrosion protection could previously be increased by a high phosphorus content of a nickel-phosphorus layer as well as by other coatings such as chromium or silver. But at least one additional application step is necessary accordingly.
  • US Pat. No. 3,485,597 discloses a gold-containing nickel coating, in which, however, gold could be introduced into the coating only to a very small extent below 1% by weight.
  • the so-called "immersion gold / nickel” technology exists.
  • a thin gold layer with a layer thickness of typically up to 0.2 microns is deposited on a nickel-phosphorus layer and then applied a wear protection layer.
  • This method has the decisive disadvantage that several process steps are necessary for the coating and that the nickel layer can corrode due to defects when the gold layer is broken through.
  • the object of the present invention is thus to provide a chemically nickel layer with improved corrosion resistance, the provision of a process with more favorable process parameters and thus the opening of new fields of application and enlargement of the potential market.
  • the object underlying the invention is achieved in a first embodiment by a nickel electroless bath for the electroless deposition of nickel, characterized in that it has a gold content in a range of 0.01 to 0.5 g / l, a content of nickel in a range of 0.5 to 50 g / l and a content of reducing agent in a range of 5 to 150 g / l.
  • the nickel bath according to the invention allows the deposition of thinner layers compared to the prior art, so that the same or better corrosion resistance of the layer can reduce the time for the deposition of the layer and thus make the process more cost effective. This allows a more flexible application of the method in industrial applications, including in large series by the shortened specific process time per coating material.
  • the nickel bath according to the invention thus enables a larger throughput per unit time.
  • the bath according to the invention advantageously consists essentially of a conventional electroless nickel electrolyte, to which an aqueous solution of, for example, potassium dicyanoaurate is added. It can also be used a commercial gold electrolyte. For the first time, chemically nickel, phosphorus and gold can be deposited simultaneously in a significant amount with the bath according to the invention.
  • the layer according to the invention is not sensitive to corrosion. Surprisingly, no local elements of nickel-phosphorus and gold domains have formed, which would make the layer sensitive to salt spray and acids, but obtained when using the bath according to the invention, a layer in which the corrosion protection is even higher than in a comparatively thick gold-free nickel-phosphorus layer.
  • the nickel bath advantageously has a gold ion content in a range of 0.05 to 0.15 g / l. If the content of gold ions above this range, it may happen that the bath does not "start", so does not lead to the electroless deposition of nickel.
  • the gold ions advantageously have weak acids as counterions since the pH of the bath does not become too acidic and the bath slows down the coating process.
  • the counterions are selected from the group of sulfites, sulfonates, cyanides or phosphonates.
  • the counterions may preferably have alkyl groups or aryl groups, which in turn may advantageously be partially fluorinated.
  • the counterions are trifluoromethanesulfonate, methanesulfonate, cyanide and / or toluenesulfonate.
  • the appropriate choice of counterions increases the solubility of the metal ions.
  • the nickel ions of the bath according to the invention are advantageously present as solutions of the salts nickel chloride, nickel sulfate and / or nickel acetate.
  • the nickel content is advantageously in a range of 3 to 10 g / l.
  • the reducing agent is preferably a hypophosphite. Most preferably, the reducing agent is sodium hypophosphite.
  • the reducing agent is advantageously present in an amount ranging from 32 to 42 g / l in the bath of the invention.
  • the bath according to the invention also advantageously contains at least one complexing agent which is in particular selected from the group consisting of monocarboxylic acids, dicarboxylic acids, hydroxycarboxylic acids, ammonia and alkanolamines.
  • the complexing agent is advantageously present in an amount ranging from 1 to 15 g / l in the bath of the invention.
  • Complexing agents are therefore particularly advantageous because they complex nickel ions and thus prevent too high concentrations of free nickel ions. This stabilizes the solution and suppresses the precipitation of, for example, nickel phosphite.
  • the bath according to the invention is advantageously also at least one accelerator contained, which is in particular selected from the group anions of mono- and dicarboxylic acids, fluorides and / or borides.
  • the accelerator is advantageously present in an amount in a range of 0.001 to 1 g / l in the bath according to the invention. Accelerators are therefore particularly advantageous according to the invention, since they activate, for example, hypophosphite ions and thus accelerate the deposition.
  • At least one stabilizer is also contained, which is in particular selected from the group consisting of lead, tin, arsenic, molybdenum, cadmium, thallium ions and / or thiourea.
  • the stabilizer is advantageously present in an amount ranging from 0.01 to 250 mg / l in the bath of the invention.
  • Stabilizers are therefore particularly advantageous according to the invention, since they prevent the decomposition of the solution by masking catalytically active reaction nuclei.
  • the bath according to the invention also advantageously contains at least one pH buffer, which is in particular a sodium salt of a complexing agent and / or the associated corresponding acid.
  • the buffer is advantageously present in an amount in the range of 0.5 to 30 g / l in the bath according to the invention. Buffers are therefore particularly advantageous according to the invention, since they can keep the pH constant over longer operating times.
  • the bath according to the invention is advantageously also at least one pH regulator contained, which is in particular selected from the group sulfuric acid, hydrochloric acid, sodium hydroxide, sodium carbonate and / or ammonia.
  • the pH regulator is advantageously present in an amount ranging from 1 to 30 g / l in the bath of the invention. pH regulators are therefore particularly advantageous according to the invention since they can readjust the pH of the bath according to the invention.
  • the bath according to the invention also advantageously contains at least one wetting agent which is in particular selected from the group of ionogenic and / or nonionic surfactants.
  • the wetting agent is advantageously present in an amount in a range of 0.001 to 1 g / l in the bath according to the invention.
  • Wetting agents are therefore particularly advantageous according to the invention, since they increase the wettability of the surface to be nickel-plated with the electrolyte bath.
  • particles, in particular polymer particles can also be dispersed in the nickel bath according to the invention. These are advantageously made of fluoropolymers, very particularly preferably of tetrafluoropolyethylene. These particles may advantageously be present in an amount of from 1 to 30 g / l.
  • the average particle size is advantageously in a range of 0.01 to 1 ⁇ m.
  • functional particles can thus be incorporated in the layer to be produced according to the invention in the form of a dispersion: for example PTFE for friction minimization or SiC or other hard materials to increase wear protection with the abovementioned proportions and particle sizes.
  • the object underlying the invention is achieved by a process for electroless production of a gold-containing chemically nickel coating, characterized in that one uses a nickel bath according to the invention, and a) either during the coating has a pH of at most 4 7, so as to obtain a homogeneous distribution of gold in the resulting coating, or b) during the coating sets a pH of more than 4.7 and thus obtain a laminar deposition of gold and nickel, so that alternating layers of gold and nickel occur, and maintaining the nickel bath at a temperature in a range of 50 to 8O 0 C during the coating.
  • the coating method of the invention is faster than conventional methods, since only thinner layers are required by the nickel bath according to the invention for comparable corrosion protection compared to the prior art.
  • only a single process step for the coating has to be carried out.
  • Nickel layers in the context of the invention are those layers which consist predominantly of nickel.
  • Gold layers within the meaning of the invention are those layers which contain at least 30% by weight of gold.
  • the pH is adjusted within a range from 4.0 to 4.65. If the pH is below 4.0, the deposition rate of the bath will decrease too much.
  • the pH is preferably adjusted within a range from 4.75 to 5.5. If the pH is above this, unfavorable gold hydroxide may form.
  • the pH is advantageously adjusted by means of ammonia solution and / or sulfuric acid.
  • the surface of the substrate to be coated is advantageously activated or passivated as required.
  • the activation can advantageously be effected by common activators commercially available on the market, in the simplest case by half-concentrated hydrochloric acid. This also applies to the corresponding passivation.
  • the process is advantageously carried out without current.
  • the anomaly effect of the layer thickness in current-carrying deposition processes, especially at edges, can be avoided, especially in the case of particularly difficult manufacturing tolerances.
  • the object underlying the invention is achieved in a further embodiment by a chemical nickel layer containing at least 1 wt.% Gold.
  • the nickel layer according to the invention contains in particular at least 2% by weight, 3% by weight and 5% by weight of gold. Due to the higher gold content, the total layer thickness can be reduced with the same corrosion resistance, whereby a considerable saving in process time and material savings can be achieved. In addition, complicated shapes can be coated more accurate.
  • the nickel layer is obtainable according to one of the variants of the method according to the invention.
  • the nickel layer has a gold content of 3 to 45% by weight and a phosphorus content of 3 to 20% by weight.
  • the nickel layer alternately comprises at least one intermediate gold layer and at least two intermediate nickel layers, at least one intermediate gold layer being adjacent to intermediate nickel layers at both interfaces of the intermediate layer.
  • This type of coating was surprisingly obtained for the first time in only one process step with the method according to the invention. Due to the sequence of layers, a particularly good corrosion protection can be achieved and thus the thickness of the overall layer can be further reduced.
  • the intermediate nickel layers have a layer thickness in a range from 1 to 10 .mu.m, in particular in a range from 2 to 5 .mu.m.
  • the intermediate gold layer preferably has a layer thickness in a range of 0.01 to 1 ⁇ m, in particular in a range of 30 nm up to 150 nm. Even with such a small layer thickness, the resistance to corrosion can be significantly improved so that the overall thickness of the nickel layer according to the invention can be considerably reduced.
  • the gold is present in increasing preference at least 4, 5, 7 or 10 wt.% And independently of at most 40, 20 or 12 wt.% Contained in the nickel layer according to the invention.
  • the nickel layer can be made even more inert in comparison with the non-preferred embodiment.
  • the phosphorus content of the nickel layer according to the invention is advantageously in a range of 5 to 17 wt.%, And regardless of the nickel content in a range of 55 to 90 wt.%, In particular in a range of 75 to 90 wt.%.
  • nickel-phosphorus alloy nickel-phosphorus alloy
  • the layer properties can be controlled via the phosphor deposited in the layer. This distinction is made according to the invention between a high (10 to 14 wt.%), medium (9 to 12 wt.%) and low (3 to 7 wt.%) phosphorus content.
  • the corrosion protection of the layer is mainly based on a high phosphorus content and the deposition of a non-porous layer, which always depends on the base material and its processing (for example, polishing, grinding, turning, milling).
  • the pre-processing of the material in turn influences the adhesion of the coating.
  • the wear protection increases according to the invention with decreasing phosphorus content and can be advantageously increased by a heat treatment of the layer at a maximum of 400 0 C and one hour hold time.
  • the layer thickness of the nickel layer according to the invention is advantageously at most 100 ⁇ m, in particular at most 20 ⁇ m, very particularly preferably at most 2 ⁇ m and independently thereof at least 6 ⁇ m, in particular at least 10 ⁇ m. Despite the preferred low maximum layer thickness surprisingly, an astonishing corrosion protection effect can be achieved with the layer according to the invention.
  • the ratio of gold to nickel in the layer is advantageously greater than or equal to the factor in a range of 0.5 to 2, or equal to the ratio of gold to nickel in the bath, based on moles.
  • particles in particular hard material particles or polymer particles, can also be present in the nickel layer according to the invention. These are advantageously made of fluoropolymers, very particularly preferably of tetrafluoropolyethylene (PTFE). These particles may advantageously be present in a range of from 1 to 30% by weight. The average particle size is advantageously in a range of 0.01 to 1 ⁇ m.
  • the substrate is advantageously a conductive substrate, in particular a metallic substrate.
  • the corrosion resistance of the layer according to the invention is extremely high.
  • the layer of the invention reacts on contact with sulfuric much less and slower than a nickel layer.
  • a steel sheet having a conventional chemical nickel plating and a steel sheet having a coating of the present invention was immersed in 1 molar aqueous sulfuric acid solution at room temperature for about 1.5 hours, and then the liquid was removed.
  • the conventionally coated sheet showed a marked blackening while the sheet coated according to the invention remained almost unchanged.
  • the wear resistance of the layer according to the invention is very good.
  • the object underlying the invention is achieved by the use of the invention Nickel layer for use selected from the group of antifouling layers, coatings of surfaces in contact with salt water, in particular seawater desalination plants, antislip layers, anticorrosion layers, good solderable layers for in particular electronic applications, mechanical and plant engineering in the chemical industry, shipping industry, medical technology, instrument manufacturing, aerospace industry, Petrol or diesel engine engines, engine components, electronics industry, in particular finish in the electronics industry, wear protection layers, decorative coatings (in particular fittings and sanitary applications), non-stick layers (especially in Entformungsvon) and / or electrically conductive layers.
  • Nickel layer for use selected from the group of antifouling layers, coatings of surfaces in contact with salt water, in particular seawater desalination plants, antislip layers, anticorrosion layers, good solderable layers for in particular electronic applications, mechanical and plant engineering in the chemical industry, shipping industry, medical technology, instrument manufacturing, aerospace industry, Petrol or diesel engine engines, engine components, electronics industry, in particular finish in the electronics industry, wear protection
  • nickel layer according to the invention is the use as an anti-adhesion layer for molds, in particular in the processing of polyurethane (PU), PVC and / or elastomers.
  • the coating can thus be used, for example, in what are known as powder slush processes or slush processes for producing, for example, so-called slush skins.
  • instrument panels made of PVC or PU can be produced with the aid of the coating.
  • the gold content changes the surface energy of the nickel layer. Gold is inert and does not give the polymer materials sticking points.
  • the hardness of the nickel layer is combined with the non-stick properties of a gold layer. So far, only forms of nickel are known for molds in the processing of PU, PVC or elastomers.
  • Chrome plating of objects is widespread. These often have cracks, so that the underlying substrate must be effectively protected against corrosion. This is particularly necessary in the paper industry, especially in the printing rollers used there. With the aid of the nickel layer according to the invention on a suitable substrate, it is possible to improve the properties of chromium layers applied thereon, since the underlying substrates can be protected against corrosion.
  • the deposition was carried out as in the laminar deposition. However, the pH was adjusted at about 4.4 with 0.5 M sulfuric acid and 25% ammonia solution.
  • a steel sheet having a conventional chemical nickel plating and a steel sheet having a coating of the present invention was immersed in a molar solution of sulfuric acid at room temperature for about 1.5 hours and then the liquid was removed.
  • the conventionally coated sheet showed a marked blackening while the sheet coated according to the invention remained almost unchanged.
  • FIG. 1 shows the element distribution as a function of the layer thickness (measured by means of glow discharge spectroscopy (GDOS) analysis) in the case of homogeneous deposition of a gold-containing layer.
  • GDOS glow discharge spectroscopy
  • Fig. 2 shows the nickel layer according to the invention with a laminar structure. Clearly visible is the approximately 80 nm thick intermediate gold layer, which is framed by intermediate nickel layers.
  • Fig. 3 shows the nickel layer according to the invention with a laminar structure in light microscopic recorded transverse section. Clearly visible are the gold intermediate layers which can be clearly distinguished from the intermediate nickel layers.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemically Coating (AREA)

Abstract

La présente invention concerne un bain de nickelage chimique contenant des ions d'un métal noble, un procédé de production d'une couche de nickel chimique contenant un métal noble ainsi que la couche de nickel ainsi obtenue et son utilisation.
PCT/EP2008/064641 2007-11-07 2008-10-29 Couche de nickel contenant de l'or Ceased WO2009059915A2 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP08846305A EP2212447A2 (fr) 2007-11-07 2008-10-29 Couche de nickel contenant de l'or
CN200880114716A CN101849035A (zh) 2007-11-07 2008-10-29 含金镍层

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE200710053457 DE102007053457A1 (de) 2007-11-07 2007-11-07 Goldhaltige Nickelschicht
DE102007053457.6 2007-11-07

Publications (2)

Publication Number Publication Date
WO2009059915A2 true WO2009059915A2 (fr) 2009-05-14
WO2009059915A3 WO2009059915A3 (fr) 2009-07-02

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2008/064641 Ceased WO2009059915A2 (fr) 2007-11-07 2008-10-29 Couche de nickel contenant de l'or

Country Status (4)

Country Link
EP (1) EP2212447A2 (fr)
CN (1) CN101849035A (fr)
DE (1) DE102007053457A1 (fr)
WO (1) WO2009059915A2 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008036211A1 (de) * 2008-08-02 2010-02-04 Nanogate Ag Verfahren für die Abscheidung von Nickel und Edelmetall aus demselben Bad
CN102706802A (zh) * 2012-06-04 2012-10-03 汕头超声印制板公司 一种化金工艺的镍镀层腐蚀快速检测方法
DE102012108067A1 (de) * 2012-08-30 2014-03-06 Paul Hettich Gmbh & Co. Kg Verfahren zur Herstellung eines metallischen Bauteils eines Beschlages, Beschlag, Backofen und Möbel oder Haushaltsgerät
DE102015118779A1 (de) 2014-11-07 2016-05-12 Harting Kgaa Elektrischer Kontakt
CN105965122B (zh) * 2016-06-25 2018-12-28 天津泊荣石油科技发展有限公司 一种海洋工程钢表面防污耐蚀合金及钎涂方法
DE102018222838A1 (de) * 2018-12-21 2020-06-25 Robert Bosch Gmbh Zündkerzengehäuse mit Nickel-haltiger Schutzschicht, einer Silizium-haltigen Versiegelungsschicht und mindestens einer Zwischenschicht und/oder einer Deckschicht, sowie eine Zündkerze mit diesem Gehäuse und Herstellungsverfahren für dieses Gehäuse
DE102018211306A1 (de) * 2018-07-09 2020-01-09 Robert Bosch Gmbh Zündkerzengehäuse mit chemischer Nickel-haltiger Schutzschicht und einer Silizium-haltigen Versiegelungsschicht, sowie eine Zündkerze mit diesem Gehäuse und Herstellungsverfahren für dieses Gehäuse

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL253834A (fr) * 1959-07-21 1900-01-01
GB1129984A (en) 1964-10-30 1968-10-09 Usa Electroless deposition of nickel-phosphorus alloys
DE102006020988B4 (de) * 2006-05-04 2012-08-30 Nanogate Ag Edelmetallhaltiges Nickelbad, dessen Verwendung zur Herstellung einer edelmetallhaltigen Nickelschicht, edelmetallhaltige Nickelschicht sowie deren Verwendung

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Publication number Publication date
WO2009059915A3 (fr) 2009-07-02
CN101849035A (zh) 2010-09-29
DE102007053457A1 (de) 2009-05-14
EP2212447A2 (fr) 2010-08-04

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