EP2875168B1 - Revêtements autocatalytiques de nickel et compositions et procédés de formation desdits revêtements - Google Patents

Revêtements autocatalytiques de nickel et compositions et procédés de formation desdits revêtements Download PDF

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EP2875168B1
EP2875168B1 EP13820572.9A EP13820572A EP2875168B1 EP 2875168 B1 EP2875168 B1 EP 2875168B1 EP 13820572 A EP13820572 A EP 13820572A EP 2875168 B1 EP2875168 B1 EP 2875168B1
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Prior art keywords
nickel
electroless nickel
electroless
acid
plating bath
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German (de)
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EP2875168A2 (fr
EP2875168A4 (fr
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Matthew Joseph WOJCIK
Ambrose SCHAFFER
Jean M. LAPLANTE
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Coventya Inc
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Coventya Inc
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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
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1646—Characteristics of the product obtained
    • C23C18/165—Multilayered product
    • C23C18/1651—Two or more layers only obtained by electroless plating
    • 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
    • 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
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1689—After-treatment
    • 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
    • C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
    • 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
    • C23C18/54—Contact plating, i.e. electroless electrochemical plating

Definitions

  • This application relates to electroless nickel coatings, methods for forming the electroless nickel coating, and electroless nickel baths for forming the electroless nickel coatings.
  • Electroless nickel plating is a widely utilized plating process, which provides a continuous deposit of a nickel metal or nickel/alloy coating on metallic or non-metallic substrates without the need for external electric plating current. Electroless plating has been described as a controlled autocatalytic chemical reduction process for depositing metals. The process involves a continuous buildup of a nickel coating on a substrate by immersion of the substrate in a nickel plating bath under appropriate electroless plating conditions.
  • the plating baths generally comprise an electroless nickel salt and a reducing agent.
  • Some electroless nickel baths use hypophosphite ions as a reducing agent, and during the process, the hypophosphite ions are oxidized to orthophosphite ions, and the nickel cations in the plating bath are reduced to form a nickel phosphorous alloy as a deposit on the desired substrate surface. As the reaction proceeds, the level of orthophosphite ions in the bath increases, and the orthophosphite ions often are precipitated from the plating solutions as insoluble metal orthophosphites.
  • the source of nickel ions in the electroless plating baths described in the prior art has included nickel chloride, nickel sulfate, nickel bromide, nickel fluoroborate, nickel sulfonate, nickel sulfamate, and nickel alkyl sulfonates.
  • the reactants In order to have a continuous and consistent electroless plating process, the reactants must be replenished.
  • the frequency at which additions of the reactants are made to the bath depends on how far the concentrations of the reacting species can be allowed to vary from their optimum concentrations without adversely affecting the plating process, or concurrently the deposit.
  • the electroless plating reaction not only yields a nickel alloy deposit; it also generates by-products, which accumulate in solution. As the concentration of the by-products increase, their influence on the plating reaction also increases.
  • Electroless nickel-phosphorous coatings can be chemically treated, e.g., etched, to produce black coatings (Ni-P black). These black electroless nickel coatings can act as efficient absorbers and be used as very low reflectance coatings in optical instruments and sensors.
  • Chemical etching of electroless nickel-phosphorous coatings typically involves acid etching of low (1-3% phosphorous) or medium-low (3-6% phosphorous) nickel phosphorous alloys. Higher phosphorous content alloys are not suitable because they are too corrosion resistant to blacken as result of acid etching.
  • Japanese patent application JP 2007/7154223 A provides an electroless nickel-plating liquid containing no lead, and a plating method using the same.
  • US patent application US 2004/0144285 A1 discloses an electrolyte for electroless deposition of metal layers with internal compressive stresses containing a metal base salt, a reducing agent, a complexing agent, an accelerator and a stabilizer, where preferably nickel, copper, silver or gold, especially preferably nickel is used as metal.
  • Japanese patent application JP 2005/ 290400 A provides an electroless nickel (alloy) plating bath capable of achieving satisfactory formation of plating film and satisfactory continuous use of the plating bath without substantially incorporating lead etc. which are hazardous substances therein.
  • the electroless nickel plating bath contains a water-soluble nickel salt, a reducing agent, molybdenum, and bismuth and the electroless nickel (alloy) plating bath contains further an alloying metal salt in addition thereto.
  • US patent 4,511,614 discloses a process for producing an optically black coating having high absorptivity and emissivity values utilizing an electroless nickel plating process, and to a substrate provided with said black coating.
  • the present invention is directed to a method for forming a multilayer electroless metal coating on a substrate, the method comprising:
  • the hypophosphorous reducing agent is selected from the group consisting of sodium hypophosphite, potassium hypophosphite, ammonium hypophosphite, and combinations thereof.
  • the second electroless nickel plating bath includes at least one pH buffer, complexing agent, or chelating agent selected from the group consisting of acetic acid, formic acid, succinic acid, malonic acid, an ammonium salt, lactic acid, malic acid, citric acid, glycine, alanine, glycolic acid, lysine, aspartic acid, ethylene diamine tetraacetic acid (EDTA), and combinations thereof.
  • acetic acid formic acid, succinic acid, malonic acid, an ammonium salt
  • EDTA ethylene diamine tetraacetic acid
  • the method comprises at least two of a pH buffer, complexing agent, and/or chelating agent.
  • the nickel is provided in the second electroless plating bath in the form of a water soluble nickel salt.
  • the nickel salt is selected from the group consisting of nickel chloride, nickel bromide, nickel iodide, nickel acetate, nickel malate, and nickel hypophosphite.
  • the pH of the second electroless nickel plating bath is maintained at 4.5 to 5.0 and the temperature at 79°C to 93°C.
  • the second electroless nickel plating bath comprises 2 g/l to 10 g/l nickel, 20 g/l to 35 g/l of the hypophosphorous reducing agent, 1 g/l to 75 g/l each of the complexing agent, chelating agent, and/or pH buffer.
  • the second electroless nickel plating bath comprises lactic acid, acetic acid, malic acid, succinic acid, sodium hypophosphite, ammonium hydroxide, nickel, zinc, and ethylenediamine tetraacetic acid.
  • the etchant agent comprises an iron blackening agent and an acid, preferably, the etchant agent comprises ferric sulfate and hydrochloric acid.
  • the substrate coated with the first and second electroless nickel coatings is contacted with an acid solution prior to contacting the substrate with the electroless copper plating bath.
  • solvent can refer to a single solvent or a mixture of solvents.
  • Approximating language may be applied to modify any quantitative representation that could permissibly vary without resulting in a change in the basic function to which it is related. Accordingly, a value modified by a term or terms, such as "about”, is not to be limited to the precise value specified. In some instances, the approximating language may correspond to the precision of an instrument for measuring the value.
  • Embodiments described herein relate to methods of forming multilayer electroless nickel coatings on a substrate.
  • the electroless nickel plating bath used to form the electroless nickel coatings, multilayer electroless nickel coatings, and/or black electroless nickel coatings described herein is free of sulfur compounds, such as organic sulfur compounds, and can form a sulfur-free electroless nickel coatings, which can be uniformly etched or blackened to provide a black electroless nickel coating.
  • the electroless nickel plating bath replaces sulfur compounds, which have been typically employed in solutions for forming black electroless nickel coatings, with metallic containing compounds, such as zinc and bismuth. Replacement of the sulfur compounds with the metallic containing compound allows for improvements in operability, stability, and uniformity over current black electroless nickel plating methods.
  • Sulfur containing electroless nickel plating baths used to form black electroless nickel coatings require the addition of spent components (e.g., nickel) at precise moments (e.g., additions made at last 5-10 minutes of plating to insure sulfur codeposition) in order to achieve a repeatable coloring effect. If the timing is not precise, the resulting effect will alter the black coloring to the point of possibly failing to produce the desired color.
  • the proposed compositions, baths, and methods require no such addition, besides the normal addition to replenish spent components, as per the normal operation of an electroless nickel plating bath.
  • Electroless nickel plating baths having a sulfur based chemistry also rely on the codeposition of the sulfur directly into the electroless nickel deposit. The result is often an uneven distribution of the sulfur across the substrate surface, resulting in a streaky, nonuniform coloring.
  • the electroless nickel plating baths described herein do not rely on the presence of sulfur for co-deposition, and instead rely on the concentration of the available bismuth to allow for blackening of the electroless nickel plating deposit when exposed to an etchant.
  • the presence of organic-sulfur compounds can cause decomposition of the sulfur compound at cathode surfaces forming very small particles of nickel sulfide which in turn adversely affects ductility, internal stress, electrical conductivity and corrosion resistance of the deposit.
  • the breakdown of the organic-sulfur compounds can result in byproducts that accumulate within the electroless nickel plating bath, which interferes with the deposition of the sulfur. This limits the potential age of the bath to 2 metal turnovers (MTOs) before issues begin to arise.
  • MTOs metal turnovers
  • the sulfur-free or non-sulfur containing electroless nickel plating baths have no such limitation, and can be plated out for at least 4 MTOs. During this time, there is no loss of uniformity or depth of color from makeup of electroless nickel deposit formed on a substrate from the electroless nickel plating bath.
  • Electroless nickel plating baths that include zinc can plate at a slower rate. Plating at a slower rate causes a black electroless nickel deposit to be formed with an increased overall phosphorous content (e.g ., at least 5% increase) compared to electroless nickel deposits formed using typical sulfur based black electroless nickel chemistry, which contains on average 1-5% phosphorous. Black electroless nickel deposits with an increased phosphorous content prepared using the sulfur-free electroless nickel plating baths described herein are more corrosion resistant than electroless nickel deposits of other available sulfur based chemistry.
  • the electroless nickel plating bath used to form the electroless nickel coating, multilayer coating, or black coating is free of a sulfur compound and can include an aqueous solution of nickel, a hypophosphorous reducing agent, zinc, at least of one of a complexing agent, chelating agent, and/or pH buffer, and a bismuth stabilizer.
  • the nickel can be provided in the bath in the form of a water soluble nickel salt.
  • the water-soluble nickel salts can include those which are soluble in the plating bath and which can yield an aqueous solution of a predetermined concentration.
  • the nickel salt can be selected from the group consisting of nickel chloride, nickel bromide, nickel iodide, nickel acetate, nickel malate, a nickel hypophosphite and combinations thereof.
  • the water-soluble nickel salts may be used alone or as a mixture.
  • the concentration of nickel in the electroless nickel plating bath can be from about 1 g/L to 70 g/L. In other embodiments, the concentration of nickel in the electroless nickel plating bath can be about 4 g/L to about 6g/L. Electroless nickel coatings formed from sulfur-free electroless nickel baths that include about 4 g/l showed decrease in blackening; whereas electroless nickel coatings formed from sulfur-free electroless nickel baths with 8 g/l showed no increase in the resulting black deposit.
  • the hypophosphorous reducing agent used in the bath can include any of a variety of hypophosphorous reducing agents used in known types of the electroless nickel plating baths.
  • the hypophosphorous reducing agent is selected from the group consisting of sodium hypophosphite, potassium hypophosphite, ammonium hypophosphite, and combinations thereof.
  • the concentration of the hypophosphorous reducing agent in the electroless nickel plating can differ with the respective types of hypophosphorous reducing agent and can be adjusted to vary the concentration of the phosphorous in the electroless nickel coating that is formed using the bath.
  • the concentration of the hypophosphorous reducing agent in the electroless nickel plating bath can be about 15 g/L to about 40 g/L.
  • the concentration of the hypophosphorous reducing agent in the electroless nickel plating bath can be about 20 to about 35 g/L.
  • a decrease in concentration of the hypophosphorous reducing agent from about 30 g/l to about 25 g/l can result in a decrease in phosphorous in the electroless nickel coating so formed by 2%. This decrease in phosphorous content can result in a deeper black being produced upon blackening of the coating.
  • the zinc or zinc ions can be incorporated into the electroless nickel plating bath by introducing a zinc compound into the bath.
  • a zinc compound examples include zinc carbonate, zinc oxide, zinc chloride, zinc benzoate, zinc nitrate, zinc phosphate, zinc stearate, and zinc salicylate.
  • the concentration of zinc in the electroless nickel plating bath is about 40 ppm to about 100 ppm.
  • a concentration of zinc in the electroless nickel plating bath below 40 ppm can result in a loss of color of the electroless nickel coating formed from the bath.
  • a concentration of zinc in the electroless nickel plating bath above 100 ppm did not adversely affect color of the electroless nickel coating formed from the bath, but the plating rate substantially decreased.
  • the bismuth stabilizer can be incorporated into the electroless nickel plating bath by introducing a bismuth salt into the bath, such as bismuth trichloride or bismuth nitrate.
  • concentration of the bismuth stabilizer in the electroless nickel plating bath is about 5 ppm to about 30 ppm. The higher the concentration of bismuth stabilizer provided in the electroless nickel plating bath the deeper the black color that can be produced from an electroless nickel coating formed from the bath. At concentration of the bismuth stabilizer over about 30 ppm, the bath can become over-stabilized and further plating is inhibited.
  • a complexing agent or a mixture of complexing agents is included in the electroless nickel plating bath.
  • Complexing agents as used herein can also include chelating agents.
  • the complexing agents and/or chelating agents generally retard the precipitation of nickel ions from the plating solution as insoluble salts, such as phosphites, by forming a more stable nickel complex with the nickel ions and provide for a moderate rate of the reaction of nickel precipitation.
  • the complexing agents and/or chelating agents can be included in the plating bath in amounts sufficient to complex the nickel ions present in the bath and to further solubilize the hypophosphite degradation products formed during the plating process.
  • complexing agents and/or chelating agents are employed in amounts of up to about 200 g/l with amounts of about 1 to about 75 g/l being more typical.
  • the complexing agents and/or chelating agents are provided in the electroless nickel plating bath at amounts from about 20 to about 40 g/l.
  • complexing agents used in known electroless nickel plating solutions, may be used.
  • specific examples of the complexing agents may include monocarboxylic acids, such as glycolic acid, lactic acid, gluconic acid or propionic acid, dicarboxylic acids, such as malic acid, malonic acid, succinic acid, tartaric acid, oxalic acid or adipic acid, aminocarboxylic acids, such as glycine or alanine, ethylene diamine derivatives, such as ethylenediamine tetraacetate, versenol (N-hydroxyethyl ethylenediamine-N,N',N'-triacetic acid) or quadrol (N,N,N', N'-tetrahydroxyethyl ethylene diamine), phosphnic acids, such as 1-hydroxyethane-1,1-diphosphonic acid, ethylene diamine tetramethylene phosphonic acid and water-soluble salts thereof.
  • the complexing agents may be used either alone or in
  • Some complexing agents such as acetic acid or succinic, for example, may also act as a pH buffering agent, and the appropriate concentration of such additive components can be optimized for any plating bath after consideration of their dual functionality.
  • At least one pH buffer, complexing agent, or chelating agent can be selected from the group consisting of an acetic acid, formic acid, succinic acid, malonic acid, an ammonium salt, lactic acid, malic acid, citric acid, glycine, alanine, glycolic acid, lysine, aspartic acid, ethylene diamine tetraacetic acid (EDTA), and combinations thereof.
  • mixtures of 2 or more of the above pH buffers, complexing agents, and/or chelating agents can be used in the electroless nickel plating bath described herein, with each pH buffer, complexing agent, and/or chelating agent being provided at a concentration of about of about 1 to about 75 g/l.
  • the plating bath may also contain, in addition to the above components, additives with various kinds of purposes so long as the properties of the plating bath are not deteriorated.
  • the aqueous electroless nickel plating baths can be operated or maintained at a pH of about 4.5 to about 5.0 during electroless nickel plating of the substrate.
  • a pH of about 4.5 to about 5.0 the reducing reaction by the hypophosphorous reducing agent is allowed to occur efficiently to prevent decomposition of the hypophosphorous reducing agent as well as to prevent the performance of precipitation for plating from being deteriorated and to prevent the plating bath from being decomposed.
  • this range of pH it is possible to prevent the plating bath from being lowered in stability as a result of the excessively high reducing potential of the reducing agent.
  • At least one pH adjustment agent can be used to adjust the pH to the above range.
  • the pH of the bath When the pH of the bath is too high, it can be adjusted by adding, for example, an acid.
  • the pH of the bath is too low, it can be adjusted by adding, for example, ammonium hydroxide.
  • the stability of the operating pH of the plating bath can be controlled by the addition of various buffer compounds such as acetic acid, propionic acid, boric acid, or the like, in amounts up to about 30 g/l with amounts of from about 2 to about 30 g/l being typical.
  • buffering compounds such as acetic acid and succinic acid may also function as complexing agents.
  • a substrate can be plated with the electroless nickel plating bath to provide an electroless nickel deposit or coating on the substrate.
  • the substrate can be any substrate capable of supporting the electroless nickel coating but is typically a material for which the electroless nickel coating displays sufficient affinity to form a stable coating thereupon.
  • Substrates may be inorganic materials, such as metals, or organic materials such as plastics, or composite materials, for example, organic polymer comprising inorganic filler.
  • the substrate is a metal substrate.
  • Non-limiting examples of metal substrates include iron, chromium, nickel, cobalt, copper, aluminum, titanium, and the like.
  • the substrate comprises steel.
  • the substrate comprises low alloy steel, for example low alloy carbon steel.
  • the substrate can be plated by contacting the substrate with or immersing the substrate in the plating bath for a duration time effective to form an electroless nickel coating or deposit on a desired surface of the substrate.
  • the substrate can be cleaned or pre-processed prior to plating.
  • the bath can be maintained at a bath temperature about 175°F to about 200°F.
  • the duration of contact of the electroless nickel plating bath with the substrate being plated will determine the thickness of the electroless nickel coating.
  • a contact time can range from as little as about one minute to several hours or even several days.
  • mild agitation can be employed.
  • the mild agitation can be, for example, a mild air agitation, mechanical agitation, bath circulation by pumping, rotation of a barrel for barrel plating, etc.
  • the electroless nickel plating bath also may be subjected to a periodic or continuous filtration treatment to reduce the level of contaminants therein. Replenishment of the constituents of the bath may also be performed, in some embodiments, on a periodic or continuous basis to maintain the concentration of constituents, and in particular, the concentration of nickel ions and hypophosphite ions, as well as the pH level within the desired limits.
  • the electroless nickel coated substrate so formed can be removed from the electroless nickel plating bath and rinsed, for example, with deionized water.
  • the electroless nickel coating formed on a surface of the substrate using the electroless nickel plating bath can have of relatively uniform thickness.
  • the electroless nickel coating can have an average thickness in a range from about 1 micron to about 250 microns.
  • the electroless nickel coating can have an average thickness in a range from about 1 micron to about 100 microns.
  • the electroless nickel coating can have an average thickness in a range from about 1 micron to about 10 microns.
  • the electroless nickel coating can also have a phosphorous content of about 8% to about 11%.
  • the electroless nickel coating can be a top coating that is plated over a mid-phosphorous (e.g., about 7% to about 9% phosphorous) or a high phosphorous (about 9% to about 13% phosphorous) electroless nickel under coating to form a duplex or multilayer electroless nickel deposit or coating.
  • the duplex or multilayer electroless nickel coating can advantageously be blackened to form a black electroless nickel coating.
  • Fig. 1 illustrates a flow diagram showing a method 10 of preparing a black electroless nickel coating on a substrate.
  • a substrate can be contacted with a first electroless nickel plating bath, by, for example, immersing the substrate in the first electroless nickel plating bath, to form a first electroless nickel coating on the substrate.
  • the first electroless nickel plating bath can include nickel, a hypophosphorous reducing agent, at least one of a complexing agent, chelating agent, or pH buffer, and optionally a sulfur compound, such as thiosulfates, thionic acid, or thiourea to provide a mid-phosphorous or high-phosphorous under coating.
  • An example of an electroless nickel plating bath that can be used to produce a high phosphorous electroless nickel coating can include about 6 g/l nickel, about 36 g/l sodium hypophosphite, about 20 g/l malic acid, about 15 g/l lactic acid, about 5 g/l succinic acid, and about 0.4 ppm lead.
  • An example of an electroless nickel plating bath that can be used to produce a mid phosphorous electroless nickel coating can include about 6 g/l nickel, about 30 g/l sodium hypophosphite, about 12 g/l malic acid, about 18 g/l lactic acid, about 14 g/l acetic acid, 1.0 ppm thiourea, and about 1.0 ppm lead.
  • the electroless nickel coating formed on a surface of the substrate using the first electroless nickel plating bath can have of relatively uniform thickness.
  • the electroless nickel under coating can have an average thickness in a range from about 5 micron to about 250 microns, or about 5 microns to about 100 microns.
  • the thickness of the electroless nickel under coating be at least two times, three times, four times, or five times greater than the thickness of the top coat.
  • the electroless nickel under coating can have an average thickness in a range from about 5 micron to about 15 microns.
  • the electroless nickel coating has a phosphorous content of about 7% to about 13%.
  • the coated substrate can be removed from the first electroless nickel plating bath, optionally rinsed, and then contacted with the second electroless nickel plating bath to form a second electroless nickel coating over the first electroless coating.
  • the coated substrate can be contacted with the second electroplating bath by, for example, immersing the coated substrate in the second electroless nickel plating bath for a duration a time effective to form the second electroless nickel coating or top coating.
  • the second electroless nickel plating bath is different that the first electroless nickel plating bath and be formulated such that it is free of a sulfur compound as described above.
  • the second electroless nickel plating bath includes nickel, a hypophosphorous reducing agent, zinc, a bismuth stabilizer, and at least one of a complexing agent, chelating agent, or pH buffer, and is free of a sulfur compound.
  • the electroless nickel plating bath can include lactic acid, acetic acid, malic acid, succinic acid, sodium hypophosphite, ammonium hydroxide, nickel, zinc, and ethylenediamine tetraacetic acid.
  • the electroless nickel plating bath can include about 2 g/l to about 10 g/l nickel, about 20 g/l to about 35 g/l of a hypophosphorous reducing agent, about 1 g/l to about 75 g/l each of the complexing agent, chelating agent, and/or pH buffer, about 40 ppm to about 120 ppm zinc, and about 5 ppm to about 30 ppm of a bismuth stabilizer.
  • the second electroless nickel coating formed on first electroless nickel coating using the second electroless nickel plating bath can have of relatively uniform thickness and an average thickness in a range from about 1 micron to about 100 microns. In some embodiments, the average thickness can be less than the thickness of the first electroless nickel coating and be in a range from about 1 micron to about 10 microns.
  • the second electroless nickel coating can also have a phosphorous content of about 8% to about 11%.
  • the multilayer or duplex coated substrate can be removed from the second electroless nickel plating bath, optionally rinsed, and then etched with an etching agent to provide the coated substrate with a black surface.
  • the etchant agent can include an aqueous solution of an iron blackening agent and an acid.
  • the etchant agent can include an aqueous solution of ferric sulfate and hydrochloric acid.
  • the etchant agent can include ferric sulfate, hydrochloric acid, and reaction enhancer, such as potassium iodate.
  • the temperature of the etchant agent can be about 70°F to 90°F and the coated substrate can be immersed in the etchant agent for a duration of time effective to blacken the coating, for example, for about 1 minute to about 3 minutes.
  • the substrate On removal black electroless nickel coated substrate from the etchant agent, the substrate can be rinsed and dried.
  • the black electroless coating so formed has a consistent uniform deposit of black electroless nickel with a uniform thickness and black coloring, which is streakless.
  • the duplex or multilayer electroless nickel coating can advantageously be further plated with another material to modify the coating.
  • Fig. 2 illustrates a flow diagram showing a method 20 of preparing an electroless copper-nickel coating on a substrate.
  • a substrate can be contacted with a first electroless nickel plating bath, by, for example, immersing the substrate in the first electroless nickel plating bath, to form a first electroless nickel coating on the substrate.
  • the first electroless nickel plating bath can include nickel, a hypophosphorous reducing agent, at least one of a complexing agent, chelating agent, or pH buffer, and optionally a sulfur compound, such as thiosulfates, thionic acid, or thiourea to provide a mid-phosphorous or high-phosphorous under coating.
  • a hypophosphorous reducing agent at least one of a complexing agent, chelating agent, or pH buffer
  • a sulfur compound such as thiosulfates, thionic acid, or thiourea to provide a mid-phosphorous or high-phosphorous under coating.
  • the electroless nickel coating formed on a surface of the substrate using the first electroless nickel plating bath can have of relatively uniform thickness.
  • the electroless nickel under coating can have an average thickness in a range from about 5 micron to about 250 microns, or about 5 microns to about 100 microns.
  • the thickness of the electroless nickel under coating be at least two times, three times, four times, or more greater that the thickness of the top coat.
  • the electroless nickel under coating can have an average thickness in a range from about 5 micron to about 15 microns.
  • the electroless nickel coating has a phosphorous content of about 7% to about 13%.
  • the coated substrate can be removed from the first electroless nickel plating bath, optionally rinsed, and then contacted with the second electroless nickel plating bath to form a second electroless nickel coating over the first electroless coating.
  • the coated substrate can be contacted with the second electroplating bath by, for example, immersing the coated substrate in the second electroless nickel plating bath for a duration a time effective to form the second electroless nickel coating or top coating.
  • the second electroless nickel plating bath is different that the first electroless nickel plating bath and be formulated such that it is free of a sulfur compound as described above.
  • the second electroless nickel plating bath is includes nickel, a hypophosphorous reducing agent, zinc, a bismuth stabilizer, and at least one of a complexing agent, chelating agent, or pH buffer, and is free of a sulfur compound.
  • the electroless nickel plating bath can include lactic acid, acetic acid, malic acid, succinic acid, sodium hypophosphite, ammonium hydroxide, nickel, zinc, and ethylenediamine tetraacetic acid.
  • the electroless nickel plating bath can include about 2 g/l to about 10 g/l of nickel, about 20 g/l to about 35 g/l hypophosphorous reducing agent, about 1 g/l to about 75 g/l each of the complexing agent, chelating agent, and/or pH buffer, about 40 ppm to about 120 ppm zinc, and about 5 ppm to about 30 ppm bismuth stabilizer.
  • the second electroless nickel coating formed on first electroless nickel coating using the second electroless nickel plating bath can have of relatively uniform thickness and an average thickness in a range from about 1 micron to about 100 microns. In some embodiments, the average thickness can be less than the thickness of the first electroless nickel coating and be in a range from about 1 micron to about 10 microns.
  • the second electroless nickel coating has a phosphorous content of about 8% to about 11%.
  • the multilayer or duplex coated substrate can be removed from the second electroless nickel plating bath, optionally rinsed, and then immersed in an acid solution, such as a hydrochloric acid solution, to reactivate the surface of the coating. Reactivation of the surface using an acid solution was found to advantageously enhance copper deposition in the subsequent copper coating step.
  • the multilayer or duplex coated substrate can be removed from the acidic solution, optionally rinsed, and then contacted with an electroless copper plating bath by, for example, immersing the duplex coated substrate in the electroless copper plating bath.
  • the electroless copper plating bath can include an aqueous solution of copper sulfate pentahydrate and sulfuric acid.
  • the coated substrate can be immersed in the electroless copper plating bath for a duration of time effective to form a copper coating, for example, for about 1 minute to about 3 minutes.
  • the substrate On removal electroless copper-nickel coated substrate from the electroless copper plating bath, the substrate can be rinsed and dried.
  • the electroless copper-nickel coating so formed had a consistent uniform deposit with a uniform thickness and copper coloring.
  • a black electroless coating was prepared using a high phosphorous nickel undercoating, a sulfur free electroless nickel top coating, and an acidic iron sulfate etchant.
  • the high-phosphorous electroless nickel plating bath was prepared with the following formulation: High Phosphorus electroless nickel plating bath Nickel Metal 6 g/l Sodium Hypophosphite 36 g/l Malic Acid 20 g/l Lactic Acid 15 g/l Succinic Acid 5 g/l Lead 0.4 ppm pH 4.6 -4.8 Temperature 190°F
  • the sulfur-free electroless nickel plating bath was prepared with the following formulation.
  • the etchant agent for blackening the sulfur-free electroless nickel plating bath was prepared with the following formulation.
  • An undercoat of the high phosphorous electroless nickel was plated on a steel substrate for a time of about 1 hour, to provide a high phosphorous electroless nickel coating having a thickness of about 0.50 mils.
  • the steel substrate was then rinsed and placed in the sulfur-free electroless nickel plating bath for 30 minutes, to provide an electroless nickel top coat with a thickness of about 0.15 mils.
  • the steel substrate was then removed from the sulfur-free electroless nickel bath, rinsed for 30 seconds, then submerged in the etchant solution for about 1 minute.
  • the steel substrate was again removed, rinsed, and allowed to set for 24 hours for maximum hardness.
  • the chemistry of the process allowed the electroless nickel coated steel substrate to be stored following the application of the undercoating for a later date, if the user desires. If this is the case, the electroless nickel coated steel substrate would need to be electrocleaned and reactivated in 50% HCl acid before the steel substrate can be submerged
  • Each component of the electroless solution was modified in an attempt to increase the black produced.
  • the concentration was adjusted in order to compensate for the increased Acetic Acid in solution. Trials to judge the effect that ammonia played in the solution, resulted in attempting to produce an ammonia-free chemistry, but the resulting solution would not blacken.
  • the Succinic acid was added to assist in controlling the phosphorus content and deepening the final color. Trialed concentrations that went up to 12 g/l. The result was a darker overall deposit up to 8 g/l, which gradually decrease as the concentrations exceed this amount.
  • Intrinsic Stress was also measured at 0 and 4 MTOs to determine the effect the higher levels of Bismuth would have on the bath. The values were measured to be 1500 PSI compressive in both cases. Further testing was also performed to determine proper adhesion. In this case, the deposit at 0 and 4 MTOs were subjected to the Quench Test (the rapid heating then cooling of the deposit), bend test (the deposit was bent to 90° and examined to look for poor adhesion for deposit to substrate), and the Scribe test (In which the deposit's surface is marred and then examined for cracks due to stress). The proposed chemistry passed all the tests.
  • the duplex coated substrate with the sulfur-free electroless nickel top coating prepared by process described above was further studied by subjecting the duplex coating to a copper immersion process for bare steel surfaces.
  • the duplex coated steel substrate described above was immersed in an electroless copper bath having the following formulation.
  • FIG. 6 An example of the deposit so formed is illustrated in Fig. 6 . Testing showed than an intermediate step is need to reactivate the surface before exposure to the electroless copper plating bath.

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Claims (11)

  1. Procédé de formation d'un revêtement métallique autocatalytique multicouche sur un substrat, le procédé comprenant :
    i. la mise en contact du substrat avec un premier bain de placage au nickel autocatalytique pour former un premier revêtement de nickel autocatalytique sur le substrat, le premier revêtement de nickel autocatalytique présentant une teneur en phosphore de 7 % à 13 % en poids ;
    ii. la mise en contact du substrat revêtu du premier revêtement autocatalytique avec un deuxième bain de placage aqueux au nickel autocatalytique pour former un deuxième revêtement de nickel autocatalytique au-dessus du premier revêtement autocatalytique, le deuxième revêtement autocatalytique présentant une teneur en phosphore de 8 % à 11 %, le deuxième bain contenant du nickel, un agent réducteur hypophosphoreux, 40 ppm à 100 ppm de zinc, au moins l'un parmi un agent complexant, un agent chélatant, et/ou un tampon de pH, et 5 ppm à 30 ppm d'un stabilisant au bismuth, lequel bain étant exempt de composé soufré organique ;
    iii. la gravure du deuxième revêtement de nickel autocatalytique avec un agent de gravure pour que le substrat revêtu soit doté d'une surface noire, ou la mise en contact du substrat revêtu des premier et deuxième revêtements de nickel autocatalytiques avec un bain de placage au cuivre autocatalytique pour former une couche de finition en cuivre.
  2. Procédé selon la revendication 1, dans lequel l'agent réducteur hypophosphoreux est choisi dans l'ensemble constitué par l'hypophosphite de sodium, l'hypophosphite de potassium, l'hypophosphite d'ammonium, et leurs combinaisons.
  3. Procédé selon la revendication 1, dans lequel le deuxième bain de placage au nickel autocatalytique contient au moins un tampon de pH, un agent complexant ou un agent chélatant qui est choisi dans l'ensemble constitué par l'acide acétique, l'acide formique, l'acide succinique, l'acide malonique, un sel d'ammonium, l'acide lactique, l'acide malique, l'acide citrique, la glycine, l'alanine, l'acide glycolique, la lysine, l'acide aspartique, l'acide éthylènediaminetétraacétique (EDTA), et leurs combinaisons.
  4. Procédé selon la revendication 3, comprenant au moins deux parmi un tampon de pH, un agent complexant, et/ou un agent chélatant.
  5. Procédé selon la revendication 1, dans lequel le nickel est fourni dans le deuxième bain de plage autocatalytique sous la forme d'un sel de nickel soluble dans l'eau.
  6. Procédé selon la revendication 5, dans lequel le sel de nickel est choisi dans l'ensemble constitué par le chlorure de nickel, le bromure de nickel, l'iodure de nickel, l'acétate de nickel, le malate de nickel, et l'hypophosphite de nickel.
  7. Procédé selon la revendication 1, dans lequel le pH du deuxième bain de placage au nickel autocatalytique est maintenu à une valeur de 4,5 à 5,0 et la température est maintenue à une valeur de 79°C à 93°C.
  8. Procédé selon la revendication 1, dans lequel le deuxième bain de placage au nickel autocatalytique comprend 2 g/l à 10 g/l de nickel, 20 g/l à 35 g/l de l'agent réducteur hypophosphoreux, 1 g/l à 75 g/l de chacun parmi l'agent complexant, l'agent chélatant, et/ou le tampon de pH.
  9. Procédé selon la revendication 1, dans lequel le deuxième bain de placage au nickel autocatalytique comprend de l'acide lactique, de l'acide acétique, de l'acide malique, de l'acide succinique, de l'hypophosphite de sodium, de l'hydroxyde d'ammonium, du nickel, du zinc, et de l'acide éthylènediaminetétraacétique.
  10. Procédé selon la revendication 1, dans lequel l'agent de gravure comprend un agent noircisseur au fer et un acide, de préférence l'agent de gravure comprend du sulfate ferrique et de l'acide chlorhydrique.
  11. Procédé selon la revendication 1, comprenant la mise en contact du substrat revêtu des premier et deuxième revêtements de nickel autocatalytiques avec une solution acide avant la mise en contact du substrat avec le bain de placage au cuivre autocatalytique.
EP13820572.9A 2012-07-17 2013-07-17 Revêtements autocatalytiques de nickel et compositions et procédés de formation desdits revêtements Active EP2875168B1 (fr)

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US10577692B2 (en) * 2017-01-05 2020-03-03 International Business Machines Corporation Pretreatment of iron-based substrates for electroless plating
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EP3617350A1 (fr) 2018-08-31 2020-03-04 Tubacex Upstream Technologies, S.A. Procédé de revêtement d'une pièce métallique destinée à être soumise à de hautes pressions de contact et pièce métallique obtenue à partir de celui-ci
US11054199B2 (en) 2019-04-12 2021-07-06 Rheem Manufacturing Company Applying coatings to the interior surfaces of heat exchangers
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CN117191723A (zh) * 2023-08-25 2023-12-08 攀西钒钛检验检测院 过磷酸钙中有效硫的提取及定量检测方法

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CA2879315C (fr) 2019-09-10
BR112015001113B1 (pt) 2021-05-18
CA2879315A1 (fr) 2014-01-23
US20150159277A1 (en) 2015-06-11
EP2875168A2 (fr) 2015-05-27
ES2663684T3 (es) 2018-04-16
BR112015001113A2 (pt) 2017-06-27
EP2875168A4 (fr) 2016-04-06
US20220145469A1 (en) 2022-05-12
WO2014015063A2 (fr) 2014-01-23
MX363621B (es) 2019-03-28
MX2015000850A (es) 2015-08-20

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