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EP4061981A1 - Bains de placage d'alliage de nickel autocatalytique, procédé de dépôt d'alliages de nickel, dépôts d'alliages de nickel et utilisations desdits dépôts d'alliages de nickel formés - Google Patents

Bains de placage d'alliage de nickel autocatalytique, procédé de dépôt d'alliages de nickel, dépôts d'alliages de nickel et utilisations desdits dépôts d'alliages de nickel formés

Info

Publication number
EP4061981A1
EP4061981A1 EP20807048.2A EP20807048A EP4061981A1 EP 4061981 A1 EP4061981 A1 EP 4061981A1 EP 20807048 A EP20807048 A EP 20807048A EP 4061981 A1 EP4061981 A1 EP 4061981A1
Authority
EP
European Patent Office
Prior art keywords
nickel alloy
acid
ions
plating bath
salts
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.)
Pending
Application number
EP20807048.2A
Other languages
German (de)
English (en)
Inventor
Sebastian Lang
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.)
Atotech Deutschland GmbH and Co KG
Original Assignee
Atotech Deutschland GmbH and Co KG
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 Atotech Deutschland GmbH and Co KG filed Critical Atotech Deutschland GmbH and Co KG
Publication of EP4061981A1 publication Critical patent/EP4061981A1/fr
Pending legal-status Critical Current

Links

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
    • C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites

Definitions

  • Electroless Nickel Alloy Plating Baths a Method for Deposition of Nickel Alloys
  • the present invention concerns electroless nickel alloy plating baths, a method for deposition of nickel alloys, nickel alloy deposits and uses of such nickel alloy deposits.
  • the nickel coatings obtained by the invention show a high uniformity and a high hardness, good wear resistance and an improved corrosion resistance. Such coatings are suitable as a functional coating in aerospace, automobile, electrical and chemical industries.
  • the metal layers deposited from such plating baths are also useful as barrier and cap layers in semiconducting devices, printed circuit boards, IC substrates and the like.
  • Electroless nickel plating deposits a nickel alloy onto a substrate that is capable of catalyzing the deposition of the alloy from a process solution containing nickel ions and a suitable chemical reducing agent capable of reducing nickel ions in solution to metallic nickel.
  • Various additives are also used in the electroless nickel plating bath to stabilize the bath and further control the rate of nickel deposition on the substrate being plated.
  • Reducing agents include, for example, borohydride (which produces a nickel boron alloy) and hypophosphite ions (which produces a nickel phosphorus alloy).
  • electroless nickel does not require rectifiers, electrical current or anodes.
  • the deposition process is autocatalytic, meaning that once a primary layer of nickel has formed on the substrate, that layer and each subsequent layer becomes the catalyst that causes the plating reaction to continue.
  • the nickel deposit comprises an alloy of nickel and phosphorus with a phosphorus content of from about 2% to more than 12%. These alloys have unique properties in terms of corrosion resistance and (after heat treatment) hardness and wear resistance.
  • compositions for electroless nickel plating solutions are known in the art.
  • US Patent 2,658,841 teaches the use of soluble organic acid salts as buffers for electroless nickel plating solutions.
  • US Patent 2,658,842 teaches the use of short chain, dicarboxylic acids as exaltants to EN baths.
  • US Patent 2,762,723 teaches the use of sulfide and sulfur bearing additives to an electroless nickel plating bath for improved bath stability.
  • US Patent 2,847,327 has introduced other means of stabilizing an electroless nickel plating solution. These include the use of higher purity starting materials; more effective stabilizers from the class of heavy metals such as Pb, Sb, Bi, Cu and Se; inorganic compounds such as iodates, and thio compounds; organic compounds such as unsaturated alkenes and alkynes and others.
  • WO 2015/187402 discloses electroless nickel alloy plating baths comprising one or more dicarboxylic acids and one or more alpha hydroxyl carboxylic acid.
  • WO2018/220220 discloses electroless nickel alloy plating baths for the preparation of data storage devices, wherein all complexing agents comprise at least two carboxylic acid moieties.
  • CN1 09112509A discloses a high corrosion resistance of a chemical nickel plating solution and its preparation method.
  • Such chemical nickel plating solution comprise nickel sulfate, sodium hypophosphite, sodium citrate, lactic acid, propionic acid, and acetic acid as well as particular wetting agents and stabilizers.
  • the electroless nickel alloy plating bath according to the invention its use, the method for depositing a nickel alloy on at least one surface of a sub strate and the nickel alloy deposits obtained from the electroless nickel alloy plating bath ac- cording to the invention and their use.
  • the electroless nickel alloy plating bath according to the invention comprises a) nickel ions; b) further reducible metal ions selected from the group consisting of molybdenum ions, rhenium ions, tungsten ions, copper ions, oxo-ions thereof, and mixtures thereof; c) at least one reducing agent suitable to reduce the nickel ions and the further reducible metal ions to their respective metallic state; preferably selected from the group con sisting of hypophosphorous acid, hypophosphite salts and mixtures of the aforemen tioned; and d) complexing agents CA1 , CA2, CA3, and, optionally (preferably not optionally but ra ther compulsively, mandatory, necessarily; i.e.
  • CA4 wherein CA1 , CA2, CA3, and CA4 are all different from each other; wherein each of CA1 and CA2 is independently selected from the group consisting of compounds having at least two carboxylic acid moieties, the respective salts thereof as well as mixtures of the aforementioned; wherein CA3 is selected from the group consisting of aliphatic compounds having exactly one carboxylic acid moiety, the respective salts thereof as well as mixtures of the aforementioned; and wherein CA4 is selected from the group consisting of aromatic compounds having at least one carboxylic acid moiety, the respective salts thereof as well as mixtures of the aforementioned.
  • the two complexing agents CA1 and CA2 are different compounds having at least two carbox ylic acid moieties, the respective salts thereof as well as mixtures of the aforementioned.
  • the electroless nickel alloy plating bath according to the invention is used to deposit a nickel alloy onto at least one surface of at least one substrate.
  • a method for depositing a nickel alloy on at least one surface of a substrate comprising in this order the following method steps
  • an electroless nickel alloy plating bath according to the present invention preferably a plating bath as described as being preferred throughout the present text
  • a nickel alloy deposit is obtainable by deposition from an electroless nickel alloy plating bath according to the present invention (preferably a plating bath as described as being preferred throughout the present text).
  • the electroless nickel alloy plating bath according to the invention and the methods of the present invention are suitable to provide nickel alloy deposits having an attractive bright or semi- bright appearance. Further, the nickel alloy deposits adhere well to the underlying substrate surface.
  • the electroless nickel alloy plating bath according to the invention is stable and does not show plate-out during plating for a sufficient period of time to be used economically.
  • CX-CY-compound refers to compounds having X to Y carbon atoms (including the carbon atoms of any carboxylic acid moieties); wherein X and Y refer to natural numbers, and X is smaller than Y.
  • Nickel alloys of the present invention comprise the elements nickel and one or more of molybdenum, tungsten, copper, and rhenium, preferably in combination with phosphorus and/or boron, more preferably with phosphorus. Even more preferred alloys comprise nickel, molybdenum and phosphorus. Most preferred alloys comprise nickel, molybdenum, copper, and phosphorus as they provide an improved corrosion protection of metallic substrates.
  • the concentration of the nickel ions in the electroless nickel alloy plating bath may vary widely and preferably ranges from 0.01 mol/L to 1.0 mol/L, more preferably from 0.03 mol/L to 0.8 mol/L, even more preferably from 0.04 mol/L to 0.5 mol/L, yet even more preferably from 0.05 mol/L to 0.3 mol/L, most preferably from 0.05 mol/L to 0.1 mol/L.
  • the inventive electroless nickel alloy plating bath comprises further reducible metal ions (other than nickel ions).
  • the further reducible metal ions are selected from the group consisting of molybdenum ions, rhenium ions, tungsten ions, copper ions, and mixtures thereof.
  • the further reducible metal ions can be provided by any water-soluble salt or any water-soluble complex of such further reducible metals.
  • molybdenum ions are provided by any one of molybdic acid, alkaline molybdate (e.g. NaaMoC ), ammonium molybdate, and mixtures thereof.
  • tungsten ions are provided by any one of tungstic acid, alkaline tungstate (e.g.
  • rhenium ions are provided by any one of perrhenic acid, alkaline perrhenate (e.g. NaReC ), ammonium perrhenate, and mixtures thereof.
  • copper ions are provided by any one of copper iodide, copper iodate, copper chloride and/or copper sulfate.
  • Molybdenum ions are preferred as ecologically uncritical stabi lizer and alloying component. Copper ions are preferred because they improve leveling and brightness and enhance process stability and corrosion resistance of the deposit.
  • the inventive electroless nickel alloy plating bath preferably comprises only molybdenum ions as the further reducible metal ions.
  • the inventive electroless nickel alloy plating bath preferably comprises a mixture of molybdenum ions and copper ions as the further reducible metal ions. More preferably, the inventive electroless nickel alloy plating bath does neither comprise any tungsten ions nor any rhenium ions, most preferably if copper ions and/or molybdenum ions are present.
  • an electroless nickel alloy plating bath of the present invention wherein the further reducible metal ions are molybdenum ions, copper ions, or a mixture thereof; preferably, the further reducible metal ions are molybdenum ions or a mixture of molybdenum ions and copper ions.
  • Insoluble components of molybdenum, rhenium and tungsten are detrimental to the nickel alloy deposit properties and are thus preferably not used in the electroless nickel alloy plating bath according to the invention.
  • the total concentration of the further reducible metal ions in the electroless nickel alloy plating bath may vary and preferably ranges from 5 * 1 O 5 to 1 * 1 O 2 mol/L, based on the total volume of the electroless nickel alloy plating bath, more preferably from 1 * 1 O 4 to 5 * 1 O 3 mol/L, and even more preferably from 2.5 * 1 O 4 to 2.5 * 1 O 3 mol/L. If more than one type of further reducible metal ions is contained in the electroless nickel alloy plating bath, the overall concentration of all further reducible metal ions used is preferably in above-defined ranges (i.e. the total concentrations thereof).
  • the total concentration of molybdenum ions and copper ions in the electroless nickel alloy plating bath may vary and preferably ranges from 1 * 1 O 5 (preferably from 5 * 1 O 5 ) to 1 * 1 O 2 mol/L, based on the total volume of the electroless nickel alloy plating bath, more preferably from 1 * 1 O 5 (preferably from 5 * 1 O 5 ) to 5 * 1 O 3 mol/L, and even more preferably from 1 * 1 O 5 (preferably from 5 * 1 O 5 ) to 5 * 1 O 4 mol/L.
  • the inventive electroless nickel alloy plating bath comprises more molybdenum ions than copper ions, based on a molar concentration. More preferred, the total concentration of molybdenum ions and copper ions in the electroless nickel alloy plating bath may vary and preferably ranges from 1 * 1 O 5 (preferably from 5 * 1 O 5 ) to 1 * 1 O 2 mol/L, based on the total volume of the electroless nickel alloy plating bath, more preferably from 1 * 1 O 5 (preferably from 5 * 1 O 5 ) to 5 * 1 O 3 mol/L, and even more preferably from 1 * 1 O 5 (preferably from 5 * 1 O 5 ) to 5 * 1 O 4 mol/L, and the molar ratio of molybdenum ions to copper ions is in the range of from 1 :1 to 30:1 , preferably from 5:1 to 20:1 , more preferably from 10:1 to 15:1.
  • the electroless nickel alloy plating bath of the present invention further comprises at least one reducing agent.
  • the at least one reducing agent is preferably a chemical reducing agent.
  • the at least one reducing agent is suitable to reduce the nickel ions and the further reducible metal ions to their respective metallic state.
  • the at least one reducing agent is selected from the group consisting of
  • hypophosphite compounds such as hypophosphorous acid and hypophosphite salts, such as alkaline hypophosphites, like sodium or potassium hypophosphite, ammonium hypophosphite, nickel hypophosphite and so forth;
  • boron based reducing agents such as aminoboranes, like dimethyl aminoboranes (DMAB) and morpholine borane, and borohydrides, like sodium borohydride;
  • hydrazine derivatives such as hydrazine sulfate, hydrazine hydrochloride, hydrazine hydrate and other such components useable as reducing agent in the context of the present invention.
  • a nickel alloy deposit comprising phosphorus is obtained.
  • Such reducing agents provide the source of phosphorous in the deposited nickel alloy.
  • a borane-based reducing agent leads to a nickel alloy deposit comprising boron and a mixture of hypophosphite compounds and borane-based reducing agents leads to a nickel alloy deposit comprising phosphorus and boron.
  • a nitrogen-based reducing agent such as hydrazine and hydrazine derivatives provide neither phosphorus nor boron to be incorporated into the nickel alloy.
  • the at least one reducing agent is more preferably selected from the group consisting of hypo- phosphorous acid, hypophosphite salts and mixtures of the aforementioned. These reducing agents are preferred as the phosphorus being built into the inventive nickel alloys inter alia improves the magnetic properties of such nickel alloy deposits significantly and gives rise to (heat- resistant) paramagnetic nickel alloys. The incorporation of high phosphorous amounts (e.g. 10 wt.-% or more) also improves the protection against corrosion. Even more preferably, the at least one reducing agent is selected to be a hypophosphite salt for such salts being cost effective and easy to use.
  • the concentration of the at least one reducing agent is generally in molar excess of the amount sufficient to reduce the nickel ions and the further reducible metal ions in the electroless nickel alloy plating bath.
  • the concentration of the reducing agent preferably ranges from 0.01 mol/L to 3.0 mol/L, more preferably from 0.1 mol/L to 1 mol/L.
  • the electroless nickel alloy plating bath comprises (different) complexing agents CA1 and CA2, wherein each of CA1 and CA2 is independently selected from the group consisting of compounds having at least two carboxylic acid moieties, the respective salts thereof (e.g. carbox- ylates) as well as mixtures of the aforementioned.
  • said compounds having at least two carboxylic acid moieties are aliphatic compounds, preferably C2-C12-aliphatic compounds, more preferably C2-C8-aliphatic compounds.
  • Aliphatic compounds include acyclic or cyclic, saturated or unsaturated carbon compounds excluding aromatic compounds; the aliphatic compounds preferably are non-cyclic.
  • Functionalizations may theoretically be obtained by replacing at least one hydrogen by a functional group.
  • the complexing agents CA1 and CA2 are independently selected from the group consisting of unfunctionalized and functionalized aliphatic dicarboxylic acids, unfunctionalized and functionalized aliphatic tricarboxylic acids, unfunctionalized and functionalized aliphatic tetracarboxylic acids, the respective salts thereof as well as mixtures of the aforementioned.
  • the complexing agent CA1 is an unfunctionalized aliphatic C2-C12-dicarboxylic acid and/or salts thereof. Even more preferably, it is an unfunctionalized aliphatic C3-C6-dicarboxylic acid and/or salts thereof. Yet even more preferably, the complexing agent CA1 is selected from the group consisting of malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, glutaconic acid, itaconic acid, salts thereof, and mixtures of the aforementioned. Most preferably, the complexing agent CA1 is malonic acid and/or salts thereof.
  • the complexing agent CA2 is a functionalized or unfunctionalized (preferably functionalized) aliphatic C3-C12-dicarboxylic acid and/or salts thereof, preferably a functionalized or unfunctionalized (preferably functionalized) aliphatic C4-C6-dicarboxylic acid and/or salts thereof. More preferably, the complexing agent CA2 comprises at least one hydroxy group (and is thus hydroxy-functionalized). Even more preferably, the complexing agent CA2 is a hydroxy- functionalized aliphatic C4-C6-dicarboxylic acid and/or salts thereof.
  • the complexing agent CA2 is selected from the group consisting of malic acid, tartaric acid, 1- hydroxyglutaric acid, 2-hydroxyglutaric acid, 1-hydroxyadipic acid, 2-hydroxyadipic acid, 3-hy- droxyadipic acid, salts thereof, and mixtures of the aforementioned. Most preferably, the complexing agent CA2 is malic acid and/or salts thereof.
  • the complexing agent CA4 is a functionalized (in some cases preferred) or unfunctionalized (in some cases preferred) aromatic carboxylic acid and/or salts thereof.
  • a preferred functionalization is a hydroxyl-functionalization.
  • “Aromatic carboxylic acids” are compounds that comprise both at least one COOH group (and its related salts) and at least one aromatic ring. The aromatic ring might comprise heteroatoms, preferably the aromatic ring does not contain heteroatoms.
  • at least one COOH group is directly bonded to an aromatic ring such as in e.g. benzoic acid, salicylic acid. More preferably, CA4 is benzoic acid and/or salts thereof. Even more preferably CA4 is sodium benzoate.
  • the complexing agents CA1 , CA2, CA3 and C4 are separately selected from each other, representing each a different complexing agent according to the aforementioned preferred embodiments regarding CA1 , CA2, and CA3.
  • complexing agent CA1 is selected from the group consisting of malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, glutaconic acid, itaconic acid, salts thereof, and mixtures of the aforementioned (particularly, the complexing agent CA1 is malonic acid and/or salts thereof);
  • complexing agent CA2 is selected from the group consisting of malic acid, tartaric acid, 1-hydroxyglutaric acid, 2-hydroxyglutaric acid, 1-hydroxyadipic acid, 2-hy- droxyadipic acid, 3-hydroxyadipic acid, salts thereof, and mixtures of the aforementioned (particularly, the complexing agent CA2 is malic acid and/or salts thereof); and complexing agent CA3 is selected from the group consisting of aliphatic monocarboxylic acids, salts thereof, and mixtures of the aforementioned.
  • the aforementioned is combined with complexing agent CA4
  • the concentration of the complexing agent CA1 ranges from 50 to 300 mmol/L, more preferably from 50 to 250 mmol/L, and even more preferably from 50 to 200 mmol/L.
  • the concentration of the complexing agent CA2 ranges from 50 to 200 mmol/L, more preferably from 60 to 180 mmol/L, and even more preferably from 70 to 150 mmol/L.
  • the concentration of the complexing agent CA3 ranges from 40 to 1000 mmol/L, more preferably from 40 to 800 mmol/L, and even more preferably from 40 to 300 mmol/L.
  • the concentration of the complexing agent CA4 ranges from 0 (preferably more than 0) to 200 mmol/L, more preferably from 7 to 150 mmol/L, even more preferably from 15 to 75 mmol/L, and yet even more preferably from 30 to 75 mmol/L.
  • the total concentration of the complexing agents CA1 , CA2, CA3 and CA4 is at least 0.15 mol/L, more preferably at least 0.20 mol/L, and even more preferably at least 0.22 mol/L.
  • the ratio of the total molar concentration of complexing agents CA1 , CA2, CA3 and, optionally, CA4 (most preferably of CA1 , CA2, CA3, and CA4 all together) to the molar concentration of nickel ions ranges from 4/1 to 8/1.
  • the electroless nickel alloy plating bath according to the invention preferably is an aqueous solution.
  • aqueous solution means that the prevailing liquid medium, which is the solvent in the solution, is water. Further liquids, that are miscible with water, as for example alcohols and other polar organic liquids, that are miscible with water, may be added. It is preferred that at least 95 wt.-%, more preferably 99 wt.-%, of all solvents used is water because of its ecologically benign character.
  • the electroless nickel alloy plating bath according to the invention is preferably prepared by dissolving all components in aqueous liquid medium, preferably in water.
  • the electroless nickel alloy plating bath according to the invention may be acidic, neutral or alkaline.
  • An acidic or an alkaline pH adjustor such as a (mineral) acid ora base may be selected from a wide range of materials such as ammonia, ammonium hydroxide, sodium hydroxide, hydrochloric acid, sulfuric acid and the like.
  • the pH of the electroless nickel alloy plating bath according to the invention is preferably from about 2 to 12.
  • the electroless nickel alloy plating bath according to the invention has preferably a neutral or acidic pH value (referred to hereinafter as “acidic electroless nickel alloy plating bath”).
  • the acidic electroless nickel alloy plating bath according to the invention has a pH value ranging from 3.5 to 7, even more preferably from 3.5 to 5.0, yet even more preferably from 4.0 to 4.8, most preferably from 4.2 to 4.7. This allows high stability of said bath and optimal results in terms of paramagnetic properties (including their maintenance at elevated temperatures) of the nickel alloy deposits formed from such bath. If tungsten ions are selected as the sole further reducible metal ions, it is preferred that the pH ranges from 8 to 10.
  • additives may be preferably included in the electroless nickel alloy plating bath according to the invention such as pH buffers, wetting agents, accelerators, brighteners, additional stabilizing agents which are known in the art, plating rate modifiers such as those disclosed in European patent application EP 3 034650 A1.
  • inventive electroless nickel alloy plating bath is free of thiourea which is conventionally used as stabilizing agent for electroless nickel plating baths because of its toxicity and ecological concerns.
  • step A) of the method according to the present invention the substrate comprising the at least one surface is provided.
  • substrates can be nickel alloy plated with the electroless nickel alloy plating bath according to the present invention and the method according to the present invention.
  • metallic substrates are used in the method according to the present invention.
  • the metallic substrates to be nickel alloy plated are preferably selected from the group consisting of copper, zinc, silver, palladium, iron, iridium, tin, aluminum, nickel, alloys thereof, and mixtures of the aforementioned.
  • the substrate provided in step A) is made entirely of metal (preferably of at least one of the aforementioned preferred metals) or it preferably comprises at least one surface made of metal, preferably at least one of the aforementioned preferred metals.
  • Such a surface made of metal may also be one or more palladium activation layers typically employed to render electrically non-conductive surfaces such as glass, plastic or ceramics receptive for nickel alloy plating.
  • the substrate is optionally pretreated prior to step B).
  • pretreatments are known in the art. Typical pretreatments include etching, cleaning, zincation and activation steps. Useful pretreatments may improve the plating result by removing undesired dirt or oxides from the surface of the substrate.
  • Activation of a surface is usually understood as deposition of a thin and possibly discontinuous layer of for example palladium on an otherwise electrically non-conductive surface to render said surface suitable for subsequent metal plating, preferably nickel alloy plating.
  • Pretreatments may vary widely depending on the substrate provided. Some guidance can ex- emplarily be found in WO 2015/161959 A1 (page 13, line 11 to page 15, line 30).
  • step B) of the method according to the present invention the at least one surface of the substrate is contacted with the electroless nickel alloy plating bath according to the present invention.
  • the substrate to be nickel alloy plated may be plated to the desired thickness and deposit quantity by contacting the substrate with the electroless nickel alloy plating bath according to the invention.
  • the inventive electroless nickel alloy plating is preferably maintained over a temperature range from 20°C to 100°C, preferably from 70°C to 95°C, more preferably from 80°C to 90°C, even more preferably from 83°C to 87°C during deposition, i.e. most preferably during step B).
  • the substrate may be contacted with the inventive electroless nickel alloy plating bath for any period of time sufficient to plate the desired thickness of the nickel alloy deposit.
  • the thickness of the nickel alloy deposit depends inter alia on the desired use of said deposit or the product containing said deposit. As a non-limiting example, a contact duration ranging from 30 to 180 min, preferably from 40 to 90 min, and more preferably from 50 to 70 min is often considered sufficient.
  • a thickness of the nickel alloy deposit of up to 100 pm, or higher may be formed.
  • the thickness of the nickel alloy deposits varies, preferably ranging from 1 to 60 pm. The thickness depends on the technical application and can be higher or lower for some applications. For example, if the nickel alloy deposit is to provide a corrosion resistant coating, a thickness ranging from 30 to 60 pm is typically desired, while for electronic applications a thickness of ranging from 1 to 15 pm is preferably applied.
  • the thickness of the nickel alloy deposit preferably ranges from 5 to 20 pm, more preferably from 7 to 16 pm.
  • the thickness of the nickel or nickel-phosphorus deposits preferably ranges from 1 to 5 pm.
  • Thicknesses of nickel alloy deposits may be measured with x-ray fluorescence (XRF) which is known in the art.
  • XRF x-ray fluorescence
  • Various means of contacting the substrate with the inventive electroless nickel alloy plating bath are known in the art.
  • the substrate can be entirely or partially immersed (which is preferred) into the inventive electroless nickel alloy plating bath, the inventive electroless nickel alloy plating bath can be sprayed or wiped thereon.
  • the inventive electroless nickel alloy plating bath is agitated before and/or during plating. Agitation may be accomplished for example by mechanical movement of the inventive electroless nickel alloy plating bath like shaking, stirring or continuously pumping of the liquids or intrinsically by ultrasonic treatment, by elevated temperatures or by gas feeds (such as purging the aqueous plating bath with an inert gas or air).
  • the plating rate is preferably at least 2.5 pm/h. This allows a sufficiently economic processes. More preferably, the plating rate in combination with the present invention ranges from 8.0 to 12.0 pm/h. Such plating rates allow not only for sufficiently economic processes while improving the desired paramagnetic properties to be maintained at elevated temperatures, but further improves the plating speed without sacrificing quality during plating.
  • the method according to the present invention optionally comprises rinsing steps, preferably with water, and/or drying steps.
  • rinsing steps preferably with water, and/or drying steps.
  • the inventive electroless nickel alloy plating bath of the present invention can be used to deposit a nickel alloy on a surface of a substrate.
  • the present invention further concerns a nickel alloy deposit obtainable by deposition from the electroless nickel alloy plating bath according to the present invention.
  • a nickel alloy deposit obtainable by deposition from the electroless nickel alloy plating bath according to the present invention.
  • the nickel alloy deposits formed from the electroless nickel alloy plating bath according to the present invention show superior corrosion resistance.
  • the content of phosphorus and/or boron (more preferably of phosphorus alone) in the nickel alloy deposit is 10 wt.-% or more, more preferably is ranging from 10.0 to 16.0 wt.-%, preferably from 10.5 to 15.0 wt.-% and more preferably from 11.0 to 14.5 wt.-%.
  • Other preferred ranges are from 10 wt.-% to 15 wt.-%, more preferably from 10.5 wt.-% to 13 wt.-%, most pref erably from 10.8 wt.-% to 12.5 wt.-%.
  • the remainder in the nickel alloy deposit which is neither further reducible metal nor phosphorus and/or boron is usually mainly nickel (usually > 98 wt.-%, preferably > 99 wt.-%, more preferably > 99.9 wt.-% of said remainder) disregarding trace impurities commonly present in technical raw materials and co-deposited other materials such as those derived from e.g. organic impurities and stabilizing agents.
  • the nickel alloy deposits according to the present inven tion consist of nickel, molybdenum and phosphorus or (essentially) consist of nickel, molybdenum, copper and phosphorus (disregarding trace impurities commonly present in technical raw materials and involuntarily co-deposited other materials such as those derived from e.g. organic impurities and optional stabilizing agents).
  • the present invention further relates to the use of a nickel alloy deposit obtainable by deposition from the electroless nickel alloy plating bath according to the present invention and the method of the present invention.
  • a nickel alloy deposit is preferably used to protect a work piece against ambient acidic corrosive conditions.
  • ‘Ambient’ means that the environment of the work piece is such that the work piece might experience acidic corrosive conditions, most preferably under outdoor, natural conditions.
  • UniClean® 155 (soak cleaner) and Nonacid® 701 (electrocleaner) are products of Atotech GmbH.
  • Determination of thickness of the metal or metal alloy deposits and plating rate Phosphorus content and deposit thickness were measured at 5 points of each substrate by XRF using the XRF instrument Fischerscope XDV-SDD (Helmut Fischer GmbH, Germany). By as suming a layered structure of the deposit, the layer thickness can be calculated from such XRF data. The plating rate was calculated by dividing the obtained layer thickness by the time nec- essary to obtain said layer thickness. pH value measurement pH values were measured with a pH meter (WTW, Typ pH 3110, electrode: SenTix®41 , gel electrode with temperature sensor, reference electrolyte: 3 mol/l KCI) at 25°C. The measure ment was continued until the pH value became constant, but in any case at least for 2 min. The pH meter was calibrated with buffer solution standards for pH values at 2, 4, and 7 supplied by Fluka and Certipur prior to use.
  • nickel alloy plating baths inventive and for comparison reasons, were prepared (each 1 L) containing the following components: nickel ions 6 g/L (102.2 mmol/L, provided as nickel sulfate), sodium hypophosphite 33 g/L (0.375 mol/L), - molybdenum ions 24 mg/L (2.50 * 1 O 4 mol/L, provided as sodium molybdate), copper ions 2.0 mg/L (3, 15 * 10 -5 mol/L, provided as copper(ll) sulfate penta hydrate), complexing agents in varying concentrations (in g/L) as given in Table 1 , pH adjusted to 4.6 with ammonia solution (25 wt.-% in water)
  • the temperature of the nickel alloy plating baths was set to 86 °C and substrates were immersed into the baths for 60 min. 15 able 1: Examples 1-16.
  • Example 14 was selected as a representative for the present invention.
  • Corrosion test 1 is performed according to the standard AASS - DIN EN ISO 9227.
  • the area of defects as red rust is determined and compared to the total area (“relative area of defects”) and rated according to the following scheme:
  • Rating 10 is assigned if no defects are detectable, i.e. 0 % relative area of defects. Accordingly, the following ratings are assigned (corresponding relative area of defects in brackets): 9 (> 0% - 0,1 %); 8 (> 0.1 % - 0.25 %); 7 (> 0.25 % - 0.5 %); 6 (> 0.5 % - 1.0 %); 5 (> 1 .0 % - 2.5 %), 4 (> 2.5 % - 5.0 %); 3 (> 5.0 % - 10 %), 2 (> 10 % - 25 %); 1 (> 25 % - 50 %); 0 (> 50 %).
  • Example 14 shows a significantly improved corrosion resistance compared to Example 12 (comparative).
  • Example 12 no aromatic car- boxylic acid is utilized.
  • an aromatic carboxylic acid clearly has a beneficial effect on corrosion resistance.
  • Example 17 is based on the general formulation as outlined above but without utilizing copper and molybdenum ions. Furthermore, Example 17 contains three carboxylic acids corresponding to CA1 , CA2, and CA3, but without an aromatic carboxylic acid (i.e. without CA4).
  • Corrosion test 2 is also performed according to the standard AASS - DIN EN ISO 9227. Table 3: Corrosion test 2 - time (in hours) until >1% red rust on surface is determined
  • Table 3 shows that also for Corrosion test 2 a significant improvement of corrosion resistance is observed. Further experiments indicate that the improved effect is attributed to the presence of CA4 (data not shown) Intrinsic Stress test
  • Stress in the coating is measured by using a stress strip with two fingers, which are lacquered on one side.
  • the test strips are made from chemically etched beryllium-copper alloy and have spring like properties.
  • the plating rate of the bath is determined with ⁇ 10% precision to determine the plating time for the stress measurement.
  • the stress strip fingers are electrically contacted to the test panel and both are immersed very carefully in the process bath.
  • Plating duration is calculated to yield a coating thickness of 10 pm, based on the known plating rate.
  • the test strip will be rinsed with Dl-waterand dried carefully using paper tissue. Since stress strips fingers are mechanically fragile and tend to deform very quickly, they need to be evaluated immediately.
  • Intrinsic stress tests were performed over bath life by linking stress values to the concentration of orthophosphite (in the following abbreviated as OP).
  • OP is a suitable indicator representing bath age because orthophosphite is the reaction product of hypophosphite oxidation and accumulating over time.
  • Table 4 Intrinsic Stress
  • Table 4 shows that on long-term bath utilization the presence of an aro- matic carboxylic acid improves the compressive stress situation. This means that the presence of an aromatic carboxylic acid creates an improved tolerance over increasing concentrations of OP and thereby maintaining the internal stress closer to an optimal level (see Example 14: “20” vs. Example 17: “92”). Thus, a more optimal compressive stress level is maintained up to higher bath age as shown for Example 14, in particular if OP reaches a concentration above 100 g/L.
  • Beaker Stability test was carried out as described below: This method is a plating test for determination of chemical stability of an electroless nickel process bath. It applies to autocatalytic deposition of nickel phosphorous coatings. First a high shaped 1 liter beaker is cleaned and stripped with a 1 :1 HNO 3 - stripper solution for 1 hour to avoid any residues on the bottom and walls on the beaker that might affect the test negatively. Afterwards 1 liter of EN bath solution (test solution) is taken and processed therein as described hereinafter. A stirrer is utilized and set to 250 rpm. The test starts when operation temperature is reached. First the EN test solution is kept for one hour without plating.
  • the beaker is checked for any nickel deposition on the bottom and walls of the beaker. If nothing is visible the beaker test can be continued and one pretreated 1 dm 2 mild steel panel is plated in the EN bath solution. The panel has to be plated for one hour without any replenishment. When this is finished one cycle is achieved. Thus, one cycle corresponds to one hour without plating + one hour with plating. Replenishment is done after the plating period. If no sedimentation or nickel deposition on the bottom or walls of the beaker occurred the test can be continued with one hour without plating and one hour with plating for the next cycle. The beaker test is finished when wild plating or plating out is visible at the bottom or walls of the beaker. The number of achieved cycles is noted. With the number of achieved cycles the evaluation of the stability is possible.

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  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

La présente invention concerne un bain de placage d'alliage de nickel autocatalytique comprenant des ions nickel ; d'autres ions métalliques réductibles choisis dans le groupe constitué par des ions molybdène, des ions rhénium, des ions tungstène, des ions cuivre, des ions oxo de ceux-ci, et des mélanges de ceux-ci ; au moins un agent réducteur approprié pour réduire les ions nickel et les autres ions métalliques réductibles à leur état métallique respectif ; des agents complexants CA1, CA2, CA3, et CA4, où CA1, CA2, CA3, et CA4 sont tous différents les uns des autres, CA1 et CA2 étant chacun choisis indépendamment dans le groupe constitué par les composés ayant au moins deux fractions d'acide carboxylique, leurs sels respectifs ainsi que des mélanges de ceux-ci ; où CA3 est choisi dans le groupe constitué par des composés aliphatiques ayant exactement une fraction d'acide carboxylique, leurs sels respectifs ainsi que des mélanges de ceux-ci ; et où CA4 est choisi dans le groupe constitué de composés aromatiques ayant au moins une fraction d'acide carboxylique, leurs sels respectifs ainsi que des mélanges de ceux-ci.
EP20807048.2A 2019-11-20 2020-11-19 Bains de placage d'alliage de nickel autocatalytique, procédé de dépôt d'alliages de nickel, dépôts d'alliages de nickel et utilisations desdits dépôts d'alliages de nickel formés Pending EP4061981A1 (fr)

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EP19210301 2019-11-20
PCT/EP2020/082699 WO2021099475A1 (fr) 2019-11-20 2020-11-19 Bains de placage d'alliage de nickel autocatalytique, procédé de dépôt d'alliages de nickel, dépôts d'alliages de nickel et utilisations desdits dépôts d'alliages de nickel formés

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CA (1) CA3158576A1 (fr)
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US2658841A (en) 1950-11-08 1953-11-10 Gen Am Transport Process of chemical nickel plating and bath therefor
US2658842A (en) 1951-01-04 1953-11-10 Gen Am Transport Process of chemical nickel plating and bath therefor
US2762723A (en) 1953-06-03 1956-09-11 Gen American Transporation Cor Processes of chemical nickel plating and baths therefor
US2847327A (en) 1954-10-25 1958-08-12 Gen Am Transport Processes of chemical nickel plating and baths therefor
JP2848103B2 (ja) * 1992-03-19 1999-01-20 上村工業株式会社 磁気記録体
US7410899B2 (en) * 2005-09-20 2008-08-12 Enthone, Inc. Defectivity and process control of electroless deposition in microelectronics applications
EP1978128A2 (fr) * 2007-03-29 2008-10-08 Ebara Corporation Bain de placage anélectrolytique et procédé de production d'élément d'appareil haute température utilisant le bain
CN103352213B (zh) * 2013-06-18 2016-08-10 宝鸡多元合金科技有限公司 环保型高抗硫化氢和高耐磨Ni-P-W-Mo四元合金镀液及其配制方法
CN106232869B (zh) 2014-04-24 2019-01-25 埃托特克德国有限公司 铁硼合金涂层及其制备方法
US11685999B2 (en) 2014-06-02 2023-06-27 Macdermid Acumen, Inc. Aqueous electroless nickel plating bath and method of using the same
ES2639300T3 (es) 2014-12-16 2017-10-26 Atotech Deutschland Gmbh Composiciones de baño de chapado para el chapado no electrolítico de metales y aleaciones metálicas
ES2826441T3 (es) 2017-06-02 2021-05-18 Atotech Deutschland Gmbh Baños de metalizado no electrolítico de aleación de níquel, un método de deposición de aleaciones de níquel, depósitos de aleación de níquel y usos de dichos depósitos de aleación de níquel formados
JP6466521B2 (ja) * 2017-06-28 2019-02-06 小島化学薬品株式会社 無電解めっきプロセス
JP6474860B2 (ja) * 2017-06-28 2019-02-27 小島化学薬品株式会社 無電解ニッケルストライクめっき液及びニッケルめっき皮膜の成膜方法
CN109112509A (zh) 2018-10-29 2019-01-01 重庆立道新材料科技有限公司 一种高耐蚀性化学镀镍液及其制备方法
CN113106431B (zh) * 2021-04-27 2023-03-28 深圳市优讯佳电子科技有限公司 一种热辅助磁记录用存储介质及其制备方法

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JP7244709B2 (ja) 2023-03-22
WO2021099475A1 (fr) 2021-05-27
CN114729455A (zh) 2022-07-08
MX2022006118A (es) 2022-06-14
KR20220103131A (ko) 2022-07-21
CN119876927A (zh) 2025-04-25
CA3158576A1 (fr) 2021-05-27
US20220389588A1 (en) 2022-12-08

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