CN114729455A - Electroless nickel alloy plating baths, methods of depositing nickel alloys, nickel alloy deposits and uses of the nickel alloy deposits thus formed - Google Patents

Electroless nickel alloy plating baths, methods of depositing nickel alloys, nickel alloy deposits and uses of the nickel alloy deposits thus formed Download PDF

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CN114729455A
CN114729455A CN202080080727.9A CN202080080727A CN114729455A CN 114729455 A CN114729455 A CN 114729455A CN 202080080727 A CN202080080727 A CN 202080080727A CN 114729455 A CN114729455 A CN 114729455A
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nickel alloy
acid
ions
electroless nickel
alloy plating
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塞巴斯蒂安·兰格
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Germany Aituoteke Co ltd
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    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C18/00Chemical 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
    • C23C18/16Chemical 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
    • C23C18/48Coating with alloys
    • C23C18/50Coating with alloys with alloys based on iron, cobalt or nickel
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C18/00Chemical 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
    • C23C18/16Chemical 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
    • C23C18/31Coating with metals
    • C23C18/32Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C23C18/34Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
    • C23C18/36Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Organic Chemistry (AREA)
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Abstract

本发明涉及无电镍合金镀覆浴,其包含镍离子;另外的可还原的金属离子,其选自由以下组成的群组:钼离子、铼离子、钨离子、铜离子、其含氧离子以及其混合物;至少一种还原剂,其适于将所述镍离子和所述另外的可还原的金属离子还原为其相应的金属态;络合剂CA1、CA2、CA3和CA4,其中CA1、CA2、CA3和CA4均彼此不同,其中CA1和CA2中的每一个独立地选自由以下组成的群组:具有至少两个羧酸部分的化合物、其相应的盐以及上述物质的混合物;其中CA3选自由以下组成的群组:具有正好一个羧酸部分的脂族化合物、其相应的盐以及上述物质的混合物;并且其中CA4选自由以下组成的群组:具有至少一个羧酸部分的芳族化合物、其相应的盐以及上述物质的混合物。The present invention relates to electroless nickel alloy plating baths comprising nickel ions; additional reducible metal ions selected from the group consisting of molybdenum ions, rhenium ions, tungsten ions, copper ions, oxygen-containing ions thereof, and mixtures thereof; at least one reducing agent suitable for reducing said nickel ion and said additional reducible metal ion to its corresponding metal state; complexing agents CA1, CA2, CA3 and 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, corresponding salts thereof, and mixtures thereof; wherein CA3 is selected from The group consisting of: aliphatic compounds having exactly one carboxylic acid moiety, their corresponding salts, and mixtures thereof; and wherein CA4 is selected from the group consisting of: aromatic compounds having at least one carboxylic acid moiety, their The corresponding salts and mixtures of the foregoing.

Description

无电镍合金镀覆浴、沉积镍合金的方法、镍合金沉积物和此些 形成的镍合金沉积物的用途Electroless nickel alloy plating baths, methods of depositing nickel alloys, nickel alloy deposits and uses of the nickel alloy deposits formed therefrom

技术领域technical field

本发明涉及无电镍合金镀覆浴、沉积镍合金的方法、镍合金沉积物和此些镍合金沉积物的用途。通过本发明获得的镍涂层显示出高均匀性和高硬度、良好的耐磨性和改善的耐腐蚀性。此些涂层适合作为航空航天、汽车、电气和化学工业中的功能涂层。由此些镀覆浴沉积的金属层也可用作半导体装置、印刷电路板、IC衬底等中的阻挡层和覆盖层。The present invention relates to electroless nickel alloy plating baths, methods of depositing nickel alloys, nickel alloy deposits and uses of such nickel alloy deposits. The nickel coatings obtained by the present invention show high uniformity and hardness, good wear resistance and improved corrosion resistance. Such coatings are suitable as functional coatings in the aerospace, automotive, electrical and chemical industries. Metal layers deposited from these plating baths can also be used as barrier and capping layers in semiconductor devices, printed circuit boards, IC substrates, and the like.

背景技术Background technique

无电镍涂层是用于提供耐腐蚀性、耐磨性、硬度、润滑性、可焊性和结合性、沉积均匀性和非磁性(在高磷镍合金的情况下)而施加的功能涂层,从而提供非多孔阻挡层或增强特定组件的性能或使用寿命。无电镍的硬度和耐腐蚀性是许多成功应用的关键因素。无电镍涂层用于各种应用,包括电连接器、微波外壳、阀体和泵体、打印机轴、计算机组件等。无电镍可用于涂覆由各种材料制成的组件,材料包括但不限于钢、不锈钢、铝、铜、黄铜、镁和数种非导电材料中的任何材料。Electroless nickel coatings are functional coatings applied to provide corrosion resistance, wear resistance, hardness, lubricity, weldability and bonding, deposition uniformity and non-magnetic properties (in the case of high phosphorus nickel alloys). layer to provide a non-porous barrier or to enhance the performance or lifespan of a particular component. The hardness and corrosion resistance of electroless nickel are key factors in many successful applications. Electroless nickel coatings are used in a variety of applications including electrical connectors, microwave housings, valve and pump bodies, printer shafts, computer components, and more. Electroless nickel can be used to coat components made from a variety of materials including, but not limited to, steel, stainless steel, aluminum, copper, brass, magnesium, and any of several non-conductive materials.

无电镍镀覆将镍合金沉积到能够催化合金从处理溶液中沉积的衬底上,该处理溶液含有镍离子和能够将溶液中的镍离子还原成金属镍的合适的化学还原剂。在无电镍镀覆浴中也使用各种添加剂以使浴稳定化并进一步控制在被镀覆的衬底上的镍沉积速率。还原剂包括例如硼氢化物(其产生镍硼合金)和次磷酸根离子(其产生镍磷合金)。与电镀覆相反,无电镍不需要整流器、电流或阳极。沉积过程是自催化的,意味着一旦在衬底上形成了镍的初生层,该层和每个后续层就变为引起镀覆反应继续的催化剂。Electroless nickel plating deposits a nickel alloy onto a substrate capable of catalyzing the deposition of the alloy from a processing solution containing nickel ions and a suitable chemical reducing agent capable of reducing the nickel ions in the solution to metallic nickel. Various additives are also used in electroless nickel plating baths to stabilize the bath and further control the rate of nickel deposition on the substrate being plated. Reducing agents include, for example, borohydrides (which produce nickel boron alloys) and hypophosphite ions (which produce nickel phosphorus alloys). In contrast to electroplating, electroless nickel does not require a rectifier, current or anode. The deposition process is autocatalytic, meaning that once a primary layer of nickel is formed on the substrate, that layer and each subsequent layer become the catalyst that causes the plating reaction to continue.

在使用次磷酸根离子作为还原剂的无电镍镀覆浴中,镍沉积物包含镍和磷的合金,磷含量为约2%至大于12%。这些合金在耐腐蚀性和(热处理后)硬度和耐磨性方面具有独特的特性。In electroless nickel plating baths using hypophosphite ions as reducing agents, the nickel deposit comprises an alloy of nickel and phosphorus with a phosphorus content ranging from about 2% to greater than 12%. These alloys have unique properties in terms of corrosion resistance and (after heat treatment) hardness and wear resistance.

用于无电镍镀覆溶液的组合物是本领域已知的。例如,美国专利2,658,841教导了使用可溶性有机酸盐作为无电镍镀覆溶液的缓冲剂。美国专利2,658,842教导了使用短链二羧酸作为EN浴的加速剂。美国专利2,762,723教导了将含硫化物和硫的添加剂用于无电镍镀覆浴中以改善浴稳定性。Compositions for electroless nickel plating solutions are known in the art. For example, 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 accelerators for EN baths. US Patent 2,762,723 teaches the use of sulfide and sulfur containing additives in electroless nickel plating baths to improve bath stability.

美国专利2,847,327介绍了使无电镍镀覆溶液稳定化的其它方法。这些包括使用更高纯度的起始材料;来自重金属类诸如Pb、Sb、Bi、Cu和Se的更有效的稳定剂;诸如如碘酸盐和硫代化合物的无机化合物;诸如不饱和烯烃和炔烃的有机化合物和其它物质。US Patent 2,847,327 describes other methods of stabilizing electroless nickel plating solutions. These include the use of higher purity starting materials; more efficient stabilizers from heavy metals such as Pb, Sb, Bi, Cu and Se; inorganic compounds such as iodates and thio compounds; unsaturated olefins and alkynes Hydrocarbon organic compounds and other substances.

WO 2015/187402公开了包含一或多种二羧酸和一或多种α羟基羧酸的无电镍合金镀覆浴。WO 2015/187402 discloses electroless nickel alloy plating baths comprising one or more dicarboxylic acids and one or more alpha hydroxycarboxylic acids.

WO2018/220220公开了用于制备数据存储装置的无电镍合金镀覆浴,其中所有络合剂包含至少两个羧酸部分。WO2018/220220 discloses electroless nickel alloy plating baths for making data storage devices, wherein all complexing agents contain at least two carboxylic acid moieties.

CN1 09112509A公开了一种高耐腐蚀性的化学镍镀覆溶液及其制备方法。此化学镍镀覆溶液包含硫酸镍、次磷酸钠、柠檬酸钠、乳酸、丙酸和乙酸以及特定的润湿剂和稳定剂。CN1 09112509A discloses a chemical nickel plating solution with high corrosion resistance and a preparation method thereof. This electroless nickel plating solution contains nickel sulfate, sodium hypophosphite, sodium citrate, lactic acid, propionic acid and acetic acid as well as specific wetting agents and stabilizers.

本发明的目的object of the present invention

因此,本发明的一个目的是提供一种无电镍合金镀覆浴,该镀覆浴改善通过所述镀覆浴处理的金属衬底的腐蚀保护。Accordingly, it is an object of the present invention to provide an electroless nickel alloy plating bath that improves corrosion protection of metal substrates processed by said plating bath.

本发明的另一目的是提供一种稳定且不显示任何积垢的无电镍合金镀覆浴。Another object of the present invention is to provide an electroless nickel alloy plating bath that is stable and does not show any fouling.

本发明的又另一目的是提供一种具有足够镀覆速率的无电镍合金镀覆浴。Yet another object of the present invention is to provide an electroless nickel alloy plating bath having a sufficient plating rate.

本发明的再一目的是提供一种无电镍合金镀覆浴,例如当镀覆在诸如铝或铝合金的金属表面上时,该镀覆浴产生良好粘附到下面的衬底表面上的镍合金沉积物。It is a further object of the present invention to provide an electroless nickel alloy plating bath which, for example when plating on a metal surface such as aluminum or an aluminum alloy, produces a good adhesion to the underlying substrate surface. Nickel alloy deposits.

发明内容SUMMARY OF THE INVENTION

上述目的通过根据本发明的无电镍合金镀覆浴,其用途,用于将镍合金沉积到衬底的至少一个表面上的方法和由根据本发明的无电镍合金镀覆浴获得的镍合金沉积物及其用途来解决。The above objects are achieved by the electroless nickel alloy plating bath according to the invention, the use thereof, the method for depositing a nickel alloy on at least one surface of a substrate and the nickel obtained from the electroless nickel alloy plating bath according to the invention Alloy deposits and their uses are addressed.

根据本发明的无电镍合金镀覆浴包含:The electroless nickel alloy plating bath according to the present invention comprises:

a)镍离子;a) nickel ions;

b)另外的可还原的金属离子,其选自由以下组成的群组:钼离子、铼离子、钨离子、铜离子、其含氧离子及其混合物;b) additional reducible metal ions selected from the group consisting of molybdenum ions, rhenium ions, tungsten ions, copper ions, oxygen-containing ions thereof, and mixtures thereof;

c)至少一种还原剂,其适于将镍离子和另外的可还原的金属离子还原至它们相应的金属态;优选地选自由以下组成的群组:次磷酸、次磷酸盐以及上述物质的混合物;以及c) at least one reducing agent suitable for reducing nickel ions and further reducible metal ions to their corresponding metallic states; preferably selected from the group consisting of hypophosphorous acid, hypophosphite and mixture; and

d)络合剂CA1、CA2、CA3和任选地(优选地非任选地,而是强迫性地,强制的,必须地;即无任选)CA4,d) complexing agents CA1, CA2, CA3 and optionally (preferably not optionally, but compulsorily, obligatory, obligatory; i.e. no optional) CA4,

其中CA1、CA2、CA3和CA4全部不同于彼此;where CA1, CA2, CA3 and CA4 are all different from each other;

其中CA1和CA2中的每一个独立地选自由以下组成的群组:具有至少两个羧酸部分的化合物、其相应的盐以及上述物质的混合物;wherein each of CA1 and CA2 is independently selected from the group consisting of compounds having at least two carboxylic acid moieties, corresponding salts thereof, and mixtures thereof;

其中CA3选自由以下组成的群组:具有正好一个羧酸部分的脂族化合物、其相应的盐以及上述物质的混合物;以及wherein CA3 is selected from the group consisting of aliphatic compounds having exactly one carboxylic acid moiety, their corresponding salts, and mixtures of the foregoing; and

其中CA4选自由以下组成的群组:具有至少一个羧酸部分的芳族化合物、其相应的盐以及上述物质的混合物。wherein CA4 is selected from the group consisting of aromatic compounds having at least one carboxylic acid moiety, their corresponding salts, and mixtures thereof.

两种络合剂CA1和CA2是具有至少两个羧酸部分的不同的化合物、其相应的盐以及上述物质的混合物。The two complexing agents CA1 and CA2 are different compounds having at least two carboxylic acid moieties, their corresponding salts and mixtures of the foregoing.

根据本发明的无电镍合金镀覆浴用于将镍合金沉积到至少一个衬底的至少一个表面上。Electroless nickel alloy plating baths according to the present invention are used to deposit nickel alloys onto at least one surface of at least one substrate.

一种将镍合金沉积到衬底的至少一个表面上的方法,该方法依次包含以下方法步骤:A method of depositing a nickel alloy onto at least one surface of a substrate, the method comprising, in sequence, the following method steps:

A)提供包含至少一个表面的衬底;A) providing a substrate comprising at least one surface;

B)使衬底的至少一个表面与根据本发明的无电镍合金镀覆浴(优选地如本文全文中优选描述的镀覆浴)接触,从而将镍合金沉积到衬底的至少一个表面上。B) contacting at least one surface of the substrate with an electroless nickel alloy plating bath according to the present invention, preferably as preferably described throughout this text, thereby depositing the nickel alloy onto at least one surface of the substrate .

镍合金沉积物可通过从根据本发明的无电镍合金镀覆浴(优选地如本文全文中优选描述的镀覆浴)沉积获得。Nickel alloy deposits can be obtained by deposition from an electroless nickel alloy plating bath according to the present invention, preferably a plating bath as preferably described throughout this text.

根据本发明的无电镍合金镀覆浴和本发明的方法适于提供具有吸引人的光亮或半光亮外观的镍合金沉积物。此外,镍合金沉积物良好粘附在下面的衬底表面上。The electroless nickel alloy plating bath according to the present invention and the method of the present invention are suitable for providing nickel alloy deposits with an attractive bright or semi-bright appearance. In addition, the nickel alloy deposits adhered well to the underlying substrate surface.

根据本发明的无电镍合金镀覆浴是稳定的,并且镀覆期间在足够的时间内不会显示出积垢而经济地使用。The electroless nickel alloy plating bath according to the present invention is stable and does not exhibit fouling during plating for a sufficient time to be used economically.

具体实施方式Detailed ways

本说明书中的百分比是重量百分比(wt.-%),除非另有说明。除非另有说明,本说明书中给出的浓度是指整个溶液的体积或质量(优选地体积)。术语“沉积”和“镀覆”在本文中可互换使用。此外,“层”和“沉积物”在本说明书中也同义使用。积垢是指镀覆浴的不期望的分解。应当理解,在本说明书中描述的本发明的优选实施例可以被组合,除非这在技术上是不可行的或被特别排除。The percentages in this specification are weight percentages (wt.-%) unless otherwise stated. Unless otherwise stated, concentrations given in this specification refer to the volume or mass (preferably volume) of the entire solution. The terms "depositing" and "plating" are used interchangeably herein. In addition, "layer" and "deposit" are also used synonymously in this specification. Fouling refers to undesired decomposition of a plating bath. It is to be understood that the preferred embodiments of the present invention described in this specification may be combined unless this is technically infeasible or specifically excluded.

在本发明的上下文中,羧酸部分是–C(=O)OH基团。如果没有明确说明,其优选地包括其盐。根据本发明的术语“CX-CY-化合物”是指具有X至Y个碳原子(包括任何羧酸部分的碳原子)的化合物;其中X和Y是指自然数,并且X可小于Y。In the context of the present invention, the carboxylic acid moiety is a -C(=O)OH group. If not explicitly stated, it preferably includes its salts. The term "CX-CY-compound" according to the present invention refers to a compound having X to Y carbon atoms (including carbon atoms of any carboxylic acid moiety); wherein X and Y refer to natural numbers, and X may be less than Y.

本发明的镍合金包含元素镍和钼、钨、铜和铼中的一或多种,优选地与磷和/或硼组合,更优选地与磷组合。甚至更优选的合金包含镍、钼和磷。最优选的合金包含镍、钼、铜和磷,因为它们提供了金属衬底的改善的腐蚀保护。The 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 in combination with phosphorus. Even more preferred alloys contain nickel, molybdenum and phosphorus. The most preferred alloys contain nickel, molybdenum, copper and phosphorous as they provide improved corrosion protection of metal substrates.

根据本发明的无电镍合金镀覆浴Electroless nickel alloy plating bath according to the invention

本发明的无电镍合金镀覆浴包含镍离子。镍离子可由任何水溶性盐或任何水溶性镍络合物提供。优选地,镍离子由硫酸镍、氯化镍、乙酸镍、甲基磺酸镍、氨基磺酸镍及其混合物中的任一种提供。The electroless nickel alloy plating bath of the present invention contains nickel ions. Nickel ions can be provided by any water-soluble salt or any water-soluble nickel complex. Preferably, the nickel ions are provided by any one of nickel sulfate, nickel chloride, nickel acetate, nickel methanesulfonate, nickel sulfamate, and mixtures thereof.

镍离子在无电镍合金镀覆浴中的浓度可广泛变化且优选的范围为0.01mol/L至1.0mol/L,更优选地为0.03mol/L至0.8mol/L,甚至更优选地为0.04mol/L至0.5mol/L,又甚至更优选地为0.05mol/L至0.3mol/L,最优选地为0.05mol/L至0.1mol/L。The concentration of nickel ions in the electroless nickel alloy plating bath can vary widely and preferably ranges from 0.01 mol/L to 1.0 mol/L, more preferably 0.03 mol/L to 0.8 mol/L, even more preferably 0.04mol/L to 0.5mol/L, and even more preferably 0.05mol/L to 0.3mol/L, most preferably 0.05mol/L to 0.1mol/L.

本发明的无电镍合金镀覆浴包含另外的可还原的金属离子(除镍离子外)。另外的可还原的金属离子选自由以下组成的群组:钼离子、铼离子、钨离子、铜离子及其混合物。另外的可还原的金属离子可以由此些另外的可还原的金属的任何水溶性盐或任何水溶性络合物提供。优选地,钼离子由钼酸、碱性钼酸盐(例如Na2MoO4)、钼酸铵及其混合物中的任一种提供。优选地,钨离子由钨酸、碱性钨酸盐(例如Na2WO4)、钨酸铵及其混合物中的任一种提供。优选地,铼离子由高铼酸、碱性高铼酸盐(例如NaReO4)、高铼酸铵及其混合物中的任一种提供。优选地,铜离子由碘化铜、碘酸铜、氯化铜和/或硫酸铜中的任一种提供。优选钼离子作为生态上不重要的稳定剂和合金组分。铜离子是优选的,因为它们改善了沉积物的流平性和亮度并增强了过程稳定性和耐腐蚀性。在本发明的一个实施例中,本发明的无电镍合金镀覆浴优选地仅包含钼离子作为另外的可还原的金属离子。在本发明的另一优选实施例中,本发明的无电镍合金镀覆浴优选地包含钼离子和铜离子的混合物作为另外的可还原的金属离子。更优选地,本发明的无电镍合金镀覆浴既不包含任何钨离子也不包含任何铼离子,最优选地,如果存在铜离子和/或钼离子的话。The electroless nickel alloy plating baths of the present invention contain additional reducible metal ions (in addition to nickel ions). The additional reducible metal ions are selected from the group consisting of molybdenum ions, rhenium ions, tungsten ions, copper ions, and mixtures thereof. Additional reducible metal ions can be provided by any water-soluble salt or any water-soluble complex of these additional reducible metals. Preferably, the molybdenum ion is provided by any one of molybdic acid , basic molybdate salts (eg, Na2MoO4), ammonium molybdate, and mixtures thereof. Preferably, the tungsten ions are provided by any one of tungstic acid , alkaline tungstate (eg, Na2WO4), ammonium tungstate, and mixtures thereof. Preferably, the rhenium ions are provided by any one of perrhenic acid, basic perrhenates (eg, NaReO 4 ), ammonium perrhenate, and mixtures thereof. Preferably, the copper ions are provided by any one of copper iodide, copper iodate, copper chloride and/or copper sulfate. Molybdenum ions are preferred as ecologically insignificant stabilizers and alloying components. Copper ions are preferred because they improve deposit leveling and brightness and enhance process stability and corrosion resistance. In one embodiment of the present invention, the electroless nickel alloy plating bath of the present invention preferably contains only molybdenum ions as additional reducible metal ions. In another preferred embodiment of the present invention, the electroless nickel alloy plating bath of the present invention preferably contains a mixture of molybdenum ions and copper ions as additional reducible metal ions. More preferably, the electroless nickel alloy plating baths of the present invention contain neither any tungsten nor any rhenium ions, most preferably copper and/or molybdenum ions if present.

因此,优选的是本发明的无电镍合金镀覆浴,其中另外的可还原的金属离子是钼离子、铜离子或其混合物;优选地,另外的可还原的金属离子是钼离子或钼离子和铜离子的混合物。Therefore, preferred are electroless nickel alloy plating baths of the present invention wherein the additional reducible metal ions are platinum ions, copper ions or mixtures thereof; preferably the additional reducible metal ions are platinum ions or platinum ions and copper ions.

钼、铼和钨的不溶性组分(诸如二硫化钼)对镍合金沉积物特性有害,并且因此优选地不用于根据本发明的无电镍合金镀覆浴中。Insoluble components of molybdenum, rhenium and tungsten, such as molybdenum disulfide, are detrimental to nickel alloy deposit properties and are therefore preferably not used in electroless nickel alloy plating baths according to the present invention.

无电镍合金镀覆浴中另外的可还原的金属离子的总浓度可以变化且基于无电镍合金镀覆浴的总体积,优选在5*10-5至1*10-2mol/L的范围内,更优选地为1*10-4至5*10- 3mol/L,且甚至更优选地为2.5*10-4至2.5*10-3mol/L。如果在无电镍合金镀覆浴中包含多于一种类型的另外的可还原的金属离子,则所使用的所有另外的可还原的金属离子的总浓度优选地在以上界定的范围内(即其总浓度)。The total concentration of additional reducible metal ions in the electroless nickel alloy plating bath can vary and is based on the total volume of the electroless nickel alloy plating bath, preferably in the range of 5* 10-5 to 1* 10-2 mol/L range, more preferably 1* 10-4 to 5 * 10-3 mol/L, and even more preferably 2.5* 10-4 to 2.5* 10-3 mol/L. If more than one type of additional reducible metal ion is included in the electroless nickel alloy plating bath, the total concentration of all additional reducible metal ions used is preferably within the range defined above (ie its total concentration).

在本发明的无电镍合金镀覆浴包含钼离子和铜离子的混合物作为另外的可还原的金属离子的那些情况下,无电镍合金镀覆浴中的钼离子和铜离子的总浓度可以变化且基于无电镍合金镀覆浴的总体积,优选在1*10-5(优选地从5*10-5)至1*10-2mol/L的范围内,更优选地为1*10-5(优选地从5*10-5)至5*10-3mol/L,且甚至更优选地为1*10-5(优选地从5*10-5)至5*10-4mol/L。优选地,基于摩尔浓度,本发明的无电镍合金镀覆浴包含比铜离子多的钼离子。更优选地,钼离子和铜离子在无电镍合金镀覆浴中的总浓度可以变化且基于无电镍合金镀覆浴的总体积,优选在1*10-5(优选地从5*10-5)至1*10-2mol/L的范围内,更优选地为1*10-5(优选地从5*10-5)至5*10-3mol/L,且甚至更优选地为1*10-5(优选地从5*10-5)至5*10-4mol/L,且钼离子与铜离子的摩尔比在1:1至30:1的范围内,优选地为5:1至20:1,更优选地为10:1至15:1。In those instances where the electroless nickel alloy plating bath of the present invention contains a mixture of molybdenum ions and copper ions as additional reducible metal ions, the total concentration of molybdenum ions and copper ions in the electroless nickel alloy plating bath may be Varies and is based on the total volume of the electroless nickel alloy plating bath, preferably in the range of 1* 10-5 (preferably from 5* 10-5 ) to 1* 10-2 mol/L, more preferably 1* 10-5 (preferably from 5* 10-5 ) to 5* 10-3 mol/L, and even more preferably 1* 10-5 (preferably from 5* 10-5 ) to 5* 10-4 mol/L. Preferably, the electroless nickel alloy plating baths of the present invention contain more molybdenum ions than copper ions on a molar basis. More preferably, the total concentration of molybdenum ions and copper ions in the electroless nickel alloy plating bath can vary and is based on the total volume of the electroless nickel alloy plating bath, preferably at 1* 10-5 (preferably from 5*10 -5 ) to 1* 10-2 mol/L, more preferably 1* 10-5 (preferably from 5* 10-5 ) to 5* 10-3 mol/L, and even more preferably is 1* 10-5 (preferably from 5* 10-5 ) to 5* 10-4 mol/L, and the molar ratio of platinum ions to copper ions is in the range of 1:1 to 30:1, preferably 5:1 to 20:1, more preferably 10:1 to 15:1.

上述范围之外的浓度在一些情况下可能是适用的,这取决于待形成的镍合金沉积物中期望的另外的金属含量。Concentrations outside the above ranges may be suitable in some cases, depending on the desired additional metal content in the nickel alloy deposit to be formed.

本发明的无电镍合金镀覆浴进一步包含至少一种还原剂。所述至少一种还原剂优选地为化学还原剂。所述至少一种还原剂适于将镍离子和另外的可还原的金属离子还原为其相应的金属态。优选地,所述至少一种还原剂选自由以下组成的群组: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 for reducing nickel ions and further reducible metal ions to their corresponding metal states. Preferably, the at least one reducing agent is selected from the group consisting of:

-次磷酸盐化合物,诸如次磷酸和次磷酸盐,诸如碱性次磷酸盐(如次磷酸钠或次磷酸钾)、次磷酸铵、次磷酸镍等;- hypophosphite compounds, such as hypophosphorous acid and hypophosphites, such as alkaline hypophosphites (such as sodium hypophosphite or potassium hypophosphite), ammonium hypophosphite, nickel hypophosphite, etc.;

-硼基还原剂,诸如氨基硼烷,如二甲基氨基硼烷(DMAB)和吗啉硼烷,以及硼氢化物,如硼氢化钠;- Boron-based reducing agents, such as aminoboranes, such as dimethylaminoborane (DMAB) and morpholineborane, and borohydrides, such as sodium borohydride;

-肼;以及- Hydrazine; and

-肼衍生物(诸如硫酸肼、盐酸肼、水合肼和在本发明的上下文中可用作还原剂的其它此些组分)。- Hydrazine derivatives (such as hydrazine sulfate, hydrazine hydrochloride, hydrazine hydrate and other such components which can be used as reducing agents in the context of the present invention).

在使用次磷酸盐化合物作为还原剂的情况下,获得包含磷的镍合金沉积物。此些还原剂在沉积的镍合金中提供磷源。In the case of using a hypophosphite compound as reducing agent, phosphorus-containing nickel alloy deposits are obtained. Such reducing agents provide a source of phosphorus in the deposited nickel alloy.

硼烷基还原剂产生包含硼以及次磷酸盐化合物的镍合金沉积物,并且硼烷基还原剂产生包含磷和硼的镍合金沉积物。Boron-based reducing agents produce nickel alloy deposits containing boron and hypophosphite compounds, and borane-based reducing agents produce nickel alloy deposits containing phosphorus and boron.

氮基还原剂诸如肼和肼衍生物既不提供待掺入镍合金中的磷也不提供待掺入镍合金中的硼。Nitrogen-based reducing agents such as hydrazine and hydrazine derivatives provide neither phosphorus nor boron to be incorporated into nickel alloys.

该至少一种还原剂更优选地选自由以下组成的群组:次磷酸、次磷酸盐以及上述物质的混合物。这些还原剂是优选的,因为构建到本发明的镍合金中的磷尤其显著改善了此些镍合金沉积物的磁特性并产生(耐热)顺磁性镍合金。高磷量(例如10wt.-%或更多)的引入还改善了防腐蚀保护。甚至更优选地,将至少一种还原剂选择为次磷酸盐,因为此些盐是成本有效的并且易于使用。至少一种还原剂的摩尔浓度通常过量于足以还原无电镍合金镀覆浴中的镍离子和另外的可还原的金属离子的量。还原剂的浓度优选的范围为0.01mol/L至3.0mol/L,更优选地为0.1mol/L至1mol/L。The at least one reducing agent is more preferably selected from the group consisting of hypophosphorous acid, hypophosphite, and mixtures of the foregoing. These reducing agents are preferred because especially the phosphorus built into the nickel alloys of the present invention significantly improves the magnetic properties of such nickel alloy deposits and produces (heat resistant) paramagnetic nickel alloys. The introduction of high phosphorus levels (eg 10 wt.-% or more) also improves corrosion protection. Even more preferably, the at least one reducing agent is selected to be hypophosphite, as such salts are cost effective and easy to use. The molar concentration of the at least one reducing agent is typically in excess of an amount sufficient to reduce the nickel ions and additional 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.

无电镍合金镀覆浴包含(不同的)络合剂CA1和CA2,其中CA1和CA2中的每一个独立地选自由以下组成的群组:具有至少两个羧酸部分的化合物、其相应的盐(例如羧酸盐)以及上述物质的混合物。优选地,所述具有至少两个羧酸部分的化合物是脂族化合物,优选地C2-C12-脂族化合物,更优选地C2-C8-脂族化合物。脂族化合物包括无环或环状、饱和或不饱和碳化合物,不包括芳族化合物;脂族化合物优选地是非环状的。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, their corresponding Salts such as carboxylates and mixtures of the foregoing. Preferably, the compound having at least two carboxylic acid moieties is an aliphatic compound, preferably a C2-C12-aliphatic compound, more preferably a C2-C8-aliphatic compound. Aliphatic compounds include acyclic or cyclic, saturated or unsaturated carbon compounds, excluding aromatic compounds; aliphatic compounds are preferably acyclic.

官能化理论上可以通过用官能团取代至少一个氢来获得。此些任选的(但在一些情况下优选的)官能团优选地选自羟基(-OH)、氨基(-NH2)、卤化物、烯烃双键(-C=C-)和三键(-C≡C-)。后两者自然地要求相邻碳原子的两个氢原子在理论上被替换。更优选地,任选的官能团选自由以下组成的群组:羟基和双键。甚至更优选地,任选的官能团是羟基。Functionalization can theoretically be achieved by substituting at least one hydrogen with a functional group. Such optional (but in some cases preferred) functional groups are preferably selected from hydroxyl (-OH), amino ( -NH2 ), halide, olefinic double bonds (-C=C-) and triple bonds (- C≡C-). The latter two naturally require two hydrogen atoms of adjacent carbon atoms to be theoretically replaced. More preferably, the optional functional group is selected from the group consisting of hydroxyl and double bonds. Even more preferably, the optional functional group is a hydroxyl group.

更优选地,无电镍合金镀覆浴包含络合剂CA1和CA2,络合剂CA1和CA2独立地选自由以下组成的群组:未官能化和官能化的脂族二羧酸、未官能化和官能化的脂族三羧酸、未官能化和官能化的脂族四羧酸、未官能化和官能化的脂族五羧酸、未官能化和官能化的脂族六羧酸、其相应的盐以及上述物质的混合物。More preferably, the electroless nickel alloy plating bath comprises complexing agents CA1 and CA2 independently selected from the group consisting of unfunctionalized and functionalized aliphatic dicarboxylic acids, unfunctionalized Unfunctionalized and functionalized aliphatic tricarboxylic acids, unfunctionalized and functionalized aliphatic tetracarboxylic acids, unfunctionalized and functionalized aliphatic pentacarboxylic acids, unfunctionalized and functionalized aliphatic hexacarboxylic acids, their corresponding salts and mixtures of the foregoing.

甚至更优选地,络合剂CA1和CA2独立地选自由以下组成的群组:未官能化和官能化的脂族二羧酸、未官能化和官能化的脂族三羧酸、未官能化和官能化的脂族四羧酸、其相应的盐以及上述物质的混合物。Even more preferably, 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, their corresponding salts, and mixtures of the foregoing.

优选地,络合剂CA1是未官能化的脂族C2-C12-二羧酸和/或其盐。甚至更优选地,其为未官能化的脂族C3-C6-二羧酸和/或其盐。又甚至更优选地,络合剂CA1选自由以下组成的群组:丙二酸、琥珀酸、戊二酸、己二酸、马来酸、富马酸、戊烯二酸、衣康酸、其盐以及上述物质的混合物。最优选地,络合剂CA1是丙二酸和/或其盐。Preferably, the complexing agent CA1 is an unfunctionalized aliphatic C2-C12-dicarboxylic acid and/or a salt thereof. Even more preferably, it is an unfunctionalized aliphatic C3-C6-dicarboxylic acid and/or a salt 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, glutaric acid, itaconic acid, Its salts and mixtures of the foregoing. Most preferably, the complexing agent CA1 is malonic acid and/or a salt thereof.

优选地,络合剂CA2是官能化或未官能化(优选地官能化)的脂族C3-C12-二羧酸和/或其盐,优选地官能化或未官能化(优选地官能化)的脂族C4-C6-二羧酸和/或其盐。更优选地,络合剂CA2包含至少一个羟基(并且因此是羟基官能化的)。甚至更优选地,络合剂CA2是羟基官能化的脂族C4-C6-二羧酸和/或其盐。又甚至更优选地,络合剂CA2选自由以下组成的群组:苹果酸、酒石酸、1-羟基戊二酸、2-羟基戊二酸、1-羟基己二酸、2-羟基己二酸、3-羟基己二酸、其盐以及上述物质的混合物。最优选地,络合剂CA2是苹果酸和/或其盐。Preferably, the complexing agent CA2 is a functionalized or unfunctionalized (preferably functionalized) aliphatic C3-C12-dicarboxylic acid and/or a salt thereof, preferably functionalized or unfunctionalized (preferably functionalized) aliphatic C4-C6-dicarboxylic acids and/or their salts. More preferably, the complexing agent CA2 comprises at least one hydroxyl group (and is thus hydroxyl functional). Even more preferably, the complexing agent CA2 is a hydroxy-functionalized aliphatic C4-C6-dicarboxylic acid and/or a salt thereof. Yet even more preferably, 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-hydroxyadipic acid, its salts and mixtures thereof. Most preferably, the complexing agent CA2 is malic acid and/or a salt thereof.

优选地,络合剂CA3是官能化或未官能化的脂族C1-C5-单羧酸和/或其盐,优选地官能化或未官能化的脂族C2-C4-单羧酸和/或其盐。更优选地,络合剂CA3是丙酸和/或其盐。最优选地,络合剂CA3是丙酸。应当清楚地注意,在本发明的上下文中,可以组合上述关于CA1、CA2和CA3的优选实施例中的两个或两个以上。Preferably, the complexing agent CA3 is a functionalized or unfunctionalized aliphatic C1-C5-monocarboxylic acid and/or a salt thereof, preferably a functionalized or unfunctionalized aliphatic C2-C4-monocarboxylic acid and/or or its salt. More preferably, the complexing agent CA3 is propionic acid and/or a salt thereof. Most preferably, the complexing agent CA3 is propionic acid. It should be clearly noted that, in the context of the present invention, two or more of the preferred embodiments described above with respect to CA1, CA2 and CA3 may be combined.

优选地,络合剂CA4是官能化(在一些情况下优选)或未官能化(在一些情况下优选)的芳族羧酸和/或其盐。优选的官能化是羟基官能化。“芳族羧酸”是包含至少一个COOH基团(及其相关盐)和至少一个芳环的化合物。芳环可包含杂原子,优选地芳环不含杂原子。优选地,至少一个COOH基团直接键合至芳环,诸如在例如苯甲酸、水杨酸中。更优选地,CA4是苯甲酸和/或其盐。甚至更优选地CA4是苯甲酸钠。Preferably, the complexing agent CA4 is a functionalized (preferred in some cases) or unfunctionalized (preferred in some cases) aromatic carboxylic acids and/or salts thereof. The preferred functionalization is hydroxyl functionalization. An "aromatic carboxylic acid" is a compound containing at least one COOH group (and related salts thereof) and at least one aromatic ring. The aromatic ring may contain heteroatoms, preferably the aromatic ring is free of heteroatoms. Preferably, at least one COOH group is bonded directly to an aromatic ring, such as in eg benzoic acid, salicylic acid. More preferably, CA4 is benzoic acid and/or a salt thereof. Even more preferably CA4 is sodium benzoate.

在本发明的一个非常优选的实施例中,络合剂CA1、CA2、CA3和C4分别选自彼此,代表根据上述关于CA1、CA2和CA3的优选实施例的各自不同的络合剂。In a very preferred embodiment of the present invention, the complexing agents CA1, CA2, CA3 and C4 are respectively selected from each other, representing respective different complexing agents according to the preferred embodiments described above for CA1, CA2 and CA3.

特别优选的是根据本发明的无电镍合金镀覆浴,其中络合剂CA1选自由以下组成的群组:丙二酸、琥珀酸、戊二酸、己二酸、马来酸、富马酸、戊烯二酸、衣康酸,其盐以及上述物质的混合物(特别地,络合剂CA1是丙二酸和/或其盐);络合剂CA2选自由以下组成的群组:苹果酸、酒石酸、1-羟基戊二酸、2-羟基戊二酸、1-羟基己二酸、2-羟基己二酸、3-羟基己二酸、其盐以及上述物质的混合物(特别地,络合剂CA2是苹果酸和/或其盐);并且络合剂CA3选自由以下组成的群组:脂族单羧酸、其盐以及上述物质的混合物。最优选地,上述物质与络合剂CA4结合的是苯甲酸和/或其盐。Particularly preferred are electroless nickel alloy plating baths according to the invention, wherein the complexing agent CA1 is selected from the group consisting of malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid acid, glutaric acid, itaconic acid, salts thereof and mixtures thereof (in particular, the complexing agent CA1 is malonic acid and/or its salts); the complexing agent CA2 is selected from the group consisting of: apple acid, tartaric acid, 1-hydroxyglutaric acid, 2-hydroxyglutaric acid, 1-hydroxyadipic acid, 2-hydroxyadipic acid, 3-hydroxyadipic acid, salts thereof and mixtures thereof (in particular, The complexing agent CA2 is malic acid and/or its salts); and the complexing agent CA3 is selected from the group consisting of aliphatic monocarboxylic acids, salts thereof, and mixtures thereof. Most preferably, the aforementioned substances are combined with the complexing agent CA4 to be benzoic acid and/or its salts.

优选地,络合剂CA1的浓度的范围为50至300mmol/L,更优选地为50至250mmol/L,并且甚至更优选地为50至200mmol/L。优选地,络合剂CA2的浓度的范围为50至200mmol/L,更优选地为60至180mmol/L,并且甚至更优选地为70至150mmol/L。优选地,络合剂CA3的浓度的范围为40至1000mmol/L,更优选地为40至800mmol/L,并且甚至更优选地为40至300mmol/L。优选地,络合剂CA4的浓度的范围为0(优选地大于0)至200mmol/L,更优选地为7至150mmol/L,甚至更优选地为15至75mmol/L,并且又甚至更优选地为30至75mmol/L。优选地,络合剂CA1、CA2、CA3和CA4的总浓度为至少0.15mol/L,更优选地为至少0.20mol/L,甚至更优选地为至少0.22mol/L。Preferably, the concentration of complexing agent CA1 is in the range of 50 to 300 mmol/L, more preferably 50 to 250 mmol/L, and even more preferably 50 to 200 mmol/L. Preferably, the concentration of complexing agent CA2 ranges from 50 to 200 mmol/L, more preferably 60 to 180 mmol/L, and even more preferably 70 to 150 mmol/L. Preferably, the concentration of complexing agent CA3 ranges from 40 to 1000 mmol/L, more preferably 40 to 800 mmol/L, and even more preferably 40 to 300 mmol/L. Preferably, the concentration of complexing agent CA4 ranges from 0 (preferably greater than 0) to 200 mmol/L, more preferably 7 to 150 mmol/L, even more preferably 15 to 75 mmol/L, and yet even more preferably It is 30 to 75 mmol/L. Preferably, the total concentration of complexing agents CA1, CA2, CA3 and CA4 is at least 0.15 mol/L, more preferably at least 0.20 mol/L, even more preferably at least 0.22 mol/L.

优选地,络合剂CA1、CA2、CA3和任选CA4(最优选地CA1、CA2、CA3和CA4一起)的总摩尔浓度与镍离子的摩尔浓度的比率的范围为4/1至8/1。Preferably, the ratio of the total molar concentration of complexing agents CA1, CA2, CA3 and optionally CA4 (most preferably CA1, CA2, CA3 and CA4 together) to the molar concentration of nickel ions ranges from 4/1 to 8/1 .

根据本发明的无电镍合金镀覆浴优选地为水溶液。术语“水溶液”是指作为溶液中的溶剂的主要液体介质是水。可以加入与水混溶的进一步的液体,例如与水混溶的醇和其它极性有机液体。优选使用的所有溶剂的至少95wt.-%,更优选地99wt.-%是水,因为其生态上良性的特征。根据本发明的无电镍合金镀覆浴优选地通过将所有组分溶解在含水液体介质中,优选地在水中来制备。The electroless nickel alloy plating bath according to the present invention is preferably an aqueous solution. The term "aqueous solution" means that the primary liquid medium that is the solvent in the solution is water. Further water-miscible liquids can be added, such as water-miscible alcohols and other polar organic liquids. Preferably at least 95 wt.-%, more preferably 99 wt.-% of all solvents used are 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 an aqueous liquid medium, preferably in water.

根据本发明的无电镍合金镀覆浴可以是酸性的、中性的或碱性的。酸性或碱性pH调节剂诸如(矿物)酸或碱可以选自宽范围的物质,诸如氨、氢氧化铵、氢氧化钠、盐酸、硫酸等。根据本发明的无电镍合金镀覆浴的pH优选地为约2至12。在一个实施例中,根据本发明的无电镍合金镀覆浴优选地具有中性或酸性pH值(下文称为“酸性无电镍合金镀覆浴”)。如果选择钼离子和/或铼离子作为另外的可还原的金属离子,则这是特别有用的;特别地,如果选择钼作为唯一的另外的可还原的金属离子。更优选地,根据本发明的酸性无电镍合金镀覆浴具有的pH值的范围为3.5至7,甚至更优选地3.5至5.0,又甚至更优选地4.0至4.8,最优选地4.2至4.7。这允许所述浴的高稳定性和从此浴形成的镍合金沉积物的顺磁性特性(包括其在高温下的保持)方面的最佳结果。如果选择钨离子作为唯一的另外的可还原的金属离子,优选pH的范围为8至10。Electroless nickel alloy plating baths according to the present invention may be acidic, neutral or basic. Acidic or basic pH adjusting agents such as (mineral) acids or bases can be selected from a wide range of substances 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 present invention is preferably about 2 to 12. In one embodiment, the electroless nickel alloy plating bath according to the present invention preferably has a neutral or acidic pH (hereinafter referred to as "acid electroless nickel alloy plating bath"). This is particularly useful if molybdenum and/or rhenium ions are chosen as the additional reducible metal ions; in particular, if molybdenum is chosen as the only additional reducible metal ion. More preferably, the acid electroless nickel alloy plating bath according to the present invention has a pH in the range of 3.5 to 7, even more preferably 3.5 to 5.0, yet even more preferably 4.0 to 4.8, most preferably 4.2 to 4.7 . This allows for optimum results in terms of high stability of the bath and paramagnetic properties of the nickel alloy deposits formed from this bath, including their retention at high temperatures. If tungsten ions are chosen as the only additional reducible metal ions, a pH range of 8 to 10 is preferred.

根据本发明的无电镍合金镀覆浴可优选地包括其它添加剂,诸如pH缓冲剂、润湿剂、促进剂、增白剂、本领域已知的其它稳定剂、诸如欧洲专利申请EP 3 034 650A1中公开的那些镀覆速率调节剂。Electroless nickel alloy plating baths according to the present invention may preferably include other additives such as pH buffers, wetting agents, accelerators, brighteners, other stabilizers known in the art, such as European Patent Application EP 3 034 Those plating rate modifiers disclosed in 650A1.

进一步优选的是,本发明的无电镍合金镀覆浴不含硫脲,硫脲由于其毒性和生态问题而通常被用作无电镍镀覆浴的稳定剂。It is further preferred that the electroless nickel alloy plating baths of the present invention do not contain thiourea, which is commonly used as a stabilizer for electroless nickel plating baths due to its toxicity and ecological concerns.

根据本发明的方法Method according to the invention

在根据本发明的方法的步骤A)中,提供了包含至少一个表面的衬底。In step A) of the method according to the invention, a substrate comprising at least one surface is provided.

可以用根据本发明的无电镍合金镀覆浴和根据本发明的方法对各种衬底进行镀覆镍合金。优选地,在根据本发明的方法中使用金属衬底。待镀覆镍合金的金属衬底优选地选自由以下组成的群组:铜、锌、银、钯、铁、铱、锡、铝、镍、其合金以及上述物质的混合物。优选地,步骤A)中提供的衬底完全由金属(优选地上述优选金属中的至少一种)制成,或者其优选地包含至少一个表面,其由金属,优选地上述优选金属中的至少一种制成。由金属制成的此表面也可以是一或多个钯活化层,通常用于使不导电表面诸如玻璃、塑料或陶瓷能接受镍合金镀覆。Various substrates can be plated with nickel alloys using electroless nickel alloy plating baths according to the present invention and methods according to the present invention. Preferably, a metal substrate is used in the method according to the invention. The metal substrate to be plated with a nickel alloy is preferably selected from the group consisting of copper, zinc, silver, palladium, iron, iridium, tin, aluminum, nickel, alloys thereof, and mixtures thereof. Preferably, the substrate provided in step A) is made entirely of metal (preferably at least one of the above-mentioned preferred metals), or it preferably comprises at least one surface made of metal, preferably at least one of the above-mentioned preferred metals a made. This surface made of metal can also be one or more palladium activated layers, typically used to make non-conductive surfaces such as glass, plastic or ceramics receptive to nickel alloy plating.

在步骤B)之前对衬底进行任选预处理。此些预处理是本领域已知的。典型的预处理包括蚀刻、清洗、锌酸化和活化步骤。有用的预处理可通过从衬底表面除去不期望的污垢或氧化物而改善镀覆结果。表面的活化通常理解为例如钯的薄且可能不连续的层在另外的不导电表面上的沉积,以使所述表面适合于后续的金属镀覆,优选地镍合金镀覆。预处理可根据所提供的衬底而广泛地变化。WO 2015/161959 A1(第13页第11行至第15页第30行)中可以示范性地找到一些指导。An optional pretreatment of the substrate is carried out prior to step B). Such pretreatments are known in the art. Typical pretreatments include etching, cleaning, zincating and activation steps. Useful pretreatments can improve plating results by removing undesired fouling or oxides from the substrate surface. Activation of a surface is generally understood as the deposition of a thin and possibly discontinuous layer of eg palladium on an otherwise non-conductive surface in order to make said surface suitable for subsequent metal plating, preferably nickel alloy plating. Pretreatment can vary widely depending on the substrate being provided. Some guidance can exemplarily be found in WO 2015/161959 A1 (page 13, line 11 to page 15, line 30).

在根据本发明的方法的步骤B)中,使衬底的至少一个表面与根据本发明的无电镍合金镀覆浴接触。In step B) of the method according to the invention, at least one surface of the substrate is brought into contact with the electroless nickel alloy plating bath according to the invention.

待镀覆镍合金的衬底可通过使衬底与本发明的无电镍合金镀覆浴接触而镀覆至期望厚度和沉积量。The substrate to be plated with nickel alloy can be plated to the desired thickness and deposition amount by contacting the substrate with the electroless nickel alloy plating bath of the present invention.

在沉积期间,即最优选地在步骤B)期间,本发明的无电镍合金镀覆优选地维持在20℃至100℃,优选地70℃至95℃,更优选地80℃至90℃,甚至更优选地83℃至87℃的温度范围内。During deposition, ie most preferably during step B), the electroless nickel alloy plating of the present invention is preferably maintained at 20°C to 100°C, preferably 70°C to 95°C, more preferably 80°C to 90°C, Even more preferably in the temperature range of 83°C to 87°C.

衬底可与本发明的无电镍合金镀覆浴接触足以镀覆期望厚度的镍合金沉积物的任何时间段。镍合金沉积物的厚度尤其取决于所述沉积物或含有所述沉积物的产品的期望用途。作为非限制性实例,通常认为30至180分钟的范围,优选地40至90分钟,并且更优选地50至70分钟的接触持续时间是足够的。The substrate can be contacted with the electroless nickel alloy plating bath of the present invention 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 intended use of the deposit or the product containing the deposit. By way of non-limiting example, contact durations in the range of 30 to 180 minutes, preferably 40 to 90 minutes, and more preferably 50 to 70 minutes are generally considered sufficient.

可以形成厚度高达100μm或更高的镍合金沉积物。优选地,镍合金沉积物的厚度变化,优选地为1至60μm的范围。厚度取决于技术应用,并且对于一些应用可以更高或更低。例如,如果镍合金沉积物要提供耐腐蚀涂层,则通常期望30至60μm的范围的厚度,而对于电子应用,优选地施加1至15μm的范围的厚度。在刚性存储盘的技术领域中,镍合金沉积物的厚度优选地为5至20μm的范围,更优选地为7至16μm。在半导体技术领域中,镍或镍-磷沉积物的厚度优选地为1至5μm的范围。镍合金沉积物的厚度可以用本领域已知的X射线荧光(XRF)测量。Nickel alloy deposits can be formed up to a thickness of 100 μm or more. Preferably, the thickness of the nickel alloy deposit varies, preferably in the range of 1 to 60 μm. 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 in the range of 30 to 60 μm is typically desired, while for electronic applications a thickness in the range of 1 to 15 μm is preferably applied. In the technical field of rigid storage disks, the thickness of the nickel alloy deposit is preferably in the range of 5 to 20 μm, more preferably 7 to 16 μm. In the field of semiconductor technology, the thickness of the nickel or nickel-phosphorus deposit is preferably in the range of 1 to 5 μm. The thickness of the nickel alloy deposit can be measured using X-ray fluorescence (XRF) as known in the art.

使衬底与本发明的无电镍合金镀覆浴接触的各种方式是本领域已知的。例如,可将衬底完全或部分浸入(此是优选的)本发明的无电镍合金镀覆浴中,可将本发明的无电镍合金镀覆浴喷涂或擦涂于其上。Various means of contacting a substrate with the electroless nickel alloy plating baths of the present invention are known in the art. For example, the substrate can be fully or partially immersed (which is preferred) in the electroless nickel alloy plating bath of the present invention, and the electroless nickel alloy plating bath of the present invention can be sprayed or wiped thereon.

任选地,在镀覆之前和/或镀覆期间搅动本发明的无电镍合金镀覆浴。搅动可例如通过本发明的无电镍合金镀覆浴的机械运动如摇动、搅拌或连续泵送液体或固有地通过超声处理、通过高温或通过气体进料(诸如用惰性气体或空气吹扫水性镀覆浴)来实现。Optionally, the electroless nickel alloy plating bath of the present invention is agitated prior to and/or during plating. Agitation can be, for example, by mechanical motion of the electroless nickel alloy plating bath of the present invention such as shaking, stirring, or continuous pumping of the liquid or inherently by sonication, by high temperature, or by gas feeds such as purging the aqueous solution with inert gas or air. plating bath) to achieve.

工业标准要求镀覆速率优选地为至少2.5μm/h。这允许足够经济的过程。更优选地,与本发明组合的镀覆速率在8.0至12.0μm/h的范围内。此些镀覆速率不仅允许足够经济的过程,同时改善期望的顺磁性特性在高温下的保持,而且进一步改善镀覆速度而不牺牲镀覆期间的质量。Industry standards require that the plating rate is preferably at least 2.5 μm/h. This allows a sufficiently economical process. More preferably, the plating rate in combination with the present invention is in the range of 8.0 to 12.0 μm/h. Such plating rates not only allow for a sufficiently economical process while improving retention of desired paramagnetic properties at high temperatures, but further improve plating rates without sacrificing quality during plating.

根据本发明的方法任选地包含冲洗步骤,优选地用水,和/或干燥步骤。根据本发明的无电镍合金镀覆浴和本发明的方法的以上参数仅提供用于实践本发明的一般指导。The method according to the invention optionally comprises a rinsing step, preferably with water, and/or a drying step. The above parameters of the electroless nickel alloy plating bath according to the present invention and the method of the present invention only provide general guidance for practicing the present invention.

本发明的无电镍合金镀覆浴可用于将镍合金沉积到衬底的表面上。The electroless nickel alloy plating baths of the present invention can be used to deposit nickel alloys onto the surface of a substrate.

根据本发明的镍合金沉积物及其用途Nickel alloy deposits according to the invention and their use

本发明进一步涉及可通过从根据本发明的无电镍合金镀覆浴沉积获得的镍合金沉积物。令人惊讶的是,尽管此些沉积物在元素组成(即镍、另外的可还原的金属离子和任选磷和/或硼的含量)方面似乎相同,但由根据本发明的无电镍合金镀覆浴形成的镍合金沉积物显示出优异的耐腐蚀性。The present invention further relates to nickel alloy deposits obtainable by deposition from electroless nickel alloy plating baths according to the present invention. Surprisingly, although such deposits appear to be identical in elemental composition (i.e. content of nickel, further reducible metal ions and optionally phosphorus and/or boron), the electroless nickel alloys according to the invention are The nickel alloy deposits formed by the plating bath exhibit excellent corrosion resistance.

镍合金沉积物中另外的可还原的金属的含量(优选地总含量)优选地在0.5至5.0wt.-%的范围内,更优选地为0.8至4.0wt.-%,甚至更优选地为1.0至3.0wt.-%,并且又甚至更优选地为1.2至2.5wt.-%。The content (preferably the total content) of the additional reducible metal in the nickel alloy deposit is preferably in the range of 0.5 to 5.0 wt.-%, more preferably 0.8 to 4.0 wt.-%, even more preferably 1.0 to 3.0 wt.-%, and again even more preferably 1.2 to 2.5 wt.-%.

优选地,镍合金沉积物中磷和/或硼(更优选地单独的磷)的含量为10wt.-%或更高,更优选地为10.0至16.0wt.-%的范围,优选地为10.5至15.0wt.-%,并且更优选地为11.0至14.5wt.-%。其它优选的范围为10wt.-%至15wt.-%,更优选地为10.5wt.-%至13wt.-%,最优选地为10.8wt.-%至12.5wt.-%。Preferably, the content of phosphorus and/or boron (more preferably phosphorus alone) in the nickel alloy deposit is 10 wt.-% or more, more preferably in the range of 10.0 to 16.0 wt.-%, preferably 10.5 to 15.0 wt.-%, and more preferably 11.0 to 14.5 wt.-%. Other preferred ranges are 10 wt.-% to 15 wt.-%, more preferably 10.5 wt.-% to 13 wt.-%, most preferably 10.8 wt.-% to 12.5 wt.-%.

不考虑通常存在于技术原材料和共沉积的其它材料(诸如衍生自例如有机杂质和稳定剂的那些)中的痕量杂质,镍合金沉积物中既不是另外的可还原的金属也不是磷和/或硼的剩余物通常主要是镍(通常为所述剩余物的≥98wt.-%,优选地≥99wt.-%,更优选地≥99.9wt.-%)。最优选地,根据本发明的镍合金沉积物(基本上)由镍、钼和磷组成,或(基本上)由镍、钼、铜和磷组成(不考虑通常存在于技术原材料和无意共沉积的其它材料(诸如衍生自例如有机杂质和任选的稳定剂的那些)中的痕量杂质)。Regardless of trace impurities typically present in technical raw materials and other materials co-deposited, such as those derived from, for example, organic impurities and stabilizers, the nickel alloy deposits are neither additional reducible metals nor phosphorus and/or Or the remainder of boron is usually predominantly nickel (usually > 98 wt.-% of said remainder, preferably > 99 wt.-%, more preferably > 99.9 wt.-%). Most preferably, the nickel alloy deposit according to the invention consists (essentially) of nickel, molybdenum and phosphorous, or (essentially) of nickel, molybdenum, copper and phosphorous (regardless of what is usually present in technical raw materials and unintentional co-depositions). trace impurities in other materials such as those derived, for example, from organic impurities and optional stabilizers).

本发明进一步涉及可通过从根据本发明的无电镍合金镀覆浴沉积获得的镍合金沉积物的用途和本发明的方法。此镍合金沉积物优选地用于保护工件免受环境酸性腐蚀条件的影响。“环境”是指工件的环境使得工件可能经历酸性腐蚀条件,最优选地在室外自然条件下。The invention further relates to the use of the nickel alloy deposits obtainable by deposition from the electroless nickel alloy plating bath according to the invention and to the method of the invention. This nickel alloy deposit is preferably used to protect the workpiece from the acidic corrosive conditions of the environment. "Environment" refers to the environment of the workpiece such that the workpiece may experience acid corrosive conditions, most preferably under natural outdoor conditions.

针对本发明的一个方面所描述的细节和优选实施例通过加以必要的变更而适用于其它方面。为了避免不必要的重复,不再描述它们。Details and preferred embodiments described for one aspect of the invention apply mutatis mutandis to other aspects. To avoid unnecessary repetition, they are not described again.

现在将通过参考以下非限制性实例来说明本发明。The invention will now be illustrated by reference to the following non-limiting examples.

实例example

除非在下文中另有说明,否则如在本说明书的提交日可获得的技术数据表中所述使用商业产品。

Figure BDA0003651535740000111
155(浸泡清洁剂)和
Figure BDA0003651535740000112
701(电清洁剂)是AtotechDeutschland GmbH(安美特德国有限责任公司)的产品。Unless otherwise stated below, commercial products were used as described in the technical data sheets available on the filing date of this specification.
Figure BDA0003651535740000111
155 (soak cleaner) and
Figure BDA0003651535740000112
701 (electric cleaner) is a product of AtotechDeutschland GmbH (Atotech Germany GmbH).

在下文所述的所有镀覆实验中使用0.7dm2面积的钢板(Q面板类型QD)。在镀覆镍合金之前,如下文所述对面板进行预处理。Steel sheets of 0.7 dm 2 area (Q panel type QD) were used in all coating experiments described below. Prior to nickel alloy plating, the panels were pretreated as described below.

Figure BDA0003651535740000113
Figure BDA0003651535740000113

金属或金属合金沉积物的厚度和镀覆速率的测定Determination of thickness and plating rate of metal or metal alloy deposits

使用XRF仪器Fischerscope XDV-SDD(菲希尔有限责任公司(Helmut FischerGmbH),德国)在每个衬底的5个点处测量磷含量和沉积厚度。通过假设沉积物的分层结构,可以从此XRF数据中计算层厚度。通过将获得的层厚度除以获得所述层厚度所需的时间来计算镀覆速率。Phosphorus content and deposition thickness were measured at 5 points per substrate using an XRF instrument Fischerscope XDV-SDD (Helmut Fischer GmbH, Germany). Layer thicknesses can be calculated from this XRF data by assuming the layered structure of the deposit. The plating rate is calculated by dividing the obtained layer thickness by the time required to obtain the layer thickness.

pH值测量pH measurement

用pH计(WTW,Typ pH 3110,电极:

Figure BDA0003651535740000114
41,具有温度传感器的凝胶电极,参比电解质:3mol/L KCl)在25℃测量pH值。继续测量直到pH值变得恒定,但在任何情况下至少持续2分钟。使用前用Fluka和Certipur提供的pH值为2、4和7的缓冲溶液标准校准pH计。With a pH meter (WTW, Typ pH 3110, electrode:
Figure BDA0003651535740000114
41. Gel electrode with temperature sensor, reference electrolyte: 3 mol/L KCl) to measure pH value at 25°C. Continue the measurement until the pH becomes constant, but in any case for at least 2 minutes. The pH meter was calibrated before use with buffer solution standards at pH 2, 4 and 7 provided by Fluka and Certipur.

沉积镍合金的组成Composition of the deposited nickel alloy

使用X射线光电子能谱(VersaProbe XPS,物理电子学有限责任公司(PhysicalElectronics GmbH))测量沉积的镍合金的组成。The composition of the deposited nickel alloys was measured using X-ray photoelectron spectroscopy (VersaProbe XPS, Physical Electronics GmbH).

工作实例Working example

出于比较的原因,制备含有以下组分的本发明的几种镍合金镀覆浴(各1L):For comparison reasons, several nickel alloy plating baths (1 L each) of the present invention were prepared containing the following components:

-镍离子 6g/L(102.2mmol/L,以硫酸镍形式提供),- nickel ion 6g/L (102.2mmol/L, provided as nickel sulfate),

-次磷酸钠 33g/L(0.375mol/L),-Sodium hypophosphite 33g/L (0.375mol/L),

-钼离子 24mg/L(2.50*10-4mol/L,以钼酸钠形式提供),-Molybdenum ion 24mg/L (2.50* 10-4 mol/L, provided as sodium molybdate),

-铜离子 2.0mg/L(3,15*10-5mol/L,以硫酸铜(II)五水合物形式提供),- Copper ions 2.0mg/L (3,15* 10-5 mol/L, provided as copper(II) sulfate pentahydrate),

-络合剂 如表1中给出的不同浓度(以g/L计),- complexing agents in different concentrations (in g/L) as given in Table 1,

-pH 用氨溶液(25wt.-%于水中)调节至4.6- pH adjusted to 4.6 with ammonia solution (25 wt.-% in water)

将镍合金镀覆浴的温度设定为86℃且将衬底浸入浴中60分钟。The temperature of the nickel alloy plating bath was set to 86°C and the substrate was immersed in the bath for 60 minutes.

表1:实例1至16Table 1: Examples 1 to 16

## 11 22 33 44 55 66 77 88 99 1010 1111 1212 1313 1414 1515 1616 丙二酸Malonate [g/L][g/L] 5.35.3 5.35.3 5.35.3 5.35.3 5.35.3 00 22 1010 2020 5.35.3 5.35.3 5.35.3 5.35.3 5.35.3 5.35.3 5.35.3 苹果酸malic acid [g/L][g/L] 1717 1717 1717 1717 1717 1717 1717 1717 1717 1010 2525 1717 1717 1717 1717 1717 丙酸propionic acid [g/L][g/L] 00 11 1010 2525 5050 3.63.6 3.63.6 3.63.6 3.63.6 3.63.6 3.63.6 3.63.6 3.63.6 3.63.6 3.63.6 3.63.6 苯甲酸钠sodium benzoate [g/L][g/L] 33 33 33 33 33 33 33 33 33 33 33 00 11 33 1010 2020 镀覆速率Plating rate [μm/h][μm/h] 8.68.6 9.29.2 10.210.2 9.19.1 8.88.8 8.58.5 9.19.1 8.98.9 7.77.7 9.79.7 7.07.0 8.98.9 9.29.2 9.39.3 9.39.3 10.610.6 磷含量Phosphorus content [wt.-%][wt.-%] 11.111.1 10.910.9 11.211.2 11.011.0 11.811.8 11.111.1 10.710.7 10.910.9 12.112.1 10.010.0 11.611.6 11.511.5 11.211.2 10.910.9 11.011.0 10.110.1 应力stress [N/mm<sup>2</sup>][N/mm<sup>2</sup>] -17-17 -20-20 -14-14 -17-17 -18-18 -8-8 -19-19 -20-20 -20-20 跳过jump over -20-20 -19-19 -18-18 -18-18 -15-15 -6-6

即使使用不同量的CA1、CA2、CA3和CA4,使用本发明的无电镍合金镀覆浴(实例2至5、7至11和13至16)的第一试验显示出足够的镀覆速率和磷含量。Even with varying amounts of CA1, CA2, CA3, and CA4, first experiments with electroless nickel alloy plating baths of the present invention (Examples 2 to 5, 7 to 11, and 13 to 16) showed adequate plating rates and Phosphorus content.

为了进一步测试和描述本发明的优点,选择实例14作为本发明的代表。To further test and describe the advantages of the present invention, Example 14 was chosen as representative of the present invention.

腐蚀测试1(时间)Corrosion Test 1 (Time)

根据标准AASS–DIN EN ISO 9227进行腐蚀测试1。Corrosion test 1 according to standard AASS – DIN EN ISO 9227.

材料:Q面板类型QD RA<0.5μm;沉积物厚度≈10μmMaterial: Q panel type QD RA<0.5μm; deposit thickness ≈ 10μm

测定作为红锈的缺陷面积并与总面积(“相对缺陷面积”)比较,并根据以下方案评级:The defect area as red rust is determined and compared to the total area ("relative defect area") and rated according to the following scheme:

如果没有检测到缺陷,即相对缺陷面积为0%,则指定等级10。因此,指定以下等级(括号中对应的相对缺陷面积):9(>0%至0,1%);8(>0.1%至0.25%);7(>0.25%至0.5%);6(>0.5%至1.0%);5(>1.0%至2.5%),4(>2.5%至5.0%);3(>5.0%至10%),2(>10%至25%);1(>25%至50%);0(>50%)。A rating of 10 is assigned if no defects are detected, ie, the relative defect area is 0%. Therefore, the following grades are assigned (corresponding relative defect areas in parentheses): 9 (>0% to 0,1%); 8 (>0.1% to 0.25%); 7 (>0.25% to 0.5%); 6 (> 0.5% to 1.0%); 5 (>1.0% to 2.5%), 4 (>2.5% to 5.0%); 3 (>5.0% to 10%), 2 (>10% to 25%); 1 (> 25% to 50%); 0 (>50%).

表2:在一定量的时间之后腐蚀测试1中的评级Table 2: Ratings in Corrosion Test 1 after a certain amount of time

0小时0 hours 24小时24 hours 48小时48 hours 72小时72 hours 96小时96 hours 实例12(对比)Example 12 (comparison) 1010 88 77 66 55 实例14(本发明)Example 14 (Invention) 1010 1010 1010 99 88

如表2所示,与实例12(对比)相比,实例14(根据本发明)显示出显著改善的耐腐蚀性。在实例12中,没有使用芳族羧酸。因此,芳族羧酸显然对耐腐蚀性具有有益效果。As shown in Table 2, Example 14 (according to the invention) showed significantly improved corrosion resistance compared to Example 12 (comparative). In Example 12, no aromatic carboxylic acid was used. Thus, aromatic carboxylic acids clearly have a beneficial effect on corrosion resistance.

腐蚀测试2(MTO)Corrosion Test 2 (MTO)

基于市售产品(

Figure BDA0003651535740000121
HP 1151,安美特的产品),用另一比较实例进行另外的测试;在下文中称为实例17。该比较允许进行深入的腐蚀性能研究。Based on commercially available products (
Figure BDA0003651535740000121
HP 1151, a product of Atotech), an additional test was performed with another comparative example; hereinafter referred to as Example 17. This comparison allows for in-depth corrosion performance studies.

实例17基于如上所列的一般配方,但不使用铜离子和钼离子。此外,实例17含有对应于CA1、CA2和CA3的三种羧酸,但不含芳族羧酸(即不含CA4)。Example 17 was based on the general formulation listed above, but without the use of copper and molybdenum ions. In addition, Example 17 contained three carboxylic acids corresponding to CA1, CA2 and CA3, but no aromatic carboxylic acids (ie, no CA4).

腐蚀测试2也根据标准AASS–DIN EN ISO 9227进行。Corrosion test 2 was also carried out according to the standard AASS – DIN EN ISO 9227.

表3:腐蚀测试2-确定直到表面上>1%红锈的时间(以小时计)Table 3: Corrosion Test 2 - Determination of time until >1% red rust on surface (in hours)

MTO*MTO* 00 22 44 66 实例14(本发明)Example 14 (Invention) 312小时312 hours 312小时312 hours 224小时224 hours 36小时36 hours 实例17(对比)Example 17 (comparison) 204小时204 hours 156小时156 hours 100小时100 hours 12小时12 hours

*表示金属翻面*Indicates metal flip

表3显示,同样对于腐蚀测试2,观察到耐腐蚀性的显著改善。进一步的实验表明改善的效果归因于CA4的存在(数据未显示)。Table 3 shows that, also for Corrosion Test 2, a significant improvement in corrosion resistance was observed. Further experiments indicated that the improved effect was due to the presence of CA4 (data not shown).

固有应力测试Intrinsic stress test

弯形条curved bar

通过使用具有两指的应力条测量涂层中的应力,两指在一侧上被涂漆。测试条由化学蚀刻的铍铜合金制成并具有类似弹簧的特性。在应力测量之前,以±10%的精度确定浴的镀覆速率,以确定用于应力测量的镀覆时间。在通过适当的预处理进行表面清洁之后,应力条指与测试面板电接触,并且将两者非常小心地浸入处理浴中。基于已知的镀覆速率,计算镀覆持续时间以产生10μm的涂层厚度。镀覆后,用去离子水冲洗测试条,并使用纸巾小心干燥。由于应力条指在机械上是易碎的并且倾向于非常快地变形,所以需要立即对它们进行评估。新镀覆的表面上的氧化物形成将随时间改变射束偏转。镀覆的应力条指将安装在测试台上,测试台测量镀覆后测试条指展开的距离。距离U确定应力条指之间的增量距离,并被包括在计算以N/mm2计的沉积物应力的公式中。The stress in the coating was measured by using a stress bar with two fingers, which were painted on one side. The test strips are made of chemically etched beryllium copper alloy and have spring-like properties. The plating rate of the bath was determined with an accuracy of ±10% prior to the stress measurement to determine the plating time for the stress measurement. After surface cleaning with appropriate pretreatment, the stress bar fingers were in electrical contact with the test panel and both were immersed very carefully into the treatment bath. Based on the known plating rates, the plating duration was calculated to yield a coating thickness of 10 μm. After plating, the test strips were rinsed with deionized water and carefully dried with paper towels. Since stress bar fingers are mechanically fragile and tend to deform very quickly, they need to be evaluated immediately. Oxide formation on the freshly plated surface will change the beam deflection over time. The plated stress bar fingers will be mounted on a test bench that measures the distance the test bar fingers spread out after plating. The distance U determines the incremental distance between the stress bar fingers and is included in the formula for calculating the sediment stress in N/ mm2 .

应力

Figure BDA0003651535740000131
stress
Figure BDA0003651535740000131

T是以μm(微米)计的沉积物厚度,并且K是由供应商提供的条校准常数。制造的每批测试条在用于沉积物应力测试时将有轻微差异。当校准每批测试条时,供应商将确定该差异程度。K值将与专业测试和开发公司(Specialty Testing&Development Co.)提供的每批测试条一起提供。应力被确定为压缩或拉伸性质。如果测试条腿向外展开在已镀覆的侧面上,则沉积物应力本质上是拉伸的。如果测试条腿向内展开在已镀覆的侧面上,则沉积物应力本质上是压缩的。压缩应力按照惯例以负数给出,从而在压缩应力的情况下以上等式的结果乘以-1。T is the thickness of the deposit in μm (micrometers) and K is a bar calibration constant provided by the supplier. Each batch of test strips manufactured will vary slightly when used for deposit stress testing. The supplier will determine this degree of variance when calibrating each batch of test strips. The K value will be provided with each batch of test strips provided by Specialty Testing & Development Co. Stress is determined as a compressive or tensile property. If the test strip legs are flared out on the plated sides, the deposit stress is tensile in nature. If the test strip legs are flared inward on the plated side, the deposit stress is compressive in nature. Compressive stress is conventionally given as a negative number, whereby the result of the above equation is multiplied by -1 in the case of compressive stress.

通过将应力值与亚磷酸根的浓度(在下文中缩写为OP)联系起来,在浴寿命期间进行固有应力测试。OP是表示浴龄的合适指示剂,因为亚磷酸根是次磷酸盐氧化和随时间累积的反应产物。Intrinsic stress testing was performed during bath life by correlating the stress value to the concentration of phosphite (abbreviated OP hereinafter). OP is a suitable indicator of bath age because phosphite is a reaction product of hypophosphite oxidation and accumulation over time.

表4:固有应力Table 4: Intrinsic Stress

Figure BDA0003651535740000141
Figure BDA0003651535740000141

表4显示初始(即OP=0)应力值非常类似/彼此接近。此外,绝对值与表1中也显示的基于OP=0的应力值一致。Table 4 shows that the initial (ie OP=0) stress values are very similar/close to each other. In addition, the absolute value agrees with the stress value based on OP=0 also shown in Table 1.

然而,在老化后,表4显示在长期浴利用中,芳族羧酸的存在改善了压缩应力情况。这意味着芳族羧酸的存在相对于增加的OP浓度产生改善的耐受性,并由此保持内应力更接近最佳水平(参见实例14:“20”对比实例17:“92”)。因此,如实例14所示,保持更优化的压缩应力水平直至更高的浴龄,特别是如果OP达到高于100g/L的浓度。However, after aging, Table 4 shows that the presence of aromatic carboxylic acid improves the compressive stress profile in long-term bath utilization. This means that the presence of aromatic carboxylic acids results in improved tolerance relative to increasing OP concentration and thus keeps internal stress closer to optimal levels (see Example 14: "20" vs. Example 17: "92"). Therefore, as shown in Example 14, more optimal compressive stress levels are maintained up to higher bath ages, especially if OP reaches concentrations above 100 g/L.

浴稳定性Bath stability

如下所述进行烧杯稳定性测试:Beaker stability testing was performed as follows:

该方法是用于测定无电镍处理浴的化学稳定性的镀覆测试。它适用于镍磷涂层的自催化沉积。首先清洁高形状的1升烧杯,并用1:1HNO3剥离剂溶液剥离1小时,以避免烧杯的底部和壁上可能负面影响测试的任何残余物。然后取1升EN浴溶液(测试溶液)并如下文所述在其中进行处理。使用搅拌器并设定为250rpm。当达到操作温度时,测试开始。首先将EN测试溶液保持1小时无镀覆。然后检查烧杯的底部和壁上的任何镍沉积。如果看不到,烧杯测试可以继续,并在EN浴溶液中镀覆一块预处理的1dm2软钢板。板必须在没有任何补充的情况下镀覆1小时。当这结束时,实现了一个循环。因此,一个循环对应于1小时无镀覆+1小时镀覆。在镀覆期后进行补充。如果在烧杯的底部或壁上没有发生沉淀或镍沉积,则在下一个循环中,可以用1小时无镀覆和1小时镀覆来继续测试。当在烧杯的底部或壁上可见广泛的镀覆或镀出时,烧杯测试结束。记录实现的循环次数。利用实现的循环次数,可以评价稳定性。This method is a plating test used to determine the chemical stability of electroless nickel treatment baths. It is suitable for autocatalytic deposition of nickel phosphorus coatings. First clean the tall-shaped 1 L beaker and strip with a 1: 1 HNO stripper solution for 1 h to avoid any residue on the bottom and walls of the beaker that could negatively affect the test. One liter of the EN bath solution (test solution) was then taken and treated therein as described below. A stirrer was used and set to 250rpm. When the operating temperature is reached, the test begins. The EN test solution was first left unplated for 1 hour. Then check the bottom and walls of the beaker for any nickel deposits. If not visible, the beaker test can continue and a piece of pretreated 1dm 2 mild steel plate is plated in the EN bath solution. Plates must be plated for 1 hour without any supplementation. When this ends, a loop is implemented. Thus, one cycle corresponds to 1 hour of no plating + 1 hour of plating. Make up after the plating period. If no precipitation or nickel deposition occurs on the bottom or walls of the beaker, the test can be continued with 1 hour of no plating and 1 hour of plating on the next cycle. The beaker test ends when extensive plating or plating is visible on the bottom or walls of the beaker. Record the number of cycles achieved. Using the number of cycles achieved, stability can be evaluated.

对于下面的测试程序,所述1升样品取自处于相应处理浴的不同年龄的处理浴。在0MTO采集的样品对应于新制备的处理浴,其中更高的MTO对应于增加的浴年龄。For the following test procedures, the 1 liter samples were taken from treatment baths of different ages in the respective treatment baths. Samples taken at 0 MTO correspond to freshly prepared treatment baths, where higher MTO corresponds to increased bath age.

表5:烧杯稳定性测试(循环次数)Table 5: Beaker Stability Test (Number of Cycles)

Figure BDA0003651535740000142
Figure BDA0003651535740000142

Figure BDA0003651535740000151
Figure BDA0003651535740000151

*表示金属翻面*Indicates metal flip

表5显示,与取自根据实例17的处理的样品相比,取自根据实例14的处理的样品具有更高的稳定性(各5个循环)。尽管实例17显示了相对恒定的循环次数(各循环3至4次),但在芳族羧酸化合物存在的情况下通过至少一个循环改善了绝对稳定性。Table 5 shows that the samples taken from the treatment according to Example 14 had higher stability (5 cycles each) than the samples taken from the treatment according to Example 17. Although Example 17 shows a relatively constant number of cycles (3 to 4 cycles each), absolute stability was improved by at least one cycle in the presence of the aromatic carboxylic acid compound.

考虑到本说明书或本文公开的本发明的实践,本发明的其它实施例对于本领域的技术人员将是显而易见的。说明书和实例仅是示范性的,本发明的真实范围仅由以下权利要求限定。Other embodiments of the invention will be apparent to those skilled in the art from consideration of this specification or practice of the invention disclosed herein. The specification and examples are exemplary only, and the true scope of the invention is limited only by the following claims.

Claims (15)

1. An electroless nickel alloy plating bath comprising:
a) nickel ions;
b) an additional reducible metal ion selected from the group consisting of: molybdenum ions, rhenium ions, tungsten ions, copper ions, oxygen-containing ions thereof, and mixtures thereof;
c) at least one reducing agent adapted to reduce the nickel ions and the additional reducible metal ions to their respective metallic states; preferably selected from the group consisting of: hypophosphorous acid, hypophosphites, and mixtures of the foregoing; and
d) complexing agents CA1, CA2, CA3, and 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, their corresponding salts, and mixtures thereof;
wherein CA3 is selected from the group consisting of: aliphatic compounds having exactly one carboxylic acid moiety, their corresponding salts, and mixtures thereof; and
wherein CA4 is selected from the group consisting of: aromatic compounds having at least one carboxylic acid moiety, their corresponding salts, and mixtures thereof.
2. The electroless nickel alloy plating bath according to claim 1, wherein 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, unfunctionalized and functionalized aliphatic pentacarboxylic acids, unfunctionalized and functionalized aliphatic hexacarboxylic acids, the corresponding salts thereof and mixtures thereof; preferably, 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, their corresponding salts, and mixtures thereof.
3. The electroless nickel alloy plating bath according to any of the foregoing claims, characterized in that the complexing agent CA1 is an unfunctionalized aliphatic C2-C12-dicarboxylic acid and/or salt thereof, preferably an unfunctionalized aliphatic C3-C6-dicarboxylic acid and/or salt thereof.
4. The electroless nickel alloy plating bath according to any of the foregoing claims, characterized in that 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 thereof.
5. The electroless nickel alloy plating bath according to any of the foregoing claims, characterized in that the complexing agent CA2 is a functionalized or unfunctionalized aliphatic C3-C12-dicarboxylic acid and/or salt thereof, preferably a hydroxyl-functionalized aliphatic C4-C6-dicarboxylic acid and/or salt thereof.
6. The electroless nickel alloy plating bath according to any of the foregoing claims, characterized in that 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-hydroxyadipic acid, salts thereof, and mixtures of the foregoing.
7. The electroless nickel alloy plating bath according to any of the foregoing claims, characterized in that the complexing agent CA3 is a functionalized or unfunctionalized aliphatic C1-C5-monocarboxylic acid and/or salt thereof, preferably a functionalized or unfunctionalized aliphatic C2-C4-monocarboxylic acid and/or salt thereof; more preferably CA3 is propionic acid and/or a salt thereof.
8. The electroless nickel alloy plating bath according to any of the foregoing claims, characterized in that the complexing agent CA4 is a functionalized or unfunctionalized aromatic carboxylic acid and/or a salt thereof, preferably CA4 is benzoic acid and/or a salt thereof, more preferably CA4 is sodium benzoate.
9. The electroless nickel alloy plating bath according to any of the preceding claims, characterized in that it has a pH value in the range of 3.5 to 5.0, preferably 4.0 to 4.8, more preferably 4.2 to 4.7.
10. The electroless nickel alloy plating bath according to any of the foregoing claims, characterized in that the further reducible metal ions are molybdenum ions, copper ions or mixtures thereof; preferably, the additional reducible metal ion is a molybdenum ion or a mixture of a molybdenum ion and a copper ion.
11. The electroless nickel alloy plating bath according to any of the preceding claims, wherein the further reducible metal ions have a valence number between 1 x 10 based on the total volume of the electroless nickel alloy plating bath-4To 5 x 10-3Total concentration in the mol/L range.
12. Use of an electroless nickel alloy plating bath according to any of claims 1 to 11 for depositing a nickel alloy onto at least one surface of at least one substrate.
13. A method of depositing a nickel alloy onto at least one surface of a substrate, comprising the following method steps in sequence:
A) providing the substrate comprising the at least one surface;
B) contacting the at least one surface of the substrate with the electroless nickel alloy plating bath of any of claims 1 to 11, thereby depositing a nickel alloy onto the at least one surface of the substrate.
14. A nickel alloy deposit obtainable by deposition from the electroless nickel alloy plating bath of any of claims 1 to 11.
15. Use of a nickel alloy deposit according to claim 14 for protecting a workpiece from environmental acidic corrosive conditions.
CN202080080727.9A 2019-11-20 2020-11-19 Electroless nickel alloy plating baths, methods of depositing nickel alloys, nickel alloy deposits and uses of the nickel alloy deposits thus formed Pending CN114729455A (en)

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