Classifications

• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
  • C25D3/00—Electroplating: Baths therefor
  • C25D3/02—Electroplating: Baths therefor from solutions
  • C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
  • C25D3/14—Electroplating: Baths therefor from solutions of nickel or cobalt from baths containing acetylenic or heterocyclic compounds
  • C25D3/16—Acetylenic compounds
• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
  • C25D3/00—Electroplating: Baths therefor
  • C25D3/02—Electroplating: Baths therefor from solutions
  • C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
  • C25D3/14—Electroplating: Baths therefor from solutions of nickel or cobalt from baths containing acetylenic or heterocyclic compounds
  • C25D3/18—Heterocyclic compounds

Definitions

• the present invention relates to a galvanic bath for depositing a bright nickel layer, a corresponding mixture for use in a galvanic bath for depositing a bright nickel layer, a corresponding method for producing an article with a bright nickel layer by depositing nickel on a corresponding workpiece, the use of a galvanic according to the invention Bath or a mixture according to the invention for the deposition or production of a bright nickel layer and an article comprising a bright nickel layer according to the invention.
• Galvanic baths and processes for the electrodeposition of a bright nickel coating are known from the prior art.
• German patent application with the publication number DE 196 10 361 A1 discloses a bath and method for the electrodeposition of semi-bright nickel.
• one or more cyclic N-allyl or N-vinylammonium compounds, in particular pyridinium compounds, are used as the brightener.
• the patent in turn, refers to a number of prior art publications concerning the electrodeposition of semi-bright nickel.
• various chemical compounds are mentioned, which can be used in the galvanic bath.
• At least one to two, possibly also more nickel salts such as, for example, nickel sulfate, nickel chloride, nickel fluoride and others, and at least one inorganic acid, such as, for example, sulfuric acid or boric acid, are always present in the baths.
• nickel salts such as, for example, nickel sulfate, nickel chloride, nickel fluoride and others
• inorganic acid such as, for example, sulfuric acid or boric acid
• German patent with the publication number describes DE 10 2008 056 470 B3 a method of inspecting a metal layer either alone on a substrate or forming part of a multilayer metal layer system, and a method of analytically controlling a deposition electrolyte for depositing such a metal layer.
• the metal layer is an electrodeposited nickel layer.
• nickel layers as corrosion-protective coatings on parts made of different materials, such as copper, brass or steel or plastic, where The nickel layers are deposited in different quality and in a specific order, namely, for example, as a semi-gloss nickel layer, shiny nickel layer, optionally. with a particularly sulfur-rich intermediate layer, and again as a semi-bright nickel layer, which is optionally deposited together with particles.
• the basic composition of a nickel deposition electrolyte is according to the publication DE 10 2008 056 470 B3 typically a so-called Watts nickel bath containing nickel, chloride, sulfate ions and boric acid, for example in the following composition: 60 g / l NiCl 2 .6H 2 O, 270 g / l NiSO 4 .6H 2 O, 45 g / l H 3 BO 3 .
• the pH of the deposition electrolyte is generally 2.5-6.0, preferably 3-4.5 and especially about 4.0.
• the deposition is carried out at a temperature of 40-70 ° C, preferably 50-60 ° C and especially about 55 ° C.
• the respective layers are electrodeposited from deposition electrolytes having different compositions, particularly with respect to the additives.
• the semi-glossy base layer on the substrate material typically contains salicylic acid, ethyne derivatives such as hexynediol or butynediol, propargyl alcohol derivatives, formaldehyde and / or chloral hydrate, or mixtures of these compounds as additives.
• the optionally deposited sulfur-rich glossy or matt intermediate layer typically contains saccharin, sulfonic acids and / or ethyne derivatives as additives.
• the shiny nickel layer typically contains sulfur-containing compounds as additives, for example toluenesulfonic acid or propargylsulfonates, and additionally saccharin instead of salicylic acid or mixtures of these compounds.
• the upper semigloss nickel layer typically contains saccharin or a saccharin salt, chloral hydrate and / or formaldehyde or else mixtures of these compounds as additives and optionally additionally particles, for example of SiO 2 , Al 2 O 3 .
• the deposition electrolytes may contain other additives, such as brighteners and wetting agents.
• CH 514683 refers to a "process and bath for electrolytic nickel plating" (title).
• the bright nickel layers are less noble than the underlying semi-bright nickel layer due to the chemical incorporation of sulfur-containing organic components.
• the sulfur-containing organic component saccharin is usually used as part of the bright nickel layer.
• the migration of nickel as a commonly used in the electroplating metal from the base material protective coating is in view of the fact that nickel is considered as one of the most common trigger of contact allergies (nickel dermatitis), a health hazard to the consumer.
• this knowledge is taken into account in Germany by the Second Ordinance to Amend the Drinking Water Ordinance (TrinkwV 2001), which came into force on 14 December 2012. Accordingly, in so-called stagnation samples of the respective alloy or coating to be examined, a maximum of 10 ⁇ g of nickel may be released into one liter of drinking water. Coatings previously used, regardless of whether duplex or triplex coatings, usually do not meet the requirements of the new drinking water ordinance.
• the galvanic bath or the corresponding mixture to be specified should enable the deposition of a bright nickel layer which also has certain typical properties of a semi-bright nickel layer. These properties include, in particular, a columnar layer structure which was hitherto known only in semi-bright nickel layers and which can be determined by measuring a significant potential difference between the semi-bright nickel layer and the bright nickel layer. An effective corrosion protection would thus already be given by a layer system of such a bright nickel layer and a final chromium layer.
• the galvanic bath according to the invention or the mixture according to the invention comprises benzoic acid sulfimide (saccharin, E954, 1,2-benzisothiazol-3 (2H) -one 1,1-dioxide, CAS Number: 81-07-2) and / or Benzoeklaresulfimidanionen as a sulfur source, which means that a bright nickel layer produced using a galvanic bath according to the invention or a mixture according to the invention is electrochemically less noble than a semi-bright nickel layer disclosed in the prior art.
• the inventive galvanic bath or mixture according to the invention comprises one, two, more than two or all compounds selected from the group consisting of chloral hydrate, bromine hydrate, formic acid, formate, acetic acid, acetate, substituted or unsubstituted aliphatic aldehydes, particularly preferably chloral hydrate (trichloroaldehyde hydrate , 2,2,2-trichloroacetaldehyde hydrate, 2,2,2-trichloro-1,1-ethanediol, CAS number: 302-17-0).
• the present invention is based on the surprising finding that bright nickel layers, which are produced by means of a galvanic bath according to the invention or a mixture according to the invention, release significantly less nickel into the drinking water than conventional nickel protective layers.
• the nickel ions originate from one, two or more than two nickel salts, such as nickel sulfate, nickel chloride, nickel fluoride, which are provided in anhydrous or differently hydrated form as constituents of the galvanic bath or mixture according to the invention.
• a galvanic bath or a mixture according to the invention comprises one or more acids (component (b)), the term "acid” encompassing both the compound in dissociated and undissociated form at the respective pH.
• the acid or the acids are used in particular for buffering the pH during the electrolysis process.
• the constituents of the invention benzoic acid sulfinimide and / or Benzoeklaresulfinimidanionen (component (c)) and the optionally present (s) allylsulfonic acid and / or allylsulfonate (component (d)) are basic gloss (also primary brightener). Under glossing in particular the balance or the Leveling of unevenness in the base material understood, usually based on the use of low molecular weight organic surface-active compounds in a galvanically deposited layer.
• leveling refers to the leveling of unevenness on a surface (ntik), as for example, after a previous polishing on the surface (ntik) remain (polishing strokes).
• the polishing of a surface (n GmbH) represents a common processing step, which is carried out in particular in valves, particularly preferably in brass, zinc or zinc die-cast fittings, before electroplating.
• Brighteners thus serve a uniform distribution of an applied by means of inventive galvanic bath or inventive mixture nickel layer in the entire current density range and the deposition of a ductile, stress-free nickel layer.
• Particular preference is given here as or in component (c) benzoic acid sulfimide sodium salt (CAS number: 128-44-9) and / or as or in component (d) allylsulfonic acid sodium salt (sodium prop-2-ene-1 sulfonate, sodium allylsulfonate, prop-2-ene-1-sulfonic acid sodium salt, CAS number: 2495-39-8).
• constituents of a galvanic bath according to the invention or a mixture according to the invention such as one or more acetylenically unsaturated compounds of the formula (I) (component (e)), one or more betaines of the formula (II) (component (f)) and one or more Wetting agents (component (g)) promote, inter alia, the gloss formation of a bright nickel layer applied to a base material by means of a galvanic bath according to the invention or by means of the inventive mixture.
• Betaine of the formula (II) (component (f)) and acetylenically unsaturated compounds of the formula (I) (component (e)) are also referred to as brighteners (also secondary brighteners).
• the wetting agents contained in a galvanic bath according to the invention or in a mixture according to the invention cause a lowering of the surface tension which promotes a rapid removal of hydrogen produced during the galvanization at the cathode.
• Particularly preferred compounds of the formula (II) used are pyridiniumpropylsulfobetaine (PPS, 1- (3-sulfopropyl) pyridinium betaine, NDSB 201, 3- (1-pyridinium) -1-propanesulfonate, CAS number: 15471- 17-7) and 1- (2-hydroxy-3-sulfopropyl) pyridinium betaine (PPS-OH, CAS number: 3918-73-8). These compounds can be used singly or in combination with each other.
• the preferred compounds of the formula (II) are preferably used with other components which are referred to above or below as being preferred.
• salts of sulfosuccinic acid preferably sodium salts
• the use of salts of sulfosuccinic acid (preferably sodium salts) as wetting agents in a galvanic bath according to the invention or in a mixture according to the invention is preferred in some cases.
• the acid or acids used are particularly preferably selected from the group consisting of sulfuric acid, boric acid and hydrochloric acid.
• a particularly preferred wetting agent is a C 13 -C 15 oxo alcohol ether sulfate (CAS number: 78330-30-0).
• Also preferred as the wetting agent is sodium lauryl sulfate (sodium dodecyl sulfate, sodium dodecyl sulfate, sodium dodecyl sulfate, SLS, SDS, NLS, CAS number: 151-21-3). These compounds may be used singly or in combination, and are preferably used together with other components referred to above or below as being preferred.
• a galvanic bath or a mixture according to the invention as described above comprises fatty alcohol ether sulfates and / or fatty alcohol sulfates and / or acids of the fatty alcohol ether sulfates and / or acids of the fatty alcohol sulfates, wherein the fatty alcohol ether sulfates are selected from the group consisting of fatty alcohol ether sulfates of the formula (III), each being independent of each other n is an integer in the range 1 to 24 and R 4 represents a branched or unbranched alkyl group having 1 to 20 carbon atoms, and X is selected from the group consisting of Li, Na, K, Rb, Cs and NH 4 , and or resulting from protonation acids, and or wherein the fatty alcohol sulfates are selected from the group consisting of fatty alcohol sulfates of the formula (IV), each being independent of each other n is an integer in the range 1 to 24 and R 4 represents a branche
• Particularly preferred compounds of the formula (IV) are 2-ethylhexylsulfate sodium salt (CAS: 126-92-1) and sodium lauryl sulfate (see above). These compounds may be used singly or in combination, and are preferably used together with other components referred to above or below as being preferred.
• compounds of the formula (V) which are selected from the group consisting of 2-butyne-1,4-diol ethoxylate (2,2 '- (but-2-yn-1,4-diylbis (oxy)) - (ethan-1-ol)), 2-butyne-1,4-diol propoxylate (4- (3-hydroxypropoxy) but-2-yn-1-ol), propargyl alcohol ethoxylate (2- (prop-2-yn-1) yloxy) ethan-1-ol), sodium propargylsulfonate (prop-2-yn-1-ylsulfite sodium salt, CAS number: 55947-46-1) and sodium vinylsulfonate (SVS, sodium ethylenesulfonate, vinylsulfonic acid sodium salt, ethylenesulfuric acid sodium salt, CAS- Number: 3039-83-6).
• These compounds may be used singly or in combination, and are preferably used together with other components referred to above or
• the individual constituents of a galvanic bath or a particularly preferred mixture according to the invention which are particularly preferred in practice are the galvanic bath or the mixture according to the invention after control analysis (for example by means of HPLC analysis) supplied on demand.
• a galvanic bath according to the invention or a mixture according to the invention in the presence of cations comprises the amount of counterions required for charge balancing.
• a galvanic bath or a mixture according to the invention comprises one, two, more than two or all anions selected from the group in addition to the constituents mentioned above out F - , Cl - , Br - , I - , SO 4 2- , OH - and ClO 4 - .
• a galvanic bath or a mixture according to the invention additionally comprises one, two, more than two or all cations selected from the group consisting of Li + , Na + , K + , Rb + , Cs + , Mg 2+ , Ca 2+ and Sr 2+ .
• a galvanic bath or a mixture according to the invention which does not comprise suspended silicon oxide particles and aluminum oxide particles.
• a galvanic bath or a mixture according to the invention which does not comprise the suspended particles in the galvanic bath or in the mixture.
• a galvanic bath according to the invention or a mixture according to the invention having a pH in the range from 2.8 to 5.2, preferably from 3.8 to 4.8.
• individual components of a preferred electroplating bath according to the invention or of a preferred mixture according to the invention are particularly readily soluble in water.
• the temperature of the galvanic bath or of the mixture in step (b) is preferably in the range from 40 to 70 ° C., preferably in the range of 50-60 ° C. At such temperatures, individual components of a preferred galvanic bath according to the invention or of a preferred mixture according to the invention are particularly readily soluble in water.
• the bright nickel layer is preferably deposited on a copper, brass or zinc surface of the workpiece.
• the electrolytic nickel deposition takes place in a steel container with an acid-resistant lining (for example PVC) which is sufficient for the particular purpose or in a plastic container.
• an acid-resistant lining for example PVC
• the above-defined (preferred) constituents of a galvanic bath or a mixture according to the invention are usually dissolved in demineralized water at a temperature of 50 ° C with stirring.
• the anode material used is metallic nickel in the form of plates, squares or crowns or in any other suitable form.
• the workpiece to be nickel plated is switched as a cathode, and the electrodes are usually connected via a rectifier with direct current provided.
• the required amount of current is typically 2-8 amps per dm 2 (A / dm 2 ) of cathode area.
• the deposition rate of nickel on the workpiece connected as a cathode is generally about 1 ⁇ m nickel / minute with a current amount of 5 A / dm 2 .
• a cathode movement is often required (relative movement to the electrolyte).
• a circulation of the galvanic bath according to the invention or of the mixture according to the invention by blowing compressed air can take place (air movement).
• air movement During the current process, filtration of the galvanic bath or the mixture according to the invention is generally required.
• the analytical control of the composition of a galvanic bath according to the invention or of a mixture according to the invention as part of the method likewise according to the invention is preferably carried out by means of titration in the case of the acid and chloride concentration, in the case of the brightener concentration by HPLC analysis, in the case of wetting agents by means of measurement the surface tension and in the case of nickel (ion) concentration by chemical analysis or AAS (Atomabsorptionsspektroskopie) performed.
• AAS can also be used to determine the concentration possibly in the galvanic bath or the mixture of foreign metals present.
• the present invention also relates to the use of a galvanic bath or a mixture as described above for the deposition or production of a bright nickel layer.
• a galvanic bath or a mixture as described above for the deposition or production of a bright nickel layer.
• the present invention also relates to the use of a galvanic bath or a mixture as described above for the deposition or production of a bright nickel coating on an element of a fitting for a water-bearing pipeline.
• a galvanic bath or a mixture as described above for the deposition or production of a bright nickel coating on an element of a fitting for a water-bearing pipeline.
• a nickel layer deposited by means of a galvanic bath or a mixture according to the invention e.g. On a workpiece, there is a reduced tendency to release nickel ions into an aqueous solution in contact with this nickel layer as compared to conventional bright nickel layers. This is confirmed by measuring the potential of the deposited nickel layers.
• the relevant parameters for the corrosion process namely the layer thicknesses of the individual nickel layers and their potential differences with each other, can be measured in a single step.
• the application of the STEP test method makes use of the fact that the electrical potential measured during dissolution against a reference electrode changes abruptly after detachment of a nickel layer. This occurs after the dissolution of the respective nickel layers, the measured dissolution potentials depending, inter alia, on the type of the respective nickel layer. This is the case with sulfur-containing and sulfur-free nickel layers. With two sulfur-containing nickel layers, however, hardly any potential jump is measurable.
• the STEP test is a measuring method that destroys the nickel layer to be analyzed or the nickel layer system to be analyzed and is performed with a couloscope.
• the potential changes measured and graphically represented by the electrolytic detachment of individual nickel layers from a nickel system show, in the event of a sudden change, a point of inflection from a nickel layer to the next in such a layer system.
• the endpoint of a STEP test measurement is the achievement of the base material, e.g. B. the copper layer.
• nickel potentials are measured in a solution of nickel chloride hexahydrate, sodium chloride and boric acid. A sufficient potential between semi-bright nickel and bright nickel layer is given in measurements in the above-mentioned electrolyte from -120 mV.
• the nickel foil to be tested whose composition is determined by the constituents of the bright nickel electrolyte, is immersed in a Corrodkote solution comprising ammonium chloride, copper nitrate and iron (III) chloride, and their rest potential compared to a reference electrode also immersed in the above-mentioned solution (US Pat. Half cell electrode).
• the reference electrode consists of a silver / silver chloride measuring chain.
• the measuring instrument is a high-impedance measuring instrument, z. B. pH meter or multi-meter.
• the average measurement duration is between 45 and 60 minutes.
• a stable potential usually sets in, the value of which represents a relative value.
• Such a measured relative value can be compared with likewise determined in the manner described above relative values of differently composed nickel foils.
• a preferred potential difference between semi-bright and bright nickel layers is z. B. approx. - 70 mV.
• Corrodkote solution 20 g / l of ammonium chloride, 3.3 g / l of ferric chloride and 0.7 g / l of copper (II) nitrate 3-hydrate in aqueous solution are used according to Brugger, Robert (1984), "The Galvanic Nickel Plating", 2nd ed. Saulgau (Eugen G. Leutze Verlag Vol. 12) p. 301 ,
• the reference bath and bath according to the invention had the same composition except for the proportion of chloral hydrate.
• the potential of a nickel foil made using a reference bath was + 484 mV; the potential of a nickel foil made using a bath of the invention with 1 g / l chloral hydrate was +582 mV; the above note applies accordingly.
• Application Examples 1 -7 Preparation of a plating solution by mixing water with selected components (components); Concentration in mol / L: The pH of the galvanic bath after mixing is between 3.8 and 4.8. The above ingredients are incorporated in the above concentration in an aqueous solution. The order of addition of the individual components in the aqueous solution is not critical here. All concentration data are based on the galvanic bath.
• Application Examples 8 -14 Preparation of a plating solution by mixing water with selected components (components); Concentration in mol / L: The pH of the galvanic bath after mixing is between 3.8 and 4.8. The above ingredients are incorporated in the above concentration in an aqueous solution. The order of addition of the individual components in the aqueous solution is not critical here. All concentration data are based on the galvanic bath.
• salts present selected components (components) of a galvanic bath according to the invention are dissolved in deionized water.
• the water preferably has a temperature in the range of 30 to 70 ° C.
• To the resulting aqueous Solution are added 0.16 to 0.25 mol / L of activated carbon.
• a mixing of the activated carbon with the aqueous solution is carried out by stirring or by precoat filtration on a circulating pump.
• the activated carbon is then removed by filtration and the pH of the remaining purified solution is adjusted to a value in the range of 3.5 to 5.0.
• the non-salts selected components (components) of a galvanic bath according to the invention are added to this purified solution.
• the galvanically coated copper tubes described above under (a), (b) and (c) (1x comparison, 2x according to the invention) were then immersed separately in city water.
• the concentration of nickel / nickel ions in city water was measured after 72 hours of service life. Further measurements are carried out after a further 48 hours, 120 hours, 72 hours and 144 hours. In all cases, the water was renewed after the measurement;
• the copper tubes to be tested were also rinsed ten times with 150 ml of city water each time before further use.
• the measurement results were determined by ICP-OES spectrometer and are given in the following table. The numerical values refer in each case to the measured nickel ion concentration in ⁇ g / l.
• chloral hydrate significantly reduces the tendency to release nickel / nickel ions into the surrounding medium (here: city water), especially with long contact times (2nd to 5th measurement).
• components (components) of the specific galvanic bath according to the invention i. the components a, c, d and f, are dissolved in the specified concentration in demineralized water.
• the water preferably has a temperature of 55 ° C.
• To the resulting aqueous solution is added 0.16 to 0.25 mol / L of activated carbon.
• a mixing of the activated carbon with the aqueous solution is carried out by stirring or by precoat filtration on a circulating pump.
• the activated carbon is then removed by filtration and the pH of the remaining purified solution adjusted to a value of 4.2.
• the non-salts selected components (components) of a galvanic bath according to the invention are added to this purified solution.
• Components (components) of the specific galvanic bath according to the invention Component: Connection: g / L M [g / mol] minor a NiSO 4 .6H 2 O 280 262.84 1.0653 a NiCl 2 .6H 2 O 60 237.68 .2524 b B (OH) 3 40 61.83 .6469 c Benzolklaresulfimid sodium salt 2 205.16 0.0097 d Allyl sulfonic acid sodium salt 1 144.12 0.0069 f Pyridiniumpropylsulfobetain 0.1 201.24 0.00050 e 2-propyn-1-ol 0.02 56.06 0.000357 e Hex-3-yne-2,5-diol 0.01 114.14 0.000088 H chloral hydrate 1 165.39 0.0060 9 Sodium lauryl ether sulfate 1 416.5 0.0024
• the coating time ie the time required to deposit a bright nickel layer by means of the specific bath according to the invention, is about 15 minutes at a current density of 4 A / dm 2 .
• the constituents of a galvanic bath not prepared according to the invention for comparison purposes are identical to those in Table "Application Example 16" and were also dissolved in the indicated concentration in demineralized water (preferred water temperature 55 ° C), but the galvanic bath prepared for comparison purposes does not comprise chloral hydrate ,
• the coating time ie the time for depositing a bright nickel layer by means of the specific bath according to the invention or by means of the galvanic bath not prepared according to the invention, was about 15 minutes at a current density of 4 A / dm 2 .
• the galvanically coated brass fittings described above under (a) and (b) were dipped separately in city water.
• the concentration of Nickel / nickel ions in city water were measured after one week's service life. Further measurements are carried out after two, three, four and five weeks. In all cases, the city water was renewed after the measurement;
• the brass fittings to be tested were also rinsed ten times with 150 ml of city water each time they were re-immersed in city water.
• the measurement results were determined by ICP-OES spectrometer and are given in the following table. The numerical values refer in each case to the measured nickel ion concentration in ⁇ g / l.
• the coated bathroom fitting body according to the invention (as an example of an article according to the invention) released less nickel than the non-inventive coated bathroom fitting body.
• the bath used according to the invention comprised chloral hydrate, whereby the tendency for the release of nickel / nickel ions in the surrounding medium (here: town water) was significantly reduced.
• the results of the fourth and fifth week show that the nickel release stagnated and at the same time was significantly lower than the nickel release of the non-inventive coated brass fittings.

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