HUE035050T2 - Galvanic bath or mixture for use in a galvanic bath for depositing a gloss nickel layer and method for producing an item with a gloss nickel layer - Google Patents
Galvanic bath or mixture for use in a galvanic bath for depositing a gloss nickel layer and method for producing an item with a gloss nickel layer Download PDFInfo
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- HUE035050T2 HUE035050T2 HUE15164491A HUE15164491A HUE035050T2 HU E035050 T2 HUE035050 T2 HU E035050T2 HU E15164491 A HUE15164491 A HU E15164491A HU E15164491 A HUE15164491 A HU E15164491A HU E035050 T2 HUE035050 T2 HU E035050T2
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- 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
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- 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
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Description
tä&lvanic bath or mixture for use in a galvanic bath for depositing a gloss nickel layer and method for producing an item erth a gloss nickel layer
The present invention relates to a galvanic tooth for depositing a gloss nickel layer, a corresponding mixture for use in a galvanic bath for depositing. a gloes nickel layer, a ccrresponding method fcr producing an item wits a gloss nickel layer fey depositing nickel ton a corresponding workpiece, the nse or a galvanic bath according to the invention or a sixmo according to the invention for depositing or producing a gloss nickel layer and an item comprising a gloss nickel layer according to the invention.
Galvanic baths and methods lor galvanic deposition of a gloss nickel layer are known f rom the prior art,
Thus, tor example, international patent application with the publication number «093/11241 Ä1 relates to a method tor producing nickel-plated shaped components fey means of galvanic deposition of nickel from, aqueous/acidic baths which contain as significant components one or more nickel salts, one or more inorganic acids and at least two brightening agents. The publication further relates to a brightening agent mixture which can be used for the method:. The following ere mentioned as brightening: agent classes:; - ouiphimides, for example., bensőic acid saiphimide,· s al ph amide s.,. benvenesuiphcnic acids, for example, mono--, di- and f ribenz© nosr1phon1c a o1d, naphtho 1 solphonic acids, for example, mono-, di- and f. r i na ph t ho 1 Sr 1 ph önt C a Old, alkyl solphonic acids, sulphuric acid, - a r y1 s n i ph ons s r1pho neta s, aliphatic compornds with ethylene and/or acetylene eempornds, tor ex amp1e, but ynediol, mononuclear and multipie-nuclesr η1trogen.-containing het erő ·· cycles which can still contain additional hetero atoms auch as sulphur or selenium, coumarin, ~ amines and quaternary ammonium compounds as levelling media , saccharin.
The international patent application having the publication number WÖ 91/16474 A1 sets cut ah acidic gloss nickel bath which contains as s i.gni f .leant components nickel sulphate, nickel osier ide, boric acid, 2-ethylhexyl sulphate sodium salt ,as a wet. ting agent, saoeharin, formaldehyde and a be taine,.
The German patent, application having the publication number DiS 196 id 361 Ai discloses a bath and method tor the galvanic deposition of semi-gloss nickel. In order to galvanically deposit a semi-gloss nickel layer on a carrier, one or more cyclical h~ allyi or h-vinyl ammonium compounds:, in particular pyrldlnium compounds, are used as brightening agents, The patent spécijlicetion itself refers again to a series of publications from the prior art which relate to galvanic deposition of semi-gloss nickel, Furthermore, there are mentioned different chemical Compounds which cah be used in the galvanic bath. Accordingly, at least one to two, where applicable also more nickel salts, such as, for example, nicked, sulphate, nickel chloride, nickel fluoride and others, and at least one inorganic acid, such as, for example, sulphuric acid or boric acid, are always contained in the baths.
The merman patent having the pub! icatl.cn number Ph 10 2003 056 4'?0 BO further describee a method for examining a metal layer which is either located alone oh a substrate or is a component of a multiple-layer metal ceating system, and a method for analytical control of a deposition electrolyte which is used to deposit such a metal layer. In a preferred embodiment of the invehtibn, the metal layer is an electrolytlceily deposited nickel layer. As set out in the introduction to the description of the German parent having the publication number DB IP 2003 056 470 Bi, electrolytica.Il y deposited nickel layers arr applied as corrosion-protecting coatings to components comprising different, materiais, for example, copper, brass or steel, or also comprising plastics materiais, wherein the nickel layers are deposited with different qualities and in a specific: sequence, that is to say, for example, as a serai •’gloss nickel layer, gloss nickel layer, where applicable ’with a particularly sulphur·-rich intermediate layer, ano again as a semi-gloss nickel layer which is deposited where applicable to gethe r wift p a r t i c1es - according to the publication Dh 10 2006 056 470 B3, the basic compos 1V.loo of a nickel deposition electrolyte is typically a so-called Watts nickel path which contains nickel, chloride, sulphate ions and boric acid, for example, in the following composition: 60 g/i niCI;.6H/O, 270 g/i PiSfc. 6il-0, it g/1 H,9O.. The pH value of the deposition eleofrolyte is generally from 2.5 to 6.0, preferably from 3 to 4,5 and in particular is approximately 4.9, The deposition is carried oat at a temperature of from 49 to 7QVC, preferably from SO to 60"C, and in particular at approximately S3 °C, The respective layers are elect rolyfcicsiiy deposited from, deposition eleotrolytos having different compositions, in particular with regard to the additives. The semi-gloss base layer on the substrate material typically contains salicylic acid, ethyne derivatives, such as hexynedioi or butynediol, propargyl alcohol derivatives; formaldehyde and/or chloral. hydrate or mixtures of those compounds as additives. The optionally deposited sulphur-rich bright or matt .intermediate layer typically contains saccharin, sulphonic acids and/or ethyne derivatives äs additives. The gloss nickel layer typically contains sulphur-containing compounds as additives, for example, tolueaesul.phonic acid or propargyl sulphonates arid additionally saccharin in place of salicyIio acid or mixtures of those compounds. The upper semi-gloss nickel layer typically contains saccharin or a saccharin salt, chloral hydrate and/or formaldehyde or mixtures of those compounds as additives and where applicable additionally particles, for example, compris ing sic··, Ai:jCn. Furthermore, the deposition electrolytes may contain additional additives, for example, brightening agent s and west ing agents,
Co 5Ü683 relates to a "method and bath for alaotroiytical nickel placing" ititle).
The above-mentioned publications and the prior art which is set cut therein describe the respective advantages of the individual compounds and the combination thereof with respect to corrosion protection, levelling, ductility, brightness and coverage degree of the galvanically deposited semi-gloss nickel or nickel layer, karticuiarly the improvement of the corrosion protection of the respective nickel layers ognstitutes in the prior art a central objective which is generally intended, to be achieved by using corrosion-prorectlng duplex and triplex nickel systems. Such systems are generally formed from a semi-gloss nickel layer, a gloss nickel layer and a chromcum layer which make use of the potential difference between: the semi-gloss nickel layer and the gloss nicke·;! layer. In this instance, as soon as the upper cihrcmium layer is damaged, first the less noble gloss nickel layer (so-called sacrificial anode) is attacked by corrosive media which are introduced through the damaged chromium: layer before the more noble semi-gioss nickel layer and finally the base material itself are attacked, in this instance, the gloss nickel layers are less noble that, the underlying semi-gloss nickel layer as a result of the chemical incorporation of sulphur-containing organic components, In this regard, saccharin is usually used as a component of the gloss nickel layer as the sulphur-containing organic component,
If the objective of the previous galvanic baths disclosed in the prior art for depositing nickel layers or the methods for producing nickel-plated shaped components was primarily a reduction of the corrosion with regard to the protection of the galvanicaliy coated base material, in particular with the passing of new drinking water regulations, finally the: requirements placed on the layers which are galvanicaliy applied to the base material with respect tc the migrati on resistance et the chemical componeíits thereof hete aise increased, Besides the reduction or prevention of corrosion as a general objective, consequently, the prevention or reduction of the migration of eempenents of the metal protection layers which are galvanically applied to the base material is Included as an additional new objective or requirement, In particular, the migration of nickel as a metal Which is often used in galvanic technology from the coating which protects the base matériái is a health hasard for consumers with regard to the fact that ni ekei is considered to be one of the most, common triggers for contact allergies {nickel dermatitis}, This knowledge is taken into account in Germany inter alia, .by the second regulation for xaodifying the drinking water regulation (TrinkwV 200i/Drinking water beg. 2001) which entered into force on
Inh'' December 1011, Aecordfngiy, in the case of so-caiiec stagnation tests of the alloy or coating which is intended to be examined, a maximum of 10 gg of nickel may be discharged into a litre of drinking water. Previously used coatings, regardless of whether they are duplex or triplex coatings, generally do not comply with the requirements of the new drinking water regulation. A primary objective of the present invention is to provide a galvanic bath for depositing a gloss nickel layer and a corresponding mixture for use in a galvanic bath for depositing a gloss nickel .layer which contributes to prevention or at least a substantial reduction of nickel migration in particular in drinking water
Preferably, the galvanic bath and the corresponding mixture which are intended to fee set cut should, allow the depcsifion of a gloss nickel, layer which also has specific typical properties of a semi-gloss nickel layer. Those properties include in particular a columnar .layer structure which was previously known only in semi-gloss nickel. layers and which can be established fey measuring a substantial potential difforesee between the semi-gloss nickel and gloss nickel layer, An effective corrosion protection would consequent1 y âXfaady ba previcted by a layer system, comprising such a gios® nichsl layer and a terminal. chromium layer.
According to the invention the primary Objective set is achieved by a galvanic bath for depositing a gloss nickel layer and a correspending mixture for ose in a galvanic bath for depositing a gloss nickel layer acoording to thé appended claim 1. The mixture according to the invention in aqueous solution or the galvanic bath according to the invention in aqueous solution comprises (c) benzoic .acid su.lphiraioe and/or benzoic acid suiphimido aniens, and ( h } c h 1 o :·":· I h yd r a to,
The galvanic bath according to the invention or the mixture according to the invention accordingly comprises benzoic acid su1phinide (saccharin, E754, 1, 2bensisethiaso1-3(2a) —one-1,1-dioxide, CAS number;: 81-07-1} and/or benzoic acid snlphimide aniens as a sulphur source which results in a gloss nickel .layer which is produced using a galvanic bath, according he the invention or a mixture according to the invention being chemically less noble than a semi-gloss nickel layer disclosed in the prior art.
The galvanic bath according to the invention or the mixture according: to the invention further comprises one, two, more than two or ail of the compounds selected from rhe group consisting of chloral hydrate, brossai hydrate, formic acid, formiute, acetic acid, acetate, substituted or near-substituted aliphatic aldehydes, particulariy preferably chloral hydrate (tricolor aldehyde hydrate, 2,2,2-hriehioroaeetsidahyde hydrate, 2,2,2-trich iorc-d ,1- ethanedio.I, CAT number: 292-17-0}.
The present invention is based on the surprising recognition that gloss nickel layers which are produced by means of a galvanic bath according to the invention or a. mixture aecerding fee the invention discharge substantially lass nickel into drinking water than conventrônai nickel protection layers.
A galvanic bath according to the invention or a mixture according to the invention in aqueous nolution further comprrees the following components; ( a} n i o ke f ions, Íb} one or core acids, as defined in claim i, (e) one or more acetylece-unsatoreted compounds of the formula (I),
• ï ? where ft sign!ties a C· to Ch alkyl which is snortitoted by hydroxy, amino, it to Cj alkyiamino or di ;C; to C;;~nIkyi) amino or hydrogen or a it to Cs aikyi and PC signifies a it to Ch alkyl which is substituted by hydroxy, amino·, C:· to C., alkyiamino Of di ;C5 to C.; -a · ky i} amino, if) on© or core betaines of the formula {1.1 )
where independently of each other the nitrogen atom is a component of an aromatic ring system selected from the group consisting of pyridine, quinoline and i s ogn i. η o i i n e, and m signifies a whole number in the range trow 1 to 24 and each hr i©dependentiy signifies a branched or non-branched alkyl group with from 1 to 20 carbon atoms or hydrogen or hydroxy, • g· one or more wetting agents as defined in claim 1, Ä galvanic bath according to the invention or a mixture according to the .invention in aqueous solution (orefenabiy a bath according to the invention or a mixture according to the invention as rotorred to below as being "preferred·" ) preferably further comprises (0.} ally;, sulphohio acid and/or allyl sulphonate,
The ting which is set out in formula ill) and which contains as a character!sing reá túré of ail the betaines of the formula ( ΓΠ a /positively charged nitrogen atom in this instance refers to the aromatic ring system which is selected Hcs the group consisting of pyridine, quinoline and 1soquinolinc.
The nickel ions (component {a}) originate in this instance iron one, two or more than two nickel salts, such as, for example, nickel sulphate, nickel chloride, nickel fluoride, which are provided in water"free of dirferectly hydrated form as components of the galvanic bath according to the invention of a mixture according to the invention. Furthermore, a galvanic bath according to the invention or a mixture according to the invention comprises one or more acids (component (id ; , wherein the term: "acid" includes both the compound in dissociated and in non-dispociated form at the respective pH value. The acid(s) is/arm used in particular to buffer the pH value during the electrolysis operation.
The components according to the invention beneoie acid sulphimide and/or benroic acid suiphimide anions (component (c) ( and the optionally present ally! suiphonic acid and/or allyl sulphonate {component idk· are basic brightening agents (also primary bri.ghtsn.ing agents) , The term "brightness formation" is particularly Intended to be understood to mean the balancing or the ieveliing of occurrences of unevenness in the base material, generally based on the use of iow-raolecular organic, surface-active compounds in a galvanically deposited layer. The term " levs 11 1 ng" is intended. v,o refer to the flattening et occurrences of unevenness on a surface ( layer) , as remain, for example, at ter a prior pofi thing action on the serface (layer) (polishing marks}, The polishing of a surface (layer) constleures a convent!anal processing step which is carried out before galvanisation in particsfar in the ease of fittings, pgrfiOuiariy preferably is brass, sine or die-cast sine fittings. brightend.n.g agents oohseguéntly serve to uniformly distribute a nickel layer which is applied by means of a galvanic bath accord?ng to the invention or a mixture according to the invention in the entire flea density range and the deposition of a ductile, tension-free nickel layer. In this case, there are particularly preferably used as or In the component (o) bensőre acid sulphimids sodium suit (CAS number: 11:0----11--? and/or as or in the component (d) ailyl snlpbhnio acid sodium salt ;sodtum-prop~2"one--i-sniphonate, sodium ailed, sulphonate, prop-2-one-l-suiphonio acid sodium, salt, Git number : 2995-39-1} .
The components of a galvanic bath according to the invention or a mixture according to the invention further set out, such as one or mere aoetyiene-unsatureted compounds of the formula (1} (çcmponeht (e) } , one or more betaines of the formula (11} (component (ft) and one or mote: vetting agents (component (g) ), promote inter alia the brightness: formation of a gloss nickel layer which is applied to a base material by means of a galvanic bath according tO: the invention or a mixture according to the invention.
Betaines of the formula (111 ( component (1)) and acetylene-onaatnraled compounds of the form?.; (a (!) (component (e) ) are also referred to as brightening agents (also secondary brightening agents}, The wetting agents which are contained in a galvanic hath according to the invention or a mixture according to the invention bring about a reduoflon of the surface tension which promotes a rapid removal of hydrogen produced during galvanisation, at the cathode , in this· instance, pertioularly preferably used compounds· of the formula {X} (component (e; } ars propargyl alcohol (z-propyn-l-ol, CAP number; 107-19··?} , 2-butyne-l, 4-diel (but-z-ync-1, 4-;?iol} , 1fi-butynedioi, bis{hydroixyme thane)acetylene, bytyhedi ol, CAS • ;u mb e r : 110-05-0}, hex - 3 - y n e -2,0 -di ο 1 (3 ·· he x y ne - z, S -diói, di i 1 - hydroxy ethyl)acetylene, bis(l-hydfoxyethyl)acetylene, CAS number: 3. 0 31 - 00 -1} a no 1 - di et by 1 ami a c- pr op - 2- y n e ( b, h d i ft t h y 1 ρ r op ·· z ··· y n 1 -amine}, These compounds may be used individually er it combinat ion.
Particularly preferably Wed compounds of the formula ( 11} (compotier·t If}} or© pyridininm propyl sniphobetsine it03, 1-(3- sulpbogpopyl;pyridinium bfttaines, WDSB zOi, 3-(l-pyridinio) ·· 1 ·· propanesulphonate, CAS number: 15471-17-7} and 1 ·· (z-hydroxy-3-sulphPpropyi}pyridiniom betaine (FPS-OH, CAS number: 3518-73:-3} , 7’hose compounds may be used individually of in combination with each other. The preferred compounds of the formula (IX; arc preferabiy used with additional components which are referred to above or below as being preferable. A galvanic bath according to tbc invention comprises or a mixture according to the invention comprises in aqueous solation to) one or more inorganic acids selected from the group consisting of: sulphuric acid, boric acid and hydrochloric acid and/or one or more organic acids selected from the group consisting of: malic arid, citric acid, lactic acid and amidosulphonic acid, and ig} cue or more wetting agents, wherein one wetting agent is selected or one or more or all of the plurality of wetting agents is/are selected from the group consisting of {id fatty alcohol ether sulphates and/or a c id s p rod coed the:: e f t. om b y p r o t O n a t i o n, (115 fatty alcohol sulphateà and/or acids prod-iced therefrem by protonation, (Ili 5 mixtures including df comprising - fatty alcohol ether sulphates and - fatty alcohol sulphates, iiy) mi stures including of comprising - acids of fatty alcohol ether sulphates and - acids of fatty alcohol sulphates, tv) mixtures including or comprising - fatty alochcl ether sulphates and acids of ratty alcohol sulphates, and (vis mixtures including or comprising -- acids of fatty alcohol ether sulphates and --- fatty alcohol sulphates,, wherein the selected wetting agent carries as a carbon chain a branched or unbranched alkyl group or the selected wetting agents carry as a carbon chain a branched or nnbranched alkyl group independently of each other.
Altornativeiy or additicnaliy, in many cases the use of salts or the suiphosuccinic acid {preferably sodium salts! is preferred as a wetting agent in a galvanic bath according to the invention or in a mixture according to the invention. l.n this instance, the aeidis) used is/are particularly preferably selected from tbs group consisting of sulphuric acid, boric acid and hydrochloric acid. There is used as a particularly preferred wetting agent a Crs^Cts OXC alcohol ether sulphate (CAS number: 78310-30-0} . There is also preferably used at a wotting agent sodium lauryl sulphate {sodium dodecyl sulphate, dodecyl sulphate sodium salt, sulphuric acid dodecyl ester sodium salt, 113, SOS, hhS, CA3 number: :.31-31-3} . Those compounds may be used individually or in combination and are preferably used together
with other composesto which are referred to above or below as bein g p r e f e r r e d, A gslvaror hoch according to the invertion or a mixture acoord Log to the invention preferably comprises, as described above, fatty alcohol ether sulphates and/or fatty alcohol sulphates and/or acids of ratty alcohol other sulphates and/or acids of fatty alcohol sulphates, wherein the fatty alcohol ether sulphates ate selected from the group consisting of fatty alcohol ether sulphates of the formula tilt),
/01/ where independently of each other n signifies a whole number in the range from: / r.o 21 and A$ signifies a branched or unpranobed alkyl group with from 1 to ./0 carbon atoms, and X is selected from the group eonsisting cf
Li, da, b, Ab, Cs and Nfh, and/or acids produced therefrom by protonation and/or where the fatty alcohol sulpha tea are selected from the group consisting: of fatty alcohol sulphates of the formula -/V),
( IV ;, where independently of each ether n aignifies a whole number in the range from 1 to 2/
and R" signifies a branched or unbranched alkyl group with from 1 to 215 carbon a cores, nod X is selected from the group cousis tiny of
Li; Na, X, Rb, Cs vt Mii.;., and/or acids of faffy alcohol sulphates produced therefrom by orctonation, in this ca.se, particularly prof erred compounds ci the formula (IV) are 2-et.hy). hexyl sulphate sodium salt (CAR; '111-11-: } and sodium layryi sulphate {of.♦ above) .. Those compounds may be used individually or in combination and are preferably used in combination with other components which are referred co above or below as being preferred.
Preferably, a galvanic bath according to the invention or a mixture according co the invention {preferably, a galvanic bath according to the invention referred to as being "preferable" or a mixture according to the invention} also comprises in addition to the above-mentioned components (:) one or more oompounds of the formula (v) ,
R1 whore signifies a ois or. trans-configured double-bond or a triple-bond and P:' signifies a Cs to lh~ui.kyi which is substituted by hydroxy or hydrogen or CH oft and •f signifies a (A to Cx-aikyi which is substituted by hydroxy or hydrogen or a saiphonic acid residue Or the sait thereof. where and lb do not simnitanehUsly signify hydrogen and wham ehe broken line signifies a bond.
There are particular iy preferred compounds of the formula (V· which are selected iron's the group consisting of 2~butyns-l, i-dio.1 othdxylate (2,2' « (but-z-yno-i, 4-diyl his (oxy· ) bis (ethan-J-cl) , 2~ butyne~ 1..,. <-diói. propoxylabs '( 4·* ( 3-diydioxypr epoxy} but-2-yne-l-oi}, prepa r gy 1 a i echo i o thdxyl ate ( 2 - · p r ο p - 2 - y n - ,1 - yloxy} e thane-1 - el } , sodium propargyl sulphonate (prop-2-yn- b-yi sulphite sodium salt, GAS number I 55247-4/-:} and sodium vinyl sulphonate (SVS, sodium methylene sulphonate, vrnyi suiphonic acid sodium salt, ethyiene suiphonic acid sodium sait, CAO number: 3039--83-/} v Those compounds may be used individually or in combination and are preferably used together with ether components which are referred to above or below as being preferred. A yulvamc bath which is particularly preferred it practice comprises the following cempenents or a mixture which is particularly preferred in practice comprises in aqueous solution one, a plurality or all of the following components (in the concentrations set out ; : (a} nickel ions in a total quantity of from 1.12 to 1.67 mol/f and/or (b? One or more inorganic acids selected from the group consisting of ; sulphuric acid, boric acid and hydrochloric acid and/or one or more organic acids selected from the group consisting of: malic acid, citric acid, lactic: acid and amidosulphonie acid, in a total quantity of item 0,485 to 0.97 moI/L end/or (c, benrole ac isi suiphimide and benzoic acrid sulphimide anions in a total quantity of from. 0.3025 to 0.027 4 moi/I. and/or (d} aliyl sulphoniq acid and allyl sulphonate in a total quantity of from 0.006 to 0,Q2b mcl/l and/or
Ce) one or more acetylens-unsaturated compound» of the formula (I)
<Γ) where •b signifie» a C-. to <h alkyl which is substituted by hydroxy,, amino, C; to Ch alkylamino or di (C to Ch^alkyl) amino or hydrogen or a Ci to C< alkyl and
Ih signifies a C:. to Ci alkyl which is substituted by hydroxy, amino, Ci to G,s a iky lam inc or di {Ci to Q-aikyl} amino, in a total quantity of from 0.00036 to 0.1438 mcl/L and/or uf} one or more betainas of the formula (XX)
ill ; whore independently of each other the nitrogen atom is a component of an aromatic ring system selected from the group consisting of pyridine, quinoline and 1scquinoline, and m signifies a whole number in the range from: 1 to 24 and each tl independently signifies a branched or nen^branohed alkyl group with from 1 to 2Q carbon atoms or hydrogen or hydroxy, in a total quantity of from 0,03025 to 0,0025 mcl/L and/or igi one or more wetting agents, wherein the wetting agent is selected or one or more or all of the plurality of wetting: agents are selected from the group consisting of (1) fatty alcohol ether salphases and/or acids: produceg therefrom by protonatien, (iig fatty alcohol sulphates
and/ er acids produced therefrom fcy prctonation, (iii) mixtures includihg of comprising - fatty alcohol· other sulphates and/or ~ fa tty a .1, c o h o ,1 s o ip ha t e s, ad X ta res i ho 1editg or comprising ·· acids of fatty alcohol other sulphates and “ acids of fatty alcohol sulphates, ;v;. mixtures: inoiuding or compris; lag ~ fatty alcohol ether sulphates 3:'id ~ acids of fatty alcohol sulphates, and fvi) mixtaros including or comprising - acids of fatty alcohol other' sulphates cU’lCt - fatty alcohol sulphates, wherein the fatly alcohol ether sulphatea are selected from the group consisting of fatty alcohol ether sulphates of the formula : ill ),
(Ilf) where independently of each ether n signifies a whole number in the range from 1 to 24 and R“ signifies a branched or unbranehed alkyl group with from 1 to 10 oarbon atoms, and h is selected from the group consisting of hr, ha, K, fto, Cs and hit;, and/or acids produced therefrom by profanation
and/or where tho fatty alcohol suiphafes arc aeiected Iran the group cor;siat 1 ng of fatty alcohol sulphates of thé formula OVy
IXV),. where Indöpepdorjtly of each other n signifies a whole number In the range from I to 24 and it' signifies a branched or ano ranched alkyl· group with: free 1 to 20 carbon atoms, and X is selected from, the group coneisllng of hi, ha, K, 8b, Cs and Hu.:, and/or acids produced therefrom by prOtonation in a total quantity of from 0,0006 to 0,02S mol/i and/or in) chloral hydrate in a total quantity of from 0,003 to 0,01.8 mol/1 and/or hi) one or more compounds of the formula ;V) ,
(V) where
signifies a cis or irans-configured double-bend dr a triple-bond and R' signifies a to C;-a.ikyi which is substituted by hydroxy or hydrogen, or CHO/h and: fi signifies a C· to íf-alXyi which is.. substituted by hydroxy or hydrogen or a sulphonic seid residue or the salt theroof, where Ft sod hl do not simnitanaousiy signify hydrogen and whore the .broken line signifies a hong in a total quantity of up to 0,0025 mol/L. A galvanic hath according to the invention or a mixtare according to the invention which contains ail the components get oat above (a), fh) t (c) , (dy, :si, (g) , (hi and (i) in the concentrations sot out above is quite particularly preferred« 'The individual components set out above in respect of a galvanic bath according to the invention which is martionlariy preferred in practice or a mixture according to rue invention which is particuiariy ore terred are supplied to the galvanic hath according to the invention or the nictate according to the invention after control analysis (for example, by menus of Htt.C analysis) in accordance with reguirements depending on the progression of the galvanic method and in accordance with the respective conhumption of the coïtbonents set out. above.
Naturally, a galvanic hath according to the invention or a mixture according to the invention comprises in the presence of cations the quantity of oppositely charged ions which is necessary for oharge egua i i sapion. preferably, a galvanic hath according ho the invention or a mixture according to the invention (preferably a galvanic bath according to the invention which is referred to above as being "preferred’'' or a mixture according to the invention) comprises, in addition to the components set out above, one, two, more than two or all of the aniohs selected from the group consisting of F , Cif, Br", h, SOy", Of“ and CiOf'l A gaivanic bath according to the Invent ion Or a mixtúra according to the invention preferably .further comprises one, two, more than two or all of the cations seiected trois the group consisting of lit ha', by top Cs', brp:, Car' and Sit'd A gaivanic bath according to the invention which is particularly preferred in practice or a particulariy preferred mixture according to the invontion comprises
Cn) two or all compounds selected from the group consisting of: chlore! hydra ίο, fcromni hydrate, formaldehyde end acetaldehyde, where one of the compounds is colorai hydrate.
There is quite particulariy preferred in practice a galvanic bath according to the invention or a mixture according to the invention which is a sing 1 e-phase solution.
There is particularly preferred a gaivanic bath according to the invention or a mixture according to the invention which does not comprise suspended silicon oxide particles and aluminium oxide particles .
There is quite particularly preferred a gaivanic bath according to the invention: or a mixture according to the invention which does net comprise suspended oxide particles«
There is also preferred a gaivanic bath according to the invention or a mixture according to the invention which does not comprise suspended particles in the galvanic bath or in the mixture.
There is particularly preferred a gaivanic bath according to the invention or a mixture according to the invention with a pH vaine in the range frem 2.8 to 2.2, preferably from 3.8 to 3.8. At such pH values and suitable fcopera tores, individual components of a preferred galvanic bath according to the invention or a preferred mixture according to the invention arc particularly water-so hsbie .
There is quite particularly preferred a galvanic Path according to the invention or a mixture according to the invention which can be produced by mixing a plurality of components, wherein a plurality of components are selected from the group cons;.seine of <a1} nic keI suIphat e, (a 2} n1ekeJ chloride, (hl} boric acid, (cl; bentoio acid sulphimide sodium salt, {dis allyl snlphonic acid sodium salt, ( e 1 ) 2 ~p r op - y n -1 -- o 1, ; e 2} 1 -d 1e t hy i ami no ~ p rop-2-yne, Í e 3} h e x - 3 - y ne - 2,5 - d i e 1, ífX; pyridinium propyl sulphobetaine, (q-Vl) sodium salt of a fatty alcohol ether sulphate of the formula (Vi)
(Vi) J' ä u signifies a whole number in the range from 1 to 23, and t' signifiée a saturated, branched or saturated, unbranched: alkyi group with from 1 to 20 carbon atoms, (hl) ohloral hydrate, (il) p r op 2 - y η - 1 ·· ο 1 ™ et h οa y late«
In addition, there is quite particularly preferred a galvanic bath according to the invention (preferably a galvanic bath according to the invention referred to above as being "preferred'7? which can be produced by mixing a plurality of components, wherein a plurality of components are selected from the group consisting of (a) nickel ions in a total quantity of from 1.12 to 1.6? mol/2, (bl) boric acid in a total quantity of from 0,4 25 to 0.2'? moI/L, (c) benzoic acid sulphimide anions in a total quantity of from 0.0020 to 0.0274 mol/f,
(d; allyl sulphonate to a total quantity of from 0,006 to 0,025 sol ./1: ,
Cel) O-ptôp-ÿïi-toôï to a total quantity of iron· 0.00036 to to to to moi / '·., (to) 1-diethyiaeino-propto-yne In a total quantity of trod 0 to U , ra.; y 5 r.c ?. .-··., , (ei) hex-3-yne-2,5-dioi to a total quantity Of from 0 to 0.0008 mol/n, (fl) pyridinium propyl sniphooetaine: in a total quantity of from 0. G O 02 5 t o 0,Ö0 25 so1/L f (q) sodium salt of a fatty aieohol otto;: sulphate of the formula ( VI )
into where n signifies independently a whole number in the range from 1 to 24 and
Id siqnifies independently a saturated, branched Of saturated, unto ranched alkyl group with from 1 to 20 carbon atoms, in a total quantity of from O.OQOfl to 0,02 5 dol./f, (hl) chloral hydrate in a total quantity of from 0,003 to 0,018 mol/1., and (11) prop-2 ·· yn-i-ο 1-ettony h;to In a total quantity of from 0 to 5,0025 mol/to
In this instance, all the concentrâtion indications are in relation to the galvanro bath.
The present invention also relates to- a method for producing an item with a gloss nickel layer by depositing nickel on a corresponding workpiece, having tho: following steps: (a) providing and/or producing a. galvanic bath aooorging to the; invention or a mixture, ív;} galvanically depositing nickel from aha provided or produced na.lvan.ic bath or; aha mixture on the workpiece ter producing the gloss nickel layer.
Preverabiy, in a method according io the invention the temperature of the galvanic hath or the mixture in step (b) is in the range from 40 to 7QnC, preferably in the range from. SO to S.Ö:Ö:C. At such tempenatures, individual coupeneats of a preferred galvanic hath according he the invention or a preferred mixture according to the i n ve nt. i on are pa r t i eu I a r .1 y va t er"" se 1 ub 1 a, tréfa rabi y, in a method aecording to the invention in step }fo} the giess nickei layer is deposited on a copper, brass or zinc surface of the workpiece.
There is quite particniariy preferred a method according to the invention in which the item is an element of a pipeline or an element of a fitting for a water-carrying pipeline.
There is farther partieulariy preferred a method according to the invention, wherein the above-explained deposition is carried but on a surface of the workpiece, wherein that surface is part of a gloss nickel layer of the workpiece.
There is: quite particularly preferred a method according to the inventi.cn having the following additional step: io} deposition, preferably galvanic deposition, of an additional metal layer on the gloss nickel layer, proverabiy galvanic deposition of a chromium, layer on the gloss nickel layer.
It is preferable in a method according to the invention to introduce air into the galvanic hath according to the invention and/or to move the workpiece on which the nickel is intended to be galvanically deposited in tile galvanic bath or in the mixture. Both the introduction of air and the movement of the workpiece in the galvanic bath according to the invent ion or in the mixture according to the invention arc used in this instance for better electrolyte exchange at the workpiece surface on which nickel is intended to be galvanically deposited.
There is further preferred a wethod according to the invention, in which the elecfcroiyt:le nickel deposition is carried cut in a steel container' with an acid-resistant lining which is sufficient for the intended purposes (for sután .pie, FVC; or in a plastics container ,
The above-defined (preferred} components of a galvanic bath according to the invention or a mixture according to the invention are generally dissolved with stirring in completely desalinated water at a temperature of aO'‘t. Metallic nickel, in the fora of plates, squares or crowns or in another suitable form is used as the anode material. The workpiece to be hiçkei-platsd is connected as the cathode and the erectrodes are generally supplied with direct current via a rectifier. The necessary current guant.ity is typieairy from 2 to ..3 ampere per Oat (h/dmf'! of cathode surface-area, The deposition rate of nickel on the workpiece which is connected as the oatnode is generally approximately 1 urn of nickel/minute at a current quantity of 5 A/ost , In order to ensure optimum electrolyte exchange at the cathode surface, movement of the cathode is often necessary (relative movement in relation to the electrolyte}< alternatively or additionally, circulation of the galvanic bath according to the invention or the mixture according to the inventich Can be carried out by introducing compressed air {..sir movement} . during the encrent method, a filtration of the galvanic hath according to the invention, or the mixture according to the invention is generally necessary.
The analytical control, of the compositn.cn of an above-described galvanic bath according to the invention or a mixture acccrding to the invention as part of the method similarly according to the invention is preferably carried out in the case of the acid and chioride concentration by means of titration, in the case of brightening agent concentration by means of HttC analysis, in the case of the wetting agent by means of measurement of the surface tension and in the case of the nickel dort concentrai ion by means of chemical analyaxa or 0Λ3 (abort absorption spectroscopy) . By means of hAS it. is farther possible to establish the concentration where applicable in the galvanic bath or the mixture ci foreign me t a .1 s p r e s en t,
The present invention farther reiaf.es to the use of a galvanic bath, according to the invention or a mixture according to the invention as described above for depositing or producing a gloss nickel layer . The above explanations in relation to preferred embodiments of baths or mixtures according to the invention apply accordingly »
The present invention also relates to the use of a galvanic bath or a mixture as described above for depositing or producing a gloss nickel layer on an element of a fitting for a water-carrying pipeline. The above expiansirons in relation to preferred embodiments of baths or mixtures according to the invention apply aooo rd ingi y,
There is further disclosed an item, particularly preferably an element of a pipeline or element of a fitting for a water-carrying pipeline, comprising a gloss nickel layer, wherein the gloss nickel layer can be produced - by depositing nickel on the corresponding 'workpiece using a galvanic hath or a mixture as described above Ö Î? - by means of a method as described above.
Specific aspects are explained in greater detail below in connection with the invention which is defined in tbs claims : 1. Galvanic bath for depositing a gloss nickel layer or mixture for use in a galvanic bath for depositing a gloss nickel layer, whsrsin tbs mixture in aqueous solution comprises of the galvanic bath in aqueous solution comprises: (c) benzoic acid sulphimide and/or benzoic acid sulphimide anions,
a rid (h) oft·«, too, more than two or all of: she costpounds selected from the group consisting of: chloral hydrate, bromal hydrate, formic acid, f ormiate, acetic acid, acetate, substituted or non-substitutod aliphatic aldehydes, wherein the galvanic hath further comprises the following components or the cistern further oomprises the foliowing components ; {a) nieke 1 i.ons, ft5 cuO: or more acids, io) oho or more aoetyieiie-tunsaturated compounds of the formula iln,
m , where: 2 signifies a (1 to it alkyl which is substituted by hydroxy, amino, Ch to C, alkyiamihO or di (C; to Cg-alkyl; amino or hydrogen or a C: to C'4 alkyl and R' signifies a C- to Ch alkyl which is substituted by hydroxy, amino, C;. to C, alkylamino or drift to Cy-alkyl·} amino, if} one or more betaines of the formula ill)
(lid , whets independentiy of each other the nitrogen atom is a component of an aromatic ring system selected from the group consisting of pyridine, quinoline ana iso gu 1 no 1 i no, and m signifies a whole number in the range from 1 to 24 and each kt independently signifies a branched or non-branched alkyl group with from 1 to 23 Carton atoms or hydrogen or hydroxy, ··::} one or more wetting agents, 2. A galvanic bate or an. x euro according to aspect 1, wherein the galvanic bath comprises vhe fallowing components or the mixture in aqueous solution comprises one, a plurality or all of tbs foliating components: he·} one or more inorganic acids selected from the group consisting of : sulphuric acid, boric acid and hydrochloric acid and/or one or pore organic acids selected from the group consisting or; malic acid, citric acid, lactic acid and amidosulphonic acid, and/or (gi one or more wetting agente, wherein one wetting agent is selected or one or more or ail of the piaruiity of wetting agents is/are selected fro:·· the group consisting of (i :· f atty alcohol ether sulphates and/or acids produced therefrom by protonétion, <11; fatty alcohol sulphates and/or acids produced therefrom by profOnatich, (ill.) mixtures including or comprising ~ tatty alcohol ether sulphates and fatty alcohol sulphates, (iv;· mixtures including or comprising ~ acids of fatty alcohol ether sulphaoes and ·· acids of fatty alcohol sulphates, :v) mixtures including or comprising - fatty alcohol ether sulphates and acids of fatty alcohol sulphates, and. (vie mixtures luoluding or comprising - acids of fatty alcohol ether sulphates
and '·· fatty aiecho! sulphates,, wherein the selected wetting agent carfles as a carbon chain a branched or uneswachen alkyl group or the seleoted: wetting agents carry as carbon chains a branched or unbranched alkyl group independently of each ether, and/or wherein the one wetting agent is selected er one or bore or all of the wetting agents are selected írom the group consisting ol salts of the su.Iphosnccinie acid, I. Galvanic hath or mixture according to aspect 2, wherein the fatty alcohol ether sulphates are selected from the group consisting of fatty alcohol ether sulphates of tbs formula /1111,
(Hl) , where independently of each other n signifies a whole number in the range from 1 to 24 and R' signifies a branched or unbranched alkyl group with from 1 to 10 carbon atoms, and X is selected from the group consisting of
Li, ha, K, Rb, Cs and LH;, and/or acids produced therefrom by pretonation and./or where the fatty alcohol sulphates are selected from the group consisting o* tatty alcohol sulphates of the formula {IV),
αν y, where independently of each other n signifies a whole number in the range from 1 to 24 and if signifies a branched or unbraneheb alkyl group with fror 1 to 20 carbon atoms, and X is selected iron the group consisting of
Li, Na, K, Rb, is and hl·:,, and/or acids produced therefrom by protonstion, 4. Galvanic bath or mixture according to any on© of the preceding aspects, Wherein the galvanic bath further comprises the following components or the mixture in agueouh solution further comprises one, a plurality er ali of the following components; G) one or more compounds of the formula (V;,
(yd where g?-gn^f-;es a cis tmsns-configured dcubie-bond or a triple--bond and hr signifies a Ct to th-aikyi which is substituted by hydroxy or hydrogen or CILOR'· and R? signifies a if to if-alkyl which is substituted by hydroxy or hydrogen or a suiphonic acid residue or the salt thereof, where R* and if do not simultaneously signify hydrogen and where the broken line signifies a bond.
5, Galvanic bath or mixture accordion to any one of too preceding aspects, wherein the galvanic bath comprises the following components or the mixture in aqueous solution comprises one, a plural)ty or ail Of the following components :
Caf nickel ions in a total quantity of from 1,12 to 1.67 moi/L and/or •b) one or more inorganic adds selected from tne group consisting of : sulphuric acid, ‘boric add and hydro chloric add and/or one or more organic acids selected from the group consisting of; made acid, citric add, lactic add and amioosulphonic add,
In a total quantity of from 0.48 5 to 8.97 moi/8 and/or Co), benzoic add sulphimide land benzoic acid: sulphimidb anions in a total quantity of from 8.0058 to 0.02,1 mol/L and/or (d) ailyi suiphonid acid aid allyl sulphonate la a: total quantity of from 0.006 to 0.025 mol/L and/or is) one or more acetylene unsafcur a ted compounds of the formula ft)
(I ) where ?h signifies a Cs to C.s alkyl which is substituted^ by hydroxy, amine, Cq to tq alkyiamine or di fC:i to Cb-alkyl) amino or hydrogen Or a Ci to C,. alkyl and
Ft signifies a Cs to c; alkyl which is substituted by hydroxy, amine, tq to iq alkyiamino or did to C-.-dkyi; amine, in a total quantity of from 0.88036 to 8,1438 mol/L and/or if} end or more betaines of the formula {11;
Π) where independent s y of each other the nitrogen atom is a. component of an a mud - r...r j ..>ysi cm selected from the group consisting of pyridinet quinoline end issmqninoline, and, m signifiât, a whole number in the range from 1 to 24 and each Ft independentiy signifies a branched or non-branched alkyl group with from 1 to 20 carbon atoms or hydrogen or hydroxy, in a total quantity of from 0.0-0-02-5 to 0.1025 mol/L aad/or ig) one or more wetting agent s, wherein the: wetting agent is ce looted or one or more or all of the plurality of wottinq agents are selected from the group consisting of (ii fatty alcohol ether sei chares and/or a c i ds p r oda ce d t her e f r om by nr o n οn a t ion: , (ii) fatty alcohc-I sulphates and/or aends produced therefrom by protonét ton, {ill.} mixtures Including or comprising - fatty alcohol ether su;.ph..rf a, and - fatty alcohol sulphates,
Civ} mixtures including or comprising - acids of fatty aioohol ether sulphates and - acids of fatty aicohoi sulphates, ian mixtures including or comerising --·· fatty alcohol ether sulphates and - acids of fatty aicohoi sulphates, and vi) mixtures including or comprising ~ acids of fatty aicohoi ether sulphates and. ~ fatty alcohol sulphates,
wherein the fatty alcohol ether sulphates are selected írom the group consisting of fatty alcohol ether sulphates of the forrnia (Ili;x
11 IB where independently of each other n signifies a whole number in the range loom 1 to 21 and R Sf gn ' f ’ e« λ t 'ancle, a ^uuru'^nd <.lkyl d'oup w·"'' t'ot 1 to 20 cardon atoms, and X is selected from the group consisting of ti, No, K, hb, Is and bin, an ci/or ..... acids produced therefrom by protonatlom and/or wherein the fatty alcohol sulphates are selectod from the group consisting of fatty alcohol sulphates of the foreurs (IV·,
(IV! , where independently of each other n signifies a whore nucOor in the range from 1 to 24 a nd 2' signifies a branched or unbranched alkyl group with from 1 to 20 carbon atoms, d liílt X is selected from the group consisting of
Li, ba, K, Rb, Is and RH;, and/on
acids pfodáöed therefrôts by protonatiosi iß a total quantity of from 0,0006 to 0,025 mo.l/L and/or (h) one,· fwo, more than two or all of the compounds selected from the group consi 81 i ng 0 f ï chloral hydrate, fo romai hydrate, formic acid, forrni ate, acetic acid, acetate, substituted or nor-substituted aliphatic aldehydes, in a total quantity of from 0.00 3 to 3,313 rtcl/L and/or (1} chc or more compounds of the forsaula (V},
rye who r e trénere a or trans-'oenf i gnrod double-bond or a triple*· bond and, id signifies a G;. -to Chalky! which is substituted by hydroxy or hydrogen or CihöPd and it signifies a Ci to C.·.-aiKyi which is substituted by hydroxy or hydrogen or a sulphcnio acid residue or the salt thereof, where fo and ft do not simul faucons ly signify hydrogen and wherein the broken line signifies a bond in a total quantity of frost 0 to 3,0025 mol/5, 0. dalvanio bath or srixtuie according to any one of the presseeing aspects, wherein the galvanic bath or mixture further comprises one, two, store than two or ail of the anions selected from the group cohsistihg of r, Cd , Be, 1", SOI-, OH" and Cloth 7. Galvanic bath or mixture according to any one of the preceding aspects, wherein the galvanic bath or mixture furs:her comprises one, two, more than two or all of the cations saicoted frost the group: consisting of
Li', Ma\ K', Eb', os', Mg"', Ca" and Sr". 8. Galvanic bath or mixture according to any one of the preceding aspects, wherein the galvanic bath or the mixtúra in aqueous eolation compfises :
Oh one, two or all of the çcmpqunds selected from the group consisting of : chloral hydrate, oromai hydrate, fo.ntaldahyde and acetaldehyde, wherein the compound or one of the compounds Is preferabiy ohioral hydrate . 9, Galvanic bath or air tore according to any one of the preceding aspects, wherein the galvanic bath or the mixture is a single--phase solution, 10. Galvanic bath or mixture according to any One of the preceding aspects, wherein the galvanic bath or the mixture does not comprise ; silicon oxide particles and alum.inium oxide particles suspended in the galvanic bath er in the mixture, 11, Galvanic bath or mixture according to any one of the preceding aspects, wherein the galvanic oath or the mixture does not comprise oxide particles suspended in the galvanic bath or in the mixture . 12» Galvanic bath or mixture according to any one of the preceding aspects, wherein the galvanic bath or the mixture does not compri se; particles suspended in the galvanic bath or in the mixture, 13» Galvanic bath or mixture according to any one of the preceding aspects, with à pH value In the range from 2.3 to 5.2, preferably from 3.3 to 4,3, 13. Galvanic bath or mixture according to any one of the preceding aspects which can be produced by mixing a plurality of components,
wherein the plurality of co;xponents are selected from the group consisting of: (a1; n1eke1 su Iphate, (ai) nickel chloride, (bi) boric scih, (cl) bonroic acid seipnimide sodium salt, (dl) allyl euiphonio acid nodi.urn. salt, ( el ) 2 - p r op - y n -1 - ei , ( el ; i - d x e t h y I ami no -p t op - 2 - yn, ( e 3 · h o z ·· 3 - y n - 2,5 -di o 1, (fl( ρy ridíni urn propyl suichobetaine, (g-Vf) sodium salt of & fatty alcohol· ether sulphate of the formula (VI)
If where n signe.fies a whole number in the rance from 1 to 21, and fi signifies a saturated, branched or saturated, rebranched alkyl group with from 1 to 20 carbon atoms, (hi) chloral hydrate, ( i 1 ) p r op- 2 ·· y n ~ 1 - o i - e f h O x y la f e - if, Saivaftic bath aeoording to any one of the preceding aspects which can he produced by mixing a plurality of components, wherein the plurality of components are selected from the group consisting of: (a) nickel ions in a total quantify of from 1.12 to I. S'? moi/L, (bi) boric acid in a total quantify of from 0.48S to 0,9? mol/1,, (o) bonsoio acid suiphxmide anions tn a total quantity of from 0.ö 055 t o 0,Q2 7 4 me1 /1, dl) allyl sulphonate in a total quantity of from D. 0(15 to 0.222 moi/L,
ί a 1 ί 2 -prop -yrs-l ·· oi in a total quantity of from 0.00036 to 0.0 OS a æo i /L., (e2( l“-cUmthylaiairio-“p:rop'--2:-yn-e it a total quantity of frort 0 to 0 . 00at w /1 / (el) ho:X--3-yto-2,S-di.ol in a total quant ;.ty of from 0 to 0,0081 (fl; pyridinium propyl suiphobetaine It a total quantity of fron 0,00325 tó 0.0020 mdl/h, (qj «odium aalt of a fatty alcohol ether sulphate of the formula ί' VI '
(Vf) where r· signifies independently a whole number in the range from I to 24 and R‘ signifies independently a saturated, branched or saturated, anbranched alkyl group with from 1 to 20 carbon atoms, in a total quantity of from. 0,0006 to 0,025 moi/L, (hl) chloral hydrate in a total quantity of from 0.001 to 0,0 18 mol/L, and (il) prôp'--2-«’yn*l"Ol’"ethexyIate in a total quantity of from Û to 0.0025 meI/O, IP, Method for producing an item with a gloss nickel layer by depositing nickel on a corresponding workpiece, haring the ft11owln0 atops; (ai providing and/or producing a galvanic bath or a mixture according to any one of the preceding aspects, (b) galvanically depositing nickel from the provided or produced galvanic bath or the mixture on the workpiece for producing the g i o ss n i ck e 1 Ia yer, 17. Method according fco aspect 16, wherein fene temperature of the galvanic bath or the fixture in step ;tg is in the range from 40 : . Í kJ ' :, : 18. Method according to either aspect 16 or aspect I'?, wherein in step (b) the gloss nickel, layer is deposited on a copper, brass or tine surface of the workpiece. 19. Method according to any on© of aspects 16 to 18, wherein the item is an element of a pipeline or an element of a fitting for a war. e r - o a try i ng pipe 1 in e . 20. Method according to any Ohe of aspects 16 to 19, wherein in stop {b ) the deposition is carried oat on a surface of the workpiece, Wherein that surface is part cf a semi-gloss nickel layer of fho workpiece , 21. Method according to any one of aspects 16 to 20, having the foilowing additional· a tan; fccl deposition, preferably galvanic deposition, of an additional metal layer on the gloss nickel layer, preferably galvanic deposition of a chromium layer on the gloss nickel layer, 22. őse of a galvanic hath or a mixture according to any one of aspects 1 to 15 for depositing or producing a gloss nickel layer. 23. dse according to aspect 22 for producing a gloss nickel layer on an element of a fitting for a water-earrying pipe line , 24. Item, preferably an element of a pipeline or element of : fitting for a water-carrying pipeline, comprising a gloss nickel layer, wherein the gloss nickel layer can he produced
- by depositing nickel on the corresponding workpiece using a galvanic bath of a nmxture according to any one of aspects 1 to IS
0 X '·· by means of a method according to any one of aspects 16 to 21,
25. Use î i ! of a mixture for use io. a galvanic bath or ( r i.) of a galvanic bath for producing a gloss nickel layer on an element of a fitting for a water-carrying pipeline, wna.reiu < r} the mixture comprises or (if) the galvanic bath in aqueous solution comprises: (c; bensőin acid suiphimide and/or bonsoir acid suiphimide anions, and (h) one, two, dote than two or all of the compounds selected from the group consisting: of: chloral hydrate, brémai hydrate, formic add, romiad, acetic acid, acetate, substituted or non-substituted aliphatic aldehydes, wherein the galvanic hath further comprises the following components or the mistare in aqueous solution further comprises ail of the following components :. fa) nickel ions, (b) one or more acids, id) allyl sulphenic acid and/or -allyl sulphonate, id) one or more acetyXene-unsabursted compounds of the formula it),
U) , whe re U signifies a Cg to C.5 alkyl which is substituted by hydroxy, amino, tg to ip alkylacino or di ifi to ih-uikylî amino or hydrogen or a C: to fh alkyl and R signifies a Cg to G4 alkyl which is substituted by hydioxyy ami.no,: <h to tg alkyi ami no or di ( C- to C.5~ alkyl) amino,: ff) one or more betaines of the formula ft)
ill), where independently of a a. eh other the nitrogen a tos is a tcmponent of an aromát ic ring system selected from the group consisting of pyridine, quinoline and i soquincline, and tn signifies a whole number in the range from 1 to 2s and each Ef independenriy signifies a branched or non-~branched alkyl group with from 1 to 20 car non atoms or hydrogen or hydroxy, (g) one or more wetting agents. A nickel layer which is deposired by moans of a galvanic bath according to the invention or a mixture aocorebng to the ixiventioh, for example, on a workpiece, has in comparison with conventional gloss nickel layers a lesser tendency to discharge nickel ions into an aqueous solution which is in contact with this nickel layer. This is confirmed by measuring the potentials of the dopes1ted ni eke1 layers<
Potential measurements ; General indications and examples :
The measurement of potentials of individual nickel layers and nickel layer combinations which are deposited on a corresponding workpiece by means of a galvanic bath according to the invention or a mixture according to the invention is generally carried out by means of the so-called STEP test (STEP:: simultaneous thickness and electrode potential determinâtion; > deference may be made to DIN 50122 with regard to the experiment conditions and the expo riment structure of the STtP test.
With the STEP test, which is a method for verifying the quality of a deposited nickel layer or a deposited nickel layer system, the parameters relevant to the corrosion progression, that is to say, the layer thicknesses of the individual nickel layers and the potential differences thereof from each other, are measured in a single operating step. During the application of the STEP test method, use is made of the fact that the electrical potential measured during dissolution changes abruptly with respect to a reference electrode altar the detachment of a nickel layer. This occurs after the dissolution of the respective nickel layers, wherein the measured dissolution potentials depend inter alia on. the type of the respective nickel layer. This is the case for surphur-containing and sulphur-free nickel layers. In the case of sulphur-containing nr chef layers, however, hardly any potential jtsmp can he measured, The STET test is a measurement method which destroys the nickel layer which is intended to he analysed or the nickel layer system which is intended to fee analysed and Is carried out with a. ooulesoope. The potential changes which are .measured by the electrolytic detachment of individual nickel layers from a nickel system: and which can be displayed graphically exhibit an inflection point from one o.Lokei layer to the next in such a layer system in the case of an abrupt change. The end point of a STEP test measurement is when the base material is reached, for example, the copper layer. Generally, nickel potentials are measured in a solution of nickel chloride hexahydrate, sodium chloride and boric acid. An adequate potential between the semi-gloss nickel and gloss nickel layer is provided in the case or measurements in the above-described electrolyte from -120 mV.
In order to measure the resting potentials of nickel fells which are produced by means of a galvanic bath according to the invention or a mixture according fee the invention, the test structure described below is used:
The nickel foil to fee examined, whose composition is determined fey the components Of the briefer nickel electrolyte, is immersed in a Coerodkote solution corner is usg ammoniurn chloride, copper nitrate and iron (111) chloride, and the resting potential is measured in comparison with a reference elec:trade (he If-cell electrode) which is also immersed in the above-described solution. The reference electrode comprises a silver/silver chloride measuring chain, A highly resistant measuring device, for example, pH tiefer or multi-measurement device, is used as the measuring device. The average measurement duration is in this instance between IS and
approximately 60 minutes. Xn the context of thia time period, there is generally estaplished a a table potential., whose value Is a relative value, Such a isieasured relative value can bo compared with relative values, which are also established in the manner described above, of nickel foils which have different compositions. A preferred potential différence between the semi-gloss and gloss nickel layers is, for example, approximately ~7Q: mV.
For the preparation of a: Corrodkotc solution, there are used 23 g/i of aWionium chloride, 3,3 g/i. of iron till) chloride and 0.7 g/i of copper (il) nitrate-3~hydrafe in aqueous solution In accordance with Snugger, Robert (1964), "bio eaivanische VemIckeiong" (Galvanic nickel plating) , 2:- edition Saulgau (Punon G. Leut.se Verlag Vol, la), page 301.
Re su1tg ;
Hea s urina the fen t nu not e nt lals of nib koi foils oWhlcft am produced by means of a galvanic bath in a Cor rodkote solution;
Ob sa r va ti g n
The comparison bath and bst h ocoord ing to the invention hod the same composition with the exception of the proportion of chioral hydrata. fiba s credent by S ? E P i. e s L :
The potential or a nickel foil which was produced using a comparison bath was 1484 mV; the potential of a nickel foil which was produced using a bath according to the invention with 1 g/.1 of chloral hydrate was i58a mV; the above observation applies accordingly.
Application examples 1-7: Producing a galvanic bate by mixing water with selected components ; concentration in moi/Ec
The pH value ei the galvanic hath is after seining bet «eue 3,3 and 4,8, The oomponents set eut above are introduced late an agueous solution in the eoheentration set ont above. The sequence of the addition of the individual consponents to the aqueous solution is not decisive in this instance, &il the concentration. indications ate in relation to the galvanic bath,
Application examples 8-14: Producing a galvanic bath by mixing water with selected coeponenrs; concent so;· Lion in rol/L:
The pH value of the galvanic bath is after mixing between 3,3 and 4,3, The eompenenta set out above are introduced into an aqueous solution in the concert tali ou set cat above:, Too sequence of the addition of too individual components to the aqueous solution is not decisive in this instance„ bll the concentration indications ate in relation to the galvanic bath. Général ©Xaroplê Hl: Producing a galvanic bath according to the invention;
Selected components of a galvanic hath according to the invention present as suits ate dissolved in completely desalinated water. In this case, the water is breferahiy at a temperature in the range froiU: 10 to ICdC, Prop 0. i 6 to 3,15 noi/L of activated carbon are added to the resultant aqueous solution, hiring of the activated carbon with the aqueous solution is carried out in this instance by stirring or by precoat filtration with a circulation pump. The activated, carbon is subsequently removed by fiit rat ion and the ph value of the remaining purtfied solution is adjusted to a value in the range from 3.5 to 5,0,
In a subsequent stop, the selected components of a galvanic bath according to the invention rot present as salts are added to this pur if ied s o1at. i on,
Stagnation tests; Examination of the niokoi migration from a gloss nickel layer according to the invention in municipal water : •a? Copper pipes having a length of 10 cm and a diameter of 2 psi were provided with a gloss nickel layer for comparison purposes by maans of a conventional galvanic bath (without chloral hydrate), in a second step, a chromium layer was gslvanioaily sppiieo to this gloss nickel layer. The layers had a thickness of approximately 10 urn of nickel or approximately from 0,2 to 0,3 pm of chromium, respectively. (ο· in a parallel ïcannor, identical copper pipes were first provided, in a galvanic bath record:ng to the invention which further contained SOO mg/i of chloral hydrate with a composition which is otherwise identical to that or the comparison bath, with a gloss nickel layer and in a second step galvanically with a encomium layer under the same conditions as id the examinations ostried out for comparison purposes, (ci Id a further parallel madder, identical copper pipes were first provided, in another galvanio bath according to the Invention which contained löOö mg/1. of chloral hydrate, with a gloss nickel layer and in a second step galvanically with a terminai chromium layer in the same manner.
The copper pipes Ç1 x comparison pipe; 2 x pipe according to the invention) which are galvanically coated, as described above under (as, (p) and (c) were subsequently immersed in municipal water separately from each other. The concentration of nickel Zn iekel. ions in the municipal water was measured after a dwell, time of 72 hours, respectively, Additional, measurements are carried out after ah additional O hours, 120 hours, 72 hours and ill hours, fn all cases, the water was replaced after the measure-rent; the copper pipes to be examined were further flushed ten times with ISO ml of municipal, water before subsequent use. The .measurement results were established with an 1G2-GE3 spectrometer and are set. out in
thé tablé below, Thé huïterical values relate in each case to the measured nickel inn concentrations in ug/i>
For each measurement, there were used five pipes which had been coated in nocerdance with (a) ,· tb) and (cd , The values set out are arithmetic mean values .
It can dearly be seen that, by adding chierai hydrate, Cha tendency co discharge nicbei/niohe 1 ions to the surronnding medium (in this case: munie.;oa1 water) is substantially reduced, in particular in the case or iong r'am c times (2SÖ to id measurem.ent : . application ©xauaple 15: Producing a specific galvanic bach according to the invention:
Components of the specific galvanic hath according to the invonrion present as salts,· that is to say, the components: a, c, d and f, are dissolved in the concentration set ont in the completely desal ineted water» in this case:, the water is preferably at a reaps rata re of 55°C, trem 0.. Le to 0.25 mol/L of activated carbon are added to the resultant aqueous solation» Mixing of the activated carbon with the aqueous solution is carried oat in this instance by stirring or by precoat filtration with a circulecion pump. The activated carbon is subsequently removed by fiifration and the ph value of the remaining purified solution is adjusted to a value of 4.2. in a subsequent step, the selected components of a galvanic bach according to the invention not present as salts are added to this pu r 1 f 1 e d. so 1 u t i on,
Components of the epecific galvanic bach according to the invent ion:
The coating Time, that is to say, she time recuicred so deposit a gloss nickel loyer by means of the specific bath eccorO.ing be trie invention is approximately 15 minutes for a current density of 4 A/dmc
Application and comparison example 16s Producing a specific itern according to the invention fa data fitting as an example of a water-cattying pipeline} with a gross nickel layer:
The components of a specific galvanic Path which is intended to be used according so the invention for producing the item according to the invention (Path fitting with gloss: nickel layer} are set out in the cable below "Application exemple it" and were dissolved in the concentration set out in completely desalinated water fPreferred water temparature t5"'C; :
The: components of a galvanic bath not aocording to the invention which is produced for ccmpariscn purposes are identical tc those aocording to the Table "Application example 16" and were· also dissolved in the concentration set out in completely desalinated water (preferable water temperature 55°C) but the galvanic bath produced for comparison purposes does not comprise chloral hydrate.
The ooatihg time, that is to say, the time for depositing a gloss nickel layer by means of the specific bath according to the invention or by -means of the galvanic bath not according to the invention which is produced for comparison purposes was approximately IS minutes for a current density of 4 A/drc.
Structurally identical bath fitting members were used, ;a) Production of an item accordant to the invention: A brass bath fitting member was provided with a gloss ruck layer by means of the galvanic bath according to the invention; the thickness of this layer was approximately IQ pm, A ohtomium layer was galvanically applied to thia gloss nickel layer in a second step ( temperature ; iaf-tf;v, current density S - 20 A/dms, time;: 2~ ο minutes}? the thickness of this layer was from 0,2 re 0,3 pm., (b> Production of an item not according to the invention (comparison): A brass bath fitring membat was provided with a gloss nickel layer by means of the galvanic bath not according to the invention,· the thickness of this layer was approximately IQ pm, A chromium layer was galvanically applied tc this gloss nickel layer in a second step (temperatufe: dSMll’c, current density 5 - 20 A/dmg time: 2-h minutes); the thickness of this layer was from 0,2 to Q ,3 pm.
Stagnation tests on bath fittings: Comparison exnmi nati on for nickel .migration from the giess nickel, layer aceordiog to the invention and not. according to the invention in municipal water:
The galvanically coated crass fittings as described above undor in; and (b; wore immersed in manicipal water separately from each other. Tue concentration of nickel/nickel ions in the municipal water was measured after a dwell time of a weak. Additional measurements are carried out after two, three, font and five weeks, in ail cases, the municipal water was replaced after the measurement; the brass fittings to he examined were further flushed ten tines with ISO mi of muni ci par water before again being immersed in municipal Water, The measurement results were established with an lit-OSt spectrometer and are sat out in the table below. The nnmerica; values relate in each case to the measured nickel ion concentration in ng/;.
The values sat out are scithmetio mean values of four measurements, respectiveiy.
It can clearly be seen that the coated bath fitting member according to the invention fas an example of an item according to the invention released loss nickel than the coated bath fitting 'member not according to the invent: ion. The bath according to the invention used Comprised chloral hydrate, whereby the tendency to discharge nioke.l/niokel ions to the surrounding medium (in this instance: municipal materi was substantially reduced. Particularly the results of the fourth and fifth weeks show that the nickel discharge stagnated and at the same time mas substantially less than the nickel discharge of the coated brass fittings not according to the invention.
Claims (13)
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102014207778.8A DE102014207778B3 (en) | 2014-04-25 | 2014-04-25 | Use of a mixture for use in a plating bath or plating bath to produce a bright nickel plating, and to a method of making an article having a bright nickel plating |
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| HUE035050T2 true HUE035050T2 (en) | 2018-05-02 |
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| HUE15164491A HUE035050T2 (en) | 2014-04-25 | 2015-04-21 | Galvanic bath or mixture for use in a galvanic bath for depositing a gloss nickel layer and method for producing an item with a gloss nickel layer |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP2937450B1 (en) |
| JP (1) | JP6687331B2 (en) |
| DE (1) | DE102014207778B3 (en) |
| HU (1) | HUE035050T2 (en) |
| PL (1) | PL2937450T3 (en) |
| PT (1) | PT2937450T (en) |
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| CN105200462A (en) * | 2015-10-19 | 2015-12-30 | 姜少群 | Electroplating method for elemental nickel transition layer of mould copper tube |
| CN105170922B (en) * | 2015-10-19 | 2017-12-01 | 重庆天春科技有限公司 | A kind of crystallizer copper pipe with elemental nickel transition zone |
| CN106245070B (en) * | 2016-10-21 | 2019-03-05 | 湘潭大学 | A method of combination plating solution and electroplating nickel on surface of magnesium alloy for magnesium alloy plating nickel |
| HUE056778T2 (en) * | 2017-06-23 | 2022-03-28 | Atotech Deutschland Gmbh | Nickel electroplating bath for depositing a decorative nickel coating on a substrate |
| WO2019215287A1 (en) * | 2018-05-09 | 2019-11-14 | Atotech Deutschland Gmbh | Nickel comprising layer array and a method for its manufacturing |
| JP6542437B1 (en) * | 2018-06-19 | 2019-07-10 | 奥野製薬工業株式会社 | Bright nickel plating method and control method of bright nickel plating film. |
| JP7190280B2 (en) * | 2018-08-10 | 2022-12-15 | 株式会社Lixil | plumbing fixtures |
| TWI734362B (en) * | 2019-01-31 | 2021-07-21 | 美商麥克達米德恩索龍股份有限公司 | Composition and method for fabrication of nickel interconnects |
| KR102293664B1 (en) * | 2019-11-12 | 2021-08-26 | 주식회사엘콤 | Composition for nickel-phosphorus alloy plating |
| JP7141780B1 (en) | 2022-05-19 | 2022-09-26 | 奥野製薬工業株式会社 | A method for producing a plating film. |
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| US3528894A (en) * | 1966-08-25 | 1970-09-15 | M & T Chemicals Inc | Method of electrodepositing corrosion resistant coating |
| US3898138A (en) * | 1974-10-16 | 1975-08-05 | Oxy Metal Industries Corp | Method and bath for the electrodeposition of nickel |
| DE2450527C2 (en) | 1974-10-24 | 1982-09-16 | Henkel KGaA, 4000 Düsseldorf | Aqueous, acidic bath for the galvanic deposition of semi-glossy nickel coatings |
| US4148797A (en) | 1977-07-15 | 1979-04-10 | Cilag-Chemie A.G. | (N-Substituted pyridyl)-alkyl sulfonic acid betaines as electroplating additives |
| DE2825966A1 (en) * | 1978-06-14 | 1980-01-03 | Basf Ag | ACID GALVANIC NICKEL BATH, WHICH CONTAINS SULFOBETAINE AS A GLOSSY AND LEVELING AGENT |
| US4430171A (en) | 1981-08-24 | 1984-02-07 | M&T Chemicals Inc. | Electroplating baths for nickel, iron, cobalt and alloys thereof |
| US4421611A (en) | 1982-09-30 | 1983-12-20 | Mcgean-Rohco, Inc. | Acetylenic compositions and nickel plating baths containing same |
| DE3722778A1 (en) | 1987-07-09 | 1989-03-09 | Raschig Ag | POLYALKYLENE GLYCOL NAPHTHYL-3-SULPHOPROPYL DIETHERS AND THEIR SALTS, PROCESS FOR PREPARING THESE COMPOUNDS AND THEIR USE AS A NETWORK IN GALVANO TECHNOLOGY |
| DE3817722A1 (en) | 1988-05-25 | 1989-12-14 | Raschig Ag | USE OF 2-SUBSTITUTED ETHANESULPHONE COMPOUNDS AS GALVANOTECHNICAL AUXILIARIES |
| DE4013349A1 (en) * | 1990-04-23 | 1991-10-24 | Schering Ag | 1- (2-SULFOAETHYL) PYRIDINIUMBETAIN, METHOD FOR THE PRODUCTION THEREOF AND ACID NICKEL BATH CONTAINING THIS COMPOUND |
| US5164069A (en) | 1990-11-05 | 1992-11-17 | Shipley Company Inc. | Nickel electroplating solution and acetylenic compounds therefor |
| JP2962598B2 (en) * | 1991-06-20 | 1999-10-12 | 荏原ユージライト株式会社 | Microporous chrome plating method |
| JPH07503282A (en) * | 1992-01-25 | 1995-04-06 | ビーエーエスエフ アクチェンゲゼルシャフト | Manufacturing method for nickel-plated molded parts |
| DE19610361A1 (en) * | 1996-03-15 | 1997-09-18 | Basf Ag | Bath and process for the electrodeposition of semi-gloss nickel |
| JP2003138396A (en) * | 2001-08-24 | 2003-05-14 | Toto Ltd | Nickel chrome plating method and appliance for water system subjected to this plating |
| DE10327374B4 (en) | 2003-06-18 | 2006-07-06 | Raschig Gmbh | Use of propanesulfonated and 2-hydroxy-propanesulfonated Alkylaminaloxylaten as an aid for the electrolytic deposition of metallic layers and plating baths containing them |
| US7442286B2 (en) * | 2004-02-26 | 2008-10-28 | Atotech Deutschland Gmbh | Articles with electroplated zinc-nickel ternary and higher alloys, electroplating baths, processes and systems for electroplating such alloys |
| PL2145986T3 (en) * | 2008-07-15 | 2010-09-30 | Atotech Deutschland Gmbh | Solution and method for electrochemically depositing a metal on a substrate |
| DE102008056470B3 (en) * | 2008-11-05 | 2010-04-22 | Atotech Deutschland Gmbh | A method of inspecting a metal layer and a method of analytically controlling a deposition electrolyte for depositing the metal layer |
| EP2396455B1 (en) | 2009-02-13 | 2018-10-24 | Nissan Motor Co., Ltd. | Chrome-plated part and manufacturing method of the same |
| DE102011106099B4 (en) | 2011-06-09 | 2016-06-02 | Keuco Gmbh & Co. Kg | Method for coating components |
| EP2801640A1 (en) | 2013-05-08 | 2014-11-12 | ATOTECH Deutschland GmbH | Galvanic nickel or nickel alloy electroplating bath for depositing a semi-bright nickel or nickel alloy |
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2014
- 2014-04-25 DE DE102014207778.8A patent/DE102014207778B3/en active Active
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| PL2937450T3 (en) | 2017-08-31 |
| DE102014207778B3 (en) | 2015-05-21 |
| PT2937450T (en) | 2017-06-30 |
| EP2937450B1 (en) | 2017-04-05 |
| SI2937450T1 (en) | 2017-07-31 |
| JP2015212417A (en) | 2015-11-26 |
| JP6687331B2 (en) | 2020-04-22 |
| EP2937450A1 (en) | 2015-10-28 |
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