CA2052583A1 - Production of nickelized articles - Google Patents
Production of nickelized articlesInfo
- Publication number
- CA2052583A1 CA2052583A1 CA002052583A CA2052583A CA2052583A1 CA 2052583 A1 CA2052583 A1 CA 2052583A1 CA 002052583 A CA002052583 A CA 002052583A CA 2052583 A CA2052583 A CA 2052583A CA 2052583 A1 CA2052583 A1 CA 2052583A1
- Authority
- CA
- Canada
- Prior art keywords
- formula
- sulfo
- group
- naphthyl
- amino group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
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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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
- C07C215/02—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C215/22—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being unsaturated
- C07C215/24—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being unsaturated and acyclic
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
- C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C309/07—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton
- C07C309/08—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton containing hydroxy groups bound to the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
- C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C309/13—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton
- C07C309/14—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton containing amino groups bound to the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C309/41—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing singly-bound oxygen atoms bound to the carbon skeleton
- C07C309/42—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing singly-bound oxygen atoms bound to the carbon skeleton having the sulfo groups bound to carbon atoms of non-condensed six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C309/45—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton
- C07C309/46—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton having the sulfo groups bound to carbon atoms of non-condensed six-membered aromatic rings
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Detergent Compositions (AREA)
Abstract
O.Z. 0050/42002 Abstract of the Disclosure: Nickelized articles are produced by electrodeposition of nickel from aqueous acidic baths containing as essential constituents one or more nickel salts, one or more inorganic acids and one or more brighteners, wherein there are used as brighteners 2-hydroxy-3-butenyl-containing compounds of the formula I
I
where n is 1, 2 or 3 and the variable A has the following meanings;
for n = 1 - hydroxyl - a group of the formula -OR1, where R1 is C1-C4-alkyl, which may be sulfo-substituted, phenyl, 3- or 4-sulfophenyl, .alpha.- or .beta.-naphthyl, 3-, 4-, 5-, 6- or 7-sulfo-.alpha.-naphthyl or 4-, 5-, 6-, 7- or 8-sulfo-.beta.-naphthyl - a phosphorus-containing group of -O-PO(OX)H or -O-PO(OX)2, where X is hydrogen or an alkali metal or ammonium cation - a sulfo group of the formula -SO3X
- an amino group of the formula -NH2, -NHR1 or -N(R1)2, where if two radicals R1 are present on the N-atom they can be identical or different for n = 2 - an amino group of the formula -NH- or -NR1-- a trivalent oxygen atom for n = 3 - a trivalent nitrogen atom.
I
where n is 1, 2 or 3 and the variable A has the following meanings;
for n = 1 - hydroxyl - a group of the formula -OR1, where R1 is C1-C4-alkyl, which may be sulfo-substituted, phenyl, 3- or 4-sulfophenyl, .alpha.- or .beta.-naphthyl, 3-, 4-, 5-, 6- or 7-sulfo-.alpha.-naphthyl or 4-, 5-, 6-, 7- or 8-sulfo-.beta.-naphthyl - a phosphorus-containing group of -O-PO(OX)H or -O-PO(OX)2, where X is hydrogen or an alkali metal or ammonium cation - a sulfo group of the formula -SO3X
- an amino group of the formula -NH2, -NHR1 or -N(R1)2, where if two radicals R1 are present on the N-atom they can be identical or different for n = 2 - an amino group of the formula -NH- or -NR1-- a trivalent oxygen atom for n = 3 - a trivalent nitrogen atom.
Description
~ O.~. 0050/42002 PROD~CTION OF NICXELIZED ARTICLES
The present inYention relates to an Lmproved process for producing nickelized articles by el~ctro-deposition of nicXel from aqueous acidic baths containing as essential constituents one or more nickel salts, one or more inorganic acids and one or more brighteners, some of these brighteners heing novel compounds. The present invention further relates to a brightener mixture useable for this purpose.
It is known that acidic nickel electrolytes must contain low level~ of organic substances if the electro-deposition of nickel is to produce a bright, ductile and planar coat of the metal. Such brighteners, which are generally s~bdivided into prLmary brighteners and second-ary brighteners, are customarily used in the form of co~binations of pluralities of brighteners, in order to increase the effect. None the less, the brightness obtained in this way is still in need of improvement.
DE-B 11 91 652 (1) describes monocyclic or polycyclic heterocyclic nitrogen bases of the aromatic type in quaternized form such as pyridinium salts, eg.
The present inYention relates to an Lmproved process for producing nickelized articles by el~ctro-deposition of nicXel from aqueous acidic baths containing as essential constituents one or more nickel salts, one or more inorganic acids and one or more brighteners, some of these brighteners heing novel compounds. The present invention further relates to a brightener mixture useable for this purpose.
It is known that acidic nickel electrolytes must contain low level~ of organic substances if the electro-deposition of nickel is to produce a bright, ductile and planar coat of the metal. Such brighteners, which are generally s~bdivided into prLmary brighteners and second-ary brighteners, are customarily used in the form of co~binations of pluralities of brighteners, in order to increase the effect. None the less, the brightness obtained in this way is still in need of improvement.
DE-B 11 91 652 (1) describes monocyclic or polycyclic heterocyclic nitrogen bases of the aromatic type in quaternized form such as pyridinium salts, eg.
2-pyridinium-1-sulfatoethane, for use as planarizers, ie.
brighteners, for acidic electronickelizing baths. These compounds are used together with c:ustomary brighteners such a8 benzene-m-disulfonic acid, diaryldisulfimides or sulfonamide~.
The monogxaph, Praktische GalvanotechniX, Eugen G. Lenze Verlag, Saulgau, 4th edi~ion 1984, pages 268 to 271 (2) describe~ classss of customary brighteners for nickel electxolytes. Although the substance in que5tion are divided into primary and secondary brightener and planarizers, there is an admission that clear-cut classification is no~ always possible. The brightness-producing substances mentioned are:
- sulfonLmides, eg. benzosulfimide - sulfonamides ~ 5~ o. z . 0050/42002 - benzenesulfonic acids, eg. mono-, di- and tri-ben~en~sulfonic acid - naphthalenesulfonic acids, eg. mono-, di- and tri-naphthalenesulfonic acid ~ alkanesulfonic acids - sulfinic acid - sulfonated arenesulfones - aliphatic compounds with double and/or triple bonds, eg. butynediol 0 - monocyclic and polycyclic nitrogen-containing heterocycles which may additionally contain further hetero atoms such a sulfur or selenium - coumarin - amines and quaternary ammonium compounds as planar-izers - sucrose.
The brighteners customarily used in practice are alkenylsulfonic acids such a~ sodium vinylsulfonate or so~ium allylsulfonate combined with other brighteners such as proparsyl alcohol, 2-but~ne-1,4-diol, propyne~
sulfonic acid or 2-pyridinium-1-sulfatoethane.
It is an ob~ect of the present invention to provide an improved proc~s3 for producing nickelized articles of higher brightness but e~ually good ductility and surface planarity.
We have found that this ob~ect i~ achieved by a process for producing nickelized articles by electro-deposition of nickel from an aqueous acidic bath contain-ing a3 essential constituents one or mor~ nickel salts, one or more inorganic acids and one or more brighteners, which comprise~ using as brightener a 2-hydroxy-3 butenyl-con~aining compound of the formula I
(CH2=cH-lH-cH2-)~ I
OH
~laSi;~5~
- 3 - O.~. 0050/42002 where n is 1l 2 or 3 and the variable A has the following meanings:
for n = 1 - hydroxyl - a group of the formula -ORl, where Rl is Cl-C4-alkyl, which may be sulfo-substituted, phenyl, 3- or 4-sulfophenyl, ~- or ~-naphthyl, 3-, 4-, 5-, 6- or 7-sulfo-~-naphthyl or 4-, 5-, 6-, 7- or 8-sulfo-~-naphthyl 0 - a phosphorus-containing group of -O-PO(OX)H Qr -O-PO ( OX ) 2 r where X is hydrogen or an alXali metal or ammonium cation - a sulfo group of the formula -S03X
- an amino group of the formula -NH2, -NHRl or -N(Rl)2, where if two radicals R1 are present on the N-atom they can be identical or diferen~
for n = 2 - an amino group of the formula -NH- or -NRl-- a trivalent oxygen atom for n = 3 - a trivalent nitrogen atom.
Cl-C4-al~yl R1 which may ladditionally carry a sulfo group i~ in particular mathyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, selc-butyl 9 tert~butyl, sulfomethyl, 2-sulfoethyl, 3-sulfopropyl or 4-sulfobutyl, the sulfo group being usually in the form of the free acidr in the form of an alkali metal salt, in particular the sodium or potassium salt, or in the form of the ammonium salt. Particularly good results are obtained with 2 sulfoethyl.
A compound I with a phosphorus-containing group of the formula -O-POtOX)H is a phosphorous monoester or a salt thereof and a compound I with a phosphorus-con-taining group of the formula -O-PO(OX~2 is a phosphoric monoester or a salt thereof.
The variable X is hydrogen or an alkali metal cation, in particular sodium or potassium, or an ammonium - 4 - O.~. 0050/42002 cation. Since the compounds I are used according to the present invention in an acidic medium, in particular in a weakly acidic medium, there is of course an equilibrium between the alkali metal or ammonium salts and the corresponding free acids.
In a preferred embodiment of the invention, the compound I used has n equal to 1 or 3 and ~ ~ariable with the following meanings:
for n = 1 - hydroxyl - a group of the formula -oR2, where R2 is 2-sulfo-ethyl, 3-sulfophenyl or 4~sulfophenyl a sulfo group of the formula -S03X
- an amino group of the formula -NHR2 for n = 3 - a trivalent nitrogen atom~
The present invention further provides novel 2-h~droxy-3-butenyl~containing compounds of the formula Ia (CH2=C~ cH-cH2-)nB Ia OH
where n is 1~ 2 or 3 and the variable B has the following meanings t where n = 1 - a group of th~ formula -oR3, where R3 i8 Cl-c4-alkyl, which is additionally ~ulfo-substituted, 3- or 4-~ulophenyl, ~- or ~-naphthyl, 3-, 4-, 5-, 6- or 7-sulfo ~-naphthyl or 4-~ 5-, 6-, 7- or 8-sulfo-~-naphthyl - a phosphorus-containing group of -O-PO(OX)H or -O-PO(OX)2, where X is hydrogen or an alkali metal or ammonium cation - an amino group of the formula -NHR3 - 5 - O.Z. 0050/42002 - an amino group of the formula -N(R4)2 possessing two identical radicals R4, where R4 is R3 or phenyl for n = 2 - an amino group of the formula -NH-- an amino group of the formula -NR3-for n = 3 - a tri~alent nitrogen atom.
A Cl-C4-al~yl R3 which additionally carries a sulfo group is in particular sulfomethyl, 2-sulfoethyl, 3-sulfopropyl or 4-~ulfobutyl, the sulfo group usually being in the form of the free acid, in the form of an alkali metal salt, in particular the sodium or po~assium salt, or in the form of the ammonium salt.
The compounds I and Ia are advantageously pre-pared by reacting vinyloxirane, 4-chloro-3-hydroxy-l-butene or 4-bromo-3-hydroxy-l~butene in the right molar ratio with reactants containing the right nucleo-philic groups. Such reactants are for example:
- water _ C1-C4 alkanols - salts of hydroxymethanesulfonic acid, 2-hydroxy-ethane~ulfonic acid (isethiollic acid), 3-hydroxy-propanesulfonic acid or 4-hydroxybutanesulfonic acid - phenol and ~- or ~-naphthol - sal~s of 3- or 4-sulfoph~enyl and 3-, 4-, 5-, 6- or 7-~ulfO-a-naphthol or 4-, 5-, 6-, 7- or ~ sulfo-~naphthol - phosphorous acid or hydrogen phosphites - phosphoric acid or hydrogen or dihydrogen phosphates - ~ulfurous acid or hydrogen sulfites ammonia - mono- or dialkylamines ha~ing from 1 ~o 4 carbon atoms per alkyl group - salts o~ aminomsthan2sulfonic acid, 2-aminoethane-sulfonic acid (taurine), 3-aminopropanesulfonic acid or 4~aminobutanesulfonic acid aniline and a- or ~-naphthylamine .
5~
~ 6 ~ O.Z. 0050/42002 - metanilic acid or sulfanilic acid and 3-, 4-, 5-, 6-or 7-sulfo-~-naphthylamine or 4-, 5-, 6-, 7- or 8-sulfo-~-naphthylamine and salts thereof.
The reaction is in general carried out under S conditions customary for epoxides and halohydrins, as described for example in M.S. Malinovskii, Epoxides and their Deri~atives, Israel Program for Scientific Transla-tions, Jerusalem, 1965, or Houben-Weyl, Methoden der Organischen Chemie, volume VI/3 (Oxygen compounds I, Part 3), Thieme Verlag Stuttgart, 13650 In a preferred embodiment o the invention, the compounds I are used together with at least one further brightener. Since the compounds I predominantly act as primary brighteners, their combination with secondary brighteners such as propargyl alcohol, 2 butyne-1,4-diol, propynesulfonic aoid or preferably a monocyclic or poly-cyclic heterocyclic nitrogen base of the aromatic type in quaternized form, eg. 2-pyridinium-1-sulfatoethane, produces particularly high brightness. However, it is also possible to detect an increased offect with certain primary brighteners such as ~ucrose.
The aqueou acidic nickel electrolyte baths used contain one or usually more than one nickel salt, eg.
nickel sulfate and nickel chloride, one or more inorganic acids, preferably boric acid and sulfuric acid, brightener compounds I alone or preferably combined with further, cu~tomary brighteners and optionally further customary assistant~ and additiYe~ in the concentrations cu~toma~y for this purpose, for example wetting agents and pore inhibitors. Cu3tomary aqueous acidic nickel electrolytes (Watts electrolytes) have the follow.ing basic composition:
from 200 to 350 gJl of NiSO4 x 7 H2O
from 30 to 150 g/l of NiC12 x 6 H2O
from 30 to 50 g/l of H3BO3.
The pH of the electrolyte bath is customarily within the range o~ from 3 to 6, preferably within the 5~
- 7 - O.Z. 0050/42002 range of from 4 to 5. This pH is advantageously set with a strong mineral acid, preferably sulfuric acid.
The compounds I are generally present in the electrolyte baths in concentrations within the range of from 0.1 to 2.0 g/l, preferably ~ithin the range of from O.2 to 1.3 g/l. The concentrations of further, customary brigh~eners are normally likewise within the range of from 0.1 to 2.0 g/l.
The nickel electrolyte baths described can be used to produce in particular nickel coatings on steel articles, but also on articles made o~ other materials, for example brass, which have been pretreated in a conv~ntional manner, by electrocoating. This is in general done at from 30 to 80C, preferably at from 40 to 60C.
The present invention further provides a brightener mixture for aqueous acidic electronickelizing baths which contain as essential constituents the com-pounds I and monocyclic or polycyclic heterocyclic nitrogen bases of the aromatic type in quaternized form in the abovemen~ioned concentratiorls.
The compounds I used according to the present invention are noteworthy for extremely high brightness formation. They produce higher brightness than customary brighteners, in some instances eve:n at lower concentra-tion~ in the nickel electrolyte baths.
Preparation of 1,2-dihydroxy-3-butene 32.7 g of vinylQxirane, 70 g of water and 0.5 g of 96% strength by weight sulfuric acid as catalyst was stirred at 85-90C for 5 hour~. The sulfuric acid was then neutralized with 50~ streng~h by weight sodium hydroxide solution. Small amounts of unconverted vinyl-oxirane were distilled off at 50C under a water jet vacuum together with excess water, leaving behind 40 g of product in the form of a viscous liquid.
- 8 - O.Z. 0050J42002 Preparation of sodium 4-(2'-hydroxy-3' buten~ yloxy)-benæenesulfonate 267.7 g of 65% strength by weight p-phenol-sulfonic acid w~re diluted with lO0 g of water and admixed with 80 g of 50% strength by weight sodium hydroxide solution. Then 70 g of vinyloxirane were added dropwise at 70-80C with stirring in the course of 30 minutes. The mixture was subsequently stirred at the same temperature for 8 hours. The water was then removed under a water jet vacuum, leaving behind 195 g of product. The product was again taken up in water and adjusted to a concentration o 50~ by weight.
Prepara~ion of sodium 2-hydroxy-3-butenesulfonate 21.5 g of vinylo~irane were added dropwise at 80C with stirring to a mixture of 80.4 g of 39% strength by weight aqueous sodium hydxogen sulfite solution and 23.b g of water in the course of 20 minutes. The mixture wa then ~tirred at the same temperatura for 8 hours.
Small amount~ of unconverted vinyloxirane and the water were removed under a water jet vacuum, leaving behind 40 g of product. The product wa~ taken up in water and adjusted to a concentration of 50~ by weight.
Preparation of tris(2-hydroxy-3-buten-1-yl)amine 126 g of vinyloxirane were added at 70-80C with skirring to a mixture of 40.8 g of 25~ strength by weight aqueou~ ammonia and 170 g of water in the course of 20 minutes. The mixture wa~ subseguently ~tirred at the same tempera~ure for 5 hours. It was then reduced under a water jet vacuum to 172 g. This left a viscous liguid having a product content of 78~ by weight.
Preparation of sodium ~-N-12'-hydroxy-3'-buten~ yl)-aminoethanesulfonate 70 g of vinyloxirane were added dropwise at 5~
- 9 - O.Z. 0050/42002 70-`80C with stirring to 313 g of a 47% strength by weight aqueous solution of the sodium salt of 2-amino-ethanesul~onic acid (taurine) in the course of 30 minutes. The mixture was subsequently stirred at the same temperature for 6 hours. The water was then removed under a water jet vacuum. This left 218 g of product. The product was taken up again in water, the solution being adjusted to a product content of 50% by weight.
Preparation of sodium 2-N,N-bis(2'-hydroxy-3'-buten-1'-yl)aminoethanesulfonate Example 5 was repeated with twice the amount of vinyloxirane, affording, after the reac~ion had taken place and the reaction mixture had been concentrated under a water ~et vacuum, 287 g of a product which was taken up again in water, the solution being adjusted to a product content of 50% by weight.
Preparation of sodium 4-N-(2'-hydroxy-3'-buten-l'-yl)-aminobenzenesulfonate 70 g of vinyloxirane were added dropwise at 70-80C with stirring to a mixture of 173 g of 4-amino-benzenesulfonic acid (sulfanilic acid), 200 g of water and 80 g of 50% strength by weight aqueous sodium hydroxide solution over 30 minutes. The mixture was subsequently stirred at the same temperature for 4 hours, giving 520 g of a ~olution having a product content of 53% by weight.
APPLIC~TION EXAMP1ES 8 TO 14 AND
3 0 COMPARATIVE EXA~LES A AND B
The products prepared in Ex~mples 1 to 7 were used as brighteners in weakly acidic electronickelizing baths.
The aqueous nickel electrolyte used had the following composition:
300 gJl of NiSO4 x 7 HzO
60 g/l of NiCl2 x 6 H2O
- 10 - O.Z. 0050~42002 45 g/l of H3~03 2 g~l of sucrose O.3 g/l of 2-pyridinium~ ulfa~oethane X g/l of brightener as per table 0.5 gJl of a fatty alcohol derivative of the formula C12H25/cl4H29-o-(cH2cH2o)2-so3Na as wetting agent The pH of khe electrolyte was adjustPd with sulfuric acid to 4.2.
The articles to be nickelized were brass panels which, prior to being plated with nickel, were cathodic-ally degreased in an alkaline ~lectrolyte in a conven-tional manner. The nickelization took place in a 250 ml Hull cell at 55C and a current strength of 2A for a period of 10 minutes. The panel~ were th~n rinsed with water and dried with compressed air.
The table below shows the results of these experLments. It can be seen that the brighteners or brightener mixtures used according to the presen~ inven-tion produce a higher brightness than the prior art agents t in some instances even at a lower concentration in the nickel electrolyte baths~
TABLE
Test results of electrodeposition of nickel Example Brightener of Concent:ration Brightness No. Exampl~ No. X [gtll [rating3 ~ . . _ , . .
8 1 0.3 4-5 9 2 0.8 4-5 3 0.~ 4-5 11 4 0~3 5 12 5 0.6 5 13 6 D.8 5 14 7 1.2 4-5 for comparison-A sodium vinylsulfonate 0.8 4 B sod~um allyl~ulfonate 0.7 4 .
5~3 ~ O.Z. 0050/42002 Ratings scheme for brightness:
S = excellent (perfect specular gloss) 4 = good (almost specular gloss) 3 = moderate 2 = poor 1 = no brigh~ness The ductility was very good with all examples No. 8 to 14 and the comparative specimens A and B.
Except in the case of Example 8, where a trace of overinhibition was found, it was impossible to detect any interference with the nickel deposition process.
t !
brighteners, for acidic electronickelizing baths. These compounds are used together with c:ustomary brighteners such a8 benzene-m-disulfonic acid, diaryldisulfimides or sulfonamide~.
The monogxaph, Praktische GalvanotechniX, Eugen G. Lenze Verlag, Saulgau, 4th edi~ion 1984, pages 268 to 271 (2) describe~ classss of customary brighteners for nickel electxolytes. Although the substance in que5tion are divided into primary and secondary brightener and planarizers, there is an admission that clear-cut classification is no~ always possible. The brightness-producing substances mentioned are:
- sulfonLmides, eg. benzosulfimide - sulfonamides ~ 5~ o. z . 0050/42002 - benzenesulfonic acids, eg. mono-, di- and tri-ben~en~sulfonic acid - naphthalenesulfonic acids, eg. mono-, di- and tri-naphthalenesulfonic acid ~ alkanesulfonic acids - sulfinic acid - sulfonated arenesulfones - aliphatic compounds with double and/or triple bonds, eg. butynediol 0 - monocyclic and polycyclic nitrogen-containing heterocycles which may additionally contain further hetero atoms such a sulfur or selenium - coumarin - amines and quaternary ammonium compounds as planar-izers - sucrose.
The brighteners customarily used in practice are alkenylsulfonic acids such a~ sodium vinylsulfonate or so~ium allylsulfonate combined with other brighteners such as proparsyl alcohol, 2-but~ne-1,4-diol, propyne~
sulfonic acid or 2-pyridinium-1-sulfatoethane.
It is an ob~ect of the present invention to provide an improved proc~s3 for producing nickelized articles of higher brightness but e~ually good ductility and surface planarity.
We have found that this ob~ect i~ achieved by a process for producing nickelized articles by electro-deposition of nickel from an aqueous acidic bath contain-ing a3 essential constituents one or mor~ nickel salts, one or more inorganic acids and one or more brighteners, which comprise~ using as brightener a 2-hydroxy-3 butenyl-con~aining compound of the formula I
(CH2=cH-lH-cH2-)~ I
OH
~laSi;~5~
- 3 - O.~. 0050/42002 where n is 1l 2 or 3 and the variable A has the following meanings:
for n = 1 - hydroxyl - a group of the formula -ORl, where Rl is Cl-C4-alkyl, which may be sulfo-substituted, phenyl, 3- or 4-sulfophenyl, ~- or ~-naphthyl, 3-, 4-, 5-, 6- or 7-sulfo-~-naphthyl or 4-, 5-, 6-, 7- or 8-sulfo-~-naphthyl 0 - a phosphorus-containing group of -O-PO(OX)H Qr -O-PO ( OX ) 2 r where X is hydrogen or an alXali metal or ammonium cation - a sulfo group of the formula -S03X
- an amino group of the formula -NH2, -NHRl or -N(Rl)2, where if two radicals R1 are present on the N-atom they can be identical or diferen~
for n = 2 - an amino group of the formula -NH- or -NRl-- a trivalent oxygen atom for n = 3 - a trivalent nitrogen atom.
Cl-C4-al~yl R1 which may ladditionally carry a sulfo group i~ in particular mathyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, selc-butyl 9 tert~butyl, sulfomethyl, 2-sulfoethyl, 3-sulfopropyl or 4-sulfobutyl, the sulfo group being usually in the form of the free acidr in the form of an alkali metal salt, in particular the sodium or potassium salt, or in the form of the ammonium salt. Particularly good results are obtained with 2 sulfoethyl.
A compound I with a phosphorus-containing group of the formula -O-POtOX)H is a phosphorous monoester or a salt thereof and a compound I with a phosphorus-con-taining group of the formula -O-PO(OX~2 is a phosphoric monoester or a salt thereof.
The variable X is hydrogen or an alkali metal cation, in particular sodium or potassium, or an ammonium - 4 - O.~. 0050/42002 cation. Since the compounds I are used according to the present invention in an acidic medium, in particular in a weakly acidic medium, there is of course an equilibrium between the alkali metal or ammonium salts and the corresponding free acids.
In a preferred embodiment of the invention, the compound I used has n equal to 1 or 3 and ~ ~ariable with the following meanings:
for n = 1 - hydroxyl - a group of the formula -oR2, where R2 is 2-sulfo-ethyl, 3-sulfophenyl or 4~sulfophenyl a sulfo group of the formula -S03X
- an amino group of the formula -NHR2 for n = 3 - a trivalent nitrogen atom~
The present invention further provides novel 2-h~droxy-3-butenyl~containing compounds of the formula Ia (CH2=C~ cH-cH2-)nB Ia OH
where n is 1~ 2 or 3 and the variable B has the following meanings t where n = 1 - a group of th~ formula -oR3, where R3 i8 Cl-c4-alkyl, which is additionally ~ulfo-substituted, 3- or 4-~ulophenyl, ~- or ~-naphthyl, 3-, 4-, 5-, 6- or 7-sulfo ~-naphthyl or 4-~ 5-, 6-, 7- or 8-sulfo-~-naphthyl - a phosphorus-containing group of -O-PO(OX)H or -O-PO(OX)2, where X is hydrogen or an alkali metal or ammonium cation - an amino group of the formula -NHR3 - 5 - O.Z. 0050/42002 - an amino group of the formula -N(R4)2 possessing two identical radicals R4, where R4 is R3 or phenyl for n = 2 - an amino group of the formula -NH-- an amino group of the formula -NR3-for n = 3 - a tri~alent nitrogen atom.
A Cl-C4-al~yl R3 which additionally carries a sulfo group is in particular sulfomethyl, 2-sulfoethyl, 3-sulfopropyl or 4-~ulfobutyl, the sulfo group usually being in the form of the free acid, in the form of an alkali metal salt, in particular the sodium or po~assium salt, or in the form of the ammonium salt.
The compounds I and Ia are advantageously pre-pared by reacting vinyloxirane, 4-chloro-3-hydroxy-l-butene or 4-bromo-3-hydroxy-l~butene in the right molar ratio with reactants containing the right nucleo-philic groups. Such reactants are for example:
- water _ C1-C4 alkanols - salts of hydroxymethanesulfonic acid, 2-hydroxy-ethane~ulfonic acid (isethiollic acid), 3-hydroxy-propanesulfonic acid or 4-hydroxybutanesulfonic acid - phenol and ~- or ~-naphthol - sal~s of 3- or 4-sulfoph~enyl and 3-, 4-, 5-, 6- or 7-~ulfO-a-naphthol or 4-, 5-, 6-, 7- or ~ sulfo-~naphthol - phosphorous acid or hydrogen phosphites - phosphoric acid or hydrogen or dihydrogen phosphates - ~ulfurous acid or hydrogen sulfites ammonia - mono- or dialkylamines ha~ing from 1 ~o 4 carbon atoms per alkyl group - salts o~ aminomsthan2sulfonic acid, 2-aminoethane-sulfonic acid (taurine), 3-aminopropanesulfonic acid or 4~aminobutanesulfonic acid aniline and a- or ~-naphthylamine .
5~
~ 6 ~ O.Z. 0050/42002 - metanilic acid or sulfanilic acid and 3-, 4-, 5-, 6-or 7-sulfo-~-naphthylamine or 4-, 5-, 6-, 7- or 8-sulfo-~-naphthylamine and salts thereof.
The reaction is in general carried out under S conditions customary for epoxides and halohydrins, as described for example in M.S. Malinovskii, Epoxides and their Deri~atives, Israel Program for Scientific Transla-tions, Jerusalem, 1965, or Houben-Weyl, Methoden der Organischen Chemie, volume VI/3 (Oxygen compounds I, Part 3), Thieme Verlag Stuttgart, 13650 In a preferred embodiment o the invention, the compounds I are used together with at least one further brightener. Since the compounds I predominantly act as primary brighteners, their combination with secondary brighteners such as propargyl alcohol, 2 butyne-1,4-diol, propynesulfonic aoid or preferably a monocyclic or poly-cyclic heterocyclic nitrogen base of the aromatic type in quaternized form, eg. 2-pyridinium-1-sulfatoethane, produces particularly high brightness. However, it is also possible to detect an increased offect with certain primary brighteners such as ~ucrose.
The aqueou acidic nickel electrolyte baths used contain one or usually more than one nickel salt, eg.
nickel sulfate and nickel chloride, one or more inorganic acids, preferably boric acid and sulfuric acid, brightener compounds I alone or preferably combined with further, cu~tomary brighteners and optionally further customary assistant~ and additiYe~ in the concentrations cu~toma~y for this purpose, for example wetting agents and pore inhibitors. Cu3tomary aqueous acidic nickel electrolytes (Watts electrolytes) have the follow.ing basic composition:
from 200 to 350 gJl of NiSO4 x 7 H2O
from 30 to 150 g/l of NiC12 x 6 H2O
from 30 to 50 g/l of H3BO3.
The pH of the electrolyte bath is customarily within the range o~ from 3 to 6, preferably within the 5~
- 7 - O.Z. 0050/42002 range of from 4 to 5. This pH is advantageously set with a strong mineral acid, preferably sulfuric acid.
The compounds I are generally present in the electrolyte baths in concentrations within the range of from 0.1 to 2.0 g/l, preferably ~ithin the range of from O.2 to 1.3 g/l. The concentrations of further, customary brigh~eners are normally likewise within the range of from 0.1 to 2.0 g/l.
The nickel electrolyte baths described can be used to produce in particular nickel coatings on steel articles, but also on articles made o~ other materials, for example brass, which have been pretreated in a conv~ntional manner, by electrocoating. This is in general done at from 30 to 80C, preferably at from 40 to 60C.
The present invention further provides a brightener mixture for aqueous acidic electronickelizing baths which contain as essential constituents the com-pounds I and monocyclic or polycyclic heterocyclic nitrogen bases of the aromatic type in quaternized form in the abovemen~ioned concentratiorls.
The compounds I used according to the present invention are noteworthy for extremely high brightness formation. They produce higher brightness than customary brighteners, in some instances eve:n at lower concentra-tion~ in the nickel electrolyte baths.
Preparation of 1,2-dihydroxy-3-butene 32.7 g of vinylQxirane, 70 g of water and 0.5 g of 96% strength by weight sulfuric acid as catalyst was stirred at 85-90C for 5 hour~. The sulfuric acid was then neutralized with 50~ streng~h by weight sodium hydroxide solution. Small amounts of unconverted vinyl-oxirane were distilled off at 50C under a water jet vacuum together with excess water, leaving behind 40 g of product in the form of a viscous liquid.
- 8 - O.Z. 0050J42002 Preparation of sodium 4-(2'-hydroxy-3' buten~ yloxy)-benæenesulfonate 267.7 g of 65% strength by weight p-phenol-sulfonic acid w~re diluted with lO0 g of water and admixed with 80 g of 50% strength by weight sodium hydroxide solution. Then 70 g of vinyloxirane were added dropwise at 70-80C with stirring in the course of 30 minutes. The mixture was subsequently stirred at the same temperature for 8 hours. The water was then removed under a water jet vacuum, leaving behind 195 g of product. The product was again taken up in water and adjusted to a concentration o 50~ by weight.
Prepara~ion of sodium 2-hydroxy-3-butenesulfonate 21.5 g of vinylo~irane were added dropwise at 80C with stirring to a mixture of 80.4 g of 39% strength by weight aqueous sodium hydxogen sulfite solution and 23.b g of water in the course of 20 minutes. The mixture wa then ~tirred at the same temperatura for 8 hours.
Small amount~ of unconverted vinyloxirane and the water were removed under a water jet vacuum, leaving behind 40 g of product. The product wa~ taken up in water and adjusted to a concentration of 50~ by weight.
Preparation of tris(2-hydroxy-3-buten-1-yl)amine 126 g of vinyloxirane were added at 70-80C with skirring to a mixture of 40.8 g of 25~ strength by weight aqueou~ ammonia and 170 g of water in the course of 20 minutes. The mixture wa~ subseguently ~tirred at the same tempera~ure for 5 hours. It was then reduced under a water jet vacuum to 172 g. This left a viscous liguid having a product content of 78~ by weight.
Preparation of sodium ~-N-12'-hydroxy-3'-buten~ yl)-aminoethanesulfonate 70 g of vinyloxirane were added dropwise at 5~
- 9 - O.Z. 0050/42002 70-`80C with stirring to 313 g of a 47% strength by weight aqueous solution of the sodium salt of 2-amino-ethanesul~onic acid (taurine) in the course of 30 minutes. The mixture was subsequently stirred at the same temperature for 6 hours. The water was then removed under a water jet vacuum. This left 218 g of product. The product was taken up again in water, the solution being adjusted to a product content of 50% by weight.
Preparation of sodium 2-N,N-bis(2'-hydroxy-3'-buten-1'-yl)aminoethanesulfonate Example 5 was repeated with twice the amount of vinyloxirane, affording, after the reac~ion had taken place and the reaction mixture had been concentrated under a water ~et vacuum, 287 g of a product which was taken up again in water, the solution being adjusted to a product content of 50% by weight.
Preparation of sodium 4-N-(2'-hydroxy-3'-buten-l'-yl)-aminobenzenesulfonate 70 g of vinyloxirane were added dropwise at 70-80C with stirring to a mixture of 173 g of 4-amino-benzenesulfonic acid (sulfanilic acid), 200 g of water and 80 g of 50% strength by weight aqueous sodium hydroxide solution over 30 minutes. The mixture was subsequently stirred at the same temperature for 4 hours, giving 520 g of a ~olution having a product content of 53% by weight.
APPLIC~TION EXAMP1ES 8 TO 14 AND
3 0 COMPARATIVE EXA~LES A AND B
The products prepared in Ex~mples 1 to 7 were used as brighteners in weakly acidic electronickelizing baths.
The aqueous nickel electrolyte used had the following composition:
300 gJl of NiSO4 x 7 HzO
60 g/l of NiCl2 x 6 H2O
- 10 - O.Z. 0050~42002 45 g/l of H3~03 2 g~l of sucrose O.3 g/l of 2-pyridinium~ ulfa~oethane X g/l of brightener as per table 0.5 gJl of a fatty alcohol derivative of the formula C12H25/cl4H29-o-(cH2cH2o)2-so3Na as wetting agent The pH of khe electrolyte was adjustPd with sulfuric acid to 4.2.
The articles to be nickelized were brass panels which, prior to being plated with nickel, were cathodic-ally degreased in an alkaline ~lectrolyte in a conven-tional manner. The nickelization took place in a 250 ml Hull cell at 55C and a current strength of 2A for a period of 10 minutes. The panel~ were th~n rinsed with water and dried with compressed air.
The table below shows the results of these experLments. It can be seen that the brighteners or brightener mixtures used according to the presen~ inven-tion produce a higher brightness than the prior art agents t in some instances even at a lower concentration in the nickel electrolyte baths~
TABLE
Test results of electrodeposition of nickel Example Brightener of Concent:ration Brightness No. Exampl~ No. X [gtll [rating3 ~ . . _ , . .
8 1 0.3 4-5 9 2 0.8 4-5 3 0.~ 4-5 11 4 0~3 5 12 5 0.6 5 13 6 D.8 5 14 7 1.2 4-5 for comparison-A sodium vinylsulfonate 0.8 4 B sod~um allyl~ulfonate 0.7 4 .
5~3 ~ O.Z. 0050/42002 Ratings scheme for brightness:
S = excellent (perfect specular gloss) 4 = good (almost specular gloss) 3 = moderate 2 = poor 1 = no brigh~ness The ductility was very good with all examples No. 8 to 14 and the comparative specimens A and B.
Except in the case of Example 8, where a trace of overinhibition was found, it was impossible to detect any interference with the nickel deposition process.
t !
Claims (2)
1. A process for producing nickelized articles by electrodeposition of nickel from an aqueous acidic bath containing as essential constituents one or more nickel salts, one or more inorganic acids and one or more brighteners, which comprises using as brightener a
2 hydroxy-3-butenyl-containing compound of the formula I
I
where n is 1, 2 or 3 and the variable A has the following meanings:
for n - 1 - hydroxyl - a group of the formula -OR1, where R1 is C1-C4-alkyl, which may be sulfo-substituted, phenyl, 3- or 4-sulfophenyl, .alpha.- or .beta.-naphthyl, 3-, 4-, 5 , 6- or 7-sulfo-.alpha.-naphthyl or 4-, 5-, 6-, 7- or 8-sulfo-.beta. naphthyl - a phosphorus-containing group of -O-PO(OX)H or -O-PO(OX)2, where X is hydrogen or an alkali metal or ammonium cation - a sulfo group of the formula -SO3X
- an amino group of the formula -NH2, -NHR1 or -N(R1)2, where if two radicals R1 are present on the N-atom they can be identical or different for n = 2 - an amino group of the formula -NH- or -NR1-- a divalent oxygen atom for n = 3 - a trivalent nitrogen atom.
2. A 2-hydroxy-3-butenyl-containing compound of the formula Ia - 2 - O.Z. 0050/42002 Ia where n is 1, 2 or 3 and the variable B has the following meanings:
for n = 1 - a group of the formula -OR3, where R3 is C1-C4-alkyl, which is additionally sulfo-substituted, 3- or 4-sulfophenyl, .alpha.- or .beta.-naphthyl, 3-, 4-, 5-, 6- or 7-sulfo-.alpha.-naphthyl or 4-, 5-, 6-, 7- or 8-sulfo-.beta.-naphthyl - a phosphorus containing group of -O-PO(OX)H or -O-PO(OX)2, where X is hydrogen or an alkali metal or ammonium cation - an amino group of the formula -NHR3 - an amino group of the formula -N(R4)2 possessing two identical radicals R4, where R4 is R3 or phenyl for n = 2 - an amino group of the formula -NH-- an amino group of the formula -NR3-for n = 3 - a trivalent nitrogen atom.
I
where n is 1, 2 or 3 and the variable A has the following meanings:
for n - 1 - hydroxyl - a group of the formula -OR1, where R1 is C1-C4-alkyl, which may be sulfo-substituted, phenyl, 3- or 4-sulfophenyl, .alpha.- or .beta.-naphthyl, 3-, 4-, 5 , 6- or 7-sulfo-.alpha.-naphthyl or 4-, 5-, 6-, 7- or 8-sulfo-.beta. naphthyl - a phosphorus-containing group of -O-PO(OX)H or -O-PO(OX)2, where X is hydrogen or an alkali metal or ammonium cation - a sulfo group of the formula -SO3X
- an amino group of the formula -NH2, -NHR1 or -N(R1)2, where if two radicals R1 are present on the N-atom they can be identical or different for n = 2 - an amino group of the formula -NH- or -NR1-- a divalent oxygen atom for n = 3 - a trivalent nitrogen atom.
2. A 2-hydroxy-3-butenyl-containing compound of the formula Ia - 2 - O.Z. 0050/42002 Ia where n is 1, 2 or 3 and the variable B has the following meanings:
for n = 1 - a group of the formula -OR3, where R3 is C1-C4-alkyl, which is additionally sulfo-substituted, 3- or 4-sulfophenyl, .alpha.- or .beta.-naphthyl, 3-, 4-, 5-, 6- or 7-sulfo-.alpha.-naphthyl or 4-, 5-, 6-, 7- or 8-sulfo-.beta.-naphthyl - a phosphorus containing group of -O-PO(OX)H or -O-PO(OX)2, where X is hydrogen or an alkali metal or ammonium cation - an amino group of the formula -NHR3 - an amino group of the formula -N(R4)2 possessing two identical radicals R4, where R4 is R3 or phenyl for n = 2 - an amino group of the formula -NH-- an amino group of the formula -NR3-for n = 3 - a trivalent nitrogen atom.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4034788.5 | 1990-11-02 | ||
| DE4034788A DE4034788A1 (en) | 1990-11-02 | 1990-11-02 | METHOD FOR PRODUCING NICKELED MOLDED PARTS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2052583A1 true CA2052583A1 (en) | 1992-05-03 |
Family
ID=6417472
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002052583A Abandoned CA2052583A1 (en) | 1990-11-02 | 1991-10-01 | Production of nickelized articles |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0483627A1 (en) |
| JP (1) | JPH04268088A (en) |
| KR (1) | KR920009942A (en) |
| CN (1) | CN1061053A (en) |
| CA (1) | CA2052583A1 (en) |
| DE (1) | DE4034788A1 (en) |
| TW (1) | TW199912B (en) |
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| KR100971555B1 (en) * | 2010-02-25 | 2010-07-21 | 주식회사 유니테크 | High concentration ni-flash plating composition for pre-treatment of cold-rolled steel sheet in electrolytic galvanized iron plating process |
| US10718059B2 (en) * | 2017-07-10 | 2020-07-21 | Rohm And Haas Electronic Materials Llc | Nickel electroplating compositions with cationic polymers and methods of electroplating nickel |
| CN111850623A (en) * | 2020-05-08 | 2020-10-30 | 德锡化学(山东)有限公司 | Electroplating solution and electroplating process for obtaining suede nickel layer |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2533085A (en) * | 1948-01-21 | 1950-12-05 | Univ Michigan | Aminohydroxybutenes |
| DE1064500B (en) * | 1956-09-05 | 1959-09-03 | Basf Ag | Process for the preparation of 1- [beta-chloroethylamino] -2-hydroxy-alkenene (3) or the derivatives substituted on the carbon atom by hydrocarbon radicals |
| US3211783A (en) * | 1963-10-01 | 1965-10-12 | Gen Aniline & Film Corp | Process of preparing salts of monosulfonic acids of monohydric and dihydric olefinic alcohols |
| CA792798A (en) * | 1967-03-23 | 1968-08-20 | Atlantic Richfield Company | Epoxide taurine condensation products and detergent compositions containing them |
-
1990
- 1990-11-02 DE DE4034788A patent/DE4034788A1/en not_active Withdrawn
-
1991
- 1991-09-25 TW TW080107552A patent/TW199912B/zh active
- 1991-10-01 CA CA002052583A patent/CA2052583A1/en not_active Abandoned
- 1991-10-07 KR KR1019910017525A patent/KR920009942A/en not_active Application Discontinuation
- 1991-10-19 EP EP91117882A patent/EP0483627A1/en not_active Withdrawn
- 1991-10-31 JP JP3285944A patent/JPH04268088A/en not_active Withdrawn
- 1991-11-02 CN CN91108396A patent/CN1061053A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| KR920009942A (en) | 1992-06-25 |
| TW199912B (en) | 1993-02-11 |
| JPH04268088A (en) | 1992-09-24 |
| CN1061053A (en) | 1992-05-13 |
| EP0483627A1 (en) | 1992-05-06 |
| DE4034788A1 (en) | 1992-05-07 |
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