US3663378A - Electroplating of nickel - Google Patents
Electroplating of nickel Download PDFInfo
- Publication number
- US3663378A US3663378A US124941A US3663378DA US3663378A US 3663378 A US3663378 A US 3663378A US 124941 A US124941 A US 124941A US 3663378D A US3663378D A US 3663378DA US 3663378 A US3663378 A US 3663378A
- Authority
- US
- United States
- Prior art keywords
- nickel
- compound
- electroplating
- baths
- plating solution
- 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.)
- Expired - Lifetime
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 49
- 238000009713 electroplating Methods 0.000 title claims description 14
- 238000007747 plating Methods 0.000 claims abstract description 27
- 150000001875 compounds Chemical class 0.000 claims abstract description 25
- 230000002378 acidificating effect Effects 0.000 claims abstract description 13
- 238000005282 brightening Methods 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims description 11
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 7
- 150000002815 nickel Chemical class 0.000 claims description 7
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 7
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 6
- UQPSGBZICXWIAG-UHFFFAOYSA-L nickel(2+);dibromide;trihydrate Chemical compound O.O.O.Br[Ni]Br UQPSGBZICXWIAG-UHFFFAOYSA-L 0.000 claims description 6
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 claims description 6
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 abstract description 7
- 229910052801 chlorine Inorganic materials 0.000 abstract description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 6
- 229910006069 SO3H Inorganic materials 0.000 abstract description 3
- 229910052794 bromium Inorganic materials 0.000 abstract description 2
- 125000004672 ethylcarbonyl group Chemical group [H]C([H])([H])C([H])([H])C(*)=O 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 abstract 1
- 125000004674 methylcarbonyl group Chemical group CC(=O)* 0.000 abstract 1
- -1 Ch O Inorganic materials 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 6
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 6
- 238000013019 agitation Methods 0.000 description 5
- 150000002596 lactones Chemical class 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 4
- 125000001309 chloro group Chemical group Cl* 0.000 description 4
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- IWYDHOAUDWTVEP-UHFFFAOYSA-N R-2-phenyl-2-hydroxyacetic acid Natural products OC(=O)C(O)C1=CC=CC=C1 IWYDHOAUDWTVEP-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 229960000956 coumarin Drugs 0.000 description 3
- 235000001671 coumarin Nutrition 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 3
- 239000000080 wetting agent Substances 0.000 description 3
- CCVYRRGZDBSHFU-UHFFFAOYSA-N (2-hydroxyphenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC=C1O CCVYRRGZDBSHFU-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical class CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 239000000872 buffer Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- RNFNDJAIBTYOQL-UHFFFAOYSA-N chloral hydrate Chemical compound OC(O)C(Cl)(Cl)Cl RNFNDJAIBTYOQL-UHFFFAOYSA-N 0.000 description 2
- 229960002327 chloral hydrate Drugs 0.000 description 2
- ZWWQRMFIZFPUAA-UHFFFAOYSA-N dimethyl 2-methylidenebutanedioate Chemical compound COC(=O)CC(=C)C(=O)OC ZWWQRMFIZFPUAA-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- KDKYADYSIPSCCQ-UHFFFAOYSA-N ethyl acetylene Natural products CCC#C KDKYADYSIPSCCQ-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- YTGSYRVSBPFKMQ-UHFFFAOYSA-N 2,2,2-tribromoacetaldehyde Chemical compound BrC(Br)(Br)C=O YTGSYRVSBPFKMQ-UHFFFAOYSA-N 0.000 description 1
- MHGOKSLTIUHUBF-UHFFFAOYSA-N 2-ethylhexyl sulfate Chemical compound CCCCC(CC)COS(O)(=O)=O MHGOKSLTIUHUBF-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- KHBQMWCZKVMBLN-UHFFFAOYSA-N Benzenesulfonamide Chemical compound NS(=O)(=O)C1=CC=CC=C1 KHBQMWCZKVMBLN-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 101100328895 Caenorhabditis elegans rol-8 gene Proteins 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- LDCRTTXIJACKKU-ONEGZZNKSA-N dimethyl fumarate Chemical compound COC(=O)\C=C\C(=O)OC LDCRTTXIJACKKU-ONEGZZNKSA-N 0.000 description 1
- 229960004419 dimethyl fumarate Drugs 0.000 description 1
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- GPUMPJNVOBTUFM-UHFFFAOYSA-N naphthalene-1,2,3-trisulfonic acid Chemical compound C1=CC=C2C(S(O)(=O)=O)=C(S(O)(=O)=O)C(S(=O)(=O)O)=CC2=C1 GPUMPJNVOBTUFM-UHFFFAOYSA-N 0.000 description 1
- 230000000063 preceeding effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- UOCCVDMCNJYVIW-UHFFFAOYSA-N prop-2-yne-1-sulfonic acid Chemical compound OS(=O)(=O)CC#C UOCCVDMCNJYVIW-UHFFFAOYSA-N 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 125000004964 sulfoalkyl group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- DZAIBGWGBBQGPZ-XQRVVYSFSA-N trimethyl (z)-prop-1-ene-1,2,3-tricarboxylate Chemical compound COC(=O)C\C(C(=O)OC)=C\C(=O)OC DZAIBGWGBBQGPZ-XQRVVYSFSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
- C25D3/14—Electroplating: Baths therefor from solutions of nickel or cobalt from baths containing acetylenic or heterocyclic compounds
- C25D3/18—Heterocyclic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
- C07D307/82—Benzo [b] furans; Hydrogenated benzo [b] furans with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the hetero ring
- C07D307/83—Oxygen atoms
Definitions
- This invention relates to the electrodeposition of semibright, or bright, sulfur-free, high leveling nickel plate from aqueous acidic nickel plating baths and more particularly, it relates to the use of an addition agent as an improved brightener in acidic nickel plating baths.
- Another object of the present invention is to provide an improved process for electroplating a ductile, lustrous nickel late. p
- the present invention includes a bath for electroplating ductile, lustrous nickel plate which comprises an aqueous acidic nickel plating solution containing at least one soluble nickel plating salt and a brightening amount of a compound having the formula:
- R and R are H, CH C l-I F, Cl, Br, Ch O, C H O Ch3CO, C2H5CO, CI-hCONl-I- C2H CONH, (Cl-I2)" -SO3 or O(CH2),1 SO3H.
- R is H,F,Clorphenyl, and n is a number from 1 to 6 inclusive.
- the plating bath is an aqueous acidic nickel plating solution which contains at least one soluble nickel plating salt, desirably selected from nickel sulfate, nickel chloride, nickel bromide, nickel sulfamate and nickel fluoroborate, and a brightening amount of a compound falling within the formula (A) given above.
- the compound used has the following structure:
- these compounds are present in amounts which will provide brightening and leveling of the nickel plate produced, amounts within the range of about 0.03 to l gram/liter being desired, with amounts within the range of about 0.1 to 0.3 grams/liter being preferred.
- the brightening additives of the present invention may be prepared, generally, by condensing the lactone of an 0- hydroxy phenyl acetic acid with an aldehyde. Such preparation is illustrated specifically with regard to the preparation of compound (B) above. In this preparation, the lactone of 0- hydroxy phenyl acetic acid is condensed with formaldehyde,
- Similar reactions may be carried out using 0- hydroxy phenyl acetic acid lactones having substituting groups on the benzene ring such as fluoro, chloro, bromo, methyl, methoxy, ethyl, ethoxy, acetyl, acetylamino, propionyl, propionylamino, and sulfoalkyl, or sulfoalkylether groups where the alkyl group is not more than six carbons. It is preferred, however, that not more than two such groups be present on the benzene ring.
- the halogenated materials may be used such as the fluoro, chloro, abromo.
- the alkyl (methyl and ethyl), alkoxy (methoxy and ethoxy) and ketones (methyl and ethyl ketone) are used in place of (D) in the reaction sodium ethoxide.
- the -Nl-ICOCI-I and -NI-ICOC,I-I substituted materials that are to be used in place of (D) in the reaction with sodium ethoxide are prepared by reacting the amine precursor with CH COCI or C H COCl as follows:
- the fluorinated materials (where R is F) are prepared by substituting chlorine with fluorine in the presence of SbF according to the Swartz reaction.
- the aqueous acidic nickel plating baths may be of various types, including the Watts type or modifications thereof.
- the nickel salts used in formulating the baths are desirably nickel sulfate, nickel chloride, nickel bromide, nickel sulfamate, nickel fluoborate, as well as mixtures of any two or more of these.
- the nickel salts are preferably used in conjunction with buffer materials,
- boric acid such as boric acid.
- Other acidic type buffers which may be used include formic acid, fluoboric acid, and the like, and these may be used either in place of or in conjunction with boric acid. It has generally been found that optimum results are obtained when the concentration of the boric acid, or its equivalent, is at least about 30 grams/liter.
- Compound (A) may be used in concentrations of 0.05 to 1 gram per liter, preferably 0.1 to 0.3 g/l, when used alone in the baths, especially Watts nickel baths, or dilute all chloride (about 100 g/l NiCI .6H,O) nickel baths. When used alone in such baths it allows the production of ductile, high leveling sulfur-free nickel plate.
- lf o-benzoyl sulfamide and/or other class 1 nickel brighteners are used in conjunction with (A) in acidic nickel baths (sulfate, chloride, bromide, fluoborate, sulfamate), full bright nickel plate is obtained. It is preferred, however, to use compound (A) in the deposition of semi-bright high leveling, sulfur-free nickel plate.
- the presence of the low foaming wetting agent 2-ethyl hexyl sulfate (sodium salt) is desirable, in concentrations of 0.1 to 0.5 g/l.
- sulfur containing anodes S D nickel
- S D nickel sulfur containing anodes
- sodium lauryl sulfate is a preferred wetting agent in concentrations of0.05 to 0.3 g/l.
- EXAMPLE 2 To the bath of Example 1, 2-10 mg/l of the l to 1 mole 1,3- dioxolane adduct of propargyl alcohol or the 1 to 2 mole propylene oxide adduct of propargyl alcohol are added, thus making it possible to use slightly lower optimum concentrations of compound (3) in the bath, that is 0.1 to 0.2 g/l instead of 0.2 to 0.6 g/l.
- Example 4 An example of fully bright plating nickel bath is shown in Example 4 below. lnstead of o-benzyl sulfimide, p-toluene sulfonumidc and the other well known class 1 nickel brighteners shown in U.S. Pat. No. 2,781,306 col 6, Table 11 may be used.
- Air agitation 1f mechanical or cathode rod agitation is used, then sodium lauryl sulfate wetting agent, in concentrations of about 0.1 to 0.5 g/l is preferred over the shorter chain similar surfactants.
- the electroplating baths of the preceeding examples may be operated at temperatures from about room temperature to almost boiling, with temperatures within the range of about 40 to 60 C being preferred.
- the pH values of these baths may range from about 2 to 5.5, although pH values within the range of about 3.0 to 4.8 are preferred.
- the cathode current densities used may also vary, values within the range of about 5 to several hundred amperes/square foot being useful. While the preferred range is about 20 to amperes/square foot, the optimum will depend in each instance on the agitation, temperature, and concentration and type of nickel salts used in the bath.
- the compounds having the formula (A) are outstanding nickel brighteners and there is produced an excellent semibright or full bright, sulfur-free high leveling nickel plate. A more passive plate is produced than would coumarin and the compounds (A), do not hydrolyze in the warm acid nickel plating baths, forming harmful products which cause dulling of the plate and decrease leveling, as do the unsaturated esters such as dimethyl itaconate, and the like.
- a bath for electroplating ductile, lustrous nickel plate which comprises an aqueous acidic nickel plating solution containing at least one soluble nickel plating salt and a brightening amount of a brightening compound having the formula R is selected from H, F, C1 or phenyl; and
- n is a number from 1 to 6 inclusive.
- a method for electroplating ductile, lustrous nickel plate which comprises electrodepositing nickel on a base from the aqueous acidic nickel plating solution as claimed in claim 1.
- nickel salts in the plating solution are selected from nickel sulfate, nickel chloride, nickel bromide, nickel sulfamate and nickel fluoborate.
- the electroplating solution as claimed in claim 4 wherein the brightener 8.
Landscapes
- 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)
Abstract
An aqueous acidic nickel plating bath which contains a brightening amount of a compound having the formula: WHEREIN R1 and R2 are H, CH3, C2H5, F, Cl, Br, CH30-, C2H5O-, CH3CO-, CH3CONH-, -O(CH2)n-SO3H, -O(CH2)n-SO3H, C2H5CO-, or C2H5CONH-. R is H, F, Cl or phenyl, and n is a number from 1 to 6 inclusive.
Description
United States Patent Brown 51 May 16, 1972 [54] E TR P ATIN 0F I KE 2,748,068 5/1956 Faust et al ..204/49 X [72] Inventor: Henry Brown, Huntington Woods, Mich. P i E min r-G, L, Kaplan Assignee Udyme Corporation Warren Mich Attorney-Stanley H. Lieberstein and William J. Schramm 221 Filed: Mar. 16,1971 ABSTRACT [21] APPL No; 124,941 An aqueous acidic nickel plating bath which contains a brightening amount of a compound having the formula: Related U.S. Application Data C=C1IR [63] Continuation-impart of Ser. No. 812,377, Apr. 1, p
=0 1969, abandoned. O
[52] U.S. Cl .204/49, 260/240 F, 260/3433 7 R2 7 a 51 Int.Cl. ..C23b 5/08,C23b 5/46 RI and R2 CzH-T 58 Field ofSearch ..204/49,43,44, 112; 106/]; CZHSO" CHQCONH" F, Cl or phenyl, and n is a number from 1 to 6 inclusive [56] References Cited UNITED STATES PATENTS 8 Claims, N0 Drawings 2,635,076 4/1953 Du Rose ..204/49 ELECTROPLATING F NICKEL This application is a continuation -in-part of application Ser. No. 812,377, filed Apr. 4, 1969, now abandoned.
This invention relates to the electrodeposition of semibright, or bright, sulfur-free, high leveling nickel plate from aqueous acidic nickel plating baths and more particularly, it relates to the use of an addition agent as an improved brightener in acidic nickel plating baths.
Heretofore, numerous brightening agents have been proposed for acidic nickel plating baths. Among those which have been successfully used commercially are coumarin and its various derivatives. Although coumarin does produce good leveling and allows the formation of a semi-bright sulfur-free nickel plate of high ductility, the nickel plate produced is not as passive as is often desired. Similarly, while the unsaturated esters, such as dimethyl fumarate, dimethyl maleate, dimethyl itaconate, trimethyl aconitate and the like also produce a leveling nickel plate of high ductility, they hydrolyze in the plating bath, merely on standing, to give harmful products which cause dulling of the plate and decrease the leveling.
It is, therefore an object of the present invention to provide an acid nickel plating bath containing an improved brightener which overcomes these difficulties.
Another object of the present invention is to provide an improved process for electroplating a ductile, lustrous nickel late. p These and other object will become apparent to those skilled in the art from the description of the invention which follows.
Pursuant to the above objects, the present invention includes a bath for electroplating ductile, lustrous nickel plate which comprises an aqueous acidic nickel plating solution containing at least one soluble nickel plating salt and a brightening amount of a compound having the formula:
2 (A) wherein R and R are H, CH C l-I F, Cl, Br, Ch O, C H O Ch3CO, C2H5CO, CI-hCONl-I- C2H CONH, (Cl-I2)" -SO3 or O(CH2),1 SO3H. R is H,F,Clorphenyl, and n is a number from 1 to 6 inclusive.
More specifically, in the practice of the present invention, the plating bath is an aqueous acidic nickel plating solution which contains at least one soluble nickel plating salt, desirably selected from nickel sulfate, nickel chloride, nickel bromide, nickel sulfamate and nickel fluoroborate, and a brightening amount of a compound falling within the formula (A) given above. Preferably, the compound used has the following structure:
In such baths these compounds are present in amounts which will provide brightening and leveling of the nickel plate produced, amounts within the range of about 0.03 to l gram/liter being desired, with amounts within the range of about 0.1 to 0.3 grams/liter being preferred.
The brightening additives of the present invention may be prepared, generally, by condensing the lactone of an 0- hydroxy phenyl acetic acid with an aldehyde. Such preparation is illustrated specifically with regard to the preparation of compound (B) above. In this preparation, the lactone of 0- hydroxy phenyl acetic acid is condensed with formaldehyde,
Other compounds falling within formula (A) may be similarly prepared by using other aldehydes and/or derivatives of the lactone of o-hydroxy phenyl acetic acid. For example, benzaldehyde may be used in place of formaldehyde in the above reaction to produce an additive having a phenyl substituted vinyl group. Similar reactions may be carried out using 0- hydroxy phenyl acetic acid lactones having substituting groups on the benzene ring such as fluoro, chloro, bromo, methyl, methoxy, ethyl, ethoxy, acetyl, acetylamino, propionyl, propionylamino, and sulfoalkyl, or sulfoalkylether groups where the alkyl group is not more than six carbons. It is preferred, however, that not more than two such groups be present on the benzene ring.
The starting materials for the above reaction are prepared according to the preparations described in Organic Synthesis," Collective, Vol. III, John Wiley 1955), pp. 715, et seg. In general an aldehyde, such as formaldehyde or benzaldehyde is reacted with (D) HO-C H -CH CN in the presence of sodium ethoxide. The lactone is formed by acidifying the product of the preceding reaction.
In place of (D), the halogenated materials may be used such as the fluoro, chloro, abromo. Likewise the alkyl (methyl and ethyl), alkoxy (methoxy and ethoxy) and ketones (methyl and ethyl ketone) are used in place of (D) in the reaction sodium ethoxide.
The -Nl-ICOCI-I and -NI-ICOC,I-I substituted materials that are to be used in place of (D) in the reaction with sodium ethoxide are prepared by reacting the amine precursor with CH COCI or C H COCl as follows:
CH2(CI 2)nCl NaHSOs NCCHz- The O(CH ),,SO H materials are prepared by reacting:
wi l
The preparation of the compounds where R is chloro or fluoro is as follows. Hydrogenate, the double bond of either The hydrogenated compound is then reacted with chlorine to replace two hydrogen atoms with two chlorine atoms and then dehydrohalogenated. If need be the product may be acidified to insure the presence of the lactone.
The fluorinated materials (where R is F) are prepared by substituting chlorine with fluorine in the presence of SbF according to the Swartz reaction.
As has been noted previously, the aqueous acidic nickel plating baths may be of various types, including the Watts type or modifications thereof. The nickel salts used in formulating the baths are desirably nickel sulfate, nickel chloride, nickel bromide, nickel sulfamate, nickel fluoborate, as well as mixtures of any two or more of these. In many instances the nickel salts are preferably used in conjunction with buffer materials,
such as boric acid. Other acidic type buffers which may be used include formic acid, fluoboric acid, and the like, and these may be used either in place of or in conjunction with boric acid. It has generally been found that optimum results are obtained when the concentration of the boric acid, or its equivalent, is at least about 30 grams/liter.
Compound (A) may be used in concentrations of 0.05 to 1 gram per liter, preferably 0.1 to 0.3 g/l, when used alone in the baths, especially Watts nickel baths, or dilute all chloride (about 100 g/l NiCI .6H,O) nickel baths. When used alone in such baths it allows the production of ductile, high leveling sulfur-free nickel plate. It also cooperates excellently with small concentrations, 0.001 to 0.2 g/l, of one or more of the following non-sulfur containing compounds: formaldehyde, chloral hydrate, bromal, coumarin, butyne diol, and the monoand di-ethylene oxide and propylene oxide adducts of propargyl alcohol and allyl alcohol, and the mono-1,3-dioxolane adduct of butyne diol, propargyl alcohol and allyl a1- cohol, in the production of semi-bright high leveling sulfurfree ductile nickel plate.
lf o-benzoyl sulfamide and/or other class 1 nickel brighteners (benzene sulfonamide, naphthalene trisulfonic acid, propargyl sulfonic acid, and the like) are used in conjunction with (A) in acidic nickel baths (sulfate, chloride, bromide, fluoborate, sulfamate), full bright nickel plate is obtained. It is preferred, however, to use compound (A) in the deposition of semi-bright high leveling, sulfur-free nickel plate.
Examples of typical preferred embodiments of the nickel plating baths of the present invention are given below. These baths are aqueous solutions containing the listed components in the amounts indicated.
The presence of the low foaming wetting agent 2-ethyl hexyl sulfate (sodium salt) is desirable, in concentrations of 0.1 to 0.5 g/l.
When no nickel chloride is used, sulfur containing anodes (S D nickel) arc to be used which dissolve anodically without the presence of chloride ions in the bath. lf cathode rod agitation is used instead of air agitation, sodium lauryl sulfate is a preferred wetting agent in concentrations of0.05 to 0.3 g/l.
EXAMPLE 2 To the bath of Example 1, 2-10 mg/l of the l to 1 mole 1,3- dioxolane adduct of propargyl alcohol or the 1 to 2 mole propylene oxide adduct of propargyl alcohol are added, thus making it possible to use slightly lower optimum concentrations of compound (3) in the bath, that is 0.1 to 0.2 g/l instead of 0.2 to 0.6 g/l.
EXAMPLE 3 To the bath of Example 1, 20 mg/l of formaldehyde and 30 to 50 mg/l of chloral hydrate are added, thus making it possible to use slightly lower concentrations of the compound (B).
An example of fully bright plating nickel bath is shown in Example 4 below. lnstead of o-benzyl sulfimide, p-toluene sulfonumidc and the other well known class 1 nickel brighteners shown in U.S. Pat. No. 2,781,306 col 6, Table 11 may be used.
Air agitation 1f mechanical or cathode rod agitation is used, then sodium lauryl sulfate wetting agent, in concentrations of about 0.1 to 0.5 g/l is preferred over the shorter chain similar surfactants.
The electroplating baths of the preceeding examples may be operated at temperatures from about room temperature to almost boiling, with temperatures within the range of about 40 to 60 C being preferred. The pH values of these baths may range from about 2 to 5.5, although pH values within the range of about 3.0 to 4.8 are preferred. The cathode current densities used may also vary, values within the range of about 5 to several hundred amperes/square foot being useful. While the preferred range is about 20 to amperes/square foot, the optimum will depend in each instance on the agitation, temperature, and concentration and type of nickel salts used in the bath.
When the plating baths of the present invention are operated in accordance with the above procedure, it is found that the compounds having the formula (A) are outstanding nickel brighteners and there is produced an excellent semibright or full bright, sulfur-free high leveling nickel plate. A more passive plate is produced than would coumarin and the compounds (A), do not hydrolyze in the warm acid nickel plating baths, forming harmful products which cause dulling of the plate and decrease leveling, as do the unsaturated esters such as dimethyl itaconate, and the like.
While there have been described various embodiments of the invention, the compositions and methods described are not intended to be understood as limiting the scope of the invention as changes therewithin are possible and it is intended that each element recited in any of the following claims is to be understood as referring to all equivalent elements for accomplishing the same results in substantially the same or equivalent manner, it being intended to cover the invention broadly in whatever form its principle may be utilized.
What is claimed is:
1. A bath for electroplating ductile, lustrous nickel plate which comprises an aqueous acidic nickel plating solution containing at least one soluble nickel plating salt and a brightening amount of a brightening compound having the formula R is selected from H, F, C1 or phenyl; and
n is a number from 1 to 6 inclusive.
2. A method for electroplating ductile, lustrous nickel plate which comprises electrodepositing nickel on a base from the aqueous acidic nickel plating solution as claimed in claim 1.
3. The method as claimed in claim 2 wherein the nickel salts in the plating solution are selected from nickel sulfate, nickel chloride, nickel bromide, nickel sulfamate and nickel fluoborate.
4. The method as claimed in claim 3 wherein the brightener 7. The electroplating solution as claimed in claim 6 wherein compound is present in the plating solution in an amount of the brightening compound is present in an amount of from from about 0.03 to 1.0 grams/liter. about 0.03 to 1.0 grams/liter.
5. The method as claimed in claim 4 wherein the brightener 8. The electroplating solution as claimed in claim 7 wherein com ound in the plating solution has the formula: 5 the brightening compound has the formula C -C H2 C=CH2 0:0 I o 10 0 =0 6. The electroplating solution as claimed in claim 1 wherein the nickel salts are selected from nickel sulfate, nickel chloride, nickel bromide, nickel sulfamate and nickel fluoborate.
Claims (7)
- 2. A method for electroplating ductile, lustrous nickel plate which comprises electrodepositing nickel on a base from the aqueous acidic nickel plating solution as claimed in claim 1.
- 3. The method as claimed in claim 2 wherein the nickel salts in the plating solution are selected from nickel sulfate, nickel chloride, nickel bromide, nickel sulfamate and nickel fluoborate.
- 4. The method as claimed in claim 3 wherein the brightener compound is present in the plating solution in an amount of from about 0.03 to 1.0 grams/liter.
- 5. The method as claimed in claim 4 wherein the brightener compound in the plating solution has the formula:
- 6. The electroplating solution as claimed in claim 1 wherein the nickel salts are selected from nickel sulfate, nickel chloride, nickel bromide, nickel sulfamate and nickel fluoborate.
- 7. The electroplating solution as claimed in claim 6 wherein the brightening compound is present in an amount of from about 0.03 to 1.0 grams/liter.
- 8. The electroplating solution as claimed in claim 7 wherein the brightening compound has the formula
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US12494171A | 1971-03-16 | 1971-03-16 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3663378A true US3663378A (en) | 1972-05-16 |
Family
ID=22417524
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US124941A Expired - Lifetime US3663378A (en) | 1971-03-16 | 1971-03-16 | Electroplating of nickel |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US3663378A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3930072A (en) * | 1974-06-28 | 1975-12-30 | Universal Oil Prod Co | Stabilization of metal plating baths |
| US4333920A (en) * | 1979-02-23 | 1982-06-08 | Van Dyk & Company, Inc. | Benzalphthalides and broad spectrum sun screens |
| US4376018A (en) * | 1979-12-31 | 1983-03-08 | Bell Telephone Laboratories, Incorporated | Electrodeposition of nickel |
| US20090309060A1 (en) * | 2006-06-30 | 2009-12-17 | Akinori Oka | Additives for Electrolyte Solution and Electrolyte Solution |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2635076A (en) * | 1947-01-29 | 1953-04-14 | Harshaw Chem Corp | Bright nickel plating |
| US2748068A (en) * | 1953-07-20 | 1956-05-29 | Rockwell Spring & Axle Co | Composition and process for electroplating bright nickel |
-
1971
- 1971-03-16 US US124941A patent/US3663378A/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2635076A (en) * | 1947-01-29 | 1953-04-14 | Harshaw Chem Corp | Bright nickel plating |
| US2748068A (en) * | 1953-07-20 | 1956-05-29 | Rockwell Spring & Axle Co | Composition and process for electroplating bright nickel |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3930072A (en) * | 1974-06-28 | 1975-12-30 | Universal Oil Prod Co | Stabilization of metal plating baths |
| US4333920A (en) * | 1979-02-23 | 1982-06-08 | Van Dyk & Company, Inc. | Benzalphthalides and broad spectrum sun screens |
| US4376018A (en) * | 1979-12-31 | 1983-03-08 | Bell Telephone Laboratories, Incorporated | Electrodeposition of nickel |
| US20090309060A1 (en) * | 2006-06-30 | 2009-12-17 | Akinori Oka | Additives for Electrolyte Solution and Electrolyte Solution |
| US8163195B2 (en) * | 2006-06-30 | 2012-04-24 | Otsuka Chemical Co., Ltd. | Additives for electrolyte solution and electrolyte solution |
| US8372300B2 (en) | 2006-06-30 | 2013-02-12 | Otsuka Chemical Co., Ltd. | Additives for electrolyte solution and electrolyte solution |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US2910413A (en) | Brighteners for electroplating baths | |
| US4421611A (en) | Acetylenic compositions and nickel plating baths containing same | |
| CA1314513C (en) | Zinc-nickel alloy electrolyte and process | |
| US4880507A (en) | Tin, lead or tin/lead alloy electrolytes for high speed electroplating | |
| US3755096A (en) | Bright acid tin plating | |
| US2840517A (en) | Nickel-iron-zinc alloy electroplating | |
| US3862019A (en) | Composition of electroplating bath for the electrodeposition of bright nickel | |
| US2550449A (en) | Electrodeposition of nickel from an acid bath | |
| US3663378A (en) | Electroplating of nickel | |
| US3795592A (en) | Nickel electroplating composition and process | |
| US3506548A (en) | Electrodeposition of nickel | |
| US3574067A (en) | Electroforming metals and electrolytes therefor | |
| US2326999A (en) | Nickel plating | |
| US3804727A (en) | Electrodeposition of nickel | |
| US3770730A (en) | Electroplating of nickel | |
| US3711384A (en) | Electrodeposition of nickel | |
| US2541700A (en) | Electroplating copper | |
| US3697392A (en) | Electrodeposition of nickel | |
| US3152975A (en) | Electrodeposition of nickel | |
| US2994648A (en) | Nickel plating additives | |
| US2757133A (en) | Electrodeposition of nickel | |
| US3709798A (en) | Electrodeposition of nickel | |
| US3367854A (en) | Nickel plating | |
| US3215610A (en) | Method and bath for electrodepositing bright silver | |
| US3699016A (en) | Bright nickel plating bath and process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AS | Assignment |
Owner name: OXY METAL INDUSTRIES CORPORATION Free format text: CHANGE OF NAME;ASSIGNOR:OXY METAL FINISHING CORPORATION;REEL/FRAME:003967/0084 Effective date: 19741220 |
|
| AS | Assignment |
Owner name: HOOKER CHEMICALS & PLASTICS CORP. Free format text: MERGER;ASSIGNOR:OXY METAL INDUSTRIES CORPORATION;REEL/FRAME:004075/0885 Effective date: 19801222 |
|
| AS | Assignment |
Owner name: OCCIDENTAL CHEMICAL CORPORATION Free format text: CHANGE OF NAME;ASSIGNOR:HOOKER CHEMICAS & PLASTICS CORP.;REEL/FRAME:004126/0054 Effective date: 19820330 |
|
| AS | Assignment |
Owner name: OMI INTERNATIONAL CORPORATION, 21441 HOOVER ROAD, Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:OCCIDENTAL CHEMICAL CORPORATION;REEL/FRAME:004190/0827 Effective date: 19830915 |
|
| AS | Assignment |
Owner name: MANUFACTURERS HANOVER TRUST COMPANY, A CORP OF NY Free format text: SECURITY INTEREST;ASSIGNOR:INTERNATIONAL CORPORATION, A CORP OF DE;REEL/FRAME:004201/0733 Effective date: 19830930 |