US3170855A - Bright nickel plating baths - Google Patents
Bright nickel plating baths Download PDFInfo
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- US3170855A US3170855A US266068A US26606863A US3170855A US 3170855 A US3170855 A US 3170855A US 266068 A US266068 A US 266068A US 26606863 A US26606863 A US 26606863A US 3170855 A US3170855 A US 3170855A
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- allyl
- nickel
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- vinyl pyridinium
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims description 45
- 229910052759 nickel Inorganic materials 0.000 title claims description 22
- 238000007747 plating Methods 0.000 title description 12
- 229940124530 sulfonamide Drugs 0.000 claims description 3
- 150000003460 sulfonic acids Chemical class 0.000 claims description 3
- 238000004070 electrodeposition Methods 0.000 claims description 2
- 150000002898 organic sulfur compounds Chemical class 0.000 claims description 2
- 150000003456 sulfonamides Chemical class 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 25
- -1 heterocyclic nitrogen compounds Chemical class 0.000 description 21
- 229910019142 PO4 Inorganic materials 0.000 description 18
- 235000021317 phosphate Nutrition 0.000 description 18
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 17
- 239000010452 phosphate Substances 0.000 description 17
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 16
- SMUQFGGVLNAIOZ-UHFFFAOYSA-N quinaldine Chemical compound C1=CC=CC2=NC(C)=CC=C21 SMUQFGGVLNAIOZ-UHFFFAOYSA-N 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 12
- 238000000034 method Methods 0.000 description 9
- 150000002815 nickel Chemical class 0.000 description 7
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- 239000002659 electrodeposit Substances 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 4
- 229960002645 boric acid Drugs 0.000 description 4
- 235000010338 boric acid Nutrition 0.000 description 4
- 239000004327 boric acid Substances 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 238000009713 electroplating Methods 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 4
- 150000003464 sulfur compounds Chemical class 0.000 description 4
- LMYRWZFENFIFIT-UHFFFAOYSA-N toluene-4-sulfonamide Chemical compound CC1=CC=C(S(N)(=O)=O)C=C1 LMYRWZFENFIFIT-UHFFFAOYSA-N 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 229910001369 Brass Inorganic materials 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 239000010951 brass Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 125000005394 methallyl group Chemical group 0.000 description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 3
- 229940053662 nickel sulfate Drugs 0.000 description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- KFDVPJUYSDEJTH-UHFFFAOYSA-O 4-ethenylpyridine;hydron Chemical compound C=CC1=CC=[NH+]C=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-O 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical group N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 230000001464 adherent effect Effects 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910017464 nitrogen compound Inorganic materials 0.000 description 2
- 230000003389 potentiating effect Effects 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- JLISPDJKVHBDFX-UHFFFAOYSA-N C1(=CC=CC=C1)S(=O)(=O)N.P(O)(O)(O)=O Chemical compound C1(=CC=CC=C1)S(=O)(=O)N.P(O)(O)(O)=O JLISPDJKVHBDFX-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 241000220010 Rhode Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 241000272534 Struthio camelus Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- SMWDFEZZVXVKRB-UHFFFAOYSA-O hydron;quinoline Chemical compound [NH+]1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-O 0.000 description 1
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 description 1
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
- C07D213/20—Quaternary compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D217/00—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems
- C07D217/02—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems with only hydrogen atoms or radicals containing only carbon and hydrogen atoms, directly attached to carbon atoms of the nitrogen-containing ring; Alkylene-bis-isoquinolines
- C07D217/10—Quaternary compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
- C25D3/14—Electroplating: Baths therefor from solutions of nickel or cobalt from baths containing acetylenic or heterocyclic compounds
- C25D3/18—Heterocyclic compounds
Definitions
- This invention relates to compositions of matter and to nickel electroplating baths and processes for the production of bright, adherent, and especially ductile nickel plates.
- R is an aliphatic group saturated or unsaturated, having from one to four carbon atoms, for example, methyl, ethyl, propyl, butyl, ally-l and methallyl
- R may be hydrogen, i.e., no substituent on the ring, or an aliphatic group of one or two carbon atoms, such as methyl,. ethyl, or vinyl, and may be substituted in any position of the pyridine, quinoline, or isoquinoline ring or rings.
- N-allyl quinaldinium diallyl phosphate N-allyl 2vinylpyridinium diallyl phosphate, N-ethyl isoquinolinium diethyl phosphate, N-butyl 4-vinyl pyridinium dibutyl phosphate, and mixtures of the pyridinium and quinolinium and quinaldinium N-alkyl dialkyl phosphates.
- Z-methylquinoline is quinaldine and the 3,170,855 Patented Feb. 23, 1965 nomenclature herein reflects this in use of quinaldinium to identify the Z-methyl quinoline moiety.
- R Br,Cl Pyridlnium compounds In the above representation, R is an allyl or methallyl group, R" is vinyl, and may be substituted in the 2 or 4 position of the pyridine.
- R is an allyl or methallyl group
- R" is vinyl, and may be substituted in the 2 or 4 position of the pyridine.
- combinations of compounds from Groups I and II are unusually potent primary brighteners in nickel plating baths. Preferably they are used in total amounts between about 0.001 and 0.30 gram per liter.
- Brighteners used in nickel plating are commonly classified broadly as primary brighteners which increase the brightness of the ordinary dull or matte deposit of nickel but do not bring out the true mirror-bright condition.
- the secondary brighteners improve the ductility of the plate.
- the secondary brighteners with which this invention is primarily concerned are used in combination with these primary brighteners to develop true mirror-bright deposits.
- the combinations of heterocyclic nitrogen compounds as described in this present invention are potent and extraordinarily elfective secondary brighteners.
- the preferred concentrations are quite low, and inasmuch as these compounds are usually of quite limited solubility in water the concentration, even though low, can be readily maintained.
- These heterocyclic nitrogen brighteners are used in as solution together with certain sulfur compounds in concentrations of about 0.1 to 80 gram per liter.
- These brighteners are water-soluble sulfur compounds in which the sulfur atom has an equivalence of +4 or +6 and are selected from the group consisting of aliphatic unsaturated sulfonic acids, mononuclear and binuclear aromatic sulfonic acids, heterocyclic sulfonic acids, mononuclear aromatic sulfinic acids, aromatic sulfonamides and sulfonimides (see Table II herein).
- the Water soluble alkali metal, ammonium, magnesium, and nickel salts of the above compounds are used in combination with the quaternary nitrogen cyclic compounds in accordance with this invention.
- the mixed brightener additives characterizing this invention that is the mixtures of compounds from Groups I and II were evaluated ina Hull cell using a standard Watts type bath containing 330 grams of nickel sulfate heXahydrate/liter, 45 grams of nickel chloride per liter, 37.5 grams per liter of boric acid, operated at a pH of 3.5, and a temperature of 50 C.
- the nickel deposits were made on brass Hull cell panels 2" by 3" by plating for five minutes at three amperes.
- the concentrations and combination of organic additives which gave brilliant mirror-like deposits of nickel over a wide current density range are listed in Table HI.
- the brighteners in accordance with this invention are useful in the conventional Watts type bath and also high chloride baths noted as follows.
- the plating conditions employed with baths of these formulations are those commonly used and reacted in plating products.
- the working temperature of the bath will range between 40 and 70 C.
- the pH value will be held between about 355 and 5.0. Close control of pH in some shops calls for holding it at about 4.0 but in a range between 3.8 and 4.5.
- the current density will of course vary in the shape of the piece and its size and the load at which it is desired to produce in the shop, but generally it will between 1 and amps. per sq. dcm.
- Current densities commonly employed with Watts type baths will generally be about 4 to 7 amps, per sq. dcm., and current densities for the high quality type baths will generally be between'S and 10 amps, per sq. dcm.
- the concentration at which the brighteners are best used are practically alike in terms of weight per unit volume.
- any of the brighteners in Table I may be used in combination with any of the brighteners in Table II.
- a Watts type bath employing about 300 grams/liter of nickel sulfate, 60 grams/liter of nickel chloride and 45 grams/liter of boricacid, e.g., a variant of this bath is the high chloride type using 45 grams/liter of nickel sulfate, 250 grams/liter 'of nickel chloride, and about 45 grams/liter of boric acid.
- the advantages obtained through utilization of the combination of heterocyclic nitrogen brighteners of Group I and Group II in accordance with this invention is in the improved ductility and brightness of the electrodeposited nickel, the improved throwing power of the bath, and the larger range of pH and temperature in which the bath maybe operated without affecting the quality of the nickel deposit.
- good electroplating practice should be followed in making the electrodeposits economically starting with clean surfaces, deposit of iron, copper, brass or other base metals conventionally used in industrial fabrication and plating at rates consistent for obtaining good adherent electrodeposits.
- the nickel electrodeposits obtained from baths utilizing the novel brightener combination of compounds from Groups I and II are advantageous in that mirror-bright, lustrous, and unusually ductile electrodeposits are obtained over a wide range of current densities.
- the bright nickel electrodeposits are preferably plated on a copper, brass, or other copper alloy. However, they may be electrodeposited directly on such metals as iron, steel, etc., although usual practice calls for plating copper before metal.
- An aqueous electrolytic bath for the electrodeposition of mirror bright ductile nickel which comprises a solution containing soluble nickel salts and at least one organic sulfur compound selected from the group consisting of unsaturated aliphatic sulfonic acids, aromatic sulfonic acids, aromatic sulfonamide and sulfonimides, and a brightener consisting essentially of a component selected from (a) and (b), wherein (a) is selected from the group consisting of:
- Ron and 11' R/ ⁇ OP (OR)1 R iii -orm and R R )n N/ (H) and (b) is selected from the group consisting of L R and wherein R is selected from the group consisting of methyl, ethyl,
- R is selected from the group consisting of methyl, ethyl,
- composition which is a mixture of N-allyl 2-vinyl pyridinium bromide and N-allyl quinaldinium diallyl phosphate.
- composition which is a mixture of N-allyl 2-vinyl pyridinium chloride and N-allyl quinaldinium diallyl phosphate.
- composition which is a mixture of N-allyl 4-vinyl pyridinium bromide and N-allyl quinaldinium diallyl phosphate. 5.
- the composition which is a mixture of N-allyl 4-viny1 pyridinium chloride and N-allyl quinaldinium diallyl phosphate. 6.
- the composition which is a mixture of N-allyl 2-vinyl pyridinium bromide and N-allyl quinaldinium diallyl phosphate. 7.
- the process for electroplating nickel comprising electrodepositing nickel from an aqueous nickel electroplating bath containing between 1 gram per liter and 20 grams per liter of a sulfur compound brightener, and between 0.001 gram per liter and 0.30 gram per liter of a brightener composition as defined in claim 1.
- the brightener composition is present in a concentration of between 0.001 gram per liter and 0.30 gram per liter and consists essentially of a mixture of N-allyl 2-vinyl pyridinium bromide ratio of about 2:1.
- the brightener composition is present in a concentration of between 0.001 gram per liter and 0.30 gram per liter and consists essentially of a mixture of N-allyl 4-vinyl pyridinium bromide and N-allyl quinaldinium diallyl phosphate in a molar ratio of about 2:1.
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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)
Description
United States Patent '0 3,170,855 BRIGHT NICKEL PLATING BATHS Harry Kroll, Kent County, R.I., assignor to Sarki Research and Development Corporation, a corporation of Rhode Island No Drawing. Filed Mar. 18, 1963, Ser. No. 266,068
10 Claims. (Cl. 204-49) This invention relates to compositions of matter and to nickel electroplating baths and processes for the production of bright, adherent, and especially ductile nickel plates.
It is an object of this invention to provide a process for producing improved nickel plates, i.e., plates having improved ductility. Another object of this invention is to provide superior baths for electrodepositing smooth, bright, and ductile nickel. The invention also contemplates providing additive compositions useful for processes for electrodepositing smooth, bright, and ductile nickel.
I have discovered that when compounds corresponding to the formulas in Group I and mixedwithcompounds corresponding to the formula of Group II in about equimolar proportions but generally within a ratio of about one mol to not more than about 2 moles of the other, that is molar percentages preferably at the level of 50% of each but variable'to 33%% of one to 33 /a% of the other, a substantial improvement in the performance of the primary brightener effected is achieved observable largely through the greatly improved ductility of the new plate. That is with essentially conventional bath formulations using either the Watts type or the high chloride type bath with essentially the conventional sulfur compounds present as auxiliary brighteners, this mixture of special selected quaternized heterocyclic nitrogen compounds is unusually effective in achieving the. final effect.
GROUP I COMPOUNDS Compounds coming within Group I have formulas given by the following:
I ll R i(0R) OP(0R),
Pyridiniurn compounds quinolinium compounds R N O Isoqulnolinlum compounds In the above representations, R is an aliphatic group saturated or unsaturated, having from one to four carbon atoms, for example, methyl, ethyl, propyl, butyl, ally-l and methallyl, R may be hydrogen, i.e., no substituent on the ring, or an aliphatic group of one or two carbon atoms, such as methyl,. ethyl, or vinyl, and may be substituted in any position of the pyridine, quinoline, or isoquinoline ring or rings. Of outstanding utility are the N-allyl quinaldinium diallyl phosphate, N-allyl 2vinylpyridinium diallyl phosphate, N-ethyl isoquinolinium diethyl phosphate, N-butyl 4-vinyl pyridinium dibutyl phosphate, and mixtures of the pyridinium and quinolinium and quinaldinium N-alkyl dialkyl phosphates. It should be noted that Z-methylquinoline is quinaldine and the 3,170,855 Patented Feb. 23, 1965 nomenclature herein reflects this in use of quinaldinium to identify the Z-methyl quinoline moiety.
GROUP II COMPOUNDS Compounds coming within Group II have a formula given by the following:
R Br,Cl Pyridlnium compounds In the above representation, R is an allyl or methallyl group, R" is vinyl, and may be substituted in the 2 or 4 position of the pyridine. Of outstanding utility are the N-allyl-2-vinyl pyridinium bromide, N-allyl-4-vinyl pyridinurn bromide, and mixtures thereof; the corresponding chlorides are also useful; and, also, the corresponding N-methallyl-Z-vinyl pyridinium bromide and chloride as well as the N-methallyl-4-vinyl pyridinium bromide and chloride are useful.
It should be noted that in developing the preferred ratio of compound or compounds from Group I with Group II, if a mixture from one group is used the total mole percentage of compounds from that group is, preferably 50%, but within the one-third latitude defined.
In my copending applications 266,032, and 266,063, which may be considered fully incorporated herein, I have described in detail the method of synthesis of these compounds. The reaction is a direct quaternization involving stoichiometric amounts of reactant, and the technique involves precautions to avoid explosive reaction rates induced by. the exothermic character of the reaction.
These. combinations of compounds from Groups I and II are unusually potent primary brighteners in nickel plating baths. Preferably they are used in total amounts between about 0.001 and 0.30 gram per liter.
Brighteners used in nickel plating are commonly classified broadly as primary brighteners which increase the brightness of the ordinary dull or matte deposit of nickel but do not bring out the true mirror-bright condition. The secondary brighteners improve the ductility of the plate. The secondary brighteners with which this invention is primarily concerned are used in combination with these primary brighteners to develop true mirror-bright deposits. The combinations of heterocyclic nitrogen compounds as described in this present invention are potent and extraordinarily elfective secondary brighteners. The preferred concentrations are quite low, and inasmuch as these compounds are usually of quite limited solubility in water the concentration, even though low, can be readily maintained. .1 have found that the combination are unusually effective for developing ductile plates which can be shown qualitatively and semiqualitatively simply by plating a length of wire and comparing the number of times it can be flexed or bent without losing or having the plating peel. Where the ordinary brighteners are used detachment of the plate occurs quickly, whereas with my combination of brighteners the wire can be bent to the point where it could break without having the plate become detached. This test can be used on a qualitative basis for control purposes in a plating shop and by controlling conditions under which conducted it could also be used as a quantitative control and measure of efficiency of the solution.
These heterocyclic nitrogen brighteners are used in as solution together with certain sulfur compounds in concentrations of about 0.1 to 80 gram per liter. These brighteners are water-soluble sulfur compounds in which the sulfur atom has an equivalence of +4 or +6 and are selected from the group consisting of aliphatic unsaturated sulfonic acids, mononuclear and binuclear aromatic sulfonic acids, heterocyclic sulfonic acids, mononuclear aromatic sulfinic acids, aromatic sulfonamides and sulfonimides (see Table II herein). The Water soluble alkali metal, ammonium, magnesium, and nickel salts of the above compounds are used in combination with the quaternary nitrogen cyclic compounds in accordance with this invention.
The mixed brightener additives characterizing this invention, that is the mixtures of compounds from Groups I and II were evaluated ina Hull cell using a standard Watts type bath containing 330 grams of nickel sulfate heXahydrate/liter, 45 grams of nickel chloride per liter, 37.5 grams per liter of boric acid, operated at a pH of 3.5, and a temperature of 50 C. The nickel deposits were made on brass Hull cell panels 2" by 3" by plating for five minutes at three amperes. The concentrations and combination of organic additives which gave brilliant mirror-like deposits of nickel over a wide current density range are listed in Table HI.
The brighteners in accordance with this invention are useful in the conventional Watts type bath and also high chloride baths noted as follows.
WATTS-TYPE BATHS Nickel sulfate 200' to 400 g. l.
Nickel chloride 30 to 75 g./l.
Boric acid 30 to 50 g./l. Temperature 3-0 to 65 C.
pH 2.5 to 4.5 electrometric.
With agitation.
The plating conditions employed with baths of these formulations are those commonly used and reacted in plating products. Generally the working temperature of the bath will range between 40 and 70 C. The pH value will be held between about 355 and 5.0. Close control of pH in some shops calls for holding it at about 4.0 but in a range between 3.8 and 4.5. The current density will of course vary in the shape of the piece and its size and the load at which it is desired to produce in the shop, but generally it will between 1 and amps. per sq. dcm. Current densities commonly employed with Watts type baths will generally be about 4 to 7 amps, per sq. dcm., and current densities for the high quality type baths will generally be between'S and 10 amps, per sq. dcm.
Table I Propor- Concentions, tration Composition Parts Range, by Wt. grams/ liter 1 N -allyl quinaldinium diallyl phosphate... l-l N-allyl 2-vinyl pyridinium bromide 2-3 N-2-methallyl 4-vinyl pyridinium chloride. 2-3 2. N -allyl 2-vinyl pyridinium diallyl phosphate 1-1 3 {N-allyl 4-vinyl pyridinium chloride 2-3 N-ethyl isoquinolinium diethyl phosphate. 1-1 N-methallyl 2-vinyl pyridinium bromide. 2-3 0) 4. N-allyl 2-vinyl pyridinium diallyl phosphate 1-1 5 N-allyl 4-vinyl pyridinium bromide 2-3 r N-butyl isoquinolinium dibutylphosphate. 1-1 N -a-llyl 2-vinyl' pyridinium chloride 2-3 6- N-allyl 2-vinyl pyridinium diallyl phosphate 1-1 N -methallyl 4-vinyl pyridinium bromidefl 2-3 7. N-allyl 4-vinyl pyridinium diallyl phosphate 1-1 8 {N-allyl 2-vinyl pyridinium chloride 2-3 N-butyl quinolinium dibutyl phosphate.-. 1-1
1 In all examples it is kept in therange 0.001030 gram/liter.
Table II ORGANIC SULFUR ADDITIVES Concentration range,
Compound: grams/ liter Benzene sulfonamide 0.1-3 P-toluenesulfonamide 0.1-2 O-benzoylsulfonimide 0.1-1.5 O-carboxybenzenesulfonamide 0.1-2.0 Benzene sulfohydroxamic acid 0.1-2.0 N-benzenesulfonyl iminodiacetic acid 0.1-2.0 N-benzenesulfonyl iminodipropionic acid 0.1-2.0 Allyl sulfonic acid 1-10 Vinyl sulfonic acid 1-10 Sodium benzenesulfonate l-l0.0 Sodium metabenzenedisulfonate 1-10.0 1,5 naphthalene disulfonic acid 1-8 2,7 naphthalene disulfonic acid 1-8 Naphthalene trisulfonic acid 1-8 Table III Bath No.:
(1) N-allyl quinaldinium diallyl phosphate N-allyl 2-vinyl pyridinium bromide o-Benzoylsulfonimide Para toluenesulfonamide (2) N-methallyl 4-vinyl pyridinium chloride N-allyl 2-vinyl pyridinium diallyl phosphate o-Benzoyl sulfonimide (3) N-allyl 4-vinyl pyridinium chloride N-ethyl isoquinolinium diethyl phosphate Benzenesulfonamide o-Benzoylsulfonimide (4) N-methallyl 2-vinyl pyridinium bromide N-allyl 2-vinyl pyridinium diallyl phosphate Benzenesulfonamide o-Benzoylsulfonimide (5) N-allyl 4-vinyl pyridinium bromide N-butyl isoquinolinium dibutyl phosphate o-Benzoylsulfonimide Para toluenesulfonamide (6') N-allyl 2-vinyl pyridinium chloride N-allyl 2-vinyl pyridinium diallyl phosphate Para toluenesulfonamide o-Benzoyl sulfonimide (7) N-methallyl 4-vinyl pyridinium bromide N-allyl 4-vinyl pyridinium diallyl phosphate o-Benzoylsulfonirnide (8) N-allyl 2-vinyl pyridinium chloride N-butyl quinolinium dibutyl phosphate Allyl sulfonic acid In the foregoing tables for convenient reference I have tabulated the primary brighteners, secondary brighteners, and in Table III some representation of this. In general the concentration at which the brighteners are best used are practically alike in terms of weight per unit volume. Actually any of the brighteners in Table I may be used in combination with any of the brighteners in Table II. In a Watts type bath employing about 300 grams/liter of nickel sulfate, 60 grams/liter of nickel chloride and 45 grams/liter of boricacid, e.g., a variant of this bath is the high chloride type using 45 grams/liter of nickel sulfate, 250 grams/liter 'of nickel chloride, and about 45 grams/liter of boric acid. In all of these baths which I have tested virtually exhaustively in various combinations of the brighteners of Table I which brighteners of Table II, brilliant mirror-bright nickel deposits were obtained. Here the advantages obtained through utilization of the combination of heterocyclic nitrogen brighteners of Group I and Group II in accordance with this invention is in the improved ductility and brightness of the electrodeposited nickel, the improved throwing power of the bath, and the larger range of pH and temperature in which the bath maybe operated without affecting the quality of the nickel deposit. In general good electroplating practice should be followed in making the electrodeposits economically starting with clean surfaces, deposit of iron, copper, brass or other base metals conventionally used in industrial fabrication and plating at rates consistent for obtaining good adherent electrodeposits.
The foregoing tables and examples illustrate specific baths and processes, the several preferred baths being those listed in Table III, in Watts type solutions.
The nickel electrodeposits obtained from baths utilizing the novel brightener combination of compounds from Groups I and II are advantageous in that mirror-bright, lustrous, and unusually ductile electrodeposits are obtained over a wide range of current densities. The bright nickel electrodeposits are preferably plated on a copper, brass, or other copper alloy. However, they may be electrodeposited directly on such metals as iron, steel, etc., although usual practice calls for plating copper before metal.
As many embodiments of this invention may be made without departing from the spirit and scope thereof, it is to be understood that the invention may be varied without departing from the scope of the appended claims.
What is claimed is: I
1. An aqueous electrolytic bath for the electrodeposition of mirror bright ductile nickel which comprises a solution containing soluble nickel salts and at least one organic sulfur compound selected from the group consisting of unsaturated aliphatic sulfonic acids, aromatic sulfonic acids, aromatic sulfonamide and sulfonimides, and a brightener consisting essentially of a component selected from (a) and (b), wherein (a) is selected from the group consisting of:
Ron and 11' R/ \OP (OR)1 R iii -orm and R R )n N/ (H) and (b) is selected from the group consisting of L R and wherein R is selected from the group consisting of methyl, ethyl,
propyl, butyl, allyl and methallyl;
R is selected from the group consisting of methyl, ethyl,
vinyl; n is 0 orl; R" is a vinyl group in the 2 or 4 position; X is a halogen. 2. As a brightener in an' aqueous electrolytic bath for depositing nickel salts in accordance with claim 1, the
1 composition which is a mixture of N-allyl 2-vinyl pyridinium bromide and N-allyl quinaldinium diallyl phosphate. 3. As a brightener in an aqueous electrolytic bath for depositing nickel salts in accordance with claim 1, the composition which is a mixture of N-allyl 2-vinyl pyridinium chloride and N-allyl quinaldinium diallyl phosphate. 4. As a brightener in an aqueous electrolytic bath for depositing nickel salts in accordance with claim 1, the composition which is a mixture of N-allyl 4-vinyl pyridinium bromide and N-allyl quinaldinium diallyl phosphate. 5. As a brightener in an aqueous electrolytic bath for depositiing nickel salts in accordance with claim 1, the composition which is a mixture of N-allyl 4-viny1 pyridinium chloride and N-allyl quinaldinium diallyl phosphate. 6. As a brightener in an aqueous electrolytic bath for depositing nickel salts in accordance with claim 1, the composition which is a mixture of N-allyl 2-vinyl pyridinium bromide and N-allyl quinaldinium diallyl phosphate. 7. The process for electroplating nickel comprising electrodepositing nickel from an aqueous nickel electroplating bath containing between 1 gram per liter and 20 grams per liter of a sulfur compound brightener, and between 0.001 gram per liter and 0.30 gram per liter of a brightener composition as defined in claim 1.
8. The process of claim 7 wherein the brightener composition is present in a concentration of between 0.001 gram per liter and 0.30 gram per liter and consists essentially of a mixture of N-allyl 2-vinyl pyridinium bromide ratio of about 2:1.
10. The process of claim 7 wherein the brightener composition is present in a concentration of between 0.001 gram per liter and 0.30 gram per liter and consists essentially of a mixture of N-allyl 4-vinyl pyridinium bromide and N-allyl quinaldinium diallyl phosphate in a molar ratio of about 2:1.
References Cited in the file of this patent UNITED STATES PATENTS 2,893,932 Haas et al July 7, 1959 2,986,500 Passal May 30, 1961 3,054,733 Heiling Sept. 18, 1962 3,084,111
Strauss et al Apr. 2, 1963
Claims (1)
1. AN AQUEOUS ELECTROLYTIC BATH FOR THE ELECTRODEPOSITION OF MIRROR BRIGHT DUCTILE NICKEL WHICH COMPRISES A SOLUTION CONTAINING SOLUBLE NICKEL SALTS AND AT LEAST ONE ORGANIC SULFUR COMPOUND SELECTED FROM THE GROUP CONSISTING OF UNSATURATED ALIPHATIC SULFONIC ACIDS, AROMATIC SULFONIC ACIDS, AROMATIC SULFONAMIDE AND SULFONIMIDES, AND A BRIGHTENER CONSISTING ESSENTIALLY OF A COMPONENT SELECTED FROM (A) AND (B), WHEREIN (A) IS SELECTED FROM THE GROUP CONSISTING OF:
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US266068A US3170855A (en) | 1963-03-18 | 1963-03-18 | Bright nickel plating baths |
GB9830/64A GB1042298A (en) | 1963-03-18 | 1964-03-09 | Improvements in or relating to the electrodeposition of nickel |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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US266068A US3170855A (en) | 1963-03-18 | 1963-03-18 | Bright nickel plating baths |
Publications (1)
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US3170855A true US3170855A (en) | 1965-02-23 |
Family
ID=23013030
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US266068A Expired - Lifetime US3170855A (en) | 1963-03-18 | 1963-03-18 | Bright nickel plating baths |
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Country | Link |
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US (1) | US3170855A (en) |
GB (1) | GB1042298A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3296103A (en) * | 1964-02-24 | 1967-01-03 | M & T Chemicals Inc | Bright nickel electroplating |
US3337556A (en) * | 1963-03-18 | 1967-08-22 | Sarki Res And Dev Corp | Allyl quinaldinium pyridinium phosphates |
US3471271A (en) * | 1965-08-16 | 1969-10-07 | Udylite Corp | Electrodeposition of a micro-cracked corrosion resistant nickel-chromium plate |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2893932A (en) * | 1953-08-13 | 1959-07-07 | Dehydag Gmbh | Production of metal electrodeposits |
US2986500A (en) * | 1959-04-21 | 1961-05-30 | Metal & Thermit Corp | Electrodeposition of bright nickel |
US3054733A (en) * | 1957-06-05 | 1962-09-18 | Langbein Pfanhauser Werke Ag | Composition for the electrolytic deposition of well levelled and ductile nickel coatings of mirror-like luster |
US3084111A (en) * | 1958-04-24 | 1963-04-02 | Dehydag Gmbh | Wetting agents for electroplating baths |
-
1963
- 1963-03-18 US US266068A patent/US3170855A/en not_active Expired - Lifetime
-
1964
- 1964-03-09 GB GB9830/64A patent/GB1042298A/en not_active Expired
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2893932A (en) * | 1953-08-13 | 1959-07-07 | Dehydag Gmbh | Production of metal electrodeposits |
US3054733A (en) * | 1957-06-05 | 1962-09-18 | Langbein Pfanhauser Werke Ag | Composition for the electrolytic deposition of well levelled and ductile nickel coatings of mirror-like luster |
US3084111A (en) * | 1958-04-24 | 1963-04-02 | Dehydag Gmbh | Wetting agents for electroplating baths |
US2986500A (en) * | 1959-04-21 | 1961-05-30 | Metal & Thermit Corp | Electrodeposition of bright nickel |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3337556A (en) * | 1963-03-18 | 1967-08-22 | Sarki Res And Dev Corp | Allyl quinaldinium pyridinium phosphates |
US3296103A (en) * | 1964-02-24 | 1967-01-03 | M & T Chemicals Inc | Bright nickel electroplating |
US3471271A (en) * | 1965-08-16 | 1969-10-07 | Udylite Corp | Electrodeposition of a micro-cracked corrosion resistant nickel-chromium plate |
Also Published As
Publication number | Publication date |
---|---|
GB1042298A (en) | 1966-09-14 |
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