US3355263A - Three-layer nickel laminate - Google Patents

Three-layer nickel laminate Download PDF

Info

Publication number
US3355263A
US3355263A US410062A US41006264A US3355263A US 3355263 A US3355263 A US 3355263A US 410062 A US410062 A US 410062A US 41006264 A US41006264 A US 41006264A US 3355263 A US3355263 A US 3355263A
Authority
US
United States
Prior art keywords
nickel
layer
selenium
sulfur
bath
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
Application number
US410062A
Other languages
English (en)
Inventor
Rose Arthur H Du
William J Pierce
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
HARSHAW/FILTROL PARTNERSHIP A PARTNERSHIP OF
Kewanee Oil Co
Original Assignee
Kewanee Oil Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Kewanee Oil Co filed Critical Kewanee Oil Co
Priority to US410062A priority Critical patent/US3355263A/en
Priority to GB43382/65A priority patent/GB1109857A/en
Priority to DE19651496827 priority patent/DE1496827B1/de
Application granted granted Critical
Publication of US3355263A publication Critical patent/US3355263A/en
Assigned to HARSHAW/FILTROL PARTNERSHIP, A PARTNERSHIP OF DE reassignment HARSHAW/FILTROL PARTNERSHIP, A PARTNERSHIP OF DE ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: HARSHAW CHEMICAL COMPANY, THE
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
    • C25D5/14—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium two or more layers being of nickel or chromium, e.g. duplex or triplex layers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/922—Static electricity metal bleed-off metallic stock
    • Y10S428/923—Physical dimension
    • Y10S428/924—Composite
    • Y10S428/926—Thickness of individual layer specified
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/922—Static electricity metal bleed-off metallic stock
    • Y10S428/9265—Special properties
    • Y10S428/927—Decorative informative
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/922—Static electricity metal bleed-off metallic stock
    • Y10S428/9265—Special properties
    • Y10S428/933—Sacrificial component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/922—Static electricity metal bleed-off metallic stock
    • Y10S428/9335—Product by special process
    • Y10S428/934—Electrical process
    • Y10S428/935—Electroplating
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/1266—O, S, or organic compound in metal component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12729—Group IIA metal-base component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12736—Al-base component
    • Y10T428/1275—Next to Group VIII or IB metal-base component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12778—Alternative base metals from diverse categories
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12806—Refractory [Group IVB, VB, or VIB] metal-base component
    • Y10T428/12826—Group VIB metal-base component
    • Y10T428/12847—Cr-base component
    • Y10T428/12854—Next to Co-, Fe-, or Ni-base component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12861—Group VIII or IB metal-base component
    • Y10T428/12931—Co-, Fe-, or Ni-base components, alternative to each other
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12861—Group VIII or IB metal-base component
    • Y10T428/12944—Ni-base component

Definitions

  • ABSTRACT OF THE DISCLOSURE This invention relates to a composite coating of adjacently bonded layers of nickel and more particularly to a composite coating of three layers wherein an intermediate layer thereof comirses a thin nickel deposit containing a
  • an intermediate layer thereof comirses a thin nickel deposit containing a
  • the composition and electrochemical properties of these layers of nickel are de- Signed to obtain as good protection of the base surface against corrosion as possible without compromising the decorative appearance.
  • the composition of the intermediate layer is adjusted so as to be anodic to both the upper and lower layers and preferably the composition of the upper layer is adjusted so as to be anodic to the lower layer.
  • Patented Nov. 28, 1967 vides differences in potential in electro-deposits of nickel but also affects other physical properties such as ductility and brightness and continuity of the deposit. For instance, if the proper potential is to be maintained between the intermediate layer and the top layer, the sulfur contents of each layer must be controlled. However, the sulfur content of sulfur-containing nickel is limited and the potential tends to level off at sulfur concentrations in the range of from about 0.2-0.3 percent by weight. Thus the degree in which the concentration of sulfur in the deposits may be varied in the nickel layer to adjust potential is very narrow. Moreover, if a plater prefers to deposit a lower layer of nickel from a sulfur-containing bath, he may have to increase the amounts of sulfur in the intermediate and upper nickel layers.
  • selenium-containing layers are strongly anodic to customary nickel deposits and can be used effectively as sacrificial layers in the three-layer group, nickel, nickel-selenium, nickel.
  • Such layers may be deposited from any common nickel plating bath, such as a standard Watts type bath having the proper concentration of a water-soluble selenium compound.
  • an improved composite coating comprising three adjacently bonded layers of nickel deposits, the lower layer being a conventional low-sulfur or sulfur-free nickel electroplate preferably 0.3 to 2 mils thick and having from 0 to about 25 percent, preferably from about .1 percent to about 25 percent cobalt by Weight alloyed therewith and a sulfur content preferably less than 0.01 percent; a top layer of a conventional bright nickel electroplate preferably 0.15 to 1 mil thick and having from 0 to 50 percent preferably about .1 to about 50 percent cobalt alloyed therewith and preferably from about 0.03 percent to about 0.3 percent sulfur by weight; and an percent cobalt alloyed therewith and containing from about 0.1 percent selenium to about 4 percent selenium based on the total weight of said intermediate deposit.
  • selenium may be used by Weight of said second electrodeposit. Sulfur in the necessary but can be present in for the lower layer.
  • alloy is used herein to include codeposit and the term alloyed is used toin-' elude codeposited.
  • selenium concentraquantity such as indicated tion in the intermediate layer is kept in the range of from about 0.10 percent to about 2.5 percent. It is not necessary to have a cobalt content in the nickel but it can be used and commercial nickel often contains it up to 0.5
  • FIG. 1 illustrates schematically a triple-layer system with a corrosion pit which has not yet penetrated the intermediate layer.
  • FIG. 2 illustrates the same triple-layer system with the corrosion pit where the pit has reached and has attacked the intermediate layer.
  • FIG. 3 illustrates the same triple-layer system with the corrosion pit widened laterally but where the lower layer has not been attacked substantially. These figures represent what is believed a typical modus operandi for corrosion pitting.
  • the composite electroplate of the present invention advantageously is employed over various substrates and particularly metal substrates susceptible to corrosion. Iron, steel, copper, brass, aluminum, zinc and magnesium with or without a copper deposit, are substrates protected by the composite electroplates of the present invention.
  • the selenium present in the intermediate layer of the instant triple-layer composites provides good corrosion protection to the substrate covered by the system.
  • the electroplate composites of the present invention are more effective than those using sulfur in the intermediate layer.
  • Corrodkote is the name given to an accelerated test in which a synthetic road soil slurry is applied to the plated surface of an article and the article is then exposed to a warm humid atmosphere.
  • a Corrodkote slurry formulation includes both soluble and insoluble elements and sufiicient liquid to give proper spreading consistency. The slurry is applied to the surface being tested by means of a paint brush, or similar device, to produce a fairly uniform coating, after which the coated specimen is eX- posed to specifiedhurnidity conditions.
  • a standard Corrodkote mixture, effective in testing chromium-nickel combinations over steel, is:
  • FIGS. l-3 of the drawing illustrate in sequence the progressive corrosion of a three-layer composite according to the invention.
  • a corrosion pit is for-med in the top nickel layer as shown in FIG. 1 (through a pore or other defeet in the chromium decorative coat), the pit progressively enlarges hemispherically. This corrosion site continually, enlarges until it reaches the more anodic intermediate layer.
  • the intermediate layer acts as the sacrificial anode primarily, while the top layer provides the bright surface for the decorative chromium; the composition of the intermediate layer need not be controlled as rigidly as the composition of the top layer in a duplex system.
  • the triple-layer system is most effective when the intermediate layer is anodic to the lower layer and the upper layer and wherein the lower layer is cathodic to the upper layer.
  • the intermediate layer acts as a primary sacrificial anode and the upper layer acts as a secondary sacrificial anode, protecting the lower layer.
  • the use of selenium as the alloying constituent with nickel in the preparation of the intermediate layer provides higher potentials. than those in deposits prepared by the use of sulfur as the alloying constituent with nickel.
  • the substrate is plated first with a lower layer of nickel and then with the intermediate layer of nickel and the upper layer of nickel. Any solution of nickel ions designed for electroplating nickel may be used.
  • the solutions should contain at least one of the following salts: nickel sulfate, nickel chloride, nickel fluoroborate and nickel sulfamate, wherein the solution is adjusted to an operating concentration of nickel.
  • the various baths useful in carrying out the present invention are (1) the various barrel plating baths generally comprising nickel sulfate and nickel chloride as the source of the nickel ion and buffer systems, for example, boric acid, (2) the all-chloride bath designed for use where a high current density is desired, comprising nickel chloride as the source of nickel ion and boric acid as the buffer, (3) the fiuoroborate bath comprising nickel fluoroborate as the source of nickel ion and free boric acid as the buffer alone or in combination with fluoroboric acid, (4) the common Watts-type bath designed for all purpose nickel plating and generally comprising nickel sulfate and nickel chloride as the source of nickel ion buttered with boric acid, (5) the all sulfamate bath comprising nickel sulfamate
  • the selenium-containing intermediate layer of nickel is deposited.
  • a selenium-supplying compound is added to one of the above named baths, the bath is adjusted to the appropriate concentration and a thin layer of selenium-containing nickel is deposited directly on the surface of the first or lower layer of nickel.
  • the composite is then completed by plating a third deposit of nickel directly on the surface of the intermediate plate. Normally this plate is fully bright to provide an optimum surface for the decorative chromium plate.
  • the decorative chromium layer advantageously is from about 0.005 mil to about 0.2 mil thick.
  • Each of the above layers of nickel may be deposited using more than one step such as, for example, by interrupting the plating cycle.
  • the composite coating of the present invention comprises a first or lower layer of ductile sulfur-free nickel.
  • This preferred plate is deposited from a typical Watts-type or fluoroborate-type bath containing an effective amount of a sulfur-free leveler such ascoumarin or the like.
  • the top layer of nickel preferably being fully bright is deposited from one of the above baths using a brightener of the first class (sulfooxygen carrier) and a brightener of the second class. Where the top layer is higher in sulfur content (0.1 to 0.3 percent) the lower layer also may be deposited from a bath containing in addition to a brightener of the first class (sulfo-oxy-gen compound) small amounts of a 7 brightener of the second class.
  • the baths disclosed in U.S. Patent 3,090,733 are useful for preparing the upper layers of nickel in the composite disclosed and claimed therein may be used to deposit the upper layers of nickel for the present invention.
  • the lower and top layers of nickel may be deposited from baths of conventional compositions and in the baths there may be present one or more brighteners of the first class.
  • These compounds generally comprise an aryl ring, a substituted aryl ring or an unsaturated aliphatic chain with a sulfur-containing radical in the form of sulfonic acids, sulfonates, sulfonamides, sulfimides, sulfinic acid and sulfones.
  • the aryl ring advantageously may be .derived from v.benzene, napthalene and the like, the substituted aryl ring may be derived from toluene, xylene, napthylamine, toluidine, benzyl naphthalene and the like and the alkylene chain may advantageously be derived from vinyl compounds or allyl compounds and the like.
  • Examples of sulfo-oxygen compounds of the above described type and which are useful particularly in the instant nickel plating baths are found in U.S. Patents 2,757,133 and 2,766,284.
  • the top layer of nickel is deposited from baths containing, in addition to brighteners of the first class, brighteners of the second class including organic compounds such as the various ketones, aldehydes,'carboxylic acids, some proteins (gelatin) and the like; compounds such as the alkylenic carboxylic esters, the alkylenic aldehyde, the aromatic compounds such as the aryl aldehydes, the sulfonated aryl aldehydes, allyl and vinyl substituted compounds, coumarin and its derivatives, and the like; .those compounds having acetylenic radicals (CEC including the acetylenic alcohols; nitrogen heterocyclics having' an N-substituted acetylenic radical and the like; those compounds such as the azine, thiazine and oxazine dyes, the triphenyl methane dyes, the quinidines, pyrimidines, pyrazoles and imi
  • organic compounds
  • Compounds considered useful as brighteners of the second class include the water-soluble aceytlenic compounds set forth in U.S. Patent (Kardos et el.) 2,712,522; the aryl, alkylene and arylalkynoxy sulfonic acids set forth in U.S. Patent 2,800,442; the alkynoxy sulfonic and carboxylic acids having the triple bond separated from the acid radical by at least one oxygen atom set forth in U.S. Patent 2,841,602; and the nitriles set forth in U.S. Patents 2,524,010; 2,647,866; 2,882,208; 2,978,391 and 3,093,557.
  • the instant bath may be adjusted by adding any of the cobalt salts well known to those skilled in the art.
  • the halides of cobalt are particularly useful including cobalt chloride, cobalt bromide, and the like.
  • Cobalt sulfate may be used also.
  • Nickel electroplating baths particularly useful in combination with these brightener systems include the Wattstype and'fluoroborate-typebaths having increased nickel content. Such baths are designed for use with organic brighteners in general; they may be operated at the higher current densities desirable for the effective use of the organic brighteners.
  • the preferred Watts-type bath essentially comprises an overall nickel content ranging from 70 to 115 grams per liter provided by 270 grams per liter to about 450 grams per liter of nickel sulfate and from about 20 grams per liter to about 90 grams per liter of nickel chloride with about 30 to 40 grams per liter of boric acid as the buffer and the preferred fluoroboratetype bath essentially comprises an over-all nickel content ranging from 75 to 110 grams per liter with about 30 grams perliter .of boric acid as the buffer.
  • boric acid is preferred as the buffer-as an additive to maintain the desired pH.
  • acetic acid, borax (sodium tetraborate), formic acid, the fluoroborates, and other compounds commonlyknown to have utility as buffers may be used with the baths of the present invention with no apparent undesirable effects.
  • wetting agents wlzu'ch may be employed in the baths for carrying out the present invention include a great number of the anionic surfactants.
  • the sulfate type particularly may be used. Included among this type are certain of the alkylsulfates, aralkylsulfates, alkylsulfonates, and aralkylsulfonates.
  • wetting agents in baths used in carrying out the present invention is desirable but optional; acceptable deposits areoften obtained from baths having no wetting agent therein.
  • selenium dioxide or other selenium-containing compound, which provides selenite ions (SeO in the electroplating bath, we may add 0.05 to 3 grams per liter of SeO (or its equivalent amount if another compound is used), and preferably 0.1 to 1 gram per liter of selenium dioxide (or its equivalent). With larger amounts of selenium dioxide, the deposits tend to become rough and spongy.
  • sodium selenate or other compounds giving selenate ions [SeO in solution) large amounts may be used up to 40 grams per liter or more, up to saturation. Large amounts are not required, however, and we prefer to use 0.2 to 5 grams per liter of sodium selenate.
  • any of the above described nickel plating baths may be used with the added selenium compound.
  • the optimum amount of the particular selenium-supplying compound necessary to impart an optimum amount of selenium in the nickel deposit varies with each compound; and, of course, the temperature of the bath and cathode current density vary the deposits.
  • many selenium-containing compounds which could be used to impart selenium into the nickel deposit are not very soluble in water and this limits the amounts which can be used.
  • the operating temperature of a typical bath is in the range of from about 130 F. to about 150 F. This range is not critical, however, and good deposits may be obtained at temperatures as low as 50 F. or as high as 180 F. or even at the boiling point of the electrolyte. Where the Watts-type bath is employed, current densities ranging from about 10 to 50 I amperes per square foot are preferred.
  • the pH should be in the range of from 1.5 to 5.5 and preferably in the range of from 4 to 5.
  • Selenium may be added to the bath used in carrying out the present invention in the form of selenic acid, selenous acid, sodium, potassium, cobalt and nickel selenates and selenites, or asv organic compounds containing selenium provided selenite or selenate ions are formed in solution.
  • a sulfooxygen compound or brightener of the first class is added to the selenium-containing bath in small amounts.
  • the selenium may be present in any form. which will provide selenate or selenite ions.
  • the sulfo-oxygen compound acts to provide a semibright deposit of enhanced lustre.
  • concentrations of the sulfo-oxygen carrier useful in forming the deposits are from about 0.5 gram per liter'to about 2 grams per liter of the sulfo-oxy-gen compound, but amounts outside this range are useful also. It has been found that relatively small amounts of sulfur are imparted into the deposit by these sulfo-oxygen compounds, an amount which is much less than is obtained in the deposit from a fully bright nickel bath containing a brightener of the second class.
  • Table A sets forth specific compositions of baths useful for depositing the lower layer in preparing the triple-layer composite electroplate of the present Table B. After rinsing again an approximately millionth of an inch layer of chromium was plated on the invention: upper surface of the top layer.
  • the amount of selenium TABLE A Boric Bath Nickel Salts, g./l. Addition Agent, g./l. Other Additives, g./l. Wetting Agents, g.ll. BAKETid pH u er, el
  • Table B sets forth specific compositions of baths useful for depositing an upper layer or top layer in preparing the triple-layer composite electroplate of the present invention:
  • the resulting deposit was bright and corrosion resistant.
  • Nickel Salts g./l.
  • Organic Sulfo-oxygen cpd g./l.
  • Brighteners g./1.
  • Wetting Agents g./l.
  • Bmtafid pH 11 er g./l.
  • NiClrnfiHiO 15. NiSO4.6HzO, 300', Benzenesulfonamide, 2 Same as 1b 37 3. 5
  • NiSO' .6H- O NiCl .6H O Boric acid H BO Na SeO Water to make 1000 ml.
  • the panel was rinsed againand a 0.4 mil top or upper layer of bright nickel was deposited from bath 4!; of
  • the sodium selenate in the bath is increased to 0.85 ,g./l.
  • the selenium-containing deposit contained about 1.5
  • Example III This example varies from Example I mainly in that the amount of sodium selenate in the bath is 1.70 grams per liter. The percentage of selenium in the deposit is about 2.4%. At 4.2 grams of sodium selenate per liter of solution the selenium-containing deposit was about 3.3% selenium. At 8.5 grams of sodium selenate per liter of solution, the selenium-containing deposit was about 3.4% selenium. Thicknesses of deposits remain substantially the same and the same high corrosion resistance is found.
  • Example IV Same as Example 1, except that 0.09 g./l. Se replaces Na SeO giving .18% Se in the deposit.
  • Example V Same except use 0.16 g./l. 8e0 gives 2.6% Se in the deposit.
  • Example VI Same except use .32 g./l. Se0 gives 0.7% Se in the deposit.
  • the present invention also includes composites or laminates of nickel having more than three layers of nickel and composites or laminates wherein the manganesenickel layer is sandwiched between layers of nickel which will have relative potentials equal substantially to each other and more cathodic than the intermediate layer.
  • a laminated coating comprising a first nickel layer on a metal base to be protected, a second nickel electrodeposit consisting essentially of 0.1-10 percent by weight of selenium and overlying said first nickel layer and a third nickel layer overlying said second nickel layer, said first nickel layer being firmly bonded to said base, said second nickel layer being firmly bonded to said first nickel layer and said third nickel layer being firmly bonded to said second nickel layer.
  • the invention defined in claim 1 wherein the said second electrodeposit is from 0.01 to 0.2 mil thick and the said second electrodeposit contains from 0.1 to 4% selenium by weight.
  • a laminate comprising three firmly bonded layers of nickel including an intermediate layer of a nickel-selenium alloy between and firmly adherent to a selenium-free lower layer and a selenium-free upper layer.
  • top layer of nickel is electroplated with a chromium deposit having a thickness ranging from about 0.005 to about 0.2 mil, said lower layer being bonded to a substrate of the class consisting of iron, steel, copper, zinc, aluminum, magnesium and alloys thereof.
  • top layer of nickel is electroplated with a chromium layer having a thickness from 0.01 to 0.2 mil.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
US410062A 1964-11-10 1964-11-10 Three-layer nickel laminate Expired - Lifetime US3355263A (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US410062A US3355263A (en) 1964-11-10 1964-11-10 Three-layer nickel laminate
GB43382/65A GB1109857A (en) 1964-11-10 1965-10-13 Composite coating of electro deposited nickel
DE19651496827 DE1496827B1 (de) 1964-11-10 1965-10-27 Verbunderzeugnis aus einem metallischen Grundkoerper und drei galvanisch abgeschiedenen Nickelschichten

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US410062A US3355263A (en) 1964-11-10 1964-11-10 Three-layer nickel laminate

Publications (1)

Publication Number Publication Date
US3355263A true US3355263A (en) 1967-11-28

Family

ID=23623050

Family Applications (1)

Application Number Title Priority Date Filing Date
US410062A Expired - Lifetime US3355263A (en) 1964-11-10 1964-11-10 Three-layer nickel laminate

Country Status (3)

Country Link
US (1) US3355263A (de)
DE (1) DE1496827B1 (de)
GB (1) GB1109857A (de)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3532587A (en) * 1966-08-04 1970-10-06 Esso Research & Chem Co Press plate
US20090283411A1 (en) * 2008-05-15 2009-11-19 Serdar Aksu Selenium electroplating chemistries and methods
US20130086971A1 (en) * 2010-01-08 2013-04-11 Toyo Kohan Cp., Ltd. Surface-Treated Metal Sheet and Process for Producing Formed Article from the Surface-Treated Metal Sheet

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3288574A (en) * 1964-04-10 1966-11-29 Harshaw Chem Corp Metal laminates and method of forming by electroplating

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3288574A (en) * 1964-04-10 1966-11-29 Harshaw Chem Corp Metal laminates and method of forming by electroplating

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3532587A (en) * 1966-08-04 1970-10-06 Esso Research & Chem Co Press plate
US20090283411A1 (en) * 2008-05-15 2009-11-19 Serdar Aksu Selenium electroplating chemistries and methods
US20130086971A1 (en) * 2010-01-08 2013-04-11 Toyo Kohan Cp., Ltd. Surface-Treated Metal Sheet and Process for Producing Formed Article from the Surface-Treated Metal Sheet
US9498933B2 (en) * 2010-01-08 2016-11-22 Toyo Kohan Co., Ltd. Surface-treated metal sheet and process for producing formed article from the surface-treated metal sheet
EP2522763A4 (de) * 2010-01-08 2017-03-08 Toyo Kohan Co., Ltd. Oberflächenbehandeltes metallblech und verfahren zur herstellung eines formartikels aus dem oberflächenbehandelten metallblech

Also Published As

Publication number Publication date
GB1109857A (en) 1968-04-18
DE1496827B1 (de) 1970-11-26

Similar Documents

Publication Publication Date Title
US3090733A (en) Composite nickel electroplate
US3354059A (en) Electrodeposition of nickel-iron magnetic alloy films
US3355267A (en) Corrosion resistant coated articles and processes of production thereof
US3866289A (en) Micro-porous chromium on nickel-cobalt duplex composite plates
US4765871A (en) Zinc-nickel electroplated article and method for producing the same
US3247082A (en) Electrodeposition of a corrosion resistant coating
US3812566A (en) Composite nickel iron electroplate and method of making said electroplate
US3471271A (en) Electrodeposition of a micro-cracked corrosion resistant nickel-chromium plate
US3697391A (en) Electroplating processes and compositions
US4411961A (en) Composite electroplated article and process
US3878067A (en) Electrolyte and method for electrodepositing of bright nickel-iron alloy deposits
US3691027A (en) Method of producing corrosion resistant chromium plated articles
US3868229A (en) Decorative electroplates for plastics
US3692641A (en) Electrodeposition of low stress ruthenium alloy
CA1083078A (en) Alloy plating
US3183067A (en) Metal having two coats of sulfurcontaining nickel and method of making same
US3615281A (en) Corrosion-resistant chromium-plated articles
US3528894A (en) Method of electrodepositing corrosion resistant coating
US3355268A (en) Corrosive protected composite having triplated nickel deposits and method of making
US3288574A (en) Metal laminates and method of forming by electroplating
US3355263A (en) Three-layer nickel laminate
US3703448A (en) Method of making composite nickel electroplate and electrolytes therefor
US7300563B2 (en) Use of N-alllyl substituted amines and their salts as brightening agents in nickel plating baths
US4435254A (en) Bright nickel electroplating
US3563864A (en) Chromium-nickel plating

Legal Events

Date Code Title Description
AS Assignment

Owner name: HARSHAW/FILTROL PARTNERSHIP, 300 LAKSIDE DRIVE, OA

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:HARSHAW CHEMICAL COMPANY, THE;REEL/FRAME:004190/0754

Effective date: 19831021