US2293810A - Electroplating stainless steel - Google Patents

Electroplating stainless steel Download PDF

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Publication number
US2293810A
US2293810A US215266A US21526638A US2293810A US 2293810 A US2293810 A US 2293810A US 215266 A US215266 A US 215266A US 21526638 A US21526638 A US 21526638A US 2293810 A US2293810 A US 2293810A
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United States
Prior art keywords
bath
wire
stainless steel
copper
plating
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Expired - Lifetime
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US215266A
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Domm Elgin Carleton
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National Standard Co
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National Standard Co
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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/34Pretreatment of metallic surfaces to be electroplated
    • C25D5/36Pretreatment of metallic surfaces to be electroplated of iron or steel
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00Stock material or miscellaneous articles
    • Y10S428/922Static electricity metal bleed-off metallic stock
    • Y10S428/9335Product by special process
    • Y10S428/934Electrical process
    • Y10S428/935Electroplating
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/12All metal or with adjacent metals
    • Y10T428/12493Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771Transition metal-base component
    • Y10T428/12861Group VIII or IB metal-base component
    • Y10T428/12951Fe-base component
    • Y10T428/12972Containing 0.01-1.7% carbon [i.e., steel]
    • Y10T428/12979Containing more than 10% nonferrous elements [e.g., high alloy, stainless]

Definitions

  • This invention relates to a process-for producing adherent electro-coatings yupon stainless steel.
  • This process has'heretofore proved extremely dimcult, and no method known by which an adherent coating can be obtainedupon a. stainless steel surface. ⁇ This is particularly true of coatings upon objects such as wires. l
  • This invention is primarily applicable to the "Y drawing of stainless steel wires of the 18-8 type or other high tensile strength materials particularly those including substantial percentages of chromium. Wires of this type are extremely diilicult to draw and the drawingfis considerably easier if a uniformly distributedV lubricant can be provided on the wire.
  • the wire is continuously cleaned and coated with an adherent lubricating metal such as copper and is then drawn with the copper on'lt, after which the copper coating is removed.
  • an adherent lubricating metal such as copper
  • Figure 1 and Figure 2 representk consecutive operations, the wire passing from the right hand portion of Figure 1 to the left hand portion of Figure 2.
  • the apparatus comprises a reel l from which a wire 2 passes first through a sulphuric acid bath 3, then through a hydrochloric acid cleaning bath 4; then through a sulphuric acid deoxidizing bath 5 from which it is passed through cloths 6 soaked in sodiumcarbon'ate to through more cloths 8 soaked in sodium carbonate solution to a. copper plating bath 9.
  • the wire is then drawn through the dies l0 and Il after which it is decoppered in the decoppering bath I2.
  • the wire which has been annealed and is cov ered with scale is first cleaned to remove the scale, which may be accomplished by passing it continuously through a cleaning solution.
  • the preferred bath is approximately a 10% solution of sulfuric acid at room temperature and a'direct current is employed using the wire as the anode.
  • This bath removes oxygen from the wire by generating nascent hydrogen in contact therewith. After this treatment oxygen is excluded at all times from vthe wire until plating is complete.
  • the oxide-free wire is then passed into a plating bath.
  • this is preferably accomplished by enclosing the wire in a cloth wetted with sodium carbonate solution while passing from the deoxidizing bath to a neutralizing bath and similarly protecting it while passing from the neutralizing bath to the plating bath.
  • the preferred neutralizing solution is sodium carbonate with a concentration of about 8 ounces of crystals of commercial sodium carbonate per gallon of water.
  • the bath is preferably kept warm (about FJ.
  • the cloths are kept wetted with sodium carbonate solution of the same concentration as the bath.
  • the make-up water added to the cloths to replace that lost by evaporation should be warm, in order to insure relative freedom of thel .water from air. 'I'he process is sensitive enough that if ordinary cold water is added as make-up, the adherence of the resulting coating will be adversely affected.
  • a plating bath which, for copper, preferably comprises a copper-cyanide plating solution.
  • a preferable solution comprises 35 grams per liter of metallic copper, approximately 25'grams per liter of free-sodium-cyanide, approximately l0 grams per liter of sodium carbonate, 5 grams per liter of thiosulfate.
  • bat-h is kept warm, ⁇ but the sodium thiosulfate also assists in keeping the bath free from oxygen.
  • a satisfactory current density is 30 amperes to .043 inch in diameter. Larger amounts are satisfactory but increase expense.
  • wires After the wires have been coated with copper they may be passed directly to the drawing dies and may be reduced in thickness as desired.
  • the wires may be drawn practically as many passes as desired. For example, drawing from l to 5 passes is quite satisfactory.
  • the copper may be removed, if desired, from the wire in any de- ⁇ sirable manner.
  • the preferred manner is to ⁇ pass it through a copper cyanide bath of the type herein described for plating and simply reversing the current. be annealed and cleaned.

Description

Aug. 25, 1942. E. c. DoMM ELECTROPLATING STAINLESS STEEL Filed June 22, 1938 Patented Aug. 25, 1942 ELEcTaoPLa'rING STAINLESS s'rEnL Elgin Carletonv Domm, Niles, Mich., assignorto National-Standard Company, a corporation of Michigan 3 Claims.
This invention relates to a process-for producing adherent electro-coatings yupon stainless steel. This process has'heretofore proved extremely dimcult, and no method known by which an adherent coating can be obtainedupon a. stainless steel surface.` This is particularly true of coatings upon objects such as wires. l
By means of the present inyention it is possible to plate stainless steel, particularly of v the austenitic or 18-8 type, with a metal, for example copper, in a uniform adherent coating Iof any desired thickness.
This invention is primarily applicable to the "Y drawing of stainless steel wires of the 18-8 type or other high tensile strength materials particularly those including substantial percentages of chromium. Wires of this type are extremely diilicult to draw and the drawingfis considerably easier if a uniformly distributedV lubricant can be provided on the wire.
In accordance with this invention, the wire is continuously cleaned and coated with an adherent lubricating metal such as copper and is then drawn with the copper on'lt, after which the copper coating is removed. The drawing diagrammatically illustrates the sequence of steps.
and is appropriately legended.
Figure 1 and Figure 2 representk consecutive operations, the wire passing from the right hand portion of Figure 1 to the left hand portion of Figure 2. The apparatus comprises a reel l from which a wire 2 passes first through a sulphuric acid bath 3, then through a hydrochloric acid cleaning bath 4; then through a sulphuric acid deoxidizing bath 5 from which it is passed through cloths 6 soaked in sodiumcarbon'ate to through more cloths 8 soaked in sodium carbonate solution to a. copper plating bath 9. The wire is then drawn through the dies l0 and Il after which it is decoppered in the decoppering bath I2.
An example of the invention will be given in connection with stainless steel wire containing approximately 18% chromium and 8% nickel and having a tensile strength of approximately 200,000 lbs. per square inch. However, other stainless steel types, including stainless steel without nickel, for example, that having approximately 17% chromium and no nickel, are satisfactory.
The wire which has been annealed and is cov ered with scale is first cleaned to remove the scale, which may be accomplished by passing it continuously through a cleaning solution. This `a sodium carbonate neutralizing bath 1; then 'Y is preferably an acidbathK in which the-wire is made the anode for an electrical circuit. The preferred bath is approximately a 10% solution of sulfuric acid at room temperature and a'direct current is employed using the wire as the anode.
While a wide range-of current density may be employed, Ihave found 75 amperes per square foot most suitable. A reaction time of about one minute is sufficient und'er these conditions.
The wire then enters a 10% solution of hydrochloric acid at room temperature, and remains therein for about 20 seconds. It is then Washed in cold running water, and again enters a 10% sulfuric acidv bath at room temperature. In thisr bath the wire is the cathode and=a current density of about 30 amperes per square foot is employed. Under these conditions a 30 second reaction time is satisfactory.
This bath removes oxygen from the wire by generating nascent hydrogen in contact therewith. After this treatment oxygen is excluded at all times from vthe wire until plating is complete.
The oxide-free wire is then passed into a plating bath. In practice this is preferably accomplished by enclosing the wire in a cloth wetted with sodium carbonate solution while passing from the deoxidizing bath to a neutralizing bath and similarly protecting it while passing from the neutralizing bath to the plating bath.
The preferred neutralizing solution is sodium carbonate with a concentration of about 8 ounces of crystals of commercial sodium carbonate per gallon of water. The bath is preferably kept warm (about FJ. The cloths are kept wetted with sodium carbonate solution of the same concentration as the bath. The make-up water added to the cloths to replace that lost by evaporation should be warm, in order to insure relative freedom of thel .water from air. 'I'he process is sensitive enough that if ordinary cold water is added as make-up, the adherence of the resulting coating will be adversely affected.
Other neutralizing solutions may be employed in the bath -or other liquids maybe employed on the cloths, the function being to keep the wires free from air.
From the neutralizing bath the wires pass through the cloths to a plating bath which, for copper, preferably comprises a copper-cyanide plating solution. A preferable solution comprises 35 grams per liter of metallic copper, approximately 25'grams per liter of free-sodium-cyanide, approximately l0 grams per liter of sodium carbonate, 5 grams per liter of thiosulfate. The
bat-h is kept warm, `but the sodium thiosulfate also assists in keeping the bath free from oxygen.
A satisfactory current density is 30 amperes to .043 inch in diameter. Larger amounts are satisfactory but increase expense.
After the wires have been coated with copper they may be passed directly to the drawing dies and may be reduced in thickness as desired. A
powdered sodium stearate lubricant is used in the dies, in addition to the copper. With a copper coating applied as herein described, the wires may be drawn practically as many passes as desired. For example, drawing from l to 5 passes is quite satisfactory.
After the drawing operation, the copper may be removed, if desired, from the wire in any de- `sirable manner. The preferred manner is to \pass it through a copper cyanide bath of the type herein described for plating and simply reversing the current. be annealed and cleaned. Y
The foregoing detailed description has been given for clear-ness of understanding only, and no unnecessary limitations should be understood therefrom, but the appended claims should be construed as` broadly as \,permissible in view of the prior art.
I claim:
l. In the continuous plating of stainless steel wire, the steps of passing a chromium-containing stainless steel Wire continuously through a bath of dilute sulfuric acid while maintaining the wirel as the anode of an electric current, clean- The wire may then again ing the wire and then passing it through a bath of dilute sulfuric acid while maintaining the'wire as the cathode of an electric circuit, maintaining the contact and electric current under conditions to generate nascent hydrogen until the Wire has become adaptable for plating during passage through the bath, and removing the stainless steel wire continuously from the bath to an alkaline cyanide copper `plating bath while preventing access of air thereto, by passing the wire continuously through. a fabric wetted with an aqueous solution of sodium carbonate during the entire distance from the acid bath to the plating bath.
2. In the continuous plating of stainless steel wire, the steps of passing a chromium-containing stainless steel wire continuously through a bath of dilute sulfuric acid while maintaining the wire as the anode of an electric circuit, cleaning the wire and then passing it through a bath of dilute sulfuric acid while maintaining the wire as the cathode of an electric circuit, maintaining the contact and electric current under conditions to generate nascent hydrogen until the wire has become adaptable for plating during passage through the bath, and removing the stainless steel wire continuously from the bath to an alkaline cyanide copper plating bath while preventing access of air thereto, by passing the wire continuously while wetted with an aqueous solution of an alkaline salt during the entire distance from the acid bath to the plating bath.
3. The method as set forth in claim 2, in which the wire is passed from the acid bath to the plating bath through fabrics wetted with the alkaline salt.
ELGIN CARLETON DOMM.
US215266A 1938-06-22 1938-06-22 Electroplating stainless steel Expired - Lifetime US2293810A (en)

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Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2445372A (en) * 1945-04-26 1948-07-20 American Steel & Wire Co Process of copper coating stainless steel
US2491126A (en) * 1944-08-02 1949-12-13 Emi Ltd Method of electroplating on chromium or chromium-iron alloys
US2517907A (en) * 1945-01-05 1950-08-08 Conmar Prod Corp Apparatus for electrotreating metal slide fasteners
US2528717A (en) * 1944-10-11 1950-11-07 Batcheller Clements Method of electroplating stainless steels and irons
US2546447A (en) * 1945-05-15 1951-03-27 American Steel & Wire Co Art of drawing fine steel wire
US2560534A (en) * 1946-07-12 1951-07-17 Nat Standard Co Method of operating a continuous electroplating system
US2603593A (en) * 1952-07-15 Electeodepositiqn of metaiis
US2742691A (en) * 1950-04-18 1956-04-24 Ohio Commw Eng Co Method of making corrosion resistant clad steel
US2762763A (en) * 1951-07-13 1956-09-11 Nat Standard Co Process and apparatus for simultaneously drawing and plating wire
US2776255A (en) * 1955-07-07 1957-01-01 Rockwell Spring & Axle Co Method of making formed, plated articles
US2856334A (en) * 1955-11-01 1958-10-14 Tiarco Corp Chromium plating
US2859161A (en) * 1957-06-13 1958-11-04 Cornell Dubilier Electric Contaminating ion removal
US2947080A (en) * 1953-01-29 1960-08-02 Leonard W Kates Method for making fuel elements
US2947676A (en) * 1952-01-29 1960-08-02 John L Zambrow Method of making wire fuel elements
US3055087A (en) * 1954-06-07 1962-09-25 Union Carbide Corp Carbonyl metal plated product
US3074857A (en) * 1957-11-23 1963-01-22 Aluminium Walzwerke Singen Method and apparatus for producing dielectric layer on the surface of an aluminum foil
FR2046934A1 (en) * 1969-06-20 1971-03-12 Bekaert Sa Nv
US3676322A (en) * 1970-01-06 1972-07-11 Furukawa Electric Co Ltd Apparatus and method for continuous production of electrolytically treated wires
FR2428687A1 (en) * 1978-06-14 1980-01-11 Ugine Aciers Electrolytic copper plating of stainless steel - using cathodic activation in sulphuric acid to improve copper adhesion
FR2648158A1 (en) * 1989-06-09 1990-12-14 Traitement Surface Mecanique Process for the electrolytic deposition of a homogeneous layer of nickel on an Ni-Cr steel
US5296127A (en) * 1986-04-25 1994-03-22 Saunders William T Composite-coated flat-rolled sheet metal manufacture
US5927131A (en) * 1996-03-26 1999-07-27 Shin-Etsu Handotai Co., Ltd. Method of manufacturing wire for use in a wire saw and wire for use in a wire saw
US6418994B1 (en) 1993-10-15 2002-07-16 Michelin Recherche Et Technique S.A. Tire having a stainless steel carcass reinforcement
US20070285954A1 (en) * 2002-10-31 2007-12-13 Minks Floyd M Regulator Control Circuit and Method

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2603593A (en) * 1952-07-15 Electeodepositiqn of metaiis
US2491126A (en) * 1944-08-02 1949-12-13 Emi Ltd Method of electroplating on chromium or chromium-iron alloys
US2528717A (en) * 1944-10-11 1950-11-07 Batcheller Clements Method of electroplating stainless steels and irons
US2517907A (en) * 1945-01-05 1950-08-08 Conmar Prod Corp Apparatus for electrotreating metal slide fasteners
US2445372A (en) * 1945-04-26 1948-07-20 American Steel & Wire Co Process of copper coating stainless steel
US2546447A (en) * 1945-05-15 1951-03-27 American Steel & Wire Co Art of drawing fine steel wire
US2560534A (en) * 1946-07-12 1951-07-17 Nat Standard Co Method of operating a continuous electroplating system
US2742691A (en) * 1950-04-18 1956-04-24 Ohio Commw Eng Co Method of making corrosion resistant clad steel
US2762763A (en) * 1951-07-13 1956-09-11 Nat Standard Co Process and apparatus for simultaneously drawing and plating wire
US2947676A (en) * 1952-01-29 1960-08-02 John L Zambrow Method of making wire fuel elements
US2947080A (en) * 1953-01-29 1960-08-02 Leonard W Kates Method for making fuel elements
US3055087A (en) * 1954-06-07 1962-09-25 Union Carbide Corp Carbonyl metal plated product
US2776255A (en) * 1955-07-07 1957-01-01 Rockwell Spring & Axle Co Method of making formed, plated articles
US2856334A (en) * 1955-11-01 1958-10-14 Tiarco Corp Chromium plating
US2859161A (en) * 1957-06-13 1958-11-04 Cornell Dubilier Electric Contaminating ion removal
US3074857A (en) * 1957-11-23 1963-01-22 Aluminium Walzwerke Singen Method and apparatus for producing dielectric layer on the surface of an aluminum foil
FR2046934A1 (en) * 1969-06-20 1971-03-12 Bekaert Sa Nv
US3676322A (en) * 1970-01-06 1972-07-11 Furukawa Electric Co Ltd Apparatus and method for continuous production of electrolytically treated wires
FR2428687A1 (en) * 1978-06-14 1980-01-11 Ugine Aciers Electrolytic copper plating of stainless steel - using cathodic activation in sulphuric acid to improve copper adhesion
US5296127A (en) * 1986-04-25 1994-03-22 Saunders William T Composite-coated flat-rolled sheet metal manufacture
FR2648158A1 (en) * 1989-06-09 1990-12-14 Traitement Surface Mecanique Process for the electrolytic deposition of a homogeneous layer of nickel on an Ni-Cr steel
US6418994B1 (en) 1993-10-15 2002-07-16 Michelin Recherche Et Technique S.A. Tire having a stainless steel carcass reinforcement
US5927131A (en) * 1996-03-26 1999-07-27 Shin-Etsu Handotai Co., Ltd. Method of manufacturing wire for use in a wire saw and wire for use in a wire saw
US20070285954A1 (en) * 2002-10-31 2007-12-13 Minks Floyd M Regulator Control Circuit and Method

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