US3054737A - Process and bath for electrosmoothing ferrous metals - Google Patents

Process and bath for electrosmoothing ferrous metals Download PDF

Info

Publication number
US3054737A
US3054737A US830713A US83071359A US3054737A US 3054737 A US3054737 A US 3054737A US 830713 A US830713 A US 830713A US 83071359 A US83071359 A US 83071359A US 3054737 A US3054737 A US 3054737A
Authority
US
United States
Prior art keywords
bath
gms
electro
electrosmoothing
per litre
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
US830713A
Inventor
Salt Frederick William
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.)
British Iron and Steel Research Association BISRA
Original Assignee
British Iron and Steel Research Association BISRA
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 British Iron and Steel Research Association BISRA filed Critical British Iron and Steel Research Association BISRA
Application granted granted Critical
Publication of US3054737A publication Critical patent/US3054737A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • 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
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25FPROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F3/00Electrolytic etching or polishing
    • C25F3/16Polishing
    • C25F3/22Polishing of heavy metals
    • C25F3/24Polishing of heavy metals of iron or steel

Definitions

  • the porosity of an electro-deposited metal coating on a ferrous surface can be reduced by electro-smoothing the metal to be plated prior to carrying out the electroplating operation.
  • electro-smoothing the metal prior to electroplating any high points of the metal surface are removed; if these high points are not removed they tend to receive a disproportionate amount of deposit at the expense of the surrounding areas, which are then less protected against wear and corrosion.
  • a process of preparing a ferrous surface for electroplating with another metal which comprises electro-smoothing the surface to be plated in a bath containing acceptor ions with a low diffusion coefficient in order to obtain low limiting current densities for anodic dissolution.
  • the present invention provides a process for the production of tinplate in which the steel is electro-smoothed in a bath containing acceptor ions with a low diffusion coeflicient in order to obtain low limiting current densities for anodic dissolution and is thereafter electroplated with tin.
  • tinplate it has been found that the number of rust spots formed on exposure to a corrosive atmosphere for a given time was similar for a 4 oz./basis box electro deposit of tin on electro-smoothed mild steel and an 8 oz./basis box electrodeposit on unsmoothed mild steel.
  • the bath is preferably operated on the rising portion of the anode potential/current graph just below the horizontal portion corresponding to the limiting current density for anodic dissolution.
  • composition of such an electro-smoothing bath in which the citrate anion is employed as the acceptor ion is, for example, as follows:
  • the electro-smoothed steel sheets thus obtained were then subjected to a conventional electrolytic tinning operation together with a further sample of the same steel sheet which had not been electro-smoothed.
  • the electrodeposited tin coating on the electro-smoothed sheets was less porous than that on the unsmoothed sheet and the tinplate obtained from the electro-smoothed sheets was more corrosion-resistant than that obtained from the unsmoothed sheet.
  • a process of preparing low carbon steel for electroplating with another metal which comprises anodically electrosmoothing the surface to be plated in a bath consisting essentially of water and from 49 to 147 gms. sodium citrate (including 2 mols. water of crystallisation) per litre, from 2 to 50 gms. citric acid per litre, and from 5 to 20 gms. sodium chloride per litre, the relative proportions of sodium citrate and citric acid being such that the bath has a pH of from 4.0 to 6.0.
  • a process for the production of tinplate which comprises the steps of anodically electrosmoothing low carbon steel in a bath consisting essentially of water and from 49 to 147 gms. sodium citrate (including 2 mols. water of crystallisation) per litre, from 2 to 50 gms. citric acid per litre and from 5 to 20 gms. sodium chloride per litre, the relative proportions of sodium citrate and citric acid being such that the bath has a pH of from 4.0 to 6.0 and then electroplating the steel with tin.
  • a bath for electrosmoothing ferrous metals which consists essentially of water and from 49 to 147 gms. sodium citrate (including 2 mols. water of crystallisation) per litre, from 2 to 5 gms. citric acid per litre, and from 2 to 20 gms. sodium chloride per litre, the relative proportions of sodium citrate and citric acid being such that the bath has a pH of from 4.0 to 6.0.
  • a process of preparing a low carbon steel surface for electroplating With another metal comprises the steps of immersing the surface to be plated in a bath consisting essentially of an aqueous solution of an organic hydroxy carboxylic acid, a water-soluble salt of an organic hydroxy carboxylic acid and chloride ion, the concentration of said salt being from 0.5 to 1.5 N, the concentration of chloride ion being from 3 to 12 guns/litre, and the concentration of said acid being such that the bath has a pH of from 4.0 to 6.0, and then passing a current between said surface, as anode, and a cathode at an anode current density of from 50 to 150 amps/sq. ft., whereby electro-smoothing of said surface is efiected.
  • a process for producing tinpla-te which process comprises the steps of immersing low carbon steel sheet material in a bath consisting essentially of an aqueous solution of an organic hydroxy carboxylic acid and chloride ion, the concentration of said salt being from 0.5 to 1.5 N, the concentration of chloride ion being from 3 to 12 gms./litre, and the concentration of said acid being such that the bath has a pH of "from 4.0 to 6.0, then passing a current between said sheet material, as anode, and a cathode at an anode current density of from to amps/sq. ft., whereby electro-srnoothing of said sheet material is efiected, and thereafter electroplating the sheet material With tin.

Description

Unite States Wales, assignor to The British Iron and Steel Research Association No Drawing. Filed July 31, 1959, Ser. No. 830,713 Claims priority, application Great Britain Aug. 7, 1958 5 Claims. (Cl. 204-1405) This invention is concerned with improvements in or relating to the electroplating of a ferrous surface with another meta-l for protective or other purposes; the invention is particularly concerned with the production of tinplate.
We have found that the porosity of an electro-deposited metal coating on a ferrous surface, more particularly a mild steel surface, can be reduced by electro-smoothing the metal to be plated prior to carrying out the electroplating operation. By electro-smoothing the metal prior to electroplating, any high points of the metal surface are removed; if these high points are not removed they tend to receive a disproportionate amount of deposit at the expense of the surrounding areas, which are then less protected against wear and corrosion.
According to one aspect of the present invention, therefore, there is provided a process of preparing a ferrous surface for electroplating with another metal, which comprises electro-smoothing the surface to be plated in a bath containing acceptor ions with a low diffusion coefficient in order to obtain low limiting current densities for anodic dissolution.
More particularly the present invention provides a process for the production of tinplate in which the steel is electro-smoothed in a bath containing acceptor ions with a low diffusion coeflicient in order to obtain low limiting current densities for anodic dissolution and is thereafter electroplated with tin. In the production of tinplate, it has been found that the number of rust spots formed on exposure to a corrosive atmosphere for a given time was similar for a 4 oz./basis box electro deposit of tin on electro-smoothed mild steel and an 8 oz./basis box electrodeposit on unsmoothed mild steel.
It is particularly preferred to effect electro-smoothing of the ferrous metal to be plated with a new type of electrolytic smoothing bath in which low limiting current densities for anodic dissolution are obtained by using acceptor ions with a low diffusion coetficient, such as the anions of organic hydroxy carboxylic acids. In order to achieve the maximum rate of smoothing, the bath is preferably operated on the rising portion of the anode potential/current graph just below the horizontal portion corresponding to the limiting current density for anodic dissolution.
The composition of such an electro-smoothing bath in which the citrate anion is employed as the acceptor ion is, for example, as follows:
Gms./ litre Sodium citrate (+2 mols. H O) 49-147 Citric acid 2-50 Sodium chloride 5-20 3,054,737 v Patented Sept. 18, 1962 position with an anode current density of from 50 to 150 amps/sq. foot for from 0.2 to 15 seconds with the bath at a temperature of from 5 to 35 C.
It will be apparent from the rapidity of the electrosmoothing action obtained with baths of this type that they are eminently suitable for inclusion in a high speed continuous electrolytic tinning line for the production of tinplate. Where an electro-smoothing step according to the invention is included in such a high speed continuous electrolytic tinning line all that is required is that a suflicient length of the steel strip, which will be dependent on the rate of travel of the strip, should be immersed in the electro-srnoothing bath for each portion of the strip to have the required time of residence in the bath. The advantages of this type of bath for use in this way are (a) economy in plant and operating costs due to the use of a low current density, (b) high degree of smoothing for quantity of metal removed, and (0) low drag-out losses due to the low concentration and viscosity of the was connected as the anode in an aqueous electro-smoothing bath containing:
Gms./litre Sodium citrate (+2 mols. H O) 98 Citric acid 35 Sodium chloride 10 and having a pH of 4.6. The bath was maintained at a temperature of 22 C. and was operated with an anode current density of 100 amps/sq. ft. It Was found that for a treatment time of 0.9 second, a reduction in the surface area of the sheet, as measured by an electrode capacitance technique, of about 33% was obtained. With treatment times of 0.2 sec. and 1.5 sec., the surface area was reduced by 15%.
The electro-smoothed steel sheets thus obtained were then subjected to a conventional electrolytic tinning operation together with a further sample of the same steel sheet which had not been electro-smoothed. The electrodeposited tin coating on the electro-smoothed sheets was less porous than that on the unsmoothed sheet and the tinplate obtained from the electro-smoothed sheets was more corrosion-resistant than that obtained from the unsmoothed sheet.
I claim: 1
1. A process of preparing low carbon steel for electroplating with another metal, which comprises anodically electrosmoothing the surface to be plated in a bath consisting essentially of water and from 49 to 147 gms. sodium citrate (including 2 mols. water of crystallisation) per litre, from 2 to 50 gms. citric acid per litre, and from 5 to 20 gms. sodium chloride per litre, the relative proportions of sodium citrate and citric acid being such that the bath has a pH of from 4.0 to 6.0.
2. A process for the production of tinplate which comprises the steps of anodically electrosmoothing low carbon steel in a bath consisting essentially of water and from 49 to 147 gms. sodium citrate (including 2 mols. water of crystallisation) per litre, from 2 to 50 gms. citric acid per litre and from 5 to 20 gms. sodium chloride per litre, the relative proportions of sodium citrate and citric acid being such that the bath has a pH of from 4.0 to 6.0 and then electroplating the steel with tin.
3. A bath for electrosmoothing ferrous metals which consists essentially of water and from 49 to 147 gms. sodium citrate (including 2 mols. water of crystallisation) per litre, from 2 to 5 gms. citric acid per litre, and from 2 to 20 gms. sodium chloride per litre, the relative proportions of sodium citrate and citric acid being such that the bath has a pH of from 4.0 to 6.0.
4. A process of preparing a low carbon steel surface for electroplating With another metal, which process comprises the steps of immersing the surface to be plated in a bath consisting essentially of an aqueous solution of an organic hydroxy carboxylic acid, a water-soluble salt of an organic hydroxy carboxylic acid and chloride ion, the concentration of said salt being from 0.5 to 1.5 N, the concentration of chloride ion being from 3 to 12 guns/litre, and the concentration of said acid being such that the bath has a pH of from 4.0 to 6.0, and then passing a current between said surface, as anode, and a cathode at an anode current density of from 50 to 150 amps/sq. ft., whereby electro-smoothing of said surface is efiected.
5. A process for producing tinpla-te, which process comprises the steps of immersing low carbon steel sheet material in a bath consisting essentially of an aqueous solution of an organic hydroxy carboxylic acid and chloride ion, the concentration of said salt being from 0.5 to 1.5 N, the concentration of chloride ion being from 3 to 12 gms./litre, and the concentration of said acid being such that the bath has a pH of "from 4.0 to 6.0, then passing a current between said sheet material, as anode, and a cathode at an anode current density of from to amps/sq. ft., whereby electro-srnoothing of said sheet material is efiected, and thereafter electroplating the sheet material With tin.
References Cited in the file of this patent UNITED STATES PATENTS 1,314,840 Weeks Sept. 2, 1919 1,334,092 Harmeling Mar. 16, 1920 2,090,966 Sailer Aug. 24, 1937 2,331,721 Ostrofsky Oct. 12, 1943 2,437,474 Orozco Mar. 9, 1948 2,607,722 Kreml Aug. 19, 1952 2,799,636 MacLachlan July 16, 1957 20 2,873,233 Schnable Feb. 10, 1959 FOREIGN PATENTS 483,503 Great Britain Apr. 21, 1938

Claims (1)

1. A PROCESS OF PREPARING LOW CARBON STEEL FOR ELECTROPLATING WITH ANOTHER METAL, WHICH COMPRISES ANODICALLY ELECTROSMOOTHING THE SURFACE TO BE PLATED IN A BATH CONSISTING ESSENTIALLY OF WATER AND FROM 49 TO 147 GMS. SODIUM CITRATE (INCLUDING 2 MOLS. WATER OF CRYSTALLISATION) PER LITRE, FROM 2 TO 50 GMS, CITRIC ACID PER LITRE, AND FROM 5 TO 20 GMS. SODIUM CHLORIDE PER LITRE, THE RELATIVE PROPORTIONS OF SODIUM CITRATE AND CITRIC ACID BEING SUCH THAT THE BATH HAS A PH OF FROM 4.0 TO 6.0.
US830713A 1958-08-07 1959-07-31 Process and bath for electrosmoothing ferrous metals Expired - Lifetime US3054737A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB25347/58A GB874366A (en) 1958-08-07 1958-08-07 Improvements in or relating to the treatment of steel surfaces

Publications (1)

Publication Number Publication Date
US3054737A true US3054737A (en) 1962-09-18

Family

ID=10226188

Family Applications (1)

Application Number Title Priority Date Filing Date
US830713A Expired - Lifetime US3054737A (en) 1958-08-07 1959-07-31 Process and bath for electrosmoothing ferrous metals

Country Status (6)

Country Link
US (1) US3054737A (en)
DE (1) DE1421960A1 (en)
FR (1) FR1235703A (en)
GB (1) GB874366A (en)
LU (1) LU37495A1 (en)
NL (2) NL241653A (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3975245A (en) * 1975-12-05 1976-08-17 United Technologies Corporation Electrolyte for electrochemical machining of nickel base superalloys
US4264418A (en) * 1978-09-19 1981-04-28 Kilene Corp. Method for detersifying and oxide coating removal
US4904312A (en) * 1987-08-22 1990-02-27 British Steel Plc Method of electrolytically etching linear impressions in electrical steel
US20110120883A1 (en) * 2009-11-23 2011-05-26 MetCon LLC Electrolyte Solution and Electropolishing Methods
US8580103B2 (en) 2010-11-22 2013-11-12 Metcon, Llc Electrolyte solution and electrochemical surface modification methods

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1314840A (en) * 1917-04-30 1919-09-02 Jackson S Weeks Composition for electrolytes for electrical etching.
US1334092A (en) * 1918-07-29 1920-03-16 John L Fay Method of preparing metal to be galvanized or coated
US2090966A (en) * 1931-07-24 1937-08-24 Mead Res Engineering Company Electrochemistry
GB483503A (en) * 1936-10-28 1938-04-21 Crosse & Blackwell Ltd Improvements in marking metal articles
US2331721A (en) * 1939-08-12 1943-10-12 Rustless Iron & Steel Corp Polishing stainless iron and steel
US2437474A (en) * 1944-03-24 1948-03-09 Gilbert H Orozco Method of anodic cleaning
US2607722A (en) * 1947-01-28 1952-08-19 Armco Steel Corp Electrolytic polishing of stainless steel
US2799636A (en) * 1954-03-03 1957-07-16 Coats & Clark Processing of separable fastener stringers
US2873233A (en) * 1956-03-21 1959-02-10 Philco Corp Method of electrodepositing metals

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1314840A (en) * 1917-04-30 1919-09-02 Jackson S Weeks Composition for electrolytes for electrical etching.
US1334092A (en) * 1918-07-29 1920-03-16 John L Fay Method of preparing metal to be galvanized or coated
US2090966A (en) * 1931-07-24 1937-08-24 Mead Res Engineering Company Electrochemistry
GB483503A (en) * 1936-10-28 1938-04-21 Crosse & Blackwell Ltd Improvements in marking metal articles
US2331721A (en) * 1939-08-12 1943-10-12 Rustless Iron & Steel Corp Polishing stainless iron and steel
US2437474A (en) * 1944-03-24 1948-03-09 Gilbert H Orozco Method of anodic cleaning
US2607722A (en) * 1947-01-28 1952-08-19 Armco Steel Corp Electrolytic polishing of stainless steel
US2799636A (en) * 1954-03-03 1957-07-16 Coats & Clark Processing of separable fastener stringers
US2873233A (en) * 1956-03-21 1959-02-10 Philco Corp Method of electrodepositing metals

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3975245A (en) * 1975-12-05 1976-08-17 United Technologies Corporation Electrolyte for electrochemical machining of nickel base superalloys
US4264418A (en) * 1978-09-19 1981-04-28 Kilene Corp. Method for detersifying and oxide coating removal
US4904312A (en) * 1987-08-22 1990-02-27 British Steel Plc Method of electrolytically etching linear impressions in electrical steel
US20110120883A1 (en) * 2009-11-23 2011-05-26 MetCon LLC Electrolyte Solution and Electropolishing Methods
US8357287B2 (en) 2009-11-23 2013-01-22 MetCon LLC Electrolyte solution and electropolishing methods
CN105420805A (en) * 2009-11-23 2016-03-23 梅特康有限责任公司 Electrolyte solution and electropolishing methods
US8580103B2 (en) 2010-11-22 2013-11-12 Metcon, Llc Electrolyte solution and electrochemical surface modification methods
US9499919B2 (en) 2010-11-22 2016-11-22 MetCon LLC Electrolyte solution and electrochemical surface modification methods

Also Published As

Publication number Publication date
DE1421960A1 (en) 1969-01-09
NL122923C (en)
LU37495A1 (en)
NL241653A (en)
GB874366A (en) 1961-08-02
FR1235703A (en) 1960-07-08

Similar Documents

Publication Publication Date Title
JPS6015716B2 (en) Method for stabilizing tin or tin alloy electroplating baths
US3989604A (en) Method of producing metal strip having a galvanized coating on one side
US1608694A (en) Corrosion-resistant article and method of making the same
DE1094245B (en) Lead dioxide electrode for use in electrochemical processes
US2693444A (en) Electrodeposition of chromium and alloys thereof
US3970537A (en) Electrolytic treating apparatus
DE1300414B (en) Object, preferably made of ferrous metal, with a dense, firmly adhering, shiny anti-corrosion coating made of an aluminum-manganese alloy and a method for its production
US4249999A (en) Electrolytic zinc-nickel alloy plating
US3054737A (en) Process and bath for electrosmoothing ferrous metals
US3933605A (en) Non-polluting pickling method
US2275223A (en) Rustproof material and process
US3959099A (en) Electrolytic method of producing one-side-only coated steel
JPS58177494A (en) Anodically oxidizing bath for aluminum-clad part and anodic oxidation
US2075623A (en) Zinc plating
US3268422A (en) Electroplating bath containing aluminum and manganese-bearing materials and method of forming aluminummanganese alloy coatings on metallic bases
US3729396A (en) Rhodium plating composition and method for plating rhodium
US3111464A (en) Electrodeposition of chromium and chromium alloys
US4167459A (en) Electroplating with Ni-Cu alloy
US4518474A (en) Device for the electrolytic treatment of metal strip
US2241585A (en) Process for removing metallic coatings from metallic parts
US2646397A (en) Electroplating zinc using titanium containing electrolyte
US1566984A (en) Electroplating method and electroplated articles
DE69210775T2 (en) Bath and electrolytic process for applying a thin coating of an iron-zinc alloy with a high iron content to a galvanized alloy substrate
US3374156A (en) Electro-depositing stainless steel coatings on metal surfaces
US3446717A (en) Cathodic treatment of metals in chromate solution to form protective coating thereon