US3285838A - Production of electrolytic tinplate - Google Patents

Production of electrolytic tinplate Download PDF

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Publication number
US3285838A
US3285838A US224185A US22418562A US3285838A US 3285838 A US3285838 A US 3285838A US 224185 A US224185 A US 224185A US 22418562 A US22418562 A US 22418562A US 3285838 A US3285838 A US 3285838A
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United States
Prior art keywords
tin
tinplate
coating
alloy
flash
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
US224185A
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English (en)
Inventor
Eric R Morgan
Irwin I Bessen
George K Notman
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Jones and Laughlin Steel Corp
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Jones and Laughlin Steel Corp
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Filing date
Publication date
Priority to NL298002D priority Critical patent/NL298002A/xx
Priority to BE637451D priority patent/BE637451A/xx
Application filed by Jones and Laughlin Steel Corp filed Critical Jones and Laughlin Steel Corp
Priority to US224185A priority patent/US3285838A/en
Priority to GB36438/63A priority patent/GB1007381A/en
Priority to LU44459D priority patent/LU44459A1/xx
Priority to DE1496835A priority patent/DE1496835C3/de
Priority to FR947725A priority patent/FR1375283A/fr
Application granted granted Critical
Publication of US3285838A publication Critical patent/US3285838A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • 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
    • C25D5/48—After-treatment of electroplated surfaces
    • C25D5/50—After-treatment of electroplated surfaces by heat-treatment
    • C25D5/505—After-treatment of electroplated surfaces by heat-treatment of electroplated tin coatings, e.g. by melting
    • 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
    • C25D5/34—Pretreatment of metallic surfaces to be electroplated
    • C25D5/36—Pretreatment of metallic surfaces to be electroplated of iron or steel
    • 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
    • Y10S205/00—Electrolysis: processes, compositions used therein, and methods of preparing the compositions
    • Y10S205/917—Treatment of workpiece between coating steps

Definitions

  • tinplate used today is provided with its tin coating by electrolytic tin processes. These processes permit the plating of a relatively thin tin coating which is relatively uniform in thickness. Because the thickness of tin on conventional tinplate is a small fraction of an inch, the amount of tin coating is more conveniently expressed in terms of its weight in pounds for a base box of tinplate.
  • base box is a measure of area or surface, and amounts to 31,3 60 square inches. Large amounts of electrolytic tinplate are made with coating weights on the order of /2 pound of tin per base box of tinplate.
  • the electrolytic tinplate used for food packs must be tested carefully to determine its resistance to corrosion by various food prod-. ucts.
  • the corrosion resistance of tinplate used for food packs can be determined by a galvanic test, known as the alloy-tin couple test.
  • the test consists of stripping the tin from a sample of tinplate down to the tin-iron alloy surface and measuring the current density developed by a galvanic couple comprising a pure tin electrode and the sample immersed in grapefruit juice containing 100 ppm.
  • ATC values Low ATC values indicate good corrosion resistance, whereas high ATC values represent poor corrosion resistance.
  • the ATC test is described in the paper, The Alloy-Tin Couple TestA New Research Tool, by G. G. Kamm, A. R. Willey, R. E. Beese and I. L. Krickl, published in Corrosion, volume 17, February 1961, pages 106-112.
  • ATC values ranging from 0.01 up to perhaps 0.5.
  • the ATC value of 0.07 has been arbitrarily selected as representing superior quality tinplate, although, as we have mentioned, it is possible to produce tinplate having lower ATC values.
  • Tin may be electro-deposited upon a steel base using either an alkaline or an acid electrolyte.
  • An alkaline process is disclosed in US. Patent 2,424,472, issued to F. A. Lowenheirn et al., on July 22, 1947. Alkaline processes have the disadvantage that they are considerably slower than acid processes, and commercial electrotinning lines, therefore, usually employ acid electrolytes.
  • One such electrolyte commonly used is that of U5. Patent 2,407,579, issued to E. W. Schweikher on September 10, 1946. The process of that patent is commonly known as the halogen process.
  • the steel base in the form of strip is electrolytically cleaned by conventional methods and is then scrubbed with brushes and rinsed with water.
  • the cleaned strip is given a light pickle in 5% sulphuric acid and is again scrubbed and rinsed with water.
  • the clean strip is then passed through an electrotinning cell employing a halogen electrolyte and is then given a flash coating of tin.
  • flash coating is commonly used to describe a very light tin deposit on the order of .02 to .10 pound of tin per base box of tinplate.
  • the flash coated strip is rinsed in water and dried in a warm air blast and is then rapidly heated to a temperature somewhat above the melting point of tin and quickly quenched.
  • the flash coated strip is again electrolytically cleaned and rinsed in water, and is then introduced a second time into an electroplating cell containing a halogen electrolyte. There it receives an additional tin deposit sufficient to bring the total weight of tin up to the desired value.
  • the strip from the second electroplating bath is rinsed, dried, refiowed and quenched a second time, the second reflowing and quenching being carried out so as to produce a bright tin coating.
  • Our process to be described more fully in detail, consistently produces tinplate having ATC values well below tthe limits for superior quality tinplate.
  • FIG- URE l is a graph showing the effect of changes in the first refiow temperature on the ATC values of tinplate of our invention for two values of the second refiow temperature.
  • FIGURE 2 is a second graph showing the effect of various first refiow temperatures on ATC values of tinplate of several coating weights of our invention.
  • FIG- URE 3 is an electromicroscope photomicrograph showing the iron-tin alloy structure of conventional halogen tinplate.
  • FIGURE 4 is an electromicroscope photomicrograph showing the nature of the iron-tin alloy produced by our process on tinplate having a flash coating of illSllfilcient weight.
  • FIGURES 5 through 10 are electromicroscope-photomicrographs showing the iron-tin alloy structure of tinplate of our invention which has been subjected to first refiow temperatures ranging from 490 F, to 705 F. as are set out below those figures.
  • FIGURE 3 is an electronmicroscope-photomicrograph at a magnification of 5,750 diameters of the iron-tin alloy formed on a sample of tinplate of conventional coating weight produced in a halogen bath, and refiowed in the conventional manner.
  • the outer layer of tin was stripped from the sample by known techniques.
  • the iron-tin alloy grows in the form of columnar or prismatic crystals 1-1 which are seen to extend in all directions and intersect or overlay one another.
  • FIGURES 5 through are electronmicroscope-photomicrographs at a magnification of 5,720 diameters of six samples which were each given a flash coating of tin amounting to .057 pounds per base box in a halogen bath. The samples were then heated to the temperature indicated below each figure to reflow the tin.
  • FIGURE 5 illustrates the crystalline alloy structure which resulted from refiowing the tin at a temperature of 490 R, which is not far above the 442 F. melting point of pure tin.
  • the iron-tin alloy has grown as somewhat elongated crystals 5-5, but those crystals are relatively flat and appear to grow more or less parallel to the tinplate surface. Between the crystals are areas 6-6 which are not covered by the alloy, but these areas are considerably smaller in extent than the corresponding areas in FIGURE 3.
  • FIGURE 6 which is a photomicrograph of the iron-tin alloy formed by reflow- I ing the tin at a temperature of 535 F.
  • the individual crystals 7-7 are flat or plate-like and the uncovered areas 8-8 are relatively insignificant.
  • FIGURE 7 which shows the alloy structure obtained by refiowing at 585 F., the individual crystals 9-9 are even more flat and platelike, and the uncovered base metal 10-10 is insignificant in extent.
  • FIGURES 8, 9 and 10 illustrate the alloy formed at refiowing temperatures of 620 F., 670 F., and 705 F., respectively. These are seen to be very similar to the structure of FIGURE 7.
  • the alloy crystals 11-11, 1212, and 13-13, respectively, are flat and overlap.
  • Tinplate produced as above described displays excellent ATC values, which are the result of the flash coating and refiowing. This conclusion is established by the data of Table I which are the results of six series of tests. Each series comprised four samples of steel, each of which was flash coated with tin in a dilferent amount as is indicated.
  • the samples of series 4 and 5 were given an additional tin coating sufficient to bring their coating weight up to /2 pound per base box. In series 4 this second coating was not refiowed.
  • the ATC values are seen to be con siderably worse than those of series 2 and 3.
  • the samples of series 5 were refiowed at temperatures around 550 F.
  • the ATC values are seen to be superior to those of any of the samples of the four previous series.
  • the samples constituting series 6 were flash plated and refiowed in the same way as those of series 2. They were given an additional tin coating sufficient to bring their coating weight to /2 pound per base box, and were reflowed a second time at a temperature about 550 F.
  • the ATC values of those samples are all in the superior quality.
  • FIGURE 1 The effect of variation in the first reflow temperature on the corrosion resistance of the tinplate is illustrated in FIGURE 1.
  • the broken line curve of that figure represents tinplate produced with a second reflow temperature of 610 F., and the solid line curve represents tinplate given a second reflow temperature 795 F, Both curves reach a minimum ATC value in the same temperature range of about 600 to 700 F., and that ATC value is in the neighborhood of .01 microamps per square inch which is indicative of exceptional corrosion resistance.
  • FIGURE 1 also shows that practically all the samples there plotted were of superior quality.
  • FIGURE 2 is similar to FIGURE 1, but includes data for tinplate of three different coating Weights ranging from .2 to .58 pounds per base box. Again, all three samples reached minimum ATC values at first reflow temperatures around 700 to 750 F.
  • FIGURE 4 illustrates Why lower flash coatings are less effective. It is an electronmicroscope-photomicrograph of the iron-tin alloy resulting from the reflow at 785 F., of a sample given a flash coating of .028 pounds per base box. The photomicrograph is at a magnification of 5,750 diameters.
  • the iron-tin alloy 33 is in relatively flat plate-like form, but leaves large uncovered areas 44 because it is insutficient in amount. This is true even though the total alloy weight of the sample after receiving its second tin coating may be of the same order as the total alloy Weight of tin-plate carrying a considerably heavier flash coating.
  • the data with respect to sample series 6 in Table I supports that conclusion.
  • the process of producing electro-tinned strip of improved corrosion resistance comprising plating the steel in an acid electro-plating bath with a flash coating of tin to a weight between about .02 and about .10 pound per base box of tinplate, reflowing the flash coating at a temperature sufiicient to convert it into a flat plate-like irontin alloy, that temperature being between about 490 F.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating Methods And Accessories (AREA)
US224185A 1962-09-17 1962-09-17 Production of electrolytic tinplate Expired - Lifetime US3285838A (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
NL298002D NL298002A (enrdf_load_stackoverflow) 1962-09-17
BE637451D BE637451A (enrdf_load_stackoverflow) 1962-09-17
US224185A US3285838A (en) 1962-09-17 1962-09-17 Production of electrolytic tinplate
GB36438/63A GB1007381A (en) 1962-09-17 1963-09-16 Improvements in or relating to the production of electrolytic tinplate
LU44459D LU44459A1 (enrdf_load_stackoverflow) 1962-09-17 1963-09-17
DE1496835A DE1496835C3 (de) 1962-09-17 1963-09-17 Verfahren zum zweistufigen galvanischen Verzinnen von Stahlblech
FR947725A FR1375283A (fr) 1962-09-17 1963-09-17 Procédé de fabrication de fer blanc par voie électrolytique et produit en résultant

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US224185A US3285838A (en) 1962-09-17 1962-09-17 Production of electrolytic tinplate

Publications (1)

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US3285838A true US3285838A (en) 1966-11-15

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US224185A Expired - Lifetime US3285838A (en) 1962-09-17 1962-09-17 Production of electrolytic tinplate

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US (1) US3285838A (enrdf_load_stackoverflow)
BE (1) BE637451A (enrdf_load_stackoverflow)
DE (1) DE1496835C3 (enrdf_load_stackoverflow)
GB (1) GB1007381A (enrdf_load_stackoverflow)
LU (1) LU44459A1 (enrdf_load_stackoverflow)
NL (1) NL298002A (enrdf_load_stackoverflow)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3428534A (en) * 1965-11-03 1969-02-18 Jones & Laughlin Steel Corp Manufacture of electrolytic tinplate
US3445351A (en) * 1964-10-21 1969-05-20 Du Pont Process for plating metals
US3468769A (en) * 1967-03-15 1969-09-23 Du Pont Process for producing tin plate of high corrosion resistance
US3481841A (en) * 1965-09-20 1969-12-02 Inland Steel Co Tin plate treating process to improve corrosion resistance
US3652234A (en) * 1969-05-20 1972-03-28 Nat Steel Corp Silvery-tone matte-finish flash coat alloy product
US3915812A (en) * 1972-06-28 1975-10-28 Nippon Kokan Kk Method of manufacturing tinned plates having high corrosion resistant property
US4236977A (en) * 1976-06-24 1980-12-02 Italsider, S.P.A. Method for preplating steel surfaces
US4726208A (en) * 1986-04-29 1988-02-23 Weirton Steel Corporation Flat-rolled steel can stock manufacture
US4863060A (en) * 1986-04-29 1989-09-05 Weirton Steel Corporation Flat-rolled steel can stock product
US5094730A (en) * 1988-12-23 1992-03-10 Mannesmann Aktiengesellschaft Method for forming a metallic coating on steel pipes
WO1997025454A3 (en) * 1995-12-22 1997-09-04 Weirton Steel Corp Electrolytic plating of steel substrate

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102013105392A1 (de) 2013-05-27 2014-11-27 Thyssenkrupp Rasselstein Gmbh Verfahren zur Beschichtung eines Stahlblechs mit einer Metallschicht

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1776603A (en) * 1926-05-25 1930-09-23 Allegheny Steel Co Tin-coated chromium iron alloy and method of making the same
US2364503A (en) * 1939-05-17 1944-12-05 Gen Motors Corp Bearing and method of making same
US3062726A (en) * 1958-08-21 1962-11-06 Inland Steel Co Electrolytic tin plate production
US3174917A (en) * 1961-07-10 1965-03-23 United States Steel Corp Method of making tin plate

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1776603A (en) * 1926-05-25 1930-09-23 Allegheny Steel Co Tin-coated chromium iron alloy and method of making the same
US2364503A (en) * 1939-05-17 1944-12-05 Gen Motors Corp Bearing and method of making same
US3062726A (en) * 1958-08-21 1962-11-06 Inland Steel Co Electrolytic tin plate production
US3174917A (en) * 1961-07-10 1965-03-23 United States Steel Corp Method of making tin plate

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3445351A (en) * 1964-10-21 1969-05-20 Du Pont Process for plating metals
US3481841A (en) * 1965-09-20 1969-12-02 Inland Steel Co Tin plate treating process to improve corrosion resistance
US3428534A (en) * 1965-11-03 1969-02-18 Jones & Laughlin Steel Corp Manufacture of electrolytic tinplate
US3468769A (en) * 1967-03-15 1969-09-23 Du Pont Process for producing tin plate of high corrosion resistance
US3652234A (en) * 1969-05-20 1972-03-28 Nat Steel Corp Silvery-tone matte-finish flash coat alloy product
US3915812A (en) * 1972-06-28 1975-10-28 Nippon Kokan Kk Method of manufacturing tinned plates having high corrosion resistant property
US4236977A (en) * 1976-06-24 1980-12-02 Italsider, S.P.A. Method for preplating steel surfaces
US4726208A (en) * 1986-04-29 1988-02-23 Weirton Steel Corporation Flat-rolled steel can stock manufacture
US4863060A (en) * 1986-04-29 1989-09-05 Weirton Steel Corporation Flat-rolled steel can stock product
US5094730A (en) * 1988-12-23 1992-03-10 Mannesmann Aktiengesellschaft Method for forming a metallic coating on steel pipes
WO1997025454A3 (en) * 1995-12-22 1997-09-04 Weirton Steel Corp Electrolytic plating of steel substrate

Also Published As

Publication number Publication date
DE1496835B2 (de) 1973-12-20
GB1007381A (en) 1965-10-13
LU44459A1 (enrdf_load_stackoverflow) 1965-03-17
BE637451A (enrdf_load_stackoverflow)
DE1496835A1 (de) 1969-12-11
NL298002A (enrdf_load_stackoverflow)
DE1496835C3 (de) 1974-10-31

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