US3620934A - Method of electrolytic tinning sheet steel - Google Patents

Method of electrolytic tinning sheet steel Download PDF

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Publication number
US3620934A
US3620934A US654433A US3620934DA US3620934A US 3620934 A US3620934 A US 3620934A US 654433 A US654433 A US 654433A US 3620934D A US3620934D A US 3620934DA US 3620934 A US3620934 A US 3620934A
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bath
pickling
acid
tinning
tin
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Joseph Endle
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FER BLANC SARL CENTRE RECH DU
SOC A RESPONSABILITE CENTRE DE RECHERCHES DU FER BLANC Ltee
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FER BLANC SARL CENTRE RECH DU
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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
    • C25D5/34—Pretreatment of metallic surfaces to be electroplated
    • C25D5/42—Pretreatment of metallic surfaces to be electroplated of light metals
    • C25D5/44—Aluminium
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/08—Iron or steel
    • 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
    • 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

Definitions

  • the present invention relates to a method of electrolytically tin-plating sheet steel, whereby tin-plated sheet steel of improved corrosion resistance can be produced.
  • One proposed method of electrolytically tin plating comprises the steps of electrolytically degreasing the sheet steel in an alkaline bath; rinsing the sheet material in water and then electrolytically pickling it in an acid bath, first cathodically and then anodically; rinsing the sheet material in water again and then subjecting the scaled and soaked material to preliminary tinning in an alkaline bath; rerinsing the pretinned sheet and then putting it into an acid-tinning bath; and finally subjecting the tinned sheet to treatment for fusing and cooling the deposited tin.
  • This proposed method necessitates careful rinsing between pickling, pretinning and tinning, not only to avoid neutralizing one bath by carry over from another, but also to avoid the precipitation of tin compounds in the acid-tinning bath, these tin compounds arising from alkaline stannates carried by the sheet when it leaves the pretinning section.
  • This method also entails modifying an existing tinning installation by the provision of extra vats for the alkaline pretinning, which makes the conversion of existing plant costly.
  • the corrosion resistance of tin plate depends mainly on the continuity of the layer of crystalline FeSn,alloy formed between the steel sheet and the coating of tin during the fusion of the deposited tin.
  • This continuity of the crystalline layer depends onthe surface condition of the steel/tin interface, this surface condition determining the density and growth of the Fesn grains.
  • the present invention at least partially eliminates the drawbacks mentioned above, one object thereof being to provide a method of electrolytic tinning whereby a sheet of steel is subjected to degreasing in an alkaline bath; pickling in an acid bath in which the sheet of steel is polarized as the cathode, preliminary coating with metal, tinning in an acid bath and treating to obtain the fusion and. cooling of the tin on the sheet.
  • This method makes it possible to produce tinplate that has a layer of Fesn which is continuous by virtue of very dense seeding and which thus has improved corrosion resistance, while enabling certain steps in the process to be simplified.
  • a method of electrolytic tinning in accordance with the invention is characterized by the fact that the metallic precoating of the sheet material is carried out in an acid pickling bath containing bivalent metal ions, the concentration of which is low in relation to that of hydrogen ions.
  • the previously degreased sheeting when rendered cathodic in relation to two parallel counterelectrodes of which it constitutes the plane of symmetry, becomes the seat of abundant evolution of hydrogen and a slight adherent deposit of metal.
  • the hydrogen liberated reduces the oxides and mechanically removes impurities from the surface of the sheeting, while the slight deposit of metal preserves it from any subsequent contamination.
  • the clectrodeposition pickling bath is substituted directly for the conventional pickling bath, the operations of pickling and precoating can take place in one and the same working vat.
  • the electrodeposition pickling may be preceded by conventional pickling when the strip is particularly heavily oxidized.
  • an extremely thin initial coating of adherent metal can be deposited in the pickling bath on the steel sheet as soon as this is clean. This coating or deposit then protects the steel/tin interface from any contamination likely to occur between emergence from the electrodeposition pickling bath and entry into the first tinning bath proper.
  • the slight deposit of metal resulting from the electrodepositon pickling is not spongy, as might have been expected, but adherent and uniform.
  • FIG. I is a micrograph of the alloy coating of tinplate obtained by the conventional method.
  • FIG. 2 is a micrograph of the alloy coating on tinplate obtained by a method in accordance with the invention, employing a stage of tinning and pickling in an acid medium;
  • FIG. 3 is a micrograph of the alloy coating on tinplate obtained by a method in accordance with the invention, employing a stage of cathode nickel plating and pickling in an acid medium;
  • FIG. 4 is a micrograph of the alloy coating on tinplate obtained by a method in accordance with the invention, employing a stage of cathode tinning, nickel plating and pickling in an acid medium.
  • a method of electrolytic tinning in accordance with the invention should preferably comprise the following steps:
  • a steel strip or sheet is first subjected to conventional degreasing; then, after drying and rinsing in water, the degreased sheet is put into an acid electrodeposition pickling bath consisting of an aqueous solution of acid containing bivalent metal ions (tin or nickel, alone or mixed, these metals preferably being used in the form of bivalent ions).
  • the sheet is polarized as the cathode, the anode consisting of a material possessing good resistance to anodic dissolution.
  • the sheet Having undergone the treatment of electrodeposition pickling (pickling and precoating with metal), the sheet is dried and rinsed in water before being put into the tinning bath or baths, in which it receives an additional coating of tin by conventional electrodeposition.
  • the tinned sheet is then subjected to a treatment for fusing the tin coating in the usual way, for example, Joule effect, induction, radiation and so forth, and is then cooled with water.
  • This procedure is economical and does not necessitate technical alterations to existing plant, the electrodeposition pickling taking place in the section provided for the conventional pickling.
  • the rinsing stage between the electrodeposition pickling and the conventional tinning can be reduced to the strict minimum or even dispensed with altogether.
  • the electrodeposition pickling bath may have an acidity of [0 to 200 gram equivalents of sulfuric acid per liter of bath.
  • the electrodeposition pickling bath may be made with sulfuric acid or some acid other than sulfuric or from a mixture of acids from which sulfuric acid may be absent.
  • the content of bivalent metal or metals in the electrodeposition pickling bath may range from 0.1 to 300 grams per liter of bath. Within the limits just quoted, however, it is important not to associate any random concentration of acid with any random concentration of metal. To obtain effective electrodeposition pickling leaving an adherent homogeneous deposit of metal, it is important that the concentration of hydrogen ions should be high-enough, in relation to the concentration of metal ions, to ensure that the cathode current output in deposited metal is low, being less than 50 percent and preferably between 5 percent and 25 percent.
  • the metal coating forms on the steel sheet or strip as soon as the steel has been stripped by reduction. There is therefore no risk of oxidation of the sheet, which, once it emerges from the electrodeposition pickling bath, can no longer oxidize during the subsequent rinsing in an atmospheric medium, because it is already protected by a very thin coating of metal.
  • the tinning pickling bath is an acid hath made with sulfuric acid, for example, containing stannous salts.
  • the tin content of such a bath may vary between 0.3 and 1.5 g. per liter of bath and the content of sulfuric acid between 15 and 100 g. per liter of bath, without the results varying appreciably.
  • a hath made with acids belonging to the phenosulfonic acid family, such as, for example, phenolsulfonic or cresolsulfonic acid, or from a mixture of sulfuric and phenolsulfonic acids. in that case, the tin deposited will be still more adherent than in a sulfuric medium alone.
  • the contents of stannous tin and acid given for the sulfuric bath are equally applicable to baths modified with phenolsulfide acids, the acidity then being expressed in gram equivalents of sulfuric acid per liter of bath.
  • the anodes employed are acid proof, being made of graphite, for example, or of stainless steel or an iron-silicon alloy containing 13 percent of Si.
  • the present invention is not limited, as regards the tinning pickling bath, to the acid or acid mixture solutions quoted as examples. it should be emphasized that the use of other acids, alone or in the form of mixtures, mineral or organic, comes within the scope of the invention.
  • the stannous ions are introduced into the tinning pickling bath in the form of stannous salts, such as stannous sulfates or else by the dissolution of one or more soluble tin anodes placed among the acid proof anodes, or again in the form of used or excess tinning bath containing stannous ions.
  • stannous salts such as stannous sulfates
  • This last method is particularly advantageous on grounds of economy, acid-tinning baths tending to become rich in stannous ions.
  • This procedure also enables the acidity of the tinning pickling bath to be kept constant.
  • the introduction of fresh stannous ions to the bath is carried out, of course, as the stannous ions in the bath are consumed by the deposition of tin and in such a way that the concentration of stannous ions remains within a definite range, for the baths mentioned above, for example, within the range of 0.3 to 1.5 g. per liter of bath.
  • the time taken by the sheet metal to pass through the tinning pickling bath may amount to up to 5 seconds.
  • the current-density values vary, being and 60 a./sq.dm., and the bath temperature lies between C. and 80 C.
  • Tests of the A.T.C. (Alloy Tin Couple) type made with sheets of tinplate manufactured in accordance with the invention have given values of between 0.5 and 0.12 p. a./sq.cm.
  • adhesion of solder to tinplate prepared by a method in accordance with the invention is in general improved on average by l5 to percent in relation to adhesion to tinplate obtained by traditional methods.
  • tinplate manufactured in accordance with the invention has a better surface shine than tinplate obtained without tinning pickling.
  • the A.T.C. test consists in determining in microamperes per square centimeter the electric current arising in a cell consisting of an electrode of pure tin and a specimen of tinplate from which the coating of tin has been dissolved and of which the FeSn, alloy coating has remained adhered to the steel sheet.
  • the two electrodes are immersed on short circuit in deaerated grapefruit juice at a temperature of 26 C.
  • the short-circuit current is measured after a 20-hour output of the cell. It is considered that the sheet of tinplate has good corrosion resistance when this current is less than 0.12 a./sq.cm.
  • the tinning pickling bath contained 100 g. of sulfuric acid and 1.5 g. of tin per liter of bath, the tin being introduced into the bath in the form of stannous sulfate.
  • the bath temperature 15 was C.
  • the current density was 17 a./sq.dm.
  • the duration of treatment was 2 seconds
  • the mass of the tin deposit obtained by the pickling operation was 0.7 g./sq.rn.
  • the current density is the current applied per face of unit surface area (sq.dm.). 2
  • the mass deposited per unit surface area is the sum of the masses deposited on each side of this unit surface area. This method of calculation is usual in the tinplate industry. The actual mass depos'ited per face of unit surface area is thus 1 one-half of that given.
  • the degreased and rinsed sheeting was passed to the tinning pickling section. On emerging from the tinning pickling, it underwent further tinning, to bring the total amount of tin deposited up to 16.8 g./sq.m.
  • the coating of tin was then fused by Joule effect and dipped into water.
  • the tinning pickling bath contained 53 g. of phenolsulfonic acid (equivalent to 15 g. of sulfuric acid) and 0.6 g. of stannous tin per liter of bath.
  • the stannous ions were introduced into the bath in the form of excess tinning electrolyte.
  • the bath temperature was C.
  • the current density was l6 a./sq.dm.
  • the time taken by the degreased sheeting to pass through the bath was 1.8 seconds.
  • the sheeting emerging from this bath was lightly tinned (0.8 g. of tin per sq.m.).
  • FIGS. 1 and 2 the micrographs (enlarged sixteen thousand times) show the appearance of the crystalline FeSn layer on one and the same kind of steel, according to whether or not the tinning pickling here proposed is used.
  • FIG. I shows the appearance of the alloy layer of the tin plate obtained with conventional cathodic acid pickling
  • FIG. 2 shows the appearance of the alloy layer of tinplate obtained with tinning cathodic acid pickling.
  • the distribution of alloy tin in FIG. 1 is 2.5 g./sq.m. and that in FIG. 2 is L9 g./sq.m.
  • the improvement in surface shine obtained on tinplate by nickel-plating pickling was less marked than with tinning pickling.
  • the appearance of the alloy coating on the tinplate obtained by this application of the invention is shown in FIG. 3.
  • the proportion of alloy tin in FIG. 3 is 1.8 g./sq.m. and the A.T.C. value 0.10 pa./sq.cm.
  • the electrodeposition pickling bath contained 15 g. of sulfuric acid, I g. ofnickel in sulfate form (NiSO -7H 0) and 0.5 g. of stannous tin in the form of used or excess acid tinning bath per liter of bath.
  • the bath temperature was 60 C., the current density 14 a./sq.dm. and the duration of treatment 2 seconds.
  • the mass of the metal clectrodeposited during pickling was 0.2 g. of tin and 0.02 of nickel per sq.m.
  • FIG. 4 The appearance of the alloy layer on tinplate obtained by this form of application of the invention is shown in FIG. 4. Here the relatively dense structure is clearly brought out.
  • the distribution of alloy tin in FIG. 4 is 1.6 g.lsq.m. and the A.T.C. value is 0.05 a a./sq.cm.
  • a method in accordance with the invention offers the important advantage of relative simplicity over other proposed methods based on the use of baths that are chemically not very compatible with the preceding and following baths, which entails thorough drying and rinsing. Before these known methods can be put into practice, too, existing acid tinning plant requires extensive modification.
  • Another not inconsiderable advantage of a method in accordance with the invention is that the recovery of excess acid tinning bath liquid is permitted.
  • the invention is naturally not limited to the forms described, but includes all variants thereof.
  • one variant of the invention consists in subjecting the sheet steel, after degreasing, to conventional acid electrolytic pickling, followed by the electrodeposition pickling described above. This procedure may be found useful when the sheeting is heavily oxidized, but the preliminary pickling is not necessary in everyday practice.
  • the improvement comprising carrying out the preliminary coating of the sheet steel, polarized as the cathode, in an acid bath having a temperature between 20 and C. containing bivalent ions of a metal selected from the group consisting of tin and nickel in an amount between 0.1 and L5 g.
  • a method according to claim 1 in which an antioxidant additive is added to the pickling bath to slow down the oxidation of the readily oxidizable metal ions in the pickling bath, which additive is compatible with the acid content in the acid pickling bath.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Electroplating Methods And Accessories (AREA)
US654433A 1966-08-08 1967-07-19 Method of electrolytic tinning sheet steel Expired - Lifetime US3620934A (en)

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FR72432A FR1500185A (fr) 1966-08-08 1966-08-08 Procédé d'étamage électrolytique d'un feuillard d'acier

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BE (1) BE700402A (enrdf_load_stackoverflow)
DE (1) DE1621046B2 (enrdf_load_stackoverflow)
FR (1) FR1500185A (enrdf_load_stackoverflow)
GB (1) GB1185527A (enrdf_load_stackoverflow)
NL (1) NL158856B (enrdf_load_stackoverflow)
SU (1) SU379103A3 (enrdf_load_stackoverflow)

Cited By (26)

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US4157694A (en) * 1978-03-16 1979-06-12 Tokyo Kohan Co. Ltd. Method of producing a tin-plated seamless container
US4236977A (en) * 1976-06-24 1980-12-02 Italsider, S.P.A. Method for preplating steel surfaces
US4601957A (en) * 1984-04-13 1986-07-22 Toyo Kohan Co., Ltd. Method for producing a thin tin and nickel plated steel sheet for welded can material
WO1997025454A3 (en) * 1995-12-22 1997-09-04 Weirton Steel Corp Electrolytic plating of steel substrate
WO1997035051A1 (en) * 1996-03-20 1997-09-25 Metal Technology, Inc. An electrolytic process for cleaning and coating electrically conducting surfaces
US5958604A (en) * 1996-03-20 1999-09-28 Metal Technology, Inc. Electrolytic process for cleaning and coating electrically conducting surfaces and product thereof
US5981084A (en) * 1996-03-20 1999-11-09 Metal Technology, Inc. Electrolytic process for cleaning electrically conducting surfaces and product thereof
US20050045100A1 (en) * 2003-03-03 2005-03-03 Derderian Garo J. Reactors, systems with reaction chambers, and methods for depositing materials onto micro-device workpieces
US20050059261A1 (en) * 2003-09-17 2005-03-17 Cem Basceri Microfeature workpiece processing apparatus and methods for controlling deposition of materials on microfeature workpieces
US20050120954A1 (en) * 2002-05-24 2005-06-09 Carpenter Craig M. Apparatus for controlling gas pulsing in processes for depositing materials onto micro-device workpieces
US20050217575A1 (en) * 2004-03-31 2005-10-06 Dan Gealy Ampoules for producing a reaction gas and systems for depositing materials onto microfeature workpieces in reaction chambers
US20060193983A1 (en) * 2003-10-09 2006-08-31 Micron Technology, Inc. Apparatus and methods for plasma vapor deposition processes
US20070102994A1 (en) * 2004-06-28 2007-05-10 Wright James P Wheel Trim Hub Cover
US7235138B2 (en) 2003-08-21 2007-06-26 Micron Technology, Inc. Microfeature workpiece processing apparatus and methods for batch deposition of materials on microfeature workpieces
US7258892B2 (en) 2003-12-10 2007-08-21 Micron Technology, Inc. Methods and systems for controlling temperature during microfeature workpiece processing, e.g., CVD deposition
US7282239B2 (en) 2003-09-18 2007-10-16 Micron Technology, Inc. Systems and methods for depositing material onto microfeature workpieces in reaction chambers
US7335396B2 (en) 2003-04-24 2008-02-26 Micron Technology, Inc. Methods for controlling mass flow rates and pressures in passageways coupled to reaction chambers and systems for depositing material onto microfeature workpieces in reaction chambers
US7344755B2 (en) 2003-08-21 2008-03-18 Micron Technology, Inc. Methods and apparatus for processing microfeature workpieces; methods for conditioning ALD reaction chambers
US7387685B2 (en) 2002-07-08 2008-06-17 Micron Technology, Inc. Apparatus and method for depositing materials onto microelectronic workpieces
US7422635B2 (en) 2003-08-28 2008-09-09 Micron Technology, Inc. Methods and apparatus for processing microfeature workpieces, e.g., for depositing materials on microfeature workpieces
US7581511B2 (en) 2003-10-10 2009-09-01 Micron Technology, Inc. Apparatus and methods for manufacturing microfeatures on workpieces using plasma vapor processes
US7588804B2 (en) 2002-08-15 2009-09-15 Micron Technology, Inc. Reactors with isolated gas connectors and methods for depositing materials onto micro-device workpieces
US7647886B2 (en) 2003-10-15 2010-01-19 Micron Technology, Inc. Systems for depositing material onto workpieces in reaction chambers and methods for removing byproducts from reaction chambers
US7699932B2 (en) 2004-06-02 2010-04-20 Micron Technology, Inc. Reactors, systems and methods for depositing thin films onto microfeature workpieces
US7906393B2 (en) 2004-01-28 2011-03-15 Micron Technology, Inc. Methods for forming small-scale capacitor structures
US8133554B2 (en) 2004-05-06 2012-03-13 Micron Technology, Inc. Methods for depositing material onto microfeature workpieces in reaction chambers and systems for depositing materials onto microfeature workpieces

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Publication number Priority date Publication date Assignee Title
GB1436855A (en) * 1972-11-14 1976-05-26 Yoshizaki K Method of producing tin coated steel sheet used for seamless steel container
FR2234389A1 (en) * 1973-06-08 1975-01-17 Magnitogorsky Dvazhdy Inert anode for electroplating processes - esp. used to replace tin anodes periodically in tinning baths
FR2516553B1 (fr) * 1981-11-16 1985-10-25 Lorraine Laminage Procede de revetement anti-corrosion de toles d'acier destinees a l'emballage et soudages electriquement, ainsi que toles obtenues
DE3147967C2 (de) * 1981-12-01 1985-10-24 Mannesmann AG, 4000 Düsseldorf Verzinnungsverfahren
JP5646105B1 (ja) * 2013-06-27 2014-12-24 日新製鋼株式会社 Ｓｎめっきステンレス鋼板

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US1417896A (en) * 1920-01-28 1922-05-30 Fletcher Electro Salvage Compa Electrodeposition of metals upon iron and alloys of iron
US1979996A (en) * 1931-04-03 1934-11-06 Gen Motors Corp Electroplating process
US1972835A (en) * 1932-03-08 1934-09-04 Tainton Urlyn Clifton Coating ferrous articles with zinc
US1898765A (en) * 1932-06-20 1933-02-21 Bullard Co Electrocleaning process
US2266330A (en) * 1935-12-23 1941-12-16 John S Nachtman Process for electroplating strip steel
US2363973A (en) * 1939-07-08 1944-11-28 Revere Copper & Brass Inc Method of copper plating stainless steel cooking vessels
US2381778A (en) * 1940-12-13 1945-08-07 Standard Steel Spring Co. Process of producing protected metal articles
US2407579A (en) * 1942-07-04 1946-09-10 Du Pont Electrodeposition of tin
US2673836A (en) * 1950-11-22 1954-03-30 United States Steel Corp Continuous electrolytic pickling and tin plating of steel strip
US2915444A (en) * 1955-12-09 1959-12-01 Enthone Process for cleaning and plating ferrous metals
US3260580A (en) * 1962-11-19 1966-07-12 American Can Co Tin plate having a tin-nickel-iron alloy layer and method of making the same
US3445351A (en) * 1964-10-21 1969-05-20 Du Pont Process for plating metals

Cited By (39)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4236977A (en) * 1976-06-24 1980-12-02 Italsider, S.P.A. Method for preplating steel surfaces
US4157694A (en) * 1978-03-16 1979-06-12 Tokyo Kohan Co. Ltd. Method of producing a tin-plated seamless container
US4601957A (en) * 1984-04-13 1986-07-22 Toyo Kohan Co., Ltd. Method for producing a thin tin and nickel plated steel sheet for welded can material
WO1997025454A3 (en) * 1995-12-22 1997-09-04 Weirton Steel Corp Electrolytic plating of steel substrate
WO1997035051A1 (en) * 1996-03-20 1997-09-25 Metal Technology, Inc. An electrolytic process for cleaning and coating electrically conducting surfaces
US5700366A (en) * 1996-03-20 1997-12-23 Metal Technology, Inc. Electrolytic process for cleaning and coating electrically conducting surfaces
US5958604A (en) * 1996-03-20 1999-09-28 Metal Technology, Inc. Electrolytic process for cleaning and coating electrically conducting surfaces and product thereof
US5981084A (en) * 1996-03-20 1999-11-09 Metal Technology, Inc. Electrolytic process for cleaning electrically conducting surfaces and product thereof
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SU379103A3 (enrdf_load_stackoverflow) 1973-04-18
GB1185527A (en) 1970-03-25
DE1621046B2 (de) 1975-08-28
BE700402A (enrdf_load_stackoverflow) 1967-12-01
FR1500185A (fr) 1967-11-03
NL6710884A (enrdf_load_stackoverflow) 1968-02-09
NL158856B (nl) 1978-12-15
DE1621046A1 (de) 1971-04-29

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