US3712826A - Method of improving the surface of galvanized steel material - Google Patents

Method of improving the surface of galvanized steel material Download PDF

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Publication number
US3712826A
US3712826A US00819251A US3712826DA US3712826A US 3712826 A US3712826 A US 3712826A US 00819251 A US00819251 A US 00819251A US 3712826D A US3712826D A US 3712826DA US 3712826 A US3712826 A US 3712826A
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US
United States
Prior art keywords
zinc
galvanized
layer
strip
galvanized steel
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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
US00819251A
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English (en)
Inventor
T Kimuro
T Ataniya
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.)
JFE Engineering Corp
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Nippon Kokan Ltd
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Publication date
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Publication of US3712826A publication Critical patent/US3712826A/en
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    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/06—Zinc or cadmium or alloys based thereon
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/26—After-treatment
    • C23C2/265—After-treatment by applying solid particles to the molten coating
    • 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
    • Y10S428/941—Solid state alloying, e.g. diffusion, to disappearance of an original layer
    • 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
    • Y10T428/12785—Group IIB metal-base component
    • Y10T428/12792—Zn-base component
    • Y10T428/12799—Next to Fe-base component [e.g., galvanized]

Definitions

  • the present invention is concerned with methods for improving the surfaces of galvanized steel materials.
  • spangle frost flower coating
  • first is to remove the spangle to make the material spangle free by heating the strip just after the coating to alloy the whole coated layer with iron-zinc in order to provide a smooth surface.
  • second is a method which fines zinc crystals by spraying water or steam onto hot-dip galvanized surface.
  • Third is a method which fines zinc crystals by similarly blowing fine powder of metal oxide onto the hot-dip galvanized surface.
  • the present invention has solved the above mentioned prior defects or disadvantages, that is, there are no spangles and it further provides good paint adhesion, of course without detracting from the forming of the coatings.
  • the basic object of this invention exists in getting the method to provide galvanized steel materials having surfaces which are non-spangled and with excellent paint adhesion without detracting from the formability of the galvanized layer.
  • this invention sprays uniformly aqueous solutions of metal salts which can alloy with zinc onto galvanized surfaces at more than 420 C. so as to form the thin alloy layer of this metal and zinc on said coated surface, thereby bringing about no alterations in the thickness of the galvanized layer or adherence, besides obtaining superior qualities in paint adhesion by the thin alloy layer.
  • Products made according to 3,712,826 Patented Jan. 23, 1973 this invention are fairly improved in corrosion resistance of the galvanized surface and high valued ones.
  • Another object of this invention is to obtain a method for applying to such products that have various sizes of spangle.
  • the temperature of the strip on which said metal salts are sprayed should be chosen suitably in the range of more than 300 C. for this invention.
  • the surface properties of the thus formed alloy layer can be suitably changed in accordance to purpose. Alloy surfaces having no spangle .is generally formed by spraying metal salt to the galvanized layer while coated zinc is still molten.
  • the above mentioned metal salt is once applied to the galvanized layer at 300 to 418 C, the formed spangle remains as it is, besides improvements in the corrosion resistance of said galvanized surface and paint adhesion can be achieved as mentioned above.
  • Another object of the present invention is to accomplish economically and advantageously the improving purpose for galvanized layer having the above stated characteristics.
  • Such a method enables an apparatus to easily provide a structure of spraying said metal salt to accomplish economically and advantageously the desired purpose by utilizing residual heat after the hot dipping.
  • the accompanying drawing is a photomicrographic illustration showing the cross-section of a galvanized steel coating prepared by the embodiment of this invention.
  • powders or aqueous solution of metal salts are sprayed to alloy with zinc to said galvanized steel material at more than 300 C., which contains the following both cases, that is, spraying powders or aqueous solution to the coated surface which is still molten such as just after zinc coating on steel material; and spraying powders or aqueous solution to the coated surface whose steel material has been cooled or once cooled down to ordinary temperature, and again heated up to 418 to 300 C.
  • This invention has such a characteristic that aqueous solutions or fine powders of halide, nitrate or sulfate of the metal are sprayed to alloy with zinc at such temperatures, thereby forming the thin alloy layer of said metal and zinc on the coated surface.
  • Strip continuously immersed into the bath is taken out after having been adjusted to suitable coatings by means of the coating roll or gaswiping methods, and while coated zinc of this strip is still molten, powders of said metal salt or aqueous solutions are uniformly sprayed onto both. sides of the hot-dip galvanized surface. Then, the metal salts are decomposed to form the thin layer alloy on the galvanized surface.
  • the present method is not only limited to such a hot dipping method, but it is equally applicable for the electroplated zinc layer or another coated layer by other methods. If the one according to the hot-dip galvanized method, or which has been once cooled to the ordinary temperature or under 300 C. is again heated up to the above said temperatures and is appropriately molten. This invention can be just similarly applied to it.
  • Iron is most usually adopted as the metal which can be alloyed with zinc, but sometimes copper or tin can be also chosen.
  • the present method uses as the surface treating agent one or more than two of a halide, nitrate or sulfate of those metals and a very thin film is formed on the zinc surface. This is the most important purpose of the invention.
  • salts are used as a surface treating agent.
  • the effect of surface-alloying may be more promoted by means of any one or a mixture selected from Group I or Group II of the Periodic Table, complex salts above mentioned salt and fluoride of boron titanium or silicon; sodium chloride, calcium chloride, ammonium chloride, ammonium fluoride, ammonium hydrogen fluoride, zinc chloride, sodium borofiuoride, ammonium siliconfluoride, sodium titanium fluoride, is further added to the spraying of powders or aqueous solution of the above metal salts as an accelerating agent of said reaction or that of the group consisting of the diluent zinc white, alumina or talc, as a diluting agent.
  • the evaporating hydrochloric acid or nitric acid is appropriately added to the solution to adjust the acidity, thereby effecting advantageously.
  • these accelerators are not critical but assistant agents for promoting the alloying.
  • the main agents is any one or a mixture selected from the group including halide, nitrate and sulfate of metal.
  • the galvanized strip through this invention method als brings the satisfactory results in the paint adhesion in each case of spraying metal salt powders and spraying aqueous solution, that is, the coated surface obtained by this method has the paint adhesion equal to that of products of galvannealing method in the case of using iron salt at spraying.
  • the coated surface obtained by this method has the paint adhesion equal to that of products of galvannealing method in the case of using iron salt at spraying.
  • melamine paint was coated on the surface of galvanized strip obtained in the later mentioned Examples 3 and 4 so as to examine its adherence, it showed the excellent equal to that of the products of 4 the galvannealing method.
  • the satisfactory paint adhesion could not be obtained without the surface treatment for painting.
  • the method of applying surface treating agents to the galvanized surface is not limited only to spraying, but adopts the roll application, electrostatic spraying or any methods available.
  • the present method brings galvanized steel products which have been voluntarily adjusted from the silver-grey and uniform surfaces having no spangle to the surface with minimized spangle having dots of alloy of zinc and said metal. Since the above said alloy layer is very thinly formed on the coated surface, the forming properties of the coating is kept well which is the same as the conventional hot-dip coating.
  • the treating method thereof is enough to spray metal salt to the surface to alloy for short period. The surface after treating is often partially covered with black-brown oxides which are easily removed by washing with brushing.
  • Example 1 When the powders of ferrous chloride of 60 mesh were sprayed 1 g./m. to the surface of galvanized steel strip at a temperature of 450 C. such a surface was obtained which had minimized spangle with rough surface of ironzinc alloy.
  • Example 2 When the particle size of ferrous chloride of Example 1 was changed into mesh, such a surface was obtained as approximately uniform iron-zinc alloy.
  • Example 3 When 30% aqueous solution or ferrous chloride was sprayed 50 mL/m. to the surface of galvanized steel strip at a temperature of 450 C., such analloyed surface was obtained as silver-white, uniform, smooth, 2 to 3 microns in thickness and having no spangle.
  • the photomicrograph of the cross-section of this strip surface has been illustrated in the drawing, wherein A is the steel substance, B is the zinc layer and C is the alloy surface according to this present treatment.
  • Example 4 When concentrated hydrochloric acid was added 20 ml./l. to the 50% aqueous solution of ferric chloride and it was sprayed 200 mL/m. to the galvanized steel strip at a temperature of 480 C., the silver-grey surface having no spangle was obtained.
  • Example 5 When ammonium chloride was added 30 g./l. to the 10% aqueous solution of ferrous chloride and it was sprayed ml./m. to the galvanized steel strip at a temperature of 430 C., the silver-white surface of thin alloy layer was obtained which had no spangle at all.
  • Example 6 When the 50% aqueous solution of ferrous chloride was sprayed 30 ml./m. to the solidified surface of the galvanized layer which was cooled down to 380 C., the silver-grey surface of thin iron-zinc alloy layer was obtained on the uneven zinc surface having spangle.
  • Example 7 When the 30% aqueous solution of ferrous nitrate was sprayed 100 mL/m. to the surface of the galvanized steel strip at a temperature of 450 C. the silver-grey surface having no spangle was obtained.
  • Example 8 When the solution containing ammonium ferrous sulfate and 1% ammonium silocofiuoride was sprayed 100 mL/m. to the surface of the galvanized steel strip at a temperature of 450 C., the thin silver-grey surface having no spangle was obtained.
  • a method for improving the surface of galvanized steel consisting in zinc-coating a. steel by a hot-dip galvanizing process, spraying powders of 30 to 150 mesh, of one or a mixture selected from the group including halide, nitrate and sulfate of metal on said zinc-coating layer, while still in its molten state, and then further forming a thin alloying layer of said metal-zinc on said zinc-coating layer.
  • Method of improving the surface of galvanized steel material as described in claim 1 including adding sodium borofluoride as reacting accelerator.
  • Group A chloride or fluoride of Li, K, Na, NH,
  • Group B chloride of Mg, Ca, Zn, Cd, Ba

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Coating With Molten Metal (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
US00819251A 1968-04-25 1969-04-25 Method of improving the surface of galvanized steel material Expired - Lifetime US3712826A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP43027587A JPS4937693B1 (ja) 1968-04-25 1968-04-25

Publications (1)

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US3712826A true US3712826A (en) 1973-01-23

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Country Status (7)

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US (1) US3712826A (ja)
JP (1) JPS4937693B1 (ja)
BE (1) BE732062A (ja)
FR (1) FR2007519A1 (ja)
GB (1) GB1225592A (ja)
LU (1) LU58486A1 (ja)
NL (1) NL142458B (ja)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3951723A (en) * 1972-05-22 1976-04-20 Monsanto Company Bonding fibers to rubber with resol condensates of unsaturate-resorcinol polymers
US4568569A (en) * 1983-02-28 1986-02-04 Stein Heurtey Method and apparatus for providing composite metallic coatings on metallic strips
US5049453A (en) * 1990-02-22 1991-09-17 Nippon Steel Corporation Galvannealed steel sheet with distinguished anti-powdering and anti-flaking properties and process for producing the same
US5711990A (en) * 1995-10-19 1998-01-27 Sollac Method of coating sheet metal
EP1831419A1 (en) * 2004-12-28 2007-09-12 Posco Co., Ltd. Galvanized steel-sheet without spangle, manufacturing method thereof and device used therefor
US20210285082A1 (en) * 2018-07-02 2021-09-16 Nippon Telegraph And Telephone Corporation Galvanized Member
CN115279945A (zh) * 2020-02-28 2022-11-01 奥钢联钢铁有限责任公司 对钢带进行电解镀锌形成条件锌层的方法

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE883723A (fr) * 1980-06-09 1980-12-09 Centre Rech Metallurgique Procede de traitement superficiel de surfaces protegees par un revetement metallique
JPS59135098U (ja) * 1983-02-28 1984-09-10 株式会社安川電機 モ−タの制動装置
FR2560219B1 (fr) * 1984-02-27 1989-09-29 Stein Heurtey Procede et dispositif pour l'amelioration des proprietes physico-chimiques des toles revetues a chaud
US4873153A (en) * 1987-06-25 1989-10-10 Occidental Chemical Corporation Hot-dip galvanized coating for steel

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3951723A (en) * 1972-05-22 1976-04-20 Monsanto Company Bonding fibers to rubber with resol condensates of unsaturate-resorcinol polymers
US4568569A (en) * 1983-02-28 1986-02-04 Stein Heurtey Method and apparatus for providing composite metallic coatings on metallic strips
US5049453A (en) * 1990-02-22 1991-09-17 Nippon Steel Corporation Galvannealed steel sheet with distinguished anti-powdering and anti-flaking properties and process for producing the same
US5711990A (en) * 1995-10-19 1998-01-27 Sollac Method of coating sheet metal
EP1831419A1 (en) * 2004-12-28 2007-09-12 Posco Co., Ltd. Galvanized steel-sheet without spangle, manufacturing method thereof and device used therefor
US20080206592A1 (en) * 2004-12-28 2008-08-28 Posco Galvanized Stell-Sheet Without Spangle, Manufacturing Method Thereof and Device Used Therefor
EP1831419A4 (en) * 2004-12-28 2009-08-12 Posco Co Ltd GALVANIZED STEEL SHEET WITHOUT FLOWERING, ITS MANUFACTURING METHOD AND ULTILIZED DEVICE FOR MANUFACTURING THE SAME
AU2005320450B2 (en) * 2004-12-28 2011-01-20 Posco Galvanized steel-sheet without spangle, manufacturing method thereof and device used therefor
US7914851B2 (en) 2004-12-28 2011-03-29 Posco Method of manufacturing hot-dipped galvanized steel sheet
US20210285082A1 (en) * 2018-07-02 2021-09-16 Nippon Telegraph And Telephone Corporation Galvanized Member
CN115279945A (zh) * 2020-02-28 2022-11-01 奥钢联钢铁有限责任公司 对钢带进行电解镀锌形成条件锌层的方法

Also Published As

Publication number Publication date
LU58486A1 (ja) 1969-07-22
NL142458B (nl) 1974-06-17
DE1921086B2 (de) 1973-02-08
BE732062A (ja) 1969-10-01
DE1921086A1 (de) 1970-06-18
GB1225592A (ja) 1971-03-17
JPS4937693B1 (ja) 1974-10-11
NL6906311A (ja) 1969-10-28
FR2007519A1 (ja) 1970-01-09

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