US3530013A - Process for the production of coloured coatings - Google Patents

Process for the production of coloured coatings Download PDF

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US3530013A
US3530013A US574684A US3530013DA US3530013A US 3530013 A US3530013 A US 3530013A US 574684 A US574684 A US 574684A US 3530013D A US3530013D A US 3530013DA US 3530013 A US3530013 A US 3530013A
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colour
zinc
yellow
bath
alloy
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Robert W Smyth
Gerald P Lewis
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Teck Metals Ltd
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Teck Metals Ltd
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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
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C13/00—Alloys based on tin
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C18/00—Alloys based on zinc
    • 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
    • C23C2/04—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
    • C23C2/08—Tin 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
    • C23C2/261—After-treatment in a gas atmosphere, e.g. inert or reducing atmosphere
    • 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
    • C23C2/28—Thermal after-treatment, e.g. treatment in oil bath
    • C23C2/29—Cooling or quenching
    • 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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
    • C23C8/10—Oxidising
    • 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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/80—After-treatment
    • 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
    • Y10S359/00—Optical: systems and elements
    • Y10S359/90—Methods
    • 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.]
    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12583—Component contains compound of adjacent metal
    • Y10T428/1259—Oxide

Definitions

  • This invention relates to a process for the production of coloured coatings and is particularly directed to a process for the production of coloured zinc coatings and to zinc alloy coating compositions therefor.
  • the production of coloured metal surfaces by oxidation of a metal is known as, for example, in the tempering of steels to increase toughness, the degree of tempering being characterized by specific surface colours.
  • the tempering process, and attendant colour which is a measure of the degree of tempering, can be arrested as desired by quenching.
  • Another object of the invention is the provision of a tightly adherent coloured galvanized coating having the normal corrosion resistant properties of zinc.
  • FIG. 1 is a graph illustrating the effect of bath temperature and composition on yellow colour formation for an Zn-Mn alloy
  • FIG. 2 is a graph illustrating the effect of bath temperature and cooling rate on variable colour formation for a Zn-Mn alloy
  • FIG. 3 is a graph illustrating the effect of bath temperature and cooling rate on variable colour formation for a Zn-Ti alloy.
  • FIG. 4 is a graph illustrating the effect of bath temperature and cooling rate on variable colour formation for a Zn-V alloy.
  • coloured zinc alloy coatings can be produced on surfaces of various metals such as iron, steel, copper, nickel, zinc and other metals, on surfaces of zinc-coated articles and on surfaces of nonmetallic materials such as graphite by applying to said surfaces a coating of zinc having alloyed therewith an oxygen-avid addition agent such as manganese, titanium and vanadium in amount sufficient to form, upon reaction of the surface of said coating with oxygen, an oxide film on said coating having light interference colours.
  • an oxygen-avid addition agent such as manganese, titanium and vanadium in amount sufficient to form, upon reaction of the surface of said coating with oxygen, an oxide film on said coating having light interference colours.
  • the colours formed on the surfaces of zinc coatings containing alloying elements are due to light interference effects produced by transparent oxide films formed on the metal surfaces and are caused by the destructive interference of light waves reflected from the front and back surfaces of the film.
  • light Waves When light Waves are reflected from a thin transparent film, those reflected from the back surface are retarded with respect to those from the front surface by an amount 2er, where n is the index of refraction of the film and t is the thickness. 'I'his assumes normal incidence and ignores any difference in phase change due to reflection at the two interfaces. When the retardation is equal to an odd number of half-wavelengths, destructive interference will occur.
  • the second and third interference bands are affecting the red and violet ends of the spectrum respectively, with the result that the film appears green for the first time as indicated in Table I.
  • Table I As the film thickness increases further, several interference bands occur in the visible spectrum at the same time and the colouring effects beyond the fourth order decrease and disappear.
  • the characteristics of the interference bands are dependent on the index of refraction and absorbing power of the film, as well as on the reflectivity of the surfaces. Hence, differing colour ⁇ shades and intensities and to some extent, different colour sequences result from interfereence effects on films of different materials.
  • the coating colour selectively attained can be achieved in part by regulating the length of effffective time of reaction of oxygen with the zinc alloy for the growth of an oxide film.
  • the Zinc-alloy coating can be applied to the metal surfaces by spraying said alloy in molten form onto said surfaces with or without subsequent heat treatment, or by immersing or dipping said surfaces into a bath of the molten alloy.
  • the thus-coated surfaces are contacted with a free-oxygen containing gas such as air and preferably cooled in said atmospheer for the formation of a thin, oxide film on the coating producing the desired colour; the eventual colour achieved being controlled by the thickness of the oxide film which is dependent upon the alloy composition, alloy temperature, and the period of time the coating is permitted to react with oxygen, i.e., the rate of cooling relative to the initial coating temperature.
  • FIG. 1 the effect of bath or initial coating temperature and composition of zinc-manganese baths is shown relative to time of contact with the oxygen in air for the occurrence of first, second and third orders of the colour yellow on the melt surface, the manganese content of the Zinc bath being controlled at levels of 0.04%, 0.07%, 0.11% and 0.33% by weight. It will be evident from the graph that the occurrence of first order yellow at manganese concentrations of 0.11% and 0.33% was almost instantaneous at all temperatures above about 419 C., ie., the melting point of the alloy. At manganese concentrations of 0.07% and below, however, considerable time was necessary for the occurrence of first order yellow even at bath temperatures up to about 480 C.
  • Comparable tests conducted on zinc-vanadium alloy baths established the occurrence of first order yellow at a bath temperature of 500 C. at 8 seconds for a 0.018% by weight vanadium content, 15 seconds for a 0.011% by weight vanadium content, and 19 seconds for a 0.009% by weight vanadium content.
  • the first order yellow appeared at 3 seconds at vanadium concentrations in the zinc of 0.076% and 0.46% by weight at an alloy bath temperature of 500 C.
  • the colour occurrence was therefore relatively consistent at vanadium contents by weight in the zinc at and above about 0.075%, the practical lower limit being about 0.1 by weight.
  • the upper operable limit is determined by the solubility of vanadium in zinc at the operating temperature and the upper practical limit is determined by the eutectic composition.
  • the lower practical limit is 0.1% by weight titanium in Zinc ⁇ and the upper practical limit is the eutectic composition.
  • the upper operable limit is determined by the solubility of titanium in zinc at the operating temperature.
  • the preferred lower limit for manganese, vanadium and titanium of 0.1% by weight in the zinc permits cornpensation for loss of the alloying element in the bath.
  • the upper practical limit for alloys of manganese, vanadium and titanium with zinc determined by the respective eutectic composition avoids precipitation of the addition agents from the solutions upon temperature variation of the bath which can be altered to provide an expedient technique for control of coating colour.
  • the eutertic composition for the above alloys of manganese and titanium with zinc can be obtained from the text by Hansen entitled The Constitution of Binary Alloys.
  • the eutectic com position for zinc-vanadium alloy was obtained from Trausactions of the Metallurgical Society of AIME, vol. 227, page 485, 1963.
  • the preferred range for the alloy compositions of manganese, vanadium and titanium with zinc is therefore from about 0.1% by weight to about the eutectic composition of the respective alloying element in Zinc, that is, from about 0.1% to about 0.45% for manganese and titanium, and from about 0.1% to about 0.15% for vanadium.
  • 555 24 40 40 1st Red-very light.
  • 555 30 128 1st Yellow-light.
  • Zn-0.004% V 555 16 L85 1st Yellow-light.
  • the following example illustrates the effect of regulating the length of effective time of reaction of oxygen with the zinc alloy.
  • a series of 16-, 24- and 30-gauge pregalvanized panels and 1/2 diameter rods were dipped itno melts of zinc containing 0.1% manganese, zinc containing 0.15% titanium and zinc containing 0.15% vanadium.
  • the panel immersion time and bath temperature were varied and the freezing time of the coating and final colour were noted. At each temperature level, the melt surface was skimmed and colour formation was also timed.
  • Results plotted on the graph in FIGS. 2, 3 and 4 show the effect of cooling rate and bath temperature on the formation of colours on the surface of dipped articles.
  • thc areas bounded by fine solid lines are the colours observed on the surface of the melt, representing a zero cooling rate
  • the areas bounded by heavy solid lines are the final colours that are formed on the surface of dipped articles, both upon exposure to air.
  • the areas defined by lboth groups of solid lines indicate the actual colours observed.
  • the broken lines represent the coating freezing times for 30, 24- and 16- gauge sheet specimens, air cooled at room temperature of 20 C., and the heavy solid-lined areas intersected indicate the nal colours that form on the specimen surfaces when dipped at particular temperatures.
  • Table III The observations tabulated in Table III may be made from the graphs of FIGS. 2-4; in all cases immersion times were sufficient for the specimens to attain bath temperature and the coatings were subsequently air cooled at room temperature (20 C.).
  • the foregoing examples relates to colours achieved where the dipped article was allowed to air cool from the bath temperature.
  • a colour appearing earlier in the colour sequence is formed.
  • Immersion times insuiiicient to attain the bath temperature also form colours appearing earlier in the sequence.
  • a colour appearing later in the colour sequence can be formed, as for example, where an article is dipped, held at both temperature (zero cooling rate) for a prolonged time, and then rapidly cooled -by quenching when the desired colour had formed.
  • the graphs indicate that the effect of cooling rate on colour formation is more pronounced on the zinc-manganese (Zn-0.1% Mn) alloy than on either the zinctitanium or zinc-vanadium (Zn-0.15% V) alloys.
  • the invention is free from hypothetical considerations, it is believed that the presence of the aluminum in amounts of 0.0005% and more results in the aluminum preferentially oxidizing to form a protective film of A1203 which prevents the formation of, for example, T102, V205, MnO or ZnO oxide films.
  • the A1203 layer is extremely thin, n0 light interference colours are obtained.
  • o isel'vcd. Zwalm, M11-0.00152, ust yellow, 3 se@ l A1 lst Silver, 100 sec.. G0 d' Yellow, 3 see D Some red at 100 sec. o' Yellow, 6 see D No change to 100 see. o' 40 ZIX).15%, Mn-O. 003% Lltglloyfllow, no change Light gold.
  • Table V lists the results of coating specimen -panels according to the process of the invention with zinc containing alloying elements from the group columbium, zirconium, thorium and mischmetal and the group cadmium, arsenic, copper, lead and chromium.
  • Alloying compositions of zinc with titanium, manganese, vanadium, columbium, zirconium, thorium or mischmetal provide coloured coatings on steel and pregalvanized materials at temperatures within the range of from about 419 C., i.e., the melting point of the alloy composition, to about 600 C. and above.
  • Alloying compositions of zinc with cadmium, arsenic, copper, lead or chromium provide coloured coatings on said substrates at temperatures of at least about 625 C.
  • titanium, manganese or vanadium in amounts of about 1.0% by weight in molten tin at an alloy bath temperature at about 500 C. permits production of coloured coatings on iron and steel surfaces by the process of the present invention. Although not as brilliant as zinc alloy colours, a complete range of colours has been produced with tin alloys at a bath temperature of 500 C.
  • the present invention provides a number of advantages. Colours produced by the process and compositions of the invention are reproducible and can readily be controlled by varying one or more of alloy bath composition and temperature and the rate of cooling of the molten surface in a free-oxygen containing atmosphere, i.e., varying the length of the time the alloy remains in its molten and relatively reactive state. Variegated colours, patterns and textures overlying zinc coatings can be produced providing, in combination, aesthetic effects andcorrosion resistant properties.
  • the coatings can be applied to substrates such as steel or zinc-coated materials in the form of sheet, wire, and formed articles such as expanded mesh, pipe and structural members.
  • a vprocess for the production of a coloured coating on an article comprising the steps of forming thereon a molten coating of an alloy of zinc and an oxygen-avid alloying element selected from the group consisting of titanium, manganese, vanadium, columbium, zirconium, thorium, mischmetal, cadmium, arsenic, copper, lead and chromium, said alloy having less than 0.002% by weight aluminum, said oxygen-avid alloying element being present in amount effective to produce an oxide -lm having discernible light interference colour eitects, contacting said molten coating with a free-oxygen containing gas for reaction therewith to provide thereon an oxide ilm having said colour eitects, and solidifying said molten coating provided with said oxide lm.
  • an oxygen-avid alloying element selected from the group consisting of titanium, manganese, vanadium, columbium, zirconium, thorium, mischmetal, cadmium
  • a process for the production of a coloured coating on a surface comprising the steps of applying thereto an alloy of zinc and an oxygen-avid alloying element selected from the group consisting of titanium, manganese, vanadium, columbium, zirconium, thorium, mischmetal, cadmium, arsenic, copper, lead, and chromium, said alloy having less than 0.002% by weight aluminum and said oxygen-avid element being present in amount effective to produce an oxide lm having discernible light interference colour effects to form a molten adherent coating thereon, forming an oxide lm on said coating having said colour elects by reacting said coating with an oxygen-containing atmosphere, and solidifying said molten coating provided with said oxide film.
  • an alloy of zinc and an oxygen-avid alloying element selected from the group consisting of titanium, manganese, vanadium, columbium, zirconium, thorium, mischmetal, cadmium, arsenic, copper, lead, and chro
  • a process for the production of a coloured coating on a surface comprising the steps of forming a substantially aluminum-free bath of zinc having an oxygen-avid alloying element therein selected from the group consisting of titanium, manganese, vanadium, columbium, zirconium, thorium, mischmetal, cadmium, arsenic, copper, lead and chromium, and present in amount effective to produce an oxide ilrn having discernible light interference colour effects, immersing the surface in said bath to form an adherent molten coating thereon, contacting said coating with a free-oxygen containing gas to provide an oxide lm having said colour effects, and solidifying said molten coating provided with said oxide lm.
  • an oxygen-avid alloying element selected from the group consisting of titanium, manganese, vanadium, columbium, zirconium, thorium, mischmetal, cadmium, arsenic, copper, lead and chromium
  • said oxygen-avid alloying element being selected from the group consisting of titanium, manganese, vanadium, columbium, zirconium, thorium and mischmetal and said molten coating having less than 0.002% by weight aluminum.
  • said oxygen-avid element being selected from the group consisting of cadmium, arsenic, copper, lead and chromium, said molten coating having less than 0.002% by weight aluminum.
  • said oxygen-avid alloying element consisting of at least about 0.02% by Weight manganese and said bath having less than 0.002% by Weight aluminum.
  • said oxygen-avid alloying element consisting of at least about 0.07% by weight manganese and said bath having less than 0.002% by weight aluminum.
  • said oxygen-avid alloying element consisting of at least about 0.001% by Weight titanium and said bath having less than 0.002% by weight aluminum.
  • said oxygen-avid alloying element consisting of at least about 0.008% by weight titanium and said bath having less than 0.002% by weight aluminum.
  • said oxygenavid alloying element consisting of at least about 0.001% by weight vanadium and said bath having less than 0.002% by weight aluminum.
  • said oxygen-avid alloying element consisting of at least about 0.075% by weight vanadium and said bath having less than 0.002% by weight aluminum.
  • said oxygenavid alloying element consisting of from about 0.1% by weight to about the respective eutectic composition of an element selected from the group consisting of manganese, titanium and vanadium and said bath having less than about 0.002% by weight aluminum.
US574684A 1966-07-11 1966-08-24 Process for the production of coloured coatings Expired - Lifetime US3530013A (en)

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CA965078 1966-07-11
US57468466A 1966-08-24 1966-08-24
AT1027867A AT291706B (de) 1966-07-11 1967-11-14 Verfahren zur Herstellung einer Zink- oder Zinnlegierung mit einer Oberflächenschicht, die Lichtinterferenzeigenschaften besitzt

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AT (1) AT291706B (de)
CA (1) CA850045A (de)
DE (1) DE1621435C3 (de)
GB (1) GB1195904A (de)
NL (1) NL148951B (de)
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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0269005A2 (de) * 1986-11-21 1988-06-01 NIPPON MINING & METALS COMPANY, LIMITED Gefärbte Zinkbeschichtung
US5022937A (en) * 1986-11-21 1991-06-11 Nippon Mining Co., Ltd. Colored zinc coating
US5141782A (en) * 1985-06-17 1992-08-25 Nippon Mining Co., Ltd. Colored zinc coating
US5541057A (en) * 1989-09-18 1996-07-30 Biostar, Inc. Methods for detection of an analyte
US5631171A (en) * 1992-07-31 1997-05-20 Biostar, Inc. Method and instrument for detection of change of thickness or refractive index for a thin film substrate
US5639671A (en) * 1989-09-18 1997-06-17 Biostar, Inc. Methods for optimizing of an optical assay device
US5955377A (en) * 1991-02-11 1999-09-21 Biostar, Inc. Methods and kits for the amplification of thin film based assays
US6060237A (en) * 1985-02-26 2000-05-09 Biostar, Inc. Devices and methods for optical detection of nucleic acid hybridization
US6569268B1 (en) 2000-10-16 2003-05-27 Teck Cominco Metals Ltd. Process and alloy for decorative galvanizing of steel
US20150152994A1 (en) * 2012-06-29 2015-06-04 Saint-Gobain Pam Outer coating for an iron-based buried piping element, coated piping element and method for depositing the coating
US20190376163A1 (en) * 2018-06-07 2019-12-12 Grillo-Werke Ag Highly malleable, ductile zinc strip

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0048270B1 (de) * 1980-03-25 1985-08-14 International Lead Zinc Research Organisation, Inc Zink-aluminium-beschichtungen
WO1984004335A1 (en) * 1983-04-22 1984-11-08 Stanford Res Inst Int Process for applying thermal barrier coatings to metals and resulting product
US5198026A (en) * 1989-04-27 1993-03-30 Nippon Mining Co., Ltd. Colored zinc powder, its method of production and method for producing colored article
JPH07110962B2 (ja) * 1989-04-27 1995-11-29 日鉱金属株式会社 着色亜鉛粉、その製造方法及び着色製品の製造方法
CA2161393A1 (en) * 1995-10-25 1997-04-26 Gary R. Adams Galvanizing alloy and process for reactive steels
DE102018128131A1 (de) * 2018-11-09 2020-05-14 Thyssenkrupp Ag Gehärtetes Bauteil umfassend ein Stahlsubstrat und eine Korrosionsschutzbeschichtung, entsprechendes Bauteil zur Herstellung des gehärteten Bauteils sowie Herstellverfahren und Verwendung

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US2263366A (en) * 1939-06-24 1941-11-18 Standard Oil Dev Co Suppressing coking on surfaces
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US6060237A (en) * 1985-02-26 2000-05-09 Biostar, Inc. Devices and methods for optical detection of nucleic acid hybridization
US6355429B1 (en) 1985-02-26 2002-03-12 Thermo Biostar Inc. Devices and methods for optical detection of nucleic acid hybridization
US5141782A (en) * 1985-06-17 1992-08-25 Nippon Mining Co., Ltd. Colored zinc coating
EP0269005B1 (de) * 1986-11-21 1993-09-08 NIPPON MINING & METALS COMPANY, LIMITED Gefärbte Zinkbeschichtung
EP0269005A2 (de) * 1986-11-21 1988-06-01 NIPPON MINING & METALS COMPANY, LIMITED Gefärbte Zinkbeschichtung
US5022937A (en) * 1986-11-21 1991-06-11 Nippon Mining Co., Ltd. Colored zinc coating
US5541057A (en) * 1989-09-18 1996-07-30 Biostar, Inc. Methods for detection of an analyte
US5639671A (en) * 1989-09-18 1997-06-17 Biostar, Inc. Methods for optimizing of an optical assay device
US5955377A (en) * 1991-02-11 1999-09-21 Biostar, Inc. Methods and kits for the amplification of thin film based assays
US5631171A (en) * 1992-07-31 1997-05-20 Biostar, Inc. Method and instrument for detection of change of thickness or refractive index for a thin film substrate
US6569268B1 (en) 2000-10-16 2003-05-27 Teck Cominco Metals Ltd. Process and alloy for decorative galvanizing of steel
US20150152994A1 (en) * 2012-06-29 2015-06-04 Saint-Gobain Pam Outer coating for an iron-based buried piping element, coated piping element and method for depositing the coating
US20190376163A1 (en) * 2018-06-07 2019-12-12 Grillo-Werke Ag Highly malleable, ductile zinc strip

Also Published As

Publication number Publication date
DE1621435A1 (de) 1970-07-16
NL148951B (nl) 1976-03-15
DE1621435B2 (de) 1973-10-04
NL6709633A (de) 1968-01-12
DE1621435C3 (de) 1975-07-24
AT291706B (de) 1971-07-26
SE351242B (de) 1972-11-20
GB1195904A (en) 1970-06-24
CA850045A (en) 1970-08-25

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