EP0177786B1 - Anti-corrosion treatment process for iron materials - Google Patents

Anti-corrosion treatment process for iron materials Download PDF

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Publication number
EP0177786B1
EP0177786B1 EP85111452A EP85111452A EP0177786B1 EP 0177786 B1 EP0177786 B1 EP 0177786B1 EP 85111452 A EP85111452 A EP 85111452A EP 85111452 A EP85111452 A EP 85111452A EP 0177786 B1 EP0177786 B1 EP 0177786B1
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EP
European Patent Office
Prior art keywords
parts
zinc
iron
halogenated hydrocarbon
acid
Prior art date
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Expired
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EP85111452A
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German (de)
English (en)
French (fr)
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EP0177786A1 (en
Inventor
Toshio Nishikawa
Shigeru Omori
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.)
Dowa Iron Powder Co Ltd
Nippon Dacro Shamrock Co Ltd
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Dowa Iron Powder Co Ltd
Nippon Dacro Shamrock Co Ltd
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Publication of EP0177786A1 publication Critical patent/EP0177786A1/en
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Classifications

    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • C23C22/37—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also hexavalent chromium compounds
    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/02—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using non-aqueous solutions
    • C23C22/04—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using non-aqueous solutions containing hexavalent chromium compounds
    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/78—Pretreatment of the material to be coated
    • 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
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/02—Coating starting from inorganic powder by application of pressure only
    • C23C24/04—Impact or kinetic deposition of particles
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates

Definitions

  • This invention relates to an anti-corrosion treatment process for iron materials (iron and iron alloys). More particularly, this invention relates to an anti-corrosion treatment process for iron materials comprising forming a zinc coating on the surface of an iron material and thereafter treating the coated surface with a non-aqueous chromating treatment composition.
  • the method of Japanese Laid-Open Patent Publication No. 45372/81 comprises projecting onto the surface of an iron material a blast material which is an aggregation of independent particles comprised of a core substantially of iron a crust substantially of zinc which is formed on the surface of the core particle with iron-zinc alloy layers between the core and the crust.
  • a blast material which is an aggregation of independent particles comprised of a core substantially of iron a crust substantially of zinc which is formed on the surface of the core particle with iron-zinc alloy layers between the core and the crust.
  • substantially of iron means the core is pure iron or iron alloy containing a small amount of silicon, manganese, chromium, nickel, etc.
  • substantially of zinc means pure zinc or zinc alloy containing a small amount of copper, aluminum, magnesium, silicon, tin, etc.
  • the intermediate iron-zinc layers are a plurality of layers of different Fe-Zn intermetallic compounds.
  • the zinc blast material can be prepared by melt coating or diffusion coating.
  • the proportion of iron and zinc in the blast material is 10-95% by weight of iron to 5-90% by weight of zinc, preferably 10-70% by weight of iron to 90-30% by weight of zinc, more preferably, 15-65% by weight of iron to 85 ⁇ 35% by weight of zinc. A suitable proportion in this range is selected in accordance with the intended use.
  • the particle size is generally under 16 mesh. Blasting can be effected using blast machines of various types including tumbler type, barrel type, etc.
  • the mechanical plating method is advantageous in that equipment cost and energy consumption are low and the environmental pollution factors are much limited.
  • the metlhod and material of said Japanese Patent Publication have radically overcome the defects of earlier mechanical plating, zinc-coating formed by this method is still insufficient in corrosion resistance and red rust is generated on an iron material coated with zinc at 100 mg/dm 2 by this method within 24 hours in the salt spray test. It is considered that this is because the formed coating film is of an iron-zinc alloy and is porous.
  • blast zinc plating improved mechanical plating method
  • a rather simple anti-corrosion measure is the chromating process, of which there are three types of the baking chromating process, aqueous chromating process and non-aqueous chromating process.
  • the baking chromating process comprises coating a surface to be treated with a composition comprising a water-soluble chromic acid compound, a reducing agent and water, and baking the coated material to reduce the chromic acid compound so as to form a water-insoluble chromate coating film.
  • a composition comprising a water-soluble chromic acid compound, a reducing agent and water
  • baking the coated material to reduce the chromic acid compound so as to form a water-insoluble chromate coating film.
  • "Hynack" of Pennwalt Company, "Dacromet 100" of Diamond Shamrock Company, etc. are well known agents for the process of this type.
  • the formation of a coating film in the baking chromating process is based on reduction of the chromic acid on heating in the presence of a reducing agent, and therefore, the reduction of the chromic acid is effected without fail, even if the substrate is an iron-zinc alloy coating formed by the blast zinc plating.
  • the aqueous chromating process comprises treating the surface of a galvanized steel material with a mixture of a water-soluble chromic acid compound, a strong acid and water. This is an age-old well known technique disclosed in several text books such as "Mekki Gijutu Binran” published by Nikkan Kogyo Sinbunsha, etc.
  • the aqueous chromating treatment is effective for pure zinc, but is not so effective for iron-zinc materials as for pure zinc, since the formed film is considerably irregular.
  • the aqueous chromating composition is a mixture of water, a water-soluble chromic acid compound and a strong acid such as sulfuric acid, the zinc reacts with the strong acid on the surface being treated to produce nascent hydrogen, which reduces the chromic acid to form a chromate film on the surface.
  • the reaction takes place at the zinc-plated surface and therefore, a thick film cannot be easily formed.
  • the aqueous chromating solution produces waste liquid containing a large amount of chromic acid and thus the cost of the equipment required for waste liquid disposal and the operation therefor is huge. Therefore, it is not suitable to combine this process with the blast zinc plating, which is free from the problem of disposition of waste liquid.
  • the composition used in the non-aqueous chromating process essentially consists of a chromic acid compound, an organic solvent (usually halogenated hydrocarbon) and an alcohol as a solubilizer, and it may contain a stabilizer and a reaction promotor for formation of chromate film and they are disclosed in Japanese Patent Publication No. 5288/65 (Du Pont), Japanese Patent Publication No. 3363/67 (Du Pont), Japanese Laid-Open Patent Publication No. 62970/81 (Tokuyama Soda), Japanese Laid-Open Patent Publication No. 97476/80 (Nippon Paint) and Japanese Laid-Open Patent Publication No. 139679/81 (Nippon Paint). Rather recently, a very stable non-aqueous chromating treatment composition containg chlorofluorocarbon as the solvent was invented (European Patent Application No. EP-A-0 170 988).
  • any non-aqueous chromating treatment composition can be used, but it will be advantageous to use a composition in which a chloroflurocarbon solvent is used.
  • This invention provides a process for treating the surface of iron materials comprising forming a zinc coating layer on the surface of an iron material by projecting a blast material which is an aggregation of particles each comprising a core comprising substantially iron, intermediate layers of iron-zinc alloys and an outer crust substantially comprising zinc; and treating the thus zinc-coated surface with a non-aqueous chromating composition comprising a chromic acid compound, halogenated hydrocarbon solvent, an alcohol solubilizer.
  • the process of this invention compensates for the insufficiency in the corrosion prevention effect of blast zinc plating without impairing its advantage.
  • the iron particles for the cores of the blast material of this invention can be manufactured by any known method such as the carbon reduction process, gas reduction process, atomizing method, mechanical pulverization process, etc. It is desirable to modify the shape and properties thereof by cold working and/or heat treatment in accordance with the treatments which the particles have undergone. That is to say, the particles should be made as round as possible, the surface layer is hardened by cold working, so as to obtain iron particles having excellent abrasion resistance and impact resistance. Further, the toughness of the iron particles can preferably be improved by alloying some of the abovementioned elements. Such improvement in the toughness of the core iron particles contributes to prevention of fracture of the blast material having zinc crust, although fracture of the blast material is not practically observed.
  • the zinc for forming the zinc crust of the blast material contains 3-5% aluminum and/or 0.2-1 % copper.
  • the impact resistance of the blast material is improved by alloying such elements.
  • the blast material having an alloy crust is prepared by the melt coating process.
  • the blast material having a neat zinc crust can also be prepared by the diffusion process.
  • the diffusion process comprises heating a mixture of iron particles and zinc powder. Specifically, neat iron or alloyed iron particles are mixed with zinc powder, preferably further with 0.5-3% on the basis of the metals of ammonium halide, preferably chloride added, in a container of iron or silicon carbide, at a temperature in the range of 400-700°C for 3-20 minutes so as to form zinc-iron alloy layers and a zinc crust around the iron cores.
  • This process can be carried out by a batch-wise or continuously. When it is continuously carried out by feeding iron powder into an auger type or a pusher type externally heated furnace. The resulting material is made into zinc-crusted iron particles by simple crushing treatment.
  • the thus obtained blast material is substantially the same as obtained by the melt coating process.
  • the organic solvent used in the non-aqueous chromating treatment is a halogenated hydrocarbon (this term encompasses chlorofluerocarbon) having 1-2 carbon atoms and chlorine and/or fluorine atoms as well as possible remaining hydrogens. That is, methylene chloride, chloroform, carbon tetrachloride, trichloroethane, trichloroethylene, perchloroethylene, trichlorotrifluoroethane, trichloromonofluoromethane, dichlorotetrafluoroethane, tetrachlorodifluoroethane, etc. and mixtures thereof can be suitably used.
  • Chromic acid used in this invention is what is called chromic acid anhydride or chromium trioxide having a chemical formula Cr0 3 .
  • Said chromic acid anhydride is used in an amount of 0.01-10 parts preferably 0.1-8 parts, more preferably 0.2-5 parts by weight hereinafter referred to simply as parts per 100 parts of the halogenated hydrocarbon solvent.
  • the solubilizer used in this invention is a secondary or tertiary alcohol having 3-20 carbon atoms which is soluble in said halogenated hydrocarbon solvent.
  • secondary propanol, tertiary butanol, tertiary amyl alcohol, triphenyl carbinol, etc. can be suitably used.
  • Tertiary butanol (hereinafter referred to as t-butanol) is most suitable because it dissolves homogeneously in most of the compositions of this invention, is stable over a long period and is inexpensive. At least 1 part of the solubilizer per 100 parts of the halogenated hydrocarbon solvent is required, and 20 parts or larger amount can be used.
  • solubilizer As an increased amount of the solubilizer is used, an increased amount of chromic acid anhydride can be dissolved. With less than 1 part of the solubilizer, solubilization in not sufficient. More than 20 parts thereof can be used, but it may make the composition inflammable according to the use condition. Therefore up to 20 parts will be preferably used. The more preferred range is 2-10 parts.
  • the stabilizer used in this invention can be selected from a wide range of known compounds such as amines, quinones, nitro-, azo-, azoxyaromatic compounds, thiourea, dienes, organic nitrite salt, zinc fluoride, zinc oxide, etc.
  • the stabilizer is unnecessary when chlorofluorocarbon is used as the solvent, and therefore, chlorofluorocarbon is preferred.
  • Examples of the stabilizer are: N-nitrodiphenylamine, azoxybenzene, hydroquinone, diisobutylamine, pentadiene, amyl nitrite, etc. These compounds can be used singly or in combinaticn, and are used in an amount 0.001-5 parts per 100 parts of the halogenated hydrocarbon solvent. Outside of this range, little or no effect is expected or no correspondingly better effect is expected.
  • the preferred range is 0.05-3 parts and the more preferred range is 0.1-2 parts.
  • the reaction promotor used in the process of this invention is hydrogen fluoride, an organic acid, water, etc. This component is not essential and can be omitted from the composition depending upon the condition.
  • An organic acid having 1-20 carbon atoms can be used.
  • an organic acid having a general formula R-(COOH) n wherein R is may be a straight-chained, branched or cyclic hydrocarbyl group, and may be substituted, and n is an integer of 1-3.
  • these organic acids are: formic acid, acetic acid, lactic acid, stearic acid, oxalic acid, fumaric acid, maleic acid, malic acid, etc. and mixtures of thereof.
  • reaction promotors can suitably be used in an amount 0.001-10 parts, preferably 0.003-1 part, and more preferably 0.005-0.5 part per 100 parts of the halogenated hydrocarbon solvent, and hydrogen fluoride and organic acids are preferably in an amount of not more than preferably 0.12 part, Water should preferably be used within the limit that it dissolves homogeneously in the system. Under the lower limit, the effect as a reaction promotor is not expected, and above the upper limit, corrosion effect thereof on the materials or articles to be treated and the apparatus becomes manifested or the homogenity of the system, is impaired.
  • the preferred content of the reaction promotor is 0.005-0.12 part.
  • the chromating treatment composition used in the process of this invention is substantially non-aqueous, and the halogenated hydrocarbon solvent acts as a degreaser as well as makes the system non- flammable; the solubilizer renders all the ingredients to dissolve homogeneously in the system. It is essential that all the ingredients dissolve homogeneously in the system. If not, the resulting coating is non-uniform and does not bring about satisfactory anti-corrosion effect.
  • the procedure of the chromating treatment is as follows.
  • the chromating treatment composition is kept at a temperature between 5°C and the boiling point and metal articles to be treated are contacted therewith for 1 second - 60 minutes, preferably for 30 seconds to 5 minutes. Thereafter, the metal surface is dried.
  • the temperature of the composition is lower than 5°C, the chromating reaction does not substantially proceed; and when the contact time is shorter than 1 second, substantially effective coating is not obtained; and when it is longer 60 minutes, non-uniform coating is sometimes formed which is not desirable because of poor appearance.
  • Iron materials to be treated should preferably be degreased beforehand. However, not too large amount of oils on the surface thereof can be removed during the chromating treatment.
  • the process of this invention is substantially non-aqueous all through the process, and no measures for waste liquid disposal are required.
  • excellent anti-corrosion coating can be formed very economically.
  • product (III) is best in corrosion resistance, product (I) comes second and product (11) is inferior. But the cost for preparing product (III) is three times that of (I). Corrosion resistance of product (II) is sufficient for ordinary uses. Thus it can be said that product (III) is of excessively superior quality.
  • Iron particles smaller than 16 mesh were filled in a cylindrical container of silicon carbide, and annealed using a tunnel kiln furnace at 920°C with a residence time of 6 hours. The lump taken out was crushed and 16-32 mesh, 32-48 mesh, 48 ⁇ 60 mesh and 60-80 mesh fraction were collected.
  • the particle fractions were mixed with a molten zinc alloy (4% aluminum, 0.5% copper and the balance zinc) kept at 620 ⁇ 5°C under the condition indicated in Table 1.
  • the mixture was cooled in the atmosphere, crushed with a hammer mill and finally pulverized with a impact type high speed pulverizer and screened.
  • the properties of the obtained blast materials are indicated in Table 2.
  • Example 2 The same iron particles as used in Example 1 were mixed with zinc powder in proportions indicated in Table 3, and further 0.6% on the basis of the weight of the metals of ammonium chloride was added and mixed for the purpose of removing oxide film of the zinc powder.
  • the mixture was filled in a cylindrical container of iron and placed in a heating furnace heated at 650°C, by which a reaction temperature of 550°C was rapidly achieved in the container, and the container was kept in the furnace for five minutes. Thereafter the container was cooled in the atmosphere and the resulting crusted particles were taken out.
  • zinc is heated higher than its melting point, iron particles and zinc do not coagulate prevented by the oxide film existing on the surface of the zinc powder. Therefore, no crushing is required.
  • Hexagonal head mild steel bolts 10 mm x 40 mm in size were degreased with trichloroethane vapor, and thereafter the bolts were subjected to projection of 32-48 mesh iron-zinc blast material obtained by Example 1 for 30 minutes so that the surface of them was coated with iron-zinc alloy with a coating weight of 100 mg/dm 2 .
  • the thus obtained iron-zinc-coated bolts were treated with the above described non-aqueous chromating treatment composition. Each 5 pieces of the treated samples were subjected to the following corrosion tests.
  • test was carried out in accordance with the method as stipulated in ASTM-B368-68 (JIS ⁇ Z-0201-1971), provided that the pH of the spray solution was 3.5.
  • the evaluation of the results was the same as above.
  • a sprinkler was provided on an asphalt-paved area and samples were placed around the sprinkler within 1.4 m in a concentrical arrangement. Water was continuously sprayed at a rate of 0.3-0.4 m 3 /hr.
  • a chromating treatment solution was prepared by dissolving 0.5 part chromic acid anhydride, 0.01 part zinc fluoride and 10 parts t-butanol in 100 parts trichloroethylene to form a homogeneous solution.
  • Samples of the above-described iron-zinc coated bolt were dipped in the above solution at the refluxing temperature for 1 minute, washed with the solvent vapor and then cooled to room temperature. The samples were subjected to the above-described various tests. The results are indicated in Table 4.
  • a chromating treatment solution was prepared in the same manner as in Example 3 except that 100 parts methylene chloride was used as the solvent. The same samples were treated in the same manner. The same tests were carried out and the results are indicated in Table 4.
  • a chromating treatment solution was prepared in the same manner as in Example 1 except that 100 parts perchlroethylene was used as the solvent. The same samples were treated in the same manner. The same tests were carried out and the results are indicated in Table 4.
  • a chromating treatment solution was prepared by dissolving 15 parts t-butanol and 2 parts chromic acid anhydride in 100 parts trichlorotrifluoroethane to form a homogeneous solution. The same treatment and tests as in Example 3 were repeated and the results as shown in Table 4 were obtained.
  • a chromating treatment solution was prepared by dissolving 15 parts t-butanol, 2 parts chromic acid anhydride and 0.01 part oxalic acid in 100 parts trichlorotrifluoroethane to form a homogeneous solution.
  • the same treatment and tests as in Example 3 were repeated and the results as shown in Table 4 were obtained.
  • Example 7 In the same manner as in Example 7 except that 0.01 part fumaric acid was used instead of oxalic acid. Immersion for the reaction was carried out at 40°C (below boiling point) and the results as shown in Table 4 were obtained.

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  • Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
EP85111452A 1984-09-11 1985-09-10 Anti-corrosion treatment process for iron materials Expired EP0177786B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP188784/84 1984-09-11
JP59188784A JPS6167773A (ja) 1984-09-11 1984-09-11 金属表面処理法

Publications (2)

Publication Number Publication Date
EP0177786A1 EP0177786A1 (en) 1986-04-16
EP0177786B1 true EP0177786B1 (en) 1989-03-01

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EP (1) EP0177786B1 (ja)
JP (1) JPS6167773A (ja)
KR (1) KR890004790B1 (ja)
AU (1) AU562978B2 (ja)
BR (1) BR8504350A (ja)
CA (1) CA1243561A (ja)
DE (1) DE3568458D1 (ja)

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* Cited by examiner, † Cited by third party
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JPS61266579A (ja) * 1985-05-22 1986-11-26 Nippon Dakuro Shamrock:Kk 金属表面処理法
JPS6293383A (ja) * 1985-10-17 1987-04-28 Sumitomo Metal Ind Ltd 耐食性に優れた表面処理鋼材およびその製造方法
JPH0673932B2 (ja) * 1986-04-11 1994-09-21 住金鋼材工業株式会社 化粧建材およびその製造に用いられる化粧鋼材製造方法
JPS63230885A (ja) * 1987-03-20 1988-09-27 Dowa Teppun Kogyo Kk 金属表面処理方法
JP2950481B2 (ja) * 1990-11-29 1999-09-20 株式会社日本ダクロシャムロック 金属表面処理方法
JPH10204654A (ja) * 1997-01-21 1998-08-04 Aoyama Seisakusho Co Ltd 金属表面処理方法
FR2790983B1 (fr) 1999-03-15 2001-06-22 Dacral Sa Procede de formage de pieces metalliques par deformation a froid
FR2799211B1 (fr) * 1999-09-30 2002-05-10 Dacral Sa Revetement et procede de traitement anticorrosion de pieces metalliques
KR100646619B1 (ko) † 2001-10-23 2006-11-23 수미도모 메탈 인더스트리즈, 리미티드 열간 프레스 방법, 이를 위한 도금 강철재 및 이의 제조방법
KR100561949B1 (ko) * 2004-03-15 2006-03-21 (주)이지테크 경금속기재 표면의 천연옥 분말 코팅 가공방법 및 천연옥분말 코팅 경금속기재
JP5007424B2 (ja) * 2005-05-23 2012-08-22 Ｄｏｗａエレクトロニクス株式会社 メカニカルプレーティング用投射材および高耐食性皮膜
TWI405917B (zh) 2006-09-06 2013-08-21 Tsubakimoto Chain Co Water rust paint, water rust coating and high corrosion resistant surface treatment chain
CN102477553B (zh) * 2010-11-25 2015-05-20 北京中科三环高技术股份有限公司 钕铁硼工件的机械镀的表面处理方法
JP6155006B2 (ja) * 2012-10-12 2017-06-28 日油株式会社 水性クロムフリー処理液
CN104523052A (zh) * 2014-12-04 2015-04-22 许昌学院 一种体育场专用看台座椅及其制作方法
DE102017211076B4 (de) * 2017-06-29 2019-03-14 Thyssenkrupp Ag Verfahren zum Herstellen eines mit einem Überzug versehenen Stahlbauteils und Stahlbauteil

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JPS6167773A (ja) 1986-04-07
BR8504350A (pt) 1986-07-08
EP0177786A1 (en) 1986-04-16
AU4694985A (en) 1986-03-20
KR890004790B1 (ko) 1989-11-27
KR860002588A (ko) 1986-04-26
DE3568458D1 (en) 1989-04-06
AU562978B2 (en) 1987-06-25
CA1243561A (en) 1988-10-25
JPH0349989B2 (ja) 1991-07-31

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