US3438799A - Method for the surface treatment of metal articles - Google Patents

Method for the surface treatment of metal articles Download PDF

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Publication number
US3438799A
US3438799A US466091A US3438799DA US3438799A US 3438799 A US3438799 A US 3438799A US 466091 A US466091 A US 466091A US 3438799D A US3438799D A US 3438799DA US 3438799 A US3438799 A US 3438799A
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weight
water
acid
group
pickling
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US466091A
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English (en)
Inventor
Fritz Eck
Gerhard Theodor Emmerichs
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CHEM ENG Ltd
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CHEM ENG Ltd
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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
    • C23C22/48—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 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • 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

Definitions

  • This invention relates to the surface treatment of metal articles in order to provide clean surfaces for further treatment, such as for applying thereon a primer coat, an enamel or other type of coating.
  • the invention is directed to a simple method for cleaning and treating metal surfaces.
  • Surface preparation has a direct effect on the performance of a coating, such as a coating of chromate primer, paint, enamel, or other surface coatings employed on metal surfaces.
  • a coating such as a coating of chromate primer, paint, enamel, or other surface coatings employed on metal surfaces.
  • the best coating applied may fail prematurely if applied to a contaminated or improperly prepared surface.
  • the treatments used heretofore were carried out in part at temperatures of up to 120 C. and were usually cumbersome, time-consuming and expensive.
  • the treating steps employed were not always effective, particularly because of the large number of operations involved, this generally being apparent by the occurrence of under-corrosion.
  • An important feature of the method is that it can be carried out at room temperature and thus does not require 3,438,799 Patented Apr. 15, 1969 the application of any heat, because of which considerable reduction in expense can be realized.
  • the first step of the method degreasing and rust removal are simultaneously effected, while creating a passivating layer having adhesive properties on the treated surface.
  • the rinsing or washing with normal tap water is effected
  • drying is effected in a single operation by displacement of the water, and passivation then effected by the application of a bond-producing layer which protects the metal against under-corrosion.
  • an article such as a vehicle body which has been treated in this manner can be stored in the open for up to a year without corrosion.
  • the layer applied in the third step is of slight thickness, in view of the relatively low solids content of the solution employed and is therefore not the same as a priming coat.
  • the workpieces are treated in the first step in a solution containing inorganic acids, a pickling accelerator, an inhibitor, an organic solvent which is miscible in every proportion with water, and a wetting agent or wetting agent mixture.
  • a solution containing inorganic acids, a pickling accelerator, an inhibitor, an organic solvent which is miscible in every proportion with water, and a wetting agent or wetting agent mixture comprises the following:
  • Inorganic acids From about 20 to 35 Pickling accelerator From about 2 to 5 Pickling inhibitor From about 1 to 2 Wetting agent or wetting agent mixture From about 7 to 12 Solvent (water soluble) From about 6 to 8 Water From about 64 to 38
  • the inorganic acids contemplated are phosphoric and hydrochloric acids which are used together in the bath. Sulfuric or sulfamic acids may be optionally present. The presence of the later acids are advantageous where a heavier degree of rust is present on the :article.
  • the pickling accelerator may comprise a substance from the group consisting of gluconic acid and its alkali salts, alkali fluoride (e.g. sodium fluoride), and alkali fluoroborates (e.g. sodium fluoroborate).
  • alkali fluoride e.g. sodium fluoride
  • alkali fluoroborates e.g. sodium fluoroborate
  • Inhibitors which are particularly advantageous in small but effective amounts when employed in the composition as corrosion inhibitors are: aldehydes, amine-s and nitriles, heterocyclic compounds, compounds in which the sulfur is bound up as mercaptan or sulfide sulfur, thiosemicarbazoles and similar compounds as customarily used as pickling inhibitors, such as 1,4-butyndiol, dibenzylsulfoxide, benzotrithion, 2-methyltrithion, 3-(p-methoxyphenyl -trithion and the like.
  • the wetting agents employed may be anion-active, nonanionic and ampholytic detergents, including mixtures thereof, provided they have good wetting and emulsifying action and are capable of screening off the solutions of high hydrochloric acid content by means of a blanket of foam.
  • Such agents are primary and secondary alkyl sulfates, sulfates of oxoand other branched alcohols, alkyl sulfonates of fatty acids and their esters, alkyl benzene sulfonates, alkyl naphthalene sulfonates, polyglycol ether, polyoxypropylene glycol, polyalkyl a ryl glycol ethers, amides of alkyl sulfonic acids, beta-ine, sulfobet-aine, and their substitution products.
  • a wetting agent known in the trade as Pluronic polyoxypropylene glycol
  • An anion agent referred to in the trade as Benax 2A1 sodium salt of dodecylated oxydibenzene disulfonate
  • Benax 2A1 sodium salt of dodecylated oxydibenzene disulfonate
  • Organic solvents which may be advantageously used in carrying out the invention are those of a polar character which are substantially miscible in water and have good dissolving power for fats, fatty acid and mineral Percent by weight Hydrogen chloride (100%) From about to 10 Orthophosphoric acid (100%) From about 9 to 22 Sulfamic acid From about 2to 1 Sodium Borogluconate From about 2 to 3 Wetting agent, sodium isalt of dodecylated oxydibenzene disulfonate From about 7to 10 Solvent, propyl glycol From about *6 to 8 Water, substantially the balance From about 59 to 46 For only slightly rusted deep-drawn steel plates such as used, inter alia, in the automobile industry, the following composition is particularly preferred:
  • hydrochloric acid about 32% and about 26% by weight of thermal phosphoric acid (about 85%) are first of all carefully introduced with continuous agitation into about 30% by weight tap water, whereupon slowly about 1% by weight sulfa'mic acid is added and then, after cooling, the above indicated quantities of sodium borogluconate, wetting agent and solvent are added, and the entire mixture then stirred until completely dissolved or mixed.
  • the workpieces are treated with this agent by manual application, dipping, spraying or atomizing.
  • the time of action depends on the degree of contamination by drawing, as well as the amount of corrosion. In case of only slight dirtying or normal rusting (for instance a thin film of rust), it is sufficient to allow the agent to act for a few minutes at room temperature. In order to obtain a passivating layer, the workpieces are exposed beyond the period of time necessary for draining also for an additional 1 to 2 minutes to the action of the still adhering liquid film.
  • the solution of the first step is removed from the workpieces by thorough washing with normal tap water.
  • the water washing can be made more intensive and shortened in time.
  • the drying by water displacement connected with the following step of the treatment makes unnecessary the drying by heat which was previously necessary after the water washing.
  • the Wet workpieces are treated with a special solution by manual aplication, dipping or spraying.
  • This product consists of a volatile nonpolar solvent, 21 wetting agent or mix-ture of wetting agents, a small amount of solubilizer and a film-forming organic substance which, after evaporation of the solvent, will form a drying, corrosion-preventing film which can be baked.
  • This film can also be baked together in one operation with one of the customary lacquer primings after the drying or hardening.
  • Such a solution may have the following composition:
  • Organic solvents that can be used include mediumto high-boiling aliphatic and aromatic hydrocarbons.
  • aliphatic hydrocarbons such as white spirits having a boiling range of between and C. are preferred.
  • the range between initial point and end point of the boiling should be as small as possible, and not exceed 30 C.
  • at least 99% by volume must distill over before the end point.
  • white spirits that may be used are nonane (B.P. 150.6 C.), decane (B.P. 174 C.), undecane (B.P. 197 C.) or crude mixtures thereof.
  • the mineral spirits used must be practically free of sulfur (less than 0.005% by weight), have a flash point of 39i1 C., density of about 0.776 (15 C.) and an evaporation number of 60.
  • aromatic hydrocarbons are n-propylbenzene (B.P. 159.2 C.), p-methylisopropylbenzene (B.P. 176 C.), and the like.
  • the aliphatic hydrocarbons such as white spirits have a boiling range of between 150 and 190 C., the range between the initial point and the end point not exceeding 30 C.
  • wetting agent or wetting agent mixture which imparts the water-displacing property to the solution, it must be readily soluble in aromatic or aliphatic hydrocarbon and diflicultly soluble to insoluble in water and have strongly predominant hydrophobic properties.
  • wetting agents are employed in small but effective amounts.
  • Various groups of non-ionic wetting agents and their mixtures have proven to be particularly suitable, such as oxethylated octylphenols, oxethylated nonylphenols, octylphenoxy-polyethoxy-ethanol, and nonyl phenol polyglycol ethers.
  • polar compounds can be used in small but effective amounts which are readily soluble in white spirits but scarcely soluble in water, and the boiling point of which lies below or within the boiling range of the solvent.
  • Those found suitable for the purpose are: benzyl alcohol, octyl alcohol, cyclohexanone, methyl cyclohexanone, methyl cyclohexanol and cyclohexanolacetate.
  • a varnish resin found useful is an oil-modified alkyd resin or mixtures of such varnish resins with slight additions of natural ceresin (paraffin wax) or saponified ceresins, neutral wool grease (lanolin), as well as a drying oil (linseed oil or wood oil).
  • Dryers which may be employed in small but effective amounts include resinates or naphthenates of cobalt, lead, manganese, zirconium and their mixtures.
  • Linseed oil alkyd resin From about 4.8 to 7.5 saponified ceresin From about 0.3 to 0.5 Lanolin (anhydrous) From about 0.8 to 1.3 Wood oil From about 0.4 to 0.6 Octylphenol polyglycol ether From about 1.0 to 1.3 Benzyl alcohol From about 0.35 to 0.75 Cobalt-naphthenate (5.5% Co) About 0.05 Zirconium naphthenate (6.0% Zr) About 0.1
  • Linseed oil alkyd resin 7.5 Castor oil alkyd resin 7.5 Saponified ceresin 1.0 Lanolin (anhydrous) 2.5 Wood oil 1.5 Octylphen-ol polyglycol ether 1.5 Benzyl alcohol 1.0 Cobalt naphthenate (5.5% Co) 0.1 Zirconium naphthenate (6.0% Zr) 0.1
  • the film-formers (alkyd resins, ceresin, lanolin [anhydrous] and wood oil) are dissolved with continuous agitation at about 40 C. in 50% by weight of white spirits. Thereupon the benzyl alcohol, the wetting agent, the two naphthenates and last of all the rest of the white spirits are added. The mixture is stirred until it has cooled down completely to room temperature and then filtered through a fine nylon screen.
  • the workpieces which have been pretreated in the first step and washed in the second step are treated with this agent by manual application or by dipping or spraying.
  • the agent is allowed to act for a few minutes. Since the added wetting agent strongly reduces the surface tension of this solution, the water adhering to the workpieces is displaced from the surface. As a result of its specific gravity, the water drops to the bottom of the bath from where it is drained oif from time to time. After the removal of the workpiece, it is allowed to drip for a short time.
  • the air-drying or hardening is completed in about 45 to 60 minutes. The hardening can be accelerated by preheated circulating air.
  • a method of treating the surface of an iron-base metal article which comprises subjecting the surface of the article to the action of a pickling solution containing about 20% to 35% by weight of a mixture of phosphoric acid and hydrochloric acid; about 2% to 5% by weight of a pickling accelerator selected from the group consisting of gluconic acid and alkali salts thereof, alkali fluorides, and alkali fluoroborate-s; a small but effective amount of a pickling inhibitor selected from the group consisting of 1,4-butyndiol, dibenxylsulfoxide, benzotrithion, 2 methyl trithion, 3 (p methoxyphenyl)- trithion; about 7% to 12% by weight of at least one wetting agent selected from the group consisting of secondary alkyl sulfates, sulfates of oxoand other branched alcohols, alkyl sulfonates of fatty acids and their esters, alkyl benzene sul
  • the acid mixture also includes an acid selected from the group consisting of sulfuric acid and sulfamic acid.
  • a pickling accelerator selected from the group consisting of gluconic acid and alkali salts thereof, alkaliborogluconates, alkali fluorides and alkali fluoroborates,
  • a corrosion inhibitor selected from the group consisting of aldehydes, amines, nitriles, heterocyclic compounds, compounds in which the sulfur is bound up as mercaptan or sulfide sulfur and thiosemicarbazoles,
  • a wetting agent selected from the group comprising anion active, non-anionic and ampholytic detergents having good wetting and emulsifying action
  • a film-former of a varnish resin which is readily soluble in mineral spirits (white spirits) and which dries by oxidation, such as an oil-modified alkyd resin or mixtures of such resins with additions selected from the gr up consisting of natural ceresin, saponified ceresin, neutral wool grease, including a drying oil, and
  • a corrosion-protective film is formed on the articles as a basic layer for a priming paint, varnish or other coatings.
  • the acid mixture also includes an acid selected from the group consisting of sulfuric acid and sulfamic acid.
  • a method of treating the surface of an iron-base metal article which comprises, subjecting the surface of the article to the action of a pickling solution containing about to by weight of an acid selected from the group consisting of phosphoric acid and hydrochloric acid and an acid from the group consisting of sulfuric and sulfamic acid; about 2% to 5% by weight of a pickling accelerator selected from the group consisting of gluconic acid and alkali salts thereof, alkali fluorides, and alkali fluoroborates; a small but effective amount of a pickling inhibitor selected from the group consisting of 1,4-butyndiol, dibenzylsulfoxide, benzotrithion, Z-methyl-trithion, 3-(p-methoxyphenyl)-trithion; about 7% to 12% by weight of at least one wetting agent selected from the group consisting of secondary alkyl sulfates, sulfates of 0140- and other branched alcohols, alkyl sulfon

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  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
US466091A 1965-06-22 1965-06-22 Method for the surface treatment of metal articles Expired - Lifetime US3438799A (en)

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AT (1) AT283077B (de)
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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3494795A (en) * 1967-08-07 1970-02-10 Fremont Ind Inc Spray cleaning method for removing oil,grease,dirt and embedded oxides from painted surfaces
US3519458A (en) * 1966-03-01 1970-07-07 Hooker Chemical Corp Method for reducing the corrosion susceptibility of ferrous metal having fluxing agent residue
JPS54100943A (en) * 1978-01-26 1979-08-09 Chiyoda Kinzoku Insatsu Kk Production of rust resistant steel plate
WO1981001298A1 (en) * 1979-11-06 1981-05-14 Boliden Ab A method of acid pickling iron and iron alloys and a composition for carrying out the method
US4534901A (en) * 1982-08-27 1985-08-13 Bayer Aktiengesellschaft Cobalt-boron compounds
US4572743A (en) * 1983-04-26 1986-02-25 Huels Aktiengesellschaft Method for pickling metallic surfaces
US6616770B2 (en) * 1997-07-03 2003-09-09 Clariant Finance (Bvi) Limited Cleaning method of containers and apparatus thereof
US20060011584A1 (en) * 2002-09-13 2006-01-19 Mitsushi Itano Etchant and etching method
US7828908B1 (en) * 2010-03-31 2010-11-09 Ecolab USA, Inc. Acid cleaning and corrosion inhibiting compositions comprising gluconic acid
US20110039122A1 (en) * 2008-02-12 2011-02-17 Thyssenkrupp Electrical Steel Gmbh Method for Producing a Grain-Oriented Magnetic Strip
US20140004380A1 (en) * 2010-12-14 2014-01-02 Thyssenkrupp Electrical Steel Gmbh Method for Producing a Grain-Orientated Electric Strip
WO2015162604A1 (en) 2014-04-22 2015-10-29 Green Future Ltd. Method and formulations for removing rust and scale from steel and for regenerating pickling liquor in hot-dip galvanization process

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT364218B (de) * 1980-03-17 1981-10-12 Wiener Brueckenbau Phosphorsaeurebeize

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1772743A (en) * 1927-01-05 1930-08-12 Gen Electric Coated metal article and process of applying coatings thereof
US2145291A (en) * 1936-02-26 1939-01-31 Clete L Boyle Preparation for cleaning metal preparatory to painting
US2559445A (en) * 1946-12-12 1951-07-03 Union Switch & Signal Co Method for removing scale from steel
GB683638A (en) * 1949-05-26 1952-12-03 Ethicon Suture Lab Inc Improvements in pickling bath
US2873210A (en) * 1957-01-17 1959-02-10 Du Pont Alkyd resin composition and metals coated therewith
US3125475A (en) * 1964-03-17 Method of producing a bright finish

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA356078A (en) * 1936-02-25 L. Boyle Clete Cleaning preparation for metals
DE1144990B (de) * 1957-03-30 1963-03-07 Philips Nv Fluessigkeit zum Trocknen wasserfeuchter Gegenstaende

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3125475A (en) * 1964-03-17 Method of producing a bright finish
US1772743A (en) * 1927-01-05 1930-08-12 Gen Electric Coated metal article and process of applying coatings thereof
US2145291A (en) * 1936-02-26 1939-01-31 Clete L Boyle Preparation for cleaning metal preparatory to painting
US2559445A (en) * 1946-12-12 1951-07-03 Union Switch & Signal Co Method for removing scale from steel
GB683638A (en) * 1949-05-26 1952-12-03 Ethicon Suture Lab Inc Improvements in pickling bath
US2873210A (en) * 1957-01-17 1959-02-10 Du Pont Alkyd resin composition and metals coated therewith

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3519458A (en) * 1966-03-01 1970-07-07 Hooker Chemical Corp Method for reducing the corrosion susceptibility of ferrous metal having fluxing agent residue
US3494795A (en) * 1967-08-07 1970-02-10 Fremont Ind Inc Spray cleaning method for removing oil,grease,dirt and embedded oxides from painted surfaces
JPS54100943A (en) * 1978-01-26 1979-08-09 Chiyoda Kinzoku Insatsu Kk Production of rust resistant steel plate
WO1981001298A1 (en) * 1979-11-06 1981-05-14 Boliden Ab A method of acid pickling iron and iron alloys and a composition for carrying out the method
US4534901A (en) * 1982-08-27 1985-08-13 Bayer Aktiengesellschaft Cobalt-boron compounds
US4572743A (en) * 1983-04-26 1986-02-25 Huels Aktiengesellschaft Method for pickling metallic surfaces
US6616770B2 (en) * 1997-07-03 2003-09-09 Clariant Finance (Bvi) Limited Cleaning method of containers and apparatus thereof
US20060011584A1 (en) * 2002-09-13 2006-01-19 Mitsushi Itano Etchant and etching method
US20110039122A1 (en) * 2008-02-12 2011-02-17 Thyssenkrupp Electrical Steel Gmbh Method for Producing a Grain-Oriented Magnetic Strip
US7828908B1 (en) * 2010-03-31 2010-11-09 Ecolab USA, Inc. Acid cleaning and corrosion inhibiting compositions comprising gluconic acid
US20140004380A1 (en) * 2010-12-14 2014-01-02 Thyssenkrupp Electrical Steel Gmbh Method for Producing a Grain-Orientated Electric Strip
US9905344B2 (en) * 2010-12-14 2018-02-27 Thyssenkrupp Electrical Steel Gmbh Method for producing a grain-orientated electric strip
WO2015162604A1 (en) 2014-04-22 2015-10-29 Green Future Ltd. Method and formulations for removing rust and scale from steel and for regenerating pickling liquor in hot-dip galvanization process
US9752238B2 (en) 2014-04-22 2017-09-05 Green Future Ltd. Method and formulations for removing rust and scale from steel and for regenerating pickling liquor in hot-dip galvanization process

Also Published As

Publication number Publication date
DE1546874B1 (de) 1971-04-01
DE1546874C2 (de) 1974-07-11
CH472512A (de) 1969-05-15
AT283077B (de) 1970-07-27

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