US3719534A - Anti-corrosive coating compositions - Google Patents

Anti-corrosive coating compositions Download PDF

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Publication number
US3719534A
US3719534A US00037488A US3719534DA US3719534A US 3719534 A US3719534 A US 3719534A US 00037488 A US00037488 A US 00037488A US 3719534D A US3719534D A US 3719534DA US 3719534 A US3719534 A US 3719534A
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solution
composition
solvent
metals
corrosion resistant
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US00037488A
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English (en)
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C Vessey
G Gibson
K Holker
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Associated Chemical Companies Ltd
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Associated Chemical Companies Ltd
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Priority claimed from GB5263166A external-priority patent/GB1190073A/en
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Classifications

    • 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
    • C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
    • C09D5/086—Organic or non-macromolecular 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

Definitions

  • the invention relates to processes for coating metal surfaces and to corrosion resistant coating composiare. restricted to those which are sufficiently soluble in the solvent at 20 C. to provide a solution containing at least 0.2% CrO w/v in the solution.
  • Preferred bases are primary, secondary or tertiary amines and quaternary ammonium bases.
  • the composition also contains a material capable of effecting reduction of at least a part of the hexavalent chromium in the comosition. or particular applications in which the composition is applied to metals which have been pretreated, washed and not dried the composition also contains a surfactant and, if necessary, a solubilizing agent for the surfactant.
  • a composition comprising a solution of a chromic acid salt of .one or more organic bases having at least one straight or branched chain containing at least six carbon atoms, in an organic solvent having a boiling point not greater than 250 C. at atmospheric pressure.
  • the chromic acid salt should be sufficiently soluble in the solvent at C. to provide a solution Containing at least 0.2% w/v CrO (equivalent) in the solution.
  • the solvent should either unact at all, or react only very slowly with the chromic acid salt at temperatures of less than 30 C.
  • Suitable solvents are ketones, hydrocarbons, halogen substituted hydrocarbons, certain nitrohydrocarbons, esters, ethers, nitriles and substituted acid amides and mixtures of any of these so]- vents.
  • the preferred chromic acid salts are those which on shaking with water give a solution .containing not more than 1% CrO (equivalent) at 20 C.
  • the preferred organic bases are those which contain branched chains.
  • the branched chains may consist solely of carbon atoms, or they may consist of nitrogen and carbon atoms.
  • the preferred bases include the simple primary, secondary and tertiary amines, and quatemary ammonium bases, possessing at least one branchedchain in the molecule, and substituted guanidines, biguanides,- and s-triazines possessing at least one branched chain in the molecule.
  • Two particularly preferred classes'of branched-chain bases are the tertiary alkyl primary amines, in'which the amino group is joined to a carbon atom which itself is attached to three alkyl groups and the'so-called beta-amines, which are derived from straight-chain saturated hydrocarbons by introducing an amino group onto the second carbon atom (the beta-carbon atom) of the chain;
  • the preferred'and particularly preferred bases are I di-(Z-ethyl-n-hexyl) amine, tri-(3,5,5- trimethyl-n-hex'yl) amine, the mixture of tertiary alkyl primary amines containing from 12 to 14 carbon atoms known as Primene 8l-R (the word Prlmene being a Trade Mark), the mixture of tertiary alkyl primary amines containing from 18 to 22 carbon atoms known as Primene JM-T, the mixture (the word Armeen secondary-alkyl primary amines derived from Z-aminon-undecane in the form known as Armeen L.ll (the word Armeen being a Trade Mark), 2,4,6-tris-( 2-ethyln-hexylamino)-s-triazine, the mixed 1,5-dialkyl biguanides derived from Primene" 81-R or Primene JM- T, and the mixed, N, N, N, N
  • the invention includes all organic base/chromic acid salts which have the appropriate solubility characteristics as defined above and that such salts can be used according to the invention either singly or in admixture with each other or one another. It will also be understood that bases which are too easily oxidized by chromic acid, and salts which too easily decompose by internal oxidation-reduction reactions, are to be avoided.
  • Another useful class of organic base according to the invention is provided by the condensation products of ethylene diamine and diethylene triamine with carboxylic acids of formula R.C0.0H, R being a branched chain group where the branching has arisen through substitution of alkyl or cycloalkyl groups on one or more of the carbon atoms of the chain, or indeed, by actual link-up of such a substituent alkyl group with the chain toform a cycloalkyl group.
  • An example of such a carboxylic acid is provided by 'the well-known class of naturally occurring petroleum carboxylic acids called naphthenic acids.
  • Such acids of formula R.C0.0H will react with ethylene diamine and diethylene triamine of heating to give the basic mono amides liCO'ffiFlfl-iifl lfiflz and R.CO.HN.CH2.CH
  • Both the two basic monoamides and the two imidazolines form chromic acid salts which are soluble in the above solvents.
  • Examples of preferred bases of this class are the imidazoline derived from ethylene diamine and the naphthenic acid marketed by Shell Chemical Company Ltd. under the name of naphthenic acid NA 230/SP, the monoamide derived from ethylene diamine and naphthenic acid NA' 230/SP, and the imidazoline derived from diethylene triamine and naphthenic acid NA 230/SP.
  • a suitable solvent will have a vapor pressure at 20 C. within the range 3-200 mm. of mercury, the preferred range being 5-100 mm. of mercury.
  • the solvent should be sufficiently volatile to evaporate rapidly from the hot coated metal, because it is not normally convenient or desirable that the curing stage should take longer than a few minutes.
  • Suitable solvents have vapor pressures greater than 200 mm. of mercury at the curing temperature.
  • the preferred solvents have boiling points below thecuring temperature.
  • Coating obtained from solvent-soluble organic hexavalent chromium compounds subjected to a curing stage which may vary from a few seconds duration at high temperatures to several minutes at temperatures as low as l C., offer considerably improved corrosion resistance as compared with the more conventional coating compositions consisting of aqueous solutions of hexavalent chromium compounds.
  • the corrosion resistance obtained is usually comparable with that which can be obtained from aqueous solutions, only by electrolytic processes.
  • the coatings are an ideal base for subsequent painting or lacquer'ing, and enable painted products of very high corrosion resistance to be obtained.
  • the metals which can be treated by this type of composition include ferrous metals, zinc, aluminum and their alloys.
  • coatings can be obtained by applying to the substrate the chromic acid salts in a solution in'a suitable solvent such as xylene and subsequently heating to obtain the required degree of reduction, we have found that it is necessary for most applications to includein the coating composition a substance which accelerates the process of reduction of some of the hexavalent chromium during the heating stage.
  • suitable substances are those which are soluble in the organic solvent, sufficiently easily oxidized on heating with the organic hexavalent chromium compounds during the curing stageanclv which do not produce deleterious oxidation products.
  • the substance accelerating reduction must be such that a composition containing it is sufficiently stable to allow normal storage.
  • Suitable substances include oxidizable materials such as linseed oil, castor oil, and fatty alcohols.
  • One example of such a material is the well known series of epoxy resins. The inclusion of these materials usually gives a coating with an even higher corrosion resistance than coatings obtained from compositions obtained using a reducing agent such as castor oil because the resin system progiving rise to products which are themselves reducing agents.
  • coatings can be obtained by applying the solution of the organic chromium compound emulsified with an aqueous solution of a mineral acid, such as nitric or sulphuric acids.
  • a mineral acid such as nitric or sulphuric acids.
  • the coating solutions or emulsions can be applied to the metal surfaces by conventional means, for example by spraying, brushing or dipping.
  • the metals which can be coated by this type of composition include ferrous metals, zinc, aluminum and their alloys.
  • coating compositions according to the invention may advantageously be employed to obtain improved corrosion resistance and better paint adhesion on surfaces which have already been treated by a conventional metal pretreatment process.
  • Such pretreatment processes include electrolyticv chromating processes, phosphating processes and processes which involve the deposition of thin layers of other metals on to the substrate, for example the electrolytic deposition of metallic chromium for the purpose of conferring improved paint/lacquer adhesion to the substrate.
  • Such dewatering compositions are normally used in white spirit solution and contain as surfactants salts of alkylsubstituted aryl sulphonic acids or polyglycol ethers of alkyl phenols or fatty alcohols. It is frequently necessary to incorporate a solubilizing agent such as benzyl alcohol or tertiary butyl alcohol to dissolve these surfactants in white spirit solution.
  • the surfactant and the solubilizing agent must be compatible with the chromic acid salt in the composition and must not react at all, or react only very slowly, with the chromic acid salt at temperatures less than 30 C.
  • a surfactant is sodium dodecyl benzene sulphonate
  • an example of such a solubilizing agent is t-butyl alcohol.
  • the minimum effective concentration of the chromic acid salt is 0.04% w/v CrO equivalent for imparting good corrosion resistance.
  • EXAMPLE 1 A 6 inch X 4 inch panel of mild steel was degreased and pickled in nitric acid and dried. The panel was then mounted in a Sheen Spinner and a quantity of a solution of thedichromate of Primene 8l-R in xylene containing 5% w/v CrO equivalent was-poured on to the center of the panel. After spinning, the solvent was allowed to evaporate at ambient temperature and the panel then exposed to neutral salt spray. After 7 hours it rated a mark of 3 on a 0 10 scale in which 0 no corrosion, and 10 100 percent corrosion. Untreated steel rated a mark of 8. A panel treated similarly but stoved at 200 C. for 3 minutes before exposure to salt spray, rated a markof 1 after 7 hours exposure.
  • EXAMPLE 2 A 6 inch X 4 inch. panel of mild steel was degreased and pickled in nitric acid and ,driedflhe panel was then coated as in Example 1 with a solution of the dichromate of Primene 81-R in'xylene containing 5% CrO equivalent, to which had been added 1 percent by volume of castor oil. After coating, the panel was stoved at 200 C for 1 minute.
  • the grey corrosion resistant surface obtained rated a marking of I after 24 hours exposure to salt spray.
  • EXAMPLE 3 A steel panel was prepared as in Example 1 and coated with a xylene solution of the dichromate of Primene 8l-R in xylene to which has been added 1% w/v of a xylene solution of the sulphate of Primene 81- R containing 5% S0 equivalent. After coating, the panel was stoved for 1 minute at 200 C. I
  • the grey corrosion resistant surface obtained rated a marking of 1 after 24 hours exposure to salt spray.
  • EXAMPLE 5 A steel panel was prepared as in Example 1 and coated with an emulsion prepared by mixing equal volumes of the following solutions A and B and shak- So lution A.
  • Example 2 25 g. of a nonyl phenol polyglycol ether containing 8 EXAMPLE 6 A steel panel was prepared as in Example 1. This was then coated with a trichloroethylene solution of Primene 8l-R dichromate containing 5% w/v CrO, Y
  • the corrosion resistant surface rated a marking of 1 after 24 hours exposure to salt spray.
  • EXAMPLE 7 A steel panel was prepared as in Example 1 and coated with a methyl ethyl ketone solution of the dichromate of methylated Primene 8 l -R containing 5% w/v CrO equivalent. The coating was cured by stoving the panel for 2 minutes at 200 C.
  • the grey corrosion resistant surface rated a marking of I after 7 hours exposure to salt spray.
  • the methylated Primene 8l-R- from which this dichromate was prepared consisted of a mixture of Primene 8l-R with its monomethyl and dimethyl derivatives, and had an equivalent weight corresponding to that of the monomethyl derivative.
  • EXAMPLE 8 A steel panel was prepared as in Example 1 and coated with a nitrobenzene solution of Primene 8l-R dichromate containing 5% w/v CrO equivalent and the coating cured by stoving the panel for 1 minute at 200 C.
  • the corrosion resistant surface rated a marking of 3 after 7 hours exposure to salt spray.
  • EXAMPLE 9 A steel panel was prepared as in Example 1 and coated with a xylene solution of the dichromate of Primene 8 1-R containing 5% w/v CrO equivalent and 25% w/v of an epoxy resin of the type formed by condensation between epichlorhydrin and diphenylolpropane (such as the Epikote 815 manufactured by Shell Chemical Company). The coating was cured for three to 5 minutes at 200 C. I
  • the treated steel was untouched after 7 days exposure to salt spray.
  • EXAMPLE 10 Steel which had been cathodically treated in a solution containing chromate ions was dipped in a xylene solution of Primene 8l-R dichromate containing 1% w/v CrO equivalent and 0.2% w/v castor oil and heated at 200 C. for 1 minute. The resultant product was unattacked after exposure to neutral salt spray for 200 hours, whereas chromated steel without after treatment began to show corrosion after 40 hours.
  • EXAMPLE 1 1 Steel which had been phosphated according to conventional processes, washed with demineralized water and dried, was treated as described in Example 10.
  • EXAMPLE 12 Steel which had been phosphated according to conventional processes and washed with tap water only and left undried'was treated with a xylene solution of Primene 8l-R dichromate containing 1% w/v CrO equivalent and 0.2% w/v of a dispersing agent consisting of equal weights of dodecyl benzene sulphonic acid and a nonyl phenol polyglycol ether containing 8 ethylene oxide units. The steel was then stoved for 1 minute at 200 C to give aproduct with similar corrosion resistance and paint/lacquer adhesion to that found in Example 1 1.
  • EXAMPLE l3 EXAMPLE 14 A clean 6 inch X 4 inch steel plate was treated with a xylene solution of 2,4,6-tris-(Z-ethyl-n-hexylamino)-striazme dichromate containing 5% w/v r 3 equivalent. After stoving for 3 minutes at 200 C. a corrosion resistant coating was obtained which formed an excellent base for subsequent lacquering or painting and which rated a marking of 1 after 24 hours exposure to salt spray.
  • EXAMPLE 15 A clean 6 inch X 4 inch steel plate was treated with a xylene solution of Armeen L1 1 dichromate containing 5% w/v CrO equivalent. After stoving for 1 minute at 200 C. a brown corrosion resistant coating was obtained, which was unattacked after 24 hours exposure to salt spray, and rated a marking of I after 48 hours.
  • a process for providing a corrosion resistant coating on metals which comprises applying to the metal surface a corrosion resistant coating composition for metals comprising a solution of a dichromate salt of at least one organic nitrogenous base having at least one straight or branched chain containing at least six carbon atoms in an organic solvent having a boiling point not greater than 250 C at atmospheric pressure and a reducing agent, the salt being sufficiently soluble in the solvent at 20 C to provide a solution containing-at least 0.2% CrO w/v in the solution.
  • organic base is a primary, secondary or tertiary amine or a quaternary ammonium base.
  • a process for providing a corrosion resistant coating on metals which comprises applying to the metal surface a corrosion resistant coating composition for metals comprising a solution of a dichromate salt of at least one organic nitrogenous base having at least one straight or branched chain containing at least six carbon atoms in an organic solvent having a boiling point not greater than 250 C at atmospheric pressure, the salt being sufficiently soluble in the solvent at 20 C to provide a solution containing at least 0.2% CrO w/v in the solution also containing a material or materials which are capable of effecting reduction of at least a part of the hexavalent chromium in the composition.
  • the reducing agent in the composition is an epoxy resinous material or materials which effect reduction of at least part of the hexavalent chromium in the composition after it has been applied to the metal surface.
  • a process for providing a corrosion resistant coating on metals which comprises applying to a metal surface a corrosion resistant coating composition for metals comprising a solution of a dichromate saltof at least one organic nitrogenous base having at least one straight or branched chain containing at least six carbon atoms in an organic solvent having a boiling point not greater than 250 C at atmospheric pressure and a reducing agent, the salt being sufficiently soluble in the solvent at 20 C to provide a solution containing at least 0.2% CrO w/v in the solution.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Paints Or Removers (AREA)
  • Chemical Treatment Of Metals (AREA)
US00037488A 1966-04-05 1970-05-20 Anti-corrosive coating compositions Expired - Lifetime US3719534A (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB05082/66A GB1184562A (en) 1966-04-05 1966-04-05 Anti-Corrosive Coating Compositions
GB5263166A GB1190073A (en) 1966-04-05 1966-04-05 Anti-Corrosive Coating Compositions
GB4363166 1966-09-29
GB4787566 1966-10-25

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BE (1) BE696617A (forum.php)
FR (1) FR1565330A (forum.php)
GB (1) GB1184562A (forum.php)
NL (1) NL6704801A (forum.php)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4186035A (en) * 1978-10-16 1980-01-29 Diamond Shamrock Corporation Chromium containing coating
US4226624A (en) * 1978-08-28 1980-10-07 The United States Of America As Represented By The Secretary Of The Navy Solubilization of hexavalent chromium compounds in organic materials
US5259884A (en) * 1989-11-06 1993-11-09 Compagnie Francaise De Produits Industriels Process adapted to provide on a metallic substrate a protective coating based on hexavalent chromium, bath used in the said process and commercial form of the components of the bath
US6190464B1 (en) * 1998-09-24 2001-02-20 Nisshin Steel Co., Ltd. Chromating solution and chromated metal sheet
CN105331977A (zh) * 2015-09-28 2016-02-17 西南交通大学 在镁金属表面构建纳米装容结构并包覆功能性分子的方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5226956A (en) * 1987-03-24 1993-07-13 Alcan International, Inc. Surface coating compositions
CN111320920A (zh) * 2020-04-16 2020-06-23 云南云岭涂料有限公司 一种醇酸铁红防锈漆及其制备方法

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1523741A (en) * 1922-09-28 1925-01-20 Western Electric Co Method of rust removal and prevention
US1837112A (en) * 1928-07-19 1931-12-15 Nat Tube Co Method of galvanizing
US1946152A (en) * 1931-06-20 1934-02-06 Aluminum Co Of America Protecting aluminum from corrosion
US2045286A (en) * 1932-12-27 1936-06-23 Aluminum Co Of America Method of stabilizing reflectors
US2270386A (en) * 1939-05-13 1942-01-20 Du Pont Aliphatic hydrocarbon ammonium chromate
US2480754A (en) * 1946-10-17 1949-08-30 Gulf Research Development Co Chromium-containing phenolic amine reaction product
US2796369A (en) * 1953-04-15 1957-06-18 Poor & Co Method of protecting zinc-copper alloys against corrosion and product thereof
US2911332A (en) * 1956-05-25 1959-11-03 Kelsey Hayes Co Process of coating metal and resulting articles
FR1447004A (fr) * 1964-09-24 1966-07-22 Ass Chem Co Composition d'enduit anticorrosion
US3376143A (en) * 1960-09-30 1968-04-02 Reynolds Metals Co Corrosion inhibiting and sealing composition

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1523741A (en) * 1922-09-28 1925-01-20 Western Electric Co Method of rust removal and prevention
US1837112A (en) * 1928-07-19 1931-12-15 Nat Tube Co Method of galvanizing
US1946152A (en) * 1931-06-20 1934-02-06 Aluminum Co Of America Protecting aluminum from corrosion
US2045286A (en) * 1932-12-27 1936-06-23 Aluminum Co Of America Method of stabilizing reflectors
US2270386A (en) * 1939-05-13 1942-01-20 Du Pont Aliphatic hydrocarbon ammonium chromate
US2480754A (en) * 1946-10-17 1949-08-30 Gulf Research Development Co Chromium-containing phenolic amine reaction product
US2796369A (en) * 1953-04-15 1957-06-18 Poor & Co Method of protecting zinc-copper alloys against corrosion and product thereof
US2911332A (en) * 1956-05-25 1959-11-03 Kelsey Hayes Co Process of coating metal and resulting articles
US3376143A (en) * 1960-09-30 1968-04-02 Reynolds Metals Co Corrosion inhibiting and sealing composition
FR1447004A (fr) * 1964-09-24 1966-07-22 Ass Chem Co Composition d'enduit anticorrosion

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4226624A (en) * 1978-08-28 1980-10-07 The United States Of America As Represented By The Secretary Of The Navy Solubilization of hexavalent chromium compounds in organic materials
US4186035A (en) * 1978-10-16 1980-01-29 Diamond Shamrock Corporation Chromium containing coating
US5259884A (en) * 1989-11-06 1993-11-09 Compagnie Francaise De Produits Industriels Process adapted to provide on a metallic substrate a protective coating based on hexavalent chromium, bath used in the said process and commercial form of the components of the bath
US6190464B1 (en) * 1998-09-24 2001-02-20 Nisshin Steel Co., Ltd. Chromating solution and chromated metal sheet
US6329067B2 (en) 1998-09-24 2001-12-11 Nisshin Steel Co., Ltd. Chromating solution and chromated metal sheet
CN105331977A (zh) * 2015-09-28 2016-02-17 西南交通大学 在镁金属表面构建纳米装容结构并包覆功能性分子的方法
CN105331977B (zh) * 2015-09-28 2018-01-23 西南交通大学 在镁金属表面构建纳米装容结构并包覆功能性分子的方法

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NL6704801A (forum.php) 1967-10-06
BE696617A (forum.php) 1967-09-18
GB1184562A (en) 1970-03-18
FR1565330A (forum.php) 1969-05-02

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