US2840498A - Composition and method for producing combination corrosion resistant and lubricatingcoatings on metals - Google Patents

Composition and method for producing combination corrosion resistant and lubricatingcoatings on metals Download PDF

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Publication number
US2840498A
US2840498A US360353A US36035353A US2840498A US 2840498 A US2840498 A US 2840498A US 360353 A US360353 A US 360353A US 36035353 A US36035353 A US 36035353A US 2840498 A US2840498 A US 2840498A
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US
United States
Prior art keywords
coating
composition
metallic
aliphatic
phosphate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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US360353A
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English (en)
Inventor
Jr Earl Eugene Logue
Ernest P Bell
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.)
Parker Rust Proof Co
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Parker Rust Proof Co
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Filing date
Publication date
Priority to NL106717D priority Critical patent/NL106717C/xx
Priority to NLAANVRAGE7714566,A priority patent/NL187985B/xx
Priority to BE529431D priority patent/BE529431A/xx
Application filed by Parker Rust Proof Co filed Critical Parker Rust Proof Co
Priority to US360353A priority patent/US2840498A/en
Priority to DEM23042A priority patent/DE1204913B/de
Priority to FR1105973D priority patent/FR1105973A/fr
Priority to GB16838/54A priority patent/GB752711A/en
Application granted granted Critical
Publication of US2840498A publication Critical patent/US2840498A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C23C22/07—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 phosphates

Definitions

  • This invention relates to a composition and method for producing a coating on metallic surfaces and particularly ferrous surfaces which functions both as a corrosion-resistant coating and as a lubricant in operations deformation is relatively severe.
  • the harder metals such as iron, steel, stainless steel and the extremely hard alloy steels have been successfully deformed by preliminarily coating the metal surface with an underlayer of a protective chemical coating suchas a phosphate, oxide, 'sulfide or oxalate together with an overlayer of a conventional lubricant.
  • Another object is to provide a method, for forming on a metallic surface an integral chemical coating which has lubricating properties.
  • a further object' is to provide an inexpensive composition and a simple one-step method, which eliminates the necessity for using the customary two-stage rinsing, for producing an integral chemical coating having lubricating properties on metallic'surfaces, and particularly ferrous surfaces.
  • a still further object is to provide an aliphatic phosphate coating on metal surfaces which has lubricating properties.
  • a metallic ion that forms a salt with the aliphatic ester of phosphoric acid which is compatible with the dispersion, said dispersion or admixture having a controlled acidity within a rangeof pH- of about 3.0 and 5.5.
  • the metal lic salt of the aliphatic phosphate is soluble in or at least semi-soluble or readily dispersible in the aqueous solution or dispersionof the aliphatic ester;
  • the "coating which is formed by this treatment has a velvety appear ance and is-an amorphous type of coating, being partially greasy and capable of being crushed to a continuous unctuous film so that it is well suited for use as a'lubricant in metal deformation operations.
  • the composition may also contain an amine which is reactive'with a portion of the aliphatic phosphoric "acid ester to form' a compatible-amine salt' thereof and an oxidizing or accelerating agent which isunderstood that the incorporation of an amine which forms a compatible amine salt with the aliphatic phosphoric ester is but one means of achieving the desired degree of acidity and that the benefits of the invention may be obtained in 'the absence of either or'both the amine and the accelerating agent.
  • the aliphatic esters of phosphoric acid which, in coins bination with a metallic salt of such ester, have been found to be useful for the purposes of this invention, are, the esters-which may be regarded as the reaction products of phosphoric acid with aliphatic alcohols containing from 818 carbon atoms.
  • the aliphatic portion ofthe ester may be either saturated or unsaturated. While the saturated alcohols are somewhat more readily commer cially available, the unsaturated aliphatic esters having unsaturation of the olefinic type havenevertheless been found to be equally suitable in the compositions of this; invention.
  • the coating which is produced does notexhibit the characteristics of a .lubri-. cant to a desirable degree, and when the length of the carbon chain exceeds about 18 carbon atoms, the. aliphatic phosphate ester is insufficiently dispersible in waterJto form a workable material;
  • Preferred materials for the, purposes of this invention are the lauryl esters and the oleyl esters. Mixtures of esters having carbon chain lengths between 8 and 18 may beused, and mixtures of esters actually represent a preferred form of the invention because alcohols of mixed carbon chain length are readily available andthe mixed esters are easily obtained.
  • esters which have been found to be suitable are in the range of about 3 grams/liter to about 201 the aliphatic phosphoric acidester, a salt which is soluble, .or at least semi-soluble or readily dispersible in, the;
  • Patented June, 24, 1Q58 a this in- Typicalmetallic ions which have been found to be useful rat this purpose ihcludeziii'c, aluminum, the alkali'metals including ammonium, cadmium, copper, nickel and iron.
  • compositions of this invention apparently. imparts to the aqueous dispersion of aliphatic phosphoricacid ester, the
  • compatiblemetal ion are. sufliciently adherent and possassedr of a greasy'nature 1such thatjupon the application of. pressure; the velvety,, amorphous coating is crushed intoacontinuous film. having, goodlubricating. properties. andlhigh resistanceto being, dislodged due to the applicationoftpressurea M TlZheproportion of metallic ion whichis necessary for the formation of theisuperior coatings of this invention is relatively restricted.
  • the metallicion content may,satisfactorily vary between about 0.3" gram per liter and 11.0 grams per liter of zinc or the equivalent proportion of other suitable metallic ion, such astthose enumerated hereinabove. When the metallic.
  • metallic ion is preferably introduced into the composition as a salt and only limited quantities may be introduced as, basic-salts or hydroxides.
  • introduction; of: the metallic ion as a basic? salt or a hydroxide is notfeasiblesince the pH islraised above the operable limit-before the desired concentration is achieved.
  • metallic salts such as the acetates or nitrates should be "employed; and: the .pH adjusted 1 with the amine being employed.
  • The. use of. salts containing a halide, such as chloride, bromide or iodide- is not recommended.
  • compositions of this invention from the desired coatings in a shorter period oftime when they include an accelerating or oxidizing agent Any oxidizing agent whichis conventionally employed for the purpose of accelerating the formation of a coating from a solution such as zinc phosphate or manganese phosphate solution, may be used for the purposes of this invention.
  • oxidizing agents include the nitrites, nitrates, peroxides; chlorates, bromates, sulfites and nitro-organic compounds such as rn-nitrobenzene sulfonate and picric acid.
  • the oxidizing agents may be added as the metallic salts such as the sodium or other alkali metal salt, and the proportion of metallic ion so introduced is small and relatively insignificant to the overall metallic ion content.
  • Suitable concentrations of these oxidizing agents whichmay be employed to decrease the time required for' producing the coatings of this invention are 0L3%'O15'% sodiummeta nitro benzene sulfonate; 0i0l%-0.5 picric acid ⁇ , ODS-0.3% hydrogen nitrate; O.Ol%--0.3'%' hydroxylamine.
  • the method of this invention comprises the steps of contacting the metal surface to be treated with the compositions ofthis invention and thereafter drying the coating thus formed on the metallic surface.
  • the step of drying, the coating on the metal surface is preferably performed at an elevated temperature less than about 250 F., though where the time required for fully preparing the metal surface to be drawn is unimportant, the coating may be dried in air. Where the coating is dried by subjecting the same to an elevated temperature, a somewhat. increaseddegree of reaction with the metal surface is thought to occur and the resultant coating is somewhat improved in its adherence to'the metal surface. Drying the coatingat an elevated temperature represents the preferred procedure.
  • EXAMPLE I A mixture was prepared by heating together 26.5 grams of monolauryl phosphoric acid and 4 grams of zinc, oxide with 500 ml. of water and mixing in a Waring blender. The resultant'mixture had a'pHof 1.2 which was adjusted with sodium carbonate to 55. Clean,.mild steel panels were immersed in the: solution at F.- F. for periods of one-halfminute to two minutes, withdrawn 'and dried. All the panels were coated with a smooth,
  • the emulsion containing the above ingredients was.
  • the pH of the solution was adjusted upwardly to 5.3 by adding 1 liter of concentrated ammonium hydroxide. A number-of pieces of steel tubing. were-immersed in the solution at 140 F.-150 F. for 5 minutes, withdrawn and force dried. The coatings were uniformly smooth and adherent.
  • the chemicals in the emulsion are depleted as the emulsion is used for coating, and may be easily replenished by the use of a replenishing concentrate.
  • Suitable formulations for replenishing or for original make-up are given below:
  • This concentrate is in the form of a heavy paste and is best compounded by heating the acids to melting and adding the morpholine thereto at about 200 F. and maintaining the temperature until the reaction is complete.
  • the sodium hydroxide may be dissolved in part of the water and the acetate and nitrate in the balance and both solutions heated to about 150 F. While the caustic is being stirred, the mixture of acids with morpholine and the acetate-nitrate solution are added slowly and after about 15 minutes of mixing a uniformly blended heavy paste is obtained.
  • a working solution may be prepared by using about'60 to 70 pounds of this concentrate per 100 gallons of solution or emulsion, and adding an oxidizing agent thereto.
  • composition of matter comprising an aqueous dispersion consisting essentially of water, a mono-aliphatic phosphoric acid ester having from 8 to 18 carbon atoms,
  • a metal ion which formsa-salt with the said phosphate and which is compatible with said dispersion in an amount f equivalent to about 03-11 grams/liter of zinc, andan amine in an amount sufficient to produce a pH between about 3.0 and 5.5.
  • a composition of matter comprising an aqueous dispersion consisting essentially of water, a mono-aliphatic phosphate having from 8 to 18' carbon atoms, a metallic ion'in an amount equivalent to about 03-11 grams/liter of zinc, an oxidizing agent and an amine in an amount sufficient to produce a pH between about 3.0 and 5.5.
  • a composition'of matter comprising an aqueous'dispersion consisting essentially of water, a monoaliphatic phopshate having from 8 to 18 carbon atoms in an amount from about 3 to grams per liter, a metallicion which yields with said phosphate a salt which is at 4.
  • the method of forming on a metallic surfaceanintegrally bonded chemical coating having lubricating properties which comprises the steps of contacting the metal surface with an aqueous dispersion consisting essentially of water, an aliphatic phosphate having 8 to 18 carbon atoms and a metal ion which'yields a salt which isvat least semi-soluble in said dispersion in an amount equivalent to about 0.3-11 grams/liter of zinc and having a pH of about 3.0 to 5.5, and thereafter drying the said coating at an elevated temperature.
  • the method of forming on the surface of a ferrous article an integrally bonded chemical coating having lubricating properties which comprises the steps of immersing the article in an aqueous dispersion at a temperature between about F. and F. for a short time, which dispersion consists essentially of water, a monoaliphatic phosphate having 8 to 18 carbon atoms in an amount of about 3 to 80 grams per liter and a metallic ion which yields with said phosphate a salt which is at least semi-soluble in said dispersion in an amount equivalent to about 0.3 to 11 grams per liter of zinc, said dispersion having a pH between about 3 and 5.5, and thereafter drying said coating at an elevated temperature less than about 250 F.
  • the method of forming on the surface of a ferrous article an integrally bonded chemical coating having lubricating properties which comprises the steps of immersing the article in an aqueous dispersion at a temperature between about 90 F. and 190 F. for a short time, said dispersion consisting essentially of water, a monoaliphatic phosphate having from 8-18 carbon atoms and a metallic ion which yields with said phosphate a salt which isat least semi-soluble in said dispersion in an amount equivalent to about 0.3-11 grams/liter of zinc, an oxidizing agent and an amine, said dispersion having a pH between about 3.0 and 5.5, withdrawing the article, and drying the coating thereon.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Paints Or Removers (AREA)
US360353A 1953-06-08 1953-06-08 Composition and method for producing combination corrosion resistant and lubricatingcoatings on metals Expired - Lifetime US2840498A (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
NL106717D NL106717C (en, 2012) 1953-06-08
NLAANVRAGE7714566,A NL187985B (nl) 1953-06-08 Werkwijze voor het tegengaan van watertoevloed tijdens of na het boren van een boorput.
BE529431D BE529431A (en, 2012) 1953-06-08
US360353A US2840498A (en) 1953-06-08 1953-06-08 Composition and method for producing combination corrosion resistant and lubricatingcoatings on metals
DEM23042A DE1204913B (de) 1953-06-08 1954-05-12 Verfahren zur Herstellung eines fest haftenden chemischen UEberzuges mit Schmiereigenschaft auf metallischen Oberflaechen
FR1105973D FR1105973A (fr) 1953-06-08 1954-06-05 Composition et procédé destinés à produire sur les métaux des revêtements résistant à la corrosion et lubrifiants
GB16838/54A GB752711A (en) 1953-06-08 1954-06-08 Improvements in the production of phosphate coatings on metallic surfaces

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US360353A US2840498A (en) 1953-06-08 1953-06-08 Composition and method for producing combination corrosion resistant and lubricatingcoatings on metals

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US2840498A true US2840498A (en) 1958-06-24

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US360353A Expired - Lifetime US2840498A (en) 1953-06-08 1953-06-08 Composition and method for producing combination corrosion resistant and lubricatingcoatings on metals

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US (1) US2840498A (en, 2012)
BE (1) BE529431A (en, 2012)
DE (1) DE1204913B (en, 2012)
FR (1) FR1105973A (en, 2012)
GB (1) GB752711A (en, 2012)
NL (2) NL106717C (en, 2012)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3129123A (en) * 1962-04-04 1964-04-14 Amchem Prod Method and solution for applying a phosphate conversion coating on ferriferous surfaces
US3129121A (en) * 1962-04-04 1964-04-14 Amchem Prod Phosphate coating solution and method of coating ferriferous metal
US3220233A (en) * 1963-03-06 1965-11-30 Universal Oil Prod Co Working of metals with salts of amine carboxylic acids and amine alkyl phosphate
US3400023A (en) * 1964-05-11 1968-09-03 Kelite Corp Composition for preservation of metals, process and article
US3411995A (en) * 1965-03-15 1968-11-19 Enthone Process and product for plating on cast,malleable,carburized and carbonitrided irons
US3445298A (en) * 1966-07-21 1969-05-20 Inland Steel Co Chemical treatment of metal surface to improve paint adherence
US4289546A (en) * 1979-08-07 1981-09-15 Hooker Chemicals & Plastics Corp. Aqueous acidic lubricant composition and method for coating metals
US4289547A (en) * 1979-08-07 1981-09-15 Hooker Chemicals & Plastics Corp. Aqueous acidic lubricant coating composition and method
US5650097A (en) * 1994-06-13 1997-07-22 E. I. Du Pont De Nemours And Company Corrosion inhibitor composition for steel

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1095239B (de) * 1957-08-23 1960-12-22 Degussa Verfahren zum Oxydationsschutz beim Metallstrangpressen
US3082116A (en) * 1961-11-20 1963-03-19 Hooker Chemical Corp Method of pickling and coating with vitreous enamel

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1900973A (en) * 1926-11-25 1933-03-14 Bohme H Th Ag Phosphoric acid esters
US1936534A (en) * 1931-09-08 1933-11-21 Du Pont Coating compositions
US2080299A (en) * 1935-04-12 1937-05-11 Du Pont Inhibiting corrosion of metals
US2285853A (en) * 1934-02-23 1942-06-09 Du Pont Lubrication
US2328540A (en) * 1940-06-08 1943-09-07 Monsanto Chemicals Method of and material for treating metal
US2432784A (en) * 1945-12-07 1947-12-16 Harold F Miller Lubricating and cooling compound for cold reducing mills
US2452321A (en) * 1943-11-05 1948-10-26 Texas Co Rust preventive composition
US2456947A (en) * 1944-12-21 1948-12-21 Westinghouse Electric Corp Corrosion resistant coating for metal surfaces
US2574955A (en) * 1948-07-14 1951-11-13 Tide Water Associated Oil Comp Esterified alkylolamine salts of acid esters of phosphorus acids
GB732286A (en) * 1952-04-07 1955-06-22 Asta Werke Ag Chem Fab New stilbestrol derivatives and preparation thereof
US2739915A (en) * 1950-07-20 1956-03-27 Schuster Ludwig Karl Multiple action lubricating composition

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB478338A (en) * 1935-04-12 1938-01-17 Du Pont Improvements in or relating to the inhibition of corrosion of metals
GB562586A (en) * 1942-11-20 1944-07-07 Du Pont Improvements in and relating to the prevention of atmospheric corrosion of metal surfaces
GB644127A (en) * 1942-12-31 1950-10-04 Wheelco Instr Company Improvements in or relating to a control system for a machine tool

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1900973A (en) * 1926-11-25 1933-03-14 Bohme H Th Ag Phosphoric acid esters
US1936534A (en) * 1931-09-08 1933-11-21 Du Pont Coating compositions
US2285853A (en) * 1934-02-23 1942-06-09 Du Pont Lubrication
US2080299A (en) * 1935-04-12 1937-05-11 Du Pont Inhibiting corrosion of metals
US2328540A (en) * 1940-06-08 1943-09-07 Monsanto Chemicals Method of and material for treating metal
US2452321A (en) * 1943-11-05 1948-10-26 Texas Co Rust preventive composition
US2456947A (en) * 1944-12-21 1948-12-21 Westinghouse Electric Corp Corrosion resistant coating for metal surfaces
US2432784A (en) * 1945-12-07 1947-12-16 Harold F Miller Lubricating and cooling compound for cold reducing mills
US2574955A (en) * 1948-07-14 1951-11-13 Tide Water Associated Oil Comp Esterified alkylolamine salts of acid esters of phosphorus acids
US2739915A (en) * 1950-07-20 1956-03-27 Schuster Ludwig Karl Multiple action lubricating composition
GB732286A (en) * 1952-04-07 1955-06-22 Asta Werke Ag Chem Fab New stilbestrol derivatives and preparation thereof

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3129123A (en) * 1962-04-04 1964-04-14 Amchem Prod Method and solution for applying a phosphate conversion coating on ferriferous surfaces
US3129121A (en) * 1962-04-04 1964-04-14 Amchem Prod Phosphate coating solution and method of coating ferriferous metal
US3220233A (en) * 1963-03-06 1965-11-30 Universal Oil Prod Co Working of metals with salts of amine carboxylic acids and amine alkyl phosphate
US3400023A (en) * 1964-05-11 1968-09-03 Kelite Corp Composition for preservation of metals, process and article
US3411995A (en) * 1965-03-15 1968-11-19 Enthone Process and product for plating on cast,malleable,carburized and carbonitrided irons
US3445298A (en) * 1966-07-21 1969-05-20 Inland Steel Co Chemical treatment of metal surface to improve paint adherence
US4289546A (en) * 1979-08-07 1981-09-15 Hooker Chemicals & Plastics Corp. Aqueous acidic lubricant composition and method for coating metals
US4289547A (en) * 1979-08-07 1981-09-15 Hooker Chemicals & Plastics Corp. Aqueous acidic lubricant coating composition and method
US5650097A (en) * 1994-06-13 1997-07-22 E. I. Du Pont De Nemours And Company Corrosion inhibitor composition for steel

Also Published As

Publication number Publication date
NL187985B (nl)
FR1105973A (fr) 1955-12-09
GB752711A (en) 1956-07-11
BE529431A (en, 2012)
NL106717C (en, 2012)
DE1204913B (de) 1965-11-11

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