[go: up one dir, main page]

US3630790A - Method of protection of metal surfaces from corrosion - Google Patents

Method of protection of metal surfaces from corrosion Download PDF

Info

Publication number
US3630790A
US3630790A US824246A US3630790DA US3630790A US 3630790 A US3630790 A US 3630790A US 824246 A US824246 A US 824246A US 3630790D A US3630790D A US 3630790DA US 3630790 A US3630790 A US 3630790A
Authority
US
United States
Prior art keywords
acid
metal
corrosion
phosphonous
phosphonic acid
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
Application number
US824246A
Inventor
Donald L Schmidt
William J Leahy
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.)
Dow Chemical Co
Original Assignee
Dow Chemical Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Dow Chemical Co filed Critical Dow Chemical Co
Application granted granted Critical
Publication of US3630790A publication Critical patent/US3630790A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
    • C23C22/02Chemical 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
    • C23C22/03Chemical 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 phosphorus compounds
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
    • C23C22/73Chemical 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 characterised by the process
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23FNON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/167Phosphorus-containing compounds
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23FNON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/167Phosphorus-containing compounds
    • C23F11/1676Phosphonic acids

Definitions

  • the present invention is a method of protecting metal surfaces from corrosion which comprises contacting the metal with an organo phosphonic, phosphonous or phosphinic acid.
  • METHOD OF PROTECTION OF METAL SURFACES FROM CORROSION BACKGROUND OF THE INVENTION inhibition of the process is provided by formation of a hydroly sis resistant MO-P bond between the metal and the acid, thus setting up a layer of organic moieties of the acid on the metal surface.
  • the layer effectively keeps water and water- Thi metal Surfaces are reactive and require protection 5 borne corrosives out of contact with the metal surface. The' from water corrosion and waterborne corrosive agents.
  • the pihtehhoh ihoiehjses as the length of the carbon chain of h surface of plastic which has been coated with a thin metal is organic moiety .ihcrehses' h i f h as the chrhhh Chhlh especially susceptible to corrosion. Aluminum has been found becomes hxceedihgiy iohg ihhihihoh h chiiosioh hecoihes to be an effective coating for polyester plastic films.
  • phosphoric acid may be used to form a cor- Phosphohie acids have been tieuhd to Provide Protection rosion resistant coating on metal surfaces.
  • the process is normally used to prosubstitutehts which ay form a P of theorgahie moiety are tect massive forms of metal and coatings having a thickness of Preferably those Whleh do not slghlfieahtly decrease from 0.000l5 to 0.0003 inch are normally applied to effecy p y- Fluorihei chlorine, bromine 'y are tively protect the metal substrate.
  • PrefeTredother Substituehts include y i mereapto and readily applicable to thin metal films due to the excessive y y p thiekhess of e coating
  • the PmeeSS also p y reagents
  • the invention is normally practices by practiced a dilute which would smp the Polyester film of its aluminum ssolution of the acid to be applied and dipping the metal into it.
  • a 3135 i 7558 teaches the use of a PhOSPhQhate ih Polar organic liquids such as acetone, tetrahydrofuran and the comhihahoh with a deieigehcy buiidei'
  • This composition is lower ethers, i.e., those ethers containing from two to 10 cartaught to have the effect of reducing the cori'osivehess of the hon atoms, are convenient solvents for the acids used in the detergency builder by the in situ formation of a protective present method water and nonpolar organic Solvents may coming the metai surface and is mended for use in aqhe' also be used although the acids are somewhat less soluble in ous solutlon wherein the acid salt acts as the corrosion inhibithese Solvents.
  • the PH of the solution should be less than 7.
  • a dipping period of from It would be deslrable and it is an ob ect of the present lnvenabout 10 to 15 Seconds is Sufficiem to impart a protective tion to provide a method for inhibiting corrosion of metal surcoating to the memL Repeated dipping may be employed to provide a more substantial protective coating.
  • the coated h h hmhhi: ohiect provide Such a meihhd ,which h metal may then be washed with the solvent and allowed to dry.
  • :sggh be carried out whhoht the use of Specihhzed equip
  • the metal may be contacted with the acid solution by other means such as spraying, brushing or roll coating.
  • the protecbeast films by lntroduclng the acld to a fluld contained in a metal vessel.
  • the method can be used to coat an of the metals which The present lhvehhoh h methhd for phhechhg metal form insoluble phosphates.
  • the comm n construction metals faces h applying pmthchve Cohhhgs metal shrfhces'
  • the such as iron. nickel, copper, zinc, lead, tin, magnesium, and method involves contacting the metal with a solutlon of an aIuminum may be coated by the present method.
  • the method it o o is especially effective for coating thin sheets of aluminum.
  • Aluminum coated polyethylene terephthalate film was Unexpectedly the aeid is h e p the acid Salts of dipped into the solution for a period of from about 10 to 15 i 8 in providing coiiosioh proiechoh to seconds. In each case the film was cut in half before treatment meiiii surfaces especiahy meiai surfaces which i'eadiiy form with the acid solution and one-half left untreated as a control. oxide surface coatings.
  • a piece of aluminum coated polyethylene terephthalate film was cut into four pieces. The pieces were designated A, B, C and D and treated as follows:
  • A was dipped in a solution of 0.1 gram dodecyl phosphonic acid in 100 milliliters of acetone for 30 seconds.
  • I l. B was dipped in a solution of 0. 1 gram of the sodium salt of dodecyl phosphonic acid in 100 milliliters of boiling water for 30 seconds.
  • C was dipped in a solution of 0.l gram of dodecyl phosphonic acid in 100 milliliters of water for 30 seconds. The water was heated to its boiling point in order to get the acid into solution.
  • protective coatings can be applied to the surfaces of metals other than aluminum, such as for example. iron, nickel, copper, zinc, lead, tin or magnesium.
  • the invention is practiced in a manner similar to that of the above examples wherein the acid employed is characterized of the formula and R is straight or branched chain, substituted or unsubstituted, pentyl, heptyl, nonyl, undecyl, tridecyl, pentadecyl, nonadecyl, docosyl and tetracosyl.
  • R is selected so that the total number of carbon atoms in the molecule does not exceed about 24.
  • n-pentyl phosphonic acid (p-t-butylstyryl) phosphonic acid, hexyl phosphonic acid, n-heptyl phosphonic acid, 3-heptyl phosphonic acid, octyl phosphonic acid, n-nonyl phosphonic acid 4-nonyl phosphonic acid, n-undecyl phosphonic acid, n-pentadecyl phosphonic acid, n-nonadecyl phosphonic acid, n-tetracosyl phosphonic acid, dipentyl phosphinic acid, heptyl butyl phosphinic acid, dinonyl phosphinic acid, benzyl butyl phosphinic acid, benzyl heptyl phosphinic acid, benzyl hexyl phosphinic acid, dibenzyl phosphonic acid, di-n-butyl
  • a method for protecting thin metal films not adaptable to treatment with phosphoric acid from corrosion which comprises contacting the metal film with a polar organic liquid solution of an acid characterized by the formula wherein R is a straight or branched chain, hydrophobic, substttuted or unsubstituted alkyl, aryl, alkaryl or arylalkyl group containing from to l4 carbon atoms; thereby setting up a layer of organic moieties of the acid on the metal surface.
  • R is an alkyl containing from 10 to 14 carbon atoms.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Chemical Treatment Of Metals (AREA)

Abstract

The present invention is a method of protecting metal surfaces from corrosion which comprises contacting the metal with an organo phosphonic, phosphonous or phosphinic acid.

Description

United States Patent Donald L. Schmidt;
William J. Leahy, both of Midland, Mich. 824,246
May 13, 1969 Dec. 28, 1971 The Dow Chemical Company Midland, Mich.
inventors Appl. No. Filed Patented Assignee METHOD OF PROTECTION OF METAL SURFACES FROM CORROSION 8 Claims, No Drawings U.S. Cl l48/6.15 R, 106/14, 252/389 Int. Cl C23! 7/00 Field 01 Search 148/615;
Faulkner, .1. Oil Col. Chem. Assn., 1967 Vol. 50 pp. 524, 525, 526, 541, 542, 544
Primary Examiner-Ralph S. Kendall Attorneys-Griswold and Burdick, William R. Norris and Lloyd S. Jowanovitz ABSTRACT: The present invention is a method of protecting metal surfaces from corrosion which comprises contacting the metal with an organo phosphonic, phosphonous or phosphinic acid.
METHOD OF PROTECTION OF METAL SURFACES FROM CORROSION BACKGROUND OF THE INVENTION inhibition of the process is provided by formation of a hydroly sis resistant MO-P bond between the metal and the acid, thus setting up a layer of organic moieties of the acid on the metal surface. The layer effectively keeps water and water- Thi metal Surfaces are reactive and require protection 5 borne corrosives out of contact with the metal surface. The' from water corrosion and waterborne corrosive agents. The pihtehhoh ihoiehjses as the length of the carbon chain of h surface of plastic which has been coated with a thin metal is organic moiety .ihcrehses' h i f h as the chrhhh Chhlh especially susceptible to corrosion. Aluminum has been found becomes hxceedihgiy iohg ihhihihoh h chiiosioh hecoihes to be an effective coating for polyester plastic films. However, i effective and aiess Protective homing is provided Acids the aforementioned difficulties are quite apparent when aluin which the organic moiety chhthihs h one to about 24 minum is applied to the polyester film in very thin layers. caihoh atoms are P h Acihs having 10 to i4 carhoh Present methods of protecting such films include anodization htohis in h organic moieiiy provide especially effective and overlacquering or laminating the aluminum Surface with a tectlon, with the aclds havlng 12 carbon atoms being the most tough corrosion resistant plastic. 15 preferred It is known that phosphoric acid may be used to form a cor- Phosphohie acids have been tieuhd to Provide Protection rosion resistant coating on metal surfaces. This method of Perior to that of the Phosphihie and Phosphohous acid and are coating metal Surfaces commonly known as parka-hing, the preferred acids for the practice of the present invention. volves coating the metal by dipping or spraying it with a solu- The Orgahie moiety y be Substituted Substitutedtion of phosphoric acid. The process is normally used to prosubstitutehts which ay form a P of theorgahie moiety are tect massive forms of metal and coatings having a thickness of Preferably those Whleh do not slghlfieahtly decrease from 0.000l5 to 0.0003 inch are normally applied to effecy p y- Fluorihei chlorine, bromine 'y are tively protect the metal substrate. Such a method would not be PrefeTredother Substituehts include y i mereapto and readily applicable to thin metal films due to the excessive y y p thiekhess of e coating The PmeeSS also p y reagents The invention is normally practices by practiced a dilute which would smp the Polyester film of its aluminum ssolution of the acid to be applied and dipping the metal into it.
a 3135 i 7558 teaches the use ofa PhOSPhQhate ih Polar organic liquids such as acetone, tetrahydrofuran and the comhihahoh with a deieigehcy buiidei' This composition is lower ethers, i.e., those ethers containing from two to 10 cartaught to have the effect of reducing the cori'osivehess of the hon atoms, are convenient solvents for the acids used in the detergency builder by the in situ formation of a protective present method water and nonpolar organic Solvents may coming the metai surface and is mended for use in aqhe' also be used although the acids are somewhat less soluble in ous solutlon wherein the acid salt acts as the corrosion inhibithese Solvents. w water is emp|oyed as the Solvent, the PH of the solution should be less than 7. A dipping period of from It would be deslrable and it is an ob ect of the present lnvenabout 10 to 15 Seconds is Sufficiem to impart a protective tion to provide a method for inhibiting corrosion of metal surcoating to the memL Repeated dipping may be employed to provide a more substantial protective coating. The coated h h hmhhi: ohiect provide Such a meihhd ,which h metal may then be washed with the solvent and allowed to dry. :sggh be carried out whhoht the use of Specihhzed equip The metal may be contacted with the acid solution by other means such as spraying, brushing or roll coating. The protecbeast films by lntroduclng the acld to a fluld contained in a metal vessel.
' By such addition, the sides of the vessel will be protected from SUMMARY OF THE INVENTION corrosion- The method can be used to coat an of the metals which The present lhvehhoh h methhd for phhechhg metal form insoluble phosphates. The comm n construction metals faces h applying pmthchve Cohhhgs metal shrfhces' The such as iron. nickel, copper, zinc, lead, tin, magnesium, and method involves contacting the metal with a solutlon of an aIuminum may be coated by the present method. The method it o o is especially effective for coating thin sheets of aluminum. (R3 on) phosphonic (R son r phosphonous (Rt 0) acid The following examples will serve to more fully illustrate the l present lnventlon. OH H The R group attached to the acid radical is a hydrophobic or- EXAMPLES i 9 gahie moiety having one to about 24 Carbon atoms- Solutions of acids were prepared by dissolving 0.1 gram of ampleS of R g p are a Straight branched chain the acid in 100 milliliters of solvent, Examples 1-5 used i h or unsubstituted y i 'y aikaryi or arylaikyi tetrahydrofuran and examples 6-9 used acetone as the soltalhlhg from one to abl1t24 vent. Aluminum coated polyethylene terephthalate film was Unexpectedly the aeid is h e p the acid Salts of dipped into the solution for a period of from about 10 to 15 i 8 in providing coiiosioh proiechoh to seconds. In each case the film was cut in half before treatment meiiii surfaces especiahy meiai surfaces which i'eadiiy form with the acid solution and one-half left untreated as a control. oxide surface coatings. Particularly useful results are achieved After the m which had been treated was allowed to dry and in the instance of thin meiai himswashed with acetone to remove unreacted acid, it and the con- DESCRIPTION OF PREFERRED EMBODIMENTS trol sample were immersed in boiling deionized water and the time requlred for removal of the metal coating was vlsually ob- While the present invention is not premised on an explanaserved. Table i represents the results of these tests for a tion of its underlying theory, it is believed that the corrosion number of acids.
TABLE I Time required to Ex. Demetalizo Demvtalizo No. Acid Formula treated him untreated film 0 1. Methyl phospllonic acid CH3? e011 1 mill. 4?. sue. 1 mill. 3 sec.
Me -ll.-
Ex. \o \t'ill l mmul l 2 lhi-nyl phosphonic acid. sllsl ()lI ,2 3 n-Octyl phosphonic acid (tllni (HI 4 ll-l)(lll\l' \l I phosphonic acid (nligs l (i ll 5 li-(irtadvcvl phosphonic acid ('nlla: l (HI l) ll U ti ()ctyl phosphinic acid ltslliml Ull 0 T 3.3.3-1rillum'opropyl phosphinic acid F11 Hit-l: l U l[ ll a lhvni'l phosphonous arid. y I 1) ll U 7 .I ||-l )orll'ryl l phosphonic acid (r ll '5 l 0 ll 'limo required to lhmv-tzilizt lhmctulizt' trvatvil lilm untreated lilni l min. 12 si'v l min. 3 sec.
min. 7 sec 1 min. 15sec.
16 111111.!) svc 1min. 3 t(.
15 min. 0 S 1 min. 3 svc.
l min. Stt 54 sec,
1 min. 30 sec. 54 sec.
1 min. 5N SI(' 54 sec.
16 min. l S l. 36 set.
I Whvn dodecyl phosphonic acid was usml, no (li'nwliilization had occurred in 16 minutes, at which Linn this-xpl-rinulit was stopped.
EXAMPLES lO-l 3 In order to compare the elTectiveness of the present method, wherein the solvent was either aqueous or nonaqueous, and the method of providing protection by using the aqueous solution of the acid salt, the following experiment was conducted:
A piece of aluminum coated polyethylene terephthalate film was cut into four pieces. The pieces were designated A, B, C and D and treated as follows:
10. A was dipped in a solution of 0.1 gram dodecyl phosphonic acid in 100 milliliters of acetone for 30 seconds.
I l. B was dipped in a solution of 0. 1 gram of the sodium salt of dodecyl phosphonic acid in 100 milliliters of boiling water for 30 seconds.
12. C was dipped in a solution of 0.l gram of dodecyl phosphonic acid in 100 milliliters of water for 30 seconds. The water was heated to its boiling point in order to get the acid into solution.
13. D was left untreated and used as a control.
Each of the treated samples was washed with the acid solvent and allowed to dry after treatment. Each sample was dipped into boiling deionized water and the time required for the metal coating to be removed was visually observed. Table ll represents the results of these tests.
The above data indicate that the sample treated with a 75 nonaqucous solution of the acid took more than twice as long to demetalize than did that treated with a water solution of the acid. The acid salt imparted some protection to the metal surface but considerably less than did the unaltered acid.
In a manner similar to that of examples l and ll protective coatings can be applied to the surfaces of metals other than aluminum, such as for example. iron, nickel, copper, zinc, lead, tin or magnesium.
The invention is practiced in a manner similar to that of the above examples wherein the acid employed is characterized of the formula and R is straight or branched chain, substituted or unsubstituted, pentyl, heptyl, nonyl, undecyl, tridecyl, pentadecyl, nonadecyl, docosyl and tetracosyl. However, R is selected so that the total number of carbon atoms in the molecule does not exceed about 24.
Specific examples of such acids are n-pentyl phosphonic acid, (p-t-butylstyryl) phosphonic acid, hexyl phosphonic acid, n-heptyl phosphonic acid, 3-heptyl phosphonic acid, octyl phosphonic acid, n-nonyl phosphonic acid 4-nonyl phosphonic acid, n-undecyl phosphonic acid, n-pentadecyl phosphonic acid, n-nonadecyl phosphonic acid, n-tetracosyl phosphonic acid, dipentyl phosphinic acid, heptyl butyl phosphinic acid, dinonyl phosphinic acid, benzyl butyl phosphinic acid, benzyl heptyl phosphinic acid, benzyl hexyl phosphinic acid, dibenzyl phosphonic acid, di-n-butyl phosphinic acid, diundecyl phosphonic acid, didocyl phosphinic acid, dihexyl phosphinic acid, di-n-octyl phosphinic acid, bis(2-ethyl hexyl) phosphinic acid, butyl phenyl phosphinic acid, decyl ethyl phosphinic acid, di-t-butyl phosphinic acid, didecyl phosphinic acid, diisobutyl phosphinic acid, diisopropyl phosphinic acid, di-n-propyl phosphinic acid, ethyl isopropyl phosphinic acid, isopropyl phenyl phosphinic acid, n-pentyl phosphonous acid, 6-undecyl phosphonous acid, n-tridecyl phosphonous l. A method for protecting thin metal films not adaptable to treatment with phosphoric acid from corrosion which comprises contacting the metal film with a polar organic liquid solution of an acid characterized by the formula wherein R is a straight or branched chain, hydrophobic, substttuted or unsubstituted alkyl, aryl, alkaryl or arylalkyl group containing from to l4 carbon atoms; thereby setting up a layer of organic moieties of the acid on the metal surface.
2. The method of claim 1 wherein R is an alkyl containing from 10 to 14 carbon atoms.
3. The method of claim 2 wherein the acid is characterized by the formula CERTIFICATE OF CORRECTION Patent No. 3,630,790 Dated 28 December 1971 In fl Donald L. Schmidt and William J. Leahy It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
Column 1, line &7, insert organo phosphinic at the end of the line following "an"; line 57 insert -ca.rbonbetween "2h" and "atoms."-
Column 2, line 25, delete practices by" and insert -by preparing-- between "practiced" and "a dilute".
Column l, line +6, delete "of" and insert -by-; in the blank space between lines k8 and 53 insert the following formulae:
Column l, line 76, insert the following after the last word in the column, "phosphonous" acid, lO-nonadecyl phosphonous acid, n-docosyl phosphonous I acid, and n-tetracosyl phosphonous acid.
Signed and sea-led this 27th day of June 1972.
(SEAL) Attest:
EDWARD M.FLETCHER,JR. ROBERT GOTTSCHALK Attesting Officer Commissioner of Patents P0405) Q UNITED STATES PATENT OFFICE CERTIFICATE 0F CORRECTION Patent No. 3,630,790 Dated 28 December 1971 Inventorv(s) Donald L. Schmidt and William Leahy It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
Column 1, line &7, insert organo phosphinicat the end ofthe line following "an"; line 5? insert --carbonbetween "2 and "atoms."
Column 2, line 25 delete "practices by" and insert by preparing-- between "practiced" and "a dilute".
Column l, line L6, delete "of" and insert -;by--; in the blank space between lines &8 and 53 insert the following formulae:
Column line 76, insert the'following after the last word in the column, "phosphonous":
- acid, lO-nonadecyl phosphonous acid, n-docosyl phosphonous acid, and n-tetracosyl phosphonous acid.
Signed and sealed this 27th day of June 1972.
(SEAL) Attest:
EDWARD M.FLETCHER,JR. ROBERT GOT'ISCHALK Attesting Officer Commissioner of Patents

Claims (7)

  1. 2. THe method of claim 1 wherein R is an alkyl containing from 10 to 14 carbon atoms.
  2. 3. The method of claim 2 wherein the acid is characterized by the formula
  3. 4. The method of claim 3 wherein R is an alkyl containing 12 carbon atoms.
  4. 5. The method of claim 1 wherein the solvent is acetone, tetrahydrofuran or a lower ether.
  5. 6. The method of claim 1 wherein the metal is selected from the group consisting of iron, nickel, copper, zinc, lead, tin, magnesium or aluminum.
  6. 7. The method of claim 1 wherein the metal is dipped into the acid solution, rinsed with the acid solvent and allowed to dry.
  7. 8. The method of claim 1 wherein the metal film is aluminum.
US824246A 1969-05-13 1969-05-13 Method of protection of metal surfaces from corrosion Expired - Lifetime US3630790A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US82424669A 1969-05-13 1969-05-13

Publications (1)

Publication Number Publication Date
US3630790A true US3630790A (en) 1971-12-28

Family

ID=25240944

Family Applications (1)

Application Number Title Priority Date Filing Date
US824246A Expired - Lifetime US3630790A (en) 1969-05-13 1969-05-13 Method of protection of metal surfaces from corrosion

Country Status (1)

Country Link
US (1) US3630790A (en)

Cited By (45)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3900370A (en) * 1972-03-10 1975-08-19 Henkel & Cie Gmbh Process for treating aluminum surfaces
US3960576A (en) * 1973-06-25 1976-06-01 Betz Laboratories, Inc. Silicate-based corrosion inhibitor
US4042324A (en) * 1975-02-08 1977-08-16 Hoechst Aktiengesellschaft Process for inhibiting the corrosions and deposition of boiler scale in water-conveying systems
US4048374A (en) * 1973-09-01 1977-09-13 Dynamit Nobel Aktiengesellschaft Functional organophosphonic acid esters as preservative adhesion promoting agents and coating for metals
EP0009247A1 (en) * 1978-09-25 1980-04-02 Henkel Kommanditgesellschaft auf Aktien Corrosion inhibitors for acidic solutions
US4202706A (en) * 1979-03-12 1980-05-13 Minnesota Mining And Manufacturing Company Corrosion resistance treatment of aluminum with N-alkyl-fluoroaliphaticsulfonamidophosphonic acids and salts thereof
US4264379A (en) * 1980-01-11 1981-04-28 Olin Corporation Process for coating copper and copper alloy
US4293441A (en) * 1979-03-12 1981-10-06 Minnesota Mining And Manufacturing Company Corrosion inhibiting heat transfer liquid
US4427459A (en) 1982-01-25 1984-01-24 Pennwalt Corporation Phosphate conversion coatings for metals with reduced coating weights and crystal sizes
US4452650A (en) * 1980-01-11 1984-06-05 Olin Corporation Copper and copper alloy coating
US4505748A (en) * 1982-11-10 1985-03-19 International Paint Anti-corrosive paint
WO1987002714A1 (en) * 1985-10-28 1987-05-07 Giovanni Bozzetto S.P.A. Process for the preservation of organic products
EP0544345A1 (en) * 1991-11-23 1993-06-02 Fmc Corporation (Uk) Limited Corrosion and/or scale inhibition
US5318838A (en) * 1988-01-22 1994-06-07 Fuji Photo Film Co., Ltd. Magnetic recording medium comprising ferromagnetic particles, binder resins and phenyl phosphonic acid
EP0520649A3 (en) * 1991-06-21 1995-03-29 American Telephone & Telegraph Process for making corrosion-resistant coatings
JPH07300595A (en) * 1995-04-12 1995-11-14 At & T Corp Lubricating method for surface of object
WO1997018905A1 (en) * 1995-11-20 1997-05-29 Berg Technology, Inc. Method of providing corrosion protection
US5904979A (en) * 1995-02-21 1999-05-18 Fuji Photo Film Co., Ltd. Magnetic recording system
US5942052A (en) * 1994-04-20 1999-08-24 Nippon Paint Co., Ltd. Surface treatment aqueous solution for metal
WO2002033749A1 (en) * 2000-10-14 2002-04-25 Robert Bosch Gmbh Method for protecting electronic or micromechanical components
US6423185B1 (en) * 1998-03-03 2002-07-23 Metso Paper, Inc. Process of surface treatment for faces that become contaminated in a paper or board machine
US20020117135A1 (en) * 2001-02-07 2002-08-29 Toshihiro Nozue Flexible transmitter tensioner for outboard motor
US6458874B1 (en) * 2000-06-22 2002-10-01 Basf Corporation Coating compositions having improved direct to metal adhesion
EP1221497A3 (en) * 1998-06-19 2003-12-03 Alcoa Inc. Method for inhibiting stains on aluminum product surfaces
US20040030088A1 (en) * 2002-08-07 2004-02-12 Basf Corporation Acidic reducer for providing increased adhesion of a two component polyurethane primer to substrates
US20040071887A1 (en) * 2002-10-10 2004-04-15 Basf Corporation Coating compositions having improved "direct to metal" adhesion and method therefore
US20040071884A1 (en) * 2002-10-10 2004-04-15 Newton David L. Coating composition with improved adhesion and method therefor
US20050268991A1 (en) * 2004-06-03 2005-12-08 Enthone Inc. Corrosion resistance enhancement of tin surfaces
US20080108537A1 (en) * 2006-11-03 2008-05-08 Rees Wayne M Corrosion inhibitor system for mildly acidic to ph neutral halogen bleach-containing cleaning compositions
US20080261025A1 (en) * 2007-04-18 2008-10-23 Enthone Inc. Metallic surface enhancement
US20080314283A1 (en) * 2007-06-21 2008-12-25 Enthone Inc. Corrosion protection of bronzes
EP2014798A1 (en) * 2007-07-10 2009-01-14 Atotech Deutschland Gmbh Solution and process for increasing the solderability and corrosion resistance of metal or metal alloy surface
US20090050143A1 (en) * 2006-03-24 2009-02-26 Boardman Larry D Medicinal formulation container with a treated metal surface
US20090121192A1 (en) * 2007-11-08 2009-05-14 Enthone Inc. Self assembled molecules on immersion silver coatings
WO2010081833A2 (en) 2009-01-14 2010-07-22 Atotech Deutschland Gmbh Solution and process for increasing the solderability and corrosion resistance of a metal or metal alloy surface
US20100291303A1 (en) * 2007-11-21 2010-11-18 Enthone Inc. Anti-tarnish coatings
CN1861842B (en) * 2005-04-20 2011-08-03 罗门哈斯电子材料有限公司 Immersion method
WO2016160766A1 (en) * 2015-04-03 2016-10-06 Moxtek, Inc Hydrophobic phosphonate and silane chemistry
US9703028B2 (en) 2015-04-03 2017-07-11 Moxtek, Inc. Wire grid polarizer with phosphonate protective coating
US9995864B2 (en) 2015-04-03 2018-06-12 Moxtek, Inc. Wire grid polarizer with silane protective coating
US10054717B2 (en) 2015-04-03 2018-08-21 Moxtek, Inc. Oxidation and moisture barrier layers for wire grid polarizer
CN110407869A (en) * 2019-07-11 2019-11-05 兰州大学 Preparation method and application of monotrifluoropropylphosphinate aluminum flame retardant
US20190360115A1 (en) * 2016-11-18 2019-11-28 National Chung Hsing University Method for manufacturing copper composite electrode with a flake structure on the surface
US11359163B2 (en) * 2018-04-20 2022-06-14 Arkema France Use of hypophosphorous acid for the esterification of free fatty acids
EP4299793A3 (en) * 2019-03-01 2024-03-20 Howmet Aerospace Inc. Metallic substrate treatment methods and articles comprising a phosphonate functionalized layer

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2885312A (en) * 1956-03-05 1959-05-05 Kelite Corp Metal coating compositions
US3272662A (en) * 1961-02-08 1966-09-13 Hoechst Ag Process for after-treating metal surfaces coated with crystalline anticorrosion layers
US3293088A (en) * 1959-11-18 1966-12-20 Hoechst Ag Method for producing adherent coatings on clean metal parts
US3468725A (en) * 1965-06-03 1969-09-23 Kalle Ag Process for the preparation of planographic printing plates

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2885312A (en) * 1956-03-05 1959-05-05 Kelite Corp Metal coating compositions
US3293088A (en) * 1959-11-18 1966-12-20 Hoechst Ag Method for producing adherent coatings on clean metal parts
US3272662A (en) * 1961-02-08 1966-09-13 Hoechst Ag Process for after-treating metal surfaces coated with crystalline anticorrosion layers
US3468725A (en) * 1965-06-03 1969-09-23 Kalle Ag Process for the preparation of planographic printing plates

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Faulkner, J. Oil Col. Chem. Assn., 1967 Vol. 50 pp. 524, 525, 526, 541, 542, 544 *

Cited By (72)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3900370A (en) * 1972-03-10 1975-08-19 Henkel & Cie Gmbh Process for treating aluminum surfaces
US3960576A (en) * 1973-06-25 1976-06-01 Betz Laboratories, Inc. Silicate-based corrosion inhibitor
US4048374A (en) * 1973-09-01 1977-09-13 Dynamit Nobel Aktiengesellschaft Functional organophosphonic acid esters as preservative adhesion promoting agents and coating for metals
US4042324A (en) * 1975-02-08 1977-08-16 Hoechst Aktiengesellschaft Process for inhibiting the corrosions and deposition of boiler scale in water-conveying systems
EP0009247A1 (en) * 1978-09-25 1980-04-02 Henkel Kommanditgesellschaft auf Aktien Corrosion inhibitors for acidic solutions
DE2841641A1 (en) * 1978-09-25 1980-04-03 Henkel Kgaa CORROSION INHIBITOR FOR ACID SOLUTIONS
US4293441A (en) * 1979-03-12 1981-10-06 Minnesota Mining And Manufacturing Company Corrosion inhibiting heat transfer liquid
US4202706A (en) * 1979-03-12 1980-05-13 Minnesota Mining And Manufacturing Company Corrosion resistance treatment of aluminum with N-alkyl-fluoroaliphaticsulfonamidophosphonic acids and salts thereof
US4264379A (en) * 1980-01-11 1981-04-28 Olin Corporation Process for coating copper and copper alloy
US4452650A (en) * 1980-01-11 1984-06-05 Olin Corporation Copper and copper alloy coating
US4427459A (en) 1982-01-25 1984-01-24 Pennwalt Corporation Phosphate conversion coatings for metals with reduced coating weights and crystal sizes
US4505748A (en) * 1982-11-10 1985-03-19 International Paint Anti-corrosive paint
WO1987002714A1 (en) * 1985-10-28 1987-05-07 Giovanni Bozzetto S.P.A. Process for the preservation of organic products
US5318838A (en) * 1988-01-22 1994-06-07 Fuji Photo Film Co., Ltd. Magnetic recording medium comprising ferromagnetic particles, binder resins and phenyl phosphonic acid
EP0520649A3 (en) * 1991-06-21 1995-03-29 American Telephone & Telegraph Process for making corrosion-resistant coatings
EP0544345A1 (en) * 1991-11-23 1993-06-02 Fmc Corporation (Uk) Limited Corrosion and/or scale inhibition
US5942052A (en) * 1994-04-20 1999-08-24 Nippon Paint Co., Ltd. Surface treatment aqueous solution for metal
US5904979A (en) * 1995-02-21 1999-05-18 Fuji Photo Film Co., Ltd. Magnetic recording system
JPH07300595A (en) * 1995-04-12 1995-11-14 At & T Corp Lubricating method for surface of object
WO1997018905A1 (en) * 1995-11-20 1997-05-29 Berg Technology, Inc. Method of providing corrosion protection
US5853797A (en) * 1995-11-20 1998-12-29 Lucent Technologies, Inc. Method of providing corrosion protection
US6423185B1 (en) * 1998-03-03 2002-07-23 Metso Paper, Inc. Process of surface treatment for faces that become contaminated in a paper or board machine
EP1221497A3 (en) * 1998-06-19 2003-12-03 Alcoa Inc. Method for inhibiting stains on aluminum product surfaces
US6458874B1 (en) * 2000-06-22 2002-10-01 Basf Corporation Coating compositions having improved direct to metal adhesion
WO2002033749A1 (en) * 2000-10-14 2002-04-25 Robert Bosch Gmbh Method for protecting electronic or micromechanical components
US20040026775A1 (en) * 2000-10-14 2004-02-12 Hans Hecht Method for protecting electronic or micromechanical components
US20020117135A1 (en) * 2001-02-07 2002-08-29 Toshihiro Nozue Flexible transmitter tensioner for outboard motor
US20040030088A1 (en) * 2002-08-07 2004-02-12 Basf Corporation Acidic reducer for providing increased adhesion of a two component polyurethane primer to substrates
US20040071887A1 (en) * 2002-10-10 2004-04-15 Basf Corporation Coating compositions having improved "direct to metal" adhesion and method therefore
US20040071884A1 (en) * 2002-10-10 2004-04-15 Newton David L. Coating composition with improved adhesion and method therefor
US6893680B2 (en) 2002-10-10 2005-05-17 Basf Corporation Coating composition with improved adhesion and method therefor
WO2004099323A1 (en) * 2003-05-02 2004-11-18 Basf Corporation Coating, coating composition and method for improving adhesion of the coating
US20050268991A1 (en) * 2004-06-03 2005-12-08 Enthone Inc. Corrosion resistance enhancement of tin surfaces
WO2005121405A1 (en) * 2004-06-03 2005-12-22 Enthone Inc. Corrosion resistance enhancement of tin surfaces
JP2008501861A (en) * 2004-06-03 2008-01-24 エントン インコーポレイテッド Improvement of corrosion resistance of tin surface
CN101001980B (en) * 2004-06-03 2011-06-15 恩索恩公司 Corrosion resistance enhancement of tin surfaces
TWI409362B (en) * 2004-06-03 2013-09-21 安頌股份有限公司 Enhancement of tin surface corrosion resistance
CN1861842B (en) * 2005-04-20 2011-08-03 罗门哈斯电子材料有限公司 Immersion method
US20090050143A1 (en) * 2006-03-24 2009-02-26 Boardman Larry D Medicinal formulation container with a treated metal surface
US20080108537A1 (en) * 2006-11-03 2008-05-08 Rees Wayne M Corrosion inhibitor system for mildly acidic to ph neutral halogen bleach-containing cleaning compositions
US20080261025A1 (en) * 2007-04-18 2008-10-23 Enthone Inc. Metallic surface enhancement
US8741390B2 (en) 2007-04-18 2014-06-03 Enthone Inc. Metallic surface enhancement
US7883738B2 (en) 2007-04-18 2011-02-08 Enthone Inc. Metallic surface enhancement
US20100151263A1 (en) * 2007-04-18 2010-06-17 Enthone Inc. Metallic surface enhancement
CN101809199B (en) * 2007-06-21 2012-11-14 恩索恩公司 Corrosion proteciton of bronzes
US10017863B2 (en) * 2007-06-21 2018-07-10 Joseph A. Abys Corrosion protection of bronzes
US20100319572A1 (en) * 2007-06-21 2010-12-23 Enthone Inc. Corrosion protection of bronzes
US20080314283A1 (en) * 2007-06-21 2008-12-25 Enthone Inc. Corrosion protection of bronzes
US20100196727A1 (en) * 2007-07-10 2010-08-05 Atotech Deutschland Gmbh Solution and process for increasing the solderability and corrosion resistance of metal or metal alloy surface
EP2014798A1 (en) * 2007-07-10 2009-01-14 Atotech Deutschland Gmbh Solution and process for increasing the solderability and corrosion resistance of metal or metal alloy surface
US8337606B2 (en) 2007-07-10 2012-12-25 Atotech Deutschland Gmbh Solution and process for increasing the solderability and corrosion resistance of metal or metal alloy surface
US20090121192A1 (en) * 2007-11-08 2009-05-14 Enthone Inc. Self assembled molecules on immersion silver coatings
US8323741B2 (en) 2007-11-08 2012-12-04 Abys Joseph A Self assembled molecules on immersion silver coatings
US8216645B2 (en) 2007-11-08 2012-07-10 Enthone Inc. Self assembled molecules on immersion silver coatings
US8703243B2 (en) 2007-11-21 2014-04-22 Enthone Inc. Anti-tarnish coatings
US20100291303A1 (en) * 2007-11-21 2010-11-18 Enthone Inc. Anti-tarnish coatings
US7972655B2 (en) 2007-11-21 2011-07-05 Enthone Inc. Anti-tarnish coatings
WO2010081833A2 (en) 2009-01-14 2010-07-22 Atotech Deutschland Gmbh Solution and process for increasing the solderability and corrosion resistance of a metal or metal alloy surface
US10054717B2 (en) 2015-04-03 2018-08-21 Moxtek, Inc. Oxidation and moisture barrier layers for wire grid polarizer
US10761252B2 (en) 2015-04-03 2020-09-01 Moxtek, Inc. Wire grid polarizer with protective coating
US9995864B2 (en) 2015-04-03 2018-06-12 Moxtek, Inc. Wire grid polarizer with silane protective coating
US9703028B2 (en) 2015-04-03 2017-07-11 Moxtek, Inc. Wire grid polarizer with phosphonate protective coating
US10025015B2 (en) 2015-04-03 2018-07-17 Moxtek, Inc. Wire grid polarizer with phosphonate protective coating
WO2016160766A1 (en) * 2015-04-03 2016-10-06 Moxtek, Inc Hydrophobic phosphonate and silane chemistry
US11513272B2 (en) 2015-04-03 2022-11-29 Moxtek, Inc. Wire grid polarizer with silane protective coating
CN107429086A (en) * 2015-04-03 2017-12-01 莫克斯泰克公司 Hydrophobicity phosphonate ester and silane chemistries material
JP2020122991A (en) * 2015-04-03 2020-08-13 モックステック・インコーポレーテッド Wire grid polarizer
US20190360115A1 (en) * 2016-11-18 2019-11-28 National Chung Hsing University Method for manufacturing copper composite electrode with a flake structure on the surface
US11359163B2 (en) * 2018-04-20 2022-06-14 Arkema France Use of hypophosphorous acid for the esterification of free fatty acids
EP4299793A3 (en) * 2019-03-01 2024-03-20 Howmet Aerospace Inc. Metallic substrate treatment methods and articles comprising a phosphonate functionalized layer
US12018380B2 (en) 2019-03-01 2024-06-25 Howmet Aerospace Inc. Metallic substrate treatment methods and articles comprising a phosphonate functionalized layer
CN110407869A (en) * 2019-07-11 2019-11-05 兰州大学 Preparation method and application of monotrifluoropropylphosphinate aluminum flame retardant

Similar Documents

Publication Publication Date Title
US3630790A (en) Method of protection of metal surfaces from corrosion
CA2651393C (en) Improved trivalent chromium-containing composition for use in corrosion resistant coatings on metal surfaces
HK24191A (en) Process for inhibiting corrosion and/or scale deposits
Elsentriecy et al. Effects of pretreatment and process temperature of a conversion coating produced by an aprotic ammonium-phosphate ionic liquid on magnesium corrosion protection
CN101939388A (en) Aqueous solution for surface treatment for forming corrosion-resistant coating film on zinc or zinc alloy coating layer and treatment method
BRPI0708467B1 (en) COMPOSITION FOR METAL SURFACE TREATMENT, METAL SURFACE TREATMENT METHOD, AND METAL MATERIAL
CA2906308C (en) Improved trivalent chromium-containing composition for aluminum and aluminum alloys
KR101350720B1 (en) Quaternary ammonium salts as a conversion coating or as anticorrosive additive in paints
ES2463446T3 (en) Chrome-free conversion coating
US6248701B1 (en) Aqueous metal coating composition and process with reduced staining and corrosion
US3133787A (en) Corrosion inhibition
JPS59133373A (en) Metal surface treatment and treating bath
US3136663A (en) Compositions and methods for preservation of metals
US3755018A (en) Composition and process for inhibiting corrosion of non-ferrous metal surfaced articles and providing receptive surface for synthetic resin coating compositions
US3400023A (en) Composition for preservation of metals, process and article
US5433773A (en) Method and composition for treatment of phosphate coated metal surfaces
US2816051A (en) Corrosion inhibiting composition for coating metal, coated metal and method of coating
US2402551A (en) Metal protective coatings
US2918390A (en) Corrosion inhibition
US1949921A (en) Cleaning and protecting metals against rusting
US3642653A (en) Water displacing corrosion preventive
US3371047A (en) Method for lubrication and for protection against corrosion, and aqueous colloidal compositions for performing this method
US3876553A (en) Corrosion inhibitor containing sodium benzoate and potassium tripolyphosphate
US3380859A (en) Metal cold forming
EP0239288B1 (en) Corrosion inhibition