US3248235A - Anti-tarnish composition for coppercontaining surfaces - Google Patents

Anti-tarnish composition for coppercontaining surfaces Download PDF

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Publication number
US3248235A
US3248235A US141292A US14129261A US3248235A US 3248235 A US3248235 A US 3248235A US 141292 A US141292 A US 141292A US 14129261 A US14129261 A US 14129261A US 3248235 A US3248235 A US 3248235A
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United States
Prior art keywords
copper
tarnish
abrasive
mercaptan
composition
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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US141292A
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English (en)
Inventor
Donald M Pryor
Louis F Cason
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3M Co
Original Assignee
Minnesota Mining and Manufacturing 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
Priority to BE622957D priority Critical patent/BE622957A/xx
Priority to NL283747D priority patent/NL283747A/xx
Application filed by Minnesota Mining and Manufacturing Co filed Critical Minnesota Mining and Manufacturing Co
Priority to US141292A priority patent/US3248235A/en
Priority to ES280824A priority patent/ES280824A1/es
Priority to SE10116/62A priority patent/SE310529B/xx
Priority to CH1126362A priority patent/CH418088A/de
Priority to FR910332A priority patent/FR1347705A/fr
Priority to DK420562AA priority patent/DK113660B/da
Priority to GB36944/62A priority patent/GB956927A/en
Application granted granted Critical
Publication of US3248235A publication Critical patent/US3248235A/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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/10—Other heavy metals
    • C23G1/103—Other heavy metals copper or alloys of copper
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0043—For use with aerosol devices
    • 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
    • C23F—NON-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
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting 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
    • 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
    • C23F—NON-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
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting 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
    • C23F11/16—Sulfur-containing compounds
    • C23F11/161—Mercaptans

Definitions

  • V W 1 am "m agents or surfactants, Eckeners or VlSCS m/Z' S L/ A 3,248,235 ANTI-TARNISH COMPOSITION FOR COPPER- CONTAINING SURFACES Donald M. Pryor and Louis F. Cason, both of St. Paul,
  • This invention relates to an anti-tarnish composition for treating tarnished copper-containing surfaces and to a method for rendering such surfaces tarnish resistant.
  • Copper-containing surfaces including copper alloys such as bronze, brass, etc.
  • copper cleaners have been suggested for the removal of tarnish deposits, e.g. copper oxides and sulfides.
  • the problem of inhibiting the tarnishing of the cleaned copper-containing surface through the use of di- is to provide a composition which simultaneously cleans copper-containing surfaces and renders such surfaces tarnish resistant for prolonged periods of time.
  • a highly eflicient composition -for cleaning copper-containing surfaces and for rendering such surfaces tarnish resistant over an extended period of time comprises an aliphatic mercaptan of the formula C H SH wherein n is from 12 to 25,
  • aliphatic mercaptans of the above formula provide a thin, colorless, non-oily protective layer on clean copper-containing surfaces, bonding to the copper through the thiol grouping, and that such mercaptans may be incorporated into copper cleaning formulations to provide a protective layer on the copper substrate as the tarnish is effectively removed by the cleaning ingredients.
  • the bond between the copper and the mercaptans is unusually strong, resisting washing with dilute alkaline or acid solutions, and with detergent solutions. of equal importance is the colorless, transparent protective layer of these mercaptan molecules, which does not adversely effect the luster of the copper-containing surface and which does not discolor or embrittle with aging.
  • the film of mercaptan is virtually invisible to the naked eye, the presence of the protective layer may be detected by the hydrophobic or water repellent properties of the protected surface.
  • the acidic cleaners are preferred because of their high efiioiency.
  • the various combinations of acidic ingredi ents suitable for cleaning copper-containing surfaces are well known. Generally, when using acidic cleaning ingredients in aqueous media, a pH of below about 2.5 is preferred.
  • Hydrochloric acid also is also is an effective non-abrasive copper cleaner. Since the anti-tarnish composition must be essentially nonoxidative, stron-g oxidizing acids, such as nitric acid, should not be used. Suitable acids having a pH between 1 and 5, which are water soluble, stable non-oxidizing the tarnish forming compounds. Con'ventionaL copper acids which do not form water insoluble compounds with cleaners frequently contain mild orgz'ifiic'iicids, such" as ESTEZE oT'sulfamic acidf t'ogether with sodium chloride, various surfactants and abrasives.
  • the copper containing surfaces are extremely reactive in contact with the corroding environment. It is therefore preferable, for providing prolonged tarnish resistance, to accomplish the cleaning and the tarnish prevention simultaneously.
  • abrasive containing mercaptan formulations effectively clean and condition the tarnished surface, the concentration or loading" of abrasive required to remove the tarnish deposits tends to remove the protective mercaptan film as it is formed.
  • the presence of non-abrasive copper cleaning ingredients permits the elimination of, or a reduction in,'
  • surfactant particularly the nonionic variety
  • Viscosity acidic media are usually employed.
  • mercaptan or mixture of mereaptans
  • mercaptan conoentration within the 0.5 to 25, preferably 0.5 to 10, weight percent range is particularly effective in formations containing a non-abrasive copper cleaner. Less than about 0.5 percent of mercaptan does not generally provide suflicient tarnish resistance.
  • the most preferred formulations usually contain from about 1 to weight percent of mercaptan, 0.01% to 25% of a weak organic f acid, 0.01% to 25% of an alkali metal halide (e.g., alkali metal chlorides, etc.), 0.05% to 1% of a surfactant, 0 to of an abrasive, sufficient water to emulsify the mercaptan, and sutiicient acid stable thickeners to provide the desired viscosity.
  • a weak organic f acid e.g., alkali metal chlorides, etc.
  • an alkali metal halide e.g., alkali metal chlorides, etc.
  • Example I Test panels of copper and brass were degreased with trichloroethylene and polished with a commercial copper cleaner containing a non-abrasive copper cleaner, i.e., citric acid and sodium chloride, to remove all traces of tarnish. Immediately after cleaning (a water rinse is preferable), the dry copper-containing surfaces were sprayed with a one percent solution of n-octadecane-lthiol in petroleum ether and buffed with a soft cloth. The panels were then exposed to hydrogen sulfide at about 70% relative humidity along with cleaned uncoated control panels. A marked difference in tarnish rate was noticed, the deposits forming on the controls in less than 15 minutes and the coated panels remaining essentially tarnish free for several hours.
  • a commercial copper cleaner containing a non-abrasive copper cleaner i.e., citric acid and sodium chloride
  • Example 11 The procedure of Example I was repeated using nheneicosane-l-thiol instead of n-ocadecane-l-thiol. After exposure to the hydrogen sulfide atmosphere, the control panels (both copper and brass) tarnished in less than 15 minutes, whereas the treated panels were essentially tarnish free for several hours.
  • Example III The following formulation was prepared, the percentages being by weight:
  • Nonionic surfactant 1 Percent Water 60 Colloidal alumina (AlOOH) 3 n-Octadecane-l-mercaptan l0 Citric acid 8 Sodium chloride 8 Abrasive (50% diatomaceous earth and 50% of 240 mesh silica) 10 Nonionic surfactant 1
  • the colloidal alumina thickener was dissolved in water and the temperature raised to C. After mixing the mercaptan and the nonion-ic surfactant and heating to 80 C., the mixture was added to the colloidal alumina solution with high speed mixing, forming a thick creamy emulsion. Once emulsification was complete, the citric acid and the abrasive were added with continued stirring until a homogeneous dispersion was obtained. Then upon adding the sodium chloride, immediate thickening to a. smooth viscous paste occurred.
  • Copper panels were treated with the above formulation using a soft cloth, followed by water rinsing and air drying. Untreated copper panels whch had been cleaned to remove tarnish were used as controls. After immersing both a treated and an untreated panel in a 1% aqueous solution of hydrogen sulfide, the untreated control was observed to tarnish after 5 seconds whereas tarnishing of the treated panel occurred only after about 2 hours. A similar comparative test using a salt bath (5% aqueous sodium chloride) resulted in tarnishing of the untreated control in 30 minutes and no visible tarnishing of the treated panel after two days.
  • a salt bath 5% aqueous sodium chloride
  • Still another comparative test was made by placing both treated and untreated panels in a high temperature (212 F.) oxidative (air) environment, resulting in tarnishing of the untreated control in 10 minutes and tarnishing of the treated panel only after 6 hours.
  • the time reported is the time required for visible signs of tarnish to appear.
  • Example IV Results similar to those in Example III are obtained with the following formulation:
  • copper is used interchangeably with copper-containing and includes, besides copper, such copper-containing alloys as brass, bronze, etc. having significant quantities of copper therein.
  • An aqueous anti-tarnish composition for copper which consists essentially of 0.01% to 25% of a weak organic acid, 0.01% to 25% of an alkali metal halide, 0.05% to 1% of a surfactant, 0 to 20% of abrasive, and 1 to 15% of a mercaptan of the formula where n is an integer from 12 to 25, the pH of said composition being below about 2.5.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Detergent Compositions (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
US141292A 1961-09-28 1961-09-28 Anti-tarnish composition for coppercontaining surfaces Expired - Lifetime US3248235A (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
BE622957D BE622957A (en(2012)) 1961-09-28
NL283747D NL283747A (en(2012)) 1961-09-28
US141292A US3248235A (en) 1961-09-28 1961-09-28 Anti-tarnish composition for coppercontaining surfaces
ES280824A ES280824A1 (es) 1961-09-28 1962-09-15 Mejoras introducidas en la preparación de composiciones contra el empañamiento en el cobre
SE10116/62A SE310529B (en(2012)) 1961-09-28 1962-09-20
CH1126362A CH418088A (de) 1961-09-28 1962-09-25 Mischung zur Verhinderung des Anlaufens von kupferhaltigen Oberflächen
FR910332A FR1347705A (fr) 1961-09-28 1962-09-25 Composition empêchant le ternissement des surfaces à base de cuivre
DK420562AA DK113660B (da) 1961-09-28 1962-09-27 Fremgangsmåde og middel til tilvejebringelse af en anløbningsforhindrende film på en dekorativ kobberoverflade eller kobberholdig overflade.
GB36944/62A GB956927A (en) 1961-09-28 1962-09-28 Anti-tarnish composition for copper-containing surfaces

Applications Claiming Priority (1)

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US141292A US3248235A (en) 1961-09-28 1961-09-28 Anti-tarnish composition for coppercontaining surfaces

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US3248235A true US3248235A (en) 1966-04-26

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BE (1) BE622957A (en(2012))
CH (1) CH418088A (en(2012))
DK (1) DK113660B (en(2012))
ES (1) ES280824A1 (en(2012))
GB (1) GB956927A (en(2012))
NL (1) NL283747A (en(2012))
SE (1) SE310529B (en(2012))

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3345295A (en) * 1963-02-13 1967-10-03 Shulton Inc Copper cleaning compositions
US3346405A (en) * 1964-12-14 1967-10-10 Gen Electric Metal protectant
US3385682A (en) * 1965-04-29 1968-05-28 Sprague Electric Co Method and reagent for surface polishing
US3410703A (en) * 1965-05-18 1968-11-12 Hunt Chem Corp Philip A Silver and copper tarnish preventatives
US3442810A (en) * 1966-02-25 1969-05-06 Garman Co Inc Chemical polishing composition and method
US3452503A (en) * 1966-05-10 1969-07-01 North American Rockwell Process and product for confining hydrogen gas
US3458300A (en) * 1966-07-05 1969-07-29 Wyandotte Chemicals Corp Abrasive cleaning compositions
US3491491A (en) * 1968-01-15 1970-01-27 Us Industries Inc Aluminous slurries containing ferric ammonium citrate
US3503883A (en) * 1964-08-19 1970-03-31 Goddard & Sons Ltd J Metal surface protecting preparations
US3518098A (en) * 1963-06-25 1970-06-30 Goddard & Sons Ltd J Metal protecting preparations
US3637508A (en) * 1970-03-06 1972-01-25 William B Willsey Process and composition for dissolving copper oxide
US3652301A (en) * 1969-10-14 1972-03-28 Almeda J Damron Polish composition
US3944491A (en) * 1975-01-20 1976-03-16 Phillips Petroleum Company Lubricants
US4305779A (en) * 1980-05-28 1981-12-15 The United States Of America As Represented By The United States Department Of Energy Method of polishing nickel-base alloys and stainless steels
US4755223A (en) * 1986-08-22 1988-07-05 Antonio Castaldo Liquid composition for cleaning and polishing cymbals comprising kaolin clay
US4853000A (en) * 1987-11-25 1989-08-01 Potter John L Process and composition for a metal polish
WO2005095675A1 (en) * 2004-03-30 2005-10-13 Middlesex Silver Co. Limited Water-based metal treatment composition
US20090068119A1 (en) * 2005-10-14 2009-03-12 Lee Cawthorne Sprayable Depilatory Composition and a Method of use
EP2278593A4 (en) * 2008-04-30 2013-08-28 Hitachi Chemical Co Ltd CONNECTING MATERIAL AND SEMICONDUCTOR ARRANGEMENT

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4100096A (en) 1976-06-04 1978-07-11 Addressograph Multigraph Corp. Cleaner for hydrophilic metal surfaces of lithographic duplicators
NL8301070A (nl) * 1983-03-28 1984-10-16 Philips Nv Matrijs en methode voor de vervaardiging van voorwerpen uit kunststof door toepassing van de matrijs.
US4640713A (en) * 1984-11-19 1987-02-03 S. C. Johnson & Son, Inc. Tarnish remover/metal polish formulation comprising a metal iodide, an acid, and water
US20120189485A1 (en) * 2011-01-21 2012-07-26 Ppg Idustries Ohio, I Nc. Methods of removing rust from a ferrous metal-containing surface
US8852357B2 (en) 2011-09-30 2014-10-07 Ppg Industries Ohio, Inc Rheology modified pretreatment compositions and associated methods of use

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2371143A (en) * 1945-03-13 Corrosion protection of metals
US2841501A (en) * 1957-04-17 1958-07-01 James G Murphy Silver polish

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2371143A (en) * 1945-03-13 Corrosion protection of metals
US2841501A (en) * 1957-04-17 1958-07-01 James G Murphy Silver polish

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3345295A (en) * 1963-02-13 1967-10-03 Shulton Inc Copper cleaning compositions
US3518098A (en) * 1963-06-25 1970-06-30 Goddard & Sons Ltd J Metal protecting preparations
US3503883A (en) * 1964-08-19 1970-03-31 Goddard & Sons Ltd J Metal surface protecting preparations
US3346405A (en) * 1964-12-14 1967-10-10 Gen Electric Metal protectant
US3385682A (en) * 1965-04-29 1968-05-28 Sprague Electric Co Method and reagent for surface polishing
US3410703A (en) * 1965-05-18 1968-11-12 Hunt Chem Corp Philip A Silver and copper tarnish preventatives
US3442810A (en) * 1966-02-25 1969-05-06 Garman Co Inc Chemical polishing composition and method
US3452503A (en) * 1966-05-10 1969-07-01 North American Rockwell Process and product for confining hydrogen gas
US3458300A (en) * 1966-07-05 1969-07-29 Wyandotte Chemicals Corp Abrasive cleaning compositions
US3491491A (en) * 1968-01-15 1970-01-27 Us Industries Inc Aluminous slurries containing ferric ammonium citrate
US3652301A (en) * 1969-10-14 1972-03-28 Almeda J Damron Polish composition
US3637508A (en) * 1970-03-06 1972-01-25 William B Willsey Process and composition for dissolving copper oxide
US3944491A (en) * 1975-01-20 1976-03-16 Phillips Petroleum Company Lubricants
US4305779A (en) * 1980-05-28 1981-12-15 The United States Of America As Represented By The United States Department Of Energy Method of polishing nickel-base alloys and stainless steels
US4755223A (en) * 1986-08-22 1988-07-05 Antonio Castaldo Liquid composition for cleaning and polishing cymbals comprising kaolin clay
US4853000A (en) * 1987-11-25 1989-08-01 Potter John L Process and composition for a metal polish
WO2005095675A1 (en) * 2004-03-30 2005-10-13 Middlesex Silver Co. Limited Water-based metal treatment composition
US20070277906A1 (en) * 2004-03-30 2007-12-06 Middlesex Silver Co., Limited Water-Based Metal Treatment Composition
US20090068119A1 (en) * 2005-10-14 2009-03-12 Lee Cawthorne Sprayable Depilatory Composition and a Method of use
US9358196B2 (en) * 2005-10-14 2016-06-07 Reckitt Benckiser (Uk) Limited Sprayable depilatory composition and a method of use
EP2278593A4 (en) * 2008-04-30 2013-08-28 Hitachi Chemical Co Ltd CONNECTING MATERIAL AND SEMICONDUCTOR ARRANGEMENT

Also Published As

Publication number Publication date
ES280824A1 (es) 1963-03-01
CH418088A (de) 1966-07-31
GB956927A (en) 1964-04-29
SE310529B (en(2012)) 1969-05-05
BE622957A (en(2012))
NL283747A (en(2012))
DK113660B (da) 1969-04-14

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