US3677827A - Composition and method for blackening metal articles - Google Patents

Composition and method for blackening metal articles Download PDF

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Publication number
US3677827A
US3677827A US856481A US3677827DA US3677827A US 3677827 A US3677827 A US 3677827A US 856481 A US856481 A US 856481A US 3677827D A US3677827D A US 3677827DA US 3677827 A US3677827 A US 3677827A
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United States
Prior art keywords
sodium
iron
triethanolamine
composition
sequestrant
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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US856481A
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English (en)
Inventor
Roger Weaver
Eugene Schaffstall
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Oxford Chemicals Inc
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Oxford Chemicals Inc
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    • 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
    • C23C22/05Chemical 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
    • C23C22/60Chemical 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 alkaline aqueous solutions with pH greater than 8
    • C23C22/62Treatment of iron or alloys based thereon

Definitions

  • This invention relates to improved chemical compositions and their use for production of black oxide coatings on ferrous metals.
  • a principal object of this invention is to provide compositions which give oxide coatings superior in depth of color and corrosion resistance.
  • Another object of the invention is to provide blackening compositions which can be stored in either dry or liquid form, the latter form obviating the mixing of highly alkaline powder with water, and the attendant risk of boil-over or danger.
  • a further object of the invention is to provide blackening compositions as liquid baths having a greatly extended service life as compared to prior art baths.
  • Still another object of the invention is to provide blackening compositions which are operable and produce good results over a much wider temperature range and with which blackening times are relatively shorter than with prior art baths.
  • a still further object of the invention is to provide blackening compositions which are useful in baths operable at lower temperatures than are prior art baths, in the range, for example, of 245 F. to 290 F., or 20 F. to 60 F. lower than operable temperature ranges for prior art baths.
  • compositions consisting essentially of sodium hydroxide, sodium nitrate, and sodium nitrite, to which triethanolamine or other specified additives have been added, which compositions may be stored as dry mixtures or as solutions made up with water.
  • iron sequestrants suitable in the present invention are triethanolamine, sodium gluconate, sodium heptagluconate, sorbitol, diethanolamine, monoethanolamine, sodium nitriloacetate, etc. Of these, triethanolamine is superior and the preferred sequestrant because of bath stability, lack of foaming, and superior sequestration of iron. Cations other than sodium are equally effective; and bath alkalinity can be achieved with sodium or potassium hydroxides. Superiority of the black oxide coating which results is in both appearance and corrosion resistance. Superiority lies also in lower temperature operations and in greater diversity of iron alloys that can be processed successfully.
  • compositions of the present invention in liquid form is an advance over the prior art because of the advantages of a composition approximating that of a working bath so that additions can be made at optimum bath temperature without risk of boil-over or danger.
  • the latter consideration is important because of the fact that the bath is operated at high temperatures.
  • iron sequestrant additive Up to 10% of iron sequestrant additive may be used, alone or in mixtures of two or more. With triethanolamine, sodium gluconate, or sodium heptagluconate, a concentration of 0.05 to 2% sufiices. For the other iron sequestrant additives, the concentration should range between 1 and 10%.
  • Baths 4, 5 Total of triethanolamine, sorbitol, sodium gluconate or sodium heptagluconate (alone or mixtures).
  • Baths 6, 7 Total of diethanolamine, monoethanolamine and sodium nitriloaeetate (alone or as mixtures).
  • compositions defined immediately above using triethanolamine as the sequestrant represents preferred embodiments of the invention.
  • a mixture of the dry ingredients (sodium hydroxide, sodium nitrite, and sodium nitrate) is formed, and can then be stored as a separate product, or may be made up with the required amount of water to achieve the desired bath concentration.
  • the triethanolamine or other sequestrant is added up to the limit of its solubility and then may be added in increments as the bath is used.
  • compositions of the invention As indicated hereinabove the preparation and storing of these compositions in liquid form represents a distinct advantage, sparing the users having to dissolve strong alkali in high concentration. Using liquid forms of the compositions of the invention, thus, the user need merely pump the liquid into the tank and heat to boiling before immersing articles to be blackened.
  • the blackening bath is used in the usual way, that is to say, once the components have been brought together, the bath is heated to almost the boiling point and then the articles to be blackened are immersed in the heated composition and are held therein until the desired depth of blackening has been achieved. On removal from the bath the articles are permitted to dry in air and subsequently rinsed to remove any salt residue.
  • a blackening composition for ferrous articles consisting essentially of the following in percent by weight:
  • Iron sequestrant 0.05-l0 balance to make Water; said iron sequestrant being stable in highly alkaline solutions at temperatures above 245 F. and capable of sequestering iron introduced into said solution and being selected from the group consisting of alcohol amines, sorbitol and derivatives, metal gluconates and derivatives, metal nitriloacetates and derivatives and combinations thereof.
  • composition of claim 1 in which the sequestrant is selected from the group consisting of:
  • composition of claim 1 wherein the alkali metal salts are sodium salts.
  • composition of claim 3 wherein the proportions are Percent Sodium hydroxide 34-38 Sodium nitrite 4.5-6
  • Sodium nitrate 2.2-4.0 'Iron sequestrant l-10 5 The composition of claim 1 wherein the iron sequestrant is a member of the group consisting of sodium gluconate, sodium heptagluconate, and triethanolamine; and its proportion is 0.05-2%.
  • a method of extending the useful life of a blackening bath which has lost its ability to blacken ferrous metal objects and which consisted essentially of sodium hydroxide, sodium nitrite and sodium nitrate dissolved in water, which comprises adding up to 10% by weight of an iron sequestrant selected from the group consisting of sodium gluconate, sorbitol, monoethanolamine, diethanolamine, sodium nitriloacetate, sodium heptagluconate, and triethanolamine to said bath.
  • a method of extending the useful life of a blackening bath which has lost its ability to blacken ferrous metal objects and which consisted essentially of sodium hydroxide, sodium nitrite and sodium nitrate dissolved in water, which comprises adding up to 10% by weight of an iron sequestrant selected from the group consisting of sodium gluconate, sodium heptagluconate, and triethanolamine.
  • a blackening composition for ferrous articles consisting essentially of the following in parts by weight:
  • composition of claim 1 in which the percentage by weight of iron sequestrant is 0.05-0.35% and the iron sequestrant is selected from the group consisting of sodium gluconate, sodium heptagluconate, t-riethanolamine and combinations thereof.
  • composition of claim 1 in which the percentage by weight of iron sequestrant is 0.350.70% and the iron sequestrant is selected from a group consisting of sodium gluconate, sodium heptagluconate, triethanolamine and combinations thereof.
  • composition of claim 1 in which the percentage by weight of the iron sequestrant is 0.7010.0% and the iron sequestrant is selected from the group consisting of triethanolamine, sodium gluconate, sorbitol, mon0- ethanolamine, diethanolamine, sodium nitriloacetate, sodium heptagluconate and combinations thereof.

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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)
  • Detergent Compositions (AREA)
US856481A 1969-09-09 1969-09-09 Composition and method for blackening metal articles Expired - Lifetime US3677827A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US85648169A 1969-09-09 1969-09-09

Publications (1)

Publication Number Publication Date
US3677827A true US3677827A (en) 1972-07-18

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US856481A Expired - Lifetime US3677827A (en) 1969-09-09 1969-09-09 Composition and method for blackening metal articles

Country Status (4)

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US (1) US3677827A (fr)
BE (1) BE780002A (fr)
CA (1) CA919063A (fr)
GB (1) GB1318297A (fr)

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3905838A (en) * 1974-04-10 1975-09-16 Hikaru Ito Bath for treating aluminum and aluminum alloys to form oxide film nonelectrolytically thereon and method for the treatment
US3920486A (en) * 1973-05-10 1975-11-18 Oxy Metal Industries Corp Method of blackening ferrous metal surfaces
US3929514A (en) * 1974-03-05 1975-12-30 Heatbath Corp Composition and method for forming a protective coating on a zinc metal surface
US4045253A (en) * 1976-03-15 1977-08-30 Halliburton Company Passivating metal surfaces
US4226646A (en) * 1979-03-26 1980-10-07 E. I. Du Pont De Nemours And Company Process of coating a ferrous metal substrate with an aqueous fluoropolymer coating
US4325749A (en) * 1980-11-04 1982-04-20 Barlet Loren E Method of treating welding rod for corrosion resistance
US4512818A (en) * 1983-05-23 1985-04-23 Shipley Company Inc. Solution for formation of black oxide
US6309476B1 (en) * 1999-05-24 2001-10-30 Birchwood Laboratories, Inc. Composition and method for metal coloring process
US20030034095A1 (en) * 2001-08-03 2003-02-20 Heimann Robert L. Electrolytic and electroless process for treating metallic surfaces and products formed thereby
US6695931B1 (en) 1999-05-24 2004-02-24 Birchwood Laboratories, Inc. Composition and method for metal coloring process
US20040250748A1 (en) * 1999-05-24 2004-12-16 Ravenscroft Keith N. Composition and method for metal coloring process
US20060014042A1 (en) * 2004-07-15 2006-01-19 Block William V Hybrid metal oxide/organometallic conversion coating for ferrous metals
US7964044B1 (en) 2003-10-29 2011-06-21 Birchwood Laboratories, Inc. Ferrous metal magnetite coating processes and reagents
US20200246921A1 (en) * 2019-02-04 2020-08-06 Lincoln Global, Inc. Coated welding wire
US10845309B2 (en) 2017-12-21 2020-11-24 Ecolab Usa Inc. Blackened optical component without fluorescence
US12497684B2 (en) 2021-07-28 2025-12-16 Birchwood Laboratories Llc Methods and compositions for forming magnetite coatings on ferrous metals

Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3920486A (en) * 1973-05-10 1975-11-18 Oxy Metal Industries Corp Method of blackening ferrous metal surfaces
US3929514A (en) * 1974-03-05 1975-12-30 Heatbath Corp Composition and method for forming a protective coating on a zinc metal surface
US3905838A (en) * 1974-04-10 1975-09-16 Hikaru Ito Bath for treating aluminum and aluminum alloys to form oxide film nonelectrolytically thereon and method for the treatment
US4045253A (en) * 1976-03-15 1977-08-30 Halliburton Company Passivating metal surfaces
US4226646A (en) * 1979-03-26 1980-10-07 E. I. Du Pont De Nemours And Company Process of coating a ferrous metal substrate with an aqueous fluoropolymer coating
US4325749A (en) * 1980-11-04 1982-04-20 Barlet Loren E Method of treating welding rod for corrosion resistance
US4512818A (en) * 1983-05-23 1985-04-23 Shipley Company Inc. Solution for formation of black oxide
US6695931B1 (en) 1999-05-24 2004-02-24 Birchwood Laboratories, Inc. Composition and method for metal coloring process
US20040250748A1 (en) * 1999-05-24 2004-12-16 Ravenscroft Keith N. Composition and method for metal coloring process
US6899769B2 (en) * 1999-05-24 2005-05-31 Birchwood Laboratories, Inc. Composition and method for metal coloring process
US6309476B1 (en) * 1999-05-24 2001-10-30 Birchwood Laboratories, Inc. Composition and method for metal coloring process
US6753039B2 (en) 2001-08-03 2004-06-22 Elisha Holding Llc Electrolytic and electroless process for treating metallic surfaces and products formed thereby
US20040217334A1 (en) * 2001-08-03 2004-11-04 Heimann Robert L. Electrolytic and electroless process for treating metallic surfaces and products formed thereby
US20030034095A1 (en) * 2001-08-03 2003-02-20 Heimann Robert L. Electrolytic and electroless process for treating metallic surfaces and products formed thereby
WO2003035942A3 (fr) * 2001-08-03 2004-01-29 Elisha Holding Llc Procede electrolytique et autocatalytique de traitement de surfaces metalliques et produits traites selon ce procede
US7964044B1 (en) 2003-10-29 2011-06-21 Birchwood Laboratories, Inc. Ferrous metal magnetite coating processes and reagents
US20060014042A1 (en) * 2004-07-15 2006-01-19 Block William V Hybrid metal oxide/organometallic conversion coating for ferrous metals
US7144599B2 (en) 2004-07-15 2006-12-05 Birchwood Laboratories, Inc. Hybrid metal oxide/organometallic conversion coating for ferrous metals
US7481872B1 (en) 2004-07-15 2009-01-27 Birchwood Laboratories, Inc. Process for making bath composition for converting surface of ferrous metal to mixed oxides and organometallic compounds of aluminum and iron
US7625439B1 (en) 2004-07-15 2009-12-01 Birchwood Laboratories, Inc. Bath composition for converting surface of ferrous metal to mixed oxides and organometallic compounds of aluminum and iron
US10845309B2 (en) 2017-12-21 2020-11-24 Ecolab Usa Inc. Blackened optical component without fluorescence
US20200246921A1 (en) * 2019-02-04 2020-08-06 Lincoln Global, Inc. Coated welding wire
US12497684B2 (en) 2021-07-28 2025-12-16 Birchwood Laboratories Llc Methods and compositions for forming magnetite coatings on ferrous metals

Also Published As

Publication number Publication date
BE780002A (fr) 1972-06-16
GB1318297A (en) 1973-05-23
CA919063A (en) 1973-01-16

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