US2863791A - Production of oxalate coatings on iron and steel - Google Patents

Production of oxalate coatings on iron and steel Download PDF

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Publication number
US2863791A
US2863791A US576238A US57623856A US2863791A US 2863791 A US2863791 A US 2863791A US 576238 A US576238 A US 576238A US 57623856 A US57623856 A US 57623856A US 2863791 A US2863791 A US 2863791A
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Prior art keywords
steel
iron
oxalic acid
sodium nitrite
concentration
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US576238A
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Cerma Paolo De
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Montedison SpA
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Montedison SpA
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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
    • C23C22/05Chemical 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
    • C23C22/06Chemical 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
    • C23C22/46Chemical 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 oxalates

Definitions

  • My invention relates to a process for forming oxalate coatings on metal surfaces, in particular iron and steel surfaces.
  • Oxalate coatings are used for the protection of iron metals and constitute an excellent basis for paint.
  • the sodium chlorate in the process of forming oxalate coatings is replaced by another oxidizing agent, particularly sodium nitrite.
  • another oxidizing agent particularly sodium nitrite.
  • concentration of the sodium nitrite in the oxalic-acid bath must be maintained within the limits of 0.2 to 4 grams per litre, the optimum concentration being 1 to 2 g./l.
  • concentration for the oxalic acid in the bath ranges from 3 g. to 50 g./l.
  • the nitrite, used in form of an aqueous solution may be fed batchwise; but the results obtained are better and above all more constant if the feeding is continuous by dripping the sodium nitrite solution into the bath. It has further been found that the starting of the bath is easier if a ferrous salt is added initially in such an amount that the bath contains from 0.1 to 1 g./l. of ferrous ions. It is not necessary to subsequently add further amounts of this salt since during operation of the bath small amounts of ferrous ions go continuously into solution.
  • the bath according to the invention can be employed either by dipping or spraying.
  • Example 1 Soft-steel sheets are treated by dipping or spraying at room temperature for 3-4 minutes with oxalic acid solution containing 15 g./l. sodium chlorate. A ferrous oxalate coating is obtained, which is continuous and compact but covered by an incoherent powder which renders the surface diflicult to paint. The result is not improved if the concentration of sodium chlorate is increased or decreased.
  • Example 2 Soft-steel sheets are treated with a solution containing 15 g./l. oxalic acid and 0.1 g./l. sodium nitrite, under the same conditions of Example 1. An incoherent and discontinuous coating is formed.
  • Example 3 Soft-steel sheets are treated under the same conditions 2,863,791 Patented Dec. 9, 1958
  • Example 4 Soft-steel sheets are treated under the same conditions as in Example 1 with a solution contatining 15 g./l. oxalic acid and 1.5 g./l. sodium nitrite.
  • the coating obtained is continuous, compact and free from incoherent powder.
  • Example 5 Soft-steel sheets are treated under the same conditions as in Example 1 but with a solution containing 15 g./l. oxalic acid and 4 g./l. sodium nitrite. A continuous and compact coating showing slight formation of incoherent powder is obtained.
  • Example 6 Soft-steel sheets are treated under the conditions of Example 1 but with a solution containing 15 g./l. oxalic acid and 6 g./l. sodium nitrite. A coating is obtained which is continuous and compact but covered with an incoherent powder as obtained in Example 1.
  • the concentration of the oxalic acid in the bath ranges from 3 g. to 50 g./l. however it is preferably maintained at 15 g./l., as described in the examples.

Description

United States Patent PRODUCTION OF OXALATE COATINGS ON IRON AND STEEL Paolo de Cerma, Milan, Italy, assignor to Montecatini, Societa Generale per IIndustria Mineraria e Chimica, a corporation of Italy No Drawing. Application April 5, 1956 Serial No. 576,238
Claims priority, application Italy April 8, 1955 4 Claims. (Cl. 148-6.14)
My invention relates to a process for forming oxalate coatings on metal surfaces, in particular iron and steel surfaces.
Oxalate coatings are used for the protection of iron metals and constitute an excellent basis for paint.
The production of oxalate coatings on iron and steel by using baths based on oxalic acid and sodium chlorate is known. However, such coatings, if used as backing for paint, show a notable deficiency. After the coating is formed, the metal surface is powdery so that sometimes the desired anchoring of the paint is not achieved or deteriorates appreciably.
It is an object of my invention to eliminate such shortcomings.
To this end, and in accordance with my invention, the sodium chlorate in the process of forming oxalate coatings is replaced by another oxidizing agent, particularly sodium nitrite. I have found that in this manner a perfectly smooth and powder-free oxalate coating is obtained. To achieve this result the concentration of the sodium nitrite in the oxalic-acid bath must be maintained within the limits of 0.2 to 4 grams per litre, the optimum concentration being 1 to 2 g./l. The applicable concentration for the oxalic acid in the bath ranges from 3 g. to 50 g./l.
The nitrite, used in form of an aqueous solution, may be fed batchwise; but the results obtained are better and above all more constant if the feeding is continuous by dripping the sodium nitrite solution into the bath. It has further been found that the starting of the bath is easier if a ferrous salt is added initially in such an amount that the bath contains from 0.1 to 1 g./l. of ferrous ions. It is not necessary to subsequently add further amounts of this salt since during operation of the bath small amounts of ferrous ions go continuously into solution. The bath according to the invention can be employed either by dipping or spraying.
The following examples will illustrate, but are not meant to limit, the invention:
Example 1 Soft-steel sheets are treated by dipping or spraying at room temperature for 3-4 minutes with oxalic acid solution containing 15 g./l. sodium chlorate. A ferrous oxalate coating is obtained, which is continuous and compact but covered by an incoherent powder which renders the surface diflicult to paint. The result is not improved if the concentration of sodium chlorate is increased or decreased.
Example 2 Soft-steel sheets are treated with a solution containing 15 g./l. oxalic acid and 0.1 g./l. sodium nitrite, under the same conditions of Example 1. An incoherent and discontinuous coating is formed.
Example 3 Soft-steel sheets are treated under the same conditions 2,863,791 Patented Dec. 9, 1958 Example 4 Soft-steel sheets are treated under the same conditions as in Example 1 with a solution contatining 15 g./l. oxalic acid and 1.5 g./l. sodium nitrite. The coating obtained is continuous, compact and free from incoherent powder.
Example 5 Soft-steel sheets are treated under the same conditions as in Example 1 but with a solution containing 15 g./l. oxalic acid and 4 g./l. sodium nitrite. A continuous and compact coating showing slight formation of incoherent powder is obtained.
Example 6 Soft-steel sheets are treated under the conditions of Example 1 but with a solution containing 15 g./l. oxalic acid and 6 g./l. sodium nitrite. A coating is obtained which is continuous and compact but covered with an incoherent powder as obtained in Example 1.
As stated above, the concentration of the oxalic acid in the bath, ranges from 3 g. to 50 g./l. however it is preferably maintained at 15 g./l., as described in the examples.
It appears from the examples that for obtaining best results and completely eliminating the defect of the known method it is necessary to operate in the presence of sodium nitrite within the concentration limits according to the invention. In fact, from Example 4 it is evident that the concentration of sodium nitrite is a factor capable of decidedly modifying the quality of the oxalate coating.
I claim:
1. The process of forming oxalate coatings on iron and steel which comprises applying to the body to be coated an aqueous solution of oxalic acid and sodium nitrite, and maintaining the nitrite concentration between 0.2 and 4 grams per litre.
2. The process of forming oxalate coatings on iron and steel which comprises applying to the body to be coated an aqueous solution of oxalic acid and sodium nitrite, and maintaining the nitrite concentration between 1 and 2 grams per litre.
3. The process of forming oxalate coatings on iron and steel which comprises passing the bodies to be coated through a bath of oxalic acid and sodium nitrite, and continuously adding the nitrite to the bath to maintain a nitrite concentration between 0.2 and 4 grams per litre.
4. The process of forming oxalate coatings on iron and steel which comprises applying to the body to be coated an aqueous solution of 3 to 50 g. per liter of oxalic acid and sodium nitrite, adding initially to the solution an amount of ferrous salt corresponding. to an initial ferrous ion concentration of 0.1 to 1 gram per litre, and maintaining the sodium nitrite concentration between 0.2 and 4 grams per litre.
Weisberg et a1 Feb. 21, 1939 Tanner Feb. 17, 1942

Claims (1)

1. THE PROCESS OF FORMING OXALATE COATINGS ON IRON AND STEEL WHICH COMPRISES APPLYING TO THE BODY TO BE COATED AN AQUEOUS SOLUTION OF OXALIC ACID AND SODIUM NITRITE, AND MAINTAINING THE NITRITE CONCENTRATION BETWEEN 0.2 AND 4 GRAMS PER LITRE.
US576238A 1955-04-08 1956-04-05 Production of oxalate coatings on iron and steel Expired - Lifetime US2863791A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
IT794294X 1955-04-08

Publications (1)

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US2863791A true US2863791A (en) 1958-12-09

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US (1) US2863791A (en)
BE (1) BE546812A (en)
FR (1) FR1145046A (en)
GB (1) GB794294A (en)
LU (1) LU34298A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3116177A (en) * 1959-10-19 1963-12-31 Montedison Spa Process for degreasing and oxalating in a single spray stage

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2148331A (en) * 1937-02-25 1939-02-21 Alrose Chemical Company Method and composition for coating iron and steel articles
US2273234A (en) * 1933-03-27 1942-02-17 Parker Rust Proof Co Method of and solution for producing a coated iron article

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2273234A (en) * 1933-03-27 1942-02-17 Parker Rust Proof Co Method of and solution for producing a coated iron article
US2148331A (en) * 1937-02-25 1939-02-21 Alrose Chemical Company Method and composition for coating iron and steel articles

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3116177A (en) * 1959-10-19 1963-12-31 Montedison Spa Process for degreasing and oxalating in a single spray stage

Also Published As

Publication number Publication date
GB794294A (en) 1958-04-30
BE546812A (en)
LU34298A1 (en)
FR1145046A (en) 1957-10-21

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