US2236549A - Method of coloring metals and product - Google Patents

Method of coloring metals and product Download PDF

Info

Publication number
US2236549A
US2236549A US147672A US14767237A US2236549A US 2236549 A US2236549 A US 2236549A US 147672 A US147672 A US 147672A US 14767237 A US14767237 A US 14767237A US 2236549 A US2236549 A US 2236549A
Authority
US
United States
Prior art keywords
dye
water
solution
articles
phosphate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US147672A
Inventor
Van M Darsey
John S Thompson
Edwin W Goodspeed
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Parker Rust Proof Co
Original Assignee
Parker Rust Proof 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 Parker Rust Proof Co filed Critical Parker Rust Proof Co
Priority to US147672A priority Critical patent/US2236549A/en
Application granted granted Critical
Publication of US2236549A publication Critical patent/US2236549A/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
    • C23C22/82After-treatment
    • C23C22/84Dyeing
    • 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
    • C23C22/34Chemical 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 fluorides or complex fluorides
    • C23C22/37Chemical 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 fluorides or complex fluorides containing also hexavalent chromium compounds
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31678Of metal

Definitions

  • This invention relates to the dyeing and rustproofing of metals, and particularly metals that have had their surfaces treated to form thereon a paint adhering surface.
  • the problem has presented itself of developing a new and improved process for dyeing metal suriaces to provide various colors therefor, and to improve the corrosion resistance as well as the appearance thereof.
  • the principal object of the present invention is to provide a new and improved method of dyeing metal surfaces and to make possible a more economical, uniform and durabl coloring of such articles as well as enhancing their corrosion inhibiting qualities.
  • a further object is to provide a, new and improved process to improve the corrosion and abrasion resistance of metals and to improve said the Society of Dyers and Colourists, first edition, January 1924, have remarkable corrosion inhibitive properties when applied to metallic surfaces, especially when these surfaces are pretreated in certain ways so as to become more suitable to as phosphates, oxalates or oxides or combinations of these surface treatments.
  • the phosphate treatments especially known as Parkerizlng' and metals in various degrees to take organic dye colors to form a. colored surface.
  • Another object of the invention is to provide a new and improved method or finishing phosphate, oxalate or oxide coated metal surfaces with a dye and rust-proofing agent to'incrcase their corrosion resistance.
  • the present invention relates particularly to a method or process by which the surface of a metal is converted superficially into a non-metallic surf-ace which effectively prevents the formation of corrosion and the immersion of the surface converted metal article into a dyeing solution containing a dye to which has been added a. hexavalent chromium compound. It has been found that a reaction takes place between the dyestufi and the hexavalent chromium compound forming a compound which has been found to be even more superior in corrosion inhibiting qualities than the dye alone. In carrying out the process it has been found that certain dyestufis, such as the Azure Induline and Nigrosine group described as Nos. 859-869 and the Tris A20" dyes described as Nos.
  • chlorcltes and certain metallic accelerators such as copper may be added to the above solutions to bring about coatings in a much shorter time.
  • the solution is operated preferably between and 210 F. and the article to be coated is submerged in the solution, or the solution may be sprayed onto the article.
  • the solution is best operated between 180 and 210 F., but may be used at lower temperatures.
  • the articles are transferred to a centrifuge and deposited therein and the centrifuge rotated to remove any water present on th work. Oil, preferably linseed, is then sprayed over the articles and the centrifuge is rotated until the articles have dried sufficiently to be handled and packed for use or shipment.
  • a convenient way of making up a powdered composition to build up such a dye solution is to in the use of a water soluble dye because the basket containing the articles to be dyed may be dipped into the dye from the rinse tank without an intermediate drying operation-
  • a spirit soluble'dye could be used, but it would necessitate an intermediate drying of the work or a removal of all of the water present.
  • the process is not limited to this type of application, but the solution may be sprayed onto the metal surface by means of any of the well-known spraying equipment.
  • the phosphate, oxalate or oxide coating on the metal surface the same is subjected to the forced impingement of a water rinse followed by the forced impingement of the dye solution and chromic acid, followed by the forced impingement of oil which may be cut with an organic solvent and the drying of the surface by heat or other well-known means.
  • the articles to be treated may be moved by conveying means through a chamber or the solution may be sprayed on the articles while they are in a stationary position.
  • a method of treating metal surfaces selected from the group consisting of iron, steel, zinc, copper and aluminum which consists in forming thereon a coating selected from the group consisting of phosphate, oxalate and oxide and coloring such surface with a tris azo dye.
  • a method of treating metal surfaces selected from the group consisting of iron, steel, zinc, copper and aluminum which consists in forming thereon a coating selected from the group consisting of phosphate, oxalate and oxide and coloring such surface with an azine induline and nigrosine dye of the #859-869 series.
  • a method of treating metal surfaces selected from the group consisting of iron, steel, zinc, copper and aluminum which consists in forming thereon a coating selected from the group consisting of phosphate, oxalate and oxide and coloring such surface with a tris azo dye to which has been added a hexavalent chromium compound.
  • a method of treating metal surfaces selected from the group consisting of iron, steel, zinc, copper and aluminum which consists in forming thereon a coating selected from the group consisting of phosphate, oxalate and oxide and coloring such surface with an azine induline and ni-- grosine dye #859-869 series, to which has been added a hexavalent chromium compound.
  • An'article the surface of which comprises a coating selected from the group consisting of phosphate, oxalate and oxide, which surface has been treated with an azine induline and nigrosine dye #859-869 series, to which has been added a hexavalent chromium compound.

Landscapes

  • 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)

Description

Patented Apr. 1, 1941 FFICE mnruon or concerns METALS AND raonucr Van M. Dorsey, John S. Thompson, and Edwin W. Goodspeed, Detroit, Mich assignors to Parker Rust=Proot Company, Wayne County, Mich.
No Drawing. Application June 11, 1937,
Serial No. 147,672. Renewed July 5, 1940 7 Claims. (c'i. 148-6) This invention relates to the dyeing and rustproofing of metals, and particularly metals that have had their surfaces treated to form thereon a paint adhering surface. The problem has presented itself of developing a new and improved process for dyeing metal suriaces to provide various colors therefor, and to improve the corrosion resistance as well as the appearance thereof.
In the of small metallic articles, such as machine parts, bolts, nuts, washers, etc, where an inexpensive finish is desired, and where the use of paints and lacquers, etc, is prohibitive, both from an economic standpoint, as well as from more physical considerations such as building up the threads of screws and bolts, a dyeing process, such as herein described, is very advantageous,
' although it should also be understood that much larger objects may be treated Just as satisfactorily.
The principal object of the present invention is to provide a new and improved method of dyeing metal surfaces and to make possible a more economical, uniform and durabl coloring of such articles as well as enhancing their corrosion inhibiting qualities.
A further object is to provide a, new and improved process to improve the corrosion and abrasion resistance of metals and to improve said the Society of Dyers and Colourists, first edition, January 1924, have remarkable corrosion inhibitive properties when applied to metallic surfaces, especially when these surfaces are pretreated in certain ways so as to become more suitable to as phosphates, oxalates or oxides or combinations of these surface treatments. The phosphate treatments especially known as Parkerizlng' and metals in various degrees to take organic dye colors to form a. colored surface.
Another object of the invention is to provide a new and improved method or finishing phosphate, oxalate or oxide coated metal surfaces with a dye and rust-proofing agent to'incrcase their corrosion resistance.
The above and other objects will appear more fully from the following more detailed description.
The present invention relates particularly to a method or process by which the surface of a metal is converted superficially into a non-metallic surf-ace which effectively prevents the formation of corrosion and the immersion of the surface converted metal article into a dyeing solution containing a dye to which has been added a. hexavalent chromium compound. It has been found that a reaction takes place between the dyestufi and the hexavalent chromium compound forming a compound which has been found to be even more superior in corrosion inhibiting qualities than the dye alone. In carrying out the process it has been found that certain dyestufis, such as the Azure Induline and Nigrosine group described as Nos. 859-869 and the Tris A20" dyes described as Nos. 531605, in the color Index or Bonderizing (trade names) have proven to be very advus. .I-t been discovered that these treatments, which are corrosion protective in themselm, are greatly improved by an addirtional treatment in solutions of certain dyestuffs, which dyestufis not only enhance the corrosion inhibiting characteristics of the metal surface, but provide an attractive colored surface which greatly aids the saleabili-ty of the finished article.
As an illustrative example for carrying out the present invention there is set below an example:
' Examples of solutions for forming phosphate coatings:
To gallons ofwater, add: 27. pounds manganese dihydrogen phosphate To 100 gallons of water, add: 27 pounds zinc dihydrogen phosphate The addition of certain oxidizing agents such as sulphites, suiphurous acid, nitrates, nitrites,
chlorcltes, and certain metallic accelerators such as copper may be added to the above solutions to bring about coatings in a much shorter time.
The solution is operated preferably between and 210 F. and the article to be coated is submerged in the solution, or the solution may be sprayed onto the article.
Examples of solutions for forming oxalate coatings:
To 100 gallons of water, add:
40lbs. oxalic acid 8 lbs. sodium nitrate To 100 gallons of water, add: I
40 lbs. oxalic acid 8 lbs. ferric oxalate Example of solution for iorming an oxide coat- Following the converting of the article from a metallic surface to a non-metallic surface. the articles are placed in a wire basket or cage and lowered into a water rinse, the same being kept at a temperature of approximately 200 F. After rinsing for one to two minutes the articles are transferred to the dyeing vat wherein the wire basket is submerged for approximately thirty seconds in a solution comprising one or more of the group of "Azine Induline and Nigrosine, Tris Azo" dyes or mixtures thereof, to which a hexavalent chromium compound has been added. The solution is best operated between 180 and 210 F., but may be used at lower temperatures. Following the dyeing operation, the articles are transferred to a centrifuge and deposited therein and the centrifuge rotated to remove any water present on th work. Oil, preferably linseed, is then sprayed over the articles and the centrifuge is rotated until the articles have dried sufficiently to be handled and packed for use or shipment.
As a specific example of the dye solution, the following is disclosed:
An example using a dye from the Azine Induline and Nigrosine group #859-869:
To 200 gallons of water, add:
50 lbs. Water Black "J #865 lbs. of chromic acid or for convenience a percentage composition of the dye solution is as follows:
, Per cent Water 96.4 Water Black J #865 3.0 Chromic acid 0.6
Per cent Water 96.4 Pontamine Black E Double #581 3.0 Chromic acid 0.6
As a specific example of treating iron and steel, the following is disclosed:
To 100 gallons of water, add:
2'7 pounds of manganese dihydrogen phosphate at a temperature rang-i118 Heat to 210 F. and submerge the article to be treated in the solution until the coating is formed. Following the formation of the phosphate coating, rinse the article with water of approximately 200 F. and apply a dyeing solution made up as follows:
To 100 gallons of water, add:
25 lbs. Water Black J" #865 5 lbs. of chromic acid Temperature 180-210 F. Transfer articles to centrifuge and rotate to remove any excess stain solution present. Spray articles with linseed oil and rotate centrifuge until articles have become dry.
A convenient way of making up a powdered composition to build up such a dye solution is to in the use of a water soluble dye because the basket containing the articles to be dyed may be dipped into the dye from the rinse tank without an intermediate drying operation- A spirit soluble'dye could be used, but it would necessitate an intermediate drying of the work or a removal of all of the water present.
It has been found to be very advantageous to not only coat ferrous metals but non-ferrous metals as well. Very satisfactory phosphate coatings have been obtained on zinc, copper, aluminum and their alloys and these coatings can be finished with the above mentioned dyes for the same purpose as outlined above.
Although there has been described above an immersion process for carrying out the present invention, the process is not limited to this type of application, but the solution may be sprayed onto the metal surface by means of any of the well-known spraying equipment. Following the formation of the phosphate, oxalate or oxide coating on the metal surface the same is subjected to the forced impingement of a water rinse followed by the forced impingement of the dye solution and chromic acid, followed by the forced impingement of oil which may be cut with an organic solvent and the drying of the surface by heat or other well-known means. The articles to be treated may be moved by conveying means through a chamber or the solution may be sprayed on the articles while they are in a stationary position.
There has been disclosed a new and improved process to be used in the dyeing of metal surfaces wherein a rust preventative coating is first formed on the surface of the metal to be treated, followed by the subsequent coloring of the surface of the metal with a dyeing agent to which has been added a hexavalent chromium compound. The process outlined above is inexpensive, easy to apply and when carried out as herein disclosed, provides increased corrosion resistance as well as an attractive color for the surface of the processed article.
We claim:
1. A method of treating metal surfaces selected from the group consisting of iron, steel, zinc, copper and aluminum which consists in forming thereon a coating selected from the group consisting of phosphate, oxalate and oxide and coloring such surface with a tris azo dye.
2. A method of treating metal surfaces selected from the group consisting of iron, steel, zinc, copper and aluminum which consists in forming thereon a coating selected from the group consisting of phosphate, oxalate and oxide and coloring such surface with an azine induline and nigrosine dye of the #859-869 series.
3. A method of treating metal surfaces selected from the group consisting of iron, steel, zinc, copper and aluminum which consists in forming thereon a coating selected from the group consisting of phosphate, oxalate and oxide and coloring such surface with a tris azo dye to which has been added a hexavalent chromium compound.
4. A method of treating metal surfaces selected from the group consisting of iron, steel, zinc, copper and aluminum which consists in forming thereon a coating selected from the group consisting of phosphate, oxalate and oxide and coloring such surface with an azine induline and ni-- grosine dye #859-869 series, to which has been added a hexavalent chromium compound.
5. A method of treating metal surfaces selected from the group consisting of iron, steel, zinc,
copper and aluminum which consists in forming been treated with a tris azo dye to which has been 10 added a hexavalent chromium compound.
7. An'article, the surface of which comprises a coating selected from the group consisting of phosphate, oxalate and oxide, which surface has been treated with an azine induline and nigrosine dye #859-869 series, to which has been added a hexavalent chromium compound.
VAN M. DARBEY. JOHN S. THOMPSON.
US147672A 1937-06-11 1937-06-11 Method of coloring metals and product Expired - Lifetime US2236549A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US147672A US2236549A (en) 1937-06-11 1937-06-11 Method of coloring metals and product

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US147672A US2236549A (en) 1937-06-11 1937-06-11 Method of coloring metals and product

Publications (1)

Publication Number Publication Date
US2236549A true US2236549A (en) 1941-04-01

Family

ID=22522445

Family Applications (1)

Application Number Title Priority Date Filing Date
US147672A Expired - Lifetime US2236549A (en) 1937-06-11 1937-06-11 Method of coloring metals and product

Country Status (1)

Country Link
US (1) US2236549A (en)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2477310A (en) * 1947-07-23 1949-07-26 Clark Thread Co Process and composition for producing a dyeable corrosion resistant surface on zinc and high zinc alloys
US2478954A (en) * 1944-04-27 1949-08-16 J N Tuttle Inc Method of treating phosphate coated surfaces
DE916253C (en) * 1949-12-12 1954-08-05 Hoechst Ag Process for the production of surface layers on iron and steel
US2832707A (en) * 1949-12-12 1958-04-29 Hoechst Ag Aqueous solution for and process for producing surface layers on iron and steel articles
US3147153A (en) * 1960-12-09 1964-09-01 M & T Chemicals Inc Process for providing a chromate coating on zinc and cadmium surface
US3546028A (en) * 1966-07-11 1970-12-08 Cominco Ltd Process of improving corrosion resistance of colored oxide coatings on titanium-rich zinc alloys and resulting product
US3917887A (en) * 1974-01-24 1975-11-04 Sandoz Ag Process for dyeing oxide layers on aluminum and aluminum alloys
US20050276989A1 (en) * 2004-06-12 2005-12-15 Dees Robert J Coating composition and methods of coating

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2478954A (en) * 1944-04-27 1949-08-16 J N Tuttle Inc Method of treating phosphate coated surfaces
US2477310A (en) * 1947-07-23 1949-07-26 Clark Thread Co Process and composition for producing a dyeable corrosion resistant surface on zinc and high zinc alloys
DE916253C (en) * 1949-12-12 1954-08-05 Hoechst Ag Process for the production of surface layers on iron and steel
US2832707A (en) * 1949-12-12 1958-04-29 Hoechst Ag Aqueous solution for and process for producing surface layers on iron and steel articles
US3147153A (en) * 1960-12-09 1964-09-01 M & T Chemicals Inc Process for providing a chromate coating on zinc and cadmium surface
US3546028A (en) * 1966-07-11 1970-12-08 Cominco Ltd Process of improving corrosion resistance of colored oxide coatings on titanium-rich zinc alloys and resulting product
US3917887A (en) * 1974-01-24 1975-11-04 Sandoz Ag Process for dyeing oxide layers on aluminum and aluminum alloys
US20050276989A1 (en) * 2004-06-12 2005-12-15 Dees Robert J Coating composition and methods of coating
WO2007001258A2 (en) 2004-06-12 2007-01-04 Allfast Fastening Systems, Inc. Dyeing of chromated aluminum or titanium fasteners
WO2007001258A3 (en) * 2004-06-12 2007-08-09 Allfast Fastening Systems Inc Dyeing of chromated aluminum or titanium fasteners
US7413777B2 (en) 2004-06-12 2008-08-19 Allfast Fastening Systems, Inc. Coating composition and methods of coating
US20080254221A1 (en) * 2004-06-12 2008-10-16 Dees Robert J Coating composition and methods of coating
US7704557B2 (en) 2004-06-12 2010-04-27 Allfast Fastening Systems, Inc. Coating composition and methods of coating

Similar Documents

Publication Publication Date Title
US5723183A (en) Metal coloring process
US2796370A (en) Composition and method for producing corrosion resistant protective coating on aluminum and aluminum alloys
CA1200470A (en) Low zinc content, replenishment
US4278477A (en) Metal treatment
US7029541B2 (en) Trivalent chromate conversion coating
US2210850A (en) Method of finishing ferrous metal surfaces
US2236549A (en) Method of coloring metals and product
US6899769B2 (en) Composition and method for metal coloring process
US2789070A (en) Composition and process for phosphatizing metal
JPS60255986A (en) Composition and method for treating iron groundwork
US2244526A (en) Process of treating metal surfaces
US4497668A (en) Phosphating process for zinc-plated metals
US3839099A (en) Iron-phosphate coating for tin-plated ferrous metal surfaces
US2564864A (en) Method of and solution for increasing resistance to corrosion
US3506499A (en) Method of surface-treating zinc,aluminum and their alloys
US3097118A (en) Process and product for removing rust and coating materials
US2315564A (en) Art of coating and fabricating steel articles
US3106484A (en) Metal treating
US2327002A (en) Coated article and method of making the same
US2271375A (en) Process of coating metal surfaces
US3338755A (en) Production of phosphate coatings on metals
US2272216A (en) Method of coating copper and its alloys
US2296070A (en) Treatment of metal primers
AU653251B2 (en) Improved coating solution
US3615892A (en) Composition and method for black coating on metals