US2927089A - Protective coatings for iron and steel - Google Patents

Protective coatings for iron and steel Download PDF

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US2927089A
US2927089A US662592A US66259257A US2927089A US 2927089 A US2927089 A US 2927089A US 662592 A US662592 A US 662592A US 66259257 A US66259257 A US 66259257A US 2927089 A US2927089 A US 2927089A
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varnish
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    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints

Definitions

  • the pigments are incorporatedin vehicles which dry to produce a somewhat elastic skin, binding the particles of the pigment together.
  • corrosive elements which may be present on the metal, surface or moisture contaminated with chemicals from the atmosphere pass through or under the skin,
  • primers that form a plastic non-skin-for-ming coating on the surface to beuprotected donot meet all the goals of an ideal protective coating.
  • the plastic primers are notcompletely resistant to direct corrosion in chemicals.
  • the plastic primers do not have a surface condition suitable for further coatings of all types. Instead, the
  • plastic primer remains soft andpliable. While the latter is an advantage over skin-forming primers, because it disallows the corrosion from spreading, yet it is desirable to have an outer surface of a hard material for many applications, A hard outer surface is more abrasion-resisting than a soft one. Also, if the outer surface is additionally porous it is a good foundation for other protective coatings, such as the vinyl plastics, oleoresinous, and oil paintsgetc. Varnish alone added to the rust resistant composition of fatty acids, sulfur, and litharge disclosed in Patent No. 2,609,302 does not produce the desired hard surface. Furthermore, varnish is not completely compatible with such a composition.
  • an object of the present invention to provide a protective coating adapted to be applied to the surface of iron or steel menrhersh'aving all theadvantages of a plastic non-skin-forming primer, and which also has a surface condition suitable for further coatings of all yp It is a further object of the invention to provide protective coatings for "iron and steel having a soft plastic undercoating with a harder coating over the primer.
  • the present invention relates to a composition containing the reaction product of a fatty acid, sulfur andlitharge; calcined gypsum, and a varnish.
  • one or the components in the composition is the reaction product of a fatty acid, lead oxide, and sulfur.
  • the product is prepared by heating the reaction mixture to elevated temperatures.
  • the fatty acid is preferably .a monobasic fatty acid containing not less than-sixteen carbon atoms and usualiy o o ha e mor han f t erbi s t he xamples of fatty acids that may be used are oleic, linseed oil fatty acid, .soy bean oil fatty acid, tung oil .fatty acid, stearic, linoleic, palmitic, linolic, linolenic, and clupanodonic. Special preferenceis .given to oleic acid.
  • the lead oxide used is preferably in the form of litharge.
  • the mixture of fatty acid, lead oxide, and sulfur are reacted at temperatures within the range of 300 F. to 500 F., preferably within the range from about 350 F. to 450 F.
  • Sample preparations may be prepared by using a fatty acid in the amount of from about to 30%, preferably about 47%, lead oxide in the form of litharge, in an amount from about 30% to 65%, preferably about 47%; and sulfur in'an amount varying from 2% to 10%, preferably about 6%, by weight of the initial mix.
  • the reaction is carried on to completion, which u sually occurs from within about .25 to about .ldhours. During .the reactionperiod the materials are continuously mixed or stirred, as by a mechanical stirrer.
  • the reaction mass is cooled with stirring below 400 F. and a volatile thinner is added in an amount to give the desired consistency to the final preparation while the reaction mass is continuously stirred until the same is cooled to atmospheric temperatures.
  • volatile thinner may comprise coal tar solvents, such as naphtha, xylol, toluol, petroleum solvents, such as mineral spirits and varnish makers and painters naphtha, turpentine and the like. In the preferred instance about 47 parts by weight of solvent is added to about 53 parts by weight of the reaction mass.
  • Example 10 Oleic acid 100 40 Litharge 130 53 Sulfur 18 7 While the number of illustrative examples of the invention are set forth hereinabove, Example 10 has been found particularly desirable as a coating material adapted for many uses.
  • 150 pounds of naphtha is stirred into the heated mass while the same is cooled to atmospheric temperatures.
  • the reaction product containing 40% by weight of thinner may be present in the composition in the range from about 35% to 89% by weight of the total components, or, apart from the thinner, in the range from about 20% to 53% by weight of the total components.
  • the composition contains calcined gypsum.
  • gypsum crystallizes with two molecules of water equal to about 21% by weight, and consequently has the formula CaSO .2H O.
  • the calcined or partially dehydrated gypsum that is used in the composition has approximately by weight of the water removed and is known in the trade as plaster of Paris.
  • the calcined gypsum is ordinarily employed in the composition in the range from 10% to 45% by weight.
  • the composition contains a minor amount, usually at least 1% by weight of the total composition of a varnish, for example, a phenolformaldehyde tung oil varnish.
  • a varnish for example, a phenolformaldehyde tung oil varnish.
  • Other varnishes may be employed in the composition.
  • the varnish may be presentin the composition from about 1% to about 20% by weight.
  • the varnish is first added to the reaction product.
  • the gypsum is next added so that the varnish plus the reaction product wets the gypsum and spreads over its surface.
  • EXAMPLE 1s Approximate percent by weight Reaction product of Example 10 50 Plaster of Paris 35 Phenol-formaldehyde varnish 15 EXAMPLE 14 Reaction product of Example 11 50 Plaster of Paris 35 Phenol-formaldehyde varnish 15 EXAMPLE 15 Reaction product of Example 3 45 Plaster of Paris 40 Phenol-formaldehyde varnish 15 EXAMPLE 16 Reaction product of Example 5 35 Plaster of Paris 40 Phenol-formaldehyde varnish 25 1 Containing 40% by weight thinner.
  • the gypsum and varnish in the composition have a unique cooperative effect contributing to the hardness of the outer surface when dried. Also, the coating dries without formation of skin, customary of paints and primers. The varnish contributes to water resistant properties of the dried coating.
  • the iron or steel surface may be first prepared by wire brushing or sandblasting.
  • the composition is coated over the surface by any of the usual mechanical methods, such as spraying, brushing, etc.
  • the outer surface of the composition is hard upon drying, protecting it against removal, as by scraping and abrasion. It also presents a surface that is well suited for the application of other protective coatings.
  • Polyvinyl resins, polystyrene resins, as well as conventional paints may be satisfactorily applied-to the dried coating. In this way a thick, inexpensive protection is given the iron and steel members.
  • Plastic resins, such as polyvinyl or polystyrene resins, which form an effective coating against direct chemical attack, have been found especially suitable for application to the composition disclosed herein.
  • a protective composition for iron and steel members consisting essentially of about 30% by weight of a reaction product of from about 30% to 65% by weight of a fatty acid having not less than sixteen and not more than forty carbon atoms, from about 30% to 65% by weight of litharge, and from about 2% to 10% by weight of sulfur; about 35% by weight of calcined gypsum;
  • a protective composition for iron and steel members consisting essentially of from about 21% to 53% by weight of the reaction product of from about 30% to 65% by weight of a fatty acid having not less than sixteen and not more than forty carbon atoms, from about 30% to 65% by weight of litharge, from about 2% to by weight of sulfur at a'temperature from about 300 F. to 500 F.; about 10% to 45% of calcined gypsum; about 1% to 20%by weight of phenol-formaldehyde varnish; and in addition to the foregoing components volatile thinner in amounts sufiicient to impart a consistency for coating said iron and steel members.
  • composition of claim 2 wherein said fatty acid is oleic acid.
  • a rust inhibitive preparation which forms a reaction product of from about to 75% by weight of a fatty acid having not less than sixteen and not more than forty carbon atoms, about 22% to 53% by weight of lead oxide, about 2.5% to 7% by weight of sulfur at a temperature within the range of from about 300 F. to 500 F.; adding volatile thinner to said reaction product in amounts suificient to impart the desired consistency to the composition; adding from about 1% to 20% by weight of phenol-formaldehyde varnish; and admixing 10% to by weight of calcined gypsum.

Description

United States Patent 2,927,089 PROTECTIVE COATINGS FOR IRON STEEL Howard N. Copthorne, Fort Lauderdale, Fla.
No Drawing. Application May 33,, 1957 SerialNo. 662,592.
5 Claims. "(CL 260-19) This invention relates to protective coatings for iron and steel, and more particularly to protective coatings which do :not form a skin and have a hard surface.
In the usualrust-inhibitive primers, the pigments are incorporatedin vehicles which dry to produce a somewhat elastic skin, binding the particles of the pigment together. When corrosive elements which may be present on the metal, surface or moisture contaminated with chemicals from the atmosphere pass through or under the skin,
rusting action spreads beneath the skin causing it to eventually'peel 'ofi exposing the rusted surface that has been hidden beneath the skinbefore the actual peeling occurs. The period of time in which primers form a protective coating before deterioration of the metal'surfacersets in, and tovyhat extent the primers are protective, dependsupon many factors, such as the preparation of thesurface'to be treated, the number .o fcoats of primer applied, and the location of the surface to be treated. In order to eliminate the inherent defects of skinforming primers, a plastic primer-wasdeve'loped, disclosed in United StatesPatent No. 2,609,302. However, primers that form a plastic non-skin-for-ming coating on the surface to beuprotected donot meet all the goals of an ideal protective coating. First of all, the plastic primers are notcompletely resistant to direct corrosion in chemicals. Also, the plastic primers do not have a surface condition suitable for further coatings of all types. Instead, the
plastic primer remains soft andpliable. While the latter is an advantage over skin-forming primers, because it disallows the corrosion from spreading, yet it is desirable to have an outer surface of a hard material for many applications, A hard outer surface is more abrasion-resisting than a soft one. Also, if the outer surface is additionally porous it is a good foundation for other protective coatings, such as the vinyl plastics, oleoresinous, and oil paintsgetc. Varnish alone added to the rust resistant composition of fatty acids, sulfur, and litharge disclosed in Patent No. 2,609,302 does not produce the desired hard surface. Furthermore, varnish is not completely compatible with such a composition.
It is, therefore, an object of the present invention to provide a protective coating adapted to be applied to the surface of iron or steel menrhersh'aving all theadvantages of a plastic non-skin-forming primer, and which also has a surface condition suitable for further coatings of all yp It is a further object of the invention to provide protective coatings for "iron and steel having a soft plastic undercoating with a harder coating over the primer.
It is a yet "further object of the invention to provide protective coating of a plastic primer and a layer that presents a porous surface to which maybe applied further layers of plastics or other paints. I
It is another object of the invention to provide protective coatings that do not'support combustion.
It is a still further object of the invention to provide a composition "for iron and steel that is water resistant.
It is yet another object of the invention to provide a thick and yet inexpensive protective coating for iron and steel members.
Patented Mar. 1, 1960 Broadly stated, the present invention relates to a composition containing the reaction product of a fatty acid, sulfur andlitharge; calcined gypsum, and a varnish.
It was discovered that a composition of varnish and gypsum, together with a fatty acid, sulfur, and litharge reaction product dries to a hard, somewhat porous surface, and that varnish in such a composition is compatible.
As previously indicated, one or the components in the composition is the reaction product of a fatty acid, lead oxide, and sulfur. The product is prepared by heating the reaction mixture to elevated temperatures.
The fatty acid is preferably .a monobasic fatty acid containing not less than-sixteen carbon atoms and usualiy o o ha e mor han f t erbi s t he xamples of fatty acids that may be used are oleic, linseed oil fatty acid, .soy bean oil fatty acid, tung oil .fatty acid, stearic, linoleic, palmitic, linolic, linolenic, and clupanodonic. Special preferenceis .given to oleic acid. The lead oxide used is preferably in the form of litharge.
The mixture of fatty acid, lead oxide, and sulfur are reacted at temperatures within the range of 300 F. to 500 F., preferably within the range from about 350 F. to 450 F. Sample preparations may be prepared by using a fatty acid in the amount of from about to 30%, preferably about 47%, lead oxide in the form of litharge, in an amount from about 30% to 65%, preferably about 47%; and sulfur in'an amount varying from 2% to 10%, preferably about 6%, by weight of the initial mix. For best results, it is desirable to have stoich-iometric amounts of lead and sulfur. The reaction is carried on to completion, which u sually occurs from within about .25 to about .ldhours. During .the reactionperiod the materials are continuously mixed or stirred, as by a mechanical stirrer. I
After the reaction is completed, the reaction mass is cooled with stirring below 400 F. and a volatile thinner is added in an amount to give the desired consistency to the final preparation while the reaction mass is continuously stirred until the same is cooled to atmospheric temperatures. Such volatile thinner may comprise coal tar solvents, such as naphtha, xylol, toluol, petroleum solvents, such as mineral spirits and varnish makers and painters naphtha, turpentine and the like. In the preferred instance about 47 parts by weight of solvent is added to about 53 parts by weight of the reaction mass.
After the reaction is cooled and the volatile thinner added, it is desirable to allow the mixture to stand for about 12 hours or more, and then stir with mixer. This additional stirring gives the product a final consistency.
The following'examples illustrate preparations which meet the requirements for a plastic primer herein disclosed and show the wide range in which the components may be mixed. Ineach of the followingexamples the fatty acid and sulfur'were heated to about 360 F. to 380 F., then .litharge was added and an exothermic reaction resulted which raised the temperature to about 410 F. to 450 F.
EXAMPLE 1 Approximate Pounds percent by weight Oleic acid p as Litharge 45 30 Sulfur J. 6 4
EXAMPLE 3 Approximate pounds percent by weight Tung oil fatty acid 100 47 Litharge 100 47 Sulfur 14 6 EXAMPLE 4 Oleic acid 100 07 Litharge 45 30 Sulfur 4 3 EXAMPLE 5 Linseed oil fatty acid 100 47 Litharge 100 47 Sulfur 14 6 EXAMPLE 6 Oleic arid 100 59, 5 Litharge 60 35. 5 Sulfur 8 5.0
EXAMPLE 7 Oleic acid 100 54 Litharge 75 41 Sulfur 10 5 I EXAMPLE 8 Oleic i 100 49 Litharge 90 45 Sulfur 12% (5 EXAMPLE 9 Oleic acid 100 61. Litharge 60 36. Sulfur 4 2. 5
EXAMPLE 10 EXAMPLE 12 Oleic acid 100 40 Litharge 130 53 Sulfur 18 7 While the number of illustrative examples of the invention are set forth hereinabove, Example 10 has been found particularly desirable as a coating material adapted for many uses. In preparing a final composition for application to metal surfaces from the reaction product of Example 10, 150 pounds of naphtha is stirred into the heated mass while the same is cooled to atmospheric temperatures. The reaction product containing 40% by weight of thinner may be present in the composition in the range from about 35% to 89% by weight of the total components, or, apart from the thinner, in the range from about 20% to 53% by weight of the total components.
In addition to the reaction product described hereinabove, the composition contains calcined gypsum. Ordinarily gypsum crystallizes with two molecules of water equal to about 21% by weight, and consequently has the formula CaSO .2H O. The calcined or partially dehydrated gypsum that is used in the composition has approximately by weight of the water removed and is known in the trade as plaster of Paris. The calcined gypsum is ordinarily employed in the composition in the range from 10% to 45% by weight.
In addition to calcined gypsum the composition contains a minor amount, usually at least 1% by weight of the total composition of a varnish, for example, a phenolformaldehyde tung oil varnish. Other varnishes may be employed in the composition. The varnish may be presentin the composition from about 1% to about 20% by weight.
In formulating the composition, the varnish is first added to the reaction product. The gypsum is next added so that the varnish plus the reaction product wets the gypsum and spreads over its surface.
The following examples illustrate the composition of the invention.
EXAMPLE 1s Approximate percent by weight Reaction product of Example 10 50 Plaster of Paris 35 Phenol-formaldehyde varnish 15 EXAMPLE 14 Reaction product of Example 11 50 Plaster of Paris 35 Phenol-formaldehyde varnish 15 EXAMPLE 15 Reaction product of Example 3 45 Plaster of Paris 40 Phenol-formaldehyde varnish 15 EXAMPLE 16 Reaction product of Example 5 35 Plaster of Paris 40 Phenol-formaldehyde varnish 25 1 Containing 40% by weight thinner.
The gypsum and varnish in the composition have a unique cooperative effect contributing to the hardness of the outer surface when dried. Also, the coating dries without formation of skin, customary of paints and primers. The varnish contributes to water resistant properties of the dried coating.
In applying the protective coatings of this invention, the iron or steel surface may be first prepared by wire brushing or sandblasting. The composition is coated over the surface by any of the usual mechanical methods, such as spraying, brushing, etc.
The outer surface of the composition is hard upon drying, protecting it against removal, as by scraping and abrasion. It also presents a surface that is well suited for the application of other protective coatings. Polyvinyl resins, polystyrene resins, as well as conventional paints may be satisfactorily applied-to the dried coating. In this way a thick, inexpensive protection is given the iron and steel members. Plastic resins, such as polyvinyl or polystyrene resins, which form an effective coating against direct chemical attack, have been found especially suitable for application to the composition disclosed herein.
Other modes of applying the'principle of the invention may be employed, change being made as re gards the details described, provided the features stated in any of the following claims or the equivalent of such be employed.
I, therefore, particularly point out and distinctly claim as my invention:
1. A protective composition for iron and steel members consisting essentially of about 30% by weight of a reaction product of from about 30% to 65% by weight of a fatty acid having not less than sixteen and not more than forty carbon atoms, from about 30% to 65% by weight of litharge, and from about 2% to 10% by weight of sulfur; about 35% by weight of calcined gypsum;
about 15% by weight of phenol-formaldehyde varnish; and in addition to the foregoing components volatile thinner in amounts sufiicient to impart a consistency for coating said iron and steel members.
2. A protective composition for iron and steel members consisting essentially of from about 21% to 53% by weight of the reaction product of from about 30% to 65% by weight of a fatty acid having not less than sixteen and not more than forty carbon atoms, from about 30% to 65% by weight of litharge, from about 2% to by weight of sulfur at a'temperature from about 300 F. to 500 F.; about 10% to 45% of calcined gypsum; about 1% to 20%by weight of phenol-formaldehyde varnish; and in addition to the foregoing components volatile thinner in amounts sufiicient to impart a consistency for coating said iron and steel members.
3. The composition of claim 2 wherein said fatty acid is oleic acid.
4. The process for producing a rust inhibitive preparation which forms a reaction product of from about to 75% by weight of a fatty acid having not less than sixteen and not more than forty carbon atoms, about 22% to 53% by weight of lead oxide, about 2.5% to 7% by weight of sulfur at a temperature within the range of from about 300 F. to 500 F.; adding volatile thinner to said reaction product in amounts suificient to impart the desired consistency to the composition; adding from about 1% to 20% by weight of phenol-formaldehyde varnish; and admixing 10% to by weight of calcined gypsum.
5. The process of claim 4 wherein said fatty acid is oleic acid.
References Cited in the file of this patent UNITED STATES PATENTS 84,421 Irish Nov. 24, 1868 1,570,169 Nelson et al I an. 19, 1926 1,763,937 Stievater June 17, 1930 2,609,302 Copthorne Sept. 2, 1952

Claims (1)

1. A PROTECTIVE COMPOSITION FOR IRON AND STEEL MEMBERS CONSISTING ESSENTIALLY OF ABOUT 30% BY WEIGHT OF A REACTION PRODUCT OF FROM ABOUT 30% TO 65% BY WEIGHT OF A FATTY ACID HAVING NOT LESS THAN SIXTEEN AND NOT MORE THAN FORTY CARBON ATOMS, FROM ABOUT 30% TO 65% BY WEIGHT OF LITHARGE, AND FROM ABUT 2% TO 10% BY WEIGHT OF SULFUR, ABOUT 35% BY WEIGHT OF CALCINED GYPSUM, ABOUT 15% BY WEIGHT OF PHENOL-FORMALDEHYDE VARNISH AND IN ADDITION TO THE FOREGOING COMPONENTS VOLATILE THINNER IN AMOUNTS SUFFICIENT TO IMPART A CONSISTENCY FOR COATING SAID IRON AND STEEL MEMBERS.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4024094A (en) * 1974-09-19 1977-05-17 Mitsubishi Gas Chemical Company, Inc. Phenolic resin composition for laminates
WO1983000105A1 (en) * 1981-06-26 1983-01-20 Deibig, Heinrich Method for the application of anticorrosion layers on metal surfaces

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US84421A (en) * 1868-11-24 Improved compound for roofing and painting
US1570169A (en) * 1925-01-09 1926-01-19 Mark W Nelson Plastic composition, a putty or a filler cement
US1763937A (en) * 1927-07-12 1930-06-17 Harry J Stievater Extender for paints, etc.
US2609302A (en) * 1949-08-03 1952-09-02 Howard N Copthorne Rust inhibiting material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US84421A (en) * 1868-11-24 Improved compound for roofing and painting
US1570169A (en) * 1925-01-09 1926-01-19 Mark W Nelson Plastic composition, a putty or a filler cement
US1763937A (en) * 1927-07-12 1930-06-17 Harry J Stievater Extender for paints, etc.
US2609302A (en) * 1949-08-03 1952-09-02 Howard N Copthorne Rust inhibiting material

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4024094A (en) * 1974-09-19 1977-05-17 Mitsubishi Gas Chemical Company, Inc. Phenolic resin composition for laminates
WO1983000105A1 (en) * 1981-06-26 1983-01-20 Deibig, Heinrich Method for the application of anticorrosion layers on metal surfaces
US4447477A (en) * 1981-06-26 1984-05-08 Battelle-Institut E.V. Method for the production of corrosion-inhibiting coatings on metallic surfaces

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