US2999767A - Coating process and coating promoter compounds for bullets - Google Patents

Coating process and coating promoter compounds for bullets Download PDF

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Publication number
US2999767A
US2999767A US787123A US78712359A US2999767A US 2999767 A US2999767 A US 2999767A US 787123 A US787123 A US 787123A US 78712359 A US78712359 A US 78712359A US 2999767 A US2999767 A US 2999767A
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metal
articles
coating
particles
group
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US787123A
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Jr Franklin B Clay
Joseph F Kenney
Marshall J Kidder
Raymond H Vandenberg
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Remington Arms Co LLC
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Remington Arms Co LLC
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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
    • C23C—COATING 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
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/02—Coating starting from inorganic powder by application of pressure only
    • C23C24/06—Compressing powdered coating material, e.g. by milling
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F42—AMMUNITION; BLASTING
    • F42B—EXPLOSIVE CHARGES, e.g. FOR BLASTING, FIREWORKS, AMMUNITION
    • F42B12/00—Projectiles, missiles or mines characterised by the warhead, the intended effect, or the material
    • F42B12/72—Projectiles, missiles or mines characterised by the warhead, the intended effect, or the material characterised by the material
    • F42B12/76—Projectiles, missiles or mines characterised by the warhead, the intended effect, or the material characterised by the material of the casing
    • F42B12/80—Coatings

Definitions

  • This invention relates to the discovery of certain chemicals which constitute improved coating promoter compounds and which make possible an improved meth od for metal coating various metal articles without the use of electrical energy, heat or molten metal.
  • Another object is the provision of a new and improved coating or plating promoter chemicals which enable the process to be carried out with the addition of a minimum amount of chemical additives and makes possible and feasible the continued reuse of such chemicals in subsequent batches of the coating operation.
  • the improved process and promoter compound of this invention has for its object the rapid and economical coating of projectiles for firearm cartridges with brass, to improve both the appearance, storage qualities, and the performance characteristics of such projectiles.
  • the method of applying the metallic coating to metallic articles generally involves a container or drum mounted for suitable agitation such as revolving or tumbling, a group of articles to be plated, a quantity of metal to form the desired coating, in finely divided powder form, and a solution containing certain chemicals which assist and accelerate the coating process.
  • suitable agitation such as revolving or tumbling
  • the articles to be coated, the powdered metal, and impact media, such as shot, if desired, and the solution containing the chemicals, are all placed in the drum which is then agitated until the powder is converted into a uniform coating on the articles by the effects of the tumbling.
  • the physical and chemical phenomena which are generally believed to take place are discussed in the above referenced patents.
  • Metal articles such as lead bullet slugs Tumble in plating promoter one-halt hour
  • Powdered metal such as brass tumble one-half hour lgor reuse if desired Drain Wash and dry Filter metal articles solution Fortiiy with citric acid weight:
  • the formulation must include at least one and preferably at least three different salts from the group of ammonium salts discussed above.
  • the drum After charging all of this material except the brass powder into the drum, the drum is tumbled for one-half hour. Next, the brass powder is added and the drum is tumbled for a total of one hour.
  • the drum circumferential speed should be in the vicinity of 147 feet per minute for a cylindrical drum with a roughened interior having a diameter of seven inches.
  • the solution is drained ofi, filtered, or settled to remove any sludge, and returned for reuse after addition of citric acid.
  • the plated slugs or articles are washed and dried and then moved onto the next processing step, if any.
  • concentration of the isopropanol mixture described above can be varied from 5 ml. per hundred pounds of lead articles or slugs to as high as 300 ml. per hundred pounds.
  • a preferred optimum operating range for lead bullets lies in the area from 25 to 100 ml. per hundred pounds of articles to be coated.
  • the process may conveniently be carried out at ordinary ambient temperatures. No heat input is required.
  • the method of metal coating successive groups of metal articles comprising mixing a batch of said articles with an aqueous solution of an organic film-forming coating promoter agent comprismg a weak organic acid and a plurality of salts taken from the group consisting of the alkyl and alkenyl trimethyl ammonium halides, agitating said mixture and spreading said coating agent as organic molecular films on the metal surfaces, adding a quantity of metal powder particles and by tumbling in a rotating drum developing high pressures between the metal surfaces of said articles and the particles of metal powder to part said films at the areas of contact and bring said surfaces together in metal-to-metal contact with each other and deposit and attach said particles to the article surf-aces and to each other to deplete said particles of metal powder in the solution and build up said particles into continuous dense strongly adherent metal coatings on the surfaces of said articles to the desired thickness, removing said group of articles, separating, cleaning and resupplying said aqueous solution and a new group of articles into mixture for continuation of the process.
  • liquid carrier comprising a citric acid-water solution and the weight proportions of metal articles to carrier to promoter agent being about 900:3021.
  • a mixture for use as the carrier liquid and plating promoter agent in a process for the metal plating of metallic articles by tumbling the articles to be plated, a quantity of metal powder to form the plate, and a liquid together in a rotating drum comprising a water solution of citric acid, isopropanol and a plurality of salts taken from the group consisting of the alkyl and alkenyl trimethyl ammonium salts, each salt taken from such group containing from eight to eighteen carbon atoms.
  • a metal plating agent for assisting in coating lead bullets with brass powder in a tumbling process comprising a water solution of a weak organic acid and a plurality of salts taken from the group consisting of the alkyl and alkenyl trimethyl ammonium halides, the plurality containing at least three dilierent salts each salt taken from such group having from eight to eighteen carbon atoms.
  • a method of mechanically plating a group of lead bullets with brass comprising mixing said bullets with an aqueous solution containing a weak organic acid, an alcohol and a plurality of salts taken from the group consisting of three to eight different alkyl and alkenyl trimethyl ammonium halides each having the alkyl and alkenyl group of each varying from eight to eighteen carbon atoms, agitating said mixture, adding a quantity of brass powder, agitating said mixture and brass powder until said powder has been transformed into a continuous dense, uniform adherent coating on the exterior surfaces of said bullets, separating said bullets from said mixture and washing said bullets.
  • Octyl trimethyl ammonium chloride At least 0.2%.
  • Decyl trimethyl ammonium chloride At least 0.2%.
  • the liquid carrier comprising a citric acid-water solution.
  • a metal plating agent for assisting in coating lead bullets with brass powder in a tumbling process comprising a Water solution of a Weak organic acid and a plurality of salts taken from the group consisting of the alkyl and alkenyl trimethyl ammonium halides, the plurality containing at least one salt having from eight to eighteen carbon atoms.

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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)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • General Engineering & Computer Science (AREA)
  • Chemically Coating (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Description

2,999,767 COATING PROCESS AND COATING PROMOTER COMPOUNDS FOR BULLETS Franklin B. Clay, Jr., Westport, Joseph F. Kenney,
Bridgeport, Marshall J. Kidder, Fairfield, and Raymond H. Vandenberg, Stratford, Conn., assignors to Remington Arms Company, Inc., Bridgeport, Comn, a corporation of Delaware No Drawing. Filed Jan. 16, 1959, Ser. No. 787,123
7 Claims. (Cl. 117-109) This invention relates to the discovery of certain chemicals which constitute improved coating promoter compounds and which make possible an improved meth od for metal coating various metal articles without the use of electrical energy, heat or molten metal.
It is a general object of this invention to provide an improved process for forming protective metallic coatings on metal articles, which method is economical to carry out, simple in operation, and produces a very strong coating of high quality on the articles.
Another object is the provision of a new and improved coating or plating promoter chemicals Which enable the process to be carried out with the addition of a minimum amount of chemical additives and makes possible and feasible the continued reuse of such chemicals in subsequent batches of the coating operation.
More particularly, the improved process and promoter compound of this invention has for its object the rapid and economical coating of projectiles for firearm cartridges with brass, to improve both the appearance, storage qualities, and the performance characteristics of such projectiles.
A general process of somewhat similar nature is disclosed in British Patent No. 534,888, dated March 21, 1941, and subsequent improvements therein have appeared with the issue of the following United States patents: No. 2,640,001, issued May 26, 1953, to E. T. Clayton; Re. 23,861, issued Aug. 31, 1954, to E. T. Clayton; and No. 2,689,808, issued Sept. 21, 1954, to E. T. Clayton.
The method of applying the metallic coating to metallic articles generally involves a container or drum mounted for suitable agitation such as revolving or tumbling, a group of articles to be plated, a quantity of metal to form the desired coating, in finely divided powder form, and a solution containing certain chemicals which assist and accelerate the coating process. The articles to be coated, the powdered metal, and impact media, such as shot, if desired, and the solution containing the chemicals, are all placed in the drum which is then agitated until the powder is converted into a uniform coating on the articles by the effects of the tumbling. The physical and chemical phenomena which are generally believed to take place are discussed in the above referenced patents.
It is, of course, a much sought-after commercial objective to achieve a dense uniform coating on the articles within a minimum time and With the most economic or minimum expenditure of promoter chemicals. The improved coating promoter compounds of applicants invention not only achieved a very excellent coating in a short time but by reason of their ability to be reused, make possible an improved and far more economical process. Smaller quantities of the promoter chemicals are required for each batch of articles coated.
The improved process of applicants invention is related to the discovery by them of compounds which can be used for promoting metal plating and which are superior to those heretofore knownv A simplified flow diagram of the process is as follows:
Metal articles such as lead bullet slugs Tumble in plating promoter one-halt hour Add powdered metal such as brass tumble one-half hour lgor reuse if desired Drain Wash and dry Filter metal articles solution Fortiiy with citric acid weight:
Percentage by Weight Octyl trimethyl ammonium chloride 1.67 Decyl trimethyl ammonium chloride 1.88 Dodecyl trimethyl ammonium chloride 17.29 Tetra decyl trimethyl ammonium chloride 4.50 Hexadecyl trimethyl ammonium chloride 17.09 Octadecyl trimethyl ammonium chloride 2.46 Octadecenyl trimethyl ammonium chloride 3.25
'Octadecadienyl trimethyl ammonium chloride 1.88 Isopropanol 35.30 Sodium chloride 1.00 Water 13.70
The range of proportions of the ammonium salts are set forth as follows:
From min. of
'Octyl trimethyl ammonium chloride 0.2% up Decyl trimethyl ammonium chloride 0.2% up Dodecyl trimethyl ammonium chloride 1.7% up Tetra decyl trimethyl ammonium chloride 0.5% up Hexadecyl trimethyl ammonium chloride 1.7% up Octadecyl trimethyl ammonium chloride 0.3% up Octadecenyl trimethyl ammonium chloride 0.3% up Octadecadienyl trimethyl ammonium choride..- 0.2% up The isopropanol and sodium chloride percentages remain constant. The practical upper limits of the ammonium chloride salts are determined by the point at which at least all the varieties, of the salt in the above minimum quantifies can be added. Excess amounts of any of these salts were not found to adversely afiect the plating process below acceptable limits although these limits were considerably below the optimum limits of the preferred proportions. The formulation must include at least one and preferably at least three different salts from the group of ammonium salts discussed above.
The specifications for a charge of material to be placed into the agitating or tumbling drum for one coating cycle are set forth as follows:
20 lbs. of lead slugs,
10 ml. of the aforementioned isopropanol-ammonium chloride compound,
0.75 oz. of citric acid,
290 ml. of water,
2.5 oz. of brass powder (80% through 325 mesh, 100% through 100 mesh).
After charging all of this material except the brass powder into the drum, the drum is tumbled for one-half hour. Next, the brass powder is added and the drum is tumbled for a total of one hour. The drum circumferential speed should be in the vicinity of 147 feet per minute for a cylindrical drum with a roughened interior having a diameter of seven inches. The solution is drained ofi, filtered, or settled to remove any sludge, and returned for reuse after addition of citric acid. The plated slugs or articles are washed and dried and then moved onto the next processing step, if any.
It has been determined that the concentration of the isopropanol mixture described above can be varied from 5 ml. per hundred pounds of lead articles or slugs to as high as 300 ml. per hundred pounds. A preferred optimum operating range for lead bullets lies in the area from 25 to 100 ml. per hundred pounds of articles to be coated.
The use of applicants improved coating promoter agent makes possible an improved and economical process in which substantially smaller quantities of promoter chemicals are used and in which the promoter agent can be reused. In addition, the coating takes place in a short time period and results in a very dense adherent strong coating of a highly attractive nature and capable of surviving the subsequent swaging operation.
The process may conveniently be carried out at ordinary ambient temperatures. No heat input is required.
Although, in accordance with the patent statutes, we have in the above specification disclosed a preferred embodiment of our invention, it is desired that the scope of our invention be determined by the language of the appended claims.
We claim:
I. The method of metal coating successive groups of metal articles comprising mixing a batch of said articles with an aqueous solution of an organic film-forming coating promoter agent comprismg a weak organic acid and a plurality of salts taken from the group consisting of the alkyl and alkenyl trimethyl ammonium halides, agitating said mixture and spreading said coating agent as organic molecular films on the metal surfaces, adding a quantity of metal powder particles and by tumbling in a rotating drum developing high pressures between the metal surfaces of said articles and the particles of metal powder to part said films at the areas of contact and bring said surfaces together in metal-to-metal contact with each other and deposit and attach said particles to the article surf-aces and to each other to deplete said particles of metal powder in the solution and build up said particles into continuous dense strongly adherent metal coatings on the surfaces of said articles to the desired thickness, removing said group of articles, separating, cleaning and resupplying said aqueous solution and a new group of articles into mixture for continuation of the process.
2. A mixture for use as an additive coating promoter agent in a method of applying a metallic coating to metallic articles by rotating in a drum 2. group of articles to be plated, a quantity of powdered metal particles to form the coating and a liquid carrier, said mixture comprising the following composition of materials by weight:
the liquid carrier comprising a citric acid-water solution and the weight proportions of metal articles to carrier to promoter agent being about 900:3021.
3. A mixture for use as the carrier liquid and plating promoter agent in a process for the metal plating of metallic articles by tumbling the articles to be plated, a quantity of metal powder to form the plate, and a liquid together in a rotating drum comprising a water solution of citric acid, isopropanol and a plurality of salts taken from the group consisting of the alkyl and alkenyl trimethyl ammonium salts, each salt taken from such group containing from eight to eighteen carbon atoms.
4. A metal plating agent for assisting in coating lead bullets with brass powder in a tumbling process comprising a water solution of a weak organic acid and a plurality of salts taken from the group consisting of the alkyl and alkenyl trimethyl ammonium halides, the plurality containing at least three dilierent salts each salt taken from such group having from eight to eighteen carbon atoms.
5. A method of mechanically plating a group of lead bullets with brass comprising mixing said bullets with an aqueous solution containing a weak organic acid, an alcohol and a plurality of salts taken from the group consisting of three to eight different alkyl and alkenyl trimethyl ammonium halides each having the alkyl and alkenyl group of each varying from eight to eighteen carbon atoms, agitating said mixture, adding a quantity of brass powder, agitating said mixture and brass powder until said powder has been transformed into a continuous dense, uniform adherent coating on the exterior surfaces of said bullets, separating said bullets from said mixture and washing said bullets.
6. A mixture for use as an additive coating promoter agent in a method of applying a metallic coating to metallic articles by rotating in a drum a group of articles to be plated, a quantity of powdered metal particles to form the coating and a liquid carrier, said mixture comprising the following composition of materials by weight:
Octyl trimethyl ammonium chloride; At least 0.2%. Decyl trimethyl ammonium chloride At least 0.2%.
the liquid carrier comprising a citric acid-water solution.
7. A metal plating agent for assisting in coating lead bullets with brass powder in a tumbling process comprising a Water solution of a Weak organic acid and a plurality of salts taken from the group consisting of the alkyl and alkenyl trimethyl ammonium halides, the plurality containing at least one salt having from eight to eighteen carbon atoms.
References Cited in the file of this patent UNITED STATES PATENTS Sloan et a1 Nov. 12, 1940 Young May 27, 1947 Clayton May 26, 1953 Wrotnowski Mar. 29, 1960

Claims (1)

1. THE METHOD OF METAL COATING SUCCESSIVE GROUPS OF METAL ARTICLES COMPRISING MIXING A BATCH OF SAID ARTICLES WITH AN AQUEOUS SOLUTION OF AN ORGANIC FILM-FORMING COATING PROMOTER AGENT COMPRISING A WEEK ORGANIC ACID AND A PLURALITY OF SALTS TAKEN FROM THE GROUP CONSISTING OF ALKYL AND ALKYENYL TRIMETHYL AMMONIUM HALIDES, AGITATING SAID MIXTURE AND SPREADING SAID COATING AGENT AS ORGANIC MOLECULAR FILMS ON THE METAL SURFACES, ADDING A QUANTITY OF METAL POWDER PARTICLES AND BY TUMBLING IN A ROTATING DRUM DEVELOPING HIGH PRESSURE BETWEEN THE METAL SURFACES OF SAID ARTICLES AND THE PARTICLES OF METAL POWDER TO PART SAID FILMS AT THE AREAS OF CONTACT AND BRING SAID SURFACES TOGETHER IN METAL-TO-METAL CONTACT WITH EACH OTHER AND DEPOSIT AND ATTACH SAID PARTICLES TO THE ARTICLE SURFACES AND TO EACH OTHER TO DEPLETE SAID PARTICLES OF METAL POWDER IN THE SOLUTION AND BUILD UP SAID PARTICLES INTO CONTINUOUS DENSE STRONGLY ADHERENT METAL COATINGS ON THE SURFACES OF SAID ARTICLES TO THE DESIRED THICKNESS, REMOVING SAID GROUP OF ARTICLES, SEPRATING, CLEANING AND RESUPPLYING SAID AQUEOUS SOLUTION AND A NEW GROUP OF ARTICLES INTO MIXTURE FOR CONTINUATION OF THE PROCESS.
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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3251711A (en) * 1962-06-20 1966-05-17 Peen Plate Inc Methods of mechanically plating metal objects with copper and alloys thereof
US3268356A (en) * 1959-01-28 1966-08-23 Minnesota Mining & Mfg Metal plating by successive addition of plating ingredients
US3460977A (en) * 1965-02-08 1969-08-12 Minnesota Mining & Mfg Mechanical plating
US3630768A (en) * 1966-06-28 1971-12-28 Electronor Corp Chemical deposition formation of anodes
US4376685A (en) * 1981-06-24 1983-03-15 M&T Chemicals Inc. Acid copper electroplating baths containing brightening and leveling additives
US4654230A (en) * 1984-10-12 1987-03-31 Tru-Plate Process, Inc. Method of impact plating selective metal powders onto metallic articles
US5156672A (en) * 1990-07-13 1992-10-20 Mcgean-Rohco, Inc. Mechanical plating paste
US5378499A (en) * 1992-12-11 1995-01-03 Neco/Nostalgia Enterprises Co. Method of applying abrasives to bullets for use in pressure (fire) lapping of gun barrels
US20100221574A1 (en) * 2009-02-27 2010-09-02 Rochester Thomas H Zinc alloy mechanically deposited coatings and methods of making the same

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2192954A (en) * 1936-07-22 1940-03-12 Du Pont Transfer of pigment to organic vehicles
US2421363A (en) * 1943-05-27 1947-05-27 Us Rubber Co Process for treating fabrics
US2640002A (en) * 1951-04-17 1953-05-26 Tainton Company Cladding metal
US2930106A (en) * 1957-03-14 1960-03-29 American Felt Co Gaskets

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2192954A (en) * 1936-07-22 1940-03-12 Du Pont Transfer of pigment to organic vehicles
US2421363A (en) * 1943-05-27 1947-05-27 Us Rubber Co Process for treating fabrics
US2640002A (en) * 1951-04-17 1953-05-26 Tainton Company Cladding metal
US2930106A (en) * 1957-03-14 1960-03-29 American Felt Co Gaskets

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3268356A (en) * 1959-01-28 1966-08-23 Minnesota Mining & Mfg Metal plating by successive addition of plating ingredients
US3251711A (en) * 1962-06-20 1966-05-17 Peen Plate Inc Methods of mechanically plating metal objects with copper and alloys thereof
US3460977A (en) * 1965-02-08 1969-08-12 Minnesota Mining & Mfg Mechanical plating
US3630768A (en) * 1966-06-28 1971-12-28 Electronor Corp Chemical deposition formation of anodes
US4376685A (en) * 1981-06-24 1983-03-15 M&T Chemicals Inc. Acid copper electroplating baths containing brightening and leveling additives
US4654230A (en) * 1984-10-12 1987-03-31 Tru-Plate Process, Inc. Method of impact plating selective metal powders onto metallic articles
US5156672A (en) * 1990-07-13 1992-10-20 Mcgean-Rohco, Inc. Mechanical plating paste
US5378499A (en) * 1992-12-11 1995-01-03 Neco/Nostalgia Enterprises Co. Method of applying abrasives to bullets for use in pressure (fire) lapping of gun barrels
US20100221574A1 (en) * 2009-02-27 2010-09-02 Rochester Thomas H Zinc alloy mechanically deposited coatings and methods of making the same

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