WO1981003292A1 - Composition for mechanically depositing heavy metallic coatings - Google Patents

Composition for mechanically depositing heavy metallic coatings Download PDF

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Publication number
WO1981003292A1
WO1981003292A1 PCT/US1981/000642 US8100642W WO8103292A1 WO 1981003292 A1 WO1981003292 A1 WO 1981003292A1 US 8100642 W US8100642 W US 8100642W WO 8103292 A1 WO8103292 A1 WO 8103292A1
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WO
WIPO (PCT)
Prior art keywords
grams
plating
plating metal
metal
promoter
Prior art date
Application number
PCT/US1981/000642
Other languages
English (en)
French (fr)
Inventor
D Erismann
Original Assignee
Minnesota Mining & Mfg
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 Minnesota Mining & Mfg filed Critical Minnesota Mining & Mfg
Priority to AU71762/81A priority Critical patent/AU541221B2/en
Publication of WO1981003292A1 publication Critical patent/WO1981003292A1/en

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Classifications

    • 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
    • C23C24/04—Impact or kinetic deposition of particles
    • C23C24/045—Impact or kinetic deposition of particles by trembling using impacting inert media

Definitions

  • This invention relates to a composition for use in the plating of metals on a substrate by application of mechanical forces to participate malleable metals and mixtures and alloys thereof, typically termed "mechanical plating”.
  • the promoter system comprises a flash promoter which comprises, per 100 square feet of plating surface area, up to about 400 grams oF a strong acid or salt thereof, from about 20 to about 80 grams of a soluble salt of a metal which is more noble that the plating metal, an effective amount of a dispersant capable of dispersing the plating metal, and an effective amount of an inhibitor capable of inhibiting corrosion of the plating metal, together with a continuing promoter which comprises, per pound of finely divided mechanical plating metal, from about 60 to about 150 grams of a strong acid or salt thereof, fromabout 5 to about 20 grams of a soluble salt of a metal which is more noble than the plating metal, an effective amount of a dispersant capable of dispersing the plating met al , and an e ffect ive amoun t o f an inh ibi tor capab le of inhibiting corrosion of the plating metal.
  • a flash promoter which comprises, per 100 square feet of plating surface area, up to about 400 grams
  • the flash promoter during the mechanical plating process, provides a thin adherent flash coating on the articles to be plated, following which the continuing promoter is incrementally added to the process in conjunction with incremental additions of the finely divided mechanical plating metal until a heavy dense metallic coating is built up on the articles to be plated.
  • the continuing promoter's function is to provide a proper chemical environment for the mechanical plating process to occur. This includes a proper pH such that the surfaces of the finely divided mechanical plating metal is clean, but there is insubstantial dissolution of the metal in the plating solution, to prevent agglomeration of the finely divided metal to insure a proper plating rate and uniform coating thicknesses. Therefore, the concentration of components in this promoter is dependent upon the quantity of finely divided mechanical plating metal to be deposited.
  • Exemplary soluble salts of metals more noble than the finely divided plating metal include cadmium, lead, and preferably, tin, e.g., stannous chloride, stannous sulfate, stannous fluoborate, etc.
  • this salt should be included at a concentration level of from about 20 to about 80 grams per 100 square feet of surface area to be plated, with about 30 grams being preferred.
  • the concentration thereof should be- from about 5 to about 20 grams per pound of finely divided plating metal charged during the incremental steps of the plating cycle, with about 10 grams being preferred.
  • concentration of adhesion of the metallic plating is exhibited.
  • the upper concentration limit is maintained in terms of economics, as opposed to functionality, the cost thereof becoming excessive relative to additional benefit provided thereby.
  • the next component which is useful in this mechanical plating process is a strong acid or salt thereof.
  • This acidity is typically utilized in the processing to remove metal oxides contained on the finely divided mechanical plating metal and the articles to be plated.
  • Typical strong acid salts include potassium or ammonium bisulfate, sulfamic acid, etc., with the preferred being sodium bisulfate.
  • the concentration of the acid salt or acid component can be included therein up to about 400 grams per 100 square feet of plating surface charged.
  • the acid salt or strong acid should be utilized in a range of from about 60 to about 150 grams per pound of finely divided plating metal charged to the plating operation. While an acid salt is preferred, because same can act as a carrier for the other components of the promoter chemistry, sulfuric acid or other strong acids can also be utilized to provide acidity, as necessary, as mechanical plating occurs.
  • Materials capable of functioning effectively for dispersing the plating metal powders include polyoxy ethylene glycols having a cloud point in a 1 percent aqueous solution below 100°C, . such as "Carbowax” 20M (available from the Union Carbide Chemicals Company), or “Polyqlycol E50,000” (available from the Dow Chemical Company); quaternary aliphatic ammonium salts such as “Arquad” S-2C (available from the Armour Industrial Chemical Company; protei naceous materials such as "Technical Protein Colloids” No. 185, 169, or 70 (available from Swift & Company); among other materials which are disclosed in U.S. Patent No. 3,531,315.
  • additives which function as dispersants are typically related to both the specific acid and the specific finely divided plating metal involved.
  • effective dispersants for zinc powder in sulfuric acid include “Carbowax” 20M and “Orzan” AH-3, which is a salt of a polymerized alkyl aryl sulfonic acid, commercially available from the Crown Zellerbach Company;
  • dispersants for zinc or tin particles in hydrochloric acid include "Nalquat” G-8-11 (which is a hydrophilic heterocyclic adduct of a hydrophilic alkyl compound containing nitrogen groups, commercially available from Nalco Chemical Company).
  • Many other examples could, of course, be cited.
  • Whether a given component will function satisfactorily for dispersing specific plating metal particles in a specific acid can be determined by adding from about 0.25 to about 0.5 grams of the material to 250 milliliters of the acid plating solution in a 400 milliliter beaker, adding 10 grams of finely divided plating metal, stirring vigorously, and allowing the beaker and its contents to stand for 5 minutes. An effective dispersant will keep the plating metal in suspension, thereby rendering the acid plating solution opaque.
  • the flash promoter can contain up to about 40 grams per 100 square feet of plating charge, with about 20 grams being preferred, while the continuing promoter can contain up to about 8 grams per pound of metal powder charged with about 3.5 grams being preferred.
  • the next component having utility in my invention is an inhibitor, same being typically utilized to inhibit corrosion of the plating metal by the acidic component, thereby preventing undesirable gassing and allowing the plating metal to perform its intended function.
  • the inhibitor component is capable of functioning itself as a dispersant, and the aforementioned dispersant is not necessary. However, optimum benefits have been found to be achieved by utilizing a dispersant in conjunction with an inhibitor.
  • cationic amine inhibitors such as "Armohib” 25 (available from the Armour Industrial Chemical Company); cationic inhibitors such as Inhibitor GC (.available from the Sinclair Mineral and Chemical Company); and other materials as are described in U.S. Patent No. 3,531,315.
  • a preferred inhibitor is designated Additive "R"*.
  • Additive "R” up to about 12 grams per 100 square feet of plating charge can be included in the flash promoter, with about 8 grams being preferred, and up to about 1.0 gram per pound of plating metal charged, with about 0.35 gram being preferred, has been found to provide satisfactory results in the continuing promoter.
  • the optimum amount of a given dispersant or inhibitor is, of course, related to the specific system in which it is used. In general, however, large volumes of liquid, open barrels, or highly acidic conditions, typically require more inhibitor than small volumes of liquid, closed barrels, or less acidic conditions. Similarly, the optimum concentration of dispersant decreases as the pH rises or as the weight of plating metal particles decreases.
  • the promoter chemistry as well as the plating metal additions are added at appropriate intervals during the plating cycle.
  • the amount of plating metal added and the frequency of such additions are dependent upon the ultimate coating thickness desired and the size, weight, and geometry of the articles to be plated. Additionally, the ratio of articles to impact media, the size of the plating barrel, and rotational speed thereof can have an affect upon the number and frequency of such
  • a sufficient quantity of plating metal to provide a predetermined thickness can be added to the plating mixture.
  • the introduction rate of the metal powder to the plating mixture which is again dependent upon the aforementioned factors, will typically be 1/30 of the total plating metal quantity required, with an addition being e ve ry 1 to 1.5 minutes. With each addition of metal, the appropriate quantity of continuing promoter is added simultaneously therewith.
  • the quantity of plating metal can be increased to about 1/12 the total amount thereof required, and each increment can be added at approximately 3 to 4 minute intervals, again with the corresponding quantity of necessary chemistry.
  • the plating cycle can be continued for an additional 3 to 5 minutes at which time the plated articles can be rinsed, separated from the impact media and dried.
  • Example 1 A 1,160 pound load of 3/4 by 2-1/2 inch bolts (232 square feet of plating surface) was precleaned in an inhibited sulfuric acid-based cleaner containing surfactants and placed in a 60 cubic foot multi-sided barrel having an angle of approximately 20° above horizontal rotating at 10 RPM's, together with an equal volume of glass beads of various sizes (4 parts 3.5 to 5 mesh, 2 parts 8-10 mesh, 1 part 14-30 mesh, and 1 part 40-70 mesh), the glass beads functioning as impact media. To the mixture, sufficient 24°C (75°F) water was added such that a puddle was formed having a width of 6 to 12 inches while the barrel was rotating, thereby providing a free flowing mixture.
  • the metallic coating was found to have a uniform thickness by magnetic thickness testing, good appearance and excellent adhesion by conventional tape peel testing. The thickness was from 2.4 to 2.6 mils (60 to 65 ⁇ ).
  • Example 1 was duplicated with the exception that the following mixture was added incrementally with the zinc powder:
  • the thickness was measured and determined to be from 2.9 to 3.1 mils (72 to 78 ⁇ ).
  • Example 3 Example 1 was duplicated with the exception that the folloiwng mixture was utilized in incremental addition with the metallic zinc powder:
  • the resultant coating exhibited excellent adhesion and uniform appearance.
  • the thickness, as measured, was found to be 2.8 to 3.3 mils (70 to 82 ⁇ ).
  • Example 4 A precleaned, as in Example 1, 200 pound load of
  • Example 5 A precleaned, as in Example 1, 6 pound load of 5/16 by 3/4 inch bolts (500 square inches of plating surface) was placed in a 0.3 cubic foot open end multisided barrel having an angle of approximately 20° above horizontal rotating at 60 RPM's, together with an equal volume of glass beads of various sizes, as in Example 1. Then 24°C water was added to the mixture with 3.0 grams of an inhibited acid solution containing 99.7 parts 66°

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Chemically Coating (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
PCT/US1981/000642 1980-05-12 1981-05-08 Composition for mechanically depositing heavy metallic coatings WO1981003292A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU71762/81A AU541221B2 (en) 1980-05-12 1981-05-08 Composition for mechanically depositing heavy metallic coatings

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US14873280A 1980-05-12 1980-05-12
US148732 1980-05-12

Publications (1)

Publication Number Publication Date
WO1981003292A1 true WO1981003292A1 (en) 1981-11-26

Family

ID=22527104

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1981/000642 WO1981003292A1 (en) 1980-05-12 1981-05-08 Composition for mechanically depositing heavy metallic coatings

Country Status (6)

Country Link
EP (1) EP0040090B1 (enrdf_load_stackoverflow)
JP (1) JPS57500568A (enrdf_load_stackoverflow)
CA (1) CA1171605A (enrdf_load_stackoverflow)
DE (1) DE3172411D1 (enrdf_load_stackoverflow)
WO (1) WO1981003292A1 (enrdf_load_stackoverflow)
ZA (1) ZA813160B (enrdf_load_stackoverflow)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0276568B1 (en) * 1986-12-29 1992-04-22 Alcan International Limited Lubricant emulsion

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4724168A (en) * 1986-07-17 1988-02-09 Macdermid, Incorporated Mechanical galvanizing coating resistant to chipping, flaking and, cracking
JPH01501071A (ja) * 1986-10-22 1989-04-13 マクダーミッド，インコーポレーテッド 酸化し易い金属の機械的メツキ
DE19547786A1 (de) 1995-12-20 1997-06-26 Basf Lacke & Farben Aufbau von modifizierten Epoxidharzen für die kathodische Elektrotauchlackierung mit Katalysator-Desaktivierung und Diolmodifizierung
DE19618379A1 (de) 1996-05-08 1997-11-13 Basf Lacke & Farben Mit Copolymeren des Vinylacetats modifizierte in Wasser dispergierbare Epoxidharze
DE19930060A1 (de) 1999-06-30 2001-01-11 Basf Coatings Ag Elektrotauchlackbad mit wasserlöslichem Polyvinylalkohol(co)polymeren

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2976169A (en) * 1958-02-12 1961-03-21 Du Pont Immersion deposition of tin
US3268356A (en) * 1959-01-28 1966-08-23 Minnesota Mining & Mfg Metal plating by successive addition of plating ingredients
US3328197A (en) * 1965-02-08 1967-06-27 Minnesota Mining & Mfg Mechanical plating
US3400012B1 (enrdf_load_stackoverflow) * 1964-06-10 1968-09-03
US3460977A (en) * 1965-02-08 1969-08-12 Minnesota Mining & Mfg Mechanical plating
US3531315A (en) * 1967-07-17 1970-09-29 Minnesota Mining & Mfg Mechanical plating
EP0012399A1 (de) * 1978-12-15 1980-06-25 Bernd Tolkmit Verfahren zum Aufbringen metallischer Überzüge auf metallische Werkstücke durch mechanisch-chemisches Behandeln der Werkstücke

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3425946A (en) * 1966-08-26 1969-02-04 William M Emons Jr Electroless plating composition
US3627558A (en) * 1968-11-27 1971-12-14 Technograph Printed Circuits L Sensitization process for electroless plating
US4287253A (en) * 1975-04-08 1981-09-01 Photocircuits Division Of Kollmorgen Corp. Catalytic filler for electroless metallization of hole walls
US4181760A (en) * 1977-06-06 1980-01-01 Surface Technology, Inc. Method for rendering non-platable surfaces platable

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2976169A (en) * 1958-02-12 1961-03-21 Du Pont Immersion deposition of tin
US3268356A (en) * 1959-01-28 1966-08-23 Minnesota Mining & Mfg Metal plating by successive addition of plating ingredients
US3400012B1 (enrdf_load_stackoverflow) * 1964-06-10 1968-09-03
US3400012A (en) * 1964-06-10 1968-09-03 Minnesota Mining & Mfg Process of plating metal objects
US3328197A (en) * 1965-02-08 1967-06-27 Minnesota Mining & Mfg Mechanical plating
US3460977A (en) * 1965-02-08 1969-08-12 Minnesota Mining & Mfg Mechanical plating
US3531315A (en) * 1967-07-17 1970-09-29 Minnesota Mining & Mfg Mechanical plating
EP0012399A1 (de) * 1978-12-15 1980-06-25 Bernd Tolkmit Verfahren zum Aufbringen metallischer Überzüge auf metallische Werkstücke durch mechanisch-chemisches Behandeln der Werkstücke

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0276568B1 (en) * 1986-12-29 1992-04-22 Alcan International Limited Lubricant emulsion

Also Published As

Publication number Publication date
DE3172411D1 (en) 1985-10-31
ZA813160B (en) 1982-08-25
CA1171605A (en) 1984-07-31
JPS57500568A (enrdf_load_stackoverflow) 1982-04-01
EP0040090A1 (en) 1981-11-18
EP0040090B1 (en) 1985-09-25

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