US2475601A - Bonding of metal carbonyl deposits - Google Patents

Bonding of metal carbonyl deposits Download PDF

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Publication number
US2475601A
US2475601A US665318A US66531846A US2475601A US 2475601 A US2475601 A US 2475601A US 665318 A US665318 A US 665318A US 66531846 A US66531846 A US 66531846A US 2475601 A US2475601 A US 2475601A
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United States
Prior art keywords
metal
coating
bonding
metal carbonyl
deposits
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Expired - Lifetime
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US665318A
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Albert O Fink
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Commonwealth Engineering Company of Ohio
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Commonwealth Engineering Company of Ohio
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Priority to US665318A priority Critical patent/US2475601A/en
Application granted granted Critical
Publication of US2475601A publication Critical patent/US2475601A/en
Priority claimed from GB764254A external-priority patent/GB751523A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
    • C23C16/16—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metal carbonyl compounds
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/02—Pretreatment of the material to be coated
    • C23C16/0272—Deposition of sub-layers, e.g. to promote the adhesion of the main coating
    • C23C16/0281—Deposition of sub-layers, e.g. to promote the adhesion of the main coating of metallic sub-layers
    • Y—GENERAL 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00—Metal working
    • Y10T29/49—Method of mechanical manufacture
    • Y10T29/49826—Assembling or joining
    • Y10T29/49885—Assembling or joining with coating before or during assembling

Definitions

  • Serial No. 665,318 g 1 This invention deals with a method of plating metals, and in particular with a method based on the decomposition of gaseous metal carbonyls.
  • the first coating step only a very thin porous film is applied to the base metal by decomposing gaseous metal carbonyl.
  • the coated article is heated.
  • the gas which has been adsorbed at the surface of the base metal is driven off and escapes through the thin metal layer due to its porosity, and the thin metal coating is thus more strongly bonded to the base metal.
  • a temperature of from 800 to 900 F. was found most advantageous. Of course, the higher'the heating temperature used, the shorter heating time required.
  • a second heat treating step may be applied; however, this is not obligatory. Sometimes by such an after-treatment by exposure to high temperatures the ductility of the coating layer is increased. I r
  • Example A copper plate was first mechanically cleaned by sanding. Thereafter the copper metal was heated to approximately 375 F. in an atmosphere containing approximately 1.4 per cent by volume of nickel carbonyl and diluted with carbon dioxide gas. The rate of gas flow was approximately 4 l. per minute at a temperature of 78 Rand mm. Hg. The copper was exposed to this atmosphere for about 2 minutes after which time a film of 0.00007 thickness had formed on the copper base. Thereafter the metal was heated in an atmosphere of natural gas to a temperature of about 800 F. for approximately 15 minutes. After these preliminary steps the coating proper was performed by subjectin the metal to the same conditions and gases as in the preliminary film-forming step. This second step was carried out for about 15 minutes when a coating of 0.0004" had formed.
  • the process of my invention is applicable for plating with all metals which form gaseous carbonyls; thus, plating with chromium, iron, tungsten, cobalt, molybdenum and other metals may be successfully carried out by the method described.
  • the heat treatment after the application of a thin porous metal film eliminates the gases adsorbed on the surface of the base metal, and the surface activity is then immediately utilized for strongly bonding this metal film,
  • the coatings obtained by the process of my invention are uniform in structure, free from blisters and well-adhering to the base metal. Heat treatment does not impair the firm bond between the coating and the base metal.

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  • 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)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Chemically Coating (AREA)

Description

1 Patented July 12, 1949 BONDING F METAL CARBONYL DEPOSITS Albert 0. Fink, Dayton, Ohio, assignor to The Commonwealth Engineering Company of Ohio, Dayton, Ohio, a corporation of Ohio No Drawing. Application April 20, 1946,
. Serial No. 665,318 g 1 This invention deals with a method of plating metals, and in particular with a method based on the decomposition of gaseous metal carbonyls.
In coatings obtained from metal carbonyls, the disadvantage heretofore has frequently been encountered of the coating not sufliciently adhering to the base metal. Moreover, the metal coating would become blistered if the object so coated was raised to elevated temperatures, for example in a heat treatment process.
2 Claims. (Cl. 11'l65) It is an object'of this invention to provide a blistering.
It is still another object of this invention to provide a method of producing metal coatings which may be subjected to a heat-treatment process without thereby impairing the adherence of the coating.
These and other objects are accomplished by depositing the metal coating in two steps and inserting a heat-treatment step therebetween.
In the first coating step, only a very thin porous film is applied to the base metal by decomposing gaseous metal carbonyl. A layer of 0.00001" to 0.00025", preferably of 0.00005" to 0.00015", was found most satisfactory; however, the invention is not restricted to this range. After this first layer has been applied, the coated article is heated. By this heating step, the gas which has been adsorbed at the surface of the base metal is driven off and escapes through the thin metal layer due to its porosity, and the thin metal coating is thus more strongly bonded to the base metal. For the the case of plating copper with nickel, a temperature of from 800 to 900 F. was found most advantageous. Of course, the higher'the heating temperature used, the shorter heating time required. Heating to temperatures of from 500 to 1200 F. for a period of from 2 to 30 minutes was found to be satisfactory. A metal coating of the desired thickness is thereafter applied to this 'pre.. treated base metal, again b decomposing metal carbonyl. The product thus obtained is characterized by an excellent bond of the coating to the base metal and by a very uniform and smooth surface structure.
After the deposition of the coating layer proper a second heat treating step may be applied; however, this is not obligatory. Sometimes by such an after-treatment by exposure to high temperatures the ductility of the coating layer is increased. I r
For the intermedIat heat treatment it isnecessary that it be carried out in a non-oxidizing, but preferably in a reducing, atmosphere. Nitrogen, carbon monoxide. carbon dioxide, hydrogen, natural gas, commercial brazing furnace gas or a mixture of such or other gases known in the art are suitable for this purpose. "*In the following, the process is described by way of example as applied to the coating of copper with nickel.
Example A copper plate was first mechanically cleaned by sanding. Thereafter the copper metal was heated to approximately 375 F. in an atmosphere containing approximately 1.4 per cent by volume of nickel carbonyl and diluted with carbon dioxide gas. The rate of gas flow was approximately 4 l. per minute at a temperature of 78 Rand mm. Hg. The copper was exposed to this atmosphere for about 2 minutes after which time a film of 0.00007 thickness had formed on the copper base. Thereafter the metal was heated in an atmosphere of natural gas to a temperature of about 800 F. for approximately 15 minutes. After these preliminary steps the coating proper was performed by subjectin the metal to the same conditions and gases as in the preliminary film-forming step. This second step was carried out for about 15 minutes when a coating of 0.0004" had formed.
In order to increase the ductility of the coating, I subjected the metal to an additional heating step. This step consisted in heating for 15 minutes to a temperature of from 800 to 900 F. in an atmosphere of natural gas.
The process of my invention is applicable for plating with all metals which form gaseous carbonyls; thus, plating with chromium, iron, tungsten, cobalt, molybdenum and other metals may be successfully carried out by the method described. The heat treatment after the application of a thin porous metal film eliminates the gases adsorbed on the surface of the base metal, and the surface activity is then immediately utilized for strongly bonding this metal film,
Thus, the coatings obtained by the process of my invention are uniform in structure, free from blisters and well-adhering to the base metal. Heat treatment does not impair the firm bond between the coating and the base metal.
It will beunderstoodthatthisinventionis not to be restrictedto the examples given in the speciflcation, but that it is e to various mod-,
iflcations and changes which come within the spirit of the disclosureand'the scope of the ap-' pended claims.
I claim:
1. ma process of depositing metal on a copperbase material by the decomposition of metal carbonyl, the steps of exposing the copper base to a carbon dioxide'atmosphere containing 1.4% by volume of a metal carbonyl from the group consisting of nickel, chromium, iron, tungsten, cobalt, and molybdenum for aperiod of time of approximately two minutes while said copper base material is heated to approximately 375' F., said gas having a rate of flow of approximately 4 1. per minute at a temperature of 78 F. and 125 mm. Hg; 0! then heating said copper base with said metal fllmthereon to approximately 800 F. for about 15 minutes in an atmosphere of natural gas and then exposing said coated article to the same metal carbonyl containing gas as the under coat until the coating of the desired thickness has been obtained.
2. In a process for depositing nickel on a copper base material by the decomposition of metal carbonyl the step of exposing it to a carbon dima amen 4 containing percent by volume of nickel carbonyl-for a periodic! tim'eot approximately 2 minutes while said copper base ms terial' is heated to approximately 375 F. said s REFERENCES CITED The following references are of record in file of this patentf UNITED s'ra'rms PATENTS the Number Name Date 1,752,239 Ferrantl Mar. 25, 1930 2,063,596 Feller Dec. 8, 1936 2,332,309 Drummond .........1 Oct, 19, 1943 FOREIGN PATENTS Number Country 7 a Date 487,854 Great Britain Sept. 22, 193B
US665318A 1946-04-26 1946-04-26 Bonding of metal carbonyl deposits Expired - Lifetime US2475601A (en)

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US665318A US2475601A (en) 1946-04-26 1946-04-26 Bonding of metal carbonyl deposits
GB764254A GB751523A (en) 1954-03-16 1954-03-16 Carbonyl-metal plated product

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Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2653879A (en) * 1949-04-06 1953-09-29 Ohio Commw Eng Co Bonding of metal carbonyl deposits
US2656283A (en) * 1949-08-31 1953-10-20 Ohio Commw Eng Co Method of plating wire
US2656284A (en) * 1949-09-07 1953-10-20 Ohio Commw Eng Co Method of plating rolled sheet metal
US2682702A (en) * 1949-04-06 1954-07-06 Ohio Commw Eng Co Carbonyl metal plated product
US2683305A (en) * 1949-07-15 1954-07-13 Sintercast Corp Molybdenum coated article and method of making
US2685532A (en) * 1951-10-08 1954-08-03 Ohio Commw Eng Co Gas plating with chromium hexacarbonyl
US2685124A (en) * 1951-04-30 1954-08-03 Ohio Commw Eng Co Method for hi-vac alloying and coated product
US2690980A (en) * 1951-03-14 1954-10-05 Bell Telephone Labor Inc Carbonyl process
US2731361A (en) * 1952-12-09 1956-01-17 Ohio Commw Eng Co Catalyzed deposition of metals from the gaseous state
US2753800A (en) * 1952-03-24 1956-07-10 Ohio Commw Eng Co Production of printing plates
US2760261A (en) * 1952-04-17 1956-08-28 Ohio Commw Eng Co Method of bonding articles
US2767464A (en) * 1952-10-24 1956-10-23 Ohio Commw Eng Co Composite metallic bodies and method of producing the same
US2779699A (en) * 1953-10-07 1957-01-29 William P Langworthy Annealing process for magnetic material
US2812270A (en) * 1954-01-28 1957-11-05 Continental Can Co Method and apparatus for depositing metal coatings on metal bases
US2814100A (en) * 1953-01-02 1957-11-26 Ohio Commw Eng Co Method of sealing a port in a glass object
US2881094A (en) * 1953-07-16 1959-04-07 Thomas B Hoover Process of coating with nickel by the decomposition of nickel carbonyl
US2886468A (en) * 1953-07-16 1959-05-12 Thomas B Hoover Nickel plating process
US2894320A (en) * 1949-05-09 1959-07-14 David H Gurinsky Coating uranium from carbonyls
US2898234A (en) * 1953-08-14 1959-08-04 Ohio Commw Eng Co Method of producing composite metallic bodies
US2934820A (en) * 1954-04-15 1960-05-03 Union Carbide Corp Metal-to-metal adhesive bonding
US3000755A (en) * 1956-10-11 1961-09-19 Gen Motors Corp Oxidation-resistant turbine blades
US3050417A (en) * 1954-03-18 1962-08-21 Union Carbide Corp Chromium nickel alloy gas plating
US3134893A (en) * 1960-11-03 1964-05-26 Ohio Commw Eng Co Apparatus for welding
US3294654A (en) * 1965-07-28 1966-12-27 Ethyl Corp Metal plating process
US3515583A (en) * 1966-03-29 1970-06-02 Matsushita Electronics Corp Method for manufacturing semiconductor devices
US3762026A (en) * 1963-01-08 1973-10-02 Nuclear Materials And Equip Co Method of making a high temperature body of uniform porosity

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1752239A (en) * 1924-03-04 1930-03-25 Ferranti Ltd Protection of metals
US2063596A (en) * 1932-02-19 1936-12-08 Ig Farbenindustrie Ag Thermal treatment of carbon compounds
GB487854A (en) * 1935-10-11 1938-06-24 Carl Trenzen Improvements in and relating to the production of metal coatings on objects
US2332309A (en) * 1940-05-20 1943-10-19 Ohio Commw Eng Co Gaseous metal deposition

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1752239A (en) * 1924-03-04 1930-03-25 Ferranti Ltd Protection of metals
US2063596A (en) * 1932-02-19 1936-12-08 Ig Farbenindustrie Ag Thermal treatment of carbon compounds
GB487854A (en) * 1935-10-11 1938-06-24 Carl Trenzen Improvements in and relating to the production of metal coatings on objects
US2332309A (en) * 1940-05-20 1943-10-19 Ohio Commw Eng Co Gaseous metal deposition

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2682702A (en) * 1949-04-06 1954-07-06 Ohio Commw Eng Co Carbonyl metal plated product
US2653879A (en) * 1949-04-06 1953-09-29 Ohio Commw Eng Co Bonding of metal carbonyl deposits
US2894320A (en) * 1949-05-09 1959-07-14 David H Gurinsky Coating uranium from carbonyls
US2683305A (en) * 1949-07-15 1954-07-13 Sintercast Corp Molybdenum coated article and method of making
US2656283A (en) * 1949-08-31 1953-10-20 Ohio Commw Eng Co Method of plating wire
US2656284A (en) * 1949-09-07 1953-10-20 Ohio Commw Eng Co Method of plating rolled sheet metal
US2690980A (en) * 1951-03-14 1954-10-05 Bell Telephone Labor Inc Carbonyl process
US2685124A (en) * 1951-04-30 1954-08-03 Ohio Commw Eng Co Method for hi-vac alloying and coated product
US2685532A (en) * 1951-10-08 1954-08-03 Ohio Commw Eng Co Gas plating with chromium hexacarbonyl
US2753800A (en) * 1952-03-24 1956-07-10 Ohio Commw Eng Co Production of printing plates
US2760261A (en) * 1952-04-17 1956-08-28 Ohio Commw Eng Co Method of bonding articles
US2767464A (en) * 1952-10-24 1956-10-23 Ohio Commw Eng Co Composite metallic bodies and method of producing the same
US2731361A (en) * 1952-12-09 1956-01-17 Ohio Commw Eng Co Catalyzed deposition of metals from the gaseous state
US2814100A (en) * 1953-01-02 1957-11-26 Ohio Commw Eng Co Method of sealing a port in a glass object
US2886468A (en) * 1953-07-16 1959-05-12 Thomas B Hoover Nickel plating process
US2881094A (en) * 1953-07-16 1959-04-07 Thomas B Hoover Process of coating with nickel by the decomposition of nickel carbonyl
US2898234A (en) * 1953-08-14 1959-08-04 Ohio Commw Eng Co Method of producing composite metallic bodies
US2779699A (en) * 1953-10-07 1957-01-29 William P Langworthy Annealing process for magnetic material
US2812270A (en) * 1954-01-28 1957-11-05 Continental Can Co Method and apparatus for depositing metal coatings on metal bases
US3050417A (en) * 1954-03-18 1962-08-21 Union Carbide Corp Chromium nickel alloy gas plating
US2934820A (en) * 1954-04-15 1960-05-03 Union Carbide Corp Metal-to-metal adhesive bonding
US3000755A (en) * 1956-10-11 1961-09-19 Gen Motors Corp Oxidation-resistant turbine blades
US3134893A (en) * 1960-11-03 1964-05-26 Ohio Commw Eng Co Apparatus for welding
US3762026A (en) * 1963-01-08 1973-10-02 Nuclear Materials And Equip Co Method of making a high temperature body of uniform porosity
US3294654A (en) * 1965-07-28 1966-12-27 Ethyl Corp Metal plating process
US3515583A (en) * 1966-03-29 1970-06-02 Matsushita Electronics Corp Method for manufacturing semiconductor devices

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