US2685124A - Method for hi-vac alloying and coated product - Google Patents

Method for hi-vac alloying and coated product Download PDF

Info

Publication number
US2685124A
US2685124A US223701A US22370151A US2685124A US 2685124 A US2685124 A US 2685124A US 223701 A US223701 A US 223701A US 22370151 A US22370151 A US 22370151A US 2685124 A US2685124 A US 2685124A
Authority
US
United States
Prior art keywords
metal
carbonyl
elementary
base
base metal
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
US223701A
Inventor
Jr Harry A Toulmin
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.)
Commonwealth Engineering Company of Ohio
Original Assignee
Commonwealth Engineering Company of Ohio
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 Commonwealth Engineering Company of Ohio filed Critical Commonwealth Engineering Company of Ohio
Priority to US223701A priority Critical patent/US2685124A/en
Priority to CH332501D priority patent/CH332501A/en
Priority to DEC9375A priority patent/DE1147101B/en
Application granted granted Critical
Publication of US2685124A publication Critical patent/US2685124A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

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
    • C23C16/44—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 method of coating
    • 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
    • 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
    • C23C16/44—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 method of coating
    • C23C16/4401—Means for minimising impurities, e.g. dust, moisture or residual gas, in the reaction chamber
    • C23C16/4402—Reduction of impurities in the source gas
    • 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
    • C23C16/44—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 method of coating
    • C23C16/4412—Details relating to the exhausts, e.g. pumps, filters, scrubbers, particle traps
    • 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
    • C23C16/44—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 method of coating
    • C23C16/455—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 method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • 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
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S29/00—Metal working
    • Y10S29/044—Vacuum
    • 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
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/922—Static electricity metal bleed-off metallic stock
    • Y10S428/9335—Product by special process
    • Y10S428/938—Vapor deposition or gas diffusion
    • 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
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12472—Microscopic interfacial wave or roughness
    • 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
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12778—Alternative base metals from diverse categories
    • 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
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12993—Surface feature [e.g., rough, mirror]

Definitions

  • This invention relates to a method of surface coating and impregnation of base metals with other elementary metals by the application of the elementary metals to the base metal in a solid state, and also relates to products obtained thereby.
  • a still further object of the invention is to deposit elementary metal onto a base metal from a vaporous compound wherein the base metal is exposed to a vacuum atmosphere to remove air from the surface of the base metal and draw out air from the interstices at the surface of the metal while the base metal is heated to a temperature of decomposition of a compound of an elementary metal to be deposited so that the subjection of the so prepared base metal to a vaporous atmosphere of a compound of the elementary metal that is to be deposited will cause decomposition of the compound of the elementary metal with subsequent intersticial deposition of the elementary metal in the base metal and on the surface thereof, and thereby obtain a secure bonding of the elementary metal onto the base metal.
  • the compound of the elementary metal may be used in the vaporous phase as obtained either by spraying of a liquid into the vacuum atmosphere this invention to coat and with other elementary the elementary metal is a solid state, and
  • the drawing figure illustrates an embodiment of the invention showing diagrammatically an apparatus for carrying out the method of this invention.
  • an object that is to be surface treated by the deposition of an elementary metal onto the surface is subjected to a vacuum atmosphere whereby air is removed from the surface of the object and any air retained within the interstices of the metal in any way'connected with the surface of the metal is removed, thereby freeing all surfaces of the metal from the existence of air at the surface thereof to provide a clean metal surface free of the monomolecular film that is normally found on metals.
  • the elementary metal can be deposited directly upon the base metal without interference of any gaseous medium.
  • While the object to be surface-treated is in desired depth.
  • Either the liquid or gaseous carbonyl compounds are introduced into the vacuum atmosphere around the object being surface-treated under pressure to obtain a high degree of dishave the surface l2 thereof treated, this being the bearing surface of a cylindrical bearing.
  • the chamber I l is connected to a vacuum pump 13 by means of the conduits l4 and 55 which have a refrigerated trap l6 therein.
  • the conduit 14 is provided with a plurality of inlet connections l1 spaced around the chamber H to provide for a uniform withdrawal of the atmosphere from within the chamber l I.
  • the object It may be supported in the chamber H in any suitable manner.
  • a series of heat lamps l8 are provided around the object thereby heating the object by the radiant heat effect from the lamps.
  • a vaporous metal carbonyl compound M(C) 4 wherein the M may be nickel, for example when a liquid carbonyl is used, or chromium, where a crystalline metal carbonyl compound is used as converted to the gaseous phase, is supplied through the conduit under pressure into a distributing head 2i.
  • the liquid or gaseous metal carbonyl is sprayed under pressure from the distributing head through a series of small jet openings 22 so that the metal carbonyl is directed toward the surface l2 of the object [0 in a vaporous condition through the series of jets 22.
  • the chamber H is preferably cooled by a cooling coil 23 which holds the internal temperature of the chamber to about 250 F. which is below a rapid decomposition temperature of the metal carbonyl. Since the object It is at or above a rapid decomposition temperature of the metal carbonyl, the metal of the carbonyl will deposit on the surface of the article and the carbonmonoxide of the compound will be released for withdrawal by the vacuum pump l3, which also retains the vacuum condition within the chamber i I during the surface treatment of the article l0.
  • a refrigerated trap 66 is placed in the conduit l5 to condense out any metal carbonyl leaving the chamber l I, thus allowing only released carbon-monoxide to flow to the pump l3.
  • a hand-operated valve 24 is provided on the trap IE to periodically remove the liquid carbonyl condensed in the trap.
  • a refrigeration coil 25 is provided around the trap I6 to reduce the temperature of the trap to the temperature of liquefaction of the metal carbonyl.
  • the trap may have a suitable opening to remove the crystals removed from the gas during passage through the trap.
  • tungsten carbonyl which is of crystalline form at normal room temperature, is vaporized at a temperature of from F. to F. This is considerably below the decomposition temperature of the carbonyl of about 250 F. at which there is a slow decomposition of the carbonyl.
  • the gaseous tungsten carbonyl is placed under pressure of from 10 to 15 pounds per square inch with any suitable pump or in a gas accumulator held at a temperature of 125 F. to maintain the carbonyl in the gaseous phase and is delivered to the surface of the object being treated in the vaporous condition upon release of the gaseous carbonyl through the small jet openings heretofore described.
  • the liquid is sprayed through the jets 22 of the distributing head 2
  • the metal carbonyl in vaporous condition is applied to the surface of the article being treated in the same manner as heretofore described.
  • the vacuum pump is not operated because of the difficulty of maintaining the high level of vacuum in the chamber I! when introducing any substantial volume of vaporous metal carbonyl into the chamber.
  • the vacuum level in the chamber falls to about 10 of mercury, the application or" the metal carbony1 will be stopped temporarily and the vacuum level of the chamber again increased to from 18" to 23 of mercury, whereupon another metal carbonyl treatment is applied to the surface of the object. This batch process is repeated until the desired thickness of metal is built up on the surface of the object E0.
  • the latter method has advantage in that the carbon monoxide released as a result of the decomposition of the metal carbonyl is removed from the surface of the deposited metal and from the interstices of the base metal between each treatment of the surface under a very high vacuum removes all mono-molecular gaseous film from the surface of the base metal, and from the surface of any deposited metal so that the subsequent treatments with the vaporous metal carbonyl will obtain a firm bond of deposited metal to that previously deposited on the base metal.
  • a more secure bond of the metal of the carbonyl to the base metal is obtained because of the removal of the mono-molecular film of gas from the surface of the base metal which allows the metal of the carbonyl to be deposited directly onto the base metal unaffected by any gas film which tends to restrict the movement of the metal of the carbonyl onto the surface of the base metal. Less scaling of the deposited metal, and more complete filling of the interstices of the metal that have any connection with, the surface of the metal, is obtained.
  • Th method of my invention is useful for treating metals and alloys to make them rustproof and subject to less corrosion and tarnishing by treating the metals with chrome or nickel carbonyls, for example.
  • the method of my invention may also be used for the purpose of surface-hardening of metals, such as by the application of a tungsten metal to a base metal.
  • a method of coating and impregnating metal surfaces with another metal by gaseous deposition which comprises the steps of subjecting said metal surface to sub-atmospheric conditions and on the order of 18 to 23" of mercury, heating said metal to be coated while retained in said sub-atmospheric condition, introducing a heatdecomposable gaseous metal compound into said atmosphere and in contact with said heated metal, the temperature to which said metal is heated being high enough to cause decomposition of said heat decomposable gaseous metal compound whereby the same is decomposed and the metal constituent thereof deposited onto said metal surface and into the pores to form a coating of metal thereover which is firmly united to the metal surface.
  • the method of depositing elementary metals in the solid state upon other base metals and bonding the same thereto comprising, exposing the base metal to a vacuum atmosphere of between 18 and 23" of mercury and elevating the temperature of the base metal to the decomposition temperature of the carbonyl of the elementary metal to be deposited thereon, and subjecting the base metal while at elevated temperature and in said vacuum atmosphere to a vaporous atmosphere of the carbonyl of the elementary metal introduced under pressure into the vacuum atmosphere whereby to decompose the carbonyl and deposit elementary metal on the base metal.
  • the method of depositing elementary metals in the solid state upon other base metals and bonding the same thereto comprising, exposing the base metal to a vacuum atmosphere of between 18 and 23" of mercury and elevating the temperature of the base metal to the decomposition temperature of the carbonyl of the elementary metal to be deposited thereon, and immediately thereafter subjecting the base metal while at elevated temperature and in said vacuum atmosphere to a vaporous atmosphere of the carbonyl of the elementary metal introduced under pressure into the vacuum atmosphere in close proximity to the surface of the base metal on which the elementary metal is to be deposited whereby to decompose the carbonyl and deposit elementary metal on the base metal.
  • the method of depositing elementary metals in the solid state upon other base metals and bonding the same thereto comprising, exposing the base metal to a high vacuum atmosphere on the order of 18 to 23" of mercury and elevating the temperature of the base metal to the decomposition temperature of the carbonyl of the elementary metal to be deposited thereon, and immediately thereafter subjecting the base metal while at elevated temperature and in the vacuum atmosphere to a vaporous atmosphere of a metal carbonyl introduced under pressure into the vacuum atmosphere in close proximity to the surface of the base metal on which the elementary metal is to be deposited whereby to decompose the compound and deposit elementary metal on the base metal.
  • the method of depositing elementary metals in the solid state upon other base metals and bonding the same thereto which comprises, subjecting the base metal to a high vacuum atmosphere on the order of 18" to 23" of mercury to remove intersticially retained and pore-occluded gas from the base metal, heating the base metal to a temperature to cause the decomposition of the carbonyl compound of the elementary metal to be deposited thereon, and subjecting the base metal while thus heated and while retained in the vacuum atmosphere to a. gaseous atmosphere containing the carbonyl of said elementary metal to be deposited and which is heat decomposed and depositing said elementary metal on the base metal.
  • the method of depositing elementary metals in the solid state upon other base metals from a heat-decomposable metal carbonyl compound and bonding the same thereto which comprises, subjecting the base metal to a vacuum atmos-. phere on the order of 18" to 23" of mercury and maintained at a temperature below the decom-.
  • the method of depositing elementary metals in the solid state upon other base metals from a heat-decomposable metal carbonyl compound and bonding the same thereto which comprises, subjecting the base metal to a vacuum atmosphere of between 18 and 23" of mercury, elevating the temperature of the base metal to between about 350 F. and 400 F., thereafter subjecting the base metal while at said elevated temperature and under said vacuum atmospheric conditions to gaseous metal carbonyl which is decomposable at the temperature of said base metal, said gaseous metal carbonyl being delivered under pressure of from 10 lbs. to 15 lbs. per square inch whereby said carbonyl is caused to decompose and deposit elementary metal on the base metal.
  • the method of depositing elementary metals in the solid state upon other base metals from a heat-decomposable metal carbonyl compound and bonding the same thereto comprising, subjecting the base metal to a high vacuum atmosphere of between about 18" and 23" of mercury, heating the base metal to the decomposition temperature of the carbonyl of the elementary metal to be deposited thereon, subjecting the base metal while at said decomposition temperature and while retained in the vacuum atmosphere to a gaseous atmosphere of the carbonyl of the elementary metal to be deposited whereby to cause decomposition of the carbonyl and deposition of the elementary metal on the base metal with resultant liberation of gas into the vacuum at mosphere, restoring the vacuum atmosphere to its initial condition while maintaining said base metal heated, and re-exposing the base metal to said gaseous atmosphere of said carbonyl of the elementary metal.
  • metal of the metal carbonyl is selected from the group consisting of nickel, cobalt, chromium, iron, tungsten and molybdenum.
  • metal of the metal carbonyl is selected from the group consisting of nickel, cobalt, chromium, iron, tungsten and molybdenum.

Description

Aug. 3, 1954 TOULMIN JR 2,685,124
METHOD FOR HIVAC ALLOYING AND COATED PRODUCT Filed April 30, 1951 INVENTOR HARRY A. TOULMIN JR.
ATTORNEYS Patented Aug. 3, 1954 METHOD FOR HI-VAC ALLOYING AND COATED PRODUCT Harry A. Toulmin, Jr., Dayton,
Ohio, assignor to The Commonwealth Engineering Company of Ohio, Dayton, Ohio, a corporation of Ohio Application April 30, 1951, Serial No. 223,701
12 Claims.
This invention relates to a method of surface coating and impregnation of base metals with other elementary metals by the application of the elementary metals to the base metal in a solid state, and also relates to products obtained thereby.
It is an object of impregnate base metals metals in a manner that deposited on the base metal in thereby eliminate any melting of either of the metals to obtain surface coating and surface impregnation of the base metal with the elementary metal.
It is another object of the invention to provide a method of depositing an elementary metal on a base metal in a manner that intersticial deposition of the elementary metal is obtained on the base metal.
It is still a further object of the invention to provide a method of obtaining deposition of an elementary metal on a base metal in which air is removed from the surface of the base metal and from the interstices at the surface of the metal to provide for a deposition and more secure bonding of an elementary metal to the surface of a base metal through intersticial deposition of the elementary metal in the base metal.
These and other objects of the invention are accomplished by depositing an elementary metal from a vaporous or gaseous or quasi-gaseous state onto the base metal under vacuum conditions whereby the deposited metal securely bonds to the base metal.
A still further object of the invention is to deposit elementary metal onto a base metal from a vaporous compound wherein the base metal is exposed to a vacuum atmosphere to remove air from the surface of the base metal and draw out air from the interstices at the surface of the metal while the base metal is heated to a temperature of decomposition of a compound of an elementary metal to be deposited so that the subjection of the so prepared base metal to a vaporous atmosphere of a compound of the elementary metal that is to be deposited will cause decomposition of the compound of the elementary metal with subsequent intersticial deposition of the elementary metal in the base metal and on the surface thereof, and thereby obtain a secure bonding of the elementary metal onto the base metal.
In accomplishing this object of the invention the compound of the elementary metal may be used in the vaporous phase as obtained either by spraying of a liquid into the vacuum atmosphere this invention to coat and with other elementary the elementary metal is a solid state, and
or by use of a gaseous state of the compound of the elementary metal.
The drawing figure illustrates an embodiment of the invention showing diagrammatically an apparatus for carrying out the method of this invention.
In the method of this invention, an object that is to be surface treated by the deposition of an elementary metal onto the surface is subjected to a vacuum atmosphere whereby air is removed from the surface of the object and any air retained within the interstices of the metal in any way'connected with the surface of the metal is removed, thereby freeing all surfaces of the metal from the existence of air at the surface thereof to provide a clean metal surface free of the monomolecular film that is normally found on metals. Thus, the elementary metal can be deposited directly upon the base metal without interference of any gaseous medium.
While the object to be surface-treated is in desired depth.
Compounds that in the process of proved to be suitable for use my invention to produce the deposition of the elementary metal on the base metals. Some of the metal carbonyls such as nickel and iron can be used as liquids, whereas volatilize it into the gaseous phase.
Either the liquid or gaseous carbonyl compounds are introduced into the vacuum atmosphere around the object being surface-treated under pressure to obtain a high degree of dishave the surface l2 thereof treated, this being the bearing surface of a cylindrical bearing. The chamber I l is connected to a vacuum pump 13 by means of the conduits l4 and 55 which have a refrigerated trap l6 therein. The conduit 14 is provided with a plurality of inlet connections l1 spaced around the chamber H to provide for a uniform withdrawal of the atmosphere from within the chamber l I. This is advantageous particularly during the period of continuous withdrawal of the atmosphere from the chamber l I while the E vaporous atmosphere of the metal carbonyl is being applied to the surface of the article being treated to avoid any directional flow of metal carbonyl which would cause non-uniform deposition on the surface of the article.
The object It may be supported in the chamber H in any suitable manner. To heat the object It, a series of heat lamps l8 are provided around the object thereby heating the object by the radiant heat effect from the lamps. A vaporous metal carbonyl compound M(C) 4, wherein the M may be nickel, for example when a liquid carbonyl is used, or chromium, where a crystalline metal carbonyl compound is used as converted to the gaseous phase, is supplied through the conduit under pressure into a distributing head 2i. The liquid or gaseous metal carbonyl is sprayed under pressure from the distributing head through a series of small jet openings 22 so that the metal carbonyl is directed toward the surface l2 of the object [0 in a vaporous condition through the series of jets 22. Release of a liquid metal carbonyl under pressure into the vacuum atmosphere obtains instant vaporization into the gas or vapor phase so that either this or the gaseous form of a metal carbonyl provides for an even distribution of the metal carbonyl at the surface that is undergoing treatment.
To avoid decomposition of the metal carbonyl within the chamber l the article It] with subsequent deposition of the metal of the carbonyl directly on the surface of the article, the chamber H is preferably cooled by a cooling coil 23 which holds the internal temperature of the chamber to about 250 F. which is below a rapid decomposition temperature of the metal carbonyl. Since the object It is at or above a rapid decomposition temperature of the metal carbonyl, the metal of the carbonyl will deposit on the surface of the article and the carbonmonoxide of the compound will be released for withdrawal by the vacuum pump l3, which also retains the vacuum condition within the chamber i I during the surface treatment of the article l0.
To prevent any excess metal carbonyl from reaching the vacuum pump 13, a refrigerated trap 66 is placed in the conduit l5 to condense out any metal carbonyl leaving the chamber l I, thus allowing only released carbon-monoxide to flow to the pump l3. A hand-operated valve 24 is provided on the trap IE to periodically remove the liquid carbonyl condensed in the trap. A refrigeration coil 25 is provided around the trap I6 to reduce the temperature of the trap to the temperature of liquefaction of the metal carbonyl.
1 except at the surface of 4 In the event the metal carbonyl is that which crystallizes from the gaseous phase, then, of course, the trap may have a suitable opening to remove the crystals removed from the gas during passage through the trap.
According to the method of this invention, for example, tungsten carbonyl, which is of crystalline form at normal room temperature, is vaporized at a temperature of from F. to F. This is considerably below the decomposition temperature of the carbonyl of about 250 F. at which there is a slow decomposition of the carbonyl. The gaseous tungsten carbonyl is placed under pressure of from 10 to 15 pounds per square inch with any suitable pump or in a gas accumulator held at a temperature of 125 F. to maintain the carbonyl in the gaseous phase and is delivered to the surface of the object being treated in the vaporous condition upon release of the gaseous carbonyl through the small jet openings heretofore described.
The object being treated, such as the bearing 10 is subjected to the vacuum atmosphere in the chamber H of from 25 to 30" of water, this vacuum being continuously maintained by operation of the vacuum pump 13. The object 10 is heated to a temperature of from 350 F. to 400 F. at which temperature the gaseous tungsten carbonyl supplied to the surface of the base metal will rapidly decompose with resultant deposition of the metal tungsten upon the surface 12 of the object iii. The carbon-monoxide released by the decomposition of the tungsten carbonyl will be withdrawn from the chamber ll through the pipe V by the vacuum pump l3. Any excess carbonyl will be crystallized in the refrigerated trap it in the manner heretofore described.
With the tungsten carbonyl being continuously supplied under pressure through the jets of the distributing head 2|, and with the vacuum atmosphere maintained in the chamber H, a surface application of tungsten of a thickness of .001" is obtained in approximately one minute, with the temperature of the article maintained at from 350 F. to 400 F.
When the metal carbonyl to be applied to the surface of the object is in the liquid form, such as nickel carbonyl, the liquid is sprayed through the jets 22 of the distributing head 2| under a pressure of from 10 to 15 pounds per square inch to obtain a vaporous condition of the liquid carbonyl which is applied to the surface of the object being treated.
To obtain an even more complete evacuation of the chamber 1 l, the vacuum treatment may be applied in what may be termed a batch treatment in which the atmosphere of the chamber ii is reduced to a vacuum of from 18 to 23" of mercury.
When this desired vacuum level has been reached, and the object if: is raised in temperature to from 350 F. to 400 F,, the metal carbonyl in vaporous condition is applied to the surface of the article being treated in the same manner as heretofore described. During this period, however, the vacuum pump is not operated because of the difficulty of maintaining the high level of vacuum in the chamber I! when introducing any substantial volume of vaporous metal carbonyl into the chamber. When the vacuum level in the chamber falls to about 10 of mercury, the application or" the metal carbony1 will be stopped temporarily and the vacuum level of the chamber again increased to from 18" to 23 of mercury, whereupon another metal carbonyl treatment is applied to the surface of the object. This batch process is repeated until the desired thickness of metal is built up on the surface of the object E0.
The latter method has advantage in that the carbon monoxide released as a result of the decomposition of the metal carbonyl is removed from the surface of the deposited metal and from the interstices of the base metal between each treatment of the surface under a very high vacuum removes all mono-molecular gaseous film from the surface of the base metal, and from the surface of any deposited metal so that the subsequent treatments with the vaporous metal carbonyl will obtain a firm bond of deposited metal to that previously deposited on the base metal.
By following the method of this invention, a more secure bond of the metal of the carbonyl to the base metal is obtained because of the removal of the mono-molecular film of gas from the surface of the base metal which allows the metal of the carbonyl to be deposited directly onto the base metal unaffected by any gas film which tends to restrict the movement of the metal of the carbonyl onto the surface of the base metal. Less scaling of the deposited metal, and more complete filling of the interstices of the metal that have any connection with, the surface of the metal, is obtained.
The degree of impregnation of the surface of the base metal is, of course, dependent on the porosity of the base metal object. In extremely porous metals, somewhat deeper impregnation is obtained than in other metals.
Th method of my invention is useful for treating metals and alloys to make them rustproof and subject to less corrosion and tarnishing by treating the metals with chrome or nickel carbonyls, for example. The method of my invention may also be used for the purpose of surface-hardening of metals, such as by the application of a tungsten metal to a base metal.
This application is a continuation-in-part application of my copending application, Serial Number 672,709, filed May 27, 1946 and now abandoned.
It will be understood that this invention is not restricted to the details given in the disclosure herein, but that it is susceptible to various modifications that fall within the spirit of the specification and the scope of the appended claims.
Having thus fully described my invention, what I claim as new and desire to secure by Letters Patent, is:
1. A method of coating and impregnating metal surfaces with another metal by gaseous deposition which comprises the steps of subjecting said metal surface to sub-atmospheric conditions and on the order of 18 to 23" of mercury, heating said metal to be coated while retained in said sub-atmospheric condition, introducing a heatdecomposable gaseous metal compound into said atmosphere and in contact with said heated metal, the temperature to which said metal is heated being high enough to cause decomposition of said heat decomposable gaseous metal compound whereby the same is decomposed and the metal constituent thereof deposited onto said metal surface and into the pores to form a coating of metal thereover which is firmly united to the metal surface.
2. The method of depositing elementary metals in the solid state upon other base metals and bonding the same thereto comprising, exposing the base metal to a vacuum atmosphere of between 18 and 23" of mercury and elevating the temperature of the base metal to the decomposition temperature of the carbonyl of the elementary metal to be deposited thereon, and subjecting the base metal while at elevated temperature and in said vacuum atmosphere to a vaporous atmosphere of the carbonyl of the elementary metal introduced under pressure into the vacuum atmosphere whereby to decompose the carbonyl and deposit elementary metal on the base metal.
3. The method of depositing elementary metals in the solid state upon other base metals and bonding the same thereto comprising, exposing the base metal to a vacuum atmosphere of between 18 and 23" of mercury and elevating the temperature of the base metal to the decomposition temperature of the carbonyl of the elementary metal to be deposited thereon, and immediately thereafter subjecting the base metal while at elevated temperature and in said vacuum atmosphere to a vaporous atmosphere of the carbonyl of the elementary metal introduced under pressure into the vacuum atmosphere in close proximity to the surface of the base metal on which the elementary metal is to be deposited whereby to decompose the carbonyl and deposit elementary metal on the base metal.
4. The method of depositing elementary metals in the solid state upon other base metals and bonding the same thereto comprising, exposing the base metal to a high vacuum atmosphere on the order of 18 to 23" of mercury and elevating the temperature of the base metal to the decomposition temperature of the carbonyl of the elementary metal to be deposited thereon, and immediately thereafter subjecting the base metal while at elevated temperature and in the vacuum atmosphere to a vaporous atmosphere of a metal carbonyl introduced under pressure into the vacuum atmosphere in close proximity to the surface of the base metal on which the elementary metal is to be deposited whereby to decompose the compound and deposit elementary metal on the base metal.
5. The method of depositing elementary metals in the solid state upon other base metals and bonding the same thereto which comprises, subjecting the base metal to a high vacuum atmosphere on the order of 18" to 23" of mercury to remove intersticially retained and pore-occluded gas from the base metal, heating the base metal to a temperature to cause the decomposition of the carbonyl compound of the elementary metal to be deposited thereon, and subjecting the base metal while thus heated and while retained in the vacuum atmosphere to a. gaseous atmosphere containing the carbonyl of said elementary metal to be deposited and which is heat decomposed and depositing said elementary metal on the base metal.
6. The method of depositing elementary metals in the solid state upon other base metals from a heat-decomposable metal carbonyl compound and bonding the same thereto which comprises, subjecting the base metal to a vacuum atmos-. phere on the order of 18" to 23" of mercury and maintained at a temperature below the decom-. position temperature of the carbonyl of the ele mentary metal to be deposited, elevating the temperature of the base metal to the decomposition temperature of the carbonyl of the elementary metal to be deposited thereon, and immediately thereafter subjecting the base metal while at elevated temperature and while retained in the vacuum atmosphere to a gaseous atmosphere 7 of the carbonyl of the elementary metalwhich is introduced under pressure into the vacuum atmosphere and said carbonyl heat-decomposed to deposit the elementary metal on the base metal.
7. The method of depositing elementary metals in the solid state upon other base metals from a heat-decomposable metal carbonyl compound and bonding the same thereto which comprises, subjecting the base metal to a vacuum atmosphere of between 18 and 23" of mercury, elevating the temperature of the base metal to between about 350 F. and 400 F., thereafter subjecting the base metal while at said elevated temperature and under said vacuum atmospheric conditions to gaseous metal carbonyl which is decomposable at the temperature of said base metal, said gaseous metal carbonyl being delivered under pressure of from 10 lbs. to 15 lbs. per square inch whereby said carbonyl is caused to decompose and deposit elementary metal on the base metal.
8. The method of depositing elementary metals in the solid state upon other base metals from a heat-decomposable metal carbonyl compound and bonding the same thereto comprising, subjecting the base metal to a high vacuum atmosphere of between about 18" and 23" of mercury, heating the base metal to the decomposition temperature of the carbonyl of the elementary metal to be deposited thereon, subjecting the base metal while at said decomposition temperature and while retained in the vacuum atmosphere to a gaseous atmosphere of the carbonyl of the elementary metal to be deposited whereby to cause decomposition of the carbonyl and deposition of the elementary metal on the base metal with resultant liberation of gas into the vacuum at mosphere, restoring the vacuum atmosphere to its initial condition while maintaining said base metal heated, and re-exposing the base metal to said gaseous atmosphere of said carbonyl of the elementary metal.
9. A method according to claim 7 in which the metal of the metal carbonyl is selected from the group consisting of nickel, cobalt, chromium, iron, tungsten and molybdenum.
10. A method according to claim 8 in which the metal of the metal carbonyl is selected from the group consisting of nickel, cobalt, chromium, iron, tungsten and molybdenum.
11. As a new article of manufacture, a metal product having a surface with minute irregularities, and a deposit of an elementary metal on the said surface obtained according to the method set forth in claim 7.
12. As a new article of manufacture, a metal product having a surface with minute irregularities, and a deposit of an elementary metal on the said surface obtained according to the method set forth in claim 8.
References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 1,497,417 Weber June 10, 1924 1,709,781 Boer et a1 Apr. 16, 1929 1,816,476 Fink et a1 July 28, 1931 2,304,182 Lang Dec. 8, 1942 2,344,138 Drummond Mar. 14, 1944 2,398,382 Lyon Apr. 16, 1946 2,475,601 Fink July 12, 1949 2,508,509 Germer et a1 May 23, 1950 2,516,058 Lander July 18, 1950

Claims (2)

  1. 7. THE METHOD OF DEPOSITING ELEMENTARY METALS IN THE SOLID STATE UPON OTHER BASE METALS FROM A HEAT-DECOMPOSABLE METAL CARBONYL COMPOUND AND BONDING THE SAME THERETO WHICH COMPRISES, SUBJECTING THE BASE METAL TO A VACUUM ATMOSPHERE OF BETWEEN 18" AND 23" OF MERCURY, ELEVATING THE TEMPERATURE OF THE BASE METAL TO BETWEEN ABOUT 350* F. AND 400*F., THEREAFTER SUBJECTING THE BASE METAL WHILE AT SAID ELEVATED TEMPERATURE AND UNDER SAID VACUUM ATMOSPHERIC CONDITIONS TO GASEOUS METAL CARBONYL WHICH IS DECOMPOSABLE AT THE TEMPERATURE OF SAID BASE METAL, AND GASEOUS METAL CARBONYL BEING DELIVERED UNDER PRESSURE OF FROM 10 LBS. TO 15 LBS. PER SQUARE INCH WHEREBY SAID CARBONYL IS CAUSED TO DECOMPOSE AND DEPOSIT ELEMENTARY METAL ON THE BASE METAL.
  2. 11. AS A NEW ARTICLE OF MANUFACTURE, A METAL PRODUCT HAVING A SURFACE WITH MINUTE IRREGULARITIES, AND A DEPOSIT OF AN ELEMENTARY METAL ON THE SAID SURFACE OBTAINED ACCORDING TO THE METHOD SET FORTH IN CLAIM 7.
US223701A 1951-04-30 1951-04-30 Method for hi-vac alloying and coated product Expired - Lifetime US2685124A (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US223701A US2685124A (en) 1951-04-30 1951-04-30 Method for hi-vac alloying and coated product
CH332501D CH332501A (en) 1951-04-30 1954-05-04 Process for applying elemental metal to a metallic substrate, device for carrying out the process and product obtained by this process
DEC9375A DE1147101B (en) 1951-04-30 1954-05-15 Method and device for plating and impregnating base metals with elemental metals by treatment with metal compounds which can be decomposed under heat

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US223701A US2685124A (en) 1951-04-30 1951-04-30 Method for hi-vac alloying and coated product

Publications (1)

Publication Number Publication Date
US2685124A true US2685124A (en) 1954-08-03

Family

ID=22837651

Family Applications (1)

Application Number Title Priority Date Filing Date
US223701A Expired - Lifetime US2685124A (en) 1951-04-30 1951-04-30 Method for hi-vac alloying and coated product

Country Status (2)

Country Link
US (1) US2685124A (en)
CH (1) CH332501A (en)

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2713196A (en) * 1953-03-17 1955-07-19 Chicago Bridge & Iron Co Method for cladding and product resulting therefrom
US2753800A (en) * 1952-03-24 1956-07-10 Ohio Commw Eng Co Production of printing plates
US2792806A (en) * 1951-10-08 1957-05-21 Ohio Commw Eng Co Apparatus for plating the interior of hollow objects
US2814100A (en) * 1953-01-02 1957-11-26 Ohio Commw Eng Co Method of sealing a port in a glass object
US2839423A (en) * 1955-06-03 1958-06-17 Ohio Commw Eng Co Method of coating alkaline earth metal with protective metal
US2854739A (en) * 1954-07-29 1958-10-07 Thompson Prod Inc Multiple coated molybdenum base article
US2878554A (en) * 1955-09-16 1959-03-24 Rand Dev Corp Method and coating for protection of molybdenum and its alloys
US2887088A (en) * 1954-08-16 1959-05-19 Ohio Commw Eng Co Apparatus for gaseous metal plating fibers
US2933415A (en) * 1954-12-23 1960-04-19 Ohio Commw Eng Co Nickel coated iron particles
US2982019A (en) * 1953-05-22 1961-05-02 Union Carbide Corp Method of protecting magnesium with a coating of titanium or zirconium
US2982017A (en) * 1953-05-22 1961-05-02 Union Carbide Corp Method of protecting magnesium with a coating of titanium
US3050417A (en) * 1954-03-18 1962-08-21 Union Carbide Corp Chromium nickel alloy gas plating
US3055089A (en) * 1958-08-06 1962-09-25 Union Carbide Corp Gaseous metal product and processes
US3150940A (en) * 1960-03-01 1964-09-29 Cincinnati Milling Machine Co Bearing surface and method of producing said surface
US3206326A (en) * 1961-11-27 1965-09-14 Ethyl Corp Aluminum intermittent plating process
US3235960A (en) * 1961-03-24 1966-02-22 Gen Electric Process for the continuous formation of intermediates
US3294059A (en) * 1963-04-15 1966-12-27 Charles R Barnes Deposition of nickel films on the interior surface of polytetrafluoroethylene tubing
US3620838A (en) * 1969-12-16 1971-11-16 Siemens Ag Method of densification of porous layers
US3691720A (en) * 1970-10-12 1972-09-19 Western Electric Co Apparatus for frequency adjusting and assembling monolithic crystal filters
US3853637A (en) * 1973-06-25 1974-12-10 Gray R And Co Inc Method of treating articles under differential vacuum conditions with external gas flow
US4619840A (en) * 1983-05-23 1986-10-28 Thermco Systems, Inc. Process and apparatus for low pressure chemical vapor deposition of refractory metal
US4709655A (en) * 1985-12-03 1987-12-01 Varian Associates, Inc. Chemical vapor deposition apparatus
US4796562A (en) * 1985-12-03 1989-01-10 Varian Associates, Inc. Rapid thermal cvd apparatus
US4817557A (en) * 1983-05-23 1989-04-04 Anicon, Inc. Process and apparatus for low pressure chemical vapor deposition of refractory metal

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL277617A (en) * 1961-05-01
US3213827A (en) * 1962-03-13 1965-10-26 Union Carbide Corp Apparatus for gas plating bulk material to metallize the same
DE1255635B (en) * 1962-06-14 1967-12-07 Siemens Ag Process for producing crystalline, in particular single-crystalline, layers from semiconducting materials

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1497417A (en) * 1919-03-31 1924-06-10 Henry C P Weber Process of coating metals
US1709781A (en) * 1925-07-25 1929-04-16 Philips Nv Process for precipitating hafnium and zirconium on an incandescent body
US1816476A (en) * 1926-09-07 1931-07-28 American Thermos Bottle Co Manufacture of double-walled receptacles
US2304182A (en) * 1939-06-19 1942-12-08 Sigmund Cohn Method of forming metallic films
US2344138A (en) * 1940-05-20 1944-03-14 Chemical Developments Corp Coating method
US2398382A (en) * 1942-11-17 1946-04-16 Dean A Lyon Method for coating optical elements
US2475601A (en) * 1946-04-26 1949-07-12 Ohio Commw Eng Co Bonding of metal carbonyl deposits
US2508509A (en) * 1945-01-13 1950-05-23 Bell Telephone Labor Inc Apparatus for coating hollow objects
US2516058A (en) * 1943-09-30 1950-07-18 Bell Telephone Labor Inc Apparatus for plating of metals

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1497417A (en) * 1919-03-31 1924-06-10 Henry C P Weber Process of coating metals
US1709781A (en) * 1925-07-25 1929-04-16 Philips Nv Process for precipitating hafnium and zirconium on an incandescent body
US1816476A (en) * 1926-09-07 1931-07-28 American Thermos Bottle Co Manufacture of double-walled receptacles
US2304182A (en) * 1939-06-19 1942-12-08 Sigmund Cohn Method of forming metallic films
US2344138A (en) * 1940-05-20 1944-03-14 Chemical Developments Corp Coating method
US2398382A (en) * 1942-11-17 1946-04-16 Dean A Lyon Method for coating optical elements
US2516058A (en) * 1943-09-30 1950-07-18 Bell Telephone Labor Inc Apparatus for plating of metals
US2508509A (en) * 1945-01-13 1950-05-23 Bell Telephone Labor Inc Apparatus for coating hollow objects
US2475601A (en) * 1946-04-26 1949-07-12 Ohio Commw Eng Co Bonding of metal carbonyl deposits

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2792806A (en) * 1951-10-08 1957-05-21 Ohio Commw Eng Co Apparatus for plating the interior of hollow objects
US2753800A (en) * 1952-03-24 1956-07-10 Ohio Commw Eng Co Production of printing plates
US2814100A (en) * 1953-01-02 1957-11-26 Ohio Commw Eng Co Method of sealing a port in a glass object
US2713196A (en) * 1953-03-17 1955-07-19 Chicago Bridge & Iron Co Method for cladding and product resulting therefrom
US2982019A (en) * 1953-05-22 1961-05-02 Union Carbide Corp Method of protecting magnesium with a coating of titanium or zirconium
US2982017A (en) * 1953-05-22 1961-05-02 Union Carbide Corp Method of protecting magnesium with a coating of titanium
US3050417A (en) * 1954-03-18 1962-08-21 Union Carbide Corp Chromium nickel alloy gas plating
US2854739A (en) * 1954-07-29 1958-10-07 Thompson Prod Inc Multiple coated molybdenum base article
US2887088A (en) * 1954-08-16 1959-05-19 Ohio Commw Eng Co Apparatus for gaseous metal plating fibers
US2933415A (en) * 1954-12-23 1960-04-19 Ohio Commw Eng Co Nickel coated iron particles
US2839423A (en) * 1955-06-03 1958-06-17 Ohio Commw Eng Co Method of coating alkaline earth metal with protective metal
US2878554A (en) * 1955-09-16 1959-03-24 Rand Dev Corp Method and coating for protection of molybdenum and its alloys
US3055089A (en) * 1958-08-06 1962-09-25 Union Carbide Corp Gaseous metal product and processes
US3150940A (en) * 1960-03-01 1964-09-29 Cincinnati Milling Machine Co Bearing surface and method of producing said surface
US3235960A (en) * 1961-03-24 1966-02-22 Gen Electric Process for the continuous formation of intermediates
US3206326A (en) * 1961-11-27 1965-09-14 Ethyl Corp Aluminum intermittent plating process
US3294059A (en) * 1963-04-15 1966-12-27 Charles R Barnes Deposition of nickel films on the interior surface of polytetrafluoroethylene tubing
US3620838A (en) * 1969-12-16 1971-11-16 Siemens Ag Method of densification of porous layers
US3691720A (en) * 1970-10-12 1972-09-19 Western Electric Co Apparatus for frequency adjusting and assembling monolithic crystal filters
US3853637A (en) * 1973-06-25 1974-12-10 Gray R And Co Inc Method of treating articles under differential vacuum conditions with external gas flow
US4619840A (en) * 1983-05-23 1986-10-28 Thermco Systems, Inc. Process and apparatus for low pressure chemical vapor deposition of refractory metal
US4817557A (en) * 1983-05-23 1989-04-04 Anicon, Inc. Process and apparatus for low pressure chemical vapor deposition of refractory metal
US4709655A (en) * 1985-12-03 1987-12-01 Varian Associates, Inc. Chemical vapor deposition apparatus
US4796562A (en) * 1985-12-03 1989-01-10 Varian Associates, Inc. Rapid thermal cvd apparatus

Also Published As

Publication number Publication date
CH332501A (en) 1958-09-15

Similar Documents

Publication Publication Date Title
US2685124A (en) Method for hi-vac alloying and coated product
US4188426A (en) Cold plasma modification of organic and inorganic surfaces
US2344138A (en) Coating method
US2847320A (en) Method for gas plating with aluminum organo compounds
US5904771A (en) Method of subliming material in CVD film preparation method
US2619433A (en) Method of gas plating
DE3722944A1 (en) THICK FILM EVAPORATION DEVICE AND METHOD
US2402269A (en) Deposition of metals
US2783164A (en) Method of coating a metal substrate with molybdenum
US3227132A (en) Apparatus for depositing coatings of tin on a flexible substrate
US2767464A (en) Composite metallic bodies and method of producing the same
DE2944500A1 (en) METHOD FOR METALIZING SEMICONDUCTOR COMPONENTS
US2880115A (en) Method of gas plating light metals
JP3135903B2 (en) Method for manufacturing reflective article
US2921868A (en) Aluminum gas plating of various substrates
US3012904A (en) Oxidizable oxide-free metal coated with metal
US2898235A (en) Metal dienyl gas plating
US3321337A (en) Process for preparing boron nitride coatings
US2847319A (en) Gas plating of aggregates
US3702780A (en) Process of plating by pyrolytic deposition
US2898234A (en) Method of producing composite metallic bodies
US3282243A (en) Movable means comprising vapor-plating nozzle and exhaust
US3206326A (en) Aluminum intermittent plating process
DE4222406A1 (en) METHOD FOR PRODUCING DIAMOND LAYERS BY STEAM PHASE SYNTHESIS
US3515095A (en) Coating process