US2966427A - Gas plating of alloys - Google Patents

Gas plating of alloys Download PDF

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US2966427A
US2966427A US772519A US77251958A US2966427A US 2966427 A US2966427 A US 2966427A US 772519 A US772519 A US 772519A US 77251958 A US77251958 A US 77251958A US 2966427 A US2966427 A US 2966427A
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phosphorous
phosphine
alloy
nickel
carbonyl
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Breining Elmer Robert
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Union Carbide Corp
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Union Carbide Corp
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • 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
    • C23C16/22—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 inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides

Definitions

  • This invention relates to the formation of alloys and particularly to phosphorous containing alloys such as those of nickel and iron.
  • Nickel-phosphorous alloys and to a lesser extent ironphosphorous alloys find utility in a variety of applications.
  • nickel containing Ni3P is relatively easily soldered, below 750 F. has good hardness characteristics and may be chrome plated for decorative applications.
  • Such alloys are useful for example in electrical connectors, aircraft parts and the like. Further, bonding to other metals such as stainless steel, aluminum, nickel, copper and magnesium is advantageously achieved.
  • Another object of the invention is to describe a process for the production of phosphorous containing alloys having a high degree of purity.
  • a particular object of the invention is the provision of an alloy of nickel phosphorous or iron phosphorous achieved by deposition of the components from the gaseous state.
  • a volatile phosphorous component such as phosphine, phosphorous itself, or organic phosphorous compounds, such as the alkyl and aryl, is volatilized.
  • Nickel carbonyl or other volatilizable, heat decomposable metal bearing compound is present to a reaction chamber with the volatilized phosphorous component.
  • the reaction chamber contains an object upon which a lm of the alloy is to be deposited and this object is suitably heated to eifect decomposition of the gases.
  • the decomposition of the metal bearing gas in the case of nickel carbonyl provides nickel as the base metal; iron pentacarbonyl provides iron as the base metal.
  • the alloy Simultaneous co-deposition of the phosphorous component and the metal bearing gas provide on the heated object the alloy. Specilic characteristics in the alloy are attained by combining more or less of the phosphorous component with the metal bearing component in the gaseous state.
  • the alloy desired contains nickel metal and NisP. The content of Ni3P controls the ultimate properties -of the product and the Ni3P is dispersed throughout the nickel phase.
  • Tri-methyl phosphine is a preferred source of the phosphorous as it has a boiling point close to that of nickel carbonyl and volatilization is more readily controllable than with phosphine, for example, where high reaction temperatures are required due to the stability of the phosphine.
  • Tri-ethyl phosphine which has a higher boiling point is more suitable when iron pentacarbonyl is employed.
  • methyl di-ethyl phosphine, methyl ethyl propyl phosphine and others though somewhat more expensive presently, will serve the purpose.
  • the alloy deposition rate is a function of the flow rate of the phosphorous and base metal components, the temperature of the article being plated and to some extent the area of the object and the size of the plating chamber. Deposition rate of 2 to l0 mils per hour are practicable while thickness may be from 0.1 mil to l0 mils or more.
  • the flow sheet illustrates the essential steps of the process.
  • a liquid phosphorous containing component and a liquid metal bearing component are passed to a flash vaporizer and then to a reaction chamber wherein the heated object is contained.
  • a carrier gas such as nitrogen, argon or carbon dioxide may be utilized to aid the flow of the vaporized materials to the reaction chamber.
  • the mixed gases contact the heated object and deposit thereon, forming a coating of the alloy.
  • liquid tri-methyl phosphine and nickel carbonyl are metered separately to a common ash vaporizer along with the flow of carrier gas and are
  • iron pentacarbonyl for the formation of an alloy containing iron and iron phosphorous the following data are applicable:
  • the phosphines particularly the alkyl phosphines and the aryl phosphines, are available and many have characteristics which would render them suitable, such as butyl phosphine and di-butyl phosphine, as well as cyclohexyl phosphine and phenyl phosphine, also alkyl halide phosphorous compounds have properties indicating utility in the process.
  • the process of alloy formation which comprises combining in the vapor state a volume of a heat decomposable phosphorous component and a Volume of a heat decomposable metal bearing gas, and contacting an object heated to the decomposition temperature of the combined vapors to effect deposition of a phosphorous containing alloy on the object.
  • the process of alloy formation which comprises the steps of combining in the vapor state a volume of tri-methyl phosphine and a volume of gaseous nickel carbonyl, and contacting an object heated to the decomposition temperatures of the vapors to eifect deposition o-f a phosphorous-nickel alloy on the object.
  • the process of alloy formation which comprises the steps of combining in the vapor state a volume of triethyl phosphine and a volume of gaseous iron pentacarbonyl, and contacting an object heated to the decompositio-n temperature of the combined vapors to effect deposition of a phosphorous-iron alloy on the object.
  • the process of alloy formation which comprises the steps of passing to a vaporizer a liquid phosphorous cornponent and a liquid heat decomposable metal bearing compound to effect vaporization of the component and compound, combining the vapors of the component and compound, and contacting an object heated to the decomposition temperature of the combined vapors to effect deposition of a phosphorous containing alloy on the object.
  • the process of alloy formation which comprises the steps of metering liquid trimethyl phosphine and liquid nickel carbonyl to a vaporizer to effect vaporization of the phosphine and carbonyl, combining the vapors of the carbonyl and phosphine in one atmopshere, and contacting an object heated to the decomposition temperature of the carbonyl and phosphine to effect deposition of a phosphorous-nickel alloy on the object.
  • the process of alloy formation which comprises the steps of metering liquid triethyl phosphine and liquid iron pentacarbonyl to a vaporizer to elfect vaporization of the phosphine and pentacarbonyl, combining the vapors of the carbonyl and phosphine in one atmosphere, and contacting an object heated to the decomposition temperature of the carbonyl and phosphine to effect deposition of a phosphorous-iron alloy on the object.
  • the process of alloy formation which comprises the steps of vaporizing tri-methyl phosphine and nickel carbonyl at a temperatures of between 112 F. and 170 F., combining the vapors in a common atmosphere with an object heated to between 350 F. and 700 F. to thereby decompose the phosphine and carbonyl together to deposit an alloy of nickel-phosphorous on the object.
  • the process of alloy formation which comprises the steps of vaporizing tri-ethyl phosphine and iron pentacarbonyl at a temperature of between 260 F. and 285 F., combining the vapors in a common atmosphere with an object heated to between 400 F. and 800 F. to thereby decompose the phosphine and pentacarbonyl together to deposit an alloy of iron-phosphorousl on the object.
  • the process of alloy formation which comprises the steps of vaporizing tri-methyl phosphine and nickel carbonyl, combining the vaporized phosphine and carbonyl in one atmosphere, providing an object heated to the decomposition tempertaure of the carbonyl and phosphine, and directing the combined phosphine and carbonyl atmosphere with a carrier gas into contact with the heated obiect to thereby effect deposition of a nickelphosphorous alloy on the object.

Description

United States Patent GAS PLATING 0F ALLOYS Elmer Robert Breining, Dayton, Ohio, assignor, by mesne assignments, to Union Carbide Corporation, New York, N.Y., a corporation of New York Filed Nov. 7, 1958, Ser. No. 772,519
11 Claims. (Cl. 117-106) This invention relates to the formation of alloys and particularly to phosphorous containing alloys such as those of nickel and iron.
Nickel-phosphorous alloys and to a lesser extent ironphosphorous alloys find utility in a variety of applications. For example, nickel containing Ni3P is relatively easily soldered, below 750 F. has good hardness characteristics and may be chrome plated for decorative applications. Such alloys are useful for example in electrical connectors, aircraft parts and the like. Further, bonding to other metals such as stainless steel, aluminum, nickel, copper and magnesium is advantageously achieved.
It is a primary object of this invention to describe a novel method for the attainment of alloys containing a base metal and a combination of the base metal with phosphorous.
Another object of the invention is to describe a process for the production of phosphorous containing alloys having a high degree of purity.
A particular object of the invention is the provision of an alloy of nickel phosphorous or iron phosphorous achieved by deposition of the components from the gaseous state.
In the practice'of the invention a volatile phosphorous component such as phosphine, phosphorous itself, or organic phosphorous compounds, such as the alkyl and aryl, is volatilized. Nickel carbonyl or other volatilizable, heat decomposable metal bearing compound is present to a reaction chamber with the volatilized phosphorous component. The reaction chamber contains an object upon which a lm of the alloy is to be deposited and this object is suitably heated to eifect decomposition of the gases.
The decomposition of the metal bearing gas in the case of nickel carbonyl provides nickel as the base metal; iron pentacarbonyl provides iron as the base metal.
Simultaneous co-deposition of the phosphorous component and the metal bearing gas provide on the heated object the alloy. Specilic characteristics in the alloy are attained by combining more or less of the phosphorous component with the metal bearing component in the gaseous state. In the case of nickel carbonyl and trimethyl phosphine the alloy desired contains nickel metal and NisP. The content of Ni3P controls the ultimate properties -of the product and the Ni3P is dispersed throughout the nickel phase.
Tri-methyl phosphine is a preferred source of the phosphorous as it has a boiling point close to that of nickel carbonyl and volatilization is more readily controllable than with phosphine, for example, where high reaction temperatures are required due to the stability of the phosphine.
Tri-ethyl phosphine which has a higher boiling point is more suitable when iron pentacarbonyl is employed. However, methyl di-ethyl phosphine, methyl ethyl propyl phosphine and others though somewhat more expensive presently, will serve the purpose.
The alloy deposition rate is a function of the flow rate of the phosphorous and base metal components, the temperature of the article being plated and to some extent the area of the object and the size of the plating chamber. Deposition rate of 2 to l0 mils per hour are practicable while thickness may be from 0.1 mil to l0 mils or more.
The flow sheet illustrates the essential steps of the process.
As will be noted from the flow sheet a liquid phosphorous containing component and a liquid metal bearing component are passed to a flash vaporizer and then to a reaction chamber wherein the heated object is contained. If desired a carrier gas, such as nitrogen, argon or carbon dioxide may be utilized to aid the flow of the vaporized materials to the reaction chamber. Within the reaction chamber the mixed gases contact the heated object and deposit thereon, forming a coating of the alloy.
As a specific example, liquid tri-methyl phosphine and nickel carbonyl are metered separately to a common ash vaporizer along with the flow of carrier gas and are As exemplary of the use of iron pentacarbonyl for the formation of an alloy containing iron and iron phosphorous the following data are applicable:
Sample area square inches 10 Substrate Steel Tri-ethyl phosphine, liquid cc./min 2.5-10 Iron pentacarbonyl, liquid cc./min 2-4 (Optional) carbon dioxide cc./min 400-850 Vaporizer temperature F 260-285 Substrate temperature F 400-800 Phosphorous content of deposit (Fe3P and Fe2P in an iron matrix) percent 2-14 Nickel do 9'8-86 Copper may be substituted for the steel substrate in the foregoing samples.
The phosphines, particularly the alkyl phosphines and the aryl phosphines, are available and many have characteristics which would render them suitable, such as butyl phosphine and di-butyl phosphine, as well as cyclohexyl phosphine and phenyl phosphine, also alkyl halide phosphorous compounds have properties indicating utility in the process.
It will be understood that this invention is susceptible to modification in order to adapt it to diiferent usages and conditions and accordingly, it is desired to comprehend such modifications within this invention as may fall within the scope of the appended claims.
What is claimed is:
1. The process of alloy formation 'which comprises combining in the vapor state a volume of a heat decomposable phosphorous component and a Volume of a heat decomposable metal bearing gas, and contacting an object heated to the decomposition temperature of the combined vapors to effect deposition of a phosphorous containing alloy on the object.
2. The process of alloy formation which comprises combining in the vapor state a Volume of a heat decomposable phosphorous component and a volume of gaseous nickel carbonyl, and contacting an object heated to the decomposition temperature of the combined vapors to effect deposition of a phosphorous-nickel alloy on the object.
3. The process of alloy formation which comprises combining in the vapor state a volume of a heat decomposa'ble phosphorous component and a volume iron pentacarbonyl, and contacting an object heated to the decomposition temperature of the combined vapors to elect deposition of a phosphorous-iron alloy on the object.
4. The process of alloy formation which comprises the steps of combining in the vapor state a volume of tri-methyl phosphine and a volume of gaseous nickel carbonyl, and contacting an object heated to the decomposition temperatures of the vapors to eifect deposition o-f a phosphorous-nickel alloy on the object.
5. The process of alloy formation which comprises the steps of combining in the vapor state a volume of triethyl phosphine and a volume of gaseous iron pentacarbonyl, and contacting an object heated to the decompositio-n temperature of the combined vapors to effect deposition of a phosphorous-iron alloy on the object.
6. The process of alloy formation which comprises the steps of passing to a vaporizer a liquid phosphorous cornponent and a liquid heat decomposable metal bearing compound to effect vaporization of the component and compound, combining the vapors of the component and compound, and contacting an object heated to the decomposition temperature of the combined vapors to effect deposition of a phosphorous containing alloy on the object.
7. The process of alloy formation which comprises the steps of metering liquid trimethyl phosphine and liquid nickel carbonyl to a vaporizer to effect vaporization of the phosphine and carbonyl, combining the vapors of the carbonyl and phosphine in one atmopshere, and contacting an object heated to the decomposition temperature of the carbonyl and phosphine to effect deposition of a phosphorous-nickel alloy on the object.
8. The process of alloy formation which comprises the steps of metering liquid triethyl phosphine and liquid iron pentacarbonyl to a vaporizer to elfect vaporization of the phosphine and pentacarbonyl, combining the vapors of the carbonyl and phosphine in one atmosphere, and contacting an object heated to the decomposition temperature of the carbonyl and phosphine to effect deposition of a phosphorous-iron alloy on the object.
9. The process of alloy formation which comprises the steps of vaporizing tri-methyl phosphine and nickel carbonyl at a temperatures of between 112 F. and 170 F., combining the vapors in a common atmosphere with an object heated to between 350 F. and 700 F. to thereby decompose the phosphine and carbonyl together to deposit an alloy of nickel-phosphorous on the object.
l0. The process of alloy formation which comprises the steps of vaporizing tri-ethyl phosphine and iron pentacarbonyl at a temperature of between 260 F. and 285 F., combining the vapors in a common atmosphere with an object heated to between 400 F. and 800 F. to thereby decompose the phosphine and pentacarbonyl together to deposit an alloy of iron-phosphorousl on the object.
11. The process of alloy formation which comprises the steps of vaporizing tri-methyl phosphine and nickel carbonyl, combining the vaporized phosphine and carbonyl in one atmosphere, providing an object heated to the decomposition tempertaure of the carbonyl and phosphine, and directing the combined phosphine and carbonyl atmosphere with a carrier gas into contact with the heated obiect to thereby effect deposition of a nickelphosphorous alloy on the object.
References Cited in the le of this patent UNITED STATES PATENTS 2,041,493 Schlecht et al. May 19, 1936 FOREIGN PATENTS 376,652 Germany June 4, 1923 OTHER REFERENCES Zeitschrift fr Anorganishe Chemie, vol. 238 (1938), pages 72 and 73.

Claims (1)

1. THE PROCESS OF ALLOY FORMATION WHICH COMPRISES COMBINING IN THE VAPOR STATE A VOLUME OF HEAT DECOMPOSABLE PHOSPHOROUS COMPONENT AND VOLUME OF A HEAT DECOMPOSABLE METAL BEARING GAS, AND CONTACTING AND OBJECT HEATED TO THE DECOMPOSITION TEMPERATURE OF THE COMBINED VAPORS TO EFFECT DEPOSITION OF A PHOSPHOROUS CONTAINING ALLOY ON THE OBJECT.
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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3113039A (en) * 1959-08-05 1963-12-03 Landis & Gyr Ag Method of producing coatings on heatresisting supports
US3360349A (en) * 1965-04-01 1967-12-26 Sperry Rand Corp Copper layer bonded to a non-conductive layer by means of a copper alloy
US3411953A (en) * 1965-02-05 1968-11-19 Allis Chalmers Mfg Co Method of producing a fuel cell electrode containing a nickel-phosphorus alloy as the catalyst
US3451852A (en) * 1966-01-25 1969-06-24 Chevron Res Method of producing electricity in a fuel cell using a hydrazine fuel and group 8 metal phosphides as catalysts
US3624158A (en) * 1966-08-23 1971-11-30 Gulf Research Development Co Hydroformylation process employing diorgano-halo phosphines as legands with cobalt carbonyl
US4714023A (en) * 1986-03-27 1987-12-22 Brown John E Non-toxic shot
US4949644A (en) * 1989-06-23 1990-08-21 Brown John E Non-toxic shot and shot shell containing same
DE4212231A1 (en) * 1992-04-11 1993-10-14 Licentia Gmbh Doping with amorphous silicon@ - by gas discharge with addn. of tri:methyl-phosphine to gas, used in prodn. of electrophotographic recording material
US5535678A (en) * 1990-10-31 1996-07-16 Robert E. Petersen Lead-free firearm bullets and cartridges including same
US20050162073A1 (en) * 2002-05-22 2005-07-28 Takeshi Suzuki Organic el luminescene device
US8240544B2 (en) * 2005-08-02 2012-08-14 Linde Aktiengesellschaft Introduction of nanoparticles

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE376652C (en) * 1922-10-13 1923-06-04 Alfred Rau alloy
US2041493A (en) * 1933-01-24 1936-05-19 Ig Farbenindustrie Ag Pulverulent alloy

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE376652C (en) * 1922-10-13 1923-06-04 Alfred Rau alloy
US2041493A (en) * 1933-01-24 1936-05-19 Ig Farbenindustrie Ag Pulverulent alloy

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3113039A (en) * 1959-08-05 1963-12-03 Landis & Gyr Ag Method of producing coatings on heatresisting supports
US3411953A (en) * 1965-02-05 1968-11-19 Allis Chalmers Mfg Co Method of producing a fuel cell electrode containing a nickel-phosphorus alloy as the catalyst
US3360349A (en) * 1965-04-01 1967-12-26 Sperry Rand Corp Copper layer bonded to a non-conductive layer by means of a copper alloy
US3451852A (en) * 1966-01-25 1969-06-24 Chevron Res Method of producing electricity in a fuel cell using a hydrazine fuel and group 8 metal phosphides as catalysts
US3624158A (en) * 1966-08-23 1971-11-30 Gulf Research Development Co Hydroformylation process employing diorgano-halo phosphines as legands with cobalt carbonyl
US3725483A (en) * 1966-08-23 1973-04-03 Gulf Research Development Co A process for the hydroformylation of olefins
US4714023A (en) * 1986-03-27 1987-12-22 Brown John E Non-toxic shot
US4949644A (en) * 1989-06-23 1990-08-21 Brown John E Non-toxic shot and shot shell containing same
US5535678A (en) * 1990-10-31 1996-07-16 Robert E. Petersen Lead-free firearm bullets and cartridges including same
DE4212231A1 (en) * 1992-04-11 1993-10-14 Licentia Gmbh Doping with amorphous silicon@ - by gas discharge with addn. of tri:methyl-phosphine to gas, used in prodn. of electrophotographic recording material
US20050162073A1 (en) * 2002-05-22 2005-07-28 Takeshi Suzuki Organic el luminescene device
US7646145B2 (en) * 2002-05-22 2010-01-12 Fuji Electric Holdings Co., Ltd. Organic EL light emitting device
US8240544B2 (en) * 2005-08-02 2012-08-14 Linde Aktiengesellschaft Introduction of nanoparticles

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