US4803127A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Vapor deposition of metal compound coating utilizing metal sub-halides and coated metal article
Assignee: Liburdi Engineering Ltd
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Filing: 1987-10-22
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Granted: 1989-02-07
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Expires: 2007-10-22
Abstract
Abstract A process for the chemical vapor deposition on substrates of coatings comprising compounds of a titanium sub-group of metals, the vanadium sub-group of metals and the chromium sub-group of metals at temperatures in the range of 250° C. is disclosed. Sub-halides, such as TiCl 3 , are reacted with N 2 and H 2 and thermodynamic and kinetic parameters are manipulated by flow rates and partial pressures of the reactants to achieve the deposition reaction in the temperature range of 250° C. to 850° C. The invention also relates to a metal compound coated article. An apparatus for performing the process is also disclosed.
Inventors
- 👤 M. Javid Hakim
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-23 03:28
CPC Classifications
C; C23; C23C; C23C16/00; C23C16/22; C23C16/30; C23C16/36; C23C16/32; C23C16/34; C23C16/44; C23C16/448; C23C16/4488; Y; Y10; Y10T; Y10T428/00; Y10T428/31504; Y10T428/31678
Claims Analysis
Total Claims: 47
Claim 1
Independent Claim
153 words
A method of producing metal compound coatings of one of the group of metals including titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten on a substrate comprising: (a) reacting in a reaction chamber in the presence of a substrate a gaseous mixture of the metal subchlorides with one member of the groups of gaseous mixtures comprising hydrogen and nitrogen; hydrogen, nitrogen and ammonia; hydrogen and a hydrocarbon; hydrogen, nitrogen and a hydrocarbon; and hydrogen, nitrogen, ammonia and a hydrocarbon; (b) manipulating the free energy value for the reaction and the kinetic parameters of the reaction to facilitate a reaction temperature in the range of 250° to 850° C.; (c) maintaining the reaction temperature of the substrate and the reaction chamber in the said reaction temperature range; whereby the coating being one of the group of a metal nitride, and a metal carbide and a metal carbonitride is deposited on the substrate.
Claim 2
Independent Claim
153 words
A method of producing metal compound coatings of one of the group of metals including titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten on a substrate comprising: (a) reacting in a reaction chamber in the presence of a substrate a gaseous mixture of the metal subchlorides with one member of the groups of gaseous mixtures comprising hydrogen and nitrogen; hydrogen, nitrogen and ammonia; hydrogen and a hydrocarbon; hydrogen, nitrogen and a hydrocarbon; and hydrogen, nitrogen, ammonia and a hydrocarbon; (b) manipulating the free energy value for the reaction and the kinetic parameters of the reaction to facilitate a reaction temperature in the range of 250° to 850° C.; (c) maintaining the reaction temperature of the substrate and the reaction chamber in the said reaction temperature range; whereby the coating being one of the group of a metal nitride, and a metal carbide and a metal carbonitride is deposited on the substrate.
Claim 3
Independent Claim
148 words
A method of producing metal compound coatings of one of the group of the metals including titanium, zirconium and hafnium on a substrate comprising: (a) reacting in a reaction chamber in the presence of a substrate of gaseous mixture of the metal subchlorides with one member of the groups of gaseous mixtures comprising hydrogen and nitrogen; hydrogen, nitrogen and ammonia; hydrogen and a hydrocarbon; hydrogen, nitrogen, and a hydrocarbon; and hydrogen, nitrogen, ammonia and a hydrocarbon; (b) manipulating the free energy value for the reaction and the kinetic parameters of the reaction to facilitate a reaction temperature in the range of 250° to 850° C.; (c) maintaining the reaction temperature of the substrate and the reaction chamber in the said reaction temperature range; whereby the coating being one of the group of a metal nitride, and a metal carbide and a metal carbonitride is deposited on the substrate.
Claim 4
Independent Claim
148 words
A method of producing metal compound coatings of one of the group of the metals including titanium, zirconium and hafnium on a substrate comprising: (a) reacting in a reaction chamber in the presence of a substrate of gaseous mixture of the metal subchlorides with one member of the groups of gaseous mixtures comprising hydrogen and nitrogen; hydrogen, nitrogen and ammonia; hydrogen and a hydrocarbon; hydrogen, nitrogen, and a hydrocarbon; and hydrogen, nitrogen, ammonia and a hydrocarbon; (b) manipulating the free energy value for the reaction and the kinetic parameters of the reaction to facilitate a reaction temperature in the range of 250° to 850° C.; (c) maintaining the reaction temperature of the substrate and the reaction chamber in the said reaction temperature range; whereby the coating being one of the group of a metal nitride, and a metal carbide and a metal carbonitride is deposited on the substrate.
Claim 5
Independent Claim
115 words
A method of producing coatings of nitrides of one of the group of the metals including titanium, zirconium and hafnium on substrates comprising: (a) reacting a reaction chamber in the presence of a substrate a gaseous mixture of the metal subchlorides with one member of the groups of gaseous mixtures comprising hydrogen and nitrogen; and hydrogen, nitrogen and ammonia; (b) manipulating the free energy value for the reaction and the kinetic parameters of the reaction to facilitate a reaction temperature in the range of 250° to 850° C.; (c) maintaining the reaction temperature of the substrate and the reaction chamber in the said reaction temperature range; whereby the metal nitride is deposited on the substrate.
Claim 6
Independent Claim
115 words
A method of producing coatings of nitrides of one of the group of the metals including titanium, zirconium and hafnium on substrates comprising: (a) reacting a reaction chamber in the presence of a substrate a gaseous mixture of the metal subchlorides with one member of the groups of gaseous mixtures comprising hydrogen and nitrogen; and hydrogen, nitrogen and ammonia; (b) manipulating the free energy value for the reaction and the kinetic parameters of the reaction to facilitate a reaction temperature in the range of 250° to 850° C.; (c) maintaining the reaction temperature of the substrate and the reaction chamber in the said reaction temperature range; whereby the metal nitride is deposited on the substrate.
Claim 7
Independent Claim
94 words
A method of producing coatings of titanium nitride on a substrate, comprising: (a) reacting in a reaction chamber in the presence of a substrate a gaseous mixture of titanium subchlorides with a gaseous mixture of hydrogen and nitrogen; (b) manipulating the free energy value for the reaction and the kinetic parameters of the reaction to facilitate a reaction temperature in the range of 250° to 850° C.; (c) maintaining the reaction temperature of the substrate and the reaction chamber in the said reaction temperature range; whereby the titanium nitride is deposited on the substrate.
Claim 8
Independent Claim
94 words
A method of producing coatings of titanium nitride on a substrate, comprising: (a) reacting in a reaction chamber in the presence of a substrate a gaseous mixture of titanium subchlorides with a gaseous mixture of hydrogen and nitrogen; (b) manipulating the free energy value for the reaction and the kinetic parameters of the reaction to facilitate a reaction temperature in the range of 250° to 850° C.; (c) maintaining the reaction temperature of the substrate and the reaction chamber in the said reaction temperature range; whereby the titanium nitride is deposited on the substrate.
Claim 9
Independent Claim
95 words
A method of producing coatings of titanium nitride on a substrate comprising: (a) reacting in a reaction chamber in the presence of a substrate a gaseous mixture of titanium subchlorides with a gaseous mixture of hydrogen, nitrogen and ammonia; (b) manipulating the free energy value for the reaction and the kinetic parameters of the reaction to facilitate a reaction temperature in the range of 250° to 850° C., (c) maintaining the reaction temperature of the substrate and the reaction chamber in the said reaction temperature range; whereby the titanium nitride is deposited on the substrate.
Claim 10
Independent Claim
95 words
A method of producing coatings of titanium nitride on a substrate comprising: (a) reacting in a reaction chamber in the presence of a substrate a gaseous mixture of titanium subchlorides with a gaseous mixture of hydrogen, nitrogen and ammonia; (b) manipulating the free energy value for the reaction and the kinetic parameters of the reaction to facilitate a reaction temperature in the range of 250° to 850° C., (c) maintaining the reaction temperature of the substrate and the reaction chamber in the said reaction temperature range; whereby the titanium nitride is deposited on the substrate.
Claim 11
Dependent Claim
30 words
A method of producing coatings of titanium nitride on a substrate as claimed in claim 4 wherein the manipulated reaction temperature is in the range of 380° to 800° C.
Claim 12
Independent Claim
32 words
A method of producing coatings of titanium nitride on a substrate as claimed in claims 4 or 5 wherein the manipulated reaction temperature is in the range of 400° to 610° C.
Claim 13
Dependent Claim
35 words
A method as claimed in claim 3 whereby the flow rates and partial pressures of the reactant gases are regulated to produce a reaction free energy value and reaction kinetics that facilitate said reaction temperature.
Claim 14
Dependent Claim
91 words
A method as claimed in claim 3 comprising the additional prior step of producing the metal sub-chlorides in a reaction area upstream of said deposit reaction in said reaction chamber, said prior step comprising: (a) passing gaseous hydrogen chloride and hydrogen over the metal in said reaction area; (b) maintaining said reaction area in the temperature range of 150° to 1100° C.; (c) maintaining the flow rates and partial pressures of hydrogen and hydrogen chloride to provide low partial pressures of hydrogen chloride and promote the production of the metal sub-chlorides.
Claim 15
Dependent Claim
90 words
A method as claimed in claim 4 comprising the additional prior step of producing titanium sub-chlorides in a reaction area upstream of said deposit reaction in said reaction chamber, said prior step comprising: (a) passing gaseous hydrogen chloride and hydrogen over titanium metal in said reaction area; (b) maintaining said reaction area in the temperature range of 150° to 1100° C.; (c) maintaining the flow rates and partial pressures of hydrogen and hydrogen chloride to provide low partial pressures of hydrogen chloride and promote the production of the titanium sub-chlorides.
Claim 16
Dependent Claim
23 words
A method as claimed in claim 9 in which said reaction area is maintained in the temperature range of 500° to 850° C.
Claim 17
Dependent Claim
90 words
A method as claimed in claim 4 comprising the additional prior step of producing titanium sub-chlorides in a reaction area upstream of said deposit reaction in said reaction chamber, said prior step comprising: (a) passing gaseous hydrogen chloride and hydrogen over titanium metal in said reaction area; (b) maintaining said reaction area in the temperature range of 500° to 850° C.; (c) maintaining the flow rates and partial pressures of hydrogen and hydrogen chloride to provide low partial pressures of hydrogen chloride and promote the production of the titanium sub-chlorides.
Claim 18
Dependent Claim
46 words
A method as claimed in claim 4 wherein the gas reactants flow into said reaction chamber continuously, the method comprising the additional step of including ammonia gas in the initial flow of gas reactants and terminating all flow of ammonia gas once said deposition has commenced.
Claim 19
Independent Claim
135 words
A method of producing metal compound coatings of at least one of the metals from groups IVB, VB and VIB on a substrate comprising: (a) reacting in a coating chamber in the presence of a substrate of gaseous mixture of metal subhalides with a gaseous mixture comprising hydrogen and nitrogen; hydrogen, nitrogen and ammonia; hydrogen and hydrocarbon; hydrogen, nitrogen, and a hydrocarbon; and hydrogen, nitrogen, ammonia or a hydrocarbon; (b) manipulating a free energy value for the reaction and kinetic parameters of the reaction to facilitate a reaction temperature in the range of about 250° to less than 900° C.; (c) maintaining the reaction temperature of the substrate and the reaction chamber in said reaction temperature range; whereby a coating of metal nitride, a metal carbide or a metal carbonitride is deposited on the substrate.
Claim 20
Independent Claim
135 words
A method of producing metal compound coatings of at least one of the metals from groups IVB, VB and VIB on a substrate comprising: (a) reacting in a coating chamber in the presence of a substrate of gaseous mixture of metal subhalides with a gaseous mixture comprising hydrogen and nitrogen; hydrogen, nitrogen and ammonia; hydrogen and hydrocarbon; hydrogen, nitrogen, and a hydrocarbon; and hydrogen, nitrogen, ammonia or a hydrocarbon; (b) manipulating a free energy value for the reaction and kinetic parameters of the reaction to facilitate a reaction temperature in the range of about 250° to less than 900° C.; (c) maintaining the reaction temperature of the substrate and the reaction chamber in said reaction temperature range; whereby a coating of metal nitride, a metal carbide or a metal carbonitride is deposited on the substrate.
Claim 21
Dependent Claim
18 words
The method according to claim 14 wherein the metal of the metal compound is titanium, zirconium or hafnium.
Claim 22
Dependent Claim
34 words
The method according to claim 15 wherein the gaseous mixture in the coating chamber is a mixture comprising hydrogen and nitrogen; or hydrogen, nitrogen and ammonia; whereby metal nitride is deposited on the substrate.
Claim 23
Dependent Claim
30 words
The method according to claim 14 wherein the metal is titanium and the gaseous mixture in the chamber is hydrogen and nitrogen; whereby titanium nitride is deposited on the substrate.
Claim 24
Dependent Claim
15 words
The method according to claim 14 wherein the temperature range is 380° to 800° C.
Claim 25
Dependent Claim
15 words
The method according to claim 14 wherein the temperature range is 400° to 610° C.
Claim 26
Dependent Claim
55 words
The method according to claim 14 further comprising producing the metal sub-halide by passing at least hydrogen halide over the metal in a reaction area, maintaining the reaction area in the temperature range of 150° to 1100° C. and controlling the flow of hydrogen halide over the metal to promote the production of metal sub-halide.
Claim 27
Dependent Claim
26 words
The method according to claim 20 further comprising introducing nitrogen gas into the process in the reaction area of where the metal sub-halide is being produced.
Claim 28
Dependent Claim
18 words
The method according to claim 14 wherein the substrate includes copper, stainless steel or nickel based super alloy.
Claim 29
Independent Claim
80 words
A method of producing titanium nitride coatings on a substrate comprising: passing a controlled flow of about 40 volumes of hydrogen and about 12 volumes of hydrogen chloride over a bed of titanium metal particles heated to about 500° C. forming subhalides; mixing 20 volumes of hydrogen and 10 volumes of nitrogen with the resulting hydrogen and titanium chloride gases; and passing the gaseous mixture over a substrate heated to about 600° C. to obtain a titanium nitride coated substrate.
Claim 30
Independent Claim
80 words
A method of producing titanium nitride coatings on a substrate comprising: passing a controlled flow of about 40 volumes of hydrogen and about 12 volumes of hydrogen chloride over a bed of titanium metal particles heated to about 500° C. forming subhalides; mixing 20 volumes of hydrogen and 10 volumes of nitrogen with the resulting hydrogen and titanium chloride gases; and passing the gaseous mixture over a substrate heated to about 600° C. to obtain a titanium nitride coated substrate.
Claim 31
Dependent Claim
27 words
The method according to claim 23 further comprising maintaining the gaseous mixture surrounding the substrate at a pressure of not more than about 4 millimeters of mercury.
Claim 32
Dependent Claim
30 words
The method according to claim 20 further comprising introducing ammonia into the coating chamber and into the gaseous mixture for a limited period of time during the initial coating process.
Claim 33
Dependent Claim
20 words
The method according to claim 23 further comprising maintaining the gaseous mixture at a pressure such that Knudsen flow predominates.
Claim 34
Dependent Claim
30 words
The method according to claim 23 further comprising introducing ammonia into the coating chamber and into the gaseous mixture for a limited period of time during the initial coating process.
Claim 35
Independent Claim
131 words
A method of producing metal compound coatings of at least one of the metals from groups IVB, VB and VIB on a substrate comprising: (a) reacting in a coating chamber in the presence of a substrate of gaseous mixture of metal subhalides with a gaseous mixture comprising hydrogen and nitrogen; hydrogen, nitrogen and ammonia; hydrogen and hydrocarbon; hydrogen, nitrogen, and hydrocarbon; and hydrogen, nitrogen, ammonia or hydrocarbon; (b) manipulating a free energy value for the reaction and kinetic parameters of the reaction to facilitate a reaction temperature avoiding a change in properties of the substrate being coated; (c) maintaining the reaction temperature of the substrate and the reaction chamber at said reaction temperature; whereby a coating of metal nitride, a metal carbide or a metal carbonitride is deposited on the substrate.
Claim 36
Independent Claim
131 words
A method of producing metal compound coatings of at least one of the metals from groups IVB, VB and VIB on a substrate comprising: (a) reacting in a coating chamber in the presence of a substrate of gaseous mixture of metal subhalides with a gaseous mixture comprising hydrogen and nitrogen; hydrogen, nitrogen and ammonia; hydrogen and hydrocarbon; hydrogen, nitrogen, and hydrocarbon; and hydrogen, nitrogen, ammonia or hydrocarbon; (b) manipulating a free energy value for the reaction and kinetic parameters of the reaction to facilitate a reaction temperature avoiding a change in properties of the substrate being coated; (c) maintaining the reaction temperature of the substrate and the reaction chamber at said reaction temperature; whereby a coating of metal nitride, a metal carbide or a metal carbonitride is deposited on the substrate.
Claim 37
Dependent Claim
93 words
A coated article consisting essentially of: (a) a metal compound coating of metal nitride, metal carbide or metal carbonitride; the metal being at least one of the metals from Group IVB, VB and VIB of the Periodic Table of the Elements; and the metal compound coating being formed using a metal subhalide and using hydrogen and not least one of nitrogen, ammonia or methane; and (b) the metal compound coating being deposited on and adhered to a metal substrate at a temperature below its softening point to avoid affecting its temper or hardness.
Claim 38
Dependent Claim
93 words
A coated article consisting essentially of: (a) a metal compound coating of metal nitride, metal carbide or metal carbonitride; the metal being at least one of the metals from Group IVB, VB and VIB of the Periodic Table of the Elements; and the metal compound coating being formed using a metal subhalide and using hydrogen and not least one of nitrogen, ammonia or methane; and (b) the metal compound coating being deposited on and adhered to a metal substrate at a temperature below its softening point to avoid affecting its temper or hardness.
Claim 39
Dependent Claim
19 words
The article according to claim 29, wherein the substrate is a copper, stainless steel or nickel based super alloy.
Claim 40
Dependent Claim
27 words
The article according to claim 29, wherein the metal of the metal compound coating being titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten or combinations thereof.
Claim 41
Dependent Claim
13 words
The article according to claim 29, wherein the metal nitride being titanium nitride.
Claim 42
Dependent Claim
39 words
The article according to claim 29, wherein the metal compound coating being zirconium nitride, hafnium nitride, carbides and carbonitrides of titanium, zirconium and hafnium nitrides, carbides and carbonitrides of vanadium, niobium and tantalum and of chromium, molybdenum and tungsten.
Claim 43
Dependent Claim
44 words
The coated article according to claim 29, further comprising manipulating a free energy value for the reaction and kinetic parameters of the reaction for forming the metal compound coating to facilitate a reaction temperature avoiding a change in properties of the substrate being coated.
Claim 44
Dependent Claim
23 words
The coated article according to claim 34, further comprising a reaction temperature in the range of about 250° to less than 900° C.
Claim 45
Dependent Claim
14 words
The coated article according to claim 29, wherein the substrate is a tool steel.
Claim 46
Dependent Claim
81 words
A coated article comprising: (a) a metal compound coating of metal nitride; the metal being at least one of the metals from Group IVB, VB, and VIB of the Periodic Table of the Elements; and the metal compound coating being formed using a metal subhalide and using hydrogen and nitrogen or ammonia; and (b) the metal compound coating being deposited on and adhered to a metal substrate at a temperature below its softening point to avoid affecting its temper or hardness.
Claim 47
Dependent Claim
81 words
A coated article comprising: (a) a metal compound coating of metal nitride; the metal being at least one of the metals from Group IVB, VB, and VIB of the Periodic Table of the Elements; and the metal compound coating being formed using a metal subhalide and using hydrogen and nitrogen or ammonia; and (b) the metal compound coating being deposited on and adhered to a metal substrate at a temperature below its softening point to avoid affecting its temper or hardness.
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| 3.5 Years (Year 4) | 1992-02-07 | 1992-08-08 | 1993-02-07 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1996-02-07 | 1996-08-08 | 1997-02-07 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2000-02-07 | 2000-08-08 | 2001-02-07 | $7700.00 | Window Closed / Lapsed |