CA2259190A1 - Thermal spraying method and apparatus - Google Patents
Thermal spraying method and apparatus Download PDFInfo
- Publication number
- CA2259190A1 CA2259190A1 CA002259190A CA2259190A CA2259190A1 CA 2259190 A1 CA2259190 A1 CA 2259190A1 CA 002259190 A CA002259190 A CA 002259190A CA 2259190 A CA2259190 A CA 2259190A CA 2259190 A1 CA2259190 A1 CA 2259190A1
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- Prior art keywords
- throat
- coating
- thermal spraying
- feedstock
- nozzle
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
- C23C4/131—Wire arc spraying
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
- B05B7/00—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas
- B05B7/16—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas incorporating means for heating or cooling the material to be sprayed
- B05B7/22—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas incorporating means for heating or cooling the material to be sprayed electrically, magnetically or electromagnetically, e.g. by arc
- B05B7/222—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas incorporating means for heating or cooling the material to be sprayed electrically, magnetically or electromagnetically, e.g. by arc using an arc
- B05B7/224—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas incorporating means for heating or cooling the material to be sprayed electrically, magnetically or electromagnetically, e.g. by arc using an arc the material having originally the shape of a wire, rod or the like
Abstract
A thermal metal spraying method involves the creation of a coating comprising titanium nitride by atomising titanium wire in the presence of nitrogen. The apparatus of the invention comprises a nozzle which has a cylindrical throat, with feedstock guides which guide the feedstock wires to a point of intersection in the throat. A current is passed through the wires to cause an arc in the throat, and a nitrogen rich gas under pressure is forced through the throat, generating a spray of molten particles which is used to coat a substrate. In a variation of the method, one of the feedstock wires comprises a binder metal, which produces a coating having enhanced toughness.
Description
W 098/OOS74 PCT/GB97~1723 TH~MAL SPRAYING MEI'HOD AND APPARATUS
THIS invention relates to a the~nal spraying method for producing a hard coating on a substrate, and to therrnal spraying apparatus which can be used for producing metallic or cermet co~ting~ on a substrate.
Arc metal spraying is used in industry to produce coatings on substrates by generating an arc between feedstock electrodes. The molten feedstock is divided into small particles of molten material by an ~orni~ino gas jet.
These molten particles are propelled by the gas jet onto the substra~e to be ~ coated. The fin~n~s5 of the particles is determined, inter alia, by the velocity of the atomising gas jet.
It is an object of the invention to provide a thermal spraying method which can be used to produce hard coatings with desirable properties, and an alternative thermal spraying apparatus.
SU~STITUTE SHEET (R~ILE 26) *rB
WO 98/00574 PCTIGB9?/01723 According to a first aspect of the invention a method of forming a coating on a substrate comprises the steps of:
providing a feedstock material cont~inin~ titanium;
~t~mi~ing the feedstock material in the presence of nitrogen; and spraying the ~torniced material onto a substrate to form a coating comprising titaniurn nitride on the substrate.
The coating may additionally comp.ise oxides and carbides of titanium.
The fee~lctorl~ material is preferably atomised by generating an arc between at least two fee~stock elements.
Preferably, at least one of the feedstock elements is a titanium wire which is fed towards a point of intersection between the feedstock elements where the arc is generated.
The point of intersection is preferably located within a throat of a nozle, the method including supplying a nitrogen rich gas under pressure to the throat of the nozzle to assist in expulsion of atomised particles therefrom.
The gas is preferably supplied to the throat of the nozle at a pressure sufficient to generate choked gas flow in the throat.
SUE~STITUTE SHEET (RULE 26) W 098~CS74 PCT/GB97101723 The gas will typically be air.
At least one of the feerl~tock elements may be a w-ire comprising a metal selected to have suitable p~ .e.lies as a binder of the titaniurn nitride in thecoating, such as nickel.
According to a second aspect of the invention there is provided thermal spraying apparatus comprising:
a nozzle defining a throat having an inlet and an outlet;
at least first and second guides arranged to guide le~,~ccLive feedstock wires via the inlet towards a point of intersection in the throat, so that connection of the wires to a power supply causes an arc in the throat between the wires, creating molten particles which are expelled from the outlet.
The throat may comprise a tubular bore which subst~nti~lly surrounds the point of intersection of the two feedstock wires.
The diameter of the throat is preferably subslantially constant along its length.
.
The length of the throat is preferably approximately equal to its ~i~m~ter.
.
Preferably, the point of intersection is between a point located about midway along the length of the throat and the outer end of the throat.
SUBSTITUTE SHEET (RULE 26) WO 9~00S74 PCT/GB97~1723 The nozle preferably defines a gas flow path which is aligned with the a:cis of the throat, so that gas under pressure can be supplied to the inlet between the feedstocLi wires to assist in e~pulsion of molten particles from the outlet.
The nozzle may define a charnber inwardly of the throat, the chamber having an inner wall which has an average internal diameter several times greater than that of the throat and which tapers inwardly towards an inner end of the throat.
The inner wall of the chamber preferably joins the inner end of the throat at an angle of approximately 45~.
In the accompanying drawings:
Figure 1 is an e.Yploded pictorial view of the front portion of a spray gun according to the invention;
Figure 2 is a sectional side view of the nozzle of the spray gun; and Figures 3~ are photographs of coatings produced by a prior art arc spray ~nd 3b gun and the apparatus of the invention, respectively.
In the method of the present invention, a high velocity therrnal spray gun is used to atomise a feedstock material cont~ininP titanium in the presence of SUBSTITUTE SHEET (RULE 26) W O 98nHK74 PCT/GB97~1723 nilrogen to obtain particles comprising titanium nitride, which are then sprayed onto a substrate to be coated.
The appa,~ s of the invention forrns part of a spray gun of this kind, which utilises two or more feedstork wires which are fed through suitable guides towards a point of intersection. A suitably high electrical current is passed through the wires, creating an arc at the point of intersection. An air jet atomises the feedstock material, which is then sprayed onto a substrate.
In a conventional spray gun of this kind, the feedstock wires are fed through a nozzle, so that their point of interseclion is beyond the end of the nozle.
An atomising air jet emitted by the nozzle carries the molten particles towards the substrate in a jet.
In the present invention, the point of inte~ecl~on of the feedstock wires is within the throat of the nozzle, rather than outside the nozzle. The creation of an arc in the throat has the effect of generating sll~,t~sonic flow in the nozzle, which would otherwise not be ~tt~in~hle. This very high flow velocity results in very fine atomic~tion of the molten feedstock particles, and very high particle speeds as the particles are emitted towards the substrate.
Referring now to Figures 1 and 2, a high velocity spray gun according to the invention comprises a nozzle 10 which defines a throat 12 in the form of a tubular bore having an inlet 14 and an outlet 16. In the prototype apparatus, the length and ~ met~r of the throat were approximately equal at 8 mrn, with the ~ mPter of the throat being constant along its length.
SUE~STITUTE SHEET (RULE 26) W O9X~74 PCTlGB97/Oln3 The interior of the nozle defines a chamber 18 which has an average internal diameter several times greater than that of the throat 12 and which is ~enerally frusto-conical in shape. At the end of the chamber adjacent the inlet 14 of the throat 12, the inner wall 20 of the chamber is tapered inwardly more sharply, and joins the inner end of the throat at an angle of approximately 4S~.
The interior of the nozle receives a pair of feedstock guides 22 and 24which are inrlinPcl towards one another and which are disposed ad~acent the inner surface of the charnber 18.
Wire fee-lctorl~ material 26 (titaniurn wire in the basic method of theinvention) is fed lor~ n~lly thorough the guides 22 and 24 by a wire feeder m~ch~T~icm (not shown), so that the two wires converge towards a point of il-L~,ae~,lion located on the axis of the throat 12 of the nozle, between a point approximately midway along the leneth of the throat and the outer end of the throat. The dimensions of the throat are selected to permit an arc between the two feedstock wires to be located slJbst~nti~lly within the throat 12.
In Figure 1, the included angle between the feedstock guides is about 30~, but a greater angle, say 60~, leads to a smaller effective point of intersectionbetween the feedstock wires, which is desirable.
In operation, air (or another nitrogen-rich gas) is forced into the spray gun head under plesauLe~ with the pressure and volume being adjusted so that the gas flow within the throat 12 is sonic (i.e. choked) or very close to being choked. Current is applied to the feedstock wires to create n electric arc SUBSTITUTE SHEET (RULE 26) WO 98/OOS74 PCTlGB97101n3 between them, so that the air or gas being forced through the throat of the nozzle is heated s~bst~nti~lly in~t~nt~n~oously to 4 000~C - 5 000~C by the arc. This rapid heating of the gas accelerates it to very high velocities, expelling the air and molten feedstock particles from the outlet 16 in a fine jet 2~.
In a prototype of the apparatus, a voltage of 3~V was applied between the feedstock wires from a constant voltage source, creating an arc current in the region of 180A to 200A. The feed rate of the feedstock wires was about 3rn/min. A supply of coulp~eajed air with a pressure of 600kPa was used, providing a gas pressure in the çh~ml~er 18 of approximately 400kPa. The choked yl~aa~c in the throat 12 was approximately 200kPa with the throat shape and dimensions given above.
The feedstock wires have a composition which is selected to create a coating having desired chemical and physical characteristics. For example, a 1.6 rnm diarneter wire of 316 st~inl~cs steel can be used as a feedstock to produce a coating of St~inl~ steel on a substrate.
Due to the high velocity of the jet, the particles are very finely atomised, improving the properties of the coating. Also due to the high velocity of the jet, the jet is well focused and the deposit it generates is very dense.
Figures 3a and 3b illustrate the difference between co~ting.~ produced by a conventional arc spray gun and the above described apparatus of the invention, ~eal,ecti~ely. The texture of the coating produced ~y the prior art apparatus is relatively coarse, whereas that produced by the apparatus of the present invention is much finer and less porous.
SUBSTITUTE SHEET (RULE 26) W098~S74 PCT/GB97~1723 Where titanium is used as a feedstock material, it is believed that the arc has the effect of ionising the nitrogen (and other elements) in the air passing through the throat of the nozzle, causing a reaction to take place between the nitrogen ions and the molten titaniurn metal particles. This results in a high proportion of the titanium metal reacting with the nitrogen to form titanium nitride. In addition, titanium oxide and titanium carbide can be expected to be formed. Due to the fine atomisation produced by the spray gun, a relatively large p~l~,e.~lage of the atolniced titani~n metal reacts with the nitrogen, with a resulting large pe~e,llage of titanium nitride in the deposited material.
Coatings forrned by the method were found to contain a~lo~ll~tely 2% to5% percent of the original titanium metal, which acts as a binder for the particles of titanium nitride and makes the coating tougher and less brittle.
Tests showed that the co~tin~ were very hard, with a Vickers hd~Lless of approximately Hv I 100.
The typical stoic-h-iometery of the coatin~c referred to above is Ti, 0 N 094 ~ 008- which is a titanium nitride compound comprising a small proportion of oxygen.
In order to increase the to~hnç~s of the coating formed by the method of the invention, while retaining the properties of the extremely hard titanium nitride, a metal selected for its properties as a binder can be incol~olat~d in the coating. This conveniently achieved by replacing one of the titanium feedstock wires with a wire of the selected binder metal, for example nickel.
The binder metal is then mixed by the arc spray process with the titanium nitride deposit, producing a composite deposit cont~ining~ say, 48% titanium SUBSTITUTE SHEET (RULE 26) wo 98/OOS74 PCT/Gs97/0l723 ni~ride and the balance comprising the metal, which acts as a binder in the titanium nitride matrix. The two fee~ctoc~ wires need not be of exactly the sarne diameter, thus permitting the percelltage of metal binder to titanium nitride to be varied according to the requirements of the particular application.
A particular advantage of the method of the invention is that it allows the creation of sl1bst~nti~lly thicker coating~ than prior art methods. Coatings of 0.5mm thil~n~c or greater are possible. Because titanium nitride is chemically inert, the method of the invention is particularly useful in coating substrates which will be subjected to corrosive or erosive enviror~m~nts such as propeller or turbine blades. It is also envisaged that the method will be useful in coating medical imrl~ntc due to the çh~mir~l inertness and biocornr~tibility of liL~iu-,l nitride. The co~ting~ produced by the method also have an attractive golden colour.
It was found tnat, when viewed under high m~gnification~ a large number of very small shrinkage cracks (of the order of 0.5,um) were exhibited within each spray particle in the deposit or co~ting In order to improve the corrosion protection properties of the coa~ing~ a sealer such as a phenolic resin sealer can be applied, for example by p~inting, to the coating after spraying. The application of a thin sealant layer onto a titanium nitride coating is particularly effective, as the micro-cracks are extensive and well distributed and the sealer is thus effectively soaked into the coating, sealin"
it. Since the sealer is then co~t~in~d within the coating matrix, the sealer is protected within the coating from mech~nical darnage, thus ensuring that it is effective for an ~xt~nded period of time.
SUBSTITUTE SHEET (RULE 26)
THIS invention relates to a the~nal spraying method for producing a hard coating on a substrate, and to therrnal spraying apparatus which can be used for producing metallic or cermet co~ting~ on a substrate.
Arc metal spraying is used in industry to produce coatings on substrates by generating an arc between feedstock electrodes. The molten feedstock is divided into small particles of molten material by an ~orni~ino gas jet.
These molten particles are propelled by the gas jet onto the substra~e to be ~ coated. The fin~n~s5 of the particles is determined, inter alia, by the velocity of the atomising gas jet.
It is an object of the invention to provide a thermal spraying method which can be used to produce hard coatings with desirable properties, and an alternative thermal spraying apparatus.
SU~STITUTE SHEET (R~ILE 26) *rB
WO 98/00574 PCTIGB9?/01723 According to a first aspect of the invention a method of forming a coating on a substrate comprises the steps of:
providing a feedstock material cont~inin~ titanium;
~t~mi~ing the feedstock material in the presence of nitrogen; and spraying the ~torniced material onto a substrate to form a coating comprising titaniurn nitride on the substrate.
The coating may additionally comp.ise oxides and carbides of titanium.
The fee~lctorl~ material is preferably atomised by generating an arc between at least two fee~stock elements.
Preferably, at least one of the feedstock elements is a titanium wire which is fed towards a point of intersection between the feedstock elements where the arc is generated.
The point of intersection is preferably located within a throat of a nozle, the method including supplying a nitrogen rich gas under pressure to the throat of the nozzle to assist in expulsion of atomised particles therefrom.
The gas is preferably supplied to the throat of the nozle at a pressure sufficient to generate choked gas flow in the throat.
SUE~STITUTE SHEET (RULE 26) W 098~CS74 PCT/GB97101723 The gas will typically be air.
At least one of the feerl~tock elements may be a w-ire comprising a metal selected to have suitable p~ .e.lies as a binder of the titaniurn nitride in thecoating, such as nickel.
According to a second aspect of the invention there is provided thermal spraying apparatus comprising:
a nozzle defining a throat having an inlet and an outlet;
at least first and second guides arranged to guide le~,~ccLive feedstock wires via the inlet towards a point of intersection in the throat, so that connection of the wires to a power supply causes an arc in the throat between the wires, creating molten particles which are expelled from the outlet.
The throat may comprise a tubular bore which subst~nti~lly surrounds the point of intersection of the two feedstock wires.
The diameter of the throat is preferably subslantially constant along its length.
.
The length of the throat is preferably approximately equal to its ~i~m~ter.
.
Preferably, the point of intersection is between a point located about midway along the length of the throat and the outer end of the throat.
SUBSTITUTE SHEET (RULE 26) WO 9~00S74 PCT/GB97~1723 The nozle preferably defines a gas flow path which is aligned with the a:cis of the throat, so that gas under pressure can be supplied to the inlet between the feedstocLi wires to assist in e~pulsion of molten particles from the outlet.
The nozzle may define a charnber inwardly of the throat, the chamber having an inner wall which has an average internal diameter several times greater than that of the throat and which tapers inwardly towards an inner end of the throat.
The inner wall of the chamber preferably joins the inner end of the throat at an angle of approximately 45~.
In the accompanying drawings:
Figure 1 is an e.Yploded pictorial view of the front portion of a spray gun according to the invention;
Figure 2 is a sectional side view of the nozzle of the spray gun; and Figures 3~ are photographs of coatings produced by a prior art arc spray ~nd 3b gun and the apparatus of the invention, respectively.
In the method of the present invention, a high velocity therrnal spray gun is used to atomise a feedstock material cont~ininP titanium in the presence of SUBSTITUTE SHEET (RULE 26) W O 98nHK74 PCT/GB97~1723 nilrogen to obtain particles comprising titanium nitride, which are then sprayed onto a substrate to be coated.
The appa,~ s of the invention forrns part of a spray gun of this kind, which utilises two or more feedstork wires which are fed through suitable guides towards a point of intersection. A suitably high electrical current is passed through the wires, creating an arc at the point of intersection. An air jet atomises the feedstock material, which is then sprayed onto a substrate.
In a conventional spray gun of this kind, the feedstock wires are fed through a nozzle, so that their point of interseclion is beyond the end of the nozle.
An atomising air jet emitted by the nozzle carries the molten particles towards the substrate in a jet.
In the present invention, the point of inte~ecl~on of the feedstock wires is within the throat of the nozzle, rather than outside the nozzle. The creation of an arc in the throat has the effect of generating sll~,t~sonic flow in the nozzle, which would otherwise not be ~tt~in~hle. This very high flow velocity results in very fine atomic~tion of the molten feedstock particles, and very high particle speeds as the particles are emitted towards the substrate.
Referring now to Figures 1 and 2, a high velocity spray gun according to the invention comprises a nozzle 10 which defines a throat 12 in the form of a tubular bore having an inlet 14 and an outlet 16. In the prototype apparatus, the length and ~ met~r of the throat were approximately equal at 8 mrn, with the ~ mPter of the throat being constant along its length.
SUE~STITUTE SHEET (RULE 26) W O9X~74 PCTlGB97/Oln3 The interior of the nozle defines a chamber 18 which has an average internal diameter several times greater than that of the throat 12 and which is ~enerally frusto-conical in shape. At the end of the chamber adjacent the inlet 14 of the throat 12, the inner wall 20 of the chamber is tapered inwardly more sharply, and joins the inner end of the throat at an angle of approximately 4S~.
The interior of the nozle receives a pair of feedstock guides 22 and 24which are inrlinPcl towards one another and which are disposed ad~acent the inner surface of the charnber 18.
Wire fee-lctorl~ material 26 (titaniurn wire in the basic method of theinvention) is fed lor~ n~lly thorough the guides 22 and 24 by a wire feeder m~ch~T~icm (not shown), so that the two wires converge towards a point of il-L~,ae~,lion located on the axis of the throat 12 of the nozle, between a point approximately midway along the leneth of the throat and the outer end of the throat. The dimensions of the throat are selected to permit an arc between the two feedstock wires to be located slJbst~nti~lly within the throat 12.
In Figure 1, the included angle between the feedstock guides is about 30~, but a greater angle, say 60~, leads to a smaller effective point of intersectionbetween the feedstock wires, which is desirable.
In operation, air (or another nitrogen-rich gas) is forced into the spray gun head under plesauLe~ with the pressure and volume being adjusted so that the gas flow within the throat 12 is sonic (i.e. choked) or very close to being choked. Current is applied to the feedstock wires to create n electric arc SUBSTITUTE SHEET (RULE 26) WO 98/OOS74 PCTlGB97101n3 between them, so that the air or gas being forced through the throat of the nozzle is heated s~bst~nti~lly in~t~nt~n~oously to 4 000~C - 5 000~C by the arc. This rapid heating of the gas accelerates it to very high velocities, expelling the air and molten feedstock particles from the outlet 16 in a fine jet 2~.
In a prototype of the apparatus, a voltage of 3~V was applied between the feedstock wires from a constant voltage source, creating an arc current in the region of 180A to 200A. The feed rate of the feedstock wires was about 3rn/min. A supply of coulp~eajed air with a pressure of 600kPa was used, providing a gas pressure in the çh~ml~er 18 of approximately 400kPa. The choked yl~aa~c in the throat 12 was approximately 200kPa with the throat shape and dimensions given above.
The feedstock wires have a composition which is selected to create a coating having desired chemical and physical characteristics. For example, a 1.6 rnm diarneter wire of 316 st~inl~cs steel can be used as a feedstock to produce a coating of St~inl~ steel on a substrate.
Due to the high velocity of the jet, the particles are very finely atomised, improving the properties of the coating. Also due to the high velocity of the jet, the jet is well focused and the deposit it generates is very dense.
Figures 3a and 3b illustrate the difference between co~ting.~ produced by a conventional arc spray gun and the above described apparatus of the invention, ~eal,ecti~ely. The texture of the coating produced ~y the prior art apparatus is relatively coarse, whereas that produced by the apparatus of the present invention is much finer and less porous.
SUBSTITUTE SHEET (RULE 26) W098~S74 PCT/GB97~1723 Where titanium is used as a feedstock material, it is believed that the arc has the effect of ionising the nitrogen (and other elements) in the air passing through the throat of the nozzle, causing a reaction to take place between the nitrogen ions and the molten titaniurn metal particles. This results in a high proportion of the titanium metal reacting with the nitrogen to form titanium nitride. In addition, titanium oxide and titanium carbide can be expected to be formed. Due to the fine atomisation produced by the spray gun, a relatively large p~l~,e.~lage of the atolniced titani~n metal reacts with the nitrogen, with a resulting large pe~e,llage of titanium nitride in the deposited material.
Coatings forrned by the method were found to contain a~lo~ll~tely 2% to5% percent of the original titanium metal, which acts as a binder for the particles of titanium nitride and makes the coating tougher and less brittle.
Tests showed that the co~tin~ were very hard, with a Vickers hd~Lless of approximately Hv I 100.
The typical stoic-h-iometery of the coatin~c referred to above is Ti, 0 N 094 ~ 008- which is a titanium nitride compound comprising a small proportion of oxygen.
In order to increase the to~hnç~s of the coating formed by the method of the invention, while retaining the properties of the extremely hard titanium nitride, a metal selected for its properties as a binder can be incol~olat~d in the coating. This conveniently achieved by replacing one of the titanium feedstock wires with a wire of the selected binder metal, for example nickel.
The binder metal is then mixed by the arc spray process with the titanium nitride deposit, producing a composite deposit cont~ining~ say, 48% titanium SUBSTITUTE SHEET (RULE 26) wo 98/OOS74 PCT/Gs97/0l723 ni~ride and the balance comprising the metal, which acts as a binder in the titanium nitride matrix. The two fee~ctoc~ wires need not be of exactly the sarne diameter, thus permitting the percelltage of metal binder to titanium nitride to be varied according to the requirements of the particular application.
A particular advantage of the method of the invention is that it allows the creation of sl1bst~nti~lly thicker coating~ than prior art methods. Coatings of 0.5mm thil~n~c or greater are possible. Because titanium nitride is chemically inert, the method of the invention is particularly useful in coating substrates which will be subjected to corrosive or erosive enviror~m~nts such as propeller or turbine blades. It is also envisaged that the method will be useful in coating medical imrl~ntc due to the çh~mir~l inertness and biocornr~tibility of liL~iu-,l nitride. The co~ting~ produced by the method also have an attractive golden colour.
It was found tnat, when viewed under high m~gnification~ a large number of very small shrinkage cracks (of the order of 0.5,um) were exhibited within each spray particle in the deposit or co~ting In order to improve the corrosion protection properties of the coa~ing~ a sealer such as a phenolic resin sealer can be applied, for example by p~inting, to the coating after spraying. The application of a thin sealant layer onto a titanium nitride coating is particularly effective, as the micro-cracks are extensive and well distributed and the sealer is thus effectively soaked into the coating, sealin"
it. Since the sealer is then co~t~in~d within the coating matrix, the sealer is protected within the coating from mech~nical darnage, thus ensuring that it is effective for an ~xt~nded period of time.
SUBSTITUTE SHEET (RULE 26)
Claims (18)
1. A method of forming a coating on a substrate, the method comprising the steps of feeding at least two feedstock elements (26), of which at least one is in the form of a titanium wire, towards a point of intersection in the region of 2 throat (12) of a nozzle (10); generating an arc between the feedstock elements at the point of intersection; supplying a nitrogen-rich gas to the throat of the nozzle thereby to generate a spray of finely atomised particles (28) from the throat; and spraying the atomised particles onto a substrate to form a coating comprising titanium nitride on the substrate; characterised in that the point of intersection is in the throat (12) of the nozzle (10); and in that the gas is supplied at a pressure sufficient to generate choked gas flow in the throat (12) and, after rapid heating by the arc, a supersonic gas flow leaving the nozzle with the spray of finely atomised particles entrained therein.
2. A method according to claim 1 wherein the nitrogen-rich gas is air, and the coating additionally comprises oxides and carbides of titanium.
3. A method according to claim 1 or 2 wherein the coating additionally comprises titanium metal.
4. A method according to claim 3 wherein the coating contains from 2% to 5% titanium metal.
5. A method according to any one of claims 1 to 4 wherein one of said at least two feedstock elements comprises a metal selected to have suitable properties as a binder of the titanium nitride in the coating.
6. A method according to claim 5 wherein the metal is nickel.
7. A method according to any one of claims 1 to 6 including the step of applying a protective layer of sealant to the coating.
8. A method according to claim 7 wherein the protective layer of sealant comprises a phenolic resin.
9. A method according to claim 7 or claim 8 wherein the sealant is soaked into micro-cracks in the coating during application thereof.
10. Thermal spraying apparatus comprising a nozzle (10) defining a throat (12) having an inlet (14) and an outlet (16) and a gas flow path (18) which is aligned with the axis of the throat, so that gas under pressure can be supplied to the inlet; at least first and second guides (22,24) arranged to guide respective feedstock wires (26) via the inlet towards a point of intersection in the throat; a power supply arranged to be connected to the feedstock wires to cause an arc in the throat between the wires; and a supply of compressed air (18) arranged to supply air to the throat, characterised in that the air supply is at a pressure sufficient to cause choked air flow in the throat, thereby to generate, in use, and after rapid heating by the arc, a supersonic air flow leaving the nozzle with a spray of finely atomised particles entrained therein.
11. Thermal spraying apparatus according to claim 10 wherein the pressure of the compressed air supply is sufficient to generate a choked pressure in the throat of approximately 200kPa.
12. Thermal spraying apparatus according to claim 10 or claim 11 wherein the power supply generates an arc current in the region of 180A to 200A.
13. Thermal spraying apparatus according to any one of claims 10 to 12 wherein the throat comprises a tubular bore which substantially surrounds the point of intersection of the two feedstock wires.
14. Thermal spraying apparatus according to claim 13 wherein the diameter of the throat is substantially constant along its length.
15. Thermal spraying apparatus according to claim 13 or 14 wherein the length of the throat is approximately equal to its diameter.
16. Thermal spraying apparatus according to any one of claims 10 to 15 wherein the point of intersection is between a point located about midway along the length of the throat and the outer end of the throat.
17. Thermal spraying apparatus according to any one of claims 10 to 16 wherein the nozzle defines a chamber inwardly of the throat, the chamber having an inner wall which has an average internal diameter several times greater than that of the throat and which tapers inwardly towards an inner end of the throat.
18. Thermal spraying apparatus according to claim 17 wherein the inner wall of the chamber joins the inner end of the throat at an angle of approximately 45°.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ZA96/5519 | 1996-06-28 | ||
| ZA965518 | 1996-06-28 | ||
| ZA96/5518 | 1996-06-28 | ||
| ZA965519 | 1996-06-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2259190A1 true CA2259190A1 (en) | 1998-01-08 |
Family
ID=27143362
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002259190A Abandoned CA2259190A1 (en) | 1996-06-28 | 1997-06-27 | Thermal spraying method and apparatus |
Country Status (10)
| Country | Link |
|---|---|
| US (2) | US6258416B1 (en) |
| EP (1) | EP0907760B1 (en) |
| JP (1) | JP2001516396A (en) |
| CN (1) | CN1156597C (en) |
| AT (1) | ATE192510T1 (en) |
| AU (1) | AU3269097A (en) |
| CA (1) | CA2259190A1 (en) |
| DE (1) | DE69701877T2 (en) |
| NO (1) | NO986162L (en) |
| WO (1) | WO1998000574A1 (en) |
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|---|---|---|---|---|
| GB2315441B (en) * | 1996-07-20 | 2000-07-12 | Special Melted Products Limite | Production of metal billets |
| US6245104B1 (en) * | 1999-02-28 | 2001-06-12 | Inflow Dynamics Inc. | Method of fabricating a biocompatible stent |
| KR100370564B1 (en) * | 1998-12-14 | 2003-03-31 | 주식회사 포스코 | Explosion spray coating method of mixed spray alloy powder |
| EP1210180A1 (en) | 1999-07-29 | 2002-06-05 | Metalspray International LC | Thermal spraying equipment |
| KR100391568B1 (en) * | 1999-12-13 | 2003-07-12 | 주식회사 포스코 | Thermal spraying method for Nitride by mixing oxides as binder |
| CN101638765A (en) | 2000-11-29 | 2010-02-03 | 萨莫希雷梅克斯公司 | Resistive heaters and uses thereof |
| US7201940B1 (en) * | 2001-06-12 | 2007-04-10 | Advanced Cardiovascular Systems, Inc. | Method and apparatus for thermal spray processing of medical devices |
| BE1014736A5 (en) * | 2002-03-29 | 2004-03-02 | Alloys For Technical Applic S | Manufacturing method and charging for target sputtering. |
| JP3965103B2 (en) * | 2002-10-11 | 2007-08-29 | 株式会社フジミインコーポレーテッド | High speed flame sprayer and thermal spraying method using the same |
| WO2004111290A1 (en) | 2003-06-06 | 2004-12-23 | Michael Walter Seitz | Composite wiress for coating substrates and methods of use |
| US8518496B2 (en) | 2003-06-06 | 2013-08-27 | Alstom Technology Ltd | Preventing tube failure in boilers |
| US6991003B2 (en) * | 2003-07-28 | 2006-01-31 | M.Braun, Inc. | System and method for automatically purifying solvents |
| DE10345827A1 (en) * | 2003-10-02 | 2005-05-04 | Daimler Chrysler Ag | Process for coating metallic substrates with oxidizing materials by means of arc wire spraying |
| US7341533B2 (en) * | 2003-10-24 | 2008-03-11 | General Motors Corporation | CVT housing having wear-resistant bore |
| US7093452B2 (en) * | 2004-03-24 | 2006-08-22 | Acma Limited | Air conditioner |
| CA2532388A1 (en) * | 2005-01-07 | 2006-07-07 | Inframat Corporation | Coated medical devices and methods of making and using |
| CA2527764C (en) * | 2005-02-11 | 2014-03-25 | Suelzer Metco Ag | An apparatus for thermal spraying |
| JP4881049B2 (en) * | 2006-04-11 | 2012-02-22 | 新日本製鐵株式会社 | Conductor roll for electroplating |
| US20080124373A1 (en) * | 2006-08-02 | 2008-05-29 | Inframat Corporation | Lumen - supporting devices and methods of making and using |
| US20080069854A1 (en) * | 2006-08-02 | 2008-03-20 | Inframat Corporation | Medical devices and methods of making and using |
| RU2485213C1 (en) * | 2012-04-24 | 2013-06-20 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Орловский государственный аграрный университет" (ФГБОУ ВПО ОрелГАУ) | Coating application method |
| JP2018141214A (en) * | 2017-02-28 | 2018-09-13 | 吉川工業株式会社 | Hydrogen embrittlement-resistant sprayed coating and hydrogen embrittlement-resistant sprayed coating member |
| CN111111961B (en) * | 2019-12-29 | 2021-07-16 | 苏州路之遥科技股份有限公司 | Spraying device and spraying method for PTC heating material for toilet seat |
| CN111085359B (en) * | 2019-12-31 | 2021-06-15 | 北京航空航天大学 | Fluid guiding device for spraying, spraying system and spraying method |
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| CH213068A (en) * | 1941-09-23 | 1941-01-15 | Dr Schoop M U | Method and device for the production of metal coatings. |
| US2749176A (en) * | 1952-09-18 | 1956-06-05 | Arnold Otto Meyer | Electro metal spraying pistol |
| CS154068B1 (en) * | 1970-09-04 | 1974-03-29 | ||
| JPS5610103B2 (en) * | 1973-09-06 | 1981-03-05 | ||
| JPS51141736A (en) * | 1975-05-31 | 1976-12-06 | Kawasaki Heavy Ind Ltd | Production method for cylinder |
| JPS51151736A (en) | 1975-06-21 | 1976-12-27 | Kiyuuroku Kk | Automatic applicator of adhesives |
| DE2746714A1 (en) * | 1977-10-18 | 1979-04-19 | Walter H R Ott | Electric arc spraying machine nozzle plate - has air passages grouped at intervals around contact nozzles |
| US5046944A (en) | 1979-11-16 | 1991-09-10 | Smith Thomas M | Infra-red generation |
| GB2086764A (en) | 1980-11-08 | 1982-05-19 | Metallisation Ltd | Spraying metallic coatings |
| JPS5827971A (en) * | 1981-08-14 | 1983-02-18 | Hitachi Ltd | Melt spraying for metal |
| PL136366B1 (en) | 1982-07-26 | 1986-02-28 | Inst Mech Precyz | Apparatus for arc spraying of metal coatings on difficult accessible surfaces,especially on internal cylindrical surfaces |
| DE3409366A1 (en) | 1984-03-12 | 1985-09-12 | Mannesmann AG, 4000 Düsseldorf | METHOD AND DEVICE FOR PRODUCING A MOLDED BODY |
| JPS6173871A (en) * | 1984-09-17 | 1986-04-16 | Ryoichi Kasagi | Method for spraying thermally metal at lower temperature by double ejector type |
| US5109150A (en) | 1987-03-24 | 1992-04-28 | The United States Of America As Represented By The Secretary Of The Navy | Open-arc plasma wire spray method and apparatus |
| US5213848A (en) * | 1990-02-06 | 1993-05-25 | Air Products And Chemicals, Inc. | Method of producing titanium nitride coatings by electric arc thermal spray |
| US5066513A (en) * | 1990-02-06 | 1991-11-19 | Air Products And Chemicals, Inc. | Method of producing titanium nitride coatings by electric arc thermal spray |
| US5191186A (en) | 1990-06-22 | 1993-03-02 | Tafa, Incorporated | Narrow beam arc spray device and method |
| US5296667A (en) | 1990-08-31 | 1994-03-22 | Flame-Spray Industries, Inc. | High velocity electric-arc spray apparatus and method of forming materials |
| DE4041810C2 (en) * | 1990-12-22 | 1995-05-24 | Castolin Sa | Multi-wire arc spray gun |
| DE4339345C2 (en) * | 1993-11-18 | 1995-08-24 | Difk Deutsches Inst Fuer Feuer | Process for applying a hard material layer by means of plasma spraying |
| US5468295A (en) | 1993-12-17 | 1995-11-21 | Flame-Spray Industries, Inc. | Apparatus and method for thermal spray coating interior surfaces |
| US5528010A (en) | 1994-05-20 | 1996-06-18 | The Miller Group, Ltd. | Method and apparatus for initiating electric arc spraying |
| US5932293A (en) * | 1996-03-29 | 1999-08-03 | Metalspray U.S.A., Inc. | Thermal spray systems |
| US5964405A (en) * | 1998-02-20 | 1999-10-12 | Sulzer Metco (Us) Inc. | Arc thermal spray gun and gas cap therefor |
| US6245390B1 (en) * | 1999-09-10 | 2001-06-12 | Viatcheslav Baranovski | High-velocity thermal spray apparatus and method of forming materials |
-
1997
- 1997-06-27 DE DE69701877T patent/DE69701877T2/en not_active Expired - Fee Related
- 1997-06-27 WO PCT/GB1997/001723 patent/WO1998000574A1/en active IP Right Grant
- 1997-06-27 CN CNB971968160A patent/CN1156597C/en not_active Expired - Fee Related
- 1997-06-27 AT AT97928370T patent/ATE192510T1/en not_active IP Right Cessation
- 1997-06-27 CA CA002259190A patent/CA2259190A1/en not_active Abandoned
- 1997-06-27 EP EP97928370A patent/EP0907760B1/en not_active Expired - Lifetime
- 1997-06-27 US US09/214,097 patent/US6258416B1/en not_active Expired - Fee Related
- 1997-06-27 JP JP50391198A patent/JP2001516396A/en not_active Ceased
- 1997-06-27 AU AU32690/97A patent/AU3269097A/en not_active Abandoned
-
1998
- 1998-12-28 NO NO986162A patent/NO986162L/en not_active Application Discontinuation
-
2001
- 2001-07-09 US US09/899,936 patent/US6431464B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2001516396A (en) | 2001-09-25 |
| EP0907760B1 (en) | 2000-05-03 |
| EP0907760A1 (en) | 1999-04-14 |
| US6258416B1 (en) | 2001-07-10 |
| US6431464B2 (en) | 2002-08-13 |
| US20010040188A1 (en) | 2001-11-15 |
| NO986162L (en) | 1999-02-19 |
| WO1998000574A1 (en) | 1998-01-08 |
| AU3269097A (en) | 1998-01-21 |
| DE69701877D1 (en) | 2000-06-08 |
| CN1156597C (en) | 2004-07-07 |
| CN1226287A (en) | 1999-08-18 |
| NO986162D0 (en) | 1998-12-28 |
| DE69701877T2 (en) | 2000-10-05 |
| ATE192510T1 (en) | 2000-05-15 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued |