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
  • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
  • C23C4/06—Metallic material
  • C23C4/08—Metallic material containing only metal elements
• • 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
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
  • Y10T428/2991—Coated
  • Y10T428/2993—Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]
• • 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
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31678—Of metal
  • Y10T428/31714—Next to natural gum, natural oil, rosin, lac or wax

Definitions

• the nickel, copper or iron is present in about 66 to 97.5 percent, the aluminum in about 2 to 18 percent and the molybdenum in about 0.5 to 16 percent.
• the material produces a selfbonded wear resistant coating which can readily be machined.
• the invention relates to a nickel or copper aluminum flame spray material which is characterized by excellent bonding and superior machinability of coated surfaces.
• the flame sprayed surface constitute an intermetallic compound.
• US. Pat. No. 3,322,515 there is described a flame spray composite material whose components exothermically interact with one another when melted so as to form such intermetallic compound which is deposited upon the substrate.
• the heat generated by the exothermic reaction aids in the bonding.
• the composite may comprise separate strands of the two components, e.g. a strand of nickel and a strand of aluminum, the strands being simultaneously fed to a flame spray gun.
• one of the components can be coated onto the other, e. g. a wire comprising a nickel core and an aluminum sheath.
• a further object of the invention is to produce superior flame sprayed bearing surfaces.
• the novel self-bonding clad material may comprise about 66 to 97.5 percent and preferably'about 73 to 89 percent by weight of nickel, copper and/or iron.
• the aluminum may comprise about 2 to 18 percent and preferably about 5 to 15 percent by weight of the total composition.
• the molybdenum may comprise about 0.5 to 16 percent and preferably about 6 to 12 percent by weight.
• the nickel, copper or iron may be present as such or as an alloy with one another optionally containing a minor amount of other ingredients, e.g. up to about 10 or even 20 percent or more by weight of. substances such as silicon, boron, chromium, cobalt, etc.
• the nickel-copper-iron component preferably constitutes a core which is clad with the aluminum and molybdenum. When used in clad-powder form, the composite of aluminum and molybdenum coated nickel-copper-iron particles should have the general overall shape and size of conventional flame spray powders.
• the initial nickel-copper-iron particles which'constitute the core or nucleus of the composite powders in accordance with the invention should have a size and shape approximating that desired in the end powders as described above.
• the nickel-copper-iron core or nucleus particles are then coated with the aluminum and molybdenum; the coating being effected by any known coating process, as for example described inU.S. Pat. No. 3,322,515.
• the aluminum and the molybdenum are deposited in finely divided form in a binder on the nickel-copper particles.
• the paint is then used to coat the nickel core particles and allowed to set or dry.
• the binder material may be any known or conventional binder material which may be used for forming a coating or for bonding particles together or to a surface.
• the binder is preferably a varnish containing a resin as the varnish solids, and may contain a resin which does not depend on solvent evaporation in order to form a dried or set film.
• the varnish may thus contain a catalyzed resin as the varnish solids.
• binders which may be used include the conventional phenolic epoxy or alkyd varnishes, varnishes containing drying oils, such as tuna oil and linseed oil, rubber and latex binders and the like.
• the coating of the nickel-copper-iron core component with the paint containing the aluminum and molybdenum may be effected in any known or desired manner. and it is simply necessary to mix the two materials together and allow the binder to set or dry which will result in a fairly free-flowing powder consisting of the nickel-copper-iron core coated with cladding of the aluminum and molybdenum.
• the molybdenum powder may be any known powder including molybdenum alloys containing more than 50 percent molybdenum and most preferably is used in a particle size range between 20 and +1 micron.
• the powders are sprayed in the conventional manner, using a powder type flame spray gun, though it is also'possible tocombine the same in the form of a wire or rod, using plasticor a similar binding, as for example polyethylene which decomposes in a heating zone of the gun.
• a powder type flame spray gun though it is also'possible tocombine the same in the form of a wire or rod, using plasticor a similar binding, as for example polyethylene which decomposes in a heating zone of the gun.
• wires Wheniformed as wires, the same may have conventional sizes and accuracy tolerances for flame spray wires and thus, for example, may vary in size between A inch'and gauge.
• the spraying is in all respectseffected in the conventional manner previously utilized for self-bonding flame spray material, and in particular nickel aluminum composites. Due to the self-bonding characteristics, special surface preparation other than a good cleaning is not required'though, of course, conventional surface preparation may be utilized if desired.
• the powder in accordance with the invention may be flame-sprayed as a bonding coat for subsequently applied flame spray material or any purposes where it is desired to form the nickel-copper aluminide coating containing molybdenum.
• the composites may furthermore be sprayed in conjunction with, or in addition to, other, flame spray materials conventionally used in the art.
• the .nickel, copper and/or iron and aluminum exothermically react, forming a nickel, cop- 4 ln order for the wires to be satisfactory for spraying, the same must not cavitate at the tip when heated, and
• 1 should preferably be capable of forming a pointed or .slightly tapered tip when'being melted and sprayed.
• the inner core cannothave a lower melting point that the outer sheath, as otherwise the inner core will initially melt, causing cavitation at the tip.
• the coating sheath must be aluminum, as otherwise during the spraying operation the wire will initially melt out, causing the cavitation which will interfere with a satisfactory spraying operation.
• the wire having the melting-point characteristics so as to'allow the melting off of the tip without this cavitation is referred to herein per and/or iron aluminide intermetallic.
• molybdenum andalumin-um also exothermically react, forming molybdenum. aluminide intermetallic.
• Complex nickelcopper-.andlorqiron-molybdenum aluminides and al- The term composite? designate a structurally integral unit and does not include-a mere mixture of components which maybe physically separated without any destruction of the structure.
• the term com posite does not'include a simple mixture of individual .granules of the separate components, but requires that each of the individual granules contain the separate components which will exotherrnically react, forming and in the claims as non-cavitating wire.”
• the components may be present in the stoichiometric proportions required for the formationof the intermetallic compound, it is, however, possible to also have an excess of one or the other provided the relative amounts are sufficient to reiease quantities of heat in the formation of the intermetallic compounds.
• the clad powders in accordance with .the invention, may be formed in any known or desired manner, in-
• - cluding known-chemical plating processes in which as used herein is intended to der are in the form of a clad composite consisting of a nucleus of one of the components and at least one coating layer of the other components.
• the composite' may consist of separate, concentric coating layers of at least two of the components and a nucleus of the third or even a fourth material.
• the composites may be in the form of a wire having a coating sheath of one material and a core of the others, alternate coating sheaths of two of the components and a core of the third or a fourth material, a wire.
• a wire formed by twisting or rolling separate wire strands of the components, a wire consisting of a sheath of one component and a core containg the other components inpowder or compacted form,'awire consisting of a sheath of one component and a core containing a compacted powder mixture of this same component material and other components, a wire consisting of a plastic sheath and a core containing a compacted powder mixture of components, etc.
• coating material is deposited on a seed or nucleus of another material, or in which multiple layers of various materials are built up on the seed material, or in which various materials are co-deposited in a single layer on the seed material.
• a mode of forming the clad powders involves the depositing of a metal from a solution by reduction on a seed or nucleus, such as by the hydrogen reduction of ammoniacal solutions of nickel and/or copper and ammonium sulfate on a seed powder catalyzed such as by the-addition of anthraquinone. It is also possible to form the coating by'otherprocesses, such as coating by vapor deposition, by the thermal decomposition of metal carbonyls, by hydrogen reduction of metal halide vapors, by thermal deposition of halides, hydrides, carbonyls, organometals, or other volatile compounds, or by displacement gasplating and the like.
• a preferred and greatly simplified mode of forming the clad powders in accordance with the invention is the depositing of two components as coating in the form of a paint on the third component.
• two of the components which are to form the coating or cladding may be dispersed in finely divided form in a binder or lacquer so as, in effect, to form a paint in which this component corresponds to the pigment.
• the paint is then used to coat core particles of the third component and the binder or lacquer allowed to set or dry.
• the binder material is preferably a resin which does not depend on solvent evaporation in order to form a dried or set film, and which film will decompose or break down in the heat of the spraying process.
• the binder for example, may be a phenolic varnish or any other known or conventional varnish, preferably containing a resin. as the varnish solids.
• the components which are initially mixed with the binder or varnish should preferably be as finely divided as possible, as for example -325 mesh.
• the other component which constitutes the core should be approximately or only slightly below the particle size ultimately desired for the spray powder.
• the coating of the core component with the paint may be effected in any known or desired manner, and it is simply necessary to mix the two materials together and allow the binder to dry or set, which will result in a fairly free-flowing powder consisting of the core component coated with a cladding of the other component bound in the binder.
• the aggregates may be formed by compacting or briquetting the various components into the individual granules, or into largeraggregates and then breaking these aggregates into the granules.
• the wires may be formed in the known conventional manner for forming wires with various components as, for example, by shrinking a sheath on a core, by forming the core with powder, by twisting the component wires, followed by rolling, drawing, swaging, or the like if desired.
• one of the components may be formed into a tube or sheath and filled with a powder of the other components or a powder comprising a mixture of the three components, or containing additional components.
• the tube ends are then sealed and the wire reduced to the desired wire diameter by swaging, rolling or drawing.
• the powder or powder mixture is first compressed into cylindrical briquettes before being placed in the sheath or core.
• the sealing of the tube ends after loading with the powder or powder mixture can be effected, for instance, by insertion of a plug, for example of the metal of the sheath, by welding, twisting, crimping, or
• Powders in accordance with the invention should have the general over-all shape and size of conventional, flame spray powders, and thus for example should have a size between 60 mesh and +3 microns andpreferably l40 mesh and microns (U.S. Standard screen mesh size). Most preferably the powder should be as uniform as possible in grain size, with the individual grains not varying by more than 250 microns and preferably 75 microns.
• the composite powder may be sprayed per se or in combination with other different composite powders, orin combination with other conventional flame spray powders or powder components.
• the powders are preferably sprayed, as such, in a powder type of flame spray gun, it is also possible to combine the same in the form of a wire or rod, using a plastic or similar binder, which decomposes in the heating zone of the gun, or in certain cases the powders may be compacted and/or sintered together in the form of a rod or wire.
• the wires must have the conventional sizes and accuracy tolerances for flame spray wires and thus for example may vary in size between A inch and gauge, and are preferably of the following sizes: 3/16 0.0005 inch to 0.0025 inch, l/8 0.0005 inch to 0.0025 inch, 11 gauge 0.0005 inch to 0.0025
• the heat generated in situ in the formation of the intermetallic compound produces novel results, in many instances forming a denser, more adhering coating, having characteristics of at. least a partially fused coating. In many instances the coating has self-bonding characteristics, so that special surface preparation, other than a good cleaning, is not required.
• the spraying in all other respects is effected in the conventional, well-known manner, using conventional flame spray equipment, and the conventional surface preparation may be utilized, if desired.
• the composites in accordance with the invention may be sprayed in conjunction with or in addition to other flame spray materials conventionally used in the art, or may be sprayed in combination or conjunction with the others.
• nickel-, copperand/or ironaluminum-molybdenum composites will generally improve the bond of the total sprayed material, and thus of the other component or components to the substrate, sometimes making the mixture self-bonding.
• the particle bond will be improved and the coating will be denser, so that its porosity may be decreased. ln general, as little as about 5 percent by weight of the composites in accordance with the invention will be sufficient to substantially improve the bonding characteristics and decrease the porosity of other flame spray materials, such as conventional flame spray metals, alloys or ceramics. There is, of course, no upper limit on the amount as the composite may be sprayed per se, but generally at least about 20 percent by weight of the other component is required if this component is to have a pronounced effect on the characteristics of the coating.
• the novel composite when blended may constitute about 5 to percent by weight of the blend, advantageously about 10 to 50 percent and preferably about 10 to 20 percent.
• novel composites may be flame sprayed.
• self-fluxing metal powders as described in U.S. Pat. Nos. 2,875,043, 2,936,224 and 3,305,326 as well as carbides as described in U.S. Pat. No. 3,305,326 and mixtures thereof.
• the self-fluxing, spray-weld powders are of the nickel or cobalt type, containing boron and most preferably boron and silicon, as the self-fluxing element.
• the most preferable spray-weldable, selffluxing metal powders are of the nickel or nickelchromium alloy type containing boron and silicon.
• the base metal i.e.
• the powder may be formed of additional alloy components, as for example up to 20 percent chromium, to impart corrosion and oxidationresistance, carbon in the amount of not more than a few percent, iron in an amount not exceeding about 10 percent and preferably 5 percent by weight of the total alloy.
• additional alloy components as for example up to 20 percent chromium, to impart corrosion and oxidationresistance, carbon in the amount of not more than a few percent, iron in an amount not exceeding about 10 percent and preferably 5 percent by weight of the total alloy.
• a typical spray-weldable alloy of the boron nickel type of which the powder is composed may, for example up to 20 percent chromium, to impart corrosion and oxidationresistance, carbon in the amount of not more than a few percent, iron in an amount not exceeding about 10 percent and preferably 5 percent by weight of the total alloy.
• a typical spray-weldable alloy of the boron nickel type of which the powder is composed may, for example
• a typical spray-weld alloy of the cobalt-base type may, for example, contain from 1.5 to 3 percent boron, to 4.5 percent silicon, 0 to 3 percent carbon, 0 to 20 percent chromium, 0 to 30 percent nickel, 0 to 20 percent molybdenum, 0 to 20 percent tungsten, and the balance cobalt.
• novel composites optionally blended with a self fluxing metal powder, are further blended with a refractory carbide, such as tungsten carbide, titanium carbide, zirconium carbide, tantalum carbide, columbium carbide, hafnium carbide, chromium carbide or the like, extremely high quality coatings are produced, which are superior in various respects to the conventional carbide coatings.
• a refractory carbide such as tungsten carbide, titanium carbide, zirconium carbide, tantalum carbide, columbium carbide, hafnium carbide, chromium carbide or the like
• the carbides used in accordance with this embodiment should have a particle size between about l40 mesh US. Standard. screen size and 8 microns, and preferably between about -270 mesh and microns, with the amount of carbide being between aboutl0-75 percent and preferably 45-55 percent by weight, based on the total powder mixture.
• the refractory carbide powder is in a form so that v illustration and notlimitation the refractory carbide is bound in a matrix, as for example a cobaltor nickel matrix containing 5-20 percent by weight of either cobalt or nickel, unusually hard and wear-resistant coatings will be produced which do not contain the individual carbide particles imbedded in a fused matrix, but instead contain alloy phases whose micro-hardness is actually substantially higher than that ordinarily obtained from a bonded carbide.
• the powder, in accordance with the invention, containing this matrix-bonded refractory carbide is plasma-sprayed, the same is self-bonding, so that the conventional surface preparation for flame spraying, as for example a deep surface roughening, is not required.
• the carbide coatings formed in accordance with the above are extremely hard and wear-resistant, and may be useful as bearing surfaces, abrasive surfaces, and for any other purpose wherein a working surface requires extremely wear-resistant coating.
• the refractory carbide need not be matrix-bound
• the crystalline carbide-containing coatings formed in accordance with the invention will have extremely high wear-resistance due to the carbide particles, which are dispersed and tightly bound in the fused coating. Coatings may be used for the same type of applications as mentioned in connection with the coatings formed with the matrix-bound carbide.
• the powder was then warmed to about 250F. to ensure complete drying.
• the powder was then screened and hand-milled to reduce the same to a l00 mesh powder.
• the powder was flamesprayed on a mild steel plate which had been surface cleaned by smooth grinding.
• the spraying was effected at a distance of 6 inches from the plate, using a powder type flame spray gun as described in US. Pat. No. 2,96l ,335 of Nov. 22, i960 and sold by Metco, Inc, of Westbury, N.Y., under the trade name Thermospray powder gun, Type 5 P.
• the spraying was effected at a rate of 5 to 10 lbs. of powder per hour, using acetylene gas as the fuel, at a pressure ofl 1 lbs.
• a coating layer was built up to a thickness of between 0.030 and 0.050 inch.
• the Alpha model LFW-l friction and wear testing machine is manufactured by Dow Corning Corporation and is designed to test friction and wear characteristics of material under simulated realistic conditions of load and speed.
• the three component composite exhibited superior bond strength, hardness, wear and machinability with resistance to shrinkage, air oxidation and salt water corrosion comparable to those of the control.
• Example 1 Material Ni-Al Av 6040 Av. 2875 Av. S620 Range Range Range 65 5170 to 6670 2620 to 3130 2720 to 8400 Ni-Al-Mo Av. 8040 Av. 3830 Av. 7300 Range Range Range 707010 8680 3555 to 4l05 4750 to 9800 EXAMPLE4 The process of Example 1 was repeated with the following changes: the nickel was replaced by copper and tool life were also improved.
• EXAMPLE 5 9 Parts of finely divided aluminum and 8 parts of finely divided molybdenumwere blended with a phenolic varnish having approximately 50 percent solid contents so as to form a mixture having the consistency of a heavy syrup and containing 60 percent by weight of the metals.
• the powder was flame-sprayed on a mild steel plate and gave coatings exhibiting superior qualitative bonding properties and improved coating hardness.
• a molybdenum 8 percent) alumitwin (9 percent) clad ferronickel core(64Fe-36Ni) when clad and sprayed under the above conditions exhibited superior qualitative bonding properties and a high hardness .of Rb 83.
• a composite wire can be formed by winding individual wires of nickel, aluminum and molybdenum to form a stranded wire of 0.125 inch comprising 83:9:8 Ni- :AlzMo.
• the wire can be sprayed using a Metco type IOEspray gun with acetylene at a pressure of p.s.i. and a flow rate of 37 cu. ft./hr. with oxygen as the oxidizing gas at'a pressure of 38 p.s.i. and a flow rate of 75 cu. ft./hr.
• EXAMPLE 7 An aluminum tube 0.375 inch in outside diameter can be filled with a mixture of nickel powder and molybdenum powder to result in a structure comprising 83:9:8 NizAlzMo.
• the wire is then annealed and coiled.
• the wire is then sprayed, using the conventional wiretype flame spray gun sold by Metco inc. as the Metco type lOE gun. Spraying is effected, using acetylene at a pressure of about l5 lbs. psi. and a flow rate Air is used as a blast gasat a pressure of lbs. p.s.i.-
• a flame spray material in the form of a composite suitable for flame spraying comprising components of aluminum, molybdenum and at least one metalselected from the group consisting of nickel, copper and iron, based on the total weight of nickel, copper, iron, aluminum and molybdenum the nickel plus copper plus iron being present in about 66 to 97.5 percent, the aluminum in about 2 to 18 percent and the molybdenum in about 0.5 to 16 percent.
• the nickel plus copper plus iron is present in about-73 to 89 percent, the aluminum in about 5 to l 5 percent and the molybdenum in about 6 to 12 percent.
• a flame spray material according to claim 4 is a flame spray material according to claim 4,
• the composite is a powder, comprises copper, aluminum and molybdenum, and based on the weight of the copper, aluminum and molybdenum the copper is present in about 73 to 89 percent, the aluminum in about 5 to 15 percent and-the molybdenum in about 6 to 12 percent.
• a flame spray material according to claim 1 in the form of a powder blended with self-fluxing alloy powder, the composite constituting about 5 to percent by weight of the blend.
• a blend according to claim 8 further containing a metal carbide, the composite constituting about 10 to 20 percent by weight of the blend.
• the composite is a powder, comprises nickel, aluminum and molybdenum, and based on the weight of nickel, aluminum and molybdenum, the nickel is present in about 73 to 89 percent, the aluminum in about 5 to 15 percent and the molybdenum in about 6 to 12 percent.
• the composite is a powder, comprises copper;aluminum and molybdenum, and based on the weight of the copper, aluminum and molybdenum, the copper is present in about 73 to 89 percent, the aluminum in about 5 to 15 percent and the molybdenum in about 6 to 12 percent.
• the composite is a powder, comprises iron, aluminum and molybdenum, and based on the weight of the iron, aluminum and molybdenum, the iron is present in about 73 to 89 percent, the aluminum in about 5 to 15 percent and the molybdenum in about 6 to 12 percent.
• the flame spray material is in the form of a composite comprising com ponents of aluminum, molybdenum and at least one metal selected from the group consisting of nickel, copper and iron, blended with self-fluxing alloy powder, the composite constituting about 5 to percent by weight of the blend.
• the flame spray material further contains a metal carbide, the composite constituting about 10 to 20 percent by weight of the blend.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Physics & Mathematics (AREA)
• Plasma & Fusion (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Materials Engineering (AREA)
• Mechanical Engineering (AREA)
• Metallurgy (AREA)
• Organic Chemistry (AREA)
• Coating By Spraying Or Casting (AREA)

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Cited By (22)

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• 1973
  • 1973-07-06 US US00377151A patent/US3841901A/en not_active Expired - Lifetime
• 1974
  • 1974-04-30 CA CA198,563A patent/CA1025243A/en not_active Expired
  • 1974-05-16 FR FR7417121A patent/FR2236014B1/fr not_active Expired
  • 1974-05-22 IT IT51179/74A patent/IT1013217B/it active
  • 1974-05-30 JP JP6138074A patent/JPS5526180B2/ja not_active Expired
  • 1974-06-03 GB GB2437174A patent/GB1459035A/en not_active Expired
  • 1974-07-04 DE DE2432125A patent/DE2432125C2/de not_active Expired

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