US3617358A - Flame spray powder and process - Google Patents
Flame spray powder and process Download PDFInfo
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- US3617358A US3617358A US671880A US3617358DA US3617358A US 3617358 A US3617358 A US 3617358A US 671880 A US671880 A US 671880A US 3617358D A US3617358D A US 3617358DA US 3617358 A US3617358 A US 3617358A
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- binder
- flame spray
- flame
- subparticles
- spray powder
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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
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- 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
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/256—Heavy metal or aluminum or compound thereof
Definitions
- Newsome Attorney-Burgess, Dinklage and Sprung ABSTRACT The flame spraying of the flame spray powder which has been formed by spray drying of a slip or slurry of fine particles of a flame spray material.
- This flame spray powder has individual particles which are of substantially spheroid shape, of a size between about 20 mesh and 1 micron, and are formed of multiple subparticles bound together without fusion by a spray-dried binder and having a crush resistance of at least 0.7 grams.
- This invention relates to an improved flame spray powder, to a process for its production, and to a flame spray process utilizing the same.
- Flame spraying involves the feeding of a heat-fusible material into a heating zone wherein the same is melted or at least heat-softened and then propelled from the heating zone in a finely divided form, generally onto a surface to be coated.
- the spraying is eflected utilizing a device known as a flame spray gun.
- the material may initially be in the form of a powder which is designated as a flame spray powder, and the guns utilized for spraying the material initially fed in this powder form are known as powder-type flame spray guns.
- the flame spray powder usually entrained in a carrier gas, is fed into the heating zone of the gun which is most commonly formed by a flame of some type.
- the powder is either melted or at least the surface of the grains heat-softened in this zone, and the thus thermally conditioned particles are propelled onto a surface to provide the coating.
- a blast gas may be provided in order to aid in accelerating the particles and propelling them toward the surface to be coated and/or to cool the workpiece and the coating being fonned thereafter.
- the heat for the heating zone while most commonly produced from a flame Tcaused by the combustion of a fuel, such as acetylene, propane, natural gas or the like, using oxygen or air as the oxidizing agent, may also be produced by an electric arc flame or plasma flame, or any other known heating device.
- a powdered heat-fusible material in order to be satisfactorilly sprayed and thus considered a flame spray powder must .have certain physical characteristics with respect to size, lphysical strength, flowability, etc.
- the powder must be suffrgciently flowable to be passed through the flame spray gun without difficulty or clogging, and this flowability not only depends on size, absence of caking materials, such as excess :moisture, but on shape and surface characteristics.
- the powder in order to produce a satisfactory coating the powder must have a specific ⁇ size range, as for example, between 20 mesh and 1 micron,
- the uniformity and quality of the coating I formed by flame spraying is often dependent on the uniformity ⁇ of size of the individual particles in the powder.
- fluid including combustion fluids and propelling fluids
- the uniformity and quality of the coating I formed by flame spraying is often dependent on the uniformity ⁇ of size of the individual particles in the powder.
- the kinetic propelling of the particles and its contact with fluid including combustion fluids and propelling fluids, often causes a classifying efiect which adversely affects the homogeneity and uniformity of the coating, and the presence of excess fines may change the nature of the coating, producling for example excessive oxides or the like.
- exltensive screening and classifying techniques are generally required and only a relatively small cut of the available .jpowder material is generally suitable for marketing as a flame spray powder.
- powders are formed by reducling, as for example, milling a larger mass which results in a 'rather wide range of particle sizes which must then be screened to obtain operative size range cuts. This is generally true, irrespective of the source of the mass which is milled, in-
- One object of this invention is the production of an improved flame spray powder. This and still further objects will become apparent from the following description read in conjunction with the drawing which is a flow sheet illustrating the process for producing powders in accordance with the invention.
- a superior and improved flame spray powder may be produced utilizing spray drying techniques.
- finely divided flame spray material suspended in a slip or slurry of liquid, preferably water, with a suitable binder and preferable auxiliary agents is atomized and the atomized suspensiondried in a hot gas stream, forming the coarser flame spray powder, the individual particles of which are of substantially spheroid shape, have a size between about 20 mesh and 1 micron, and are formed of a multiple number of subparticles bound together without fusion by the spray dried binder, and which have a crush resistance of at least 0.7 grams.
- any of the known or conventional flame spray materials may be used.
- oxides as for example refractory oxides, such as alumina Al,0,, Beryllia BeO, Ceria CeO,, Chromia CR,O,, cobalt oxide C00, gallum oxide 021,0 hafnia l-lfO,, magnesia MgO, nickel oxide NiO, tantalum oxide TA,O thoria ThC,, Titania TiC,, yttrium oxide Y,O zirconia ZrC,, vanadium oxide V0, niobium oxide NbO, manganese oxide MnO, iron oxides Fe,0,, zinc oxide ZnO; complex aluminates such as BaO-Al,O, i
- sro'Algoa SYO'2A1205, ZYgOa'AlgOa, ZnO-A1,0,; zit conates such as CaO-ZrO SrO-ZrO,, BaO'ZrO,; titanates such as A1 0 'TiO 2Ba0-Ti0 CaO'TiO,, HfO,-Ti0,, 2M- gO-TiO,, SrO'TiO chromites, such as CaO-Cr,0,, ce'oc o, MgO'Cr o FeO-Cr,0,; phosphates such as A1,o,-P,0., 3BaO-PO 3CaO'P O 3SrO'P O and other mixed oxides, such as La O -Fe 0;, MgO'Fe,O 2MgO'GeO,, CaO-HfO,, La O -2HfO Nd O
- Borides such as TiBg, ZrB; HfB 6mm, borides of-V, mm srm bbriaes oTTafborids'bf Cr, bbFidesofMo, borides of W, borides of the rare earth metals;
- Silicides such as silicides of Ti eg Ti,Si
- silicides of V eg V;,Si or VSi are silicides of V eg V;,Si or VSi,
- silicides of TA eg Ta Si or TaSi
- silicides of the rare earth metals are silicides of the rare earth metals.
- Nitrides such as boron nitrides and silicon nitrides.
- Sulfides such as MgS, BaS, GrS, TiS ZrS, ZrS,, HfS, VS, V 8 CrS, M05 W8 the various rare earth sulfides;
- Metalloid elements such as boron, silicon, germanium.
- Cermets such as WC/Co, W,C/Co, WC+W,C/Co, Cr/Al,0,,,.- $6 0 NiAl/Al,0,, NiAl/ZrO Co/Zr0,, Cr/Cr,C,,O Co/TiC, Ni/TiC, Co/WC-i-TiC, Cr-l-Mo/Al f Ni, Fe and/or their alloys, Cu and/or its alloys such as aluminum bronze, phosphor bronze, etc., with the disulfides or deselenides of Mo, W, Nb, Ta, Ti, or V, or boron nitride for self-lubricating coatings with very low friction coefficient.
- Cermets which contain an active metal from the group composed of Ti, Zr, Ta, Cr, etc., or hydrides or other compounds or alloys of these active metals, which will alloy with the metal phase of the cermet and promote adhesion of the metal phase to the refractory phase by promoting wetting" of the surface of the refractory phase.
- Cermets for instance those containing a metal and a carbide as the refractory phase, which also contain free carbon, such as high purity graphite or the like, which will effectively reduce or prevent oxidation of the carbide phase and reduce solutioning of the carbide phase in the metal binder phase.
- Mixtures of any desired combinations of these or any known flame spray material may be used for any purpose, including for the formation of synergistic composites of the type mentioned in U.S. Pat. No. 3,254,970 or combinations which will exothermically react to form an intermetallic compound as disclosed in the aforesaid patent and U.S. Pat. No. 3,322,515.
- combinations which when flame sprayed, will endothermically react, or combinations or components which will decompose to form desired coating materials as for example carbonates, oxalates, nitrates or oxychlorides which will decompose to form oxide coatings, as for instance those of thorium, zirconium, magnesium or yttrium may be used.
- mixtures of oxides and metals which react in a redox-type of reaction, converting a metal to an oxide and an oxide to a metal, forming metal-oxide mixtures into metaloxide or intermetallic-oxide or cermets or the like, as for instance may be used.
- metal oxides and reducing agents such as boron, silicon, nitrogen, sulfur, phosphorus or the like.
- metals and nonmetals such as boron, silicon, nitrogen, sulfur, phosphorus or the like.
- metal hydrides alone or in mixture with other materials, such as metal oxides and the like.
- These finely divided components should preferably be in the form of fine or superfine particles having, for example, a particle size below 200 mesh and preferably below 325 mesh, and most preferably below microns.
- the concentration of the fine or superfine particles in the slip may vary between about 40 weight percent and 99 weight percent, and preferably between 50 weight percent and 98 weight percent.
- the slip must additionally contain a binder which is capable of ultimately binding the subparticles together into the flame spray particles of the required strength and crush resistance.
- any material which can be dissolved or suspended in the mother liquid of the slip and which when dried will form a film and/or adhere to the material being agglomerated can be used as a binder providing that the same is sufficiently hard and tenacious to form an agglomerate of the required strength and hardness.
- film-forming organic resins which are soluble in the liquid of the slip may be used.
- Examples of these include polyvinyl alcohol, gum arabic and other natural gums, carboxy methyl cellulose salts, polyvinyl acetate, methyl cellulose, ethyl cellulose, polyvinyl butyral dispersions, protein colloids, acrylic resin emulsions, ethylene oxide polymers, water-soluble phenolics, wood extracts such as sodium, ammonium, or calcium lignin sulfonates, sodium,
- ammonium, potassium or propylene glycol alginates, various flour and starches are ammonium, potassium or propylene glycol alginates, various flour and starches.
- a potential binder-material combination can be selected and a small quantity of a test slip formulated, including in the slip any additive required for specific purpose and compatible with the binder, i.e., wetting agent, suspending agent, deflocculents, etc., the need for which is determined by observation during the mixing and evaluation of the slip.
- the binder must not be precipitated from solution by any additive or the solid; the solids must remain reasonably well suspended and completely dispersed in the liquid; the slip must not gel nor should the solids precipitate out as a solid cake; nor should there by any unusual chemical reaction between ingredients in the slip such as to result in the evolution of a gas.
- a qualitative measure of the effectiveness of the binder in cementing the particles to each other can be made by drying a film of the slip on a glass microscope slide and judging the hardness abrasion resistance of the composite film, the adhesion of the binder to the solid particles, and, by destructively abrading the dried film gross segregation of the binder from the solids in drying. Relative film hardness for various binder concentrations is very simply determined in this manner.
- inorganic binders such as sodium silicate, boric acid, borax, magnesium or other soluble carbonates, nitrates, oxalates, or oxychlorides may be used.
- binders may be chosen to perform auxiliary functions, or to impart additional desirable characteristics to the flame spray powder.
- pigments or dyes may be added to the binder or to the slip for ultimate incorporation in the dried binder in order to permit color coding of the flame spray powder.
- hydrocarbon binders may be chosen which will produce a protective inert coating or reducing atmosphere adjacent the melting or reacting particles during the flame spraying in order to suppress such oxidation. If it is desirable to add a further element or prevent loss of an element in the flame sprayed coating, a binder may be selected which will perform this function.
- a carbon-containing binder such as an organic binder
- Binders which will decompose to form a reducing atmosphere or containing reduction agents may be used in connection with practically all metal or alloy components in order to reduce the oxide films inherently present on the subparticle surfaces and thus improve consolidation, bonding, alloying, or reaction between constituents as the case may be.
- the binder may additionally be chosen to rapidly decompose in the flame generating the gas or vapor in order to, in effect, rapidly break up the agglomerated flame spray particles in the flame into a number of smaller consolidated, fused or reacted particles, which often are desirable for producing denser coatings. Binders may also be chosen which will decompose in the flame to form a protective atmosphere adjacent the melting particles in order to minimize or prevent hardening of susceptible metals, such as molybdenum, tungsten, tantalum, or niobium by contaminants such as oxygen, nitrogen, or carbon.
- susceptible metals such as molybdenum, tungsten, tantalum, or niobium by contaminants such as oxygen, nitrogen, or carbon.
- binder materials which act as, or which contain, fluxes such as sodium silicate, boric acid, borax or the like, may be used to perform a fluxing function in order to aid interparticle cohesion, adhesion to the substrate, and produce a superior coating of lesser porosity and higher hardness.
- the binder material should be present in a concentration in the slip to form ultimate dried binder content in the particles of up to 10.0 weight percent, or preferably 0.1 to 5.0 weight percent.
- concentrations of up to 10.0 weight percent, or preferably from 0.1 to 5.0 weight percent are generally required in the slip, based on the fine starting powder contained in the slip.
- the slip may contain auxiliary agents, such as plasticizers, wetting agents, deflocculants, suspending agents, preservatives, corrosion inhibitors, antifoam agents or defoamers, deoxidants and/or oxidizing agents when required.
- plasticizers are preferable in connection with binder materials which form hard, brittle films or which may tend to crack when drying, as for example sodium carboxymethylcellulose.
- plasticizers include glycerine, ethylene glycol, triethylene glycol, dibutyl phthalate, diglycerol, ethanolamines, propylene glycol, glycerol monochlorohydrin, polyoxyethylene aryl ether, etc. These plasticizers are generally used in amounts of 1 weight percent to 50 weight percent and preferably 5 weight percent to 30 weight percent, based on the dry binder materials.
- suspending agents may be desirable to prevent premature settling of the solids in the slip.
- high molecular weight water-soluble synthetic resins or gums as for example sodium carboxymethylcellulose of molecular weight 200,000, methyl cellulose of molecular weight 140,000, or polymers of ethylene oxide of molecular weight higher than around 125,000, may be used.
- sodium carboxymethylcellulose of molecular weight 200,000, methyl cellulose of molecular weight 140,000, or polymers of ethylene oxide of molecular weight higher than around 125,000 may be used.
- only relatively low concentrations ranging from a few parts per million to a few weight percent based on the fine starting powder contained in the slip, are required.
- Deflocculating agents may be used to aid in the slip formation and to prevent agglomeration in the slip.
- these include sodium hexametaphosphate, sodium molybdate, tetrasodium pyrophosphate, ammonium citrate, ammonium oxalate, ammonium tartrate, ammonium chloride, monoethylamine, etc.
- Conventional amounts as are used in forming suspensions and colloids may be used which, for example, may range from zero to 1.0 weight percent, and preferably from 0.05 to 0.2 weight percent.
- Wetting agents may also be used to aid in maintaining the solid suspension in the slip.
- These are the conventional synthetic detergents, such as alltylaryl sulfonates, sulfates, soaps, and the like, which may be used in the conventional quantities, for example ranging from 1 p.p.m. to 10.0 weight percent.
- binder materials may be susceptible to bacterial degradation or mold growth during storage, in which case it may be desirable to add a preservative to the binder material prior to incorporation in the slip, or the slip itself.
- a preservative such as sodium benzoate, phenol, or phenol derivatives, formaldehyde, merthiolate, etc. may be used in the conventional amounts and generally between about 0.1 and 0.5 weight percent of the initial binder solution. It may be preferable to use nontoxic preservatives due to the danger of decomposition in the flame.
- the binder In connection with fine powder materials which are susceptible to corrosion, or in connection with which the binders show a corrosive action, the binder should additionally contain conventional anticorrosion agents in conventional amounts.
- conventional antifoaming agents or defoamers may be added in the conventional amounts, as for example from 0.1 p.p.m. to 200 p.p.m.
- miscellaneous additives may be included in the slips for specific effects in the production or handling of the slip the slip or in the ultimate flame spraying of the powder produced, as for example chemical activators which will aid in the sintering of high melting refractory materials.
- chemical activators which will aid in the sintering of high melting refractory materials.
- chlorine or a chlorine-generating compound may be added to enhance the sintering of the carbides.
- Hydrophobic binders may be used in connection with MgO as water vapor enhances sintering of this material.
- Conventional acids or bases may be added as buffering agents to control the pH of the slip.
- the slip is simply formed by mechanically mixing the liquid, fine powder and the additives, with sufficient agitation to form a uniform suspension.
- the slip is then pumped into a conventional spray dryer where it is atomized and spray-dried.
- the heavier particles recovered from the bottom of the tower are used as the flame spray powder while the smaller particles which are also recovered from the spray drying may be reconstituted into the slip and again passed through the device.
- the slip is made up in the mixing tank 1, as described, and pumped by the metering pump 2 to the atomizing head 3 of the spray dryer tower 4. Atomizing air is passed into the atomizing head 3 from the compressor 5. The slip is atomized into the fine spray 6. Air is pumped by the fan or ventilator 7 through the heater 8, as for example a conventional combustion heater, into the top of the spray tower and passes downward as is indicated at 9, drying the atomized slip into the agglomerated flame spray particles which fall the bottom of the tower and are collected in the collector to. The gas is exhausted at 11 through the cyclone separator 12, in which the finer suspended particles are separated and recovered in the collector 13.
- the spraydryer may be operated in any of the conventional elevated temperatures and gas flow rates, as for example drying gas inlet temperatures between about 400 F. and 800 F. and preferably between 500 F. and 700 F.
- the liquid slip is generally evaporated at a rate between 2 and l2 gallons per hour, and preferably between 2.5 and 8 gallons per hour, based on a drying gas outlet temperature of 225 F. to 400 F. and preferably from 250 F. to 350 F.
- the flame spray powder in accordance with the invention has a general overall spheroid shape.
- Some of the spheroids are somewhat collapsed, i.e. toroidal or donut shaped, and the term spheroid" as used herein and in the claims includes this collapsed form of the spheroid, as well as other somewhat distorted spheroid shapes.
- These powders as compared with the conventional flame spray powders, are unusually free flowing and may be handled in all of the conventional powder type flame spray equipment without difficulty.
- the powder may be produced at a substantially lower cost than was previously'possible and quite surprisingly shows superior characteristics when sprayed, allowing for example a higher spray rate and a substantially improved deposit efficiency.
- the invention further allows almost unlimited possibilities of combining desired components into integral individual powder particles, which was not previously possible.
- the combined component particles in accordance with the invention show many advantages over the prior art mixtures or conventional aggregates or coated powders, having a uniform distribution of the constituents and very intimate and close contact with each other. In the spraying process this allows complete alloying, solutioning, or reacting of the components, allowing the formation of a much more homogeneous and uniform coating.
- the constituents of the composite particles are materials which will form a a cennet, the ceramic and other phases of a very fine size are uniformly distributed.
- coatings produced from the spray dried powder particles in accordance with the invention often show higher density and abrasion resistance than those produced by the conventional powders of the same type. The unusual characteristics and flowability not only allow for better handling in the flame spray equipment but also allow for better screening and classification in order to obtain extremely uniform size cuts.
- the powders may generally be used as produced, with the binders remaining soluble in the particular liquid solvent of the slip from which they were formed, it is also possible to insolubilize same by a curing, cross-linking, or tanning treatment.
- the particles may initially be treated with a dilute alcoholic solution of chromic nitrate followed by removal of the excess solution and drying.
- lnsolubilization may also be effected by treatment with concentrated solutions of dichromates, followed by exposure to actinic, such as ultraviolet light.
- the dichromates may, for example, by any of the alkaline or metal dichromates, such as ammonium, sodiurn, potassium or cupric.
- lnsolubilization may also be effected by treatment with copper ammonium hydroxide, as for example prepared from copper sulfate, ammonium hydroxide, and sodium hydroxide.
- the compressive strength tester is a modified analytical balance on which the pan on one side was replaced by an anvil atop the horizontal beam and a counterweight, the sum weight of which exactly equalled the weight of the pan removed.
- a shallow depression on the upper surface of the anvil allows precise orientation of the particle to be tested.
- An adjustable platen is mounted above and closely adjacent to the anvil surface; the height is adjusted such that, with the particle to be tested in position, the zero-indicating arm of the balance is at zero on the reference scale when the particle is just contacting the platen face.
- the load is then applied gradually and without shock by unwinding a fine chain from a calibrated rotating cylinder into the other pan of the balance, the calibrations showing the weight of chain deposited on the pan.
- Compressive failure of the particle is indicated by movement of the zero-indicating arm relative to the reference scale.
- the weight of chain required to do this is directly read from the calibrated cylinder.
- the particles must thus be substantially stronger and have a higher crush resistance than powders produced for most powder metallurgy purposes where the same are to be pressed into shapes or fonns.
- Particles, such as ceramic particles intended for initial press forming, must have a relatively low crush resistance in order to be pressed into a green form of uniform consistency.
- the powder in accordance with the invention may, of course, be sprayed in any desired mixture or combination with other powder produced in accordance with the invention or any known or conventional flame spray powder.
- Tungsten Carbide'cobalt Cermet Powder Tungsten carbide (WC) powder of 1.3-1.6 micron average Fisher subsieve Size (FSS) particle size and metallic cobalt powder of 2 micron average (FSS) particle size were blended in the proportion 88 weight percent WC:l2 weight percent Co.
- the blend of materials was then dry ball milled according to standard practice in the industry, so that the cobalt was smeared onto the WC particles and each WC particle was, in effect, clad with cobalt.
- a gum arabic binder was dissolved in water to form a concentrated solution containing 30 weight percent gum arabic and 70 weight percent water. Phenol in the proportion of 0.05 weight percent, based on the total weight of the solution, was added as a preservative for the binder concentrate.
- Sodium carboxy methyl cellulose of very high (approximately 200,000) molecular weight was used as a suspending agent.
- Sodium hexametaphosphate (Calgon) was used as a dispersing and deflocculating agent. A concentrated solution, 25 weight percent of the solid in 75 weight percent of water, was prepared in advance.
- Sodium lauryl sulfate (Proctor and Gamble Orvus WA Paste, 34 weight percent solids in H,O) was used as a wetting agent. Because of its high efiiciency and the need in ppm. only, dilute solution was prepared by dissolving 0.3 g. of the commercial paste in 100 g. of water, resulting in a solids concentration of 0.1 g. per I00 grams of water.
- a slip was formulated according to the following table, using the prepared concentrates described above, where applicable, and in the proportions indicated.
- the rated capacity of this dryer was approximately 20 lb./hr. of chamber product based on drying an Al,0, slip containing 60 percent to percent by weight of solids together with a suitable binder system; the chamber product consists of approximately percent of the total product, the remaining 25 percent being deposited in the cyclone collector and usually consists of fines.
- Heated air was introduced in a cyclonic flow pattern at the top of a vertical straight-cylindrical drying chamber.
- the slip is atomized into droplets near the bottom of the drying chamber and directed upwards along the vertical centerline by a blast of compressed air. The particles travel twice through the drying chamber upwards against the flow of heated air and then downward to the bottom, and then settle by gravity into a collecting receptacle.
- the Hall Flow Rate of the 325 mesh cut of the chamber product was 2.99 g./second and the apparent density (not vibrated) was 3.80 g./ml. Compressive strength of 60 +80 mesh particles was 10.0 grams.
- a 325 mesh cut from the chamber product was flame sprayed, using a Metco Type 2M plasma flame spray gun, using argon plasma gas at lp.s.i., 100 SCFH, hydrogen plasma gas at 50 p.s.i., 2.5 SCFH, and argon carrier gas-at l00p.s.i., 15 SCFH.
- argon plasma gas at lp.s.i., 100 SCFH
- hydrogen plasma gas at 50 p.s.i., 2.5 SCFH
- argon carrier gas-at l00p.s.i., 15 SCFH With a Type ES nozzle, input power was 500 amperes at 43 volts, spray distance was 3 inches, and the spray rate was 8.2 lblhour.
- the same powder was flame sprayed using a Metco Type 5 P ThermoSpray gun with a type P70 nozzle, 012 powder flow meter valve, at 4-5 spray distance, using hydrogen at 31 p.s.i., 315 SCFH, and oxygen as the combustion supporting and carrier gas at 31 p.s.i., 54 SCHFH.
- the spray rate was 8.7 lb./hr. of powder.
- 50 weight percent of the -l40 +325 mesh cut of the chamber product was blended with 50 percent of a -140 +325 mesh cut of a conventional spheroid powder of the self-fluxing, hard-facing, alloy type, to make a powder blend equal in proportion and chemistry to Metco 31C, which uses conventional cobalt-bonded tungsten carbide powder of the same chemistry and particle size range as the spray dried material.
- the blended material was flame sprayed, using a Metco Type 2 P ThermoSpray gun with a Type P7 nozzle, 2 powder flow meter valve, using acetylene at 10 p.s.i., 25 SCFH, and oxygen at 12 p.s.i., 35 SCFH, with acetylene as the carrier gas, and at 9.5 lb./hr.
- the resultant coating was a fully fused, pore-free, homogeneous mixture of the coating ingredients and fully fused to the substrate.
- the coating system was then fused, the overcoat material being absorbed by the first coating during the fusing, to effectively fill all of the pores and weld the whole to the substrate. The result was a homogenous mixture of the coating ingredients, very high in WC content, and fully fused to the base.
- Tungsten Carbide Cobalt Cermet Powder Tungsten carbide powder of 1.3-1.6 micron average (FSS) particle size and metallic cobalt powder of 2 microns average (FSS) particle size were blended in a simple mixture, in the proportion 88 weight percent WC:l2 weight percent Co., for incorporation in a slip as a simple mixture of powders.
- the preblending was accomplished as a convenience only in preparing powders for a number of experimental batches; but could be added to the slip without prior mixing.
- binders The binders, suspending agents, deflocculent (dispersing agent) agent) and wetting agent, etc. were prepared for use in concentrated. solutions, the same as in example l.
- a slip was fonnulated according to the following table, using the prepared concentrates where applicable, and in the proportions indicated.
- the slip was blended in the same manner as described in example Specific gravity of the slip was 3.84 g./ml.
- the slip was spray dried in the same equipment and in the same manner as described in example 1.
- the cyclone product comprised 16 percent of the total collected and was essentially 325 mesh size.
- the Hall Flow Rate of the l40+325 mesh size cut of the chamber product was 1.95 g./second and the apparent density (not vibrated) was 2.62 g./ml. Compressive strength of 60+80 mesh particles was 17.0 grams.
- a 325 mesh cut from the chamber product was flame sprayed with the Metco Type 2M plasma flame spray gun, using the argon/hydrogen and nitrogen/hydrogen plasma gases, and with the Metco Type 5P ThermoSpray gun as described in example I. In all three cases excellent hard, dense, adherent, and wear-resistant coatings were deposited.
- EXAMPLE 3 Self-Fluxing, Hard-Facing Alloy Powder
- the binders, suspending agents, wetting agents, and deflocculent were prepared for use in concentrated solutions and/or dispersions as described in example 1, or used dry.
- the plasticizer, glycerin, was a liquid as received.
- a slip was fonnulated according to the following table, using the prepared constituents where applicable, and in the proportions indicated.
- the powder was of the following composition:
- the slip was spray dried in the same equipment and in the same manner as described in example I.
- the following machine parameters were used:
- the cyclone product comprised 19 percent of the total product and was essentially 325 mesh.
- the Hall Flow Rate of the l40+325 particle size cut of the chamber product was 1.24 g./second and the apparent density (not vibrated) was 1.66 g./ml.
- the Hall Flow Rate of the 325 mesh cut of the chamber product was 0.86 g./second and the apparent density (not vibrated) was 1.68 g./ml.
- Compressive strength of 60+80 mesh particles was 6.0 grams.
- the l40+325 cut of the chamber product was flame sprayed, using a Metco Type 5P ThermoSpray gun with a Type P7G nozzle, 0ll powder flow meter valve, at 7 inches spray distance using acetylene as the combustible and carrier gas at 12 p.s.i., 33 SCFl-l, and oxygen at 21 p.s.i., 60 SCFl-l.
- the spray 'rate was 9.2 lb./hr. After deposition of the coating on the mild steel substrate, which previously had been gritblasted to improve adhesion of the as-sprayed coating, the whole was heated to around l,900-2,000 F to fuse the particles in the coating to each other and the coating to the substrate.
- the 325 out of the chamber product was flame sprayed the same as the previous l40+325 cut except that a Type P7B nozzle was used and cooling air surrounded the flame of the gun. Spray rate was 7 lb./hr.
- the result was a smooth, even layer of a hard, weanresistant overlay which was welded to the substrate.
- composition of the alloy fused to the substrate surface was typically:
- Composite Mullite Powder Fine Mullite, 3A1,0,2Si0 can be formed into particles suitable for flame spraying by the spray drying method, by agglomerating fine particles of mullite per se. lt can also be formed as a composite by combining available and cheap commodity raw materials, such as superfine molochite and high purity A1 0, in the correct proportion in the spray dried powder.
- Molochite is a naturally occurring mineral of the following typical composition:
- binders, suspending agents, deflocculants, wetting agents, etc. were prepared in concentrated solutions, the same as in example i.
- a slip was formulated according to the following table, using the prepared concentrates where applicable, and in the proportions indicated:
- the slip was blended in the same manner as described in example l. Specific gravity of the slip was 1.7 g./ml.
- Type 21 Type 51 Type 2M Nozzle PTC PTG EII Cnt'riet'gas Oxygen Nitrogen 50/15 Oxygen pr re/llow, s H1 14/47 Acetylene pr sure/llon 12/28 13/35 Nitrogen pressure/flow, 50/ (5 Hydrogen pressure/lion 50/15: Voltage r l n Ainperes .103
- the following table compares spray rates and deposit efficiencies for spray dried composite mullite powder as compared with Metco XPl 146 conventional mullite powder.
- the conventional material was heavily contaminated with metal, and the spray dried mullite coatings produced were vastly superior to the conventional mullite coatings.
- the cyclone product comprised 21 percent of the total product and had a particle size distribution as follows:
- ThermoS- Optimum particle size based on the spray rates and deposit efficiencies for ThermoSpray equipment is either 325 or 270 mesh, and for plasma flame is -230 or 270 mesh.
- the poor flowability of the conventional powder is also readily apparent from the data shown in the above table.
- the spray dry spray rate was 2.8 times that of the conventional material and deposit efficiency, even at the higher rate, is L46 times that of the conventional material.
- feed rate was 3.2 times that of the conventional material and deposit efficiency is slightly more than twice that of the conventional material.
- ThermoSpray 5P feed rate was up to 5 times that of the conventional material and deposit efficiency is more than twice that of the conventional material, even at the vastly higher spray rate.
- Nickel-aluminum composites corresponding to the known Metco 404 (nominally aluminum clad with weight percent Ni) and Metco 450 powder (nominally Ni clad with 5 weight percent Al) can be manufactured using this method.
- Ni-Al powders containing 5 weight percent Al and 7.5 weight per cent Al have been manufactured by spray drying. The spray dried composites result in the formation of an homogenous reaction product by virtue of the homogenous mixture of very fine particles.
- binders The binders, suspending agents, deflocculent, wetting agent, etc., were prepared for use in concentrated solutions, the same as in example 1.
- a slip was formulated according to the following table,
- the slip was blended in the same manner as described in example 1. Specific gravity of the slip was 2.93 g./ml.
- the slip was spray dried in the same equipment and in the same manner as described in example 1.
- the cyclone product comprised 7.5 percent of the total and was essentially 325 mesh.
- Compressive strength of 60+80 mesh particles was 3.6 grams.
- the l 7 325 cut of the chamber product was flame sprayed with a Metco Type 2P ThermoSpray gun, using a Type P7 nozzle, acetylene as the combustible and carrier gas at 10 p.s.i., 25 SCFH, and oxygen at 12 p.s.i., 35 SCFH. Spray rate was approximately 6 lb./hr.
- the nickel and aluminum particles in the composite particle combined exothermically in the flame to produce an homogenous particle consisting of the nickel aluminides, the heat generated aiding in making the particles self-bonding to the clean, smooth surface of the steel substrate. There was practically no smoke" produced in spraying the spray-dried powder.
- the standarized Coating is sprayed on flat end of l inch diameter rod. Another rod end is bonded to the sprayed coating. Rods are pulled apart in a Universal Testing Machine, and breaking strength determined. (Metco Lab Report 0106,
- the minimum bond/coating strength was determined as being 3,280 p.s.i., the breaking strength with failure occurring at the bond coattop coat interface.
- Compressive strength of 60+ mesh particles was 3.6 grams.
- binders, suspending agents, deflocculent, etc. were prepared in concentrated solutions for use the same as in example A slip was formulated according to the following table, using the prepared concentrates, where applicable, and in the proportions indicated:
- the slip was blended in the same manner as described in example l. Specific gravity of the slip was 4.50 g./ml.
- the slip was spray dried in the same equipment and in the same manner as described in example 1.
- the following machine parameters were used:
- Compressive strength of the -60+80 mesh particles was 1.3 grams.
- ThermoSpray 2P 2 Deposit efliclency, percent Spray rate, #lhr.
- Hall flow Apparent rate of density of powder powder g./second g./m1.
- Binder wt. percent PVA. 1 wt. percent PVA- 2 wt. percent PVA. 3 wt. percent PVA.
- ZIOg Zirconia Powder Lime stabilized zirconia
- binders, suspending agents, deflocculents, etc. were prepared in concentrated solutions for use the same as in example l.
- a slip was formulated according to the following table, using the prepared concentrates where applicable, and in the proportions indicated.
- the slip was spray dried in the same equipment and in the same manner as described in example I.
- the following machine parameters were used:
- the Hall Flow Rate of the 2oo+32s cut of the chambe? product was L08 g./second and the apparent density was 1.35 g./ml. (not vibrated).
- the 325 out of the chamber product did not flow smoothly through the meter orifice of the Hall Flow Test Apparatus without vibration, so an accurate test of the flow rate could not be made; the apparent density (not vibrated) was 1.35 g./ml.
- Compressive strength of the -60+80 mesh particles was 3.5 grams.
- the 2 weight percent PVA bonded powder was ob- 1o served to have significantly more fully fused hollow particles than the 1 weight percent PVA bonded powder.
- the coating produced with l The results are the same except that the powder produced is colored orange, which aided in identifying it.
- EXAMPLE 9 EXAMPLE l6
- the slip from example 1 was spray dried in a pilot plant size spray dryer as manufactured by Bowen Engineering Inc., am 15 repeated except that welsh! Percent North Branch, New Jersey 08856
- the rated capacity of this borosiltcate glass based on the Cr O was included in the slip. dryer is 100 lbs/hour of chamber product based on drying an The result rezem'auy the Same eXcFPt that the A1203 slip containing 60 percent to 70 percent by weight of mate glass effectively bonded the subpart cles of Cr,O to each solids together with a suitable binder system.
- the results were othcf durmg flame Spraymg and m "npmvmg Pamdc to the Same particle cohesion in the coating, resulting in a harder, denser,
- EXAMPLE 10 40 Example 4 is repeated except that the subparticles of flame EXAMPLE spray material suspended in the slip consisted of 70 weight: Example 8 is repeated except that NiO with methyl cellu- Percent 9f 5 mixture of 8 and 2 weight Percent of z lose as the binder replaced the ZrO, and its binder in the slip. based on the 8 The results are essentially identical.
- Compressive strength of the 60+80 mesh powder particles is greater than 0.7 grams.
- EXAMPLE 18 The powder is flame sprayed in the same manner as in example 4. The result is a dense, adherent, abrasion-resistant coating consisting of essentially MgO but in which the TiO; combined with the MgO in the flame, permitting the deposition by enhancing the melting and coalescence of the MgO EXAMPLE l9 subparticles.
- Example 8 is repeated except that CeO, replaced the ZrO, in the slip.
- Example 8 is repeated except that TiO replaced the ZrO, in
- Example 2 is repeated except that boron carbide 8 C replaced the tungsten carbide and aluminum replaced the cobalt.
- Example 11 was repeated except that 0.1 weight percent of Example 2 is l'ePeated except that chwmillm carbide s sodium nitrite based on the solids contained in the slip was p aced the ungsten carbide and a nickel-chrome alloy added as an oxidizing agent. pH of the slip was buffered to 7.0, replaced th o alt. using sodium hydroxide before the addition of the nitrite to The results are e sential y h m prevent decomposition of the nitrite and evolution of the toxic EXAMPLE 22 Compressive strength of the 60+80 mesh particles was greater than 0.7 grams.
- Example 5 is repeated except that chromium replaced the The powder was flame sprayed in the same manner as examnickel incorporated in the slip in example 5.
- a flame spray powder the individual particles of which are of a substantially spheroid shape having a size between about 1 micron and minus mesh and formed of multiple subparticles bound together without fusion by a spray dried binder and having a crush resistance of at least 0.7 grams, substantially all of said subparticles having a size of the same order of magnitude below about 200 mesh.
- Flame spray powder according to claim 1 having a size between about 100 mesh and 3 microns.
- Flame spray powder according to claim 6 having a size of 20 mesh and 1 micron and in which said subparticles have a size below about 200 mesh.
- Flame spray powder according to claim I in which said binder contains a material capable of thermally combining with said subparticles upon flame spraying to form a flame sprayed coating.
- Flame spray powder according to claim 1 in which said subparticles are of at least two metals capable when melted together of exothermically reacting to form an intermetallic compound.
- Flame spray powder according to claim 1 in which said subparticles are tungsten carbide and cobalt and said binder is sodium carboxy methyl cellulose.
- a flame spray powder in which a flame spray powder is at least heat-softened in a heating zone and propelled onto a surface to be coated, the improvement which comprises utilizing a flame spray powder the individual particles of which are of a substantially spheroid shape having a size between about 1 micron and minus 20 mesh, and formed of multiple subparticles bound together without fusion by a spray-dried binder and having a crush resistance of at least 0.7 grams.
- said binder contains material capable of combining with the subparticles at the temperature in the heating zone to form the flame sprayed coating.
- a process which comprises spray drying a slip containing fine particles of a flame spray material and a binder to form spray-dried aggregate particles having a crush resistance in excess of about 0.7 gram, passing these spray-dried particles into a heating zone, heating the particles to at least heat-soi tened condition in the zone and propelling the heated particles onto a surface to form a coating.
- said organic binder is a member selected from the group consisting of polyvinyl alcohol, polyvinyl acetate, gum arabic, carboxy methyl cellulose salts, methyl cellulose, ethyl cellulose, and polyvinyl butyral dispersions.
- two different flame spray materials are materials capable of exothermically reacting with each other at the temperature in the heating zone to form an intermetallic compound.
- the slip additionally contains a material capable of thermally combining with the flame spray material to form a flame sprayed coating.
Abstract
The flame spraying of the flame spray powder which has been formed by spray drying of a slip or slurry of fine particles of a flame spray material. This flame spray powder has individual particles which are of substantially spheroid shape, of a size between about 20 mesh and 1 micron, and are formed of multiple subparticles bound together without fusion by a spray-dried binder and having a crush resistance of at least 0.7 grams. For the spray drying, fine particles of any known or conventional flame spray material or combination thereof, such as metals, ceramics, carbides, etc., suspended in a slip or slurry of a liquid, preferably water, with a suitable binder and preferable auxiliary agents, is atomized into a hot drying gas stream forming the spheroid larger composite particles.
Description
United States Patent [72] Inventor [21] Appl. No.
[22] Filed [45] Patented [73] Assignee [54] FLAME SPRAY POWDER AND PROCESS 35 Claims, 1 Drawing Fig.
[52] U.S.Cl ll7/l05.2, 117/100, 264/12, 264/117, 75/.5,1l7/93.1 [51] Int. Cl 844d U097 [50] Field of Search 117/1052,
93.1, 100 M, 1001, 46 PS; 264/12, 13, 117, 5,6,7,
14; 75/.5, 211, .5 A, .5 AA, .5 AB, .5 B, .5 BA;
3,322,515 5/1967 Dittrich et a1 29/192 X 3,338,688 8/1967 Longo ll7/l05.2 X 3,372,054 3/1968 Wishnie et al.. 75/.5 (B) X 3,373,119 3/1968 Krystyniak 75/.5 UX 3,378,392 4/1968 Longo 75/.5 (B) X 3,419,415 12/1968 Dittrich 117/100 Primary ExaminerAlfred L. Leavitt Assistant Examiner.lohn H. Newsome Attorney-Burgess, Dinklage and Sprung ABSTRACT: The flame spraying of the flame spray powder which has been formed by spray drying of a slip or slurry of fine particles of a flame spray material. This flame spray powder has individual particles which are of substantially spheroid shape, of a size between about 20 mesh and 1 micron, and are formed of multiple subparticles bound together without fusion by a spray-dried binder and having a crush resistance of at least 0.7 grams. For the spray drying, fine particles of any known or conventional flame spray material or combination thereof, such as metals, ceramics, carbides, etc., suspended in a slip or slurry of a liquid, preferably water, with a suitable binder and preferable auxiliary agents, is atomized into a hot drying gas stream forming the spheroid larger composite particles.
FLAME SPRAY POWDER AND PROCESS This invention relates to an improved flame spray powder, to a process for its production, and to a flame spray process utilizing the same.
Flame spraying involves the feeding of a heat-fusible material into a heating zone wherein the same is melted or at least heat-softened and then propelled from the heating zone in a finely divided form, generally onto a surface to be coated. The spraying is eflected utilizing a device known as a flame spray gun. The material may initially be in the form of a powder which is designated as a flame spray powder, and the guns utilized for spraying the material initially fed in this powder form are known as powder-type flame spray guns. In powder type flame spray guns, the flame spray powder, usually entrained in a carrier gas, is fed into the heating zone of the gun which is most commonly formed by a flame of some type. The powder is either melted or at least the surface of the grains heat-softened in this zone, and the thus thermally conditioned particles are propelled onto a surface to provide the coating. While not required, a blast gas may be provided in order to aid in accelerating the particles and propelling them toward the surface to be coated and/or to cool the workpiece and the coating being fonned thereafter. The heat for the heating zone while most commonly produced from a flame Tcaused by the combustion of a fuel, such as acetylene, propane, natural gas or the like, using oxygen or air as the oxidizing agent, may also be produced by an electric arc flame or plasma flame, or any other known heating device.
Flame spraying in the initial stages of its commercial development was mostly used for spraying metals and still is often referred to as metallizing, though the same is now used for spraying a much wider group of materials, including higher melting point or refractory metals, ceramics, cermets,
I carbides, and other metal compounds.
, A powdered heat-fusible material in order to be satisfactorilly sprayed and thus considered a flame spray powder must .have certain physical characteristics with respect to size, lphysical strength, flowability, etc. The powder must be suffrgciently flowable to be passed through the flame spray gun without difficulty or clogging, and this flowability not only depends on size, absence of caking materials, such as excess :moisture, but on shape and surface characteristics. in order to produce a satisfactory coating the powder must have a specific {size range, as for example, between 20 mesh and 1 micron, |and preferably between 100 mesh and 3 microns, and the individual particles should not vary too greatly in their size distribution, i.e., the powder should be free of excessive fines and larger particles. The uniformity and quality of the coating I formed by flame spraying is often dependent on the uniformity {of size of the individual particles in the powder. During spraying the kinetic propelling of the particles and its contact with fluid, including combustion fluids and propelling fluids, often causes a classifying efiect which adversely affects the homogeneity and uniformity of the coating, and the presence of excess fines may change the nature of the coating, producling for example excessive oxides or the like.
[ in obtaining suitable commercial flame spray powders exltensive screening and classifying techniques are generally required and only a relatively small cut of the available .jpowder material is generally suitable for marketing as a flame spray powder. In most instances powders are formed by reducling, as for example, milling a larger mass which results in a 'rather wide range of particle sizes which must then be screened to obtain operative size range cuts. This is generally true, irrespective of the source of the mass which is milled, in-
cluding pressed, cast, calendered or extruded masses.
One object of this invention is the production of an improved flame spray powder. This and still further objects will become apparent from the following description read in conjunction with the drawing which is a flow sheet illustrating the process for producing powders in accordance with the invention.
In accordance with the invention 1 have discovered that a superior and improved flame spray powder may be produced utilizing spray drying techniques. In accordance with the invention finely divided flame spray material suspended in a slip or slurry of liquid, preferably water, with a suitable binder and preferable auxiliary agents, is atomized and the atomized suspensiondried in a hot gas stream, forming the coarser flame spray powder, the individual particles of which are of substantially spheroid shape, have a size between about 20 mesh and 1 micron, and are formed of a multiple number of subparticles bound together without fusion by the spray dried binder, and which have a crush resistance of at least 0.7 grams.
As the starting finely divided material utilized in the formation of the slip, any of the known or conventional flame spray materials, or any known combination thereof, may be used. In addition to the conventional metals or alloys or metal mixtures, which will ultimately form alloys or semialloys when flame sprayed, there may be mentioned oxides, as for example refractory oxides, such as alumina Al,0,, Beryllia BeO, Ceria CeO,, Chromia CR,O,, cobalt oxide C00, gallum oxide 021,0 hafnia l-lfO,, magnesia MgO, nickel oxide NiO, tantalum oxide TA,O thoria ThC,, Titania TiC,, yttrium oxide Y,O zirconia ZrC,, vanadium oxide V0, niobium oxide NbO, manganese oxide MnO, iron oxides Fe,0,, zinc oxide ZnO; complex aluminates such as BaO-Al,O,, i.e. Bao'Al O CeO'Al,O,, CoOAl,O,, Gd,O,-Al,0,, K,O-Al,0,, Li',0- Algono's A1203, Mgo'Algoa, NiO'AlgOg, srgoa'Algoa. sro'Algoa, SYO'2A1205, ZYgOa'AlgOa, ZnO-A1,0,; zit conates such as CaO-ZrO SrO-ZrO,, BaO'ZrO,; titanates such as A1 0 'TiO 2Ba0-Ti0 CaO'TiO,, HfO,-Ti0,, 2M- gO-TiO,, SrO'TiO chromites, such as CaO-Cr,0,, ce'oc o, MgO'Cr o FeO-Cr,0,; phosphates such as A1,o,-P,0., 3BaO-PO 3CaO'P O 3SrO'P O and other mixed oxides, such as La O -Fe 0;, MgO'Fe,O 2MgO'GeO,, CaO-HfO,, La O -2HfO Nd O -2HfO 6BaO-Nb O Dy O -Nb O 2MgO-SnO BaO-ThO SrO-UO CaO-UO, CeO -Cr O silicates such as 3Al O.-,-2SiO (mullite), BaO-2SiO- BaO-Al O -2SiO BaO-TiO -Si0 2CaO-SiO Dy203- SiO Er O 'SiO ZrO -SiO(zircon), 2MgO-SiO ZrO-Zr- O -SiO carbides, such as titanium carbide TiC, zirconium carbide ZrC, hafnium carbide HfC, vanadium carbide VC, niobium carbide NbC, tantalum carbides TaC, Ta C, chromium carbides Cr C Cr C Cr C molybdenum carbides Mo C, MoC, tungsten carbides WC, W C, thorium carbides ThC, Th0 complex carbides, such as WC+W C, ZrC+ TiC, HfC, NbC, TaC, or VC, TiC+l-lfC, TaC, NbC, or VC; VC+NbC, TaC, or l-lfC; HfC+TaC or NbC; HbC +TaC; W WC+TaC, NbC, ZrC, TiC; WC+TiC or ZrC; TiC+Cr3C- TiC+mo C.
Borides, such as TiBg, ZrB; HfB 6mm, borides of-V, mm srm bbriaes oTTafborids'bf Cr, bbFidesofMo, borides of W, borides of the rare earth metals;
Silicides, such as silicides of Ti eg Ti,Si
silicides of Zr eg Zr,Sr
silicides of Hf eg Hasi,
silicides of V eg V;,Si or VSi,
silicides of Nb cg Nb sr or NbSi,
silicides of TA eg Ta Si or TaSi,
silicides of Mo eg MoSi,
silicides of W eg WSi silicides of Cr eg Cr Si or Cr Si,
silicides of B eg B,Si or B, Si
silicides of the rare earth metals.
Nitrides such as boron nitrides and silicon nitrides.
Sulfides such as MgS, BaS, GrS, TiS ZrS, ZrS,, HfS, VS, V 8 CrS, M05 W8 the various rare earth sulfides;
Metalloid elements, such as boron, silicon, germanium.
Cermets, such as WC/Co, W,C/Co, WC+W,C/Co, Cr/Al,0,,,.- $6 0 NiAl/Al,0,, NiAl/ZrO Co/Zr0,, Cr/Cr,C,,O Co/TiC, Ni/TiC, Co/WC-i-TiC, Cr-l-Mo/Al f Ni, Fe and/or their alloys, Cu and/or its alloys such as aluminum bronze, phosphor bronze, etc., with the disulfides or deselenides of Mo, W, Nb, Ta, Ti, or V, or boron nitride for self-lubricating coatings with very low friction coefficient.
Cermets which contain an active metal from the group composed of Ti, Zr, Ta, Cr, etc., or hydrides or other compounds or alloys of these active metals, which will alloy with the metal phase of the cermet and promote adhesion of the metal phase to the refractory phase by promoting wetting" of the surface of the refractory phase.
Cermets, for instance those containing a metal and a carbide as the refractory phase, which also contain free carbon, such as high purity graphite or the like, which will effectively reduce or prevent oxidation of the carbide phase and reduce solutioning of the carbide phase in the metal binder phase.
Mixtures of any desired combinations of these or any known flame spray material may be used for any purpose, including for the formation of synergistic composites of the type mentioned in U.S. Pat. No. 3,254,970 or combinations which will exothermically react to form an intermetallic compound as disclosed in the aforesaid patent and U.S. Pat. No. 3,322,515. In addition, combinations which when flame sprayed, will endothermically react, or combinations or components which will decompose to form desired coating materials, as for example carbonates, oxalates, nitrates or oxychlorides which will decompose to form oxide coatings, as for instance those of thorium, zirconium, magnesium or yttrium may be used. Furthermore, mixtures of oxides and metals which react in a redox-type of reaction, converting a metal to an oxide and an oxide to a metal, forming metal-oxide mixtures into metaloxide or intermetallic-oxide or cermets or the like, as for instance may be used.
There also may be mentioned mixtures of metal oxides and reducing agents, metals and nonmetals, such as boron, silicon, nitrogen, sulfur, phosphorus or the like. Still further, there may be mentioned metal hydrides alone or in mixture with other materials, such as metal oxides and the like.
These finely divided components should preferably be in the form of fine or superfine particles having, for example, a particle size below 200 mesh and preferably below 325 mesh, and most preferably below microns.
These fine or superfine particles are then mechanically mixed with water or another liquid and the binder forming a suspension which is termed a slip. The concentration of the fine or superfine particles in the slip may vary between about 40 weight percent and 99 weight percent, and preferably between 50 weight percent and 98 weight percent.
While water is the preferable liquid used to form the slip, due to its ready availability, low cost, nonflammability, high evaporation rate at relatively low temperature, relative inertness and ability to dissolve or suspend useful binders, it is also possible to use other liquids, such as hydrocarbon solvents, alcohols or other organic liquids, alone or in admixture. When using, however, flammable liquids, care must be taken to avoid combustion or explosion in the drying.
The slip must additionally contain a binder which is capable of ultimately binding the subparticles together into the flame spray particles of the required strength and crush resistance.-
As a binder any material which can be dissolved or suspended in the mother liquid of the slip and which when dried will form a film and/or adhere to the material being agglomerated, can be used as a binder providing that the same is sufficiently hard and tenacious to form an agglomerate of the required strength and hardness. In general, film-forming organic resins which are soluble in the liquid of the slip, may be used. Examples of these include polyvinyl alcohol, gum arabic and other natural gums, carboxy methyl cellulose salts, polyvinyl acetate, methyl cellulose, ethyl cellulose, polyvinyl butyral dispersions, protein colloids, acrylic resin emulsions, ethylene oxide polymers, water-soluble phenolics, wood extracts such as sodium, ammonium, or calcium lignin sulfonates, sodium,
ammonium, potassium or propylene glycol alginates, various flour and starches.
Empirically, a potential binder-material combination can be selected and a small quantity of a test slip formulated, including in the slip any additive required for specific purpose and compatible with the binder, i.e., wetting agent, suspending agent, deflocculents, etc., the need for which is determined by observation during the mixing and evaluation of the slip. The binder must not be precipitated from solution by any additive or the solid; the solids must remain reasonably well suspended and completely dispersed in the liquid; the slip must not gel nor should the solids precipitate out as a solid cake; nor should there by any unusual chemical reaction between ingredients in the slip such as to result in the evolution of a gas.
A qualitative measure of the effectiveness of the binder in cementing the particles to each other can be made by drying a film of the slip on a glass microscope slide and judging the hardness abrasion resistance of the composite film, the adhesion of the binder to the solid particles, and, by destructively abrading the dried film gross segregation of the binder from the solids in drying. Relative film hardness for various binder concentrations is very simply determined in this manner.
In addition to organic binders, inorganic binders, such as sodium silicate, boric acid, borax, magnesium or other soluble carbonates, nitrates, oxalates, or oxychlorides may be used.
In addition to serving strictly a binding function, binders may be chosen to perform auxiliary functions, or to impart additional desirable characteristics to the flame spray powder. Thus, for example, pigments or dyes may be added to the binder or to the slip for ultimate incorporation in the dried binder in order to permit color coding of the flame spray powder. If the flame spray material is prone to undesirable oxidation when flame sprayed, hydrocarbon binders may be chosen which will produce a protective inert coating or reducing atmosphere adjacent the melting or reacting particles during the flame spraying in order to suppress such oxidation. If it is desirable to add a further element or prevent loss of an element in the flame sprayed coating, a binder may be selected which will perform this function. Thus, a carbon-containing binder, such as an organic binder, may be used in order to introduce carbon to form a carbide or to prevent carbon depletion in the spraying of the carbide. Binders which will decompose to form a reducing atmosphere or containing reduction agents may be used in connection with practically all metal or alloy components in order to reduce the oxide films inherently present on the subparticle surfaces and thus improve consolidation, bonding, alloying, or reaction between constituents as the case may be.
The binder may additionally be chosen to rapidly decompose in the flame generating the gas or vapor in order to, in effect, rapidly break up the agglomerated flame spray particles in the flame into a number of smaller consolidated, fused or reacted particles, which often are desirable for producing denser coatings. Binders may also be chosen which will decompose in the flame to form a protective atmosphere adjacent the melting particles in order to minimize or prevent hardening of susceptible metals, such as molybdenum, tungsten, tantalum, or niobium by contaminants such as oxygen, nitrogen, or carbon. Still further, binder materials which act as, or which contain, fluxes such as sodium silicate, boric acid, borax or the like, may be used to perform a fluxing function in order to aid interparticle cohesion, adhesion to the substrate, and produce a superior coating of lesser porosity and higher hardness.
In the case ofspraying of oxides, such as ceramics, undesirable reduction may be prevented by including an oxidation agent, such as a nitrite, nitrate, or permangenate, in the binder or in the slip for depositing with the binder. In general, the binder material should be present in a concentration in the slip to form ultimate dried binder content in the particles of up to 10.0 weight percent, or preferably 0.1 to 5.0 weight percent. For this purpose concentrations of up to 10.0 weight percent, or preferably from 0.1 to 5.0 weight percent are generally required in the slip, based on the fine starting powder contained in the slip.
ln addition to the fine starting powder material, the liquid and the binder, the slip may contain auxiliary agents, such as plasticizers, wetting agents, deflocculants, suspending agents, preservatives, corrosion inhibitors, antifoam agents or defoamers, deoxidants and/or oxidizing agents when required. The use of plasticizers is preferable in connection with binder materials which form hard, brittle films or which may tend to crack when drying, as for example sodium carboxymethylcellulose. Examples of plasticizers include glycerine, ethylene glycol, triethylene glycol, dibutyl phthalate, diglycerol, ethanolamines, propylene glycol, glycerol monochlorohydrin, polyoxyethylene aryl ether, etc. These plasticizers are generally used in amounts of 1 weight percent to 50 weight percent and preferably 5 weight percent to 30 weight percent, based on the dry binder materials.
suspending agents may be desirable to prevent premature settling of the solids in the slip. For this purpose high molecular weight water-soluble synthetic resins or gums, as for example sodium carboxymethylcellulose of molecular weight 200,000, methyl cellulose of molecular weight 140,000, or polymers of ethylene oxide of molecular weight higher than around 125,000, may be used. In general, only relatively low concentrations ranging from a few parts per million to a few weight percent based on the fine starting powder contained in the slip, are required.
Deflocculating agents may be used to aid in the slip formation and to prevent agglomeration in the slip. Examples of these include sodium hexametaphosphate, sodium molybdate, tetrasodium pyrophosphate, ammonium citrate, ammonium oxalate, ammonium tartrate, ammonium chloride, monoethylamine, etc. Conventional amounts as are used in forming suspensions and colloids may be used which, for example, may range from zero to 1.0 weight percent, and preferably from 0.05 to 0.2 weight percent.
Wetting agents may also be used to aid in maintaining the solid suspension in the slip. These are the conventional synthetic detergents, such as alltylaryl sulfonates, sulfates, soaps, and the like, which may be used in the conventional quantities, for example ranging from 1 p.p.m. to 10.0 weight percent.
Certain of the binder materials may be susceptible to bacterial degradation or mold growth during storage, in which case it may be desirable to add a preservative to the binder material prior to incorporation in the slip, or the slip itself. Any of the known or conventional preservatives, such as sodium benzoate, phenol, or phenol derivatives, formaldehyde, merthiolate, etc. may be used in the conventional amounts and generally between about 0.1 and 0.5 weight percent of the initial binder solution. It may be preferable to use nontoxic preservatives due to the danger of decomposition in the flame.
In connection with fine powder materials which are susceptible to corrosion, or in connection with which the binders show a corrosive action, the binder should additionally contain conventional anticorrosion agents in conventional amounts.
If the slip tends to foam during its production or during handling, conventional antifoaming agents or defoamers, may be added in the conventional amounts, as for example from 0.1 p.p.m. to 200 p.p.m.
Other miscellaneous additives may be included in the slips for specific effects in the production or handling of the slip the slip or in the ultimate flame spraying of the powder produced, as for example chemical activators which will aid in the sintering of high melting refractory materials. Thus for example chlorine or a chlorine-generating compound may be added to enhance the sintering of the carbides. Hydrophobic binders may be used in connection with MgO as water vapor enhances sintering of this material. Conventional acids or bases may be added as buffering agents to control the pH of the slip.
The slip, as mentioned, is simply formed by mechanically mixing the liquid, fine powder and the additives, with sufficient agitation to form a uniform suspension.
The slip is then pumped into a conventional spray dryer where it is atomized and spray-dried. The heavier particles recovered from the bottom of the tower are used as the flame spray powder while the smaller particles which are also recovered from the spray drying may be reconstituted into the slip and again passed through the device.
Referring to the embodiment shown in the drawing, the slip is made up in the mixing tank 1, as described, and pumped by the metering pump 2 to the atomizing head 3 of the spray dryer tower 4. Atomizing air is passed into the atomizing head 3 from the compressor 5. The slip is atomized into the fine spray 6. Air is pumped by the fan or ventilator 7 through the heater 8, as for example a conventional combustion heater, into the top of the spray tower and passes downward as is indicated at 9, drying the atomized slip into the agglomerated flame spray particles which fall the bottom of the tower and are collected in the collector to. The gas is exhausted at 11 through the cyclone separator 12, in which the finer suspended particles are separated and recovered in the collector 13. These finer particles may be reconstituted into the slip by the addition of further liquids, such as water, and repassed through the device. The spraydryer may be operated in any of the conventional elevated temperatures and gas flow rates, as for example drying gas inlet temperatures between about 400 F. and 800 F. and preferably between 500 F. and 700 F. In the equipment I have used, the liquid slip is generally evaporated at a rate between 2 and l2 gallons per hour, and preferably between 2.5 and 8 gallons per hour, based on a drying gas outlet temperature of 225 F. to 400 F. and preferably from 250 F. to 350 F.
The flame spray powder in accordance with the invention has a general overall spheroid shape. Some of the spheroids are somewhat collapsed, i.e. toroidal or donut shaped, and the term spheroid" as used herein and in the claims includes this collapsed form of the spheroid, as well as other somewhat distorted spheroid shapes. These powders, as compared with the conventional flame spray powders, are unusually free flowing and may be handled in all of the conventional powder type flame spray equipment without difficulty. The powder may be produced at a substantially lower cost than was previously'possible and quite surprisingly shows superior characteristics when sprayed, allowing for example a higher spray rate and a substantially improved deposit efficiency. The invention further allows almost unlimited possibilities of combining desired components into integral individual powder particles, which was not previously possible. The combined component particles in accordance with the invention show many advantages over the prior art mixtures or conventional aggregates or coated powders, having a uniform distribution of the constituents and very intimate and close contact with each other. In the spraying process this allows complete alloying, solutioning, or reacting of the components, allowing the formation of a much more homogeneous and uniform coating. When, for example, the constituents of the composite particles are materials which will form a a cennet, the ceramic and other phases of a very fine size are uniformly distributed. Furthermore, coatings produced from the spray dried powder particles in accordance with the invention often show higher density and abrasion resistance than those produced by the conventional powders of the same type. The unusual characteristics and flowability not only allow for better handling in the flame spray equipment but also allow for better screening and classification in order to obtain extremely uniform size cuts.
While the powders may generally be used as produced, with the binders remaining soluble in the particular liquid solvent of the slip from which they were formed, it is also possible to insolubilize same by a curing, cross-linking, or tanning treatment. Thus, for example the particles may initially be treated with a dilute alcoholic solution of chromic nitrate followed by removal of the excess solution and drying. lnsolubilization may also be effected by treatment with concentrated solutions of dichromates, followed by exposure to actinic, such as ultraviolet light. The dichromates may, for example, by any of the alkaline or metal dichromates, such as ammonium, sodiurn, potassium or cupric. lnsolubilization may also be effected by treatment with copper ammonium hydroxide, as for example prepared from copper sulfate, ammonium hydroxide, and sodium hydroxide.
It is critical that the individual spray-dried powder particles in accordance with the invention have a crush resistance of at least 0.7 grams. This crush resistance is simply measure of the weight that individual particles will support before the same are broken, crushed or destroyed. This crush strength is most simply determined by placing an individual particle on anvil and detennine the maximum weight that the same will support while remaining intact. l have found that this crush resistance can be most accurately determined with the use of an analytical balance as follows:
The compressive strength tester is a modified analytical balance on which the pan on one side was replaced by an anvil atop the horizontal beam and a counterweight, the sum weight of which exactly equalled the weight of the pan removed. A shallow depression on the upper surface of the anvil allows precise orientation of the particle to be tested. An adjustable platen is mounted above and closely adjacent to the anvil surface; the height is adjusted such that, with the particle to be tested in position, the zero-indicating arm of the balance is at zero on the reference scale when the particle is just contacting the platen face.
The load is then applied gradually and without shock by unwinding a fine chain from a calibrated rotating cylinder into the other pan of the balance, the calibrations showing the weight of chain deposited on the pan.
Compressive failure of the particle is indicated by movement of the zero-indicating arm relative to the reference scale. The weight of chain required to do this is directly read from the calibrated cylinder.
The particles must thus be substantially stronger and have a higher crush resistance than powders produced for most powder metallurgy purposes where the same are to be pressed into shapes or fonns. Particles, such as ceramic particles intended for initial press forming, must have a relatively low crush resistance in order to be pressed into a green form of uniform consistency.
In addition to being sprayed per se in any of the known or conventional manners for flame spraying using any of the known or conventional powder-type flame spray equipment, the powder in accordance with the invention may, of course, be sprayed in any desired mixture or combination with other powder produced in accordance with the invention or any known or conventional flame spray powder.
The following examples are given by way of illustration and not limitation:
EXAMPLE I Tungsten Carbide'cobalt Cermet Powder Tungsten carbide (WC) powder of 1.3-1.6 micron average Fisher subsieve Size (FSS) particle size and metallic cobalt powder of 2 micron average (FSS) particle size were blended in the proportion 88 weight percent WC:l2 weight percent Co. The blend of materials was then dry ball milled according to standard practice in the industry, so that the cobalt was smeared onto the WC particles and each WC particle was, in effect, clad with cobalt.
A gum arabic binder was dissolved in water to form a concentrated solution containing 30 weight percent gum arabic and 70 weight percent water. Phenol in the proportion of 0.05 weight percent, based on the total weight of the solution, was added as a preservative for the binder concentrate.
Sodium carboxy methyl cellulose of very high (approximately 200,000) molecular weight was used as a suspending agent. A concentrated solution, 1.4 weight percent of CMC and 98.6 weight percent of water, was prepared in advance.
Sodium hexametaphosphate (Calgon) was used as a dispersing and deflocculating agent. A concentrated solution, 25 weight percent of the solid in 75 weight percent of water, was prepared in advance.
Sodium lauryl sulfate (Proctor and Gamble Orvus WA Paste, 34 weight percent solids in H,O) was used as a wetting agent. Because of its high efiiciency and the need in ppm. only, dilute solution was prepared by dissolving 0.3 g. of the commercial paste in 100 g. of water, resulting in a solids concentration of 0.1 g. per I00 grams of water.
A slip was formulated according to the following table, using the prepared concentrates described above, where applicable, and in the proportions indicated.
In blending the ingredients to fonn the slip, all liquids and solutions were first weighted into the mixing tank with the mixer running. The dry powder was then fed into the mixing tank such that deflocculation occurred immediately, and after a short mixing time, the slip was uniform in consistency. At this point, pH was measured and adjusted to pH 7.4 by buffering with phosphoric acid, and samples were taken for viscosity and specific gravity measurements. Specific gravity was 5.5 g./m. Deflocculation of the powder was complete so that screening of the slip was not required. The slip was spray dried in a Laboratory Tower Spray Dryer (LT-04-l/2) as manufactured by Bowen Engineering lnc., North Branch, New Jersey 08856. The rated capacity of this dryer was approximately 20 lb./hr. of chamber product based on drying an Al,0, slip containing 60 percent to percent by weight of solids together with a suitable binder system; the chamber product consists of approximately percent of the total product, the remaining 25 percent being deposited in the cyclone collector and usually consists of fines. Heated air was introduced in a cyclonic flow pattern at the top of a vertical straight-cylindrical drying chamber. The slip is atomized into droplets near the bottom of the drying chamber and directed upwards along the vertical centerline by a blast of compressed air. The particles travel twice through the drying chamber upwards against the flow of heated air and then downward to the bottom, and then settle by gravity into a collecting receptacle.
Approximately l0,000 grams of slip were fed by pumping into the atomizing nozzle from which the atomized slip was propelled through the drying chamber, to be finally collected in the chamber and cyclone collectors as a dry powder. The following machine parameters were used:
Atomizing Air Flow approximately 15 SCFM Approximately 6,500 g. of the 9000 g. of powder blended in the slip was collected as finished product in the chamber and cyclone collectors. The other 2500 g. was loss in the mixing The cyclone product was 9 percent of the total collected and was essentially -325 mesh size. The Hall (ASTM 8-21348 (1965)) Flow Rate of the l40 +325 mesh size cut of the chamber product was 2.96 gJsecond and the apparent density (not vibrated) was 3.94 g./ml. The Hall Flow Rate of the 325 mesh cut of the chamber product was 2.99 g./second and the apparent density (not vibrated) was 3.80 g./ml. Compressive strength of 60 +80 mesh particles was 10.0 grams.
A 325 mesh cut from the chamber product was flame sprayed, using a Metco Type 2M plasma flame spray gun, using argon plasma gas at lp.s.i., 100 SCFH, hydrogen plasma gas at 50 p.s.i., 2.5 SCFH, and argon carrier gas-at l00p.s.i., 15 SCFH. With a Type ES nozzle, input power was 500 amperes at 43 volts, spray distance was 3 inches, and the spray rate was 8.2 lblhour.
' The same powder was flame sprayed with the same equipment except using a Type E nozzle and using nitrogen plasma gas at 50 p.s.i., 150 SCI-H flow, hydrogen plasma gas at 50p.s.i., l0 SCFH flow, and nitrogen carrier gas at 50 p.s.i., l5 SCFH flow. Input power was 300 amperes at 73 volts, spray distance was 3 inches, and the spray rate was 9.4 lb./hr.
The same powder was flame sprayed using a Metco Type 5 P ThermoSpray gun with a type P70 nozzle, 012 powder flow meter valve, at 4-5 spray distance, using hydrogen at 31 p.s.i., 315 SCFH, and oxygen as the combustion supporting and carrier gas at 31 p.s.i., 54 SCHFH. The spray rate was 8.7 lb./hr. of powder.
In all 3 cases above, excellent, hard, dense, adherent, and wear-resistant coatings were deposited.
50 weight percent of the -l40 +325 mesh cut of the chamber product was blended with 50 percent of a -140 +325 mesh cut of a conventional spheroid powder of the self-fluxing, hard-facing, alloy type, to make a powder blend equal in proportion and chemistry to Metco 31C, which uses conventional cobalt-bonded tungsten carbide powder of the same chemistry and particle size range as the spray dried material. The blended material was flame sprayed, using a Metco Type 2 P ThermoSpray gun with a Type P7 nozzle, 2 powder flow meter valve, using acetylene at 10 p.s.i., 25 SCFH, and oxygen at 12 p.s.i., 35 SCFH, with acetylene as the carrier gas, and at 9.5 lb./hr. After post deposition fusing, the resultant coating was a fully fused, pore-free, homogeneous mixture of the coating ingredients and fully fused to the substrate.
A powder similar to that of the 31C (previous example) exceptcontaining 80 weight percent of the spray dried WC/Co powder and 20 weight percent of the self-fluxing, hard-facing powder, was flame sprayed in he same manner as in the previous example except that, after deposition of the coating, a subsequent overcoating of the self-fluxing, hard-facing alloy alone was deposited in thickness equal to 20 percent to 25 percent of the first coating. The coating system was then fused, the overcoat material being absorbed by the first coating during the fusing, to effectively fill all of the pores and weld the whole to the substrate. The result was a homogenous mixture of the coating ingredients, very high in WC content, and fully fused to the base.
In each of the last two spraying examples cited, the result was a coating which showed a superior grind finish, lower porosity, and equal wear-resistance and other characteristics to its conventional counterpart.
EXAMPLE 2 Tungsten Carbide Cobalt Cermet Powder Tungsten carbide powder of 1.3-1.6 micron average (FSS) particle size and metallic cobalt powder of 2 microns average (FSS) particle size were blended in a simple mixture, in the proportion 88 weight percent WC:l2 weight percent Co., for incorporation in a slip as a simple mixture of powders. The preblending was accomplished as a convenience only in preparing powders for a number of experimental batches; but could be added to the slip without prior mixing.
The binders, suspending agents, deflocculent (dispersing agent) agent) and wetting agent, etc. were prepared for use in concentrated. solutions, the same as in example l.
A slip was fonnulated according to the following table, using the prepared concentrates where applicable, and in the proportions indicated.
The slip was blended in the same manner as described in example Specific gravity of the slip was 3.84 g./ml.
The slip was spray dried in the same equipment and in the same manner as described in example 1.
The following machine parameters were used:
Slip Feed Rate Approximately mIJmin. inlet Gas Temp. 465 F.
OutletGas Temp. 275 F.
Type Heat Direct Gas Atomizer Type Countercurrent SW Nozzle Atomizer Description 9-028 Atomizing Air Pressure 30 p.s.i.
Atomizing Air Flow Approximately l5 SCFM Approximately 3,900 g. of the 4,700 g. of powder blended in the slip was recovered as finished product in the chamber and cyclone collectors. The result was a free-flowing powder having essentially spheroid particles. The chamber product comprised 84 percent of the total collected and had a particle size distribution as follows:
Screen Size Weight Percent l5.7 t 40 es 170 +200 2.: 2o0 +230 5.5 2a0 +270 3.5 -210 +325 14.5 a2s 41.5
The cyclone product comprised 16 percent of the total collected and was essentially 325 mesh size. The Hall Flow Rate of the l40+325 mesh size cut of the chamber product was 1.95 g./second and the apparent density (not vibrated) was 2.62 g./ml. Compressive strength of 60+80 mesh particles was 17.0 grams.
A 325 mesh cut from the chamber product was flame sprayed with the Metco Type 2M plasma flame spray gun, using the argon/hydrogen and nitrogen/hydrogen plasma gases, and with the Metco Type 5P ThermoSpray gun as described in example I. In all three cases excellent hard, dense, adherent, and wear-resistant coatings were deposited.
50/50 and 80/20 weight percent mixtures of the spray dried WC/Co powder and conventional self-fluxing, hard-facing alloy powders were blended and flame sprayed according to the procedure described in example 1. The results were essentially identical. The sprayed coatings as compared to conventional sprayed coatings of the same material had smaller pores and more uniform distribution of deposited particles and crystallites.
EXAMPLE 3 Self-Fluxing, Hard-Facing Alloy Powder The binders, suspending agents, wetting agents, and deflocculent were prepared for use in concentrated solutions and/or dispersions as described in example 1, or used dry. The plasticizer, glycerin, was a liquid as received.
A slip was fonnulated according to the following table, using the prepared constituents where applicable, and in the proportions indicated. The powder" was of the following composition:
The ingredients for the slip were blended together in the manner described in example I. Specific gravity of the slip was 3.03 g./ml.
The slip was spray dried in the same equipment and in the same manner as described in example I. The following machine parameters were used:
Slip Feed Rate 90 mlJminute Inlet Gas Temp. 5 l F.
Outlet Gal Temp. 300 F.
Type Heat Direct Ga:
Atomizer Type Countercurrcnt SW Nozzle Atomizer Description 9-02B Atomizing Alr Pressure 30 p.s.i.
Atomizing Air Flow Approximately SCFM Approximately l,l00 g. of the 2,l00 g. of powder blended in the slip were recovered as finished product in the chamber and cyclone collectors. The result was a free-flowing powder having essentially spheroid particles. The chamber product comprised 8 1 percent of the total product and had 'a particle size distribution as follows:
Particle Size Weight Percent l 40 29.8 -l 40 +l 70 7.0 -l 70 +200 ll 200 +2 30 5.7 -230 +270 3.9 270 +325 10.5 325 36.2
The cyclone product comprised 19 percent of the total product and was essentially 325 mesh. The Hall Flow Rate of the l40+325 particle size cut of the chamber product was 1.24 g./second and the apparent density (not vibrated) was 1.66 g./ml. The Hall Flow Rate of the 325 mesh cut of the chamber product was 0.86 g./second and the apparent density (not vibrated) was 1.68 g./ml. Compressive strength of 60+80 mesh particles was 6.0 grams.
The l40+325 cut of the chamber product was flame sprayed, using a Metco Type 5P ThermoSpray gun with a Type P7G nozzle, 0ll powder flow meter valve, at 7 inches spray distance using acetylene as the combustible and carrier gas at 12 p.s.i., 33 SCFl-l, and oxygen at 21 p.s.i., 60 SCFl-l. The spray 'rate was 9.2 lb./hr. After deposition of the coating on the mild steel substrate, which previously had been gritblasted to improve adhesion of the as-sprayed coating, the whole was heated to around l,900-2,000 F to fuse the particles in the coating to each other and the coating to the substrate. Melting and coalescence of the coating was apparent by the formation of a layer of slag on the surface. Upon and during cooling to room temperature, the slag layer spalled of? exposing the bright, smooth surface of the hard, wear-resistant overlay which was welded to the substrate.
The 325 out of the chamber product was flame sprayed the same as the previous l40+325 cut except that a Type P7B nozzle was used and cooling air surrounded the flame of the gun. Spray rate was 7 lb./hr. Upon heating the deposited layer to around l,900-2,000 F to fuse the coating particles to each other and to the substrate, melting and coalescence was apparent by the formation of a thin layer of slag on the surface which coalesced into beads and permitted an excellent shine" to be observed. The result was a smooth, even layer of a hard, weanresistant overlay which was welded to the substrate.
The composition of the alloy fused to the substrate surface was typically:
C0.7-l.0wt.% Crl6-l8 Si 3.5-4.5 wt. '1. Ni+Co BillflCC B 2.75-3.75 wt. b Others 1.0 Max. Fe 3.54.5 wt. lt
EXAMPLE 4 Composite Mullite Powder Fine Mullite, 3A1,0,2Si0, can be formed into particles suitable for flame spraying by the spray drying method, by agglomerating fine particles of mullite per se. lt can also be formed as a composite by combining available and cheap commodity raw materials, such as superfine molochite and high purity A1 0, in the correct proportion in the spray dried powder. Molochite is a naturally occurring mineral of the following typical composition:
SiO, 54-55 percent A1 0 42-43 percent Others 1.5-2 percent Mullite, theoretically, is 71.80 weight percent A1 0; and 28.20 weight percent SiO,. Therefore 50.8 weight percent molochite and 49.2 weight percent Alp, should result in the theoretical chemistry of mullite.
The binders, suspending agents, deflocculants, wetting agents, etc. were prepared in concentrated solutions, the same as in example i.
A slip was formulated according to the following table, using the prepared concentrates where applicable, and in the proportions indicated:
The slip was blended in the same manner as described in example l. Specific gravity of the slip was 1.7 g./ml.
The slip was spray dried in the same equipment and in the same manner as described in example I. The following pray Guns, and with the Metco Type 2M plasma flame gun. The following table lists the operating parameters:
Type 21 Type 51 Type 2M Nozzle PTC PTG EII Cnt'riet'gas Oxygen Oxygen Nitrogen 50/15 Oxygen pr re/llow, s H1 14/47 Acetylene pr sure/llon 12/28 13/35 Nitrogen pressure/flow, 50/ (5 Hydrogen pressure/lion 50/15: Voltage r l n Ainperes .103
Spray distance. inches.
The following table compares spray rates and deposit efficiencies for spray dried composite mullite powder as compared with Metco XPl 146 conventional mullite powder. The conventional material was heavily contaminated with metal, and the spray dried mullite coatings produced were vastly superior to the conventional mullite coatings.
Plasma flame 2M, Ell nozzle, N:/H: 3 spray distance ThermoSpray 2P, 3" spray distance ThermoSpray 51, 2" spray distance Spray Deposit Spray Deposit Sprn) Deposit rate, eiliclency rnte, eilicieney rate, ellicloncy percent #/l1r. percent #[hr percent Spray dried:
210 2.8 94 5.5 84 -230 4 V v V 5. 3 87 Conventional: XP1146 l 1.9 61
1 Deposit eflicicncy figures corrected [or hinder burnout.
machine parameters were used:
Slip Feed Rate Approximately 1 l0 mlJminute inlet (in Temperature 600' F. Outlet Gus Temperature 300' F. Type Heat Direct Gas Alomiler Type Countercurrent SW Nozzle Atomizer Description 9-028 Atomizing Air Pressure p.s.i.
The cyclone product comprised 21 percent of the total product and had a particle size distribution as follows:
Screen Size Weight Compressive strength of 6080 mesh particles was 2.5 grams.
Various particle size cuts of the chamber product were flame sprayed with the Metco Type 2? and Type 5? ThermoS- Optimum particle size based on the spray rates and deposit efficiencies for ThermoSpray equipment is either 325 or 270 mesh, and for plasma flame is -230 or 270 mesh. The poor flowability of the conventional powder (based on spray rate for equivalent feed conditions) is also readily apparent from the data shown in the above table. With plasma flame, the spray dry spray rate was 2.8 times that of the conventional material and deposit efficiency, even at the higher rate, is L46 times that of the conventional material. With the ThermoS- pray 2P, feed rate was 3.2 times that of the conventional material and deposit efficiency is slightly more than twice that of the conventional material. With ThermoSpray 5P, feed rate was up to 5 times that of the conventional material and deposit efficiency is more than twice that of the conventional material, even at the vastly higher spray rate.
EXAMPLE 5 Nicket-Aluminum Exothermic Composites Nickel-aluminum composites corresponding to the known Metco 404 (nominally aluminum clad with weight percent Ni) and Metco 450 powder (nominally Ni clad with 5 weight percent Al) can be manufactured using this method. Ni-Al powders containing 5 weight percent Al and 7.5 weight per cent Al have been manufactured by spray drying. The spray dried composites result in the formation of an homogenous reaction product by virtue of the homogenous mixture of very fine particles.
Carbonyl nickel, 3-5 microns average particle size, and high purity spheroid Al powder, 3.5-4.5 microns, were blended in the slips in the proportion required to produce the desired composites. While the 7.5 weight percent Al powder is used as a specific example, it is understood that the Ni:Al proportion can be anything between 99.5 weight percent Al and 0.5 weight percent Al, depending on the reaction product and the properties desired.
The binders, suspending agents, deflocculent, wetting agent, etc., were prepared for use in concentrated solutions, the same as in example 1.
A slip was formulated according to the following table,
using the prepared concentrates where applicable, and in the proportions indicated:
The slip was blended in the same manner as described in example 1. Specific gravity of the slip was 2.93 g./ml.
The slip was spray dried in the same equipment and in the same manner as described in example 1.
The following machine parameters were used:
Slip Feed Rate Approximately lSO ml./minute lnlet gas temperature 550' F.
Outlet gas temperature 300 F.
Type Heat Direct gas Atomizer Type Countercurrent SW Nozzle Atomizer Description 9-02B Atomizing Air Pressure 25 p.s.i.
Atomizing Air Flow Approximately 15 SCFM Approximately 3,500 g. of the 4,000 g. of powder blended in the slip were recovered as finished product in the chamber and cyclone collectors. The result was a free-flowing powder having essentially spheroid particles. The chamber product comprised 92.5 percent of the total collected and had a particle size distribution as follows:
Mesh Size Weight Percent The cyclone product comprised 7.5 percent of the total and was essentially 325 mesh.
Compressive strength of 60+80 mesh particles was 3.6 grams.
The l 7 325 cut of the chamber product was flame sprayed with a Metco Type 2P ThermoSpray gun, using a Type P7 nozzle, acetylene as the combustible and carrier gas at 10 p.s.i., 25 SCFH, and oxygen at 12 p.s.i., 35 SCFH. Spray rate was approximately 6 lb./hr. The nickel and aluminum particles in the composite particle combined exothermically in the flame to produce an homogenous particle consisting of the nickel aluminides, the heat generated aiding in making the particles self-bonding to the clean, smooth surface of the steel substrate. There was practically no smoke" produced in spraying the spray-dried powder. In the standarized Coating is sprayed on flat end of l inch diameter rod. Another rod end is bonded to the sprayed coating. Rods are pulled apart in a Universal Testing Machine, and breaking strength determined. (Metco Lab Report 0106,
-Metco lnc. I963 coating/bond strength test, the minimum bond/coating strength was determined as being 3,280 p.s.i., the breaking strength with failure occurring at the bond coattop coat interface.
EXAMPLE 6 Nickel-aluminum Exothermic Composites Example 5 was repeated except that the Ni and Al were combined in the proportion 5 weight percent A1295 weight percent Ni, with identical result.
Compressive strength of 60+ mesh particles was 3.6 grams.
EXAMPLE 7 Molybdenum Powder Molybdenum powder of less than 8 microns maximum, approximately 5 microns average particle size, was agglomerated by spray drying into a powder, from which particle sizes desirable for spraying could be separated.
The binders, suspending agents, deflocculent, etc. were prepared in concentrated solutions for use the same as in example A slip was formulated according to the following table, using the prepared concentrates, where applicable, and in the proportions indicated:
TABLE Total Wt. Wt. Wt. Added Addition Solids Liquid 9!:
4000 g. Molybdenum Powder 4000 g. 87.5
l33 g. Gum Arabic at 30% solids 40 g. 93 g. l 16 g. Calgon at 25% solid: 4 g. 12 g. 0.l 40 g. Polyox at wt. k
solids 0.2 40 0.0"
4044.2 I45 g. 440 g. Water 585 440 g. 12.5
The slip was blended in the same manner as described in example l. Specific gravity of the slip was 4.50 g./ml.
The slip was spray dried in the same equipment and in the same manner as described in example 1. The following machine parameters were used:
Slip Feed Rate ml./minute Inlet Gas Temperature 450" F.
Outlet Gas Temperature 275 F.
Type Heat Direct Gas Atomizer Type Countercurrent SW Nozzle Atomizer Description 9-02B Atomizing Air Pressure 20 p.s.i.
Screen Size Weight Percent The cyclone product comprised 10 percent of the total product collected and had a particle size distribution as follows:
Screen Size Weight Percent Trace Trace Trace Trace The Hall Flow Rate of the l70+325 cut of the chamber product was 2.25 g./second and the apparent density (not vibrated) was 2.8 g./ml. The 325 cut of the chamber product did not flow smoothly without vibration, so an accurate test of the flow rate could not be made; the apparent density (not vibrated) was 2.48 g./ml.
Compressive strength of the -60+80 mesh particles was 1.3 grams.
The -170+325 cut of this and other similar molybdenum powders were flame sprayed with the Metco 2? and Metco Type 5? ThermoSpray Gun and the Metco Type 2M plasma flame gun, using spray parameters previously described.
Some of the other Mo powders manufactured using the spray dry equipment included, in addition to the 1 weight percent gum arabic binder, another with 1.6 weight percent gum arabic binder, one-half weight percent, 1 weight percent, 2 weight percent, 3 weight percent polyvinyl alcohol binder, and 1 weight percent sugar binder.
The following table shows spray rates and deposit efficiencies achieved with several types of equipment flame spraying spray dried and conventional molybdenum powders:
Plasma flame 2M,
Spray rate, #/hr.
Deposit efliclency, percent Spray dried:
$4 wt. percent PVA,
1 wt. percent arable, 170 +325. Conventional: Metco #63 l Corrected for blnder burnout.
Hall flow Apparent rate of density of powder powder, g./second g./m1.
Spray Deposit efficiency,
percent Binder wt. percent PVA. 1 wt. percent PVA- 2 wt. percent PVA. 3 wt. percent PVA.
EXAMPLE 8 Zirconia Powder Lime stabilized zirconia (ZIOg) Powder, containing approximately 5 weight percent of CaO to stabilize the crystal structure in thermal cycling, of less than 10 microns maximum particle size and approximately 3 microns average particle size, was agglomerated by spray drying into a powder from which particle sizes desirable for flame spraying could be separated. While the prealloyed powder is used in this example, it is understood that the spray dried particles could contain ZrO, plus CaO in the form of one of its many compounds, including calcium zirconate in the correct proportion, such that the CaO content of the agglomerated and sprayed powder would be the desired amount.
The binders, suspending agents, deflocculents, etc. were prepared in concentrated solutions for use the same as in example l. A slip was formulated according to the following table, using the prepared concentrates where applicable, and in the proportions indicated.
Total Wt. Wt. Wt. Added Addition Solids Liquid i 3000 g. Zirconia Powder 3000 g. 72 I00 g. PVA at 30% Solids 30 g. g. 1
l2 g. Calgon at 25% Solids 3 g. 9 g. 0.l
7.5 g. CMC (dry) 7.5 0.25
3040.5 79 g. H03 g. Water H82 1103 28 The slip was blended in the same manner as described in example Specific gravity ofthe slip was 2.04 g./ml.
The slip was spray dried in the same equipment and in the same manner as described in example I. The following machine parameters were used:
Slip Feed Rate Approximately I50 mlJminute lnlet'Gus Temperature 500 F.
Outlet Gas Temperature 275' F.
Type Heal Direct Gas Atomizer Type Countercurrent SW Nozzle Atomizer Description 9-025 Atomizing Air Pressure 40 p.s.i.
Screen Size Weight Percent The cyclone product comprised l9 percent of the total product collected and was essentially 325 mesh.
The Hall Flow Rate of the 2oo+32s cut of the chambe? product was L08 g./second and the apparent density was 1.35 g./ml. (not vibrated). The 325 out of the chamber product did not flow smoothly through the meter orifice of the Hall Flow Test Apparatus without vibration, so an accurate test of the flow rate could not be made; the apparent density (not vibrated) was 1.35 g./ml.
Compressive strength of the -60+80 mesh particles was 3.5 grams.
The -200+325 and the 325 cuts of the chamber product powder were flame sprayed, using the Metco Type 2? ThermoSpray gun and with the Metco Type 2M plasma flame system using spray parameters described in the previous examples. Spray rates and deposit efiiciencies resulting from the test work and a comparison with tests using identical equipment and spray parameters with conventional Metco 20] (325+microns) and Metco 201B (-200+325) zirconia powders are shown in the following table:
sidered sprayable Spray rates and deposit efficiencies with spray dried powdecomposition in flame spraying was to harden the particles of ders have been consistently better than their conventional molybdenum from KHN 386 to KHN 549 by virtue of incounterparts where direct comparisons have been made. In tcrsti ia containment in the molybdenum particles. addition hardness and abrasion-resistance of the spray dry powder coatings has been consistently better. 5 EXAMPLE 13 One run each of zirconia powder using 1 weight percent and 2 weight percent of polyvinyl alcohol binder was made and Example 4 is repaated except that 3 weight Percent of flame spray tested in direct comparison with each other. Molybdate Orange When flame sprayed into water, dried and microscopically ex- DuPont Color based on the dry binder was incorporated in the slip.
amined, the 2 weight percent PVA bonded powder was ob- 1o served to have significantly more fully fused hollow particles than the 1 weight percent PVA bonded powder. In the preliminary coating evaluation, the coating produced with l The results are the same except that the powder produced is colored orange, which aided in identifying it.
weight percent PVA bonded powder was apparently denser [5 EXAMPLE and more abrasion-resistant. In addition, with identical Ther- Example 8 is repeated except that A1 0 with sodium silm p y yp 2P gu and p y p r a higher deposit icate as the binder replaced the zro and the PVA BINDER. effic ency Was achieved Wlth the l Welght Percent PVA The results are essentially the same except that the sodium bonded powder: silicate decomposed in the flame, the decomposition products p y p y including Si0 acting to bind the A1 0 particles together. Rate Deposit Rate Deposit lbJhr. Eff. lbjhr. Err.
EXAMPLE 15 2:2: :32 32:3: :3 :2: 2:: Example 8 is repeated except that C50 with sodium carboxymethyl cellulose as the binder replaced the ZrO and the o t it td r b d b r PVA binder' EPOSI e ICIBIICIBS are COlleC t: 0| in CI UI'IIOUL BIC [GU05 O ZIlCOfllfl depositedzzimniaimhe powderspmyei The compressive strength of the 60+80 mesh particles IS greater than 0.7 grams.
The results are essentially the same.
EXAMPLE 9 EXAMPLE l6 The slip from example 1 was spray dried in a pilot plant size spray dryer as manufactured by Bowen Engineering Inc., am 15 repeated except that welsh! Percent North Branch, New Jersey 08856 The rated capacity of this borosiltcate glass based on the Cr O was included in the slip. dryer is 100 lbs/hour of chamber product based on drying an The result fassem'auy the Same eXcFPt that the A1203 slip containing 60 percent to 70 percent by weight of mate glass effectively bonded the subpart cles of Cr,O to each solids together with a suitable binder system. The results were othcf durmg flame Spraymg and m "npmvmg Pamdc to the Same particle cohesion in the coating, resulting in a harder, denser,
more abrasion-resistant coating. EXAMPLE 10 40 Example 4 is repeated except that the subparticles of flame EXAMPLE spray material suspended in the slip consisted of 70 weight: Example 8 is repeated except that NiO with methyl cellu- Percent 9f 5 mixture of 8 and 2 weight Percent of z lose as the binder replaced the ZrO, and its binder in the slip. based on the 8 The results are essentially identical.
Compressive strength of the 60+80 mesh powder particles is greater than 0.7 grams. EXAMPLE 18 The powder is flame sprayed in the same manner as in example 4. The result is a dense, adherent, abrasion-resistant coating consisting of essentially MgO but in which the TiO; combined with the MgO in the flame, permitting the deposition by enhancing the melting and coalescence of the MgO EXAMPLE l9 subparticles.
Example 8 is repeated except that CeO, replaced the ZrO, in the slip.
The results are essentially the same.
Example 8 is repeated except that TiO replaced the ZrO, in
EXAMPLE 11 the Example 7 was repeated except that 0.2 weight percent am- The results are essemlany the Same monium alginate replaced the gum arabic as the binder.
The results were essentially the same except that the am- EXAMPLE 2o monium alginate being more protective and by providing a more reducing atmosphere, the particle hardness was less by 0 approximately 100 Knoop hardness because a higher purity material was deposited and particle boundary oxides in the coating were significantly reduced.
Example 2 is repeated except that boron carbide 8 C replaced the tungsten carbide and aluminum replaced the cobalt.
The results are essentially the same.
EXAMPLE 12 EXAMPLE 21 Example 11 was repeated except that 0.1 weight percent of Example 2 is l'ePeated except that chwmillm carbide s sodium nitrite based on the solids contained in the slip was p aced the ungsten carbide and a nickel-chrome alloy added as an oxidizing agent. pH of the slip was buffered to 7.0, replaced th o alt. using sodium hydroxide before the addition of the nitrite to The results are e sential y h m prevent decomposition of the nitrite and evolution of the toxic EXAMPLE 22 Compressive strength of the 60+80 mesh particles was greater than 0.7 grams. Example 5 is repeated except that chromium replaced the The powder was flame sprayed in the same manner as examnickel incorporated in the slip in example 5.
pie 1 l. The action of the oxygen supplied by the oxidizer on its The results are essentially the same.
EXAMPLE 23 Example 4 was repeated except that aluminum oxide A1 and Titania TiO, replaced the solids in the slip in that example.
The results are essentially the same.
While the invention has been described in detail with reference to certain specific embodiments, various changes and modifications which fall within the spirit of the invention and scope of the appended claims will become apparent to the skilled artisan. The invention is therefore only intended to be limited by the appended claims or their equivalents wherein I have endeavored to claim all inherent novelty.
lclaim:
l. A flame spray powder the individual particles of which are of a substantially spheroid shape having a size between about 1 micron and minus mesh and formed of multiple subparticles bound together without fusion by a spray dried binder and having a crush resistance of at least 0.7 grams, substantially all of said subparticles having a size of the same order of magnitude below about 200 mesh.
2. Flame spray powder according to claim 1 having a size between about 100 mesh and 3 microns.
3. Flame spray powder according to claim 1 in which said binder is a water-soluble binder.
4. Flame spray powder according to claim 3 in which said binder is an organic polymer.
5. Flame spray powder according to claim 4 in which said binder is selected from the group consisting of polyvinyl alcohol, polyvinyl acetate, gum arabic, carboxy methyl cellulose salts, methyl cellulose, ethyl cellulose, and polyvinyl butyral dispersions.
6. Flame spray powder according to claim 1 in which said subparticles are of at least two different flame spray components.
7. Flame spray powder according to claim 6 having a size of 20 mesh and 1 micron and in which said subparticles have a size below about 200 mesh.
8. Flame spray powder according to claim 7 in which said binder is a water-soluble organic binder.
9. Flame spray powder according to claim 8 in which said binder is selected from the group consisting of polyvinyl alcohol, polyvinyl acetate, gum arabic, carboxy methyl cellulose salts, methyl cellulose, ethyl cellulose, and polyvinyl butyral dispersions.
l0. Flame spray powder according to claim 1 in which said binder contains a fluxing material.
11. Flame spray powder according to claim I in which said binder contains a pigment.
12. Flame spray powder according to claim 1 in which said binder is capable of producing a reducing atmosphere upon thermal decomposition.
13. Flame spray powder according to claim 1 in which said binder contains an oxidizing agent.
14. Flame spray powder according to claim I in which said binder contains a material capable of thermally combining with said subparticles upon flame spraying to form a flame sprayed coating.
15. Flame spray powder according to claim 1 in which said subparticles are tungsten carbide subparticles.
l6. Flame spray powder according to claim 1 in which said subparticles are tungsten carbide and cobalt subparticles.
l7. Flame spray powder according to claim 1 in which said subparticles are components of a self-fluxing hard facing alloy.
18. Flame spray powder according to claim 1 in which said subparticles are components of mullite.
l9. Flame spray powder according to claim 1 in which said subparticles are of at least two metals capable when melted together of exothermically reacting to form an intermetallic compound.
20. Flame spray powder according to claim 19 in which said subparticles are nickel and aluminum subparticles.
21. Flame spray powder according to claim 1 in which said subparticles are tungsten carbide and cobalt and said binder is sodium carboxy methyl cellulose.
22. in the flame spray process in which a flame spray powder is at least heat-softened in a heating zone and propelled onto a surface to be coated, the improvement which comprises utilizing a flame spray powder the individual particles of which are of a substantially spheroid shape having a size between about 1 micron and minus 20 mesh, and formed of multiple subparticles bound together without fusion by a spray-dried binder and having a crush resistance of at least 0.7 grams.
23. Improvement according to claim 22 in which said binder is an organic water-soluble binder.
24. Improvement accordin to claim 22 in which said subparticles are of at least two di erent flame spray components.
25. improvement according to claim 24 in which said components are metal which exothermically react together at the temperature in the heating zone forming an intermetallic compound.
26. improvement according to claim 22 in which said binder contains material capable of combining with the subparticles at the temperature in the heating zone to form the flame sprayed coating.
27. Improvement according to claim 22 in which said subparticles are selected from the group consisting of tungsten carbide with cobalt or molybdenum and in which said binder is selected from the group consisting of carboxy methyl cellulose and polyvinyl alcohol.
28. A process which comprises spray drying a slip containing fine particles of a flame spray material and a binder to form spray-dried aggregate particles having a crush resistance in excess of about 0.7 gram, passing these spray-dried particles into a heating zone, heating the particles to at least heat-soi tened condition in the zone and propelling the heated particles onto a surface to form a coating.
29. Process according to claim 28 in which said slip is an aqueous slip containing an organic water-soluble binder.
30. Process according to claim 29 in which said organic binder is a member selected from the group consisting of polyvinyl alcohol, polyvinyl acetate, gum arabic, carboxy methyl cellulose salts, methyl cellulose, ethyl cellulose, and polyvinyl butyral dispersions.
31. Process according to claim 28 in which said subparticles have a particle size below 200 mesh.
32. Process according to claim 28 in which said slip contains fine sparticles of at least two different flame s ray materials.
3 Process according to claim 32 in w rch sald two different flame spray materials are materials capable of exothermically reacting with each other at the temperature in the heating zone to form an intermetallic compound.
34. Process according to claim 28 in which the slip additionally contains a material capable of thermally combining with the flame spray material to form a flame sprayed coating.
35. Process according to claim 28 in which said fine particles of flame spray material are tungsten carbide and cobalt, and said binder is sodium carboxy methyl cellulose.
Claims (34)
- 2. Flame spray powder according to claim 1 having a size between about 100 mesh and 3 microns.
- 3. Flame spray powder according to claim 1 in which said binder is a water-soluble binder.
- 4. Flame spray powder according to claim 3 in which said binder is an organic polymer.
- 5. Flame spray powder according to claim 4 in which said binder is selected from the group consisting of polyvinyl alcohol, polyvinyl acetate, gum arabic, carboxy methyl cellulose salts, methyl cellulose, ethyl cellulose, and polyvinyl butyral dispersions.
- 6. Flame spray powder according to claim 1 in which said subparticles are of at least two different flame spray components.
- 7. Flame spray powder according to claim 6 having a size of 20 mesh and 1 micron and in which said subparticles have a size below about 200 mesh.
- 8. Flame spray powder according to claim 7 in which said binder is a water-soluble organic binder.
- 9. Flame spray powder according to claim 8 in which said binder is selected from the group consisting of polyvinyl alcohol, polyvinyl acetate, gum arabic, carboxy methyl cellulose salts, methyl cellulose, ethyl cellulose, and polyvinyl butyral dispersions.
- 10. Flame spray powder according to claim 1 in which said binder contains a fluxing material.
- 11. Flame spray powder according to claim 1 in which said binder contains a pigment.
- 12. Flame spray powder according to claim 1 in which said binder is capable of producing a reducing atmosphere upon thermal decomposition.
- 13. Flame spray powder according to claim 1 in which said binder contains an oxidizing agent.
- 14. Flame spray powder according to claim 1 in which said binder contains a material capable of thermally combining with said subparticles upon flame spraying to form a flame sprayed coating.
- 15. Flame spray powder according to claim 1 in which said subparticles are tungsten carbide subparticles.
- 16. Flame spray powder according to claim 1 in which said subparticles are tungsten carbide and cobalt subparticles.
- 17. Flame spray powder according to claim 1 in which said subparticles are components of a self-fluxing hard facing alloy.
- 18. Flame spray powder according to claim 1 in which said subparticles are components of mullite.
- 19. Flame spray powder according to claim 1 in which said subparticles are of at least two metals capable when melted together of exothermically reacting to form an intermetallic compound.
- 20. Flame spray powder according to claim 19 in which said subparticles are nickel and aluminum subparticles.
- 21. Flame spray powder according to claim 1 in which said subparticles are tungsten carbide and cobalt and said binder is sodium carboxy methyl cellulose.
- 22. In the flame spray process in which a flame spray powder is at least heat-softened in a heating zone and propelled onto a surface to be coated, the improvement which comprises utilizing a flame spray powder the individual particles of which are of a substantially spheroid shape having a size between about 1 micron and minus 20 mesh, and formed of multiple subparticles bound together without fusion by a spray-dried binder and having a crush resistance of at least 0.7 grams.
- 23. ImpRovement according to claim 22 in which said binder is an organic water-soluble binder.
- 24. Improvement according to claim 22 in which said subparticles are of at least two different flame spray components.
- 25. Improvement according to claim 24 in which said components are metal which exothermically react together at the temperature in the heating zone forming an intermetallic compound.
- 26. Improvement according to claim 22 in which said binder contains material capable of combining with the subparticles at the temperature in the heating zone to form the flame sprayed coating.
- 27. Improvement according to claim 22 in which said subparticles are selected from the group consisting of tungsten carbide with cobalt or molybdenum and in which said binder is selected from the group consisting of carboxy methyl cellulose and polyvinyl alcohol.
- 28. A process which comprises spray drying a slip containing fine particles of a flame spray material and a binder to form spray-dried aggregate particles having a crush resistance in excess of about 0.7 gram, passing these spray-dried particles into a heating zone, heating the particles to at least heat-softened condition in the zone and propelling the heated particles onto a surface to form a coating.
- 29. Process according to claim 28 in which said slip is an aqueous slip containing an organic water-soluble binder.
- 30. Process according to claim 29 in which said organic binder is a member selected from the group consisting of polyvinyl alcohol, polyvinyl acetate, gum arabic, carboxy methyl cellulose salts, methyl cellulose, ethyl cellulose, and polyvinyl butyral dispersions.
- 31. Process according to claim 28 in which said subparticles have a particle size below 200 mesh.
- 32. Process according to claim 28 in which said slip contains fine particles of at least two different flame spray materials.
- 33. Process according to claim 32 in which said two different flame spray materials are materials capable of exothermically reacting with each other at the temperature in the heating zone to form an intermetallic compound.
- 34. Process according to claim 28 in which the slip additionally contains a material capable of thermally combining with the flame spray material to form a flame sprayed coating.
- 35. Process according to claim 28 in which said fine particles of flame spray material are tungsten carbide and cobalt, and said binder is sodium carboxy methyl cellulose.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US67188067A | 1967-09-29 | 1967-09-29 |
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Publication Number | Publication Date |
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US3617358A true US3617358A (en) | 1971-11-02 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US671880A Expired - Lifetime US3617358A (en) | 1967-09-29 | 1967-09-29 | Flame spray powder and process |
Country Status (5)
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---|---|
US (1) | US3617358A (en) |
AT (1) | AT304728B (en) |
DE (1) | DE1794214B2 (en) |
FR (1) | FR1602527A (en) |
GB (1) | GB1198745A (en) |
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WO2018046871A1 (en) | 2016-09-09 | 2018-03-15 | H.E.F | Multimaterial powder with composite grains for additive synthesis |
EP3974053A1 (en) | 2016-09-09 | 2022-03-30 | Hydromecanique Et Frottement | Multimaterial powder with composite grains for additive synthesis |
RU2710094C1 (en) * | 2019-05-13 | 2019-12-24 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Кубанский государственный технологический университет" (ФГБОУ ВО "КубГТУ") | Method of obtaining coating on part surface from nonferrous metals |
RU2710246C1 (en) * | 2019-05-13 | 2019-12-25 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Кубанский государственный технологический университет" (ФГБОУ ВО "КубГТУ") | Method of obtaining coating on part surface from steel |
WO2021072173A1 (en) * | 2019-10-11 | 2021-04-15 | Global Tungsten & Powders Corp. | Printable and sinterable cemented carbide and cermet powders for powder bed-based additive manufacturing |
CN114921744A (en) * | 2022-06-01 | 2022-08-19 | 佳木斯大学 | Preparation method of quaternary composite powder for reactive thermal spraying |
Also Published As
Publication number | Publication date |
---|---|
GB1198745A (en) | 1970-07-15 |
FR1602527A (en) | 1970-12-21 |
DE1794214B2 (en) | 1979-10-25 |
DE1794214A1 (en) | 1971-07-29 |
AT304728B (en) | 1973-01-25 |
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