Classifications

• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
  • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material

Definitions

• the present invention relates to plasma spraying and plasma sprayed coatings, most particularly those which contain fibers.
• Plasma spraying offers the ability to create coatings and free standing structures of virtually any material which can be melted.
• High temperature structures generally utilize high tem ⁇ perature metals, such as superalloy ⁇ of iron, nickel, and cobalt. These materials characteristically have high thermal expansion coefficients of the order of 10-14 x 10""6 per °C.
• the ceramics which are of most interest tend to be those containing alumina, zirconia, magnesia, and like materials which have low thermal expansion co ⁇ efficients, of the order of 5-10 x 10 ⁇ 6 per °C.
• An object of the invention is to provide a technique for plasma spraying fibers onto a surface.
• a further object is to form plasma coatings and other coatings hav- ing fibers as an integral part thereof.
• fibers are partially melted and adhered to one another when they are deposited on a workpiece surface using a thermal spray process, such as plasma spraying.
• a thermal spray process such as plasma spraying.
• the fibers are adhered to the workpiece surface, as well.
• the surface is optionally made more receptive by the use of a preliminary bond coating.
• the deposited fibers may be caused to have a random pattern or a more normally aligned pattern, according to the fiber aspect ratios and the spraying parameters which are used. In both instances, a substantial portion of the fibers pro ⁇ ject from the surface, as opposed to aligning generally parallel to it. During spraying, only portions of the fibers are melted.
• the fibers are injected into the hot plasma gas stream at a point between the plasma generating nozzle and the workpiece.
• Matrix material can be infiltrated among the fibers, after they are deposited on the workpiece surface.
• the matrix may be applied by a variety of techniques, but the invention will be found principally useful when the ma- trix is comprised of a layered plasma sprayed coating.
• the fibers aid in holding the plasma sprayed matrix onto the substrate.
• the invention provides
• the matrix material is a plasma sprayed coating
• a bonding coat may be deposi ⁇ ted on the fibers, before the principal matrix material is applied.
• the invention- is particularly suitable for forming a metal-ceramic airseal for a gas turbine engine.
• the substrate is a superalloy and the matrix material is a zirconia base ceramic material; the fibers are a metal having high temperature strength and corrosion resistance.
• This embodiment is further improved by the following practice of the invention: After the fibers have been deposited, but before the matrix is deposited, a fugitive material, such as a polymer, is placed on the substrate so that it fully envelopes a portion of the fibers on the workpiece.
• the fiber portions which project furthest from the workpiece are not fully enveloped by the polymer.
• the matrix material when the matrix material is subsequently sprayed, it envelopes the projecting ends of the fibers.
• the fugitive polymer material is removed, such as by combustion.
• This network of metal fibers has relatively good structural compliance. That is, it is adapted to deform with rela ⁇ tively low resistance, to accommodate differences in ther ⁇ mal expansion between the ceramic and the metal substrate.
• the ceramic is held closely to the substrate, but is not subject to damaging strains.
• the inclusion of fibers in coatings will in ⁇ crease strength or other properties, such as thermal con ⁇ ductivity.
• the invention is felt useful with all manner coatings, in addition to plasma coatings.
• O PI ay be of any material which may be plasma sprayed. Fibers alone, without any matrix material, will be useful when adhered to a substrate to increase its surface area.
• Figure 1 illustrates the steps in forming certain inventive articles, by end views of a substrate.
• Figure 2 shows in a cross section a ceramic matrix surrounding metal fibers, both on a metal substrate.
• Figure 3 is similar to Figure 2, but the specimen has a purposeful gap between the ceramic and the sub- strate.
• Figure 4 shows the relationship of the plasma spray ⁇ ing apparatus and workpiece.
• Figure 5 is a photograph of sprayed copper fibers, adhered to a workpiece.
• Figure 6 is a higher magnification photograph of the fibers of Figure 5.
• Figure 7 is similar to Figure 6 , but at higher magni ⁇ fication.
• the invention is described in terms of the applica ⁇ tion of a zirconia ceramic coating to a stainless steel substrate using stainless steel fibers. However, it will be seen that the invention is equally applicable to other material combinations.
• Figure- 1 illustrates generally the preferred steps in the invention.
• a bond coat 22 is first plasma sprayed onto the clean surface of a metal substrate or workpiece 20, as shown in Figure 1(a) , to provide a particularly receptive surface 23 for the later deposited materials.
• fine metal fibers 24 are plasma sprayed so they adhere to the bond coated workpiece surface. As illus ⁇ trated by Figure 1(b) , many of the fibers will project above the surface of the- workpiece.
• the next step is to plasma spray powders to form a typical layered ceramic structure 26, which will envelope the projecting fibers, as shown in Figure 1(c). Prior to this step it may be preferred to plasma spray ' a light bond coat of metal powder onto the adhered fibers, although generally we have not found this necessary.
• the resul-. tant article 27, seen in Figure 1(d), is comprised of a substrate 20 witH a fiber and ceramic matrix coating 27 adhered to its surface 23.
• FIG. 1(e)-(g) An optional procedure, illustrated by Figures 1(e)-(g), is to produce an article where the ceramic matrix-fiber composite material is separated from the substrate, by a compliant low stiffness structure of fibers.
• a polymer layer 30 is plasma or
• OMPI WIFO otherwise sprayed onto the workpiece surface 23, so that it envelopes a portion of the fibers which project from the surface.
• the thickness of the layer 30 is chosen so that portions of the projecting fibers 24 protrude above the mean surface of the layer.
• the ceramic matrix material is sprayed onto the polymer layer, as illustrated by Figure 1(f), using a procedure analogous to that which resulted in the structure shown in Figure 1(c).
• the layered ceramic material 26' will adhere to the polymer surface and envelope the portions of the fiber which protrude above the polymer.
• the stir- face 28* of ceramic is optionally ground to produce a smooth and even finish.
• the article is placed in a furnace having an oxidizing atmosphere to cause the polymer to combust, converting it to a gas which is carried away.
• the polymer has functioned as a fugitive material, to temporarily bar the infiltration of ceramic materials into the said space.
• the coating on the substrate can be characterized as having a first portion 26 * comprised of fiber reinforced ceramic matrix, and second portion 30' comprised of fibers substantially free of matrix particles.
• Figure 2 shows in cross section an actual article corresponding to Figure 1(c) comprised of fibers 24a
• GI ⁇ PI Protuberances 28a are caused by plasma build up on the fibers.
• Figure 3 shows in perspective and cross section an analogous specimen corresponding with Figure 1(g) , ex ⁇ cept the ceramic surface protuberances 28b have not been removed. Between the composite structure of matrix 26b and fibers is a space 30b about 0.1 mm wide created by polymer which has been removed. A fiber 24c crossing the space and holding the ceramic 26.
• Specimens like those in Figures 2 and 3 were made as follows.
• the bond coat was a nickel chromium aluminun alloy powder sized 45-120 x 10 m, (Alloy 443, Metco, Inc, infra) .
• the fibers were AISI 304 stainless steel, with a 0.25 x 0.25 mm square cross section and a length of about 30 mm.
• the ceramic powder was an admixture of 80% zirconia and 20% yttria, sized 10-90 x 10 "6 m (Metco Material 202NS) .
• a conventional gun and power supply were used, namely, a Metco Model 7M systems and gun with a style G tapered nozzle having a 7.8 mm exit dia. (Metco, Inc., Westbury, New York).
• the gun was traversed across the flat worpiece at a rate of about 0.3 m/s, with each successive pass being offset about 3 mm from the preceding pass.
• Fibers were fed using a Thermal Arc P1-A0V-2 Feeder (Sylvester & Co., Cleveland, Ohio.)
• the fibers were injected into the plasma stream outside the nozzle, as more particularly described below.
• the powders were injected into the stream immediately downstream from the exit face of the conventional manner, with feed rates at about 0.05 g/s.
• the bond coat was applied to a thickness of about 0.05-0.14 mm.
• the fibers were applied to the sur- face in a manner which caused them to adhere.
• the fibers When the fibers are injected, they are entrained in the plasma stream and impelled toward the workpiece. Only portions of the fibers are melted, and they adhere to the work- piece.
• the heat transfer a function of plasma gas en ⁇ thalpy and residence time in the stream, must be suffi ⁇ cient to melt a portion of the fibers, to cause them to adhere to the workpiece and to each other.
• the heat transfer must not be so high as to cause complete melting of the fibers, which because of surface tension forces, would cause them to be converted into droplets.
• the density of sprayed fibers was estimated to be in the range of 10-25% of the bulk metal density of 7.9 g/cc. Nominally it is characterized herein as being of about 15% den ⁇ sity.
• the ceramic powders were sprayed in a conventional manner, with the gun nozzle oriented 90 degrees to the substrate.
• Parameters for spraying the powders were conventional, generally comprising a gun to workpiece distance of about 64 mm, 700 amps, 70 volts, about 62 cm- s nitrogen in combination with 9 cm /s hydrogen.
• the same parameters were used for spraying the fibers, as described below.
• the ceramic penetrated through to the work ⁇ piece and gave a relatively uniform density. Usually, it is expectable that there will be some shielding of the areas underneath fibers which project across the plane of the workpiece. But this did not seem to cause sig ⁇ nificant voids in the particular example.
• the gun may be inclined at varied oblique angles to the workpiece surface, to better deposit ceramic under the fibers, and obtain higher density.
• a poly ⁇ mer or other coating is used as a fugitive material, to produce an absence of ceramic matrix near the substrate surface when this is desired.
• the poly ⁇ ester (Metco 600 material) , with particle size distribu ⁇ tion between 44-106 x 10 , was sprayed in a conventional mode to a thickness of about 0.25 mm. It was removed by furnace heating for 3 hr at 550 C.
• Other fugitive materials may be used, such as Lucite 4F acrylic resin (Dupont Co. , Wilmington, Delaware) . Polymers are pre ⁇ ferred because they may be removed easily by oxidation and moderate heating. Also usable will be soluble or meltable materials, such as salts, and other materials used to coat mandrels when free-standing structures are created by plasma coating.
• the substrate would be a nickel, iron or cobalt superalloy.
• the fibers would be a material with strength and corrosion resistance at high temperature. They may have a similar composition to the substrate, or another composition.
• One specific example of another useful high temperature fiber is Hoskins 875 alloy (by weight, 22.5 Cr, 5.5A1, 0.5Si, 01.C, balance Fe) produced by the Hoskins Manufacturing Co., Detroit, Michigan, USA.
• the previously described zirconia base ceramic would be useful.
• Ceramics which will be useful will be meltable refractory compounds of metals with melting points over 1400°C / preferably oxides, but also including borides, nitrides, carbides, as pure com ⁇ pounds or combinations.
• the spacing between the ceramic and the substrate, where there are only fibers may be varied over the range of about 0.25-12 mm, by applying sufficient fibers and sufficient fugitive material. The thickness of the space having fibers only will depend on the particular application. Greater spacings will pro ⁇ vide greater capability for absorbing thermal mis-match strains.
• a plasma gun 32 is positioned a distance D from a workpiece or sub ⁇ strate 3 .
• the plasma gas stream 36 issues f om the opening 38 of the nozzle 39.
• the conventional pow- der injection conduit 42 is positioned proximate to the nozzle face 40.
• fibers 44 are injected by means of a separate conduit, tube 46,spaced a distance from the nozzle face.
• Tube 46 is preferably positioned normal to the centerline 47 of the plasma gas stream, although some inclination of the pipe toward the workpiece may be used.
• the pipe outlet 48 through which the fibers 44 exit, is spaced apart from the center ⁇ line of the plasma stream a distance E, sufficient to ensure that it will not be directly impacted by the stream.
• Fibers are conveyed through the tube 46 by a carrier gas; e. g. , a flow of about 10 cm * - ! /s was used to convey the aforementioned 0.25 mm stainless steel fi ⁇ bers through a 6 -mm dia. tube 46.
• the fibers Upon exiting from the outlet 44 of the tube, the fibers become entrained in the gas stream.
• the exact position of the fiber injection tube may be varied, dependent on the specific operating conditions, and fiber size and results desired. Generally, the tube axis 57 will approximately intersect the centerline 47 of the plasma stream.
• the point of injec ⁇ tion of fibers preferably is located downstream from the point at which powders are ordinarily injected. This is reflective of the need for comparatively less heating of the fibers, relative to powders, to carry out the ob- jects of the invention and have the fibers adhere to the workpiece with substantially an acicular configuration, as described further herein.
• the aforemen ⁇ tioned 0.25 mm dia. steel fibers were injected at a dis ⁇ tance F of approximately 8 mm from the nozzle face when the nozzle face to workpiece distance D was about 64 mm.
• the spacing E, off the centerline 47 was about 6 mm.
• the dis ⁇ tance F at which the fibers are introduced we vary the dis ⁇ tance F at which the fibers are introduced, to control the precise degree of fiber melting which is needed. Generally, fibers in which less energy is needed for melt ⁇ ing will be introduced at points closer to the workpiece surface.
• the plasma stream power level may be set more independently. Thus, high velocities associated with high power levels may be attained, but the fiber residence time will not be so great as to cause undue melting.
• our approach enables the power setting of the gun to be set at that required by a powder being sprayed, thus facilitating practice of various em- bodiments of our invention, especially, that involving simultaneous introduction of powder and fibers.
• the fibers will be introduced at distances E which are within 5-80% of the nozzle face to workpiece surface distance D; preferably, the foregoing range will be 10-50%.
• This distance D will vary as it does for spraying powders. Generally it will be in the range 50-175 mm, depending on materials being sprayed, ambient environment, etc.
• fibers are introduced too close to the work ⁇ piece surface there will be insufficient residence time in the stream to cause melting and obtain adherance of the fibers to the workpiece. ( In such circumstances, how- ever, the fibers may still be included within a plasma coating if powders are impinged on the surface simulta ⁇ neously) .
• Figure 5 shows 0.35 mm dia. by 3-6 mm long copper fibers deposited onto a Metco Alloy 443 coated workpiece. The fiber-density was estimated at about 40%.
• Figures 6 and 7 are higher mag ⁇ nification views from a 30 degree angle off surface per ⁇ pendicular. It is seen from Figure 5 that the fibers 50 have a variety of orientations with substantial numbers of the fibers projecting, at various angles approaching normal, up to 3 mm into space from the plane of the work ⁇ piece 52. This is in contrast to a 1.8 mm thick fiber mat which might be brazed on the workpiece in accord with the prior art in U. S.
• Patent 4,273,824 where all the fibers would lie approximately parallel to the plane of the workpiece surface.
• Figures 6 and 7 show that portions 54 of the fibers are melted. Also seen is some fiber fracture 56 and oxidation scale 58. Some of the bond coated substrate surface 60 is visible. Usually, the ends of the fibers are melted, and applying force to the fibers shows they are mostly bonded to the workpiece sur ⁇ face. There is also some surface melting along the length of the fibers, which provide bonding between the fibers where they contact one another. While some are broken and some excessively melted, the preponderance maintain an acicular shape, substantially of their original diame- ter.
• metal fibers In our practice of the invention thus far, we have utilized metal fibers. Basically, these have been chop ⁇ ped up pieces of commercial wrought wire or pieces of foil which have been slit to very narrow widths (which results in a fiber with essentially a square or rectangu ⁇ lar cross section) .
• dia ⁇ meter of our fiber for non-circular cross section fibers, we mean the diameter of the mean circle which fits within the non-circular cross section.
• the diameters between about 0.05 and 0.35 mm to be useful with conventional plasma spray equipment.
• the minimum fiber diameter will be determined by the minimum plasma gun heat transfer con ⁇ ditions which result in an effective coating. When we sprayed 0.01 mm dia.
• the fibers it was not possible to avoid entirely melting them with our equipment.
• the maximum diameter will be a function of heat transfer con ⁇ dition also, especially the residence time of the fiber in the plasma stream before it contacts the workpiece.
• the fibers should be of sub ⁇ stantially uniform diameters. If undersize fibers are included, they are likely to melt; too many would defeat the objects of the invention. However, the fibers with ⁇ in a lot may vary in length, since this parameter will not substantially affect the results, except regarding the orientation, as discussed elsewhere.
• the fibers will be incorporated into the matrix in a manner which provides the strengthening or property improvement most desired.
• a major limitation of plasma coatings is their bonding to the substrate.
• Plasma coatings are deposited in successive ⁇ sive passes, and thus are characterizable as layers of solidified particles. There is a propensity for failure between the layers, and thus when the fibers are incorpo ⁇ rated so that 'they project through the layers, strengthen ⁇ ing is provided.
• a layer may have a thickness of the order of 0.08 mm, and thus a fiber would project through at least half of two such abutting layers, for a total fiber length of about 0.08 mm, to provide a bene ⁇ fit.
• the fibers must be adequately bonded to the matrix.
• the fiber length along which bonding must be present to strengthen the matrix is a function of the shear strength of the bond. This will vary with the composition of the fiber and matrix, but generally, we believe that a fiber must be bonded along a length equal to about three fiber diameters to provide adequate strength. Thus, for this application, the minimum fiber aspect ratio would be 6:1.
• the aspect ratio is an important parameter. First, it affects the pattern which the fibers form when they adhere to the workpiece. Based on limited observa- tion, it appears that if fibers have high aspect ratios, e. g. , about 20:1 for 0.25 mm dia. stainless steel fibers, they will tend to be deposited in a random orientation fashion. However, when the aspect ratio of such fibers is less than about 15:1, they tend to be deposited in a more aligned pattern, that is, more nearly normal to the surface of the workpiece. Thus when one orientation or the other is preferred, the fiber aspect ratio would be selected accordingly. It is not fully understood why the foregoing effects are observed. But, it is believed that all fibers tend to become aligned parallel to the flow direction of the plasma gas stream. However, when they impact the workpiece the longer fibers will tend to bend over more, and thus become more randomly oriented.
• the density of the fibers which are deposited prior to the matrix may be varied by selection of parameters, especially fiber size, feed rate, carrier gas flow, and stream conditions. Generally, for fibers deposited in ⁇ dependently, the bulk density will range up to 60% of the solid metal density.
• the density of articles comprised of deposited fibers and subsequently sprayed matrix will depend on the degree to which the matrix is able to pene ⁇ trate the fibers. (Of course the matrix will have an in ⁇ herent density of its own, irrespective of the presence of fibers.) Because our fibers tend to be oriented in more nearly normal orientation, higher matrix-fiber com ⁇ posite density can be obtained, compared to fiber mats in previous use, such as described in U. S. Patent 4,273,824. Based on limited evidence, for fiber deposits such as shown
• a plasma coating which can especially benefit from the inclusion of metal fibers is a porous (40% density) metal coating, used as a relatively soft abradable material, such as is made by spraying in com ⁇ bination a polymer and nichrome powder, and subsequently removing the polymer.
• a porous (40% density) metal coating used as a relatively soft abradable material, such as is made by spraying in com ⁇ bination a polymer and nichrome powder, and subsequently removing the polymer.
• thermal conductivity of the metal article will be enhanced.
• the degree of bonding between fiber and matrix is of less importance, but it is desired that the fibers be aligned to the best degree possible, along the direction in which the heat transfer is desired.
• One application for such a material would be as an abradable seal used in the compressor of a gas turbine.
• Heat will be trans ⁇ ferred from a local rub spot to adjacent areas of the seal, minimizing localized heating which might degrade the seal or the structure with which it interacts. While we believe the major initial use of our invention will be as an improvement for supplanting fiber mats, in certain in ⁇ stances, our techniques will enable-a direct substitution for fiber mats. To do so, we would plasma spray using fibers and parameters which tended to give a fiber orien ⁇ tation parallel to the surface. A hot or cold pressing step may be subsequently used to deform the fibers after deposition, to cause them to become more nearly parallel to the surface.
• plasma coatings can be used for forming free-standing articles, such as crucibles, rocket nozzles, and the like.
• Our fiber spraying tech ⁇ niques may be used to improve the properties of such arti- cles, in accord with the foregoing embodiments of the in ⁇ vention.

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• 1982
  • 1982-11-15 DE DE8383900217T patent/DE3277364D1/de not_active Expired
  • 1982-11-15 EP EP19830900217 patent/EP0093779B1/de not_active Expired
  • 1982-11-15 JP JP83500280A patent/JPS58501944A/ja active Pending
  • 1982-11-15 DE DE1983900217 patent/DE93779T1/de active Pending
  • 1982-11-15 WO PCT/US1982/001614 patent/WO1983001751A1/en active IP Right Grant

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