Classifications

• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
  • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
  • C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
  • C23C4/11—Oxides

Definitions

• This invention relates to a flame spray zirconium oxide material which will produce coatings characterized by low thermal conductivity, and to a process of flame spraying such coatings.
• Flame spraying involves the heat softening of a heat fusible material, such as a metal or ceramic, and propelling the softened material in particulate form against a surface which is to be coated.
• the heated particles strike the surface and bond thereto.
• a conventional flame spray gun is used for the purpose of both heating and propelling the particles.
• the heat fusible material is supplied to the gun in powder form.
• Such powders are typically comprised of small particles, e.g., below 100 mesh U.S. standard Screen size to about 5 microns.
• a flame spray gun normally utilizes a combustion or plasma flame to produce the heat for melting of the powder particles. It is recognized by those of skill in the art, however, that other heating means may be used as well, such as electric arcs, resistance heaters or induction heaters, and these may be used alone or in combination with other forms of heaters.
• the carrier gas for the powder can be one of the combustion gases or an inert gas such as nitrogen, or it can be simply compressed air.
• the primary plasma gas is generally nitrogen or argon. Hydrogen or helium is usually added to the primary gas.
• the carrier gas is Generally the same as the primary plasma gas, although other gases, such as hydrocarbons, may be used in certain situations.
• the material alternatively may be fed into a heating zone in the form of a rod or wire.
• the rod or wire of the material to be sprayed is fed into the heating zone formed by a flame of some type, where it is melted or at least heat-softened and atomized, usually by blast gas, and thence propelled in finely divided fcrm onto the surface to be coated.
• the rod or wire may be conventionally formed as by drawing, or may be formed by sintering together finely divided material, or by bonding together finely divided material by means of an organic binder or other suitable binder which disintegrates in the heat of the heating zone, thereby releasing the material to be sprayed in finely divided form.
• zirconium oxide Flame sprayed ceramic coatings containing refractories such as zirconium oxide are often used for thermal barrier protection of metal components, such as in gas turbine engines.
• the zirconium oxide may contain some hafnium oxide and incidental impurities. It typically is stabilized with calcium oxide or yttrium oxide or may be in the form of magnesium zirconate. Yttrium oxide is a preferable stabilizer because it renders long term stability at high temperatures.
• Such zirconium oxide coatings are generally used for thermal barrier purposes such as in gas turbine engines, requiring low thermal conductivity as well as resistance to thermal shock, hot corrosion and erosion.
• Flame sprayed ceramic coatings usually are not fully dense, having some porosity typically up to about 20% depending on composition, powder size distribution, flame pray method and parameters. A higher porosity generally contributes to lower thermal conductivity and a higher degree of resistance to thermal stress than the denser coatings. However, a more porous coating will have lower resistance to corrosion and erosion and other wear conditions that exist in the environments where such coatings are used.
• U.S. Patent No. 3,645,894 describes plasma spraying spherical agglomerate particles formed by spray drying certain two-/or three-component metallic oxide powders.
• the three component particles consist of a first metallic oxide powder characterized by oxygen-ion conductivity upon stabilization, a stabilizing metallic oxide powder and a metallic oxide powder selected from a group consisting of nine oxides.
• the first constituent may be zirconium oxide or thorium oxide and the stabilizing oxide may be calcium oxide, yttrium oxide, ytterbium oxide or a mixture of rare earth oxides.
• the group of nine oxides broadly includes zinc oxide, but of a list of 18 examples having more than two components, there are only two entries showing zinc oxide.
• a further object of this invention is to provide an improved flame spray process for producing a ceramic coating characterized by low thermal conductivity.
• the foregoing and other objects of the present invention are achieved by a flame spray material for producing a ceramic coating characterized by low thermal conductivity.
• the flame spray material according to the present invention comprises a homogeneous composition of zirconium oxide, yttrium oxide, zinc oxide and, optionally, an organic binder.
• a ceramic composition has been developed for flame spraying onto substrates by conventional flame spray equipment.
• the coating produced by the flame spraying of the novel ceramic composition has low thermal conductivity compared to prior art flame sprayed ceramic coatings. Dense coatings of the composition also, have excellent resistance to erosion, hot corrosion and thermal shock.
• the flame spray material comprises a homogeneous ceramic composition consisting of zirconium oxide, yttrium oxide, zinc oxide, optionally an organic binder in an amount up to about 10 percent, and incidental impurities in an amount up to about 1 percent.
• the yttrium oxide is present in an amount between about 2 and 40 percent and preferably between about 5 and 25 percent by weight of the total of the zirconium oxide, yttrium oxide and zinc oxide. It is important that the zinc oxide not exceed about 8%, as it has been found that higher amounts result in inferior coatings that are soft, porous and weak.
• the flame spray material may be in any form that is suitable for flame spraying such as a rod but is preferably in the form of a powder.
• the powder should have conventional size limits, generally between about -100 mesh (U.S. standard screen size) and +5 microns and preferably between about -200 mesh and +25 microns.
• the term "homogeneous" means that there is a plurality of subparticles of each of the individual oxide constituents forming the structure of the ceramic composition, the subparticles being less than 25 microns in size and preferably less than 10 microns. In one embodiment the constituents may be fully in solution together on a molecular scale. Where the flame spray material is a powder, the subparticles of the individual constituents are substantially smaller than the average size of the powder particles, for example, less than one third of the size.
• the reason for the requirement that the composition be homogeneous is that the crystalline Structures in the flame sprayed ceramic coatings are influence critically by the chemical compositions on a microscopic or even molecular scale and, therefore, the coating compositions on such a scale should contain significant amounts of all the oxide constituents in solution.
• the constituent clad on the surface apparently does not sufficiently diffuse into the core particle during flame spraying.
• the homogeneous ceramic composition may be formed by any known or desired method.
• the powder may be made by the conventional method of fusing or sintering together the three constituent oxides, and then crushing and screening the fused product to form powder of the proper size.
• Another alternative is to combine and sinter subparticles of zinc oxide and subparticles of zirconium oxide that are previously and conventionally stabilized with yttrium oxide.
• a preferred method is to fabricate the powder in the form of composite particles each of which contains a plurality of subparticles of each of the three oxide constituents bonded with an organic binder which may be present in an amount up to 10 percent and preferably at least 0.2 percent by weight.
• Such powder may be produced, for example, by a spray drier process such as described in U.S. Patent No. 3, 617,358. Any known or desired organic binder such as listed in that referenced patent may be used. Generally the binder will burn or evaporate from the material in the heat of the flame spray process resulting in a coating which is free of the binder constituents and has the desired characteristic of thermal shock resistance.
• Another method for preparing the powder is to form composite particles with a spray drier as above, feed the particles through a zone of high temperature to fuse the particles, allow the particles to cool and solidify individually, and collect the powder particles so formed.
• the zone of high temperature may be created with an induction plasma, a plasma spray gun through which the powder may be fed in the ordinary manner, or the like.
• the powder collected is comprised of solid, fused, substantially spherical particles that are homogeneous in accordance with + he present invention.
• zirconium oxide constituent may be used in its unstabilized form, or, as described above, may have been previously stabilized with the yttrium oxide. Also, unless highly purified, zirconium oxide typically may contain a small proportion of hafnium oxide which has similar physical and chemical characteristics and, except for certain nuclear applications, does not substantially change the physical characteristics of coatings. Hafnium oxide may be present, for P xample, in an amount up to about 10 percent by weight of the total of the zirconium oxide and hafnium oxide.
• zirconium oxide as used herein and in the claims is intend to include zirconium oxide that may contain such a proportion of hafnium oxide.
• Incidental impurities may be present in an amount up to about 1 percent by weight. However, if oxide impurities are present in significant excess of this amount, the resulting coating has inferior thermal shock resistance. This is particularly true of iron oxide which may produce inferior thermal shock resistance compared to coatings produced with the composition of the present invention.
• the homogeneous ceramic composition of the present invention preferably is used as is, the same optionally may be combined with other flame spray materials such as another ceramic composition or a metal.
• the homogeneous ceramic composition may bo blended with another flame spray ceramic powder having desired characteristics such a wear resistance, for example aluminum oxide.
• a flame sprayed coating of such a powder blend will have the combined properties of erosion resistance and thermal shock resistance.
• the ceramic coating will be a cermet with properties enhanced by the metal.
• the coatings according to the present invention may be used wherever it is desirable to form a thermally insulating barrier to protect a surface against the effects of high temperature, especially where conditions for erosion, hot corrosion or thermal shock are also present.
• Typical applications include gas turbine burner cans, shrouds and other turbine engine components.
• Other areas are rocket thrust chambers and nozzles, furnace chambers and stacks, fluid bed coal gasifiers, power plant heating surfaces, and piston domes, cylinder heads and cylinder walls of internal combustion engines, especially adiabatic diesel engines.
• Coatings of the present invention also have sliding wear characteristics and may be used, for example, on piston ring surfaces.
• Zr0 2 zirconium oxide
• Y 2 0 3 yttrium oxide
• ZnO zinc oxide
• a binder of sodium carboxyl methyl cellulose was dissolved in water to form a concentrated solution containing 113.5 grams of binder and 4653.5 grams of water.
• a slip was formulated according to the following table, using the prepared concentrations described above, where applicable, and in the proportions indicated:
• the slip was fed by pumping into the atomizing nozzle from which the atomized slip was propelled through the drying chamber, to be finally collected in chamber and cyclone collectors as a dry powder.
• the powder collected in the spray dryer chamber was screened with a 200 mesh screen to yield a free flowing powder having a size in the range -200 mesh to +25 microns.
• the composition was, by weight, 87% zirconium oxide, 8% yttrium oxide and 5% zinc oxide, based on the total of these oxides.
• the powder was flame sprayed with a standard plasma flame spray gun of the general type described in U.S. Patent No. 3,145,287 and sold by METCO Inc., Westbury, New York, under the trademark METCO Type 7MB, using a GH nozzle with No. 2 powder port, and a powder feeder of the type described in U.S. Patent No. 3, 501,097 and sold under the trademark METCO Type 3MP.
• Parameters were argon plasma gas at 100 p.s.i. pressure and 80 CFH flow, hydrogen secondary gas at 50 p.s.i. and 15 CFH, 500 amperes, 68 volts, carrier gas 15 CFH, powder feed rate 6 pounds per hour, spray distance 3 inches.
• Example 1 The process of Example 1 was repeated except the proportions of the oxide powders were adjusted to yield a composite powder, by weight, 82.8 percent zirconium oxide, 7.2% yttrium oxide and 10 percent zinc oxide, a composition outside the scope of the present invention. Coatings were flame sprayed in a similar manner but coating hardness was relatively low at about Rb 93.
• coatings were prepared from commercially available powders for comparison.
• One such coating tested was produced with a composite powder of zirconium oxide and 20% yttrium oxide in the manner of Example 1 except without 7 inc oxide.
• the powder is sold by METCO Inc., Westbury, New York, under the trademark METCO 202-NS.
• Another commercial costing tested was from a pre-stabilized powder of zirconium oxide and 8% yttrium oxide, sold under the trademark METCO 204-NS.
• thermal conductivities of the coating of the examples and the similar commercial coatings containing no zinc oxide were measured by a recognized method utilizing a laser. Details are given in "Flash Method of Determining Thermal Diffusivity, Heat Capacity and Thermal Conductivity” hy Parker et al., Journal of Applied Physics, Vol. 32, No. 9 (September 1961). Briefly a high-intensity short-duration light pulse is absorbed in the front surface of a thermally insulated specimen a few millimeters thick coated with camphor black, and the resulting temperature history of the rear surface is measured by a sensor and recorded with an oscilloscope and camera. The thermal diffusivity is determined by the shape of the temperature versus time curve at the rear surface, and the thermal conductivity by the product of the heat capacity, thermal diffusivity, and the density.
• coatings were flame sprayed to about 0.75mm thick on a nickel alloy substrate prepared with a bond coat as in Example 1. The samples were exposed to alternating impingement of a combustion flame and a jet of cold air. Results are reported as the number of cycles run, or to failure where such occurred.
• Thermal shock resistance was measured on those same samples that survived the flame/air cycling. The survived samples were heated in a furnace to 1000°C and then quenched into water at room temperature. Results are reported as cycles to failure, defined by spalling.
• an erosion test was developed for testing the coating.
• a substrate with the coating was mounted on a water cooled sample holder and a propane-oxygen burner ring surrounding an abrasive feed nozzle was located to impinge on the sample.
• a -270 mesh to +15 micron aluminum oxide abrasive was fed through a nozzle having a diameter of 4.9mm with a compressed air carrier gas at 3 1/sec flow to produce a steady rate of abrasive delivery.
• the flame from the burner produced a surface temperature of approximately 980°C.
• the results of this test are expressed as coating volume loss per unit time.
• Coatings also showed excellent resistance to a molten mixture of sodium sulphate at 750°C for 29 hours.

Landscapes

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

Applications Claiming Priority (2)

Publications (1)

Family

ID=24426571

Family Applications (1)

Country Status (2)

Cited By (11)

Families Citing this family (1)

Citations (7)

• 1985
  • 1985-04-11 EP EP85104424A patent/EP0167723A1/fr not_active Withdrawn
  • 1985-05-02 JP JP60093989A patent/JPS60238469A/ja active Pending

Patent Citations (7)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events