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  • 专利说明
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    • 专利摘要:
    slurry composition, thermal or environmental barrier coating, and, methods for producing an aqueous slurry and for applying a thermal or environmental barrier coating with an aqueous slurry to an improved slurry formulation for producing a barrier coating thermal and environmental protection is provided that can withstand high temperature applications. the slurry includes a combination of a fraction of coarse ceramic powder having closed porosity particles and a fraction of fine ceramic powder. the combination of the two powders produces a bimodal particle size distribution having a controlled amount of closed porosity that with only desirable properties to the coating produced. the finer solid particles are interdispersed within an aqueous binder to produce a ceramic matrix with sufficient mechanical strength. the thick particles containing closed porosity are embedded within the resulting ceramic matrix and do not disintegrate under high temperature conditions to communicate a closed temperature-resistant porosity, non-collapsing to the coating that can also act as an environmental barrier. .
    公开号:BR112014015249B1
    申请号:R112014015249-7
    申请日:2012-12-19
    公开日:2021-04-13
    发明作者:Vladimir V. Belov；Irina Belov
    申请人:Praxair S.T. Technology, Inc；
    IPC主号:
    专利说明:

    Field of the Invention
    [01] The present invention relates to an improved slurry formulation that can be used for the production of an enhanced thermal barrier coating as well as an enhanced environmental barrier coating, along with a process for the manufacture of such aqueous slurry. , and a process for applying such slip on a substrate. Fundamentals of the Invention
    [02] Extensive efforts have been made to develop thermal barrier coatings (hereinafter, referred to as “TBCs”) for use in various applications on metal substrates. Various metal substrates require thermal protection. For example, superalloy substrates used in aircraft engines with gas turbines and industrial gas turbines based on land require thermal protection. In addition, steel substrates for the exhaust system of internal combustion engines require thermal protection. Currently, the use of TBCs can potentially allow a reduction in temperatures on the metal substrate by as much as approximately 160 ° C, thus increasing the life span of a metal substrate by up to four times.
    [03] A typical TBC system requires a binder coating, such as a MCrAlY coating coating or diffusion aluminide, which protects the metal substrate from oxidation and corrosion, and a top coating that reduces the flow of heat into the component . The top coatings are invariably based on ceramic materials. Yttria stabilized zirconia (YSZ) is often used because of its high temperature stability, low thermal conductivity and good resistance to erosion. YSZ is also preferred because of the relative ease with which it can be deposited by different techniques such as thermal spraying techniques (plasma, flame and HVOF) and electron beam physical vapor deposition (EBPVD).
    [04] TBCs applied by the atmospheric plasma process (APS) are formed by the flattened particles of a ceramic material, and contain laminar pores and micro-cracks between the particles. This microstructure is an important factor that contributes to the thermal barrier properties of the YSZ coating because these pores and crevices can dramatically reduce the thermal conductivity of the coating when compared to the solid material, as well as relieve thermally induced stress and thus increase the resistance to thermal shock.
    [05] It is important for a TBC to preserve its low thermal conductivity for the life of a coated component. However, plasma-sprayed TBC layers are often in an inherently thermodynamically metastable state because of the rapid extinction of particles fused to a substrate during the spraying process. Upon exposure to high service temperatures, the transformation to an equilibrium state occurs and the intrinsic thermal instability of the material's microstructure results in the sintering and degradation of the TBC porosity and thus in the deterioration of the thermal barrier properties of the coating.
    [06] YSZ coatings with EBPVD have a thin columnar microstructure that is better able to accommodate a mismatch between the thermal substrate and the coating compared to the layers sprayed with plasma. As a result, TBCs with EBPVD are often used in some of the most demanding and advanced applications. However, EBPVD coatings are quite expensive, and thus not economically viable for some applications. In addition, its columnar structure provides paths for the penetration of corrosive species through the coating, thus decreasing the corrosion resistance of the covering.
    [07] The EBPVD and plasma spray deposition methods are line of sight processes that are suitable for applying coating to the visible areas of a substrate. Therefore, the substrates that can be coated by these spraying methods are limited to geometries or simple substrates only requiring a coating on the essential external parts.
    [08] Coating based deposition processes can also be used.
    [09] TBC coatings based on slurry and their application have been investigated many times in the past. A slurry process comprises preparing an aqueous or solvent-based slurry, applying the slurry to the substrate, drying and heat treating or sintering to obtain a coating layer. This process can be repeated to form a coating of desirable thickness. However current developments in the technique have additionally not solved problems associated with the application of TBC derived from slurry, such as creating a coating that is thick enough to provide the required thermal insulation (which is greater than at least 300 to 350 microns), as well as to prevent excessive contraction of the coating during drying and curing of the applied layers which results in problems of bonding the coating to the surface of a coated part and eventual fragmentation of the coating.
    [10] Sol-gel techniques are generally known to release good coating - substrate adhesion. However, they cannot provide a practical means of obtaining a coating thickness higher than 10 to 50 microns which is not sufficient for thermal insulation.
    [11] In view of the various shortcomings of current TBC technology, an unmet need remains for TBCs that can withstand high service temperatures and retain their structural integrity. As will be discussed, the inventors here identified the problem of coating degradation and corrected the problem in accordance with the present invention in order to provide a protective coating that exhibited thermal and environmental barrier properties suitable for high temperature applications. Summary of the Invention
    [12] The present invention selectively uses a mixture of porous particles having closed porosity and substantially solid ceramic particles to form an improved slurry formulation. The slurry solidifies in a cured state to form a resulting structure having a controlled distribution of closed pores. The closed porosity is substantially non-collapsing and has a sufficiently low thermal conductivity. In this way, the thermal barrier coating that is formed is suitable for high temperature applications. The controlled distribution and the size of the closed pores also allows for the production of improved environmental barrier coatings.
    [13] In a first aspect, an aqueous slurry composition for the production of a porous thermal barrier or environmental coating on a ceramic or metal substrate is provided. A first powder comprising an oxide material with a thermal conductivity lower than about 5 W / m K is provided. The first powder is characterized as coarse particles having a first average size ranging from about 5 microns to about 60 microns, with at least a portion of the coarse particles having a closed porosity that is resistant to temperature and substantially impermeable to gas and liquid . A second powder is provided which comprises an oxide material with a thermal conductivity lower than about 5 W / m K. The second powder is characterized as fine particles having a second average size ranging from about 0.1 to about 5 microns, where the second average size is at least about 5 times less than the first average size of the first powder.
    [14] The coarse particles of the first powder and the fine particles of the second powder form a bimodal particle size distribution in the slurry. A plurality of elemental Boron particles are also provided in an effective amount. An inorganic binder suspending at least a portion of the plurality of elemental Boron particles, coarse particles and fine particles in aqueous medium is provided. The closed porosity of the coarse particles is temperature resistant and communicates a non-collapsing closed pore structure to the coating.
    [15] In a second aspect, a slurry composition for the production of a thermal or environmental barrier coating is provided. A first ceramic material is provided which comprises oxide-based particles having a first average particle size ranging from about 5 microns to about 60 microns, the particles being temperature resistant and substantially impermeable to gas and liquid. A second ceramic material is provided which comprises oxide based particles which are substantially solid. The substantially solid particles have a second average particle size ranging from about 0.1 to about 5 microns. A binder is also provided in combination with at least a portion of the first and second materials in relative proportions to form a bimodal particle distribution. When in a cured state, the closed porosity of the first ceramic material provides a porous structure stable at high temperature, non-degrading, to the thermal barrier coating produced.
    [16] In a third aspect, a thermal or environmental barrier coating is provided. A vitro-ceramic matrix is provided. The matrix is formed by a binder and a fine fraction of dust particles. The particles have a first average particle size. A plurality of particles have a closed porosity that is non-collapsing at elevated temperatures of at least about 1000 ° C and is substantially impermeable to gas and liquid. The plurality of particles containing closed porosity have a second average particle size that is substantially not overlapped with the first average particle size to form a bimodal particle distribution. The second average particle size is at least about five times larger than the first average particle size. The plurality of particles that contain closed porosity are dispersed in the vitro-ceramic matrix in an amount effective to decrease a thermal conductivity of the coating by about 2 W / m K or lower.
    [17] In a fourth aspect, a method for producing an aqueous slurry is provided. An aqueous binder solution is provided in which a first powder and a second powder are introduced into it. Each of the first and second powders comprises oxide materials with a thermal conductivity of not more than about 5 W / m K. The first powder is composed of a first plurality of particles comprising closed porosity of not less than 4 percent, preferably not less than 14 percent, and having an average particle size in the range of about 10 microns to about 60 microns, and the second powder is composed of a second plurality of dense particles with a particle size average in the range of about 0.1 micron to about 5.0 microns. A bimodal particle size distribution comprising the first plurality of particles and the second plurality of dense particles is formed. Additionally, elemental boron is introduced. The first and second powders and elemental Boron with the aqueous binder are mixed to form a particle suspension in the aqueous binder solution.
    [18] In a fifth aspect, a method for applying a thermal or environmental barrier coating with an aqueous slurry is provided. An aqueous slurry is provided. The aqueous slurry comprises a first ceramic powder comprising particles having closed porosity and a first average particle size between about 10 microns to about 60 microns; a second ceramic powder comprising dense particles with a second average particle size between about 0.1 micron to about 5 microns; whereby the first and second powders form a bimodal particle size distribution. Elemental boron and an aqueous, substantially inorganic, binder. The aqueous slurry is applied to a substrate surface, and then cured in the coating. Brief Description of Drawings
    [19] The objectives and advantages of the invention will be better understood from the detailed description that follows of its preferred embodiments in connection with the attached figures in which equal numbers indicate the same characteristics throughout and in which: Figure 1 shows a ceramic oxide powder with closed porosity of a hollow microspherical structure (designated as Type A); Figure 2 shows a ceramic oxide powder with a closed porosity structure having multiple pores of sub-micron and nano size (designated as Type B); Figure 3 shows the SEM cross section of a TBC slurry coating as deposited, cured and heat treated on a substrate that incorporates the principles of the invention; Figure 4 shows the SEM cross section of a TBC slurry coating as deposited on a substrate that incorporates the principles of the invention and thereafter cured to form an independent coating that has been heat treated; Figure 5 shows independent TBCs after being subjected to various heat treatments; Figure 6 shows the SEM cross section of a TBC coating according to the principles of the present invention that has been subjected to a heat treatment of 1100C for 100 hours; Figure 7 shows the SEM cross section of a TBC coating according to the principles of the present invention that has been subjected to a heat treatment of 1200C for 100 hours; Figure 8 shows the SEM cross section of a TBC coating according to the principles of the present invention that has been subjected to a heat treatment of 1400 C for 100 hours; and Figure 9 shows X-ray diffraction (XRD) data for YSZ particles with closed porosity as such and when exposed to 1350C for 4 hours. Detailed Description of the Invention
    [20] The relationship and functioning of the various elements of this invention are best understood by the detailed description that follows. However, the embodiments of this invention as described below are by way of example only.
    [21] A slurry formulation for the production of a coating according to an aspect of the present invention comprises at least two powders of materials with lower thermal conductivity than about 5 W / m K which are dispersed in an inorganic binder and form a bimodal particle size distribution with fine powder particles being combined with coarse powder particles, where these coarse particles are porous with closed porosity. The respective average particle sizes of the coarse and fine fractions of the created bimodal particle size distribution are selected so that the average particle size of the coarse fraction is at least five times larger than the average particle size of the fine fraction. In a preferred embodiment, the combination of coarse and fine fractions in particular proportions with a binder in the slurry has a synergistic effect to produce a coating with low thermal conductivity of about 2 W / m K or lower and thermodynamically porous improved stable that exhibits superior temperature resistance and non-degradation under high temperature conditions. It should be understood that the term "coating" is used here and throughout the specification interchangeably with the term "layer" or "film" and is intended to generally cover materials that are independent or that cover a desired area over a surface. The term “coating” is not limited by size. In other words, the covered area created by the coating can be as large as an entire surface, for example, of a substrate or just a portion of it.
    [22] Powders that can be used include any suitable powder of a material with a thermal conductivity lower than about 5 W / m K, such as, for example, a ceramic oxide powder. In one example, the ceramic oxide powder is zirconia. The zirconia powder is preferably chemically stabilized by various materials, such as yttria, calcium or magnesia, or mixtures of any of these materials. More preferably, yttria stabilized zirconia (YSZ) is used as the powder for both the coarse and fine fraction.
    [23] YSZ powders can contain about 1% by weight to about 14% by weight of yttria, based on the total weight of the powder. Preferably, the YSZ powder can contain about 4% by weight to about 10% by weight of yttria, and more preferably from about 7% by weight to about 8% by weight of yttria.
    [24] Various types of closed porosity structures of coarse dust fraction particles are considered in the present invention. "Closed porosity" as used herein refers to a pore that is essentially an autonomous pore, which is not interconnected to other pores in order to allow gases or liquid to substantially permeate through it. The closed pore structure can be present in the individual particles. Alternatively, closed porosity can occur as a result of an agglomeration of several particles packaged together to create interstitial space between them and closed by a continuous outer boundary.
    [25] In one example, the closed porosity may include a hollow spherical morphology. Figure 1 shows an example of coarse YSZ particles in a powder designated as a Type A. The YSZ particles exhibit a particular type of hollow spherical morphology suitable for the present invention. The particle size is on the order of the micron scale of magnitude. Consequently, the particles are considered to be microparticles. The microparticles of Figure 1 are designated as having a -325 mesh fraction. The microparticles have a continuous structure as an outer shell. The shell-like structure of each of the microparticles is shown to extend in a continuous manner to define an enclosed external volume that is hollow. The chemical composition YSZ ranges from about 7% by weight to about 8% by weight of Y2O3 - ZrO2. Microspherical powders, as shown in Figure 1, can be obtained commercially from various sources, such as, for example, Sulzer Metco and Z-TECH LLC. In addition, methods for forming the spheres known in the art, as disclosed in U.S. Patent No. 4,450,184 and which is incorporated herein by reference in their entirety, can be used to produce the hollow microspheres suitable for the present invention.
    [26] Other types of particles that contain closed porosity can be used. Figure 2 shows an example of YSZ particles in a powder designated as Type B. The YSZ particles are characterized by a different pore size and microstructure than those shown in Figure 1. Specifically, Figure 2 shows a porous particle having multiple closed pores of size in the sub-micron and nano scales. The YSZ particles in Figure 2 are designated as having a -325 mesh fraction.
    [27] Methods for making such YSZ particles in which the zirconia has a stabilized tetragonal or cubic structure are disclosed in U.S. Patent No. 6,703,334 and incorporated herein by reference in their entirety.
    [28] Although the pore size and microstructure for each of the powders shown in Figures 1 and 2 are different, the overall percentage of closed pores in each of the respective powders is comparable. Table 1 provides a comparison of% closed porosity for Type A and Type B powders with particle sizes in the range of about less than about 20 microns to about 60 microns. As observed from the data, the% of closed pores is quite similar for Type A and Type B when the same particle sizes are being compared.
    [29] As noted further from the data, the% closed porosity is drastically reduced to the -635 fraction of particles that correspond to particles that are smaller than about 20 microns. Consequently, the size of the coarse particles used in the slurries of the present invention is preferably greater than 20 microns with preferably not less than 14% closed porosity, to guarantee a sufficient amount of closed pores in the resulting coatings.
    [30] However, it should be understood that coarse particles having a size below about 20 microns can communicate a sufficient amount of closed porosity to carry out the present invention. Table 1. Closed pores in YSZ Type A and Type B coarse fraction powders in the bimodal particle size distribution


    [31] Because the overall amount of closed pores in both types of powders is substantially similar, each powder may be suitable for combination with the fine powder fraction to create the specific bimodal particle size distribution despite potential differences in the respective powder sizes and pore distributions. Using particles containing closed porosity as the coarse fraction in the slurries of the present invention exhibits several favorable properties of slurries and the TBCs produced therefrom. "TBCs" as used herein refer to coatings that can reduce thermal flow within the underlying substrate.
    [32] The closed porosity particles reduce thermal conductivity and thus enhance the thermal barrier properties of a thermal insulation layer, when compared to a layer composed of completely solid particles of the same material. In addition, the TBCs produced by the slurries of the present invention are thermodynamically stable and are characterized by a specifically designated "incorporated" porosity that is temperature resistant and non-degrading when exposed to relatively high temperature operating conditions, to which TBCs are typically exposed. Such properties are an improvement for the intrinsic thermal instability of the typical porous microstructure of conventional plasma sprayed TBC coatings.
    [33] Particles containing closed porosity can generally have an average D50 particle size ranging from about 5 microns to about 60 microns. More preferably, the D50 of the coarse fraction particles is from about 20 microns to about 50 microns.
    [34] It should be understood that the hollow microspheres of Figure 1 and the closed pore particles of the size of the sub-micron and nano scale of Figure 2 are illustrative examples of materials containing closed porosity suitable for the present invention. Other types of powders with particles containing closed porosity that exhibit the properties described above are considered by the present invention. By way of example, particles that individually contain closed porosity that are in non-spherical form can be used in the inventive slurry.
    [35] Coarse particles containing closed porosity in coatings derived from the slurries of the present invention can be embedded within, encapsulated within, included within, or otherwise adhered to a coating matrix. Figures 3 and 4 show SEM data for some coatings derived from the slurries of the present invention: as seen from the data, coarse particles containing Type A closed porosity are incorporated within the coating matrix to form the closed porous structure. The coating matrix, as shown in Figures 3 and 4, is formed by a binder with a fraction of fine powder dispersed in it. The formation of the coating matrix provides the necessary mechanical strength for the coating, together with its adhesion to the substrate. The densification of the coating matrix formed by a suitable binder with the fine powder fraction under exposure to high temperature results in the formation of a composite structure of a vitro-ceramic matrix suitable for the present invention.
    [36] The fine fraction is significantly smaller in particle size than the coarse fraction of particles containing closed porosity at least five times and can have an average D50 particle size ranging from about 0.1 microns to about 5.0 microns. Preferably, D50 ranges from about 1.0 to about 4.0 microns. The surface area of the fine powder can be less than about 5 m2 / g.
    [37] Preferably, the fine particle fraction is also composed of a ceramic oxide powder. Preferably, the ceramic oxide powder is a zirconia-based powder that is chemically stabilized with a predetermined amount of yttria. However, as with the coarse material, it should be mentioned that the present invention considers other stabilizing agents, such as, for example, calcium or magnesia. In addition, the fine fraction can also be composed of other types of oxide-based materials that have low thermal conductivity. For example, in an embodiment of the present invention, the fine fraction may have a pyrochlorine-like crystalline structure represented by the formula Ln2M2O7, where M is Zr, Ce, and / or Hf, and Ln is La, Gd, Sm, Nd, Eu and / or Yb. The fine oxide particles can also comprise a mixture of oxide compounds having a perovskite-type crystalline structure represented by the formula AMO3, where M is Zr or Ti and A is an alkaline earth element, rare earth element or any combination thereof. Alternatively, the mixture of oxide compounds may include rare earth metal aluminates.
    [38] According to an embodiment of the present invention, slurries comprise a powder of a fine particle fraction and a powder of a coarse particle fraction. The powders can be mixed in various relative proportions. For example, the coarse powder can comprise from about 30% by weight to about 60% by weight of the slurry composition, and both powders in combination can comprise at least about 55% by weight at about 85% by weight. weight of the slurry composition. In some embodiments, when both coarse and fine fractions are YSZ particles, the coarse fraction of closed porosity particles comprises from about 35% to about 55% by weight, and the powder ratio of the fine fraction for the coarse fraction it is in the range of about 1: 1 to about 1: 2.5 by weight. Preferably, this ratio can vary from about 1: 1.8 to about 1: 2.2 by weight, and the total YSZ powder content comprises between 60% to 80% by weight of the aqueous slurry composition.
    [39] An inorganic binder in the slurry formulation of the present invention can include any suitable material that, in curing the coating, provides a matrix that works to facilitate the receipt and containment of powders within it. The binder can interact with the fine powder fraction (for example, fine YSZ fraction) in a cured state and under high temperature service conditions to form a vitro-ceramic matrix with particle packaging and adequate mechanical strength. Examples of suitable binders include aqueous solutions of alkali metal silicates, metal phosphates or combinations thereof. In one embodiment, the aqueous binder is a solution of Na silicate and / or K. silicate. Preferably, sodium silicate with a relatively high weight ratio of SiO2 / Na2O, such as higher than 2.5, it is selected to provide relatively faster drying of a spray coating and sufficient mechanical strength to a cured coating. In some instances, the binder is a Na silicate binder with a SiO2 / M2O ratio higher than about 3.0.
    [40] The content of the binder can vary from about 15% by weight to about 45% by weight of the total coating. Preferably, the total YSZ binder and powders are present in an amount of about 25% by weight of binder - 75% by weight of total YSZ powder. Alternatively, the total YSZ binder and powders are present in an amount of 30% by weight of binder - 70% by weight of total YSZ powder.
    [41] Elemental boron can also be included in the slurry formulation, preferably in the amount of 0.2 to 2.0% by weight, and more preferably in the amount of about 0.5 to 1.5% by weight. It was discovered in the present invention that using Boron in the slurries provides a surprising improvement in the adhesion of the high temperature coating to the stainless steel substrates and super alloys, as well as increases in the thermal shock resistance of the coating, thus preventing its fragmentation from a substrate under service conditions.
    [42] Various types of additives and dopants can also be incorporated into the slurry formulation to obtain functional properties that are suitably adapted for specific end-use applications. For example, one or more additives can be incorporated, which include anti-corrosive pigments, such as aluminum phosphates, polyphosphates, polyphosphate-silicates, strontium, zinc, molybdenum and combinations thereof. In addition, viscosity modifiers such as aluminum magnesium silicate clays can be incorporated into the slurry.
    [43] The coatings of the present invention are heat resistant. As an example shown in Figure 5, independent YSZ coatings exhibit high structural integrity under prolonged exposure to high temperatures, such as at 1200 C for 100 hours.
    [44] The microstructures of the coating of the present invention remain intact after heat treatments. Figures 6 and 7 show SEM cross-section data for the YSZ coating after heat treatments of 1100C for 100 hours and 1200C for 100 hours, respectively. In addition, Figure 8 indicates an absence of substantial thermal deterioration of the coating microstructure, as well as the closed pore structure of the hollow YSZ spheres used when exposed to an elevated temperature of 1400 C for a period of 100 hours. Some sintering of the outer shell of the microspheres can be seen, but, advantageously, a majority of the microspheres do not collapse, thus preserving the internal holes intact and providing temperature-stable closed porosity, non-degrading of the resulting TBC coating. Advantageously, the inventive closed porous structures, as shown in these Figures, have the ability to remain intact without exhibiting significant collapsing or thermal degradation of the closed porous structure.
    [45] The YSZ-based coatings of the present invention exhibit high thermal stability of their phase composition, as confirmed by X-ray diffraction (XRD) data. In particular, substantially no phase transformation from the tetragonal Zr (Y) O2 structure to the monoclinic M-ZrO2 structure occurs. In particular, exposure to high temperature does not cause any phase transformation of closed porosity YSZ particles. As an example, Figure 9 shows the high thermal stability of the YSZ hollow ball phase composition used in the coatings of the present invention (Type A powder, particle size of less than about 37 microns in size) when exposed to a elevated temperature of 1350 C for 4 hours: no tetragonal Zr (Y) O2 phase transformation to the harmful monoclinic (M-ZrO2) phase occurs. The absence of the M-ZrO2 structure may be an indication that the adverse effects of sintering, which can typically occur at elevated temperatures, are substantially reduced or eliminated. Eliminating said phase transformation can improve coating performance and prolong the life of TBCs in applications that require high temperature, such as aerospace and land based gas turbine engines.
    [46] Thus, as confirmed by the SEM and XRD data, the closed porosity particles of YSZ are generally temperature resistant. Consequently, the particles provide a barrier for heat transfer in the coating. When embedded in a slurry, YSZ closed porosity particles can provide an accumulation of closed porosity that is “embedded” and distributed within the coating that is produced from the slurry. Such a specifically designed accumulation of thermally stable closed porosity contained within the coating provides protection against thermal degradation of the coating. As a result, the thermal conductivity of the TBC coatings of the present invention can be maintained at about 2 W / m K or lower.
    [47] The thermal conductivity of coatings applied to low-steel substrates using the slurries of the present invention, was determined using laser scintillation techniques in the temperature range of room temperature up to 900 C. It was discovered that the coatings of the present invention when derived from preferred slurry formulations, they provided thermal conductivity of about 1 W / m K and lower.
    [48] Thus, exposure to high temperatures for prolonged periods of time, as usual in various applications in aerospace gas turbine engines and land based, do not significantly degrade the closed porosity in a structural way. In addition, the structural integrity of the grain boundaries including the closed porous structure allows the coarse material to serve as a substantial barrier to gas and liquid permeation.
    [49] The combination of the coarse powder having a closed porous structure with fine powders to form a unique bimodal particle distribution provides a synergistic effect. In particular, a closed structure of thermodynamically stable porosity for the resulting coating is produced. The combination of the two sets of powder particles produces a controlled amount of closed porosity, which communicates desired properties to the resulting cured coating. Because the closed porous particles do not degrade and collapse under high temperature conditions, they communicate a temperature-resistant closed porosity, not collapsing to the resulting coating when subjected to high temperatures for extended periods of time. The finest solid particles are interdispersed within the binder to provide sufficient mechanical strength. The difference in the distributions of the average particle size between the coarse fraction and the finer fraction makes it possible to package enough particle to produce a relatively high volumetric density. Consequently, these characteristics collectively allow the structural integrity of the coating to withstand high operating temperature environments for an extended time, thereby enhancing the thermal barrier properties of the coating.
    [50] The slurries of the present invention are also suitable for the production of environmental barrier coatings (hereinafter, referred to as "EBCs"). “EBCs” as used herein and throughout the specification refer to coatings that can substantially prevent the passage of contaminants of interest (eg, air, oxygen, hydrogen, organic vapors, moisture) as well as substantially prevent chemical attack and physical damage caused by the high temperature, aqueous and corrosive environments to which EBCs are typically exposed.
    [51] Because of its impermeability, EBC can function as a protective, passivating coating or layer or film that can inhibit oxidation, corrosion and erosion when exposed to a variety of high temperature and demand operating conditions. The EBC also creates a non-reactive barrier that is chemically inert to the constituents contained in such environments.
    [52] It was surprisingly found that the incorporation of elemental Boron into the slurries of the present invention resulted in a significant increase in the protection against corrosion provided by coatings derived from these slurries. As an example, low carbon steel panels (1010 steel) coated with the about 250 micron thick coating of the present invention that contained Boron were tested in a salt spray booth according to ASTM B117 Standard by 2000 hours. The tests revealed a considerable absence of any induced red rust development, thereby validating the coating's environmental barrier protection against corrosion.
    [53] Further testing indicated that exposure to high temperature of EBCs within an oxidizing rich atmosphere did not produce any visible formation of oxide flaking on the metal substrate, thereby substantiating the upper barrier protection of EBCs against oxidation.
    [54] The TBCs and EBCs of the present invention have several advantages. For example, coatings can be applied over various substrate components by well-established techniques such as spray painting, immersion, dip-centrifugation and brush application. Coatings can also be applied over complex geometries using techniques other than line of sight. In addition, due to the strong protection of a substrate from oxidation and corrosion provided by the TBCs of the present invention, for some types of substrate and applications there is no need to use a binder layer on the substrate surface, if a binder layer is selected to be used, the binder layer can be, such as coating of MCrAlY sprayed on plasma or diffusing aluminide, as well as coating of MCrAlY based on slurry. Another advantage of the inventive slurry formulation is its versatility, such that various additives and dopants can be easily incorporated into it for specific applications without adversely affecting the barrier performance properties or the structural integrity of the closed pore structure.
    [55] Although it has been shown and described what is considered to be certain embodiments of the invention, it will naturally be understood that various modifications and changes in shape or detail can easily be made without departing from the spirit and scope of the invention. It is, therefore, intended that this invention is not limited to the exact form and details shown and described herein, or to anything less than the whole of the invention disclosed and hereinafter claimed.
    权利要求:
    Claims (13)
    [0001]
    1. Composition of aqueous slurry for the production of a porous thermal or environmental barrier coating on a metal or ceramic substrate, the composition, characterized by the fact that it comprises: a first powder comprising an oxide material with a more thermal conductivity lower than 5 W / m K, coarse particles having a first average size ranging from 5 microns to 60 microns, with at least a portion of the coarse particles having a closed porosity that is temperature resistant and impermeable to gas and liquid; a second powder comprising an oxide material with a thermal conductivity lower than 5 W / m K, the second powder characterized as fine particles having a second average size ranging from 0.1 to 5 microns, with the second size medium is at least 5 times smaller than the first average size of the first powder, whereby the coarse particles of the first powder and the fine particles of the second powder form a bimodal particle size distribution in the slurry; a plurality of elemental Boron particles provided in an effective amount, wherein said elemental Boron is contained in an amount of 0.2 to 2.0% by weight; and an inorganic binder that suspends at least a portion of the plurality of elemental Boron particles, the coarse particles and the fine particles in an aqueous solution; wherein the closed porosity of the coarse particles is temperature resistant and communicates a closed porous non-collapsing structure to the coating.
    [0002]
    Aqueous slurry composition according to claim 1, characterized in that the first average particle size ranging from 20 microns to 50 microns and the second average particle size ranging from 1.0 micron to 4.0 microns , in which the closed porosity of the coarse particles is not less than 14 percent.
    [0003]
    Aqueous slurry composition according to claim 1, characterized in that the first average particle size ranging from 20 microns to 50 microns and the second average particle size ranging from 1.0 micron to 4.0 microns , in which the coarse and fine particles are composed of yttria stabilized zirconia.
    [0004]
    Aqueous slurry composition according to claim 1, characterized in that the coarse particles and the fine particles are composed of yttria-stabilized zirconia, calcium-stabilized zirconia, magnesia-stabilized zirconia or a mixture thereof.
    [0005]
    Aqueous slurry composition according to claim 1, characterized in that the first powder comprises from 30% by weight to 60% by weight of the aqueous slurry composition and the first and second powders in combination comprise a total of at least 55% by weight to 85% by weight of the aqueous slurry composition.
    [0006]
    An aqueous slurry composition according to claim 1, characterized in that the binder is selected from the group consisting of a metal silicate binder or a metal phosphate binder.
    [0007]
    Aqueous slurry composition according to claim 5, characterized in that the binder is a metal silicate binder with a SiO2 / M2O ratio higher than 2.5, where M is a selected metal of Na, K and Li or a combination of them.
    [0008]
    Aqueous slurry composition according to claim 6, characterized in that the binder is a metal phosphate binder with a P2O5 / M ratio of not less than 0.1, where M is a metal selected from Groups I, II, III or IV of the Periodic Table of the Elements or a combination thereof.
    [0009]
    Aqueous slurry composition according to claim 1, characterized in that it additionally comprises an anti-corrosive pigment, a viscosity modifier or a combination thereof.
    [0010]
    Aqueous slurry composition according to claim 1, characterized in that the fine oxide particles comprise a mixture of oxide compound with an average particle size distribution ranging from 0.1 micron to 5 microns, at mixture of the oxide compounds having a pyrochlorine-like crystalline structure represented by the formula Ln2M2O7, where M is Zr, Ce and / or Hf; and Ln is La, Gd, Sm, Nd, Eu, Yb or any combination thereof.
    [0011]
    Aqueous slurry composition according to claim 1, characterized in that the fine oxide particles comprise a mixture of oxide compound having a crystalline structure of the perovisque type represented by the formula AMO3 and in which M is Zr e / or Ti; A is an alkaline earth element, a rare earth element or any combination thereof.
    [0012]
    Aqueous slurry composition according to claim 1, characterized in that the fine oxide particles are a mixture of oxide compounds comprising rare earth metal aluminates.
    [0013]
    13. A water-based slurry composition according to claim 3, characterized in that the first powder and the second powder comprise yttria-stabilized zirconia, the binder selected from the group consisting of an alkali metal silicate binder and metal phosphate, wherein said first powder comprises from 35% to 55% by weight, the ratio of the second powder to the first powder is in the range of 1: 1 to 1: 2.5 by weight and the first and second Combined powders comprise between 60% to 80% by weight of the aqueous slurry composition.
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    同族专利:
    公开号 | 公开日
    KR20140106702A|2014-09-03|
    ES2702472T3|2019-03-01|
    CA2859942A1|2013-06-27|
    BR122020020238B1|2021-09-08|
    EP2794956B1|2018-10-17|
    JP2015505898A|2015-02-26|
    PL2794956T3|2019-06-28|
    US20130156958A1|2013-06-20|
    CA3009733A1|2013-06-27|
    SG11201403404WA|2014-09-26|
    CN104126028B|2017-02-22|
    MX2014007464A|2014-11-14|
    US9096763B2|2015-08-04|
    WO2013096477A1|2013-06-27|
    RU2014129858A|2016-02-10|
    MX339254B|2016-05-18|
    KR102113356B1|2020-05-20|
    EP2794956A1|2014-10-29|
    RU2627823C2|2017-08-11|
    AU2012358959A1|2014-07-10|
    CN104126028A|2014-10-29|
    BR112014015249A2|2018-05-22|
    AU2012358959B2|2018-02-08|
    JP6082755B2|2017-02-15|
    CA2859942C|2019-03-19|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US4450184A|1982-02-16|1984-05-22|Metco Incorporated|Hollow sphere ceramic particles for abradable coatings|
    DE3938657A1|1988-11-21|1990-05-23|Hitachi Metals Ltd|CERAMIC COATING ATTACHING TO AN IRON PART AND METHOD FOR THE PRODUCTION THEREOF|
    US5820976A|1988-12-05|1998-10-13|Adiabatics, Inc.|Thin insulative ceramic coating and process|
    WO1993010057A1|1991-11-15|1993-05-27|Gosudarstvenny Nauchno-Issledovatelsky Institut Konstruktsionnykh Materialov Na Osnove Grafita |Method for obtaining protective coating on carbon article|
    RU2036978C1|1993-05-18|1995-06-09|Евгений Григорьевич Иванов|Pieces protection cover application method|
    JPH08127736A|1994-10-31|1996-05-21|Riboole:Kk|Heat-insulating coating material|
    US6465090B1|1995-11-30|2002-10-15|General Electric Company|Protective coating for thermal barrier coatings and coating method therefor|
    US5759932A|1996-11-08|1998-06-02|General Electric Company|Coating composition for metal-based substrates, and related processes|
    US6197424B1|1998-03-27|2001-03-06|Siemens Westinghouse Power Corporation|Use of high temperature insulation for ceramic matrix composites in gas turbines|
    US7563504B2|1998-03-27|2009-07-21|Siemens Energy, Inc.|Utilization of discontinuous fibers for improving properties of high temperature insulation of ceramic matrix composites|
    US6235370B1|1999-03-03|2001-05-22|Siemens Westinghouse Power Corporation|High temperature erosion resistant, abradable thermal barrier composite coating|
    US6641907B1|1999-12-20|2003-11-04|Siemens Westinghouse Power Corporation|High temperature erosion resistant coating and material containing compacted hollow geometric shapes|
    US6521356B2|2001-02-02|2003-02-18|General Electric Company|Oxidation resistant coatings for niobium-based silicide composites|
    DE10143837A1|2001-09-06|2003-03-27|Itn Nanovation Gmbh|Highly porous ceramic layer, used as self-cleaning oven lining or carrier for medicine, bactericide, catalyst or perfume, is produced from mixture of porous ceramic powder with inorganic nanoparticles in solvent as binder|
    US6884384B2|2001-09-27|2005-04-26|Siemens Westinghouse Power Corporation|Method for making a high temperature erosion resistant material containing compacted hollow geometric shapes|
    US6703334B2|2001-12-17|2004-03-09|Praxair S.T. Technology, Inc.|Method for manufacturing stabilized zirconia|
    US6998172B2|2002-01-09|2006-02-14|General Electric Company|Thermally-stabilized thermal barrier coating|
    JP4027265B2|2003-05-13|2007-12-26|菊水化学工業株式会社|Fireproof finishing structure and fireproof finishing method|
    EP1484427A3|2003-06-06|2005-10-26|General Electric Company|Top coating system for industrial turbine nozzle airfoils and other hot gas path components and related method|
    JP2004010903A|2003-10-06|2004-01-15|Nagashima Tokushu Toryo Kk|Thermal insulation coating|
    US20080260952A1|2004-01-22|2008-10-23|The University Of Manchester|Ceramic Coating|
    US7354651B2|2005-06-13|2008-04-08|General Electric Company|Bond coat for corrosion resistant EBC for silicon-containing substrate and processes for preparing same|
    US8029704B2|2005-08-25|2011-10-04|American Thermal Holding Company|Flexible protective coating|
    US7754342B2|2005-12-19|2010-07-13|General Electric Company|Strain tolerant corrosion protecting coating and spray method of application|
    US7604867B2|2005-12-20|2009-10-20|General Electric Company|Particulate corrosion resistant coating composition, coated turbine component and method for coating same|
    US8034153B2|2005-12-22|2011-10-11|Momentive Performances Materials, Inc.|Wear resistant low friction coating composition, coated components, and method for coating thereof|
    JP4959213B2|2006-03-31|2012-06-20|三菱重工業株式会社|Thermal barrier coating member and manufacturing method thereof, thermal barrier coating material, gas turbine, and sintered body|
    US20070298277A1|2006-06-21|2007-12-27|General Electric Company|Metal phosphate coating for oxidation resistance|
    EP1908859A1|2006-10-02|2008-04-09|Siemens Aktiengesellschaft|Pyrochlore materials and a thermal barrier coating with these pyrochlore materials|
    US20090239061A1|2006-11-08|2009-09-24|General Electric Corporation|Ceramic corrosion resistant coating for oxidation resistance|
    US7648605B2|2007-05-17|2010-01-19|Siemens Energy, Inc.|Process for applying a thermal barrier coating to a ceramic matrix composite|
    JP2009040966A|2007-08-10|2009-02-26|Panasonic Electric Works Co Ltd|Resin composition for forming low thermal conductivity film, low thermal conductivity film, and method for producing low thermal conductivity film|
    JP5311438B2|2007-10-31|2013-10-09|国立大学法人名古屋工業大学|Method for producing hollow particle-containing heat insulating paint|
    US7789953B2|2008-03-28|2010-09-07|Praxair S.T. Technology, Inc.|High temperature resistant coating compositions|
    GB0808685D0|2008-05-14|2008-06-18|Dow Corning|Anti-friction coating compositions|
    CA2724691C|2008-05-23|2016-08-16|Yoichi Takaoka|Perovskite-type infrared reflective material|
    CH701373A1|2009-06-30|2010-12-31|Alstom Technology Ltd|Schlickerformulierung for the manufacture of thermal barrier coatings.|
    US9062564B2|2009-07-31|2015-06-23|General Electric Company|Solvent based slurry compositions for making environmental barrier coatings and environmental barrier coatings comprising the same|
    US20110027517A1|2009-07-31|2011-02-03|Glen Harold Kirby|Methods of improving surface roughness of an environmental barrier coating and components comprising environmental barrier coatings having improved surface roughness|
    CN101768380B|2009-12-30|2014-12-17|中国科学院上海硅酸盐研究所|Thermal protection coating with component gradient change and preparation method|US9561476B2|2010-12-15|2017-02-07|Praxair Technology, Inc.|Catalyst containing oxygen transport membrane|
    CN103987681B|2011-12-15|2016-08-24|普莱克斯技术有限公司|Compound oxygen transport membrane|
    US9486735B2|2011-12-15|2016-11-08|Praxair Technology, Inc.|Composite oxygen transport membrane|
    US9034199B2|2012-02-21|2015-05-19|Applied Materials, Inc.|Ceramic article with reduced surface defect density and process for producing a ceramic article|
    US9212099B2|2012-02-22|2015-12-15|Applied Materials, Inc.|Heat treated ceramic substrate having ceramic coating and heat treatment for coated ceramics|
    EP2935155B1|2012-12-19|2019-02-13|Praxair Technology Inc.|Method for sealing an oxygen transport membrane assembly|
    US9453644B2|2012-12-28|2016-09-27|Praxair Technology, Inc.|Oxygen transport membrane based advanced power cycle with low pressure synthesis gas slip stream|
    US9296671B2|2013-04-26|2016-03-29|Praxair Technology, Inc.|Method and system for producing methanol using an integrated oxygen transport membrane based reforming system|
    US9938145B2|2013-04-26|2018-04-10|Praxair Technology, Inc.|Method and system for adjusting synthesis gas module in an oxygen transport membrane based reforming system|
    US9611144B2|2013-04-26|2017-04-04|Praxair Technology, Inc.|Method and system for producing a synthesis gas in an oxygen transport membrane based reforming system that is free of metal dusting corrosion|
    US9212113B2|2013-04-26|2015-12-15|Praxair Technology, Inc.|Method and system for producing a synthesis gas using an oxygen transport membrane based reforming system with secondary reforming and auxiliary heat source|
    US9850568B2|2013-06-20|2017-12-26|Applied Materials, Inc.|Plasma erosion resistant rare-earth oxide based thin film coatings|
    US9711334B2|2013-07-19|2017-07-18|Applied Materials, Inc.|Ion assisted deposition for rare-earth oxide based thin film coatings on process rings|
    US9583369B2|2013-07-20|2017-02-28|Applied Materials, Inc.|Ion assisted deposition for rare-earth oxide based coatings on lids and nozzles|
    US9719176B2|2013-09-20|2017-08-01|Hrl Laboratories, Llc|Thermal barrier materials and coatings with low heat capacity and low thermal conductivity|
    US10647618B2|2014-09-19|2020-05-12|Hrl Laboratories, Llc|Thermal and environmental barrier coating for ceramic substrates|
    US9776153B2|2013-10-07|2017-10-03|Praxair Technology, Inc.|Ceramic oxygen transport membrane array reactor and reforming method|
    BR112016007641B1|2013-10-08|2021-05-04|Praxair Technology, Inc|method for controlling temperature in a reactor, and reactor|
    CA2926757C|2013-12-02|2020-02-25|Praxair Technology, Inc.|Method and system for producing hydrogen using an oxygen transport membrane based reforming system with secondary reforming|
    US9725799B2|2013-12-06|2017-08-08|Applied Materials, Inc.|Ion beam sputtering with ion assisted deposition for coatings on chamber components|
    WO2015123246A2|2014-02-12|2015-08-20|Praxair Technology, Inc.|Oxygen transport membrane reactor based method and system for generating electric power|
    US10822234B2|2014-04-16|2020-11-03|Praxair Technology, Inc.|Method and system for oxygen transport membrane enhanced integrated gasifier combined cycle |
    US9976211B2|2014-04-25|2018-05-22|Applied Materials, Inc.|Plasma erosion resistant thin film coating for high temperature application|
    US9869013B2|2014-04-25|2018-01-16|Applied Materials, Inc.|Ion assisted deposition top coat of rare-earth oxide|
    US10730798B2|2014-05-07|2020-08-04|Applied Materials, Inc.|Slurry plasma spray of plasma resistant ceramic coating|
    WO2016153543A2|2015-03-24|2016-09-29|Hrl Laboratories, Llc|Thermal and environmental barrier coating for ceramic substrates|
    US9789445B2|2014-10-07|2017-10-17|Praxair Technology, Inc.|Composite oxygen ion transport membrane|
    CN104744081B|2015-03-20|2016-10-05|中国人民解放军国防科学技术大学|A kind of high temperature resistance wet oxygen corrosion resistant coating and preparation method thereof|
    US10441922B2|2015-06-29|2019-10-15|Praxair Technology, Inc.|Dual function composite oxygen transport membrane|
    CN104988454A|2015-07-09|2015-10-21|北京航空航天大学|Melted CMAS-corrosion resistant rare-earth aluminate thermal barrier coating and preparation method thereof|
    US10118823B2|2015-12-15|2018-11-06|Praxair Technology, Inc.|Method of thermally-stabilizing an oxygen transport membrane-based reforming system|
    US9938146B2|2015-12-28|2018-04-10|Praxair Technology, Inc.|High aspect ratio catalytic reactor and catalyst inserts therefor|
    EP3436185A1|2016-04-01|2019-02-06|Praxair Technology Inc.|Catalyst-containing oxygen transport membrane|
    CN106391433A|2016-08-31|2017-02-15|重庆新红旗缸盖制造有限公司|Processing technology for internal surface of cylinder head|
    US10994287B2|2016-12-02|2021-05-04|General Electric Company|Coating system and method|
    US10214825B2|2016-12-29|2019-02-26|GM Global Technology Operations LLC|Method of depositing one or more layers of microspheres to form a thermal barrier coating|
    US11155721B2|2017-07-06|2021-10-26|General Electric Company|Articles for high temperature service and related method|
    US20190106780A1|2017-10-11|2019-04-11|United Technologies Corporation|Methods for Applying Thermal Barrier Coatings|
    US10710109B2|2017-11-14|2020-07-14|General Electric Company|Spray nozzle device for delivering a restorative coating through a hole in a case of a turbine engine|
    US10851711B2|2017-12-22|2020-12-01|GM Global Technology Operations LLC|Thermal barrier coating with temperature-following layer|
    US20190316246A1|2018-04-17|2019-10-17|General Electric Company|Reactive phase spray formulation coatings|
    EP3797085A1|2018-05-21|2021-03-31|Praxair Technology, Inc.|Otm syngas panel with gas heated reformer|
    JP2020002431A|2018-06-28|2020-01-09|日本パーカライジング株式会社|Surface treatment agent for metal material, metal material with surface treatment coating, and manufacturing method thereof|
    RU2737838C1|2020-03-27|2020-12-03|Акционерное общество "Объединенная двигателестроительная корпорация" |Method of producing protective composite coating on steel part|
    CN113929474B|2021-12-16|2022-03-04|矿冶科技集团有限公司|Particulate matter for thermal barrier coating, preparation method of particulate matter, thermal barrier coating and engine|
    法律状态:
    2018-06-05| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-08-20| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-06-30| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2021-02-02| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-04-13| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 19/12/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201161577370P| true| 2011-12-19|2011-12-19|
    US61/577370|2011-12-19|
    US61/577,370|2011-12-19|
    PCT/US2012/070668|WO2013096477A1|2011-12-19|2012-12-19|Aqueous slurry for the production of thermal and environmental barrier coatings and processes for making and applying the same|BR122020020238-6A| BR122020020238B1|2011-12-19|2012-12-19|FLUID PASTURE COMPOSITION, THERMAL OR ENVIRONMENTAL BARRIER COATING, AND, METHODS FOR PRODUCING AN AQUEOUS FLUID PASTURE, AND FOR APPLYING A THERMAL OR ENVIRONMENTAL BARRIER COATING WITH AN AQUEOUS FLUID PASTURE|
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