WO2015079906A1 - Matériau de projection thermique et film de revêtement de projection thermique - Google Patents

Matériau de projection thermique et film de revêtement de projection thermique Download PDF

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WO2015079906A1
WO2015079906A1 PCT/JP2014/079869 JP2014079869W WO2015079906A1 WO 2015079906 A1 WO2015079906 A1 WO 2015079906A1 JP 2014079869 W JP2014079869 W JP 2014079869W WO 2015079906 A1 WO2015079906 A1 WO 2015079906A1
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thermal spray
particles
ceramic
spray material
thermal
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PCT/JP2014/079869
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English (en)
Japanese (ja)
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和人 佐藤
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株式会社フジミインコーポレーテッド
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Priority to JP2015550635A priority Critical patent/JP6979754B2/ja
Publication of WO2015079906A1 publication Critical patent/WO2015079906A1/fr

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    • C04B2235/5436—Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 micron
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/549—Particle size related information the particle size being expressed by crystallite size or primary particle size
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/78—Grain sizes and shapes, product microstructures, e.g. acicular grains, equiaxed grains, platelet-structures
    • C04B2235/785—Submicron sized grains, i.e. from 0,1 to 1 micron
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/78—Grain sizes and shapes, product microstructures, e.g. acicular grains, equiaxed grains, platelet-structures
    • C04B2235/786—Micrometer sized grains, i.e. from 1 to 100 micron

Definitions

  • the present invention relates to a thermal spray material and a thermal spray coating. More specifically, the present invention relates to a thermal spray material containing ceramic particles and a thermal spray coating made of the ceramic material.
  • Thermal spraying which is one of the dry coating technologies, is a method in which a particulate thermal spray material made of metal, ceramics, cermet, etc. is melted by a heat source such as a combustion flame or electric energy, and the thermal spray particles are accelerated to accelerate the surface of the substrate. This is a method of forming a film by spraying and depositing on the film.
  • thermal spraying technology using ceramic particles as a thermal spray material is relatively economical because of its excellent chemical and mechanical properties such as heat resistance, wear resistance, corrosion resistance, and insulation resistance, which are the characteristics of ceramic materials.
  • thermal spraying technology using ceramic particles as a thermal spray material is relatively economical because of its excellent chemical and mechanical properties such as heat resistance, wear resistance, corrosion resistance, and insulation resistance, which are the characteristics of ceramic materials.
  • Patent Documents 1 and 2 examples include Patent Documents 1 and 2.
  • ceramic materials generally have a high melting point, they are usually sprayed by a high temperature process such as plasma spraying. According to the thermal spraying in this high temperature process, ceramic particles as the thermal spray material grow during flight in the molten state. Therefore, it has been difficult to form a sprayed coating having a fine structure.
  • a thermal spray material containing ceramic particles and perform thermal spraying by a low temperature process such as a high-speed flame spraying method.
  • a low temperature process is applied to the thermal spraying of ceramic particles, there is a problem that the ceramic particles are not sufficiently melted, and the deposition rate of the thermal spray coating and the thermal spray adhesion rate are lowered.
  • the state of the slurry (for example, the dispersed state) is likely to change even in a short time from the preparation of the slurry to being subjected to thermal spraying, which affects the quality of the thermal spray coating to be formed.
  • the problem that the thermal spray adhesion rate and the film formation rate are low has not been solved.
  • the present invention has been made in view of such a point, and an object of the present invention is to provide a thermal spray material capable of forming a thermal spray coating composed of a ceramic having a dense and fine structure with high productivity. Another object of the present invention is to provide a thermal spray coating made of a ceramic having a dense and fine structure.
  • the present invention provides a thermal spray material.
  • a thermal spray material is characterized by containing ceramic particles having an average particle diameter of 30 ⁇ m or less and a specific surface area of 0.5 m 2 / g or more.
  • the average particle diameter of the ceramic particles can be a size suitable for supplying the thermal spray material as described above.
  • the specific surface area is increased so that heat sufficient to soften or melt the sprayed material can be supplied at a spraying temperature at which grain growth can be suppressed.
  • the thermal spray material has a complicated shape (structure) in which the surface is three-dimensionally complicated, and the substantial dimension (for example, the thickness of the uneven portion of the surface) is reduced.
  • the ceramic melt particles are prevented from growing and can reach the substrate in a sufficiently melted state.
  • the thermal spray material which can form the thermal spray coating which consists of ceramics which have a precise
  • the “average particle diameter” relating to ceramic particles means, unless otherwise specified, a particle diameter at an integrated value of 50% in a particle size distribution measured by a particle size distribution measuring apparatus based on a laser scattering / diffraction method ( Means 50% volume average particle size; D50).
  • the “specific surface area” is determined by measuring the amount of gas (typically nitrogen (N 2 ) gas) physically adsorbed on the surface of the thermal spray material based on the BET method. It means a value obtained by dividing all the external and internal surface areas of the primary particles constituting the thermal spray material by their masses. Such a specific surface area can be measured in accordance with JIS Z 8830: 2013 (ISO 9277: 2010) “Method for measuring specific surface area of powder (solid) by gas adsorption”.
  • the ceramic particles are characterized by having a form of secondary particles in which primary particles are three-dimensionally bonded with a gap.
  • Such primary particles may be in a more desirable form with an average particle size of less than 6 ⁇ m. That is, the ceramic particle which comprises the thermal spray material disclosed here may be a form comprised from a single porous particle, for example.
  • the form of secondary particles in which fine primary particles are combined is preferable.
  • the ceramic particles contained in the thermal spray material can be appropriately softened and melted, and a dense thermal spray coating is suitably obtained. Can do.
  • a sprayed coating having a finer structure derived from the size of the primary particles can be obtained.
  • the thermal spray material which can form the thermal spray coating consisting of ceramics as a thing which has a denser and fine structure with high quality is realized.
  • a thermal spray material that can be more easily designed to obtain a thermal spray coating having desired characteristics is provided.
  • the “average particle diameter” relating to the primary particles is a value calculated as the diameter (spherical equivalent diameter) of the spherical particles capable of realizing the above specific surface area.
  • the average particle diameter (D ave ) of the primary particles can be obtained based on the following formula, where S m is the specific surface area of the ceramic particles (secondary particles) and ⁇ is the density.
  • S m is the specific surface area of the ceramic particles (secondary particles)
  • ⁇ is the density.
  • the “gap” here means a larger space than a space inevitably formed when the primary particles are packed most closely.
  • such a “gap” may be a space that is 1.2 times or more the space that is inevitably formed when the primary particles are closest packed.
  • the ceramic particles have an average roundness in a plan view of less than 1.5.
  • ceramic particles that have not been spheroidized have a high crystallinity, and thus have a tendency that the outer shape of the crystal system tends to appear in the form of particles as they are.
  • nanometer-sized ceramic particles that are difficult to spheroidize and ceramic particles crushed along the crystal plane have a strong tendency. Therefore, the thermal spray material containing ceramic particles having ridges, corners (which may be vertices) or corners derived from the crystal system is supplied from the supply device or the spray gun to the frame before being supplied to the frame. Ridges, corners, corners, and the like are caught on the surface of the gun, and ceramic particles tend to mesh with each other, which tends to reduce fluidity.
  • the average roundness of the ceramic particles is limited to be small as described above, and has an outer shape close to a perfect circle. Therefore, when this thermal spray material is made to flow, it is suppressed that fluidity
  • it is easy and stable to supply the thermal spray material to the thermal spraying device and it is possible to suitably supply the thermal spray material to the center of the thermal spray frame and gas, improving the thermal spray efficiency and improving the quality of the thermal spray coating. Improvements can be made.
  • the “average roundness” of the ceramic particles is obtained for a planar view image (for example, a secondary electron image) of 100 or more ceramic particles observed by an observation means such as an electron microscope. It means the arithmetic average value of roundness.
  • the roundness is a value defined by the following expression from the peripheral length that is the length of the outline of the ceramic particle and the area surrounded by the outline in the plan view image of the ceramic particle.
  • the roundness is an index that more easily reflects the smoothness of the surface morphology of the ceramic particles.
  • the ceramic particles are characterized in that an average aspect ratio in a plan view is less than 1.4.
  • the roundness described above is an index that more easily reflects the surface form among the circularity (can be spherical) of the ceramic particles, and the value becomes more complicated as the contour line in the plan view of the ceramic particles becomes more complicated. Tend to grow. That is, in the ceramic particles having an average roundness closer to 1 as described above, the roundness may more reflect the surface form than the overall form of the ceramic particles. Therefore, in the technology disclosed herein, the form of the ceramic particles is evaluated not only by the roundness but also by the aspect ratio. According to this configuration, it is possible to realize a thermal spray material including ceramic particles whose shape of ceramic particles is closer to a perfect sphere (that is, a perfect circle in plan view) as a whole.
  • the “average aspect ratio” means the arithmetic operation of the aspect ratio obtained for a planar view image (secondary electron image, etc.) of 100 or more ceramic particles observed by an observation means such as an electron microscope. Mean value.
  • the aspect ratio is defined as a / b, where a is the major axis length and b is the minor axis length of the corresponding ellipse of the ceramic particle.
  • the equivalent ellipse is an ellipse having the same area as the ceramic particles and equal primary and secondary moments.
  • Such an average aspect ratio can be obtained, for example, by analyzing an electron microscope image acquired at an appropriate magnification using image processing software or the like.
  • the ceramic particles are characterized by having an average fractal dimension of less than 1.07.
  • Fractal dimension (FD) can be an index used to measure the complex morphology of the particle surface.
  • FD Fractal dimension
  • the ceramic particles have the above average fractal dimension, it is realized as having a smoother surface and improved fluidity of the thermal spray material.
  • the supply of the thermal spraying powder to the thermal spraying apparatus can be further stabilized, and the spraying material can be easily put into the frame or the working gas central part.
  • the thermal spraying material can suitably receive the effects of heating and acceleration by the thermal spraying process, improving the thermal spraying efficiency and improving the quality of the coating film to be formed.
  • the angle of repose is less than 35 °.
  • the angle of repose is an index that can indicate the fluidity of the powder, and since it depends on the particle size (average particle diameter) of the powder, etc.
  • the angle of repose can be increased in the case of a powder having a small particle size and poor fluidity. According to such a configuration, for example, it is possible to determine that the thermal spraying material having an average particle diameter of less than 30 ⁇ m has high fluidity, and it is possible to provide a thermal spraying material capable of forming a thermal spray coating with higher productivity.
  • the “repose angle” is a bottom calculated from the diameter and height of the conical deposit generated by dropping the sprayed material from a funnel having a certain height onto a horizontal substrate. Means a corner.
  • Such angle of repose can be measured in accordance with the provisions of JIS R 9301-2-2: 1999 “Alumina powder physical property measurement method-2: angle of repose”.
  • the ceramic particles are selected from the group consisting of alumina, zirconia, yttria, silica, silicon carbide, boron carbide, silicon nitride, sialon, aluminum nitride, and hydroxyapatite. It is characterized by containing a seed or two or more ceramic materials. According to this configuration, for example, there is provided a thermal spray material capable of forming a thermal spray coating having a function corresponding to the function of a single material of the above ceramic material or the function of a material obtained by mixing or combining two types of ceramic materials. Is done.
  • the invention disclosed herein provides a thermal spray coating in which thermal spray particles made of a ceramic material are deposited on a substrate.
  • the thermal spray coating is characterized in that the average particle diameter of the thermal spray particles in a cross section perpendicular to the surface of the substrate is less than 5 ⁇ m. According to such a configuration, even if the sprayed coating is made of a ceramic material, a fine and dense sprayed coating having a particle diameter as described above can be realized.
  • the “average particle diameter” relating to the spray particles is a value obtained by image analysis of an observation image of the structure in a cross section substantially perpendicular to the base material of the spray coating. Specifically, the observation image obtained by observing a cross-sectional structure substantially perpendicular to the base material of the thermal spray coating with a microscope with a predetermined magnification is binarized to separate the pore portion and the solid phase portion. By analyzing this using image analysis software, it is a value obtained as an arithmetic average value of equivalent circle diameters for 100 or more sprayed particles.
  • the invention disclosed herein also provides a substrate with a thermal spray coating, in which the above thermal spray coating is provided on the surface of the substrate.
  • a base material with a thermal spray coating may be capable of imparting a function close to the bulk of the ceramic material to the base material since the surface of the base material is coated with a ceramic material having a fine and dense structure.
  • FIG. 1 is a diagram illustrating a scanning electron microscope (SEM) image of a thermal spray material according to an embodiment.
  • FIG. 2 is a partially enlarged view of FIG.
  • FIG. 3 is a diagram illustrating a scanning electron microscope (SEM) image of a cross section of the thermal spray coating according to an embodiment.
  • FIG. 4 is a diagram illustrating a scanning electron microscope (SEM) image of a conventional thermal spray material.
  • thermal spray material of the present invention will be described with reference to the drawings as appropriate. It should be noted that matters other than matters specifically mentioned in the present specification (forms of thermal spray material, etc.) and matters necessary for carrying out the present invention (for example, thermal spraying method and thermal spraying device using such thermal spray material, etc.) General matters relating to thermal spraying) can be understood as design matters of those skilled in the art based on the prior art in the field. The present invention can be carried out based on the contents disclosed in this specification and common technical knowledge in the field.
  • the thermal spray material disclosed here essentially includes ceramic particles having an average particle diameter of 30 ⁇ m or less and a specific surface area of 0.5 m 2 / g or more. That is, the thermal spray material is mainly composed of ceramic particles having a very large specific surface area. Specifically, for example, since the specific gravity of silica (SiO 2 ) is 2.2 [g / ml], the specific surface area of the spherical silica particles having a radius of r [m] is 1.36 / r ⁇ It is represented by 10 ⁇ 6 [m 2 / g].
  • the specific surface area of a true spherical silica particle having a radius of 30 [ ⁇ m] is represented by 1.36 / 900 ⁇ 10 6 [m 2 / g].
  • the specific surface area of the thermal spray material disclosed herein is defined to be 0.5 [m 2 / g] or more.
  • the thermal spray material disclosed herein has a complicated shape (structure) in which the surface form is complicated three-dimensionally. That is, substantial dimensions (for example, the thickness of the uneven portions on the surface) can be significantly reduced without being restricted by the average particle diameter of the thermal spray material itself.
  • a ceramic material having a high melting point can efficiently absorb heat from a heat source such as a relatively low temperature spraying frame to achieve sufficient softening and melting.
  • a thermal spray material capable of forming a thermal spray coating made of ceramics with good adhesion to a substrate is provided. Furthermore, the structure of the sprayed coating formed can be fine without depending on the average particle size of the ceramic particles.
  • the specific surface area of the ceramic particles is not particularly limited as long as it is in the above range, but it is desirable that the specific surface area be larger. For example, it can be set to 0.8 m 2 / g or more, preferably 1 m 2 / g or more, and more preferably 10 m 2 / g or more.
  • the average particle size of the ceramic particles can be a size suitable for supplying the thermal spray material as described above. Therefore, for example, even when such a thermal spray material is supplied to a high-speed thermal spray frame, the ceramic particles have an appropriate size and weight, and thus are not easily repelled by the thermal spray frame. Therefore, also in this respect, thermal spraying can be performed while maintaining a high thermal spraying adhesion rate and film formation rate. Moreover, since it is possible to maintain the supply property of the thermal spray material high, it is possible to suppress the problem of deterioration in the quality of the thermal spray coating due to the non-uniform supply of the thermal spray material.
  • the average particle size of the ceramic particles is not particularly limited as long as it is about 30 ⁇ m or less, and the lower limit of the average particle size is not particularly limited. In the case of a smaller one, for example, it can be 2 ⁇ m or less, preferably 1 ⁇ m or less, for example 400 nm or less. For example, specifically, so-called nanoparticles having an average particle diameter of 100 nm or less can be used. However, for example, in consideration of handling when forming such ceramic particles, the lower limit of the average particle diameter is preferably 100 nm or more, more preferably 1 ⁇ m or more, for example, 5 ⁇ m or more. Illustrated.
  • the thermal spray material Normally, when fine ceramic particles having an average particle diameter of less than about 6 ⁇ m, for example, are used as the thermal spray material, the fluidity decreases with an increase in specific surface area, and the film forming ability decreases. Furthermore, due to its small mass, it may be difficult to fly such a thermal spray material on a frame or jet stream.
  • the thermal spray material disclosed here a plurality of particles are three-dimensionally bonded with a gap to primary particles having an average particle diameter of less than 6 ⁇ m. As a result, weighting is achieved so as not to be repelled from a frame, a jet stream, or the like while substantially maintaining the form of the primary particles. This can provide a completely new thermal spray material that has both the advantage of using ceramic particles having a smaller average particle diameter and the advantage of using ceramic particles having a larger average particle diameter.
  • the component which can become a film formation component at the time of formation of the thermal spraying film by thermal spraying among the structural components of the above thermal spraying material is mainly said ceramic particle.
  • “mainly” means that the ceramic particles occupy 95% by mass or more of the film forming component.
  • the ceramic particles can occupy 98% by mass or more, more preferably 99% by mass or more, for example, 99.5% by mass or more, and substantially 100% by mass.
  • the composition of the ceramic particles is not particularly limited.
  • it may be a ceramic material (oxide ceramic) made of oxide, or a ceramic material made of non-oxide such as carbide, nitride, halide, apatite.
  • oxide ceramics are not particularly limited and may be oxides of various metals. Examples of metal elements constituting such oxide ceramics include metalloid elements such as B, Si, Ge, Sb, and Bi, Mg, Ca, Sr, Ba, Zn, Al, Ga, In, Sn, and Pb.
  • the oxide-based ceramic disclosed herein preferably contains a halogen element such as F, Cl, Br, or I in addition to the above metal elements.
  • the oxide ceramics include, for example, alumina, zirconia, yttria, chromia, titania, cobaltite, magnesia, silica, calcia, ceria, ferrite, spinel, zircon, nickel oxide, silver oxide, copper oxide, Zinc oxide, gallium oxide, strontium oxide, scandium oxide, samarium oxide, bismuth oxide, lanthanum oxide, lutetium oxide, hafnium oxide, vanadium oxide, niobium oxide, tungsten oxide, manganese oxide, tantalum oxide, terpium oxide, europium oxide, oxide Neodymium, tin oxide, antimony oxide, antimony-containing tin oxide, indium oxide, tin-containing indium oxide, zirconium oxide aluminate, zirconium oxide silicate, hafnium oxide aluminate, acid Hafnium silicate, titanium silicate oxide, lanthanum silicates, lan
  • Non-oxide ceramics include, for example, carbides such as silicon carbide and boron carbide, nitrides such as silicon nitride and aluminum nitride, forsterite, steatite, cordierite, mullite, barium titanate, lead titanate. , Lead zirconate titanate, Mn—Zn ferrite, Ni—Zn ferrite, sialon and other composite materials, hydroxyapatite, phosphate compounds such as calcium phosphate, and the like. Furthermore, any one of these ceramic materials may constitute ceramic particles alone, or two or more thereof may be combined to constitute ceramic particles. For example, when two or more kinds of ceramic materials are included in the ceramic particles, some or all of these ceramic materials may form a composite oxide.
  • Such composite ceramic particles include, for example, composites such as yttria stabilized zirconia, partially stabilized zirconia, gadolinium doped ceria, lanthanum doped lead zirconate titanate, and the above sialon. An oxide etc. are mentioned.
  • ceramic materials for example, other elements (for example, transition metal elements, elements other than those exemplified above such as Na, K, Rb, etc.) are introduced for the purpose of adjusting the color tone of the formed thermal spray coating. Alternatively, other elements may be introduced for the purpose of enhancing functionality. A part of the elements constituting the ceramic material may be included in the form of ions or complexes. Among these ceramic materials, it is more preferable to include any of alumina, zirconia, yttria, silica, silicon carbide, boron carbide, silicon nitride, sialon, aluminum nitride, and hydroxyapatite.
  • the purity of these ceramic particles is not particularly limited. However, for example, in the case of an application for forming a thermal spray coating having a higher functionality, it is preferable to avoid mixing an unintended substance (element), and the higher the purity of the thermal spray material is preferable. From this viewpoint, it is preferable that the ceramic particles have a higher purity.
  • the purity is preferably 95% by mass or more, further 99% by mass or more, more preferably 99.9% by mass or more, for example, 99.99% by mass or more.
  • components other than ceramic particles may be included, or may not be included.
  • the sprayability of the sprayed material is improved as described above, it may not be prepared in the form of a slurry (including suspension, ink, and base). That is, the component which cannot become a film formation component does not need to be substantially contained.
  • an additive such as a dispersion medium for dispersing the ceramic particles and a dispersant for improving dispersibility in the dispersion medium is included in order to prepare the thermal spray material in a slurry state.
  • Typical examples of such a dispersion medium include water and a mixed solvent of water and a water-affinity alcohol.
  • a material other than such ceramics typically, a particulate material such as metal powder
  • a material other than such ceramics typically, a particulate material such as metal powder
  • the specific structure and manufacturing method of the ceramic particles having an increased specific surface area as described above are not particularly limited.
  • the specific surface area as described above may be realized by using ceramic particles having a porous structure, and the average particle diameter may be adjusted. Or you may make it manufacture the ceramic particle which implement
  • ceramic particles having the following configuration may be prepared.
  • FIG. 1 is an SEM image illustrating an embodiment of such ceramic particles
  • FIG. 2 is an enlarged image thereof.
  • the average particle diameter of the primary particles is not particularly limited, but is preferably less than 6 ⁇ m, for example.
  • the average particle diameter of the primary particles is preferably 5 ⁇ m or less, and more preferably 1 ⁇ m or less, for example.
  • the average particle diameter of the primary particles is further preferably 500 nm or less, for example, nanoparticles of 100 nm or less, 50 nm or less, 30 nm or less, 20 nm or less, 10 nm or less can be obtained.
  • the average particle diameter of the primary particles fine, for example, it can be softened or melted at a temperature lower than the melting point of the ceramic material itself constituting the thermal spray material. This can be a completely new finding that has not been anticipated. Therefore, such a thermal spray material can be particularly suitably used for, for example, a thermal spraying method using a low temperature process.
  • a thermal spray coating made of ceramic can be formed with high quality, for example, as a dense one with good adhesion.
  • the low temperature process can reliably prevent the nanometer-sized primary particles from becoming coarse.
  • the thermal spray coating formed by such a low temperature process can have a finer and denser structure derived from the size of the primary particles in the ceramic particles. Thereby, for example, it may be possible to form a thermal spray coating having characteristics close to the bulk of the ceramic material.
  • the average particle size of the primary particles relative to the average particle size of the ceramic particles is The smaller one is preferable because ceramic particles that can better reflect the above-described advantages can be realized.
  • the average particle diameter of ceramic particles is Ra and the average particle diameter of primary particles is ra
  • the ratio ra / Ra is smaller.
  • the value of ra / Ra is preferably 0.1 or less, more preferably 0.05 or less, for example, 0.01 or less, and even more preferably 0.005 or less.
  • a thermal spray material composed of secondary particles formed by bonding primary particles is also known.
  • the conventional granulated-sintered particles have a relatively large average particle diameter of primary particles (for example, 6 ⁇ m or more). It was not considered at all.
  • the specific surface area of conventional granulated-sintered particles is typically about 0.4 m 2 / g or less, and cannot be realized to be 0.5 m 2 / g or more. From this point of view, the characteristics of the morphology of the ceramic particles disclosed herein can be a novel one that has not been seen so far.
  • Such ceramic particles to which finer primary particles are bonded are not particularly limited in the production method.
  • it can be produced using a known granulation method such as dry granulation or wet granulation.
  • granulation methods include, for example, rolling granulation method, fluidized bed granulation method, stirring frame granulation method, crushing granulation method, melt granulation method, spray granulation method, microemulsion granulation method Etc.
  • a spray granulation method is a preferable granulation method.
  • such ceramic particles can be prepared by the following procedure as an example. That is, first, ultrafine ceramic particles (for example, nanoparticles having a diameter of several nanometers (eg, 1 nm) to 100 nm) that can form primary particles are prepared, and the surface thereof is stabilized with a protective agent or the like. . Then, the stabilized ultrafine particles of the ceramics are dispersed in an appropriate solvent together with spacer ultrafine particles made of, for example, an organic material, a binder, or the like as necessary to prepare a spray solution.
  • ultrafine ceramic particles for example, nanoparticles having a diameter of several nanometers (eg, 1 nm) to 100 nm
  • spacer ultrafine particles made of, for example, an organic material, a binder, or the like as necessary to prepare a spray solution.
  • the primary particles can be dispersed in the solvent using, for example, a mixer such as a homogenizer or a blade-type stirrer, a disperser, or the like. Then, by spraying this spray liquid using an ultrasonic sprayer or the like, droplets of an appropriate size including a plurality of ceramic ultrafine particles are formed. Such droplets are, for example, placed in an air stream and passed through a continuous furnace. Then, while being transported in the continuous furnace, the droplets are dried in a low temperature zone provided relatively upstream in the furnace to remove the solvent component, and then fired in a high temperature zone provided relatively downstream in the furnace. Is done. Thereby, ceramic particles in the form of secondary particles in which the primary particles are bonded with a gap can be obtained.
  • a mixer such as a homogenizer or a blade-type stirrer, a disperser, or the like.
  • droplets of an appropriate size including a plurality of ceramic ultrafine particles are formed.
  • Such droplets are, for example, placed in an
  • the average particle diameter of the ceramic particles obtained is considerably smaller than the size of the droplets due to the disappearance of components other than the ceramic and the sintering of the ceramic ultrafine particles due to firing during the period from drying to sintering.
  • the average particle diameter of these ceramic particles and primary particles and the size and ratio of the gaps formed between the primary particles can be appropriately designed according to the desired form of the ceramic particles.
  • ceramic particles having the following configuration may be prepared. That is, it is composed of ceramic particles having a microporous structure typified by a zeolite structure and a mesoporous structure.
  • a so-called mesoporous material called a microporous structure made of a ceramic material having pores (mesopores) having a diameter of 2 nm to 50 nm can be used.
  • Such a microporous structure uses, for example, a structure-defining amphiphile (typically, a block copolymer, a surfactant, etc.) as a template, and uses a self-assembly process or a sol-gel process on its surface. It can be formed by forming a microporous structure made of a ceramic precursor such as an alkoxide of the target metal and then removing the template.
  • the ceramic material having such a microporous structure is not particularly limited, and examples thereof include mesoporous silica, mesoporous titania, mesoporous alumina, and mesoporous aluminosilicate.
  • a ceramic material having pores (micropores) having a diameter of 2 nm or less and pores (macropores) having a diameter of 50 nm or more. Etc. may also be included.
  • the thermal spray material disclosed herein preferably contains ceramic particles having an average roundness of less than 1.5 (for example, 1 or more and less than 1.5).
  • the average roundness is employed as an index that can indirectly represent the average sphericity of ceramic particles having a relatively small particle diameter.
  • Means roundness When the ceramic particles are viewed in plan from an arbitrary direction, Means roundness. Therefore, this average roundness does not necessarily mean that the ceramic particles are two-dimensionally close to a perfect circle, but is essentially three-dimensionally close to a perfect sphere. Is intended.
  • thermal spray materials ceramic particles that have not been spheroidized have a high crystallinity, and thus have a tendency that the outer shape of the crystal system tends to appear in the form of particles as they are.
  • the ceramic particles as a pulverized product were crushed along the crystal plane, and the tendency was strong.
  • the thermal spray material made of ceramic particles having ridges, corners (which may be vertices) or corners derived from the crystal system is supplied from the supply device or the spray gun to the frame before being supplied to the frame.
  • the thermal spray material having the form of the secondary particles disclosed herein may have a form reflecting the high crystallinity of the ceramic material, for example, an outer shape such as a prismatic shape or a lump shape.
  • high fluidity can be secured by satisfying the above average roundness.
  • the average roundness can be an index that can reflect the average sphericity at a level that cannot be expressed by an index such as an average aspect ratio.
  • the thermal spray material that can improve the fluidity in the supply device and the supply capability to the thermal spray gun during thermal spraying and can suitably supply the thermal spray material to the center of the thermal spray frame, gas, etc. Realized.
  • the average roundness of such ceramic particles is preferably as close to 1 as possible, and may be a value of 1 or more.
  • the average roundness is preferably 1.4 or less, more preferably 1.2 or less, and may be 1.15 or less, for example, 1.1 or less.
  • the average aspect-ratio is less than 1.4. This is because, as described above, in ceramic particles having an average roundness closer to 1, the roundness may reflect the surface morphology more than the overall morphology of the ceramic particles. In other words, in the case of evaluating ceramic particles that are close to a perfect circle, the roundness described above becomes more complex as the contour line in the plan view of the ceramic particles becomes more complex at a micro level. It tends to be larger than the degree of change of the outer shape.
  • the outer shape of the ceramic particles by the aspect ratio in addition to the roundness, it is possible to obtain ceramic particles whose overall outer shape is closer to a perfect sphere, that is, closer to a perfect circle in plan view. it can.
  • the average aspect ratio is preferably 1.3 or less, and more preferably 1.2 or less in consideration of the fluidity of the thermal spray material. Further, for example, it can be set to 1.15 or less, and is preferably 1 or closer to 1.
  • an average fractal dimension is preferably less than 1.07. This is because such ceramic particles may have a complicated surface morphology at a micro level. Therefore, by defining the complicated shape of the particle surface with more various indexes, the outer shape of the ceramic particle can be made closer to a true sphere.
  • the fractal dimension is an index that is widely used to measure the complex morphology of individual particle surfaces, and the average fractal dimension is a suitable index for indicating the smoothness of the surface of ceramic particles disclosed herein. possible. By defining the average fractal dimension to be less than 1.07, it is possible to realize a thermal spray material with further improved fluidity.
  • the average fractal dimension is preferably 1.05 or less and more preferably 1.03 or less in consideration of the fluidity of the thermal spray material. Furthermore, for example, it can be set to 1.02 or less and 1.01 or less, and is desirably 1 or closer to 1.
  • the angle of repose is less than 35 °.
  • the angle of repose can be one of the indexes that have been widely adopted to show the fluidity of powders.
  • it may be an index that can actually reflect the spontaneous fluidity when the thermal spray material is conveyed in the supply apparatus and the thermal spray apparatus. Therefore, by defining the angle of repose to be small, a spray material having high fluidity can be realized. As a result, it can be a thermal spray material capable of forming a homogeneous thermal spray coating with higher productivity.
  • the angle of repose is preferably 34 ° or less, and more preferably 32 ° or less.
  • the angle may be 30 ° or less.
  • the lower limit of the angle of repose is not particularly limited. However, if the angle of repose is too small, the sprayed material may be easily scattered or the supply amount of the sprayed material may be difficult to control. Therefore, as an approximate guide, the angle of repose is exemplified as 20 ° or more.
  • the thermal spray material disclosed herein preferably has a flow function of 3 or more.
  • the angle of repose is an index that can evaluate the fluidity of the thermal spray material in a no-load state.
  • this flow function evaluates the flow characteristics by measuring the shear stress in a compacted state of the thermal spray material, and can be an index that can more practically express the handling property of the thermal spray material. Therefore, even with such a configuration, for example, it is possible to determine that the thermal spraying material having an average particle diameter of less than 30 ⁇ m has high fluidity, and it is possible to provide a thermal spraying material that can form a thermal spray coating with higher productivity.
  • the “flow function” is a value called a so-called Relative Flow Index (RFI), and a predetermined amount of thermal spray material is placed in a container having an inner diameter of 50 mm. Measure the maximum principal stress and uniaxial collapse stress of the thermal spray material when a shearing force of 9 kPa is applied to the thermal spray material under humidity, and divide the measured value of the maximum principal stress by the measured value of the uniaxial collapse stress. This is the value obtained by. The larger the flow function, the better the fluidity of the sprayed material.
  • RFI Relative Flow Index
  • the thermal spray material provided by the technique disclosed herein maintains a relatively large average particle diameter of the ceramic particles contained therein, and thus, for example, the heat source supplyability to the thermal spray frame or the like ( Including fluidity). Further, since the specific surface area is defined to be extremely large, it can be sufficiently softened and melted at a lower temperature, and a fine structure can be realized. Therefore, it can be a thermal spray material capable of forming a thermal spray coating having a dense and fine structure with high productivity.
  • such a thermal spray material can be suitably realized as a suitable form, for example, including ceramic particles as secondary particles formed by bonding finer primary particles.
  • it may be ceramic particles in a form in which nanometer-sized primary particles are bonded.
  • the ceramic particles as such secondary particles it is possible to provide a sufficient gap between the finer primary particles, and the ceramic particles constitute secondary particles while maintaining the form of the primary particles. be able to. Therefore, for example, by using such a thermal spray material for thermal spraying, a high-quality thermal spray coating having the same characteristics as the case of thermal spraying using a thermal spray material having dimensions (for example, nanometer size) corresponding to primary particles is formed. be able to.
  • thermal spraying at a lower temperature is possible.
  • thermal spraying in the same manner as when using a thermal spray material having a dimension (for example, micrometer size) corresponding to the secondary particles.
  • a thermal spray material can be supplied to a thermal spraying apparatus with good fluidity, and a thermal spray coating with high efficiency and good adhesion can be formed at a high film forming speed.
  • a sprayed coating obtained by spraying such a sprayed material by, for example, a high-speed flame spraying method is a sprayed coating in which sprayed particles made of a ceramic material are deposited on a base material, and the cross section is perpendicular to the surface of the base material.
  • the average particle diameter of the spray particles is less than 5 ⁇ m, fine molten particles may be densely deposited.
  • the particle size of the spray particles is preferably 4 ⁇ m or less, more preferably 3 ⁇ m or less, further preferably 1 ⁇ m or less, and even more preferably 100 nm or less. Therefore, it may have characteristics comparable to the bulk of the thermal spray material.
  • thermo spray coating excellent in electrical characteristics such as denseness and insulation, corrosion resistance, and environmental barrier properties. Therefore, a film-formed product provided with such a thermal spray coating can be suitably applied to a wide variety of uses by being formed using a thermal spray material containing ceramic particles having desired characteristics.
  • a sprayed coating exhibiting high electrical insulation, wear resistance, and corrosion resistance can be obtained, and therefore, it can be suitably used as a protective coating for various members.
  • a thermal spray coating exhibiting high plasma erosion resistance can be obtained, and therefore, it can be suitably used as a protective coating inside a chamber of a semiconductor device manufacturing apparatus or the like.
  • the resulting sprayed coating is preferable because the plasma erosion resistance is further enhanced.
  • thermal spray coating that is hard and has excellent ion conductivity can be obtained, so that the solid oxide fuel cell (Solid Oxide Fuel Cel1: SOFC) solid It can be suitably used as an electrolyte or the like.
  • the thermal spray coating according to a desired use can be suitably formed with the thermal spray coating material disclosed here.
  • the above-mentioned thermal spray material can be applied to various thermal spraying methods without particular limitation.
  • it can be applied to a thermal spraying method in a high temperature process in which the temperature of the heat source is 2500 ° C. or higher, such as a plasma welding method, as in the past.
  • a thermal spraying method for example, when using a thermal spray material containing ceramic particles that are not in the form of secondary particles, the thermal spray material can be sufficiently softened and melted, and high-quality thermal spraying can be performed.
  • the plasma spraying method is a spraying method using a plasma flame as a thermal spraying heat source for softening or melting a thermal spray material.
  • the plasma spraying method includes a general coating technique in which a thermal spray material is put into this plasma jet, heated and accelerated, and deposited on a substrate by deposition.
  • Plasma spraying methods include atmospheric plasma spraying (APS) performed in the atmosphere, low pressure plasma spraying (LPS) performed at a pressure lower than atmospheric pressure, and pressure higher than atmospheric pressure. It may be an embodiment such as high pressure plasma spraying in which plasma spraying is performed in a pressure vessel.
  • APS atmospheric plasma spraying
  • LPS low pressure plasma spraying
  • the thermal spray material is heated and accelerated by a plasma jet at about 2500 ° C. to 10000 ° C. to cause the thermal spray particles to collide with the substrate at a speed of about 300 m / s to 600 m / s. Can be deposited.
  • the thermal spray material including ceramic particles formed by bonding finer primary particles
  • it can be sprayed at a temperature lower than the melting point of the ceramic material itself constituting the ceramic particles contained therein, for example, It is preferable to apply to a thermal spraying method in a low-temperature process where the temperature of the heat source is about 2500 ° C. or less (less than 2500 ° C.) because the advantages are manifested. Therefore, such a thermal spray material can be preferably applied to a thermal spraying method by a low temperature process represented by, for example, a high-speed flame spraying method or a foam spraying method.
  • such a thermal spray material can suitably realize a softened or molten state even when the ceramic particles are at a lower temperature.
  • the thermal spray material adheres to the base material with good adhesion and becomes finer.
  • a sprayed coating can be formed.
  • the spraying speed can be adjusted as appropriate using, for example, about 300 m / s or more and 2000 m / s or less.
  • Examples of the high-speed flame spraying method include an oxygen-flammable high-speed flame (HVOF) thermal spraying method, a warm spray thermal spraying method, and an air-flammable (High Velocity Air flame: HVAF) high-speed flame spraying method.
  • HVOF oxygen-flammable high-speed flame
  • the HVOF spraying method is a kind of flame spraying method in which a combustion flame in which fuel and oxygen are mixed and burned at high pressure is used as a heat source for spraying. By increasing the pressure in the combustion chamber, a high-temperature (which may be supersonic) high-temperature gas flow is ejected from the nozzle while being a continuous combustion flame.
  • the HVOF thermal spraying method includes a general coating technique in which a thermal spray material is put into this gas flow, and heated and accelerated to deposit it on a substrate to obtain a thermal spray coating.
  • the thermal spray material is melted and accelerated with a jet of a supersonic combustion flame of 1800 ° C. to 2500 ° C., so that the thermal spray particles can be obtained at a high speed of 500 m / s to 1000 m / s. It can be deposited by colliding with the material.
  • the fuel used in high-speed flame spraying may be a hydrocarbon gas fuel such as acetylene, ethylene, propane, or propylene, or a liquid fuel such as kerosene or ethanol. Further, the higher the melting point of the thermal spray material, the higher the temperature of the supersonic combustion flame is preferable. From this viewpoint, it is preferable to use gas fuel.
  • the warm spray spraying method is the above-described HVOF spraying method in which the temperature of the combustion flame is lowered by mixing the combustion flame with a cooling gas composed of nitrogen or the like at a room temperature. This is a technique for forming a sprayed coating.
  • the thermal spray material is not limited to a completely melted state.
  • a thermal spray material that is partially melted or softened below the melting point can be sprayed. According to this warm spray spraying method, for example, the sprayed material is melted and accelerated by a jet of a supersonic combustion flame at 1000 ° C.
  • the HVAF thermal spraying method is a thermal spraying method in which air is used in place of oxygen as a combustion support gas in the HVOF thermal spraying method.
  • the spraying temperature can be lowered as compared with the HVOF spraying method.
  • a thermal spray material is melted and accelerated by a jet of a supersonic combustion flame at 1600 ° C. to 2000 ° C., so that the thermal spray particles collide with a substrate at a high speed of 500 m / s to 1000 m / s and are deposited.
  • the thermal spray material disclosed herein thermal spraying at a temperature lower than the melting point of the ceramic material constituting the ceramic particles contained in the thermal spray material is enabled.
  • the As a result it is possible to form a film made of ceramics having a dense and fine structure by realizing sufficient melting while suppressing grain growth of ceramic particles having a three-dimensionally complicated structure.
  • the spraying temperature at a lower temperature is, for example, about 10 ° C. to 4000 ° C., for example, about 50 ° C. to 350 ° C. lower than the melting point.
  • a thermal spray coating made of alumina having a melting point of 2050 ° C. is formed at a thermal spray temperature of 2000 ° C. or lower, more specifically 1700 ° C. or lower. It is possible.
  • a thermal spray coating made of yttria stabilized zirconia having a melting point of 2600 ° C. or higher can be sprayed to 2550 ° C. or lower, more specifically 2300 ° C. or lower. It is possible to form at temperature.
  • a thermal spray coating made of mullite having a melting point of 1915 ° C. can be formed at a thermal spray temperature of 1900 ° C. or lower, more specifically 1860 ° C. or lower. It is said.
  • the thermal spray material disclosed herein can maintain high fluidity without depending on the average particle diameter, the thermal spray material can be efficiently and smoothly supplied to the thermal spraying device, and high-quality thermal spraying can be performed. A film can be formed with good productivity. Therefore, the method of supplying the spray material to the spraying device is not particularly limited. For example, it is preferable to perform the axial feed method, that is, to supply the thermal spray material in the same direction as the axis of the jet flow generated in the thermal spraying apparatus. From the viewpoint that the thermal spray material is less likely to adhere to the thermal spraying device, the thermal spray material can be kept in a more fluid state by supplying the thermal spraying material to the thermal spraying device by an axial feed method, and a uniform thermal spray coating can be obtained. It is preferable because it can be formed efficiently.
  • the spraying distance can be appropriately set depending on the spraying method and the spraying apparatus.
  • the distance from the nozzle tip to the substrate is preferably about 30 mm or more and 200 mm or less. If the spraying distance is too short, the thermal spray heat source is close to the base material, and therefore the base material may be altered or deformed, which is not preferable. If the spraying distance is too long, the speed of the molten particles is reduced and the cooling proceeds, so that sufficient adhesion may not be obtained, which is not preferable.
  • the spraying distance is within the above range, for example, the sufficiently heated sprayed particles can reach the substrate at an appropriate speed while maintaining the temperature, so that a sprayed coating having a dense and good adhesion is obtained. be able to.
  • the base material which is a sprayed material What consists of various materials can be used.
  • various materials include various metals or alloys. Specifically, for example, aluminum, aluminum alloy, iron, steel, copper, copper alloy, nickel, nickel alloy, gold, silver, bismuth, manganese, zinc, zinc alloy and the like are exemplified.
  • steels represented by various SUS materials which may be so-called stainless copper
  • heat resistant alloys represented by Inconel, Invar, Kovar, etc. which have a relatively large coefficient of thermal expansion among metal materials that are widely used.
  • a base material made of a low expansion alloy represented by, etc., a corrosion resistant alloy represented by Hastelloy, etc., an aluminum alloy represented by 1000 series to 7000 series aluminum alloys useful as a lightweight structural material, etc. is disclosed herein.
  • This method is preferable in that a finely sprayed coating having good adhesion can be formed suitably, and the advantages of the present invention can be clarified.
  • thermal spray materials of Samples 1 to 6 are all composed of alumina particles having an average particle diameter of 24 ⁇ m.
  • the thermal spray material of Sample 1 is manufactured by the melt-pulverization method, and the average particle diameter of primary particles made of alumina (Al 2 O 3 ) is 24 ⁇ m.
  • the thermal spray materials of Samples 2 to 6 are composed of alumina secondary particles having the above average particle diameter by forming and sintering primary particles made of alumina each having the average particle diameter shown in the table. Yes.
  • the thermal spray materials of Samples 7 and 8 contain particles having an average particle size of 24 ⁇ m, each composed of yttria (Y 2 O 3 ) and 8% Yttria-Stabilized Zirconia (8% YSZ). . These particles also form secondary particles having the above average particle diameter by granulating and sintering primary particles having the average particle diameter shown in the table.
  • the sprayed material was prepared by the following procedure by the melt-pulverization method. That is, first, raw material powder is blended so as to obtain a target ceramic (in this case, Al 2 O 3 ), the raw material powder is heated and melted, and then cooled to prepare a solidified product (ingot). .
  • the solidified product was pulverized by mechanical means and classified as necessary to obtain a thermal spray material.
  • the alumina particles contained in the thermal spray material of Sample 1 obtained by this melt-pulverization method were relatively dense and strong, and had a square or lump shape with an edge characteristic of the pulverized powder. .
  • the sprayed material was prepared by the granulation-sintering method according to the following procedure. That is, first, a ceramic (primary particles, in this case, ultrafine particles such as Al 2 O 3 , Y 2 O 3 , 8% YSZ) having a predetermined average particle diameter is subjected to surface treatment, together with a binder (PVA: polyvinyl alcohol). A slurry is prepared by thoroughly mixing and dispersing in a solvent (such as a mixed solution of water and alcohol). Next, the slurry is granulated into droplets using a spray granulator and a dry sintering furnace, and dried and sintered to obtain ceramic particles (secondary particles). And it was set as the thermal spray material by classifying this ceramic particle as needed.
  • a ceramic primary particles, in this case, ultrafine particles such as Al 2 O 3 , Y 2 O 3 , 8% YSZ
  • PVA polyvinyl alcohol
  • a slurry is prepared by thoroughly mixing and dispersing in a solvent
  • the ceramic particles contained in the thermal spray materials of Samples 2 to 8 obtained by the granulation-sintering method are substantially the same as shown in FIGS. 1 and 2, in which very fine primary particles are bonded to each other. It constitutes spherical secondary particles.
  • FIG. 1 is an image obtained by observing the thermal spray material of Sample 6 with a scanning electron microscope described later.
  • FIG. 2 is an image obtained by observing one ceramic particle in FIG. 1 at a high magnification.
  • very fine primary particles were observed in detail, they had a prismatic or massive shape with a specific crystal plane developed.
  • the specific surface area of the ceramic particles was measured based on the BET method using nitrogen gas as an adsorbed gas, using a flow type specific surface area automatic measuring device (manufactured by Shimadzu Corporation, Flowsorb II 2300). Specifically, after putting ceramic particles as a sample into a sample tube, the sample is cooled, nitrogen gas is introduced into the sample tube, and an adsorption / desorption isotherm by a constant volume method gas adsorption method is prepared.
  • the average aspect ratio of the ceramic particles is a planar view image (magnification 1000) obtained by observing the sprayed materials of Samples 1 to 8 with a scanning electron microscope (SEM, manufactured by Hitachi High-Technologies Corporation, S-3000N). ⁇ 2000 times) was calculated by calculating the arithmetic average of the aspect ratios measured for 100 or more ceramic particles using image analysis software (Image-Pro Plus, manufactured by Nippon Rover Co., Ltd.).
  • the aspect ratio specifies the contour of the ceramic particle from the contrast of the SEM image, and the major axis length of the corresponding ellipse (the ellipse having the same area and the same primary and secondary moments) is the major axis a and the minor axis length. This is a value obtained by determining the aspect ratio defined by a / b from these values, where the minor axis is b.
  • the measurement result of the average aspect ratio of the ceramic particles is shown in the column of “Average aspect ratio” in Table 1.
  • the average fractal dimension of the ceramic particles is the image of a planar view image obtained by observing the sprayed materials of Samples 1 to 8 with a scanning electron microscope (SEM, manufactured by Hitachi High-Technologies Corporation, S-3000N). Using an analysis software (Image-Pro Plus, manufactured by Nippon Rover Co., Ltd.), the arithmetic average value of the fractal dimension measured for 100 or more ceramic particles was calculated. SEM analysis conditions were as follows: magnification: 2000 times, bit depth: 8, scanning speed: 80/100 s. In addition, the SEM image used for the measurement of the fractal dimension is prepared to realize a resolution in which the peripheral length of the ceramic particles is 30 pixels or more (preferably 1280 pixels or more.
  • the angle of repose of the thermal spray material is the same as that of the thermal spray material of Samples 1-8.
  • B. D. This is a value obtained by applying to a powder property measuring instrument (ABD-72, manufactured by Tsutsui Science Instruments Co., Ltd.).
  • the measurement results of the repose angle of the thermal spray material are shown in the column “Repose angle” in Table 1.
  • [Flow function] For reference, the thermal spray material of Sample 6 was measured with a powder fluidity analyzer (Powder Rheometer FT4, manufactured by Freeman Tchnology). As a result, the flow function of the thermal spray material of Sample 6 was 9.2.
  • the spraying material prepared above was sprayed by the HVOF spraying method, which is a low-temperature process, to evaluate the film formability of the sprayed coating by the spraying material.
  • the thermal spraying conditions were as follows. That is, first, an SS400 steel plate (70 mm ⁇ 50 mm ⁇ 2.3 mm) was prepared as a base material, and the surface was roughened by performing a blasting process using a # 40 alumina grid. A commercially available high-speed flame sprayer (Praxair / TAFA, JP-5000) was used for HVOF spraying.
  • the upper limit of the flame temperature is about 2000 ° C., which is much lower than the melting point of the ceramic used for the thermal spray material.
  • the thermal spray material was supplied to the burner chamber of the thermal sprayer at a supply rate of about 15 g / min in a dry powder state using a powder feeder (TechnoServ, AM-30).
  • the thermal sprayer was supplied with acetylene gas as a fuel gas at a flow rate of 75 L / min and oxygen gas as a combustion aid at a flow rate of 230 L / min.
  • a supersonic jet of about 1500 ° C. to 2500 ° C.
  • the unit ( ⁇ m / pass) representing the film formation rate is formed by a single spraying operation (1 pass) performed by the spraying device (spraying gun) along the operating direction of the spraying device or the object to be sprayed (base material).
  • the thickness ( ⁇ m) of the sprayed coating that can be obtained is shown.
  • the size (equivalent circle diameter) of the thermal spray particles constituting the solid phase portion was measured.
  • the measurement of the size of the thermal spray particles constituting the thermal spray coating was obtained by observing with a scanning electron microscope (Scanning Electron Microscope: SEM, manufactured by Hitachi High-Technologies Corporation, S-3000N) 2000.
  • Fig. 3 illustrates an SEM image of the cross-sectional structure of the sprayed coating obtained by spraying the sprayed material of Sample 5.
  • the observation image used for the measurement of the size of the spray particles constituting the coating is, for example, a resolution in which the peripheral length of the ceramic particles is 30 pixels or more as shown in FIG. Preferably.
  • the thermal spray material of Sample 1 has a small specific surface area of 0.1 m 2 / g, the thermal spray material cannot be sufficiently softened and melted by HOVF thermal spraying, which is a low temperature process. The deposited particles could not be deposited on the substrate.
  • the thermal spray material of Sample 1 has an average particle diameter of 24 ⁇ m, which is not extremely large, but the average roundness is as large as 1.8, and the spray material is unevenly conveyed in the powder feeder and the thermal spraying apparatus. Was confirmed to occur.
  • thermal spray material of Sample 1 was prepared by the melt-pulverization method and was not subjected to special polishing or the like, so that there were many corners in the ceramic particles, and the fluidity of the thermal spray material was reduced. It is considered a thing.
  • a thermal spray coating can be formed by adopting a plasma spray method or the like which is a high temperature process.
  • the fluidity of the thermal spray material is not sufficiently obtained, the supply amount of the thermal spray material is not constant, spitting occurs, and the quality of the thermal spray coating is not necessarily sufficient. I could not say.
  • the thermal spray material of sample 2 has a specific surface area of 0.4 m 2 / g, which is larger than the thermal spray material of sample 1, it is not sufficient. Therefore, the thermal spray material is softened by HVOF thermal spraying, which is a low temperature process, and the molten particles adhere to the substrate. However, particles that are not sufficiently softened could not contribute to film formation.
  • the thermal spray material of Sample 2 has a slightly large average roundness of 1.5, and a sufficient fluidity was not obtained. Therefore, there is a slight unevenness in the conveyance of the thermal spray material in the powder feeder and the thermal spraying apparatus. It was confirmed.
  • thermal spray material of sample 2 is prepared by a granulation-sintering method, and the average roundness is suppressed to be lower than that of the thermal spray material of sample 1, but the shape is sufficiently close to a perfect sphere. It was thought that it was because it was not possible. Although the average aspect value of the thermal spray material of Sample 2 was the smallest among all samples, the fluidity of such a thermal spray material can be roughly estimated from the average aspect value, but it has been confirmed that it cannot be fully evaluated up to the detailed range. did it. Although not specifically shown, even with such a thermal spray material, a thermal spray coating can be formed by employing a plasma thermal spraying method or the like. However, even in that case, since the fluidity of the thermal spray material is not sufficiently obtained, the supply amount of the thermal spray material is not constant, spitting occurs, and the quality of the thermal spray coating is not necessarily sufficient. I could not say.
  • the thermal spray material of Samples 3 to 8 has a sufficiently large specific surface area of 0.5 m 2 / g or more, as described above, the thermal spray material is also used in HVOF thermal spraying at a temperature lower than the melting point of the thermal spray material. It was confirmed that the film could be sufficiently melted and heated to form a homogeneous film.
  • the specific surface area can be suitably used for thermal spraying at a lower temperature by increasing the specific surface area to 0.5 m 2 / g or more. It was confirmed that it was possible.
  • the thermal spray materials of Samples 3 to 8 have an average particle diameter of 30 ⁇ m or less, but are sufficiently large as 20 ⁇ m or more, and an average roundness of less than 1.5. It was possible to supply the spray frame at a constant flow rate without clogging in the apparatus.
  • the thermal spray material of Samples 3 to 8 can form a thermal spray coating consisting of a fine and dense structure with a particle diameter of less than 5 ⁇ m.
  • the thermal spray materials of Samples 3 to 6 are made of alumina.
  • the thermal spray temperatures of Samples 3-6 are significantly lower than 1800 ° C. and 1600 ° C., respectively, which is about 2050 ° C., which is the melting point of alumina.
  • the thermal spray materials of Samples 7 and 8 are made of yttria and yttria stabilized zirconia.
  • the thermal spray temperatures of Samples 7 and 8 are 2300 ° C.
  • thermal spray material disclosed here, it is possible to form a thermal spray coating composed of a sufficiently dense and fine structure even by HVOF thermal spraying at a temperature lower than the melting point of the thermal spray material itself. Was confirmed.
  • the average particle diameter is less than 6 ⁇ m (for example, 0.01 ⁇ m to 3 ⁇ m) and very fine primary particles are bonded with a gap. It is comprised from the ceramic particle formed by this. Therefore, even if the temperature of the frame does not reach the melting point, it is considered that such a thermal spray material is sufficiently softened and melted to form a thermal spray coating suitably. That is, according to the thermal spray material composed of ceramic particles in the form of secondary particles in which ultrafine particles are bonded with a gap as disclosed herein, a high-quality thermal spray coating is produced even in a low-temperature process below the melting point, for example. It was shown that it can be formed with good properties.
  • the primary particles are in the form of nanoparticles or a form close thereto. Therefore, it has been found that the average primary particle diameter of the thermal spray particles constituting the thermal spray coating formed using such a thermal spray material is refined to about 1 ⁇ m or less, and an extremely dense coating structure is formed.
  • the thermal spray coating formed from the thermal spray material of Samples 5 to 8 can be extremely dense, for example, the porosity determined by cross-sectional SEM observation is about 1% or less.

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Abstract

La présente invention concerne un matériau de projection thermique capable de former, avec une productivité satisfaisante, un film de revêtement de projection thermique qui est constitué d'une céramique ayant une structure dense et fine. Le matériau de projection thermique de la présente invention contient des particules de céramique ayant un diamètre de particule moyen de 30 µm au moins et une surface spécifique de 0,5 m2/g ou plus. Dans un mode de réalisation préféré, ces particules de céramique sont sous la forme de particules secondaires toutes constituées de particules primaires conjointement fixées de façon tridimensionnelle de manière à comporter des interstices entre celles-ci.
PCT/JP2014/079869 2013-11-26 2014-11-11 Matériau de projection thermique et film de revêtement de projection thermique WO2015079906A1 (fr)

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CN106868443A (zh) * 2017-02-24 2017-06-20 中国人民解放军装甲兵工程学院 一种超音速等离子喷涂工艺涂层优化方法
CN112410719A (zh) * 2020-10-20 2021-02-26 安徽华飞机械铸锻有限公司 一种抗磨性的耐热钢
CN113365964A (zh) * 2019-01-29 2021-09-07 福吉米株式会社 覆盖颗粒、包含其的分散液和成型体、以及使用其而形成的烧结体
EP4201881A1 (fr) * 2021-12-23 2023-06-28 SENIC Inc. Poudre de carbure de silicium et procédé de fabrication de lingot de carbure de silicium l'utilisant

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