WO2012099350A2 - 상온진공과립분사 공정을 위한 취성재료 과립 및 이를 이용한 코팅층의 형성방법 - Google Patents
상온진공과립분사 공정을 위한 취성재료 과립 및 이를 이용한 코팅층의 형성방법 Download PDFInfo
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- WO2012099350A2 WO2012099350A2 PCT/KR2012/000086 KR2012000086W WO2012099350A2 WO 2012099350 A2 WO2012099350 A2 WO 2012099350A2 KR 2012000086 W KR2012000086 W KR 2012000086W WO 2012099350 A2 WO2012099350 A2 WO 2012099350A2
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C24/00—Coating starting from inorganic powder
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Definitions
- the present invention relates to brittle material granules whose properties are controlled for a room temperature vacuum granule injection process and a method of forming a coating layer using the same.
- the aerosol deposition process is made by injecting brittle material particles of the size of hundreds of 1 ⁇ ⁇ ⁇ J into which the plastic deformation does not occur in the powder accommodating mechanism or the aerosolization apparatus, and injecting the conveying gas into the aerosolization apparatus while applying mechanical vibration. It is a process of manufacturing a dense coating layer at room temperature by spraying an aerosol composed of gas and brittle material fine particles with a nozzle.
- the aerosol deposition process is to form a coating layer by laminating fine particles to the substrate at a speed of 100 ⁇ 400 m / s to form a coating layer by laminating the metal powder, the plastic deformation occurs to the substrate at a supersonic speed of 400 ⁇ 1500 m / s
- the source energy for brittle powders to form a dense coating layer is the movement energy, which depends on the mass and kinetic velocity of the particles. If the kinetic energy of the particles is too small, the coating layer is not formed or a porous green compact is formed. If the kinetic energy of the particles is too large, erosion occurs to cut the substrate or the already formed coating layer. Can be formed.
- the fine particles used to form the coating layer should be fine particles having an average diameter of 0.1 to 5 /, and the coarse particles in which the fine particles are aggregated do not contribute to or form a coating layer. is itdi but t is the fine particles are fine particles in the material powder to a powder receiving mechanism jolhwa mechanism or air are ungjip over time, there is a problem in forming or applying a coating layer onto the achievement of a large area.
- the particles of several hundreds of millimeters in size used in the aerosol deposition process are characterized by being physically bound and bonded by adsorption of water or electrostatic attraction. Due to the coagulation of the particles of brittle material, the particulate powder in the aerosol deposition apparatus powder feeder or the aerosol mechanism is difficult to see. It is changed to coarse particles of various sizes that are not controlled according to the simple flow, which makes it impossible to supply uniform and uniform powder, and becomes uneven even when sprayed through the nozzle, and affects the productivity and workability of the coating layer manufacturing process. It also affects the quality of the deposited coating layer.
- 242942 describes a method of deliberately collecting fine particles having an average diameter of primary particles of 0.1 to 5 to form a granulated particle having an average diameter of 20 to 500 n and a compressive strength of 0.015 0.47 MPa and using it as a raw material. Since these preparation particles have a sufficiently large size, coarse grains between the preparation particles are suppressed, so that powder supply can be smoothly performed for a long time.
- the raw powder composed of the granulated particles is stored in a powder container, and the powder is uniformly injected from the powder container into a separate disintegrating apparatus, whereby the granulated particles are again pulverized into fine particles having an average diameter of 0.1 to 5,
- Korean Patent Laid-Open No. 10—2007-0008727 relates to a composite structure in which a structure made of a brittle material such as ceramic or metal is formed on a surface of a substrate, and a method and apparatus for manufacturing the composite structure.
- a method of forming a coating layer by pulverizing brittle material fine particles such as applied ceramics or metals at high speed toward a substrate and colliding the brittle material fine particles is described.
- the coating layer prepared by the method disclosed in the prior patent has a problem that the thickness is not uniform.
- the inventors of the present invention while studying how to prevent the coagulation of the brittle material particles and the resulting uneven powder supply phenomenon in the aerosol deposition process, it is possible to impart fluidity by controlling the characteristics of the brittle material powder It suppresses the pores caused by the physical bonds between the fine particles, and directly sprays the multiparticulate coarse particles having an average strength of 5 / zm or more without disintegration, so that there is no non-uniformity such as pores, cracks or lamellas.
- the present invention has been developed a method of controlling the characteristics of a brittle material multiparticulate aggregate or granules and a method of manufacturing a brittle material coating layer using the same.
- aerosol means a state in which the ultra-fine particles and gas is mixed, but in the present invention, since the particles mixed with the gas is a granule of 5 ⁇ 500 ⁇ size, it is difficult to name the aerosol, accordingly Instead of an aerosol deposition using an aerosol in which fine particles and a carrier gas are mixed, the coating process in the present invention will be referred to as a room temperature vacuum granulation process.
- An object of the present invention is to provide a brittle material granules for the room temperature vacuum granulation spray process.
- Another object of the present invention is to provide a method of forming a coating layer using the granules of brittle material.
- It provides granules of brittle material, characterized in that the granules of 0.1 to 6 size is granulated to form a coating layer through a vacuum granulation process.
- ⁇ 16> a material preparation step of charging granules of brittle material into a mixing container and fixing the substrate to a stage (step 1);
- ⁇ ! 7> a gas supply step of supplying a carrier gas into the mixing container to mix the granules and the carrier gas of the brittle material (step 2);
- a brittle material coating layer including a granulation spraying step (step 3) of transporting the mixed carrier gas and the brittle material granules in the mixing vessel of step 2 to the nozzle and then spraying the substrate to the substrate of step 1 through the nozzle. It provides a method of forming.
- the brittle material granules according to the present invention can supply granules through a room temperature vacuum granule injection process and can carry out a coating process continuously, and have high kinetic energy as the mass of granules injected through the nozzle is relatively large.
- the coating layer can be prepared even at low gas flow rates, and the deposition rate can be increased, which can be usefully used for preparing ceramic coating layers.
- the coating layer forming method according to the invention exhibits a porosity of 10% or less, it is possible to produce a coating layer having a uniform microstructure without any non-uniformity, such as cracks, macropores or layered structure.
- FIG. 1 is a conceptual diagram schematically showing granulation of brittle material granules according to the present invention
- FIG. 2 is a conceptual diagram schematically showing a room temperature vacuum spraying apparatus for manufacturing a brittle material coating worm according to the present invention
- Figure 5 is a graph analyzing the particle diameter of the raw material powders that can be used as a raw material of the brittle material granules according to the present invention
- Figure 6 is a graph comparing the particle size of the brittle material granules and the raw material powder according to the present invention.
- FIG. 7 and 8 are photographs analyzing the formation of the coating layer of the brittle material granules (A1 2 0 3 ) and the raw material powder (A1 2 0 3 ) similar in average particle diameter to the brittle material granules according to the present invention
- FIG. 9 is a graph showing a change in compressive strength according to the heat treatment temperature of Pb (Zr, Ti) 0 3 granules according to the present invention and a photograph of a coating layer formed using the granules;
- FIG. 10 is a graph showing a change in compressive strength according to the heat treatment temperature of Ti0 2 granules according to the present invention, and a photograph of a coring layer formed using the granules;
- FIG. 11 is a graph showing the change in compressive strength according to the heat treatment temperature of the yttria stabilized zirconia (YSZ) granules according to the present invention and a photograph of the coating layer formed using the granules;
- YSZ yttria stabilized zirconia
- FIG. 13 is a photograph of a coating layer formed using molybdenum disulfide granules according to the present invention, and a coating layer formed using molybdenum disulfide raw powder used for preparing the granules.
- Example 14 is a graph of X-ray diffraction analysis of Pb (Zr, Ti) 0 3 granol prepared in Example 1 according to the present invention.
- Example 15 shows aluminum nitride (A1N) granules prepared in Example 31 according to the present invention.
- X-ray diffraction graph is a graph obtained by X-ray diffraction analysis of a coating layer formed by vacuum spraying Pb (Zr, Ti) 0 3 granules prepared in Examples 2 and 8 according to the present invention;
- FIG. 19 is a photograph of a coating layer-ol scanning electron microscope formed using Pb (Zr, Ti) 0 3 granules prepared in Example 8 according to the present invention.
- Example 20 is a photograph of a GDC granules prepared in Example 23 according to the present invention and a coating layer formed using GDC / Gd 2 O 3 granules prepared in Examples 25 and 27 with a scanning electron microscope;
- FIG. 21 is a photograph of hydroxyapatite granules prepared in Example 49 according to the present invention with a microscope before injection;
- FIG. 22 is a photograph of hydroxyapatite granules prepared in Example 52 according to the present invention according to the present invention with a scanning electron microscope; FIG.
- FIG. 23 is a photograph of a coating layer formed using a hydroxyapatite granules prepared in Example 49 according to the present invention and a coating layer formed using a raw powder used for preparing the granules by scanning electron microscopy;
- Example 24 and 25 are photographs analyzing the coating characteristics of the yttria stabilized zirconia (YSZ) granules prepared in Example 21 according to the present invention according to the coating conditions;
- 26 is a photograph showing the large-area coating capacity of the brittle material granules according to the present invention.
- FIG. 27 is a photograph observing the state of the particles before and after coating of the brittle material granules according to the present invention.
- FIG. 28 is a graph showing electrical properties of a coating layer formed using Pb (Zr, Ti) 0 3 granules prepared in Example 7 according to the present invention.
- the present invention provides a brittle material granules, characterized in that the granules of 0.1 to 6 IM size is granulated to form a coating layer through a room temperature vacuum granulation process.
- the brittle material granules according to the present invention has an average diameter of 5 500, pressure
- the axial strength is 0 ⁇ 05 ⁇ 20 MPa, which is suitable for the room temperature vacuum granulation process.
- the aerosol deposition process uses brittle material fine particles of several hundred nm ⁇ number of sizes, there may be a problem of uneven supply of powder during continuous coating due to the adsorption and congestion of moisture.
- the brittle material granules according to the present invention have an average diameter of 5 ⁇ 500, it is possible to suppress the coarse grain between the granules by physical bonding, it is possible to supply a continuous and uniform powder due to the fluidity, the strength of the granules 0.05 to 20 MPa (compressive strength) can be exhibited by spraying the granules through a nozzle to form a dense coating layer on the surface of the substrate.
- the brittle material granules according to the present invention may exhibit a strength (compressive strength) of 0.05 to 20 MPa so as to prevent the above problems to be sprayed through a nozzle to form a dense coating layer on the substrate.
- the aerosol in the aerosol deposition process means a state in which the ultra-fine particles and the gas is mixed, the brittle material granules according to the present invention is a particle size of 5 to 500 because the coating process in the present invention It is referred to as a room temperature vacuum granulation process, not an aerosol deposition.
- the brittle material granules according to the present invention may form a coating layer through the phase silver vacuum granule spraying process, and the room temperature vacuum granule spraying process includes an artificial disintegration process.
- the aerosolized raw material is not sprayed through the nozzle, and that the brittle material granules according to the present invention are sprayed through the nozzle while maintaining the original form.
- Japanese Patent Laid-Open Publication No. 2009-242942 performs an aerosol deposition process using preparation particles in which particles are intentionally condensed as raw materials, but aerosols are supplied by disintegrating the preparation particles into a separate disintegrating apparatus. And then the nozzle Spraying through. That is, although the raw material is used as a raw material, the injection through the nozzle is an aerosolized raw material can not be applied to the material that can not form a coating layer through the aerosol deposition.
- the brittle material granules according to the present invention simply by granulating a material such as MoS 2 that could not form a coating layer in the conventional aerosol deposition process and spraying through a nozzle without performing an artificial disintegration process. It is possible to form a coating layer, it is possible to quickly coat a dense coating layer.
- the brittle material granules include hydroxyapatite, phosphate, bioglass,
- Pb (ZrJi) 0 3 PZT
- Alumina Titanium Dioxide, Zirconia (Zr0 2 ), Yttria (Y 2 0 3 ), Yttria stabilized Zirconia (YSZ, Yttria stabilized Zirconia), Dy 2 0 3 ), Gadolinia (Gd 2 0 3 ), ceria (Ce0 2 ), gadolinia doped Ceria, magnesia (MgO), barium titanate (BaTi0 3 ), nickel manganate (NiMn 2 0 4 ), Potassium sodium niobate (KNaNb0 3 ), bismuth potassium titanate (BiKTi0 3 ), bismuth sodium titanate
- Mn x Co 3 ) 4 (where x is a positive real number of 3 or less) and the like, bismuth ferrite (BiFe0 3 ), bismuth zinc niobate (Bi Zr NbuO?), Lithium aluminum phosphate germanium glass ceramic, Lithium Aluminum Phosphate Titanium Glass Ceramic, Li-La-Zr— 0 Garnet Oxide, Li-La-Ti-0 Perovskite Oxide, La-Ni-0 Oxide, Lithium Iron Phosphate, Li-Cobalt Oxide, Li-Mn -0 Spinel oxide (lithium manganese oxide), lithium aluminum phosphate gallium oxide, tungsten oxide, tin oxide, lanthanum nickel nickel, lanthanum-strontium-manganese oxide, lanthanum-strontium iron-cobalt oxide, silicate-based phosphor, SiAlON-based Metal oxides such as phosphors, aluminum nitrides
- the brittle material granules according to the present invention may include pores having a size of 0.1 to 10 mm 3. The pores invade substances such as antibiotics and growth factor proteins.
- the brittle material granules according to the present invention may contain drugs, growth factor proteins and the like, and the brittle material granules can be applied to the pharmaceutical field.
- a material preparation step (step 1), in which granules of brittle material are charged into a mixing vessel and a substrate is provided in a chamber of a vacuum atmosphere;
- a gas supply step of supplying a carrier gas into the mixing container of step 1 to mix the brittle material granules and the carrier gas step 2;
- Granule spraying step of transporting the mixed carrier gas and the brittle material granules in the mixing vessel of step 2 to the nozzle, and then spraying to the substrate of the step 1 through the nozzle (step
- the method of forming the brittle material coating coating according to the present invention may be performed using the coating apparatus as disclosed in Figure 2 of the Republic of Korea Patent Publication No. 10-2011-0044543 as an example, but is not limited thereto.
- the aerosol deposition apparatus can be modified to be suitable for granulation.
- step 1 is a step of charging the brittle material granules into a mixing container and providing a substrate in a chamber of a vacuum atmosphere, where the raw material brittle material granules and coating layer are formed.
- the substrate to be loaded is charged and provided in a coating apparatus.
- step a preparing a slurry by mixing a brittle material particle powder of 0.1 to 6 size with a solvent and then adding a binder (step a);
- ⁇ 2> can be prepared through a manufacturing process comprising the step (step b) of granulating the slurry prepared in step a1.
- Step a of the manufacturing process is a step of preparing a slurry by mixing a brittle material particulate powder of 0.1 to 6 ⁇ size, which is a raw material of the brittle material granules and a solvent, and adding a binder, wherein the binder is a brittle material particulate powder
- a brittle material particulate powder of 0.1 to 6 ⁇ size
- the binder is a brittle material particulate powder
- 9 TKR2012 / 000086 Content may vary, but polyvinyl alcohol (PVA), polyacrylic acid (PAA), 2-octane (2-octanol), polyvinyl butyral (PVB), polyethylene glycol (PEG), etc. And combinations thereof may also be used as binders.
- the amount of the binder may vary depending on the type of binder with respect to the brittle material particulate powder, but may be added in the range of 0.2 to 3.0% by weight, but is not limited thereto.
- the binder When the binder is added below the range, the interparticle bonding becomes weak, and there is a problem that it is difficult to control the shape of brittle materials, and when the binder is exceeded, the granulation yield decreases as the excess binder is used. There is a problem that the manufacturing cost increases.
- the solvent may be ethanol, methane, acetone, isopropyl alcohol, ethyl acetate, methyl ethyl ketone, or the like.
- the mixing of the brittle material particulate powder and the solvent is preferably a weight ratio of 5-8: 2-5, the mixing range may increase the weight ratio of the brittle material particulate powder to 8 to increase the yield, but is not limited thereto. It is not.
- a dispersant and an antifoaming agent may be further added.
- an organic solvent as a solvent, it is easy to control the viscosity and concentration without dispersing agent and antifoaming agent, but it is suitable to spray the prepared granules through a nozzle, but when using water, it may be difficult to control the viscosity and concentration of the slurry. Accordingly, by further adding a dispersant and an antifoaming agent, it is preferable to make the granules of the brittle material prepared to be sprayed through a nozzle, but is not limited thereto.
- Step b of the manufacturing process is a step of granulating the slurry prepared in step a, wherein the slurry prepared in step 1 contains a large amount of binder, and the ball mill process and the spray drying process Rurry can be granulated. At this time, the binding force between the particles can be maintained as it is by the organic binder, brittle material granules according to the present invention can be produced through the granulation.
- the brittle material granules according to the present invention are composed of fine particles bound by a binder, it is possible to represent ⁇ (not even ⁇ ) in a room temperature vacuum granulation process, so that a dense coating layer can be obtained through a room temperature vacuum granulation process. Can be formed.
- granulated brittle material granules may be used without performing heat treatment.
- the granulated brittle material granules may be heat treated to remove it.
- the heat treatment is carried out at a temperature of 200 to 1500 ° C. It can be carried out for 1 to 24 hours, thereby removing the binder present in the brittle material granules and to produce granules of appropriate strength. If the heat treatment temperature is less than 200 ° C, there is a problem that some of the binders of the brittle material granules remain. If the heat treatment temperature exceeds 1500 ° C, the brittle material granules are excessively calcined and excessive energy is generated. There is a problem of exhaustion.
- the heat treatment temperature may be designed by optimizing according to the composition and size of the brittle material particulate powder used as a raw material (for example, hydroxyapatite: 500 1200 "C, PZT: 400-900 ° CY 2 0 3 : 500 ⁇ 1500 ° C , YSZ: 500
- 1 is a schematic diagram showing the aggregation state of the brittle material granules before and after the heat treatment process. Before performing the heat treatment process, the brittle material particulate powders are bound by the binder, and after performing the heat treatment process, it can be seen that the binder is removed and bound through the primary interparticle bonding. In addition, the brittle material granules of step 1
- step a Mixing a brittle material particulate powder, a polymer material and a solvent having a size of 0.1 to 6 ⁇ and then adding a binder to prepare a slurry (step a);
- step b Granulating the slurry prepared in step a (step b);
- Heat-treating the granulated granules in step b can be prepared through a manufacturing process comprising the step of removing the polymer material in the granules (step c).
- Step a of the manufacturing process is a step of preparing a slurry by mixing a brittle material particulate powder polymer material and a solvent of 0.1 to 6 size, which is the raw material of the brittle material granules, and adding a binder, wherein the binder is a composition of the brittle material particulate powder Type and content may vary depending on particle size, polyvinyl alcohol (PVA), polyacrylic acid (PM), 2-octanol (2-octanol), polyvinyl butyral (PVB), polyethylene glycol (PEG) ) May be used, and a mixture thereof may also be used as a binder.
- PVA polyvinyl alcohol
- PM polyacrylic acid
- PM 2-octanol
- PVB polyviny
- the amount of the binder is brittle material, but may vary depending on the kind of the binder with respect to the fine particles powder, 0.2 ⁇ a g r effort ⁇ ka ⁇ ring ⁇ ⁇ ⁇ 4 the ⁇ 2 when added to less than 2 t the range to ngeol
- the binding between the particles is weak, difficult to control the shape of the brittle material granules, when the excess of the binder is used, the granulation yield is lowered as the excess binder is used, there is a problem that the manufacturing cost increases.
- Water or an organic solvent may be used as the solvent, and the mixing of the brittle material fine particle powder and the solvent is preferably in a weight ratio of 5 8: 2 to 5.
- the mixing range is 11 T / KR2012 / 000086
- the weight ratio of the brittle material particulate powder can be increased to 8 to increase the yield.
- the polymer material may be polyvinylidene fluoride, polyimide, polyethylene, polystyrene, polymethyl methacrylate, polytetrafluoroethylene, starch, or the like, and a combination thereof may also be used.
- the polymers are materials that can be burned out by heat treatment. By removing the polymers after granulation, pores may be formed at the positions where the polymers are located and particle strength may be controlled.
- Step b of the manufacturing process is a step of granulating the slurry prepared in step a, wherein the slurry prepared in step a contains a large amount of binder, and the slurry is prepared through a ball mill process and a spray drying process. Can be granulated. At this time, the binding force between the particles can be maintained as it is by the organic binder, brittle material granules according to the present invention can be produced through the granulation,
- Step C of the manufacturing process is a step of removing the polymer material in the granules by heat-treating the granules granulated in the step b may remove the polymer material to form pores in the granules.
- the heat treatment of step c may be carried out for 1 to 24 hours at a temperature of 200-1500 ° C, through which the polymer in the granules of brittle material can be removed to form pores, and also remove the binder present in the granules can do.
- the pores formed in step 3 can penetrate substances such as drugs, growth factor proteins, such as antibiotics, through which the brittle material granules according to the present invention can be applied to the pharmaceutical field.
- brittle material granulate of step 1 may comprise a pore size of 0.1 to 10.
- the pores may penetrate substances such as antibiotics and growth factor proteins, so that the brittle material granules may include drugs and growth factor proteins.
- step 2 is
- Step 1 is to mix the brittle material granules and the carrier gas by supplying a carrier gas in the mixing vessel of (1).
- the brittle material granules should be transferred to the nozzle using a carrier gas.
- the carrier gas is supplied into the mixing container, and thus the brittle material and the brittle material inside the mixing container are supplied.
- the lip mixes with the carrier gas and scatters.
- a carrier gas may be additionally injected, but is not limited thereto.
- the brittle material granules unlike the raw material powder in the general powder spraying process is characterized by excellent fluidity and large mass, does not require an excess carrier gas. Therefore, the brittle material granules can be transferred to the nozzle even when a relatively small amount of carrier gas is supplied.
- step 3 is the step
- step 2 is a granulation spraying step of transporting the mixed carrier gas and the brittle material granules in the mixing vessel of 2, and then spraying the substrate to the substrate of step 1 through a nozzle.
- the carrier gas flow rate is preferably in the range of 0.1 6 L / min per 1 Mf of the nozzle slit, but is not limited thereto.
- the coating layer can be prepared only when the carrier gas flow rate is 2 L / min or more per 1 f of the nozzle slit (the room temperature vacuum granulation process of the present invention All other conditions are the same).
- the brittle material granules have better fluidity than powders, so no excess carrier gas is required.
- the mass of the brittle material granules is larger than that of the general powder, it has a high kinetic energy, resulting in an improved deposition rate even at a gas flow rate of 1 L / min or less per 1 ⁇ 2 of the nozzle slit, and the coating layer can be prepared ( Experimental Example 3). Furthermore, unlike the powder, the brittle material granules can be continuously supplied, so that continuous coating is possible.
- the method of forming the coating layer according to the present invention is carried out by spraying the brittle material granules as raw materials to the substrate through the nozzle. At this time, the brittle material granule is
- the granules of the brittle material are not artificially disintegrated, but are laminated with the substrate to the same size as before being sprayed through the nozzle to form a coating layer.
- the coating layer By forming the coating layer as a raw material of the brittle material granules, it is possible to prevent the raw material from being crowded by using the raw material in a powder state in a conventional room temperature vacuum spraying process, it is also possible to further improve the quality of the resulting coating layer. . ⁇ 10>
- the present invention provides a brittle material coating layer manufactured by the method of forming the coating layer.
- the brittle material coating layer prepared by the coating layer forming method has an average diameter of 5 ⁇ 500
- Brittle material granules having a compressive strength of 0.05 to 20 MPa are produced by direct injection into a substrate in a vacuum atmosphere without performing an artificial disintegration process.
- a coating layer having a dense microstructure having a porosity of 10% or less without cracking or micron size pores is prepared.
- the coating shows a microstructure without lamellar (see Experimental Example 5).
- the brittle material coating layer may be used for the drug release function implant and the composite coating for the composite functional device.
- the brittle material granules as raw materials include PVDF, polyimide, polyethylene, pulleystyrene, PMMA, starch and the like, the porous coating layer may be provided by removing the materials as necessary.
- Pb (Zr, Ti) 0 3 powder and water are mixed at a weight ratio of 1: 1, polyvinyl alcohol is used as a binder, 2% by weight relative to Pb (Zr, Ti) 0 3 powder, and polyacrylic acid is 0.5 Weight 3 ⁇ 4 and 2-octane
- Slurry was prepared by adding 0.3% by weight. The slurry was ball milled and then spray dried to prepare Pb (Zr, Ti) 0 3 granules.
- Pb (Zr, Ti) 0 3 powder and water are mixed at a weight ratio of 1: 1, and polyvinyl alcohol as a binder 2% by weight of Pb (Zr, Ti) 0 3 powder, 0.5% by weight of polyacrylic acid and 2-octanol
- Slurry was prepared by adding 0.3% by weight. The slurry was ball milled, spray dried, and heat treated at 500 ° C. for 5 hours to prepare Pb (Zr, Ti) 0 3 granules.
- Pb (Zr, Ti) 0 3 granules were prepared in the same manner as in Example 2, except that the heat treatment was performed at 500 ° C. for 10 hours.
- Pb (Zr, Ti) 0 3 granules were prepared in the same manner as in Example 2, except that the heat treatment was performed at 600 ° C. for 5 hours.
- Pb (ZrJi) 0 3 granules were prepared in the same manner as in Example 2, except that heat treatment was performed at 600 ° C. for 10 hours.
- Pb (Zr, Ti) 0 3 granules were prepared in the same manner as in Example 2, except that the heat treatment was performed at 650 ° C. for 5 hours.
- Pb (Zr, Ti) 0 3 granules were prepared in the same manner as in Example 2, except that the heat treatment was performed at 700 ° C. for 5 hours.
- Pb (Zr, Ti) 0 3 granules were prepared in the same manner as in Example 2, except that the heat treatment was performed at 700 ° C. for 6 hours.
- Pb (Zr, Ti) 0 3 granules were prepared in the same manner as in Example 2, except that heat treatment was performed at 800 ° C. for 5 hours.
- Pb (Zr, Ti) 0 3 granules were prepared in the same manner as in Example 2, except that heat treatment was performed at 900 ° C. for 5 hours.
- Pb (Zr, Ti) 0 3 granules were prepared in the same manner as in Example 2, except that heat treatment was performed at 1200 ° C. for 5 hours.
- Ti0 2 granules were prepared in the same manner as in Example 1, except that Ti0 2 powder was used instead of Pb (Zr, Ti) 0 3 powder.
- Ti0 2 granules were prepared in the same manner as in Example 2, except that Ti0 2 powder was used instead of Pb (Zr, Ti) 0 3 powder.
- Ti0 2 granules were prepared in the same manner as in Example 13 except that the heat treatment was performed at a temperature of 600 ° C.
- Ti0 2 granules were prepared in the same manner as in Example 13, except that heat treatment was performed at a temperature of 700 ° C. for 2 hours. i62> Example 16 Preparation of Ti0 2 Granules 5
- Ti0 2 granules were prepared in the same manner as in Example 13, except that heat treatment was performed at a temperature of 800 ° C. for 2 hours.
- Ti0 2 granules were prepared in the same manner as in Example 13 except that the heat treatment was performed at a temperature of 900 ° C. '
- Ti0 2 granules were prepared in the same manner as in Example 13 except that heat treatment was performed at a temperature of ⁇ 6> 1000 ° C.
- Yttria stabilized zirconia (YSZ) granules were prepared in the same manner as in Example 1 except that yttria stabilized zirconia (YSZ) powder was used instead of Pb (Zr, Ti) 0 3 powder.
- the yttria stabilized zirconia (YSZ) granules of Example 19 were removed at a temperature of 600 'C.
- the yttria stabilized zirconia (YSZ) granules were prepared in the same manner as in Example 19 except that the heat treatment was performed for a period of time.
- Yttria stabilized zirconia (YSZ) granules were prepared in the same manner as in Example 20 except that the heat treatment was performed at a temperature of 800 ° C.
- Yttria stabilized zirconia (YSZ) granules were prepared in the same manner as in Example 20 except that heat treatment was performed at a degree of silver of 1000 ° C.
- YSZ Yttria stabilized zirconia
- GDC gadolinic-containing ceria
- Gadolinia-added ceria (GDC) granules were prepared in the same manner as in Example 1 except that GDC) powder was used.
- Gadolinia-added ceria (GDC) / Gadolinia (Gd) was carried out in the same manner as in Example 1 except that GDC) powder and gadolinia (Gd 2 0 3 ) powder (4 wt%) were used in combination. 2 0 3 ) granules were prepared.
- Gadolinia-added ceria (GDC) / gadolinia (Gd 2 0 3 ) granules of Example 24 were subjected to the same procedure as Example 24 except that the granules were heat-treated at 600 t for 2 hours. Added Ceria (GDC) / Gadolinia (Gd 2 O 3 ) granules were prepared.
- Gadolinian-added ceria (GDC) / Gadolinia was carried out in the same manner as in Example 24 except that the gadolinia (Gd 2 0 3 ) powder of Example 24 was mixed at a ratio of 10 weight 3 ⁇ 4 (Gd 2 0 3 ) granules were prepared.
- the gadolinian-added ceria (GDC) / gadolinia (Gd 2 0 3 ) granules of Example 26 were 1000 Gadolinia-added ceria (GDC) / gadolinia (Gd 2 0 3 ) granules were prepared in the same manner as in Example 26 except that the mixture was heat-treated at ° C for 2 hours.
- Tungsten carbide (WC) powder and ethanol, an organic solvent, are mixed at a weight ratio of 1: 1, and polyvinyl butyral (PVB) is added at a ratio of 1% by weight to tungsten carbide powder as a binder.
- PVB polyvinyl butyral
- Tungsten carbide (WC) granules were prepared in the same manner as in Example 29, except that the tungsten carbide (WC) granules of Example 29 were heat-treated at 700 ° C. for 3 hours in an ultrahigh-purity argon atmosphere. .
- Aluminum nitride (A1N) granules were prepared in the same manner as in Example 29, except that aluminum nitride (A1N) powder was used instead of tungsten carbide 0) powder.
- Aluminum nitride (A1N) granules of Example 31 were prepared in the same manner as in Example 31 except that the aluminum nitride (A1N) granules of Example 31 were heat-treated in a nitrogen atmosphere at 500 ° C. for 2 hours.
- ammonium aluminum nitride (A1N) granules were prepared.
- Example 32 except that the mixture was heat-treated in a nitrogen atmosphere at 800 ° C. for 2 hours.
- Aluminum nitride (A1N) granules were prepared in the same manner as in the following. 19 R2012 / 000086
- Aluminum nitride (A1N) granules were prepared in the same manner as in Example 32 except that the mixture was heat-treated in a nitrogen atmosphere at 1000 ° C. for 2 hours.
- Aluminum boride (A1B 12 ) granules were prepared in the same manner as in Example 29, except that aluminum boride (A1B 12 ) powder was used instead of tungsten carbide (WC) powder.
- the aluminum boride (A1B 12 ) granules of Example 36 were prepared in the same manner as in Example 36, except that the granulated aluminum boride (A1B 12 ) granules were heat-treated at 700 ° C. for 3 hours in an ultrapure argon atmosphere to prepare aluminum boride (A1B 12 ) granules. It was.
- Lanthanum borohydride (La3 ⁇ 4) granules were prepared in the same manner as in Example 29, except that lanthanum boride (LaB 6 ) powder was used instead of tungsten carbide (WC) powder.
- Example 39 boronated lanthanum (LaB 6) 2 embodiment Preparation of granules
- Example 38 boronated lanthanum of (LaB 6) in the example except that the heat-treating the granules at 700 ° Ah at C for 3 hours ultrapure Zorgon atmosphere
- Lanthanide boron (LaB 6 ) granules were prepared in the same manner as in 38.
- Silicon (Si) granules were prepared in the same manner as in Example 1 except that silicon (Si) powder was used instead of Pb (Zr, Ti) 0 3 powder.
- a molybdenum disulfide (MoS 2 ) granule was prepared in the same manner as in Example 29 except that molybdenum disulfide (MoS 2 ) powder was used instead of tungsten carbide (WC) powder.
- a yttria (Y 2 0 3 ) granules were prepared in the same manner as in Example 44 except that the mixture was heat treated at 1050 ° C.
- a yttria (Y 2 0 3 ) granules were prepared in the same manner as in Example 44 except that the mixture was heat treated at 1100 ° C.
- a yttria (Y 2 0 3 ) granules were prepared in the same manner as in Example 44 except that the mixture was heat treated at 1150 ° C. 1 12000086
- a yttria (Y 2 0 3 ) granol was prepared in the same manner as in Example 44 except for the heat treatment at 1200 ° C.
- a hydroxyapatite granules were prepared in the same manner as in Example except that hydroxyapatite powder was used instead of Pb (Zr, Ti) 0 3 powder.
- a hydroxyapatite (HA) granules of Example 49 were prepared in the same manner as in Example 49 except that the hydroxyapatite (HA) granules were heat treated at 600 ° C. for 1 hour.
- HA Hydroxyapatite
- Granules were prepared.
- a hydroxyapatite granules were prepared in the same manner as in Example 50 except that PMMA) was used in combination. At this time, the prepared hydroxyapatite granules were removed from the polymethyl methacrylate during the heat treatment process to prepare a porous granules.
- Example 12 Ti0 2 --Example 13 Ti0 2 500 5
- Example 20 Yttria stabilized Zirco 600 2
- Example 23 GDC--Example 24 GDC / Gd 2 0 3 --Example 25 GDC / Gd 2 0 3 600 2
- Example 26 GDC / Gd 2 0 3 --Example 27 GDC / GdOs 800 2
- Example 29 Tungsten Carbide (wc)-Example 30 Lungste Carbide (WC) 700 3
- the brittle material granules prepared in the above example were introduced into a room temperature vacuum co-injection apparatus schematically shown in FIG. 2, and the brittle material granules were sprayed onto the substrate through a nozzle to prepare a brittle material coating layer.
- the particle diameters of the respective material powders were measured using a particle size analyzer and a scanning electron microscope. The results are shown in FIGS. 3 to 6. As shown in Fig. 3, the average particle diameter (d50) of the Pb (Zr, Ti) 0 3 raw material powder is about 1.36.
- the average particle diameter of the raw material powder that can be used as a raw material for producing the brittle material granules is 0.1 to 6.
- the particle sizes of the brittle material granules and the raw material powders prepared in Examples 12, 43 and 49 according to the present invention were analyzed. It can be seen that it is larger than the size of the powder particles. Through this, raw material particles can be combined to infer that brittle material granules are formed.
- the brittle material granules according to the present invention exhibit excellent fluidity.
- the powder used in the conventional aerosol deposition did not appear any flow rate so that the flow rate could not be measured. It can be seen that the brittle material granules according to the present invention exhibits excellent fluidity and can be continuously transported even with a relatively small amount of carrier gas.
- the brittle material granules according to the present invention can form a coating layer through room temperature vacuum spraying.
- the raw powder having a size similar to that of the granules cannot form a coating layer through room temperature vacuum spraying as shown in FIG. 8. That is, it can be seen that the coating layer can be formed by vacuum spraying the granules of brittle material according to the present invention, and it can be seen that a raw material powder having only a large size cannot form a coating layer.
- the brittle material granules according to the present invention is a material suitable for forming a coating layer through room temperature vacuum spraying.
- the change according to the heat treatment temperature in 12 to 18, the Ti0 2 granules of Example 17 and Example 18 having a high heat treatment temperature was found to have a relatively higher compressive strength.
- the coating layer can be formed even if the compressive strength of the Ti0 2 granules changes according to the heat treatment temperature, and through this, the heat treatment of the brittle material granules according to the present invention. It was confirmed that the compression strength value can be controlled by appropriately adjusting the temperature.
- the compressive strength of the yttria stabilized zirconia (YSZ) granules according to the present invention changes depending on the heat treatment temperature in Examples 20 to 22, and the higher the heat treatment temperature, the higher the compressive strength. It was found that the strength was high.
- the coating layer can be formed even if the compressive strength of the yttria stabilized zirconia (YSZ) granules changes according to the heat treatment temperature. It was confirmed that the compressive strength value can be controlled by appropriately adjusting the heat treatment temperature of the granules.
- the brittle material granules having a compressive strength of 0.72 MPa and the brittle material granules having a compressive strength of 3 MPa can be seen to form a coating layer through room temperature vacuum spraying.
- the brittle material granules having a compressive strength of more than 27 MPa do not form a coating layer.
- the brittle material granules according to the present invention can form a coating layer through Sangmon 3 ⁇ 4 ⁇ spray as it has a compressive strength value of 0.05 to 20 MPa.
- the molybdenum disulfide granules according to the present invention can be vacuum sprayed at room temperature to form a coating layer.
- the coating layer is not properly formed, it can be seen that the coated portion is also easily washed.
- the molybdenum disulfide granules according to the present invention was smoothly coated even when the flow rate was 0.69 L / min, but in the case of molybdenum disulfide powder, a green compact was formed at the same flow rate as the granules. Furthermore, it can be seen that the coating does not proceed smoothly even when a relatively large flow rate is supplied.
- Pb (Zr, Ti) 0 3 granules according to the present invention have a heat treatment temperature of 500 ° C, 600 ° C, 650 ° C, 700 ° C, 800 ° C, 900 ° C. It can be seen that the crystal phase does not change even if the heat treatment time is performed for 5 hours, 6 hours, 24 hours.
- the aluminum nitride (A1N) granules according to the present invention can be seen that the crystal phase does not change even if the heat treatment temperature is performed at 600 ° C, 800 ° C, 1000 ° C. . Through this, the brittle material granules according to the present invention have no texture change even after heat treatment.
- the Pb (Zr, Ti) 0 3 granules prepared in Examples 2 and 8 according to the present invention were formed by vacuum spraying at room temperature to form a coating layer, followed by heat treatment of the formed coating layer, which was then subjected to X-ray diffraction analysis (XRD).
- XRD X-ray diffraction analysis
- the post-heat-treated coating layer does not generate secondary phase or change in crystal structure.
- the crystal structure of the coating layer does not appear according to the heat treatment conditions during granulation.
- the Pb (Zr, Ti) 0 3 (PZT) granules according to the present invention are made of spherical granules.
- the higher the heat treatment temperature shows a granule shape combined with the larger particles. .
- the coating layer was formed by vacuum spraying the Pb (Zr, Ti) 0 3 (PZT) granules prepared in Example 8 according to the present invention, and the formed coating layer was heat-treated at a temperature of 700 ° C for 1 hour.
- the microstructure change before and after the heat treatment was observed through a scanning electron microscope, and the results are shown in FIG. 19.
- the coating layer formed by vacuum spraying Pb (ZrJi) 0 3 (PZT) granules exhibits a healthy microstructure without the occurrence of cracks. It can be seen that it has a uniform microstructure that is not made. In addition, it can be seen that the crack does not occur in the coating layer even after the heat treatment of the coating layer.
- the brittle material according to the present invention can be 3 ⁇ 4 3 ⁇ 4 in the nose by spraying at room temperature vacuum, and the microstructure of the formed coating layer is dry. The battleship was identified.
- the coating layer may be formed by vacuum spraying the GDC granules prepared in Example 23, and the GDCs prepared in Examples 25 and 27 and Gd 2 0 3 may be mixed with each other. It can be seen that the coating layer can be formed by vacuum spraying the prepared GDC / Gd 2 O 3 granules at room temperature. Through this, it was confirmed that the brittle material granules according to the present invention were easy to form a coating layer even when prepared using a mixed powder.
- the hydroxyapatite lime granules prepared in Example 49 according to the present invention are prepared in the form of spherical granules.
- the hydroxyapatite granules prepared in Example 52 include PMMA particles before heat treatment, but it can be seen that pores are formed at the positions where PMMA particles are located by removing PMMA particles through heat treatment.
- the coating layer formed using the hydroxyapatite granules of Example 49 has no difference in microstructure with the coating layer formed using the hydroxyapatite powder.
- the hydroxyapatite granules are manufactured in a spherical shape, and pores can be formed by adding a polymer material.
- the brittle material granules according to the present invention are coated with a coating layer formed using a conventional powder. In comparison, it was confirmed that a coating layer having no structural difference could be formed.
- the yttria stabilized zirconia according to the present invention As shown in FIG. 24, the yttria stabilized zirconia according to the present invention.
- the Ti0 2 granules and the Ti0 2 raw powder prepared in Example 12 have a 600 X 650 (mm 2 ) area.
- the coating conditions of Ti0 2 granules and Ti0 2 powder were carried out in the same manner, the results are shown in FIG.
- the granules before supplying to the room temperature vacuum injection device Example 1
- granules remaining in the common container without being transported to the nozzle And granules sprayed through the nozzles and remaining in the vacuum chamber were observed with a scanning electron microscope, and the results are shown in FIG. 27.
- the granules and the nozzles remaining without being transported to the nozzles are sprayed and sprayed to allow the vacuum chamber to flow into the vacuum chamber ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ , which is supplied to the room temperature vacuum spraying device. It can be seen that it matches the previous granule form. Through this, the brittle material granules according to the present invention was in the room temperature vacuum granule injection process, was sprayed through a nozzle in the state of not disintegrated, it was confirmed that the granules remain intact even after being sprayed through the nozzle.
- the dielectric properties of the Pb (Zr, Ti) 0 3 coating layer prepared using the Pb (Zr, Ti) 0 3 granules according to the present invention (FIG. 23 (a)) and the ferroelectric Analysis of the hysteresis curve (FIG. 23 (b)) shows that the typical ferroelectric coating layer exhibits characteristics .
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Abstract
Description
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CN201280013407.7A CN103501888B (zh) | 2011-01-18 | 2012-01-04 | 室温真空颗粒喷射的脆性材料颗粒及其形成涂膜的方法 |
JP2013550391A JP6101634B2 (ja) | 2011-01-18 | 2012-01-04 | 常温真空顆粒噴射工程のための脆性材料顆粒を用いたコーティング層の形成方法 |
US13/980,313 US20130295272A1 (en) | 2011-01-18 | 2012-01-04 | Granules of a Brittle Material for Room Temperature Granule Spray in Vacuum, and Method for Forming a Coating Film Using Same |
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---|---|---|---|---|
KR20060110352A (ko) * | 2004-01-22 | 2006-10-24 | 쇼와 덴코 가부시키가이샤 | 금속산화물 분산액, 금속산화물 전극막, 및 색소 증감 태양전지 |
KR20070008727A (ko) * | 1999-10-12 | 2007-01-17 | 도토기키 가부시키가이샤 | 복합 구조물 |
KR20080071193A (ko) * | 2005-11-23 | 2008-08-01 | 아이언우드 파마슈티컬스, 인코포레이티드 | 위장 장애의 치료 방법 및 치료 조성물 |
JP2009242942A (ja) * | 2008-03-10 | 2009-10-22 | Toto Ltd | 複合構造物形成方法、調製粒子、および複合構造物形成システム |
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2012
- 2012-01-04 WO PCT/KR2012/000086 patent/WO2012099350A2/ko active Application Filing
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20070008727A (ko) * | 1999-10-12 | 2007-01-17 | 도토기키 가부시키가이샤 | 복합 구조물 |
KR20060110352A (ko) * | 2004-01-22 | 2006-10-24 | 쇼와 덴코 가부시키가이샤 | 금속산화물 분산액, 금속산화물 전극막, 및 색소 증감 태양전지 |
KR20080071193A (ko) * | 2005-11-23 | 2008-08-01 | 아이언우드 파마슈티컬스, 인코포레이티드 | 위장 장애의 치료 방법 및 치료 조성물 |
JP2009242942A (ja) * | 2008-03-10 | 2009-10-22 | Toto Ltd | 複合構造物形成方法、調製粒子、および複合構造物形成システム |
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