WO2016035870A1 - 溶射用スラリー、溶射皮膜および溶射皮膜の形成方法 - Google Patents
溶射用スラリー、溶射皮膜および溶射皮膜の形成方法 Download PDFInfo
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- WO2016035870A1 WO2016035870A1 PCT/JP2015/075139 JP2015075139W WO2016035870A1 WO 2016035870 A1 WO2016035870 A1 WO 2016035870A1 JP 2015075139 W JP2015075139 W JP 2015075139W WO 2016035870 A1 WO2016035870 A1 WO 2016035870A1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
- C23C4/134—Plasma spraying
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/06—Metallic material
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/06—Metallic material
- C23C4/08—Metallic material containing only metal elements
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
- C23C4/11—Oxides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
- C23C4/129—Flame spraying
Definitions
- the present invention relates to a thermal spray slurry containing thermal spray particles, a thermal spray coating formed using the thermal spray slurry, and a method for forming the thermal spray coating.
- thermal spraying sprayed particles made of materials such as ceramics, cermet and metal on the surface of a base material in a softened or molten state by combustion energy or electric energy for imparting new functionality by coating the surface of a substrate with various materials.
- a thermal spraying method for forming a thermal sprayed coating comprising:
- thermal spray particles as a coating material are supplied in a powder state to a thermal spraying apparatus.
- the thermal spraying apparatus has been supplied to a thermal spraying apparatus in a slurry (including suspension, suspension, etc.) in which thermal spray particles are dispersed in a dispersion medium.
- Patent Document 1 can be cited.
- the thermal spray particles sometimes settle and precipitate during storage of the slurry due to the difference in specific gravity between the thermal spray particles and the dispersion medium and the particle size of the thermal spray particles. Since the deposited thermal spray particles lose fluidity, the thermal spraying slurry that is likely to precipitate is not suitable as a thermal spraying material. Further, when the amount of the sprayed particles to be precipitated is increased, there is a possibility that the amount of sprayed particles supplied is reduced or clogging occurs in the supply device.
- the present invention has been created based on the above knowledge, and an object thereof is to provide a slurry for thermal spraying that can form a suitable thermal spray coating. Another object of the present invention is to provide a thermal spray coating formed using the slurry for thermal spraying and a method for forming the thermal spray coating.
- the present invention provides a slurry for thermal spraying having the following characteristics as a solution to the above problems.
- the slurry for thermal spraying includes thermal spray particles made of at least one material selected from the group consisting of ceramics, cermets, and metals, and a dispersion medium. Then, the spray particles contained in 800 mL of the thermal spray slurry is Akg, and the thermal spray slurry 800 mL in which the thermal spray particles are in a dispersed state is placed in a horizontally disposed tube with an inner diameter of 5 mm and a length of 5 m.
- the thermal spraying apparatus it is possible to evaluate the supply property when supplying the slurry to the thermal spraying apparatus in consideration of the dispersibility and fluidity of the thermal spray particles in the thermal spraying slurry. And it can be said that the slurry for thermal spraying whose feedability index If is 70% or more is in a state in which the sedimentation of particles is suppressed, and the feedability to the thermal spraying apparatus is good. Thereby, even if it is the slurry for thermal spraying which produces precipitation in long-term storage, the precipitation solidification of the thermal spray particle is suppressed, and the thermal spraying slurry which can be stably supplied to the thermal spraying apparatus in a suitable dispersion and flow state Realized.
- a preferable embodiment of the slurry for thermal spraying disclosed herein is characterized by further containing a dispersant. With such a configuration, the dispersion stability of the spray particles in the slurry is improved, and a slurry for thermal spraying with improved feedability is provided.
- a preferred embodiment of the slurry for thermal spraying disclosed herein is characterized in that the thermal spray particles are contained in a proportion of 10 wt% or more and 50 wt% or less.
- a slurry for thermal spraying is provided in which the deposition of the thermal spray particles is suitably suppressed while containing the thermal spray particles at an appropriate concentration.
- the sprayed particles have an average particle diameter of 0.01 ⁇ m or more and 10 ⁇ m or less. With this configuration, a slurry for thermal spraying in which sedimentation of thermal spray particles is suitably suppressed is provided.
- the “average particle diameter” related to the sprayed particles employs an average particle diameter (equivalent sphere diameter) calculated based on the specific surface area for sprayed particles having an average particle diameter of less than 1 ⁇ m.
- S the specific surface area of the spray particles
- ⁇ the density of the material constituting the spray particles.
- the spray particles are yttria (yttrium oxide; Y 2 O 3 )
- the density ⁇ can be calculated as 5.01 g / cm 3 .
- the value measured by a gas adsorption method can be employ
- This specific surface area can be measured according to the provisions of JIS Z 8830: 2013 (ISO 9277: 2010) “Method for measuring specific surface area of powder (solid) by gas adsorption”.
- the specific surface area of the spray particles can be measured by using a surface area measuring device manufactured by Micromeritics, Inc., trade name “FlowSorb II 2300”.
- the particle diameter (50% volume average particle diameter) in the volume-based particle size distribution measured by a particle size distribution measuring apparatus based on the laser diffraction / scattering method is 50%. ) Is adopted as the “average particle size”.
- the critical value (1 ⁇ m) of the particle diameter of the sprayed particles to which the above measurement method is applied is not necessarily exact.
- the average particle diameter may be measured based on the laser diffraction / scattering method, depending on the accuracy of the analytical instrument used.
- the viscosity of the said slurry for thermal spraying is 1000 mPa * s or less, It is characterized by the above-mentioned. With such a configuration, a slurry for thermal spraying is provided in which sedimentation of the thermal spray particles is suppressed and the flow state is suitably adjusted.
- the viscosity of the slurry for thermal spraying is a viscosity at room temperature (25 ° C.) measured using a rotary viscometer.
- a value measured using a B-type viscometer for example, Viscotester VT-03F manufactured by Rion Co., Ltd.
- the dispersion medium is an aqueous dispersion medium.
- a thermal spray material with reduced environmental load is provided without using or requiring the use of an organic solvent.
- the use of an aqueous dispersion medium is advantageous in that the surface of the obtained thermal spray coating becomes smoother and the surface roughness is reduced as compared with the case of using a non-aqueous dispersion medium.
- the dispersion medium is a non-aqueous dispersion medium.
- the thermal spray material which can be sprayed at lower temperature is provided.
- the use of a non-aqueous dispersion medium is advantageous in that the porosity of the obtained sprayed coating is reduced as compared with the case where an aqueous dispersion medium is used.
- the present invention provides a thermal spray coating obtained by thermal spraying any one of the above thermal spraying slurries.
- a thermal spray coating can be formed, for example, by thermal spraying with high efficiency using thermal spray particles having a relatively small average particle diameter. Therefore, it can be formed as a dense sprayed coating with high adhesion and coating strength.
- the technology disclosed herein provides a method for forming a thermal spray coating.
- This method is characterized in that a thermal spray coating is formed by spraying one of the above slurry for thermal spraying.
- spray particles having a relatively small average particle diameter can be supplied to a spraying device and a spray frame with good fluidity and high efficiency, for example, a dense spray coating with high adhesion and coating strength. Can be formed.
- the thermal spray slurry is supplied to a thermal spraying apparatus at a flow rate of 10 mL / min to 200 mL / min and sprayed.
- a flow rate 10 mL / min to 200 mL / min and sprayed.
- the thermal spray coating is formed by high-speed flame spraying or plasma spraying of the slurry for thermal spraying.
- the dispersion medium in the slurry for thermal spraying may be either an aqueous solvent or a non-aqueous solvent. Therefore, it is possible to form a sprayed coating by adopting a spraying method suitable for realizing desired coating properties.
- the thermal spray slurry is supplied to the thermal spraying apparatus by an axial feed method.
- the “axial feed method” is a method of supplying a slurry for thermal spraying from the center of a thermal spray heat source (for example, a plasma arc or a combustion flame) in the generation direction of the thermal spray heat source or the axial direction of the torch nozzle.
- the slurry for thermal spraying is used with two feeders so that the fluctuation periods of the amount of the thermal spray slurry supplied from both feeders are in opposite phases to each other. And supplying to the thermal spraying apparatus. According to such a configuration, it is possible to further suppress the thermal spray material having a relatively large average particle diameter from aggregating and settling in the slurry, and to supply the slurry at a substantially constant rate without unevenness. This is preferable because a sprayed coating with less variation can be formed on the coating structure.
- the slurry for thermal spraying is sent out from a feeder, temporarily stored in a tank immediately before the thermal spraying apparatus, and slurry for thermal spraying in the tank is used by utilizing natural fall. And supplying to the thermal spraying apparatus.
- the state of the slurry for thermal spraying can be adjusted in the tank immediately before the thermal spraying device, and the thermal spraying material having a relatively large average particle diameter is prevented from agglomerating or settling in the slurry, It becomes possible to supply at a substantially constant rate without unevenness. This is also preferable because a sprayed coating with little variation can be formed on the coating structure.
- the thermal spray slurry is supplied to the thermal spraying apparatus via a conductive tube.
- a conductive tube Such a configuration is preferable because generation of static electricity is suppressed in the slurry for thermal spraying flowing in the conductive tube, and the supply amount of the thermal spray particles is hardly changed.
- the technique disclosed herein provides a thermal spray slurry preparation material (hereinafter, simply referred to as “preparation material”) used to prepare a thermal spray slurry.
- the slurry for thermal spraying includes thermal spray particles made of at least one material selected from the group consisting of ceramics, cermets, and metals, and a dispersion medium. Then, the spray particles contained in 800 mL of the slurry for spraying are set to A kg, and 800 mL of the slurry for spraying in which the spray particles are in a dispersed state are placed in a horizontally arranged tube having an inner diameter of 5 mm and a length of 5 m.
- the slurry preparation material disclosed here is characterized by including at least any one or more constituents constituting the thermal spraying slurry.
- the above-mentioned slurry for thermal spraying is suppressed in precipitation and solidification even if its constituent components can cause precipitation. Therefore, for example, even when the constituents of the slurry for thermal spraying are divided into a plurality of units (for example, when they are packaged), the slurry for thermal spraying is suitably and easily prepared by mixing them. Can do. Further, it is preferable to divide the slurry for thermal spraying into a plurality of units, so that the storage stability can be further improved, and space saving and easy transportability during storage can be realized.
- the preparation material is further provided with information for preparing the slurry for thermal spraying.
- this preparation material is a part of constituent material of the slurry for thermal spraying, the slurry for thermal spraying can be prepared appropriately.
- any one or more of the constituent components may include the spray particles.
- any one or more of the constituent components may include the spray particles and at least a part of the dispersion medium.
- this preparation material may further contain a dispersing agent. That is, the preparation material disclosed herein can be provided in various modes according to the user's request, for example.
- the thermal spraying slurry disclosed herein essentially includes thermal spray particles made of at least one material selected from the group consisting of ceramics, cermets and metals, and a dispersion medium.
- the supply index If defined below is 70% or more.
- the thermal spray particles contained in 800 mL of the thermal spray slurry are Akg.
- the mass of the spray particles contained in the slurry is Bkg.
- a value calculated by the following formula: If (%) B / A ⁇ 100;
- the slurry for thermal spraying disclosed herein can include thermal spray particles made of at least one material selected from the group consisting of ceramics, cermets, and metals.
- the ceramic is not particularly limited.
- oxide ceramics composed of various metal oxides carbide ceramics composed of metal carbide carbides, nitride ceramics composed of metal nitrides, other metal borides, fluorides, hydroxides
- Non-oxide ceramics composed of non-oxides such as oxides, carbonates and phosphates
- the oxide ceramics are not particularly limited and may be oxides of various metals.
- metal elements that constitute such oxide ceramics include metalloid elements such as B, Si, Ge, Sb, and Bi, Na, Mg, Ca, Sr, Ba, Zn, Al, Ga, In, Sn, and the like.
- Typical metal elements such as Pb and P, transition metal elements such as Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Ag, and Au
- transition metal elements such as Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Ag, and Au
- lanthanoid elements such as La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tu, Yb, and Lu.
- 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.
- oxide ceramics include alumina, zirconia, yttria, chromia, titania, cobaltite, magnesia, silica, calcia, ceria, ferrite, spinel, zircon, forsterite, steatite, and cordierite.
- Mullite 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, neodymium oxide, tin oxide, antimony oxide, tin oxide containing antimony, indium oxide, barium titanate, lead titanate, lead zirconate titanate, n-Zn ferrite, Ni-Zn ferrite, sialon, tin-containing indium oxide, zirconium oxide aluminate, zirconium oxide silicate, hafnium oxide aluminate, hafnium oxide silicate, titanium oxide silicate, lanthanum oxide silicate, lanthanum oxide aluminate, yttrium oxide
- Examples include silicate, titanium oxide silicate, tantalum
- non-oxide ceramics include carbide ceramics such as tungsten carbide, chromium carbide, niobium carbide, vanadium carbide, tantalum carbide, titanium carbide, zirconium carbide, hafnium carbide, silicon carbide and boron carbide, and silicon nitride. , Nitride ceramics such as aluminum nitride, borate ceramics such as hafnium boride, zirconium boride, tantalum boride and titanium boride, hydroxide ceramics such as hydroxyapatite, phosphate ceramics such as calcium phosphate, etc. Is mentioned.
- carbide ceramics such as tungsten carbide, chromium carbide, niobium carbide, vanadium carbide, tantalum carbide, titanium carbide, zirconium carbide, hafnium carbide, silicon carbide and boron carbide, and silicon nitride.
- Nitride ceramics such as aluminum nit
- the metal is not particularly limited, and examples thereof include various kinds of metal elements listed as constituent elements of the above ceramics and alloys composed of these elements and one or more other elements.
- Typical examples of the simple metal include nickel, copper, aluminum, iron, chromium, niobium, molybdenum, tin, and lead.
- Examples of the alloy include a nickel base alloy, a chromium base alloy, a copper base alloy, and steel.
- an alloy here is the meaning which includes the substance which consists of said metal element and one or more other elements, and shows a metallic property, Comprising:
- the mixing method is a solid solution, an intermetallic compound. And a mixture thereof.
- the cermet is not particularly limited, and general composite materials in which ceramic particles are bonded with a metal matrix can be considered.
- a cermet can be, for example, a composite of ceramic and metal raised as described above. More specifically, for example, titanium compounds such as titanium carbide (TiC) and titanium carbonitride (TiCN), carbide ceramics such as tungsten carbide (WC) and chromium carbide (CrC), or alumina (Al 2 O 3 ).
- TiC titanium carbide
- TiCN titanium carbonitride
- CrC tungsten carbide
- CrC chromium carbide
- a typical example is a composite (cermet) of an oxide ceramic such as iron (Fe), chromium (Cr), molybdenum (Mo), or nickel (Ni).
- Such a cermet can be prepared, for example, by firing desired ceramic particles and metal particles in an appropriate atmosphere.
- the ceramic, cermet, and metal may be a mixture or composite of materials each having two or more compositions. Moreover, any two or more of ceramics, cermet, and metal may be made into a mixture.
- the above sprayed particles are not particularly limited as long as the average particle size is about 30 ⁇ m or less, and there is no particular limitation on the lower limit of the average particle size.
- the average particle diameter of the spray particles can be, for example, 10 ⁇ m or less, preferably 8 ⁇ m or less, more preferably 5 ⁇ m or less, for example, 1 ⁇ m or less.
- the viscosity and fluidity of the slurry for thermal spraying for example, it can be 0.01 ⁇ m or more, preferably 0.05 ⁇ m or more, more preferably 0.1 ⁇ m or more, For example, it can be 0.5 ⁇ m or more.
- the slurry for thermal spraying disclosed herein for example, even spray particles having an average particle diameter of 10 ⁇ m or less are prepared as a slurry in consideration of the supply ability to the thermal spraying device. Adhesion to a route or the like is suppressed, and the film forming ability can be kept high. In addition, since it is supplied to the frame or jet stream in the state of slurry, it can ride on the flow without being bounced by such frame or jet, and the dispersion medium is removed during the flight, so the thermal spraying efficiency is improved. Further, it is possible to form a thermal spray coating while maintaining the height higher.
- the thermal spray particles are not necessarily limited to this, but if the specific surface area is too large, the viscosity of the slurry for thermal spraying becomes too high, and the supply property is inferior.
- the specific surface area of the spray particles is preferably 50 m 2 / g or less, more preferably 40 m 2 / g or less, and 30 m 2 / g or less (for example, 20 m 2 / g or less, further 10 m 2 / g or less).
- the lower limit of the specific surface area is not strictly limited, but can be, for example, 0.1 m 2 / g or more.
- a value measured by a gas adsorption method can be adopted as the specific surface area.
- the specific surface area can be measured according to the provisions of JIS Z 8830: 2013 (ISO 9277: 2010) “Method for measuring specific surface area of powder (solid) by gas adsorption”.
- the specific surface area of the spray particles can be measured by using a surface area measuring device manufactured by Micromeritics, Inc., trade name “FlowSorb II 2300”.
- the slurry for thermal spraying disclosed herein can contain an aqueous or non-aqueous dispersion medium.
- the aqueous dispersion medium include water or a mixture of water and a water-soluble organic solvent (mixed aqueous solution).
- water tap water, ion exchange water (deionized water), distilled water, pure water, or the like can be used.
- organic solvent other than water constituting this mixed aqueous solution one or more organic solvents (for example, lower alcohols or lower ketones having 1 to 4 carbon atoms) that can be homogeneously mixed with water are appropriately selected. Can be used.
- aqueous solvent for example, it is preferable to use a mixed aqueous solution in which 80% by mass or more (more preferably 90% by mass or more, more preferably 95% by mass or more) of the aqueous solvent is water.
- aqueous solvent substantially composed of water for example, tap water, distilled water, pure water, purified water
- Non-aqueous solvents typically include organic solvents that do not contain water (eg, cannot be diluted with water).
- organic solvent is not particularly limited.
- alcohols such as methanol, ethanol, n-propyl alcohol, and isopropyl alcohol
- organic solvents such as toluene, hexane, and kerosene may be used alone or in combination of two or more.
- the kind and composition of the dispersion medium to be used can be appropriately selected according to, for example, the spraying method of the slurry for thermal spraying. That is, for example, when the thermal spray slurry is sprayed by the high-speed flame spraying method, either an aqueous solvent or a non-aqueous solvent may be used.
- Use of an aqueous dispersion medium is advantageous in that the surface roughness of the resulting sprayed coating is improved (smoothed) as compared to the case of using a non-aqueous dispersion medium.
- Use of a non-aqueous dispersion medium is advantageous in that the porosity of the resulting sprayed coating is reduced as compared with the case of using an aqueous dispersion medium.
- the slurry for thermal spraying disclosed here may further contain a dispersant as necessary.
- the dispersant is a general compound that can improve the dispersion stability of the spray particles in the dispersion medium in the slurry for thermal spraying.
- a dispersant may be, for example, a compound that essentially acts on the spray particles or a compound that acts on the dispersion medium. Further, for example, it may be a compound that improves the wettability of the surface of the sprayed particles by acting on the sprayed particles or the dispersion medium, or may be a compound that unwinds the sprayed particles.
- a compound that suppresses or inhibits reaggregation of spray particles may be used.
- the dispersant can be appropriately selected from an aqueous dispersant and a non-aqueous dispersant according to the dispersion medium.
- a dispersant may be any of a polymer type dispersant, a surfactant type dispersant (also referred to as a low molecular type dispersant), or an inorganic type dispersant. Either ionic or nonionic may be used. That is, the dispersant may have at least one functional group of an anionic group, a cationic group, and a nonionic group in the molecular structure of the dispersant.
- polymeric dispersants include, as aqueous dispersants, dispersants made of polycarboxylic acid compounds such as polycarboxylic acid sodium salt, polycarboxylic acid ammonium salt, polycarboxylic acid polymer, polystyrene sulfonate sodium salt Polystyrene sulfonate ammonium salt, polyisoprene sulfonate sodium salt, polyisoprene sulfonate ammonium salt, naphthalene sulfonate sodium salt, naphthalene sulfonate ammonium salt, sodium salt of naphthalene sulfonate formalin condensate, naphthalene sulfonate formalin condensate Examples thereof include a dispersant composed of a sulfonic acid compound such as an ammonium salt, and a dispersant composed of a polyethylene glycol compound.
- a dispersant made of an acrylic compound such as polyacrylate, polymethacrylate, polyacrylamide, polymethacrylamide, or the like, a polycarboxylic acid having an alkyl ester bond in part of the polycarboxylic acid is used.
- examples thereof include a dispersant composed of an acid partial alkyl ester compound, a dispersant composed of a polyether compound, and a dispersant composed of a polyalkylene polyamine compound.
- polycarboxylic acid compound in the present specification includes the polycarboxylic acid compound and salts thereof. The same applies to other compounds.
- a compound classified as either an aqueous dispersant or a non-aqueous dispersant may be used as the other non-aqueous dispersant or aqueous dispersant depending on the detailed chemical structure and usage. possible.
- surfactant type dispersants include aqueous dispersants, dispersants composed of alkylsulfonic acid compounds, dispersants composed of quaternary ammonium compounds, and alkylene oxide compounds.
- a dispersing agent etc. can be raised.
- the non-aqueous dispersant include a dispersant made of a polyhydric alcohol ester compound, a dispersant made of an alkyl polyamine compound, and a dispersant made of an imidazoline compound such as an alkyl imidazoline.
- inorganic dispersants include aqueous dispersants such as phosphates such as orthophosphate, metaphosphate, polyphosphate, pyrophosphate, tripolyphosphate, hexametaphosphate, and organic phosphate.
- phosphates such as orthophosphate, metaphosphate, polyphosphate, pyrophosphate, tripolyphosphate, hexametaphosphate, and organic phosphate.
- Iron salts such as ferric sulfate, ferrous sulfate, ferric chloride, and ferrous chloride, aluminum salts such as aluminum sulfate, polyaluminum chloride, and sodium aluminate, calcium sulfate, calcium hydroxide, and Examples thereof include calcium salts such as dicalcium phosphate.
- any of the above dispersants may be used alone or in combination of two or more.
- the content of the dispersant is not necessarily limited because it depends on the composition (physical properties) of the spray particles, but typically 0.01 to 10 when the mass of the spray particles is 100% by mass. It can be used as an approximate standard to be in the mass% range.
- the slurry for thermal spraying can be prepared by mixing and dispersing thermal spray particles in the above dispersion medium.
- a homogenizer such as a blade-type stirrer, a disperser, or the like can be used.
- the slurry for thermal spraying thus prepared is characterized by being adjusted so that the feedability index If obtained in the above (1) to (3) is 70% or more.
- the feedability index is an index that can evaluate the feedability of the thermal spray particles in the thermal spraying slurry to the thermal spraying apparatus.
- the supply speed as a flow rate of 35 mL / min
- turbulent flow can be generated in the slurry for thermal spraying that is transferred through the tube having the above dimensions.
- the material of the tube used for the evaluation of the supply property is not strictly limited, but flexible materials such as polyurethane, vinyl chloride, polytetrafluoroethylene, etc. can be used so as to realize smooth supply conditions of the slurry for thermal spraying. It is preferable to use a certain resin tube. A transparent or translucent tube can be used so that the state of the sprayed particles flowing in the tube from the outside can be confirmed.
- the supply ability of the spray particles to the thermal spraying apparatus is sufficient when the supplyability index If is 70% or more.
- the feedability index If is preferably 75% or more, more preferably 80% or more, and even more preferably 85% or more, for example 90% or more (ideally 100%). .
- settling of the thermal spraying particles is suppressed, and more thermal spraying particles can be supplied to the thermal spraying device.
- a difference in slurry concentration hardly occurs immediately after supply of the slurry for thermal spraying and at the end of supply. Thereby, a thermal spray particle can be efficiently and stably supplied to a thermal spraying apparatus, and a high quality thermal spray coating can be formed.
- the ratio of the thermal spray particles in the slurry for thermal spraying is not particularly limited.
- the ratio of the thermal spray particles to the entire slurry for thermal spraying is preferably 10% by mass or more, and more preferably 15% by mass. For example, it can be set to 20% by mass or more.
- the thickness of the thermal spray coating produced per unit time from the slurry for thermal spraying that is, the thermal spray efficiency can be improved.
- grains in the slurry for thermal spraying can be 50 mass% or less, Preferably it can be 45 mass% or less, for example, 40 mass% or less.
- fluidity suitable for supplying the slurry for thermal spraying to the thermal spraying apparatus can be realized.
- the viscosity of the slurry for thermal spraying can be 1000 mPa ⁇ s or less, preferably 500 mPa ⁇ s or less, more preferably 100 mPa ⁇ s or less, for example, 50 mPa ⁇ s or less. Can do.
- the fluidity can be further improved by reducing the viscosity of the slurry for thermal spraying.
- the slurry for thermal spraying with a low viscosity can mean that the ratio of a thermal spray particle is few.
- the viscosity of the slurry for thermal spraying is preferably 0.1 mPa ⁇ s or more, for example.
- the feedability index can be adjusted within a preferable range.
- the absolute value of the zeta potential of the thermal spray particles is preferably 50 mV or less. As the absolute value of the zeta potential in the slurry for thermal spraying approaches 0 mV, the value of the feedability index can be improved.
- the value of the zeta potential of the spray particles can be measured by, for example, electrophoresis, ultrasonic attenuation, electroacoustic method, or the like.
- electrophoresis manufactured by Otsuka Electronics Co., Ltd.
- DT-1200 manufactured by Dispersion Technology Inc.
- the measurement by electroacoustic method can be carried out using, for example, ZetaProb manufactured by Colloidal Dynamics LLC.
- the pH of the slurry for thermal spraying is not particularly limited, but is preferably 2 or more and 12 or less. From the viewpoint of easy handling of the slurry for thermal spraying, the pH is preferably 6 or more and 8 or less. On the other hand, for example, for the purpose of adjusting the zeta potential of the spray particles, the pH may be outside the range of 6 to 8, for example, 7 to 11, or 3 to 7.
- the pH of the slurry for thermal spraying is adjusted with various known acids, bases, or salts thereof.
- organic acids such as carboxylic acid, organic phosphonic acid and organic sulfonic acid
- inorganic acids such as phosphoric acid, phosphorous acid, sulfuric acid, nitric acid, hydrochloric acid, boric acid and carbonic acid
- tetramethylammonium hydroxide trimethanolamine
- organic bases such as monoethanolamine, inorganic bases such as potassium hydroxide, sodium hydroxide and ammonia, or salts thereof are preferably used.
- the pH of the slurry for thermal spraying is adjusted to a pH standard solution (for example, phthalate pH standard by using a glass electrode type pH meter (eg, Horiba, Ltd., desktop pH meter (F-72)).
- a pH standard solution for example, phthalate pH standard by using a glass electrode type pH meter (eg, Horiba, Ltd., desktop pH meter (F-72)).
- Solution pH: 4.005 / 25 ° C
- neutral phosphate pH standard solution pH: 6.865 / 25 ° C
- carbonate pH standard solution pH: 10.12 / 25 ° C
- a value measured according to JIS Z8802: 2011 can be adopted.
- the thermal spray particles in the thermal spray slurry form secondary particles.
- the feedability index can be adjusted by adjusting the amount of secondary particles formed by the spray particles and the average particle size. Whether or not the sprayed particles form secondary particles is determined by, for example, the value of the average particle diameter (D50) measured by a particle size distribution measuring apparatus based on the laser diffraction / scattering method being the value of the sprayed particles before the slurry for thermal spraying is adjusted. It can be judged by whether it is larger than the primary particle size.
- the average particle diameter of secondary particles of the spray particles formed in the slurry for thermal spraying is preferably 30 ⁇ m or less, more preferably 25 ⁇ m or less, and further preferably 15 ⁇ m or less.
- the average particle diameter of the secondary particles of the thermal spray particles in the thermal spray slurry is larger than the primary particle diameter of the thermal spray particles before adjusting the thermal spray slurry.
- the average particle diameter of the secondary particles of the spray particles formed in the slurry for thermal spraying is preferably 1.2 times or more than the primary particle diameter of the spray particles before preparation of the slurry for thermal spraying, more preferably. Is 1.5 times or more.
- the slurry for thermal spraying may further contain a viscosity modifier as necessary.
- the viscosity modifier refers to a compound that can reduce or increase the viscosity of the slurry for thermal spraying.
- Examples of compounds that can be used as viscosity modifiers include nonionic polymers such as polyethers such as polyethylene glycol, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl acetate, polyvinyl benzyl trimethyl ammonium chloride, aqueous urethane resins, Examples include gum arabic, chitosan, cellulose, crystalline cellulose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, carboxymethyl cellulose ammonium, carboxymethyl cellulose, carboxyvinyl polymer, lignin sulfonate, and starch.
- the content of the viscosity modifier can be in the range of 0.01 to 10% by mass.
- the slurry for thermal spraying may further contain a flocculant (also referred to as a redispersibility improver, an anti-caking agent, etc.) as necessary.
- a flocculant also referred to as a redispersibility improver, an anti-caking agent, etc.
- the flocculant refers to a compound that can agglomerate the spray particles in the slurry for thermal spraying.
- it refers to a compound that can softly agglomerate spray particles in a slurry for thermal spraying.
- the thermal spraying particles are in a state where the coagulant is interposed between the thermal spraying particles.
- the agglomeration of the precipitated spray particles is suppressed, and the redispersibility is improved. That is, even if the deposited thermal spray particles are precipitated, the individual particles can be prevented from agglomerating closely (which can be agglomerated) (also referred to as caking or hard caking). Accordingly, since the slurry can be re-dispersed relatively easily by the turbulent flow generated in the slurry when the slurry is transferred to the thermal spraying apparatus or the like, settling during the transfer is suppressed and the supply capability to the thermal spraying apparatus is improved.
- the slurry for thermal spraying is put in a container and stored, even if the thermal spray particles are settled by standing for a long period of time, for example, by holding the container by hand and shaking it up and down, Since redispersion is possible, the supply property to the thermal spraying apparatus is improved.
- Such a flocculant or redispersibility improver may be any of an aluminum compound, an iron compound, a phosphate compound, and an organic compound.
- the aluminum compound include aluminum sulfate (also referred to as a sulfate band), aluminum chloride, polyaluminum chloride (also referred to as PAC and PACl), and the like.
- iron-based compounds include ferric chloride and polyferric sulfate.
- phosphoric acid compounds include sodium pyrophosphate. Etc.
- organic compound may be anionic, cationic or nonionic, for example, organic acids such as malic acid, succinic acid, citric acid, maleic acid, maleic anhydride, diallyldimethylammonium chloride
- organic acids such as malic acid, succinic acid, citric acid, maleic acid, maleic anhydride, diallyldimethylammonium chloride
- examples thereof include a polymer, lauryltrimethylammonium chloride, naphthalenesulfonic acid condensate, sodium triisopropylnaphthalenesulfonate, sodium polystyrenesulfonate, isobutylene-maleic acid copolymer, carboxyvinyl polymer, and the like.
- the slurry for thermal spraying may further contain an antifoaming agent as necessary.
- the defoaming agent refers to a compound that can prevent bubbles from forming in the slurry for thermal spraying during the production of the slurry for thermal spraying or a compound that can eliminate the foam generated in the slurry for thermal spraying.
- the antifoaming agent include silicone oil, silicone emulsion antifoaming agent, polyether antifoaming agent, fatty acid ester antifoaming agent and the like.
- the slurry for thermal spraying may further contain additives such as antiseptics, antifungal agents, antifreezing agents and the like as necessary.
- preservatives or fungicides examples include isothiazoline compounds, azole compounds, propylene glycol and the like.
- antifreezing agent examples include polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, and glycerin.
- a slurry for thermal spraying is used.
- these additives may be added to the dispersion medium at the same timing as the spray particles, or may be added at another arbitrary timing.
- the compound as various additives illustrated above may express the function as another additive other than the effect
- a slurry for thermal spraying in which the thermal spray particles are precipitated includes a constituent part (typically a supernatant part) that does not contain thermal spray particles or has a lower content, and contains all or more thermal spray particles.
- the above-mentioned slurry for thermal spraying can be obtained by dividing it into components (typically, the remaining part from which the supernatant is removed) and mixing them appropriately and subjecting them to shaking treatment and the like. .
- the above-mentioned slurry for thermal spraying can be obtained by separately preparing the constituent components of the slurry for thermal spraying as several constituent parts, mixing them appropriately and subjecting them to shaking treatment and the like. Therefore, in this slurry for thermal spraying, for example, each constituent component constituting the slurry for thermal spraying is put into a separate container one by one or as a mixture of two or more types, and is combined into one before being supplied to thermal spraying. It may be prepared by mixing.
- the technology disclosed herein provides a thermal spray slurry preparation material used for preparing the thermal spray slurry.
- This preparation material contains at least any one or more components constituting the above-mentioned slurry for thermal spraying. And when all the components which comprise the slurry for thermal spraying containing this preparation material are mixed together and a liquid mixture is prepared, it is comprised so that said feedability index If may satisfy 70% or more Has been.
- This preparation material may be only a part of the constituent components constituting the slurry for thermal spraying. Further, by combining one preparation material A and another one preparation material B or two or more preparation materials B, C, etc., all the components constituting the slurry for thermal spraying are included.
- the volume ratio is the relationship of (volume of thermal spray particles Akg (mL)) :( 800-volume of thermal spray particles Akg (mL)).
- the weight ratio between the spray particles and the dispersion medium can be determined.
- the preparation material contains only some constituents, obtain other constituents and their amounts (eg, weight and volume) necessary to obtain the thermal spray slurry disclosed herein. Can do.
- a component which comprises the slurry for thermal spraying arbitrary components (additives), such as said dispersing agent and a viscosity modifier, etc. other than a thermal spray particle and a dispersion medium can be included. Therefore, specific examples of such a combination of preparation materials include the following configurations.
- Preparation material A1 Spray particles
- Preparation material B1 Dispersion medium
- Preparation material A2 Sprayed particles and part of dispersion medium
- Preparation material B2 remainder of dispersion medium
- Preparation material A3 Thermal spray particles
- Preparation material B3 Dispersion medium and optional components (additives)
- Preparation material A4 Thermal spray particles
- Preparation material B4 Dispersion medium
- Preparation material C4 Optional components (additives)
- the thermal spray slurry preparation material disclosed herein has one component each constituting the thermal spray slurry, such as thermal spray particles, a dispersion medium, a dispersant, and other optional components, or two of them. It may be in a separate package as a mixture of more than one type.
- the thermal spray slurry preparation material may be mixed with other constituents (may be other thermal spray slurry preparation materials) before being supplied to thermal spraying to prepare a thermal spray slurry.
- the components other than the dispersion medium are used as a slurry preparation material for thermal spraying in one package, and the dispersion medium is used as a slurry preparation material for thermal spraying in another package (for preparing other thermal spray slurry).
- components other than the dispersion medium may be in a powder state (solid).
- the dispersion medium may be obtained and prepared by the user of the slurry for thermal spraying. From the viewpoint of the uniformity of the slurry for thermal spraying and the stability of the coating performance, the slurry for thermal spraying supplied to the thermal spraying is preferably prepared as a high-concentration slurry in which the thermal spray particles are contained at a higher concentration.
- the above-mentioned slurry preparation material for thermal spraying may be provided with information for preparing the slurry for thermal spraying.
- This information can also be understood as a preparation method for preparing a thermal spray slurry using a thermal spray slurry preparation material. For example, information on the amount (volume or weight) of each constituent component in a separate package, a mixing procedure thereof, materials necessary other than the thermal spray slurry preparation material, and the like is shown.
- the said slurry preparation material for thermal spraying is comprised so that the supply property index If may be 70% or more, the information for raising If value may be shown. Such information may be shown in the container of each component, the exterior material that stores these containers, and the like. Or the paper etc.
- the thermal spray slurry preparation material in which the information was described may be set (enclosed) with the container of each component. Further, a user who has obtained the thermal spray slurry preparation material may be in a state where such information can be obtained through the Internet or the like. Thereby, a thermal spray coating can be more easily and reliably formed with high efficiency by using the thermal spray slurry preparation material disclosed herein.
- the base material on which the thermal spray coating is formed is not particularly limited.
- a substrate made of various materials can be used as long as it is made of a material that can be subjected to such thermal spraying and have a desired resistance.
- examples of such 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 typified by various SUS materials (so-called stainless steels) and the like, heat resistant alloys typified by Inconel, Invar, Kovar, etc., which have a relatively large thermal expansion coefficient among metal materials that are widely used.
- heat resistant alloys typified by Inconel, Invar, Kovar, etc.
- base materials made of low expansion alloys typified by, etc.
- corrosion resistant alloys typified by Hastelloy, etc.
- aluminum alloys typified by 1000 series to 7000 series aluminum alloys useful as lightweight structural materials, and the like.
- the slurry for thermal spraying disclosed here can be used as a thermal spraying material for forming a thermal spray coating by using a thermal spraying apparatus based on a known thermal spraying method.
- a thermal spraying apparatus typically, it is allowed to stand for a predetermined time or more for the purpose of storage or the like, so that the thermal spray particles start to settle and can settle in the dispersion medium. Therefore, the slurry for thermal spraying in the technique disclosed herein is set so that the supply index If as described above becomes 70% or more at the time of being subjected to thermal spraying (for example, in the preparation stage for supplying to the thermal spraying apparatus). It only has to be prepared.
- a slurry for thermal spraying (also referred to as a precursor solution) in a storage state before being supplied to thermal spraying, for example, it may be prepared as a high-concentration slurry in which thermal spray particles are contained at a higher concentration.
- thermal spraying method for thermally spraying the slurry for thermal spraying
- a thermal spraying method such as a plasma spraying method or a high-speed flame spraying method.
- 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 flow is ejected from the nozzle as a high-temperature and high-speed plasma jet.
- the plasma spraying method includes a general coating technique in which a thermal spraying material is put into this plasma jet, and heated and accelerated to deposit on a substrate by heating.
- 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. According to such plasma spraying, for example, the thermal spray material is melted and accelerated by a plasma jet of about 5000 ° C. to 10000 ° C., so that the sprayed particles collide with the substrate at a speed of about 300 m / s to 600 m / s. And can be deposited.
- APS atmospheric plasma spraying
- LPS low pressure plasma spraying
- the high-speed flame spraying method for example, an oxygen-supported high-speed flame (HVOF) spraying method, a warm spray spraying method, an air-supported flame (HVAF) high-speed flame spraying method, or the like can be considered.
- 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.
- a thermal spray material for example, by supplying a slurry for thermal spraying to a jet of a supersonic combustion flame at 2000 ° C. to 3000 ° C., the dispersion medium can be removed from this slurry (combustion or evaporation; the same applies hereinafter).
- the spray particles can be softened or melted and collided with the substrate at a high speed of 500 m / s to 1000 m / s to be deposited.
- 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, by supplying a slurry for thermal spraying to a jet of a supersonic combustion flame at 1000 ° C.
- the dispersion medium can be removed from this slurry (combustion or evaporation).
- combustion or evaporation The same applies hereinafter), and the sprayed particles can be softened or melted and collided with the substrate at a high speed of 500 m / s to 1000 m / s for deposition.
- the HVAF spraying method is a spraying method in which air is used in place of oxygen as a combustion support gas in the above-described HVOF spraying method.
- the spraying temperature can be lowered as compared with the HVOF spraying method.
- the dispersion medium is removed from the slurry (combustion or evaporation; the same applies hereinafter) and thermal spraying is performed.
- the particles can be softened or melted, and the spray particles can be deposited by colliding with the substrate at a high speed of 500 m / s to 1000 m / s.
- the sprayed material when the above-mentioned slurry for thermal spraying is sprayed by high-speed flame spraying or plasma spraying, the sprayed material is sufficiently softened and melted even when a sprayed material having a relatively large particle size is included.
- a slurry for thermal spraying with a high content of thermal spray particles can be sprayed with good fluidity, and a dense thermal spray coating can be efficiently formed.
- supply of the slurry for thermal spraying to a thermal spray apparatus is not necessarily limited, However, It is preferable to set it as the flow rate of 10 mL / min or more and 200 mL / min or less.
- the slurry flowing in the slurry supply device for thermal spraying (for example, the slurry supply tube) can be in a turbulent state, and the pushing force of the slurry is increased.
- the settling of the spray particles is suppressed.
- the flow rate at the time of supplying the slurry for thermal spraying is preferably 20 mL / min or more, and more preferably 30 mL / min or more.
- the flow rate when supplying the slurry for thermal spraying is appropriately 200 mL / min or less, preferably 150 mL / min or less, for example, 100 mL / min or less.
- the spraying slurry is supplied to the thermal spraying apparatus by an axial feed method, that is, the thermal spraying slurry is supplied in the same direction as the axis of the jet flow generated in the thermal spraying apparatus.
- the thermal spraying material in the thermal spraying slurry is less likely to adhere to the thermal spraying apparatus because of the good fluidity of the thermal spraying slurry, A dense sprayed coating can be efficiently formed, which is preferable.
- the slurry for thermal spraying is supplied to the thermal spraying apparatus using a general feeder, it is considered that stable supply becomes difficult because the supply amount periodically varies. If unevenness occurs in the supply amount of the slurry for thermal spraying due to this periodic change in the supply amount, the sprayed material becomes difficult to be heated uniformly in the spraying apparatus, and a non-uniform spray coating may be formed. Therefore, in order to stably supply the slurry for thermal spraying to the thermal spraying apparatus, the fluctuation cycle of the supply amount of the slurry for thermal spraying from both feeders is made to be opposite in phase using a two-stroke method, that is, two feeders. May be.
- the supply method may be adjusted such that the supply amount from the other feeder decreases.
- the slurry for thermal spraying of the present invention is supplied to the thermal spraying apparatus by a two-stroke method, the fluidity of the slurry for thermal spraying is good, so that a dense thermal spray coating can be efficiently formed.
- the slurry sent from the feeder is temporarily stored in a storage tank provided immediately before the thermal spraying device, and the natural falling from the storage tank is performed.
- the slurry may be supplied to the thermal spraying device, or the slurry in the tank may be forcibly supplied to the thermal spraying device by means such as a pump.
- the thermal spray material in the slurry is less likely to adhere in the tube even if the tank and the thermal spraying device are connected by a tube.
- a means for stirring the thermal spray slurry in the tank may be provided.
- the supply of the slurry for thermal spraying to the thermal spraying apparatus is preferably performed via a metal conductive tube, for example.
- a metal conductive tube for example.
- the inner surface of the conductive tube preferably has a surface roughness Ra of 0.2 ⁇ m or less.
- the spraying distance is preferably set so that the distance from the nozzle tip of the spraying device to the substrate is 30 mm or more. If the spraying distance is too close, the dispersion medium in the slurry for thermal spraying will not be removed, and sufficient time will not be secured to soften or melt the thermal spray particles, or the thermal spray heat source will be close to the base material. Is not preferable because there is a risk of deterioration or deformation.
- the spray distance is preferably about 200 mm or less (preferably 150 mm or less, for example, 100 mm or less). When the distance is such, spray particles that are sufficiently heated can reach the base material while maintaining the temperature, so that a denser spray coating can be obtained.
- a thermal spray coating made of a thermal spray material having a desired composition constituting the thermal spray particles is formed.
- the thermal spray coating is formed by using a slurry for thermal spraying having a supply ability index If of 70% or more and good supply ability. Therefore, the thermal spray particles maintain a suitable dispersed state and flow state in the thermal spray slurry, and are stably supplied to the thermal spraying device to form a thermal spray coating. Further, the spray particles can be efficiently supplied to the vicinity of the center of the heat source without being blown by a frame or a jet, and can be sufficiently softened or melted. Therefore, the sprayed particles that have been softened or melted adhere with good adhesion to the substrate and between the particles. As a result, a sprayed coating having good homogeneity and adhesion is formed at a suitable film forming speed.
- the value is measured with a laser diffraction / scattering particle size distribution measuring apparatus (LA-950, manufactured by Horiba, Ltd.).
- the specific gravity of the spray particles is a value measured in accordance with a specific gravity measurement method using a specific gravity bottle defined by Z 8804: 2012.
- dispersion medium distilled water is used as the aqueous dispersion medium, and ethanol (EtOH), isopropyl alcohol (i-PrOH), and normal propyl alcohol (n-PrOH) are used as the non-aqueous dispersion medium 85: 5: A mixed solution containing 10 by volume was prepared. Further, as optional additives, a dispersant (alkyl imidazoline compound or aqueous polycarboxylic acid polymer dispersant) and a viscosity modifier (polyethylene glycol) shown in Table 1 below were prepared. These spray particles and dispersion medium were prepared in a state of being contained in different containers at a blending ratio of 30% by mass of the spray particles.
- the thermal spraying slurries 1 to 12 were prepared by mixing the thermal spray particles and the dispersion medium together with the dispersant and the viscosity modifier in the proportions shown in Table 1 below.
- the amount of the dispersant used is appropriately adjusted while observing the dispersion state of the spray particles in the slurry for thermal spraying.
- the usage-amount of the viscosity modifier was made constant with 0.1 mass%.
- “ ⁇ ” in the column of the viscosity modifier means not used.
- the average particle size of the thermal spray particles prepared for the preparation of the slurry for thermal spraying is compared with the average particle size of the thermal spray particles in the slurry, and the average particle size of the thermal spray particles in the slurry is 1.5 times or more. In such a case, it was judged that the spray particles were aggregated in the slurry to form secondary particles. For the example in which the sprayed particles are determined to form secondary particles, “Yes” is shown in the column of secondary particle formation in Table 1, and for the example in which it is determined that secondary particles are not formed. Indicated "no".
- the spray particles in each of the prepared slurry for spraying were measured for zeta potential using an ultrasonic particle size distribution / zeta potential measuring device (manufactured by Dispersion Technology, DT-1200). Since the zeta potential of the spray particles in each example was bipolarized in a region of 50 mV or less or 100 mV or more, the measurement results are shown in Table 1 as “50 mV or less” or “100 mV or more”.
- thermal spray coating was formed by thermal spraying by an atmospheric pressure plasma spraying (APS) method.
- the thermal spraying conditions were as follows. That is, first, SS400 steel plate (70 mm ⁇ 50 mm ⁇ 2.3 mm) was prepared as a base material which is a sprayed material, and roughened and used. APS spraying was performed using a commercially available plasma spraying device (Praxair, SG-100).
- the plasma generation conditions were as follows: argon gas as a plasma working gas was supplied at a pressure of 100 psi, helium gas was supplied at a pressure of 90 psi, and the plasma generation power was 40 kW.
- a slurry feeder was used, and the slurry was supplied to the burner chamber of the thermal spraying apparatus at a supply rate of about 100 mL / min.
- a storage tank is installed right next to the thermal spraying device, and after the prepared thermal spraying slurry is temporarily stored in the storage tank, the slurry is removed from the storage tank using natural fall. It was made to supply to a thermal spraying apparatus.
- the plasma jet is sprayed from the nozzle of the thermal spraying device, and the dispersion medium in the slurry is removed while the thermal spraying slurry supplied to the burner chamber is placed on the jet to fly, and the thermal spray particles are melted to form the base material.
- a film was formed on the substrate by spraying on the substrate.
- the moving speed of the spray gun was 600 mm / min, and the spray distance was 50 mm.
- the film formation efficiency (adhesion efficiency) of the spray particles when the slurry for thermal spraying in each example was sprayed to form a coating was evaluated. Specifically, it is a numerical value obtained by measuring the thickness ( ⁇ m) of the sprayed coating formed per one pass (referred to that spraying is performed once on the base material from the spraying apparatus) under the above spraying conditions. is there.
- Example 1 As shown in Table 1, it was confirmed that as Examples 2 to 8 and 10 to 12, slurry for thermal spraying having a feedability index If disclosed herein of 70% or more was obtained.
- the slurry for thermal spraying in Example 1 uses yttria as the thermal spray particles, and is adjusted so that the concentration of the thermal spray particles is 30% by mass as in the other examples.
- the sprayed particles settled in the tube in the measurement of the feedability index If and the tube was not blocked, the sprayed particles were deposited with a thickness of about 1/5 of the tube cross-sectional area. confirmed.
- the sprayed particles in the slurry were deposited (attached) in the slurry supply path of the spraying device, and the film formation efficiency was as low as the feedability index If. .
- the slurry for thermal spraying of Example 2 compared with the slurry of Example 1, the addition amount of the dispersion medium, the dispersant and the viscosity modifier is changed, the viscosity of the slurry is higher, and the zeta potential of the thermal spray particles in the slurry is increased. Is adjusted to be lower than 50 mV. As a result, the supplyability index If was as high as 95.8%. In actual spraying, it was confirmed that almost all of the sprayed particles used for the preparation of the slurry could be introduced into the spraying device and stably supplied to the frame. As a result, it was confirmed that the film formation efficiency was more than twice that of Example 1, and the film thickness of the sprayed coating formed per pass was greatly increased.
- the slurry for thermal spraying of Example 3 has the same properties as the slurry of Example 1, the thermal spray particles having a smaller particle diameter are used, and the type of additive is changed. Thereby, the supply property index If was 70% or more, and it was confirmed that the slurry could be stably supplied to the frame.
- the slurry for thermal spraying of Example 4 is obtained by further adding a viscosity modifier to the slurry of Example 3. Thereby, the sprayed particles in the slurry form secondary particles, the viscosity of the slurry is higher, and the zeta potential of the sprayed particles in the slurry is adjusted to be as low as 50 mV or less. As a result, it was confirmed that the supply ability index If exceeded 90%, 91.7%, and the supply ability of the slurry was greatly improved.
- the thermal spraying slurry of Example 5 uses thermal spraying particles having a smaller particle diameter compared with the slurry of Example 1. There was no significant difference in the viscosity of the slurry and the zeta potential of the spray particles. However, since the fine spray particles having an average particle diameter of 1.6 ⁇ m can exist in such a dispersion medium in a good dispersion state, the feedability index If exceeds 81.0% and 80%. Was confirmed to be relatively good.
- the slurry for thermal spraying of Example 6 is obtained by increasing the amount of the dispersant and adding a viscosity modifier to the slurry of Example 5, further increasing the viscosity of the slurry, and increasing the zeta potential of the thermal spray particles in the slurry.
- Example 7 The slurry for thermal spraying of Example 7 is obtained by making the average particle diameter of the thermal spray particles in the slurry extremely small compared to the slurry of Example 4, and the specific surface area of the thermal spray particles and the viscosity of the slurry are higher. However, the stability of the sprayed particles in the slurry was the same as in Example 4, and the feedability index If was a high value of 97.0%. It was also confirmed that high film formation efficiency was obtained despite the use of extremely fine spray particles having an average particle diameter of 0.01 ⁇ m.
- the slurry for thermal spraying in Examples 8 to 10 uses alumina as the thermal spray particles.
- alumina as the thermal spray particles.
- the sprayed particles in the slurry were deposited (attached) in the slurry supply path of the spraying device, and the film formation efficiency was as low as the feedability index If. .
- a viscosity modifier is added to the slurry of Example 9 so that the viscosity of the slurry is higher and the zeta potential of the thermal spray particles in the slurry is lower.
- the availability index If of the slurry of Example 10 was 92.6%, which was significantly increased compared with 57.0% of Example 7, by using the viscosity modifier together.
- the slurry for thermal spraying of Example 8 is obtained by adding a viscosity modifier to Example 9 and increasing the average particle diameter of the thermal sprayed particles of Examples 9 and 10.
- the stability of the thermal spray particles in this slurry was as high as in Example 10, and it was confirmed that both the slurry supplyability index If and the film formation efficiency were good values.
- the slurry for thermal spraying of Example 11 uses hydroxyapatite having a relatively small specific gravity as spray particles.
- the specific gravity of the thermal spray particles is small, the specific surface area increases and the viscosity tends to increase.
- an excessive increase in viscosity is suppressed by the addition of a viscosity modifier.
- the slurry for thermal spraying of Example 12 uses a metal (copper) powder having a large specific gravity as spray particles.
- the spray particles having a large specific gravity are likely to precipitate in the slurry, and since it is a metal powder, the viscosity of the slurry is difficult to increase, and the feedability index If tends to be extremely small.
- an appropriate viscosity and zeta potential are realized by adding a dispersant and a viscosity modifier, and a slurry having a high supplyability index If and good fluidity and film forming efficiency is realized. It has been confirmed that.
- the sprayability is such that the zeta potential is adjusted to 50 mV or less or secondary particles are formed regardless of the type (composition, specific gravity) of the thermal spray particles. It can be seen that the index If increases and the film formability tends to be good. Therefore, even if the sprayed particles have properties that tend to form precipitates, the stability of the sprayed particles in the slurry for thermal spraying is improved by adjusting the particles so that the zeta potential is 50 mV or less. It is thought that you can. As a result, it is considered that a thermal spraying slurry having a good fluidity is realized without causing the thermal spraying particles to be clogged in the thermal spraying apparatus or the tube.
- the supplyability index If disclosed herein the supplyability of the slurry for thermal spraying using thermal spray particles of various compositions and forms to the thermal spraying apparatus can be easily evaluated. It was. It was confirmed that when the feedability index If is 70% or more, it can be determined that the feedability of the slurry is good regardless of the physical properties of the spray particles. By adopting such feedability index If, for example, a slurry in an appropriate state can be prepared by thermal spraying without wasting a large amount of the slurry preparation material. It has also been found that a thermal spray coating can be formed with high efficiency by using such a slurry for thermal spraying.
Abstract
Description
本出願は、2014年9月3日に出願された日本国特許出願2014-178710号に基づく優先権を主張しており、その出願の全内容は本明細書中に参照として組み入れられている。
この溶射法においては、通常、被覆材料である溶射粒子を粉末の状態で溶射装置に供給している。そして近年では、溶射粒子を分散媒に分散させたスラリー(懸濁液、サスペンション等を包含する)の状態で溶射装置に供給することが行われてもいる。この溶射用スラリーに関連する従来技術としては、例えば、特許文献1が挙げられる。
そして、平均粒子径が1μm以上の溶射粒子については、レーザ回折・散乱法に基づく粒度分布測定装置により測定された体積基準の粒度分布における積算値50%での粒径(50%体積平均粒子径)を「平均粒子径」として採用している。なお当業者であれば理解できるように、上記測定法を適用すべき溶射粒子の粒子径の臨界値(1μm)は必ずしも厳密なものではない。例えば、使用する分析機器の精度等に応じて、溶射粒子の粒子径が1μm近傍の場合は、レーザ回折・散乱法に基づき平均粒子径を測定しても良い。
本明細書において、溶射用スラリーの粘度は、回転式粘度計を用いて測定される、室温(25℃)における粘度である。かかる粘度は、例えば、B型粘度計(例えば、リオン株式会社製,ビスコテスタVT-03F)を用いて測定した値を採用することができる。
なお、「アクシャルフィード方式」とは、溶射熱源(例えば、プラズマアークや燃焼炎)の中心から、かかる溶射熱源の発生方向やトーチノズルの軸方向に溶射用スラリーを供給する手法である。
かかる構成によると、溶射装置直前のタンクにおいて溶射用スラリーの状態を整えることができ、比較的平均粒子径の大きい溶射材がスラリー中で凝集したり沈降するのを抑制して、溶射用スラリーをムラなくほぼ一定の割合で供給することが可能となる。これによっても、皮膜組織にバラつきの少ない溶射皮膜を形成することができるために好ましい。
ここに開示される溶射用スラリーは、本質的に、セラミックス、サーメットおよび金属からなる群から選択される少なくとも一種の材料からなる溶射粒子と、分散媒と、を含む。そして、以下で規定される供給性指数Ifが70%以上であることを特徴としている。
(1)溶射用スラリー800mL中に含まれる溶射粒子をAkgとする。
(2)溶射粒子が分散状態にある溶射用スラリー800mLを、内径5mm、長さ5mで、水平に配置されているチューブに、流速35mL/minで供給して回収される回収スラリーについて、該回収スラリーに含まれる溶射粒子の質量をBkgとする。
(3)上記A,Bにもとづき、次式:If(%)=B/A×100;で算出される値を供給性指数Ifとする。
ここに開示される溶射用スラリーは、セラミックス、サーメットおよび金属からなる群から選択される少なくとも一種の材料からなる溶射粒子を含むことができる。
ここで、酸化物系セラミックスとしては、特に限定されることなく各種の金属の酸化物とすることができる。かかる酸化物系セラミックスを構成する金属元素としては、例えば、B,Si,Ge,Sb,Bi等の半金属元素、Na,Mg,Ca,Sr,Ba,Zn,Al,Ga,In,Sn,Pb,P等の典型金属元素、Sc,Y,Ti,Zr,Hf,V,Nb,Ta,Cr,Mo,W,Mn,Fe,Co,Ni,Cu,Ag,Au等の遷移金属元素、La,Ce,Pr,Nd,Pm,Sm,Eu,Gd,Tb,Dy,Ho,Er,Tu,Yb,Lu等のランタノイド元素から選択される1種または2種以上が挙げられる。なかでも、Mg,Y,Ti,Zr,Cr,Mn,Fe,Zn,Al,Erから選択される1種または2種以上の元素であることが好ましい。なお、ここに開示される酸化物系セラミックスは、以上の金属元素に加えて、F,Cl,Br,I等のハロゲン元素を含むことも好ましい。
ここに開示される溶射用スラリーは、水系または非水系の分散媒を含むことができる。
水系分散媒としては、水または、水と水溶性の有機溶媒との混合物(混合水溶液)が挙げられる。水としては、水道水、イオン交換水(脱イオン水)、蒸留水、純水等を用いることができる。この混合水溶液を構成する水以外の有機溶媒としては、水と均質に混合し得る有機溶剤(例えば、炭素数が1~4の低級アルコールまたは低級ケトン等)の1種または2種以上を適宜選択して用いることができる。水系溶媒としては、例えば、該水系溶媒の80質量%以上(より好ましくは90質量%以上、さらに好ましくは95質量%以上)が水である混合水溶液の使用が好ましい。特に好ましい例として、実質的に水からなる水系溶媒(例えば、水道水、蒸留水、純水、精製水)が挙げられる。
使用する分散媒の種類や組成は、例えば、溶射用スラリーの溶射方法に応じて適宜に選択することができる。すなわち、例えば、溶射用スラリーを高速フレーム溶射法により溶射する場合には、水系溶媒または非水系溶媒のいずれを用いても良い。水系分散媒を用いると、非水系分散媒を用いた場合と比べて、得られる溶射皮膜の表面粗さが向上する(滑らかとなる)点で有益である。非水系分散媒を用いると、水系分散媒を用いた場合と比べて、得られる溶射皮膜の気孔率が低下する点で有益である。
なお、ここに開示される溶射用スラリーは、必要に応じて分散剤をさらに含有してもよい。ここで分散剤とは、溶射用スラリーにおいて、分散媒中での溶射粒子の分散安定性を向上させることができる化合物一般をいう。かかる分散剤は、例えば、本質的に、溶射粒子に作用する化合物であっても良いし、分散媒に作用する化合物であっても良い。また、例えば、溶射粒子または分散媒への作用により、溶射粒子の表面の濡れ性を改善する化合物であっても良いし、溶射粒子を解こうさせる化合物であっても良いし、解こうされた溶射粒子の再凝集を抑制・阻害する化合物であっても良い。
また、便宜上、水系分散剤または非水系分散剤のいずれかに分類した化合物であっても、その詳細な化学構造や使用形態により、他方の非水系分散剤または水系分散剤として使用される化合物もあり得る。
無機型分散剤の例としては、水系分散剤として、例えば、オルトリン酸塩、メタリン酸塩、ポリリン酸塩、ピロリン酸塩、トリポリリン酸塩、ヘキサメタリン酸塩、及び有機リン酸塩等のリン酸塩、硫酸第二鉄、硫酸第一鉄、塩化第二鉄、及び塩化第一鉄等の鉄塩、硫酸アルミニウム、ポリ塩化アルミニウム、及びアルミン酸ナトリウム等のアルミニウム塩、硫酸カルシウム、水酸化カルシウム、及び第二リン酸カルシウム等のカルシウム塩などが挙げられる。
かかる供給性指数とは、溶射用スラリーにおける溶射粒子の溶射装置への供給性を評価し得る指標である。
800mLの溶射用スラリーについて上記供給性指数Ifを規定することで、多様な溶射条件(例えば、より大規模化された溶射条件等)で使用され得る溶射用スラリーについての供給性をより適切に評価することができる。延いては、多様な溶射条件においても良好な溶射を行うことができる溶射用スラリーの多様な設計基準を得ることができる。
また、溶射用スラリーにおける溶射粒子の割合は、50質量%以下とすることができ、好ましくは45質量%以下、例えば40質量%以下とすることができる。固形分濃度を50質量%以下とすることで、溶射用スラリーを溶射装置に供給するのに適した流動性を実現することができる。
溶射用スラリーのpHは公知の各種の酸、塩基、又はそれらの塩により調整される。具体的には、カルボン酸、有機ホスホン酸、有機スルホン酸などの有機酸や、燐酸、亜燐酸、硫酸、硝酸、塩酸、ホウ酸、炭酸などの無機酸、テトラメチルアンモニウムハイドロオキサイド、トリメタノールアミン、モノエタノールアミンなどの有機塩基、水酸化カリウム、水酸化ナトリウム、アンモニアなどの無機塩基、又はそれらの塩が好ましく用いられる。
溶射用スラリーは、必要に応じて粘度調整剤をさらに含有してもよい。ここで粘度調整剤とは、溶射用スラリーの粘度を減少または増大させることができる化合物をいう。溶射用スラリーの粘度を適切に調整することにより、溶射用スラリー中の溶射粒子の含有量が比較的高い場合でも溶射用スラリーの供給性の低下を抑えることができる。粘度調整剤として使用することが可能な化合物の例としては、非イオン性ポリマー、例えばポリエチレングリコールなどのポリエーテルや、ポリビニルアルコール、ポリビニルピロリドン、ポリ酢酸ビニル、ポリビニルベンジルトリメチルアンモニウムクロリド、水系ウレタン樹脂、アラビアゴム、キトサン、セルロース、結晶セルロース、メチルセルロース、エチルセルロース、ヒドロキシエチルセルロース、カルボキシメチルセルロース、カルボキシメチルセルロースアンモニウム、カルボキシメチルセルロース、カルボキシビニルポリマー、リグニンスルホン酸塩、澱粉などが挙げられる。粘度調整剤の含有量は、0.01~10質量%の範囲にすることができる。
溶射用スラリーは、必要に応じて防腐剤又は防カビ剤、凍結防止剤などの添加剤をさらに含有してもよい。防腐剤または防カビ剤の例としては、イソチアゾリン系化合物、アゾール系化合物、プロピレングリコールなどが挙げられる。凍結防止剤の例としては、エチレングリコール、ジエチレングリコール、プロピレングリコール、グリセリン等の多価アルコール類などが挙げられる。
なお、上記に例示された各種添加剤としての化合物は、主たる添加剤用途としての作用の他に、他の添加剤としての機能を発現することもあり得る。換言すると、例えば、同一の種類または組成の化合物であっても、異なる2以上の添加剤としての作用を示す場合があり得る。
上記のとおり、ここに開示される溶射用スラリーは、たとえ溶射粒子が沈殿した場合であっても、再度の振とうや撹拌等の分散処理等により、良好な再分散性が確保され得る。したがって、例えば、溶射粒子が沈殿した状態の溶射用スラリーを、溶射粒子が含まれない又はより含有量が少ない構成部分(典型的には、上澄み部分)と、溶射粒子を全て含む又はより含有量が多い構成部分(典型的には、上澄み部分を取り除いた残部)と、に分割しておき、適宜これを混合して振とう処理等を施すことにより、上記の溶射用スラリーを得ることができる。さらには、溶射用スラリーの構成成分を、幾つかの構成部分として別個に用意しておき、適宜これを混合して振とう処理等を施すことにより、上記の溶射用スラリーを得ることができる。したがって、この溶射用スラリーは、例えば、溶射用スラリーを構成する各構成成分が、1種類ずつ、あるいは2種類以上の混合物として別個の容器に入れられおり、溶射に供給される前に一つに混合されることで調製されてもよい。
調製用材料A1:溶射粒子
調製用材料B1:分散媒
(例2)
調製用材料A2:溶射粒子と分散媒の一部
調製用材料B2:分散媒の残部
調製用材料A3:溶射粒子
調製用材料B3:分散媒と任意成分(添加剤)
(例4)
調製用材料A4:溶射粒子
調製用材料B4:分散媒
調製用材料C4:任意成分(添加剤)
ここで任意成分が複数の場合、調製用材料C4は、例えば、任意成分ごとに調製用剤C4n(n=1,2…)を構成していても良い。
(基材)
ここに開示される溶射皮膜の形成方法において、溶射皮膜が形成される対象たる基材については特に限定されない。例えば、かかる溶射に供して所望の耐性を備え得る材料からなる基材であれば、各種の材料からなる基材を用いることができる。かかる材料としては、例えば、各種の金属または合金等が挙げられる。具体的には、例えば、アルミニウム、アルミニウム合金、鉄、鉄鋼、銅、銅合金、ニッケル、ニッケル合金、金、銀、ビスマス、マンガン、亜鉛、亜鉛合金等が例示される。なかでも、汎用されている金属材料のうち比較的熱膨張係数の大きい、各種SUS材(いわゆるステンレス鋼であり得る。)等に代表される鉄鋼、インコネル等に代表される耐熱合金、インバー,コバール等に代表される低膨張合金、ハステロイ等に代表される耐食合金、軽量構造材等として有用な1000シリーズ~7000シリーズアルミニウム合金等に代表されるアルミニウム合金等からなる基材が挙げられる。
なお、ここに開示される溶射用スラリーは、公知の溶射方法に基づく溶射装置に供することで、溶射皮膜を形成するための溶射用材料として用いることができる。かかる溶射用スラリーにおいては、典型的には、保存等の目的で一定時間以上静置されることで、溶射粒子が沈降を始めて分散媒中に沈殿し得る。したがって、ここに開示される技術における溶射用スラリーは、溶射に供する時点において(例えば、溶射装置に供給するための準備段階において)、上記のとおりの供給性指数Ifが70%以上となるように調製されていれば良い。例えば、溶射に供給される前の、保存状態にある溶射用スラリー(前駆液ともいえる)においては、例えば、溶射粒子がより高濃度に含まれる高濃度スラリーとして調製されていても良い。
プラズマ溶射法とは、溶射材料を軟化または溶融するための溶射熱源としてプラズマ炎を利用する溶射方法である。電極間にアークを発生させ、かかるアークにより作動ガスをプラズマ化すると、かかるプラズマ流はノズルから高温高速のプラズマジェットとなって噴出する。プラズマ溶射法は、このプラズマジェットに溶射用材料を投入し、加熱、加速して基材に堆積させることで溶射皮膜を得るコーティング手法一般を包含する。なお、プラズマ溶射法は、大気中で行う大気プラズマ溶射(APS:atmospheric plasma spraying)や、大気圧よりも低い気圧で溶射を行う減圧プラズマ溶射(LPS:low pressure plasma spraying)、大気圧より高い加圧容器内でプラズマ溶射を行う加圧プラズマ溶射(high pressure plasma spraying)等の態様であり得る。かかるプラズマ溶射によると、例えば、一例として、溶射材料を5000℃~10000℃程度のプラズマジェットにより溶融および加速させることで、溶射粒子を300m/s~600m/s程度の速度にて基材へ衝突させて堆積させることができる。
HVOF溶射法とは、燃料と酸素とを混合して高圧で燃焼させた燃焼炎を溶射のための熱源として利用するフレーム溶射法の一種である。燃焼室の圧力を高めることにより、連続した燃焼炎でありながらノズルから高速(超音速であり得る。)の高温ガス流を噴出させる。HVOF溶射法は、このガス流中に溶射用材料を投入し、加熱、加速して基材に堆積させることで溶射皮膜を得るコーティング手法一般を包含する。HVOF溶射法によると、例えば、一例として、溶射用スラリーを2000℃~3000℃の超音速燃焼炎のジェットに供給することで、このスラリーから分散媒を除去(燃焼または蒸発であり得る。以下同じ。)するとともに、溶射粒子を軟化または溶融させて、500m/s~1000m/sという高速度にて基材へ衝突させて堆積させることができる。高速フレーム溶射で使用する燃料は、アセチレン、エチレン、プロパン、プロピレンなどの炭化水素のガス燃料であってもよいし、灯油やエタノールなどの液体燃料であってもよい。また、溶射材料の融点が高いほど超音速燃焼炎の温度が高い方が好ましく、この観点では、ガス燃料を用いることが好ましい。
溶射に際しては、基材を被溶射面とは反対側の面から冷却することが好ましい。かかる冷却は、水冷の他、適切な冷媒による冷却とすることができる。
以上のここに開示される技術により、溶射粒子を構成する所望の組成の溶射材料からなる溶射皮膜が形成される。
かかる溶射皮膜は、上記のとおり、供給性指数Ifが70%以上と、供給性の良好な溶射用スラリーを用いて形成されている。したがって、溶射粒子は溶射用スラリー中で好適な分散状態および流動状態を維持し、溶射装置に安定して供給されて、溶射皮膜が形成される。また、溶射粒子は、フレームやジェットに弾かれることなく熱源の中心付近に効率よく供給されて、十分に軟化または溶融され得る。したがって、軟化または溶融された溶射粒子は、基材に対して、また互いの粒子間で、密着性良く付着する。これにより、均質性および付着性の良好な溶射皮膜が、好適な皮膜形成速度で形成される。
溶射粒子としては、下記の表1に示す平均一次粒子径を有するイットリア(Y2O3)、アルミナ(Al2O3)、ハイドロキシアパタイト(Ca10(Po4)6(OH)2、および銅(Cu)の粉末を用意した。また、これらの溶射粒子の比重と比表面積を測定した結果を表1に示した。
なお、溶射粒子の平均粒子径は、上述のとおり、1μm未満の微細なものについては、ガス流動法による比表面積測定装置(マイクロメリティックス社製,FlowSorb II 2300)を用いて測定される溶射粒子の比表面積から算出した球相当径である。また、1μm以上の溶射粒子については、レーザ回折・散乱式粒子径分布測定装置((株)堀場製作所製、LA-950)により測定した値である。溶射粒子の比重は、Z 8804:2012で規定される、比重瓶による比重の測定方法に準拠して測定した値である。
用意した各溶射用スラリー中の溶射粒子について、レーザ回折・散乱式粒子径分布測定装置(株式会社堀場製作所製,LA-950)を用いて、平均粒子径を測定した。そして、溶射用スラリーの調整のために用意した溶射粒子の平均粒子径と、スラリー中の溶射粒子の平均粒子径とを比較し、スラリー中の溶射粒子の平均粒子径が1.5倍以上であった場合に、スラリー中で溶射粒子が凝集し、二次粒子を形成していると判断した。そして、溶射粒子が二次粒子を形成していると判断された例について、表1の二次粒子形成の欄に「有」と示し、二次粒子を形成していないと判断された例については「無」と示した。
用意した各溶射用スラリーについて、粘度測定器(リオン株式会社製,ビスコテスタVT-03F)を用い、室温(25℃)環境下、回転速度62.5rpmにおける各溶射用スラリーの粘度を測定した。その結果を表1に示した。
用意した各溶射用スラリー中の溶射粒子について、超音波方式粒度分布・ゼータ電位測定装置(ディスパージョンテクノロジー社製,DT-1200)を用い、ゼータ電位を測定した。各例における溶射粒子のゼータ電位は、50mV以下または100mV以上の領域に2極化したため、測定結果は、「50mV以下」または「100mV以上」として表1に示した。
用意した各溶射用スラリーについて、下記の手順で供給性指数Ifを調べた。すなわち、まず、内径が5mmで長さが5mのポリウレタン製チューブ(CHIYODA製 タッチチューブ(ウレタン) TE-8 外径8mm×内径5mm)を高低差なしの試験台の上に水平に配置させ、チューブの一方の端部にスラリー供給用のローラーポンプを取り付け、他方の端部にはスラリー回収容器を設置した。そして、用意した溶射用スラリーを、マグネチックスターラーで撹拌することで溶射粒子の分散状態が良好であることを確認したのち、35mL/minの流速でチューブ内に供給した。その後、チューブを通過した溶射用スラリーを回収容器にて回収し、回収スラリーに含まれる溶射粒子の質量Bを測定した。そして、予め算出しておいた調製後の800mLの溶射用スラリーに含まれる溶射粒子の質量Aと回収スラリーに含まれる溶射粒子の質量Bとから、次式に基づき、供給性指数Ifを算出し、これらの結果を表1に示した。
If(%)=B/A×100
上記で用意した各溶射用スラリーを用い、大気圧プラズマ溶射(APS)法により溶射することにより溶射皮膜を形成した。溶射条件は、以下の通りとした。
すなわち、まず、被溶射材である基材としては、SS400鋼板(70mm×50mm×2.3mm)を用意し、粗面化加工を施して用いた。APS溶射には、市販のプラズマ溶射装置(Praxair社製、SG-100)を用いて行った。プラズマ発生条件は、大気圧にて、プラズマ作動ガスとしてのアルゴンガスを100psi、ヘリウムガスを90psiの圧力で供給し、プラズマ発生電力を40kWとするものとした。溶射装置への溶射用スラリーの供給には、スラリー供給機を用い、約100mL/分の供給量で溶射装置のバーナー室に供給した。なお、スラリーを溶射装置に供給するに当たり、溶射装置のすぐ脇に貯留タンクを設置し、調製した溶射用スラリーをこの貯留タンクにいったん貯留した後、かかる貯留タンクから自然落下を利用してスラリーを溶射装置に供給するようにした。これにより、溶射装置のノズルからプラズマジェットを噴射させ、バーナー室に供給した溶射用スラリーを、かかるジェットに載せて飛行させながらスラリー中の分散媒を除去するとともに、溶射粒子を溶融させて基材に吹き付けることで、基材上に皮膜を形成した。なお、溶射ガンの移動速度は600mm/min、溶射距離は50mmとした。
各例の溶射用スラリーを溶射して皮膜を形成したときの、溶射粒子の成膜効率(付着効率)を評価した。具体的には、上記の溶射条件で1パス(溶射装置から基材に対して1回溶射を行うことをいう。)あたりに成膜された溶射皮膜の厚さ(μm)を測定した数値である。
例1の溶射用スラリーは、溶射粒子としてイットリアを用い、他の例と同様に溶射粒子の濃度が30質量%となるように調整している。例1では、供給性指数Ifの測定においてチューブ内に溶射粒子が沈殿してしまい、チューブが閉塞することはなかったものの、チューブ断面積の1/5程度の厚みで溶射粒子が沈殿したことが確認された。また、溶射に際しては、溶射装置のスラリー供給経路にスラリーの中の溶射粒子が沈殿(付着)しているのが確認でき、成膜効率は供給性指数Ifと同様に低いものとなってしまった。
例4の溶射用スラリーは、例3のスラリーに対してさらに粘度調整剤を加えたものである。これにより、スラリー中の溶射粒子は二次粒子を形成し、スラリーの粘度はより高く、スラリー中の溶射粒子のゼータ電位は50mV以下と低く調整されている。その結果、供給性指数Ifは91.7%と90%を超過し、スラリーの供給性が大幅に高められたことが確認された。
例6の溶射用スラリーは、例5のスラリーに対して分散剤の量を増大させ、さらに粘度調整剤を加えたものであり、スラリーの粘度をより高く、スラリー中の溶射粒子のゼータ電位を50mV以下に調整している。これにより、供給性指数Ifは90.5%と、例5と比較して約10%ほど向上し、また成膜効率も約1.5倍程度向上することが確認できた。
例7の溶射用スラリーは、例4のスラリーに対して、スラリー中の溶射粒子の平均粒子径を極めて小さくしたものであり、溶射粒子の比表面積とスラリーの粘度がより高くなっている。しかしながら、スラリー中の溶射粒子の安定性は例4と同様であって、供給性指数Ifは97.0%と高い値となった。また、平均粒子径が0.01μmと極微小の溶射粒子を用いたにもかかわらず、高い成膜効率が得られることが確認できた。
例8の溶射用スラリーは、例9に対して粘度調整剤を加え、例9,10に対して溶射粒子の平均粒子径を大きくしたものである。このスラリー中の溶射粒子の安定性は、例10と同程度に高く、スラリーの供給性指数Ifおよび成膜効率ともに良好な値であることが確認できた。
例12の溶射用スラリーは、溶射粒子として、比重の大きい金属(銅)粉末を用いたものである。比重が大きい溶射粒子はスラリー中で沈殿し易く、また金属粉末であることからスラリーの粘度も上がり難く、供給性指数Ifは極めて小さくなりやすい。しかしながら、例12の溶射用スラリーでは、分散剤および粘度調整剤の添加により適度な粘度とゼータ電位が実現されており、供給性指数Ifが高く、流動性および成膜効率ともに良好なスラリーが実現されていることが確認できた。
以上、本発明の具体例を詳細に説明したが、これらは例示にすぎず、特許請求の範囲を限定するものではない。特許請求の範囲に記載の技術には、以上に例示した具体例を様々に変形、変更したものが含まれる。たとえば、上記実施形態では、分散剤および粘度調整剤の添加量を溶射用スラリーにおける溶射粒子の分散状態を見ながら調整した。しかしながら、If値を70%以上とし得る好適な量の添加剤を分包して用意しておくなどしても良い。
Claims (20)
- セラミックス、サーメットおよび金属からなる群から選択される少なくとも一種の材料からなる溶射粒子と、
分散媒と、
を含む溶射用スラリーであって、
前記溶射用スラリー800mL中に含まれる前記溶射粒子をAkgとし、
前記溶射粒子が分散状態にある前記溶射用スラリー800mLを、内径5mm、長さ5mで、水平に配置されているチューブに、流速35mL/minで供給して回収される回収スラリーについて、該回収スラリーに含まれる前記溶射粒子の質量をBkgとしたとき、
次式:If(%)=B/A×100;で算出される供給性指数Ifが70%以上である、溶射用スラリー。 - さらに、分散剤を含む、請求項1に記載の溶射用スラリー。
- 前記溶射粒子は、10重量%以上50重量%以下の割合で含まれる、請求項1または2に記載の溶射用スラリー。
- 前記溶射粒子は、平均粒子径が0.01μm以上10μm以下である、請求項1~3のいずれか1項に記載の溶射用スラリー。
- 前記溶射用スラリーの粘度は、1000mPa・s以下である、請求項1~4のいずれか1項に記載の溶射用スラリー。
- 前記分散媒は、水系分散媒である、請求項1~5のいずれか1項に記載の溶射用スラリー。
- 前記分散媒は、非水系分散媒である、請求項1~5のいずれか1項に記載の溶射用スラリー。
- 請求項1~7のいずれか1項に記載の溶射用スラリーの溶射物からなる溶射皮膜。
- 請求項1~7のいずれか1項に記載の溶射用スラリーを溶射することで溶射皮膜を形成する、溶射皮膜の形成方法。
- 前記溶射用スラリーを、10mL/min以上200mL/min以下の流速で溶射装置に供給して溶射する、請求項9に記載の溶射皮膜の形成方法。
- 前記溶射用スラリーを高速フレーム溶射またはプラズマ溶射して溶射皮膜を形成する、請求項9または10の溶射皮膜の形成方法。
- 前記溶射用スラリーをアクシャルフィード方式で溶射装置に供給することを含む、請求項9~11のいずれか1項に記載の溶射皮膜の形成方法。
- 前記溶射用スラリーを、2つのフィーダを用いて、両フィーダからの溶射用スラリーの供給量の変動周期が互いに逆位相となるようにして溶射装置に供給することを含む、請求項9~12のいずれか1項に記載の溶射皮膜の形成方法。
- 前記溶射用スラリーをフィーダから送り出して溶射装置の直前でタンクにいったん貯留し、自然落下を利用してそのタンク内の溶射用スラリーを溶射装置に供給することを含む、請求項9~12のいずれか1項に記載の溶射皮膜の形成方法。
- 導電性チューブを介して溶射装置へ前記溶射用スラリーを供給することを含む、請求項9~14のいずれか1項に記載の溶射皮膜の形成方法。
- 溶射用スラリーを調製するために用いられる材料であって、
前記溶射用スラリーは、構成成分として、
セラミックス、サーメットおよび金属からなる群から選択される少なくとも一種の材料からなる溶射粒子と、分散媒と、を含み、
前記溶射用スラリー800mL中に含まれる前記溶射粒子をAkgとし、
前記溶射粒子が分散状態にある前記溶射用スラリー800mLを、内径5mm、長さ5mで、水平に配置されているチューブに、流速35mL/minで供給して回収される回収スラリーについて、該回収スラリーに含まれる前記溶射粒子の質量をBkgとしたとき、
次式:If(%)=B/A×100;で算出される供給性指数Ifが70%以上であり
少なくとも、前記溶射用スラリーを構成するいずれか1種類以上の構成成分を含む、溶射用スラリー調製用材料。 - さらに、前記溶射用スラリーを調製するための情報を備える、請求項16に記載の溶射用スラリー調製用材料。
- 前記いずれか1種類以上の構成成分は、
前記溶射粒子を含む、請求項16または17に記載の溶射用スラリー調製用材料。 - 前記いずれか1種類以上の構成成分は、
前記溶射粒子と、
前記分散媒の少なくとも一部と、を含む、請求項18に記載の溶射用スラリー調製用材料。 - さらに、分散剤を含む、請求項16~19のいずれか1項に記載の溶射用スラリー調製用材料。
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KR20190027880A (ko) * | 2016-07-14 | 2019-03-15 | 신에쓰 가가꾸 고교 가부시끼가이샤 | 서스펜션 플라스마 용사용 슬러리, 희토류산 불화물 용사막의 형성 방법 및 용사 부재 |
KR102459191B1 (ko) * | 2016-07-14 | 2022-10-26 | 신에쓰 가가꾸 고교 가부시끼가이샤 | 서스펜션 플라스마 용사용 슬러리, 희토류산 불화물 용사막의 형성 방법 및 용사 부재 |
KR102656926B1 (ko) * | 2016-07-14 | 2024-04-16 | 신에쓰 가가꾸 고교 가부시끼가이샤 | 서스펜션 플라스마 용사용 슬러리, 희토류산 불화물 용사막의 형성 방법 및 용사 부재 |
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CN106605008A (zh) | 2017-04-26 |
KR20170051457A (ko) | 2017-05-11 |
CN106605008B (zh) | 2019-08-27 |
EP3190205A4 (en) | 2017-10-11 |
KR102419886B1 (ko) | 2022-07-12 |
EP3190205A1 (en) | 2017-07-12 |
JP6291069B2 (ja) | 2018-03-14 |
JPWO2016035870A1 (ja) | 2017-06-15 |
US20170283933A1 (en) | 2017-10-05 |
US11066734B2 (en) | 2021-07-20 |
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