WO2023188873A1 - Buse et procédé de formation de film - Google Patents

Buse et procédé de formation de film Download PDF

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Publication number
WO2023188873A1
WO2023188873A1 PCT/JP2023/004712 JP2023004712W WO2023188873A1 WO 2023188873 A1 WO2023188873 A1 WO 2023188873A1 JP 2023004712 W JP2023004712 W JP 2023004712W WO 2023188873 A1 WO2023188873 A1 WO 2023188873A1
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WIPO (PCT)
Prior art keywords
nozzle
powder
nozzle pipe
inner circumferential
particle size
Prior art date
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PCT/JP2023/004712
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English (en)
Japanese (ja)
Inventor
正樹 平野
侑平 大塚
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タツタ電線株式会社
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Publication of WO2023188873A1 publication Critical patent/WO2023188873A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B7/00—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas
    • B05B7/16—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas incorporating means for heating or cooling the material to be sprayed
    • 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
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/02—Coating starting from inorganic powder by application of pressure only
    • C23C24/04—Impact or kinetic deposition of particles

Definitions

  • the present disclosure relates to a nozzle and a film forming method.
  • a cold spray method which is one of the thermal spray methods, is conventionally known.
  • a film is formed on a base material by injecting a film forming raw material together with a carrier gas onto the base material from the nozzle tip of a spray gun.
  • oxidation and thermal deterioration of the film forming raw material in the atmosphere can be suppressed, and a dense and highly adhesive film can be formed on the substrate.
  • blockage may occur on the inner peripheral surface of the passage through which the carrier gas and film forming raw material flow. The blockage occurs when powder adheres to the inner circumferential surface of the passage during the film forming process and the passage narrows.
  • Patent Document 1 discloses a cold spray device having a nozzle that can prevent powder of a film-forming raw material from adhering to the inner peripheral surface of the nozzle.
  • Patent No. 6404532 describes that the nozzle body is made of a metal or metal alloy having a cohesive energy of 170 kcal/g-atom or more.
  • Patent No. 6404532 from the viewpoint of increasing the adhesion efficiency of the powder material to the object to be film-formed and suppressing the embrittlement and wear of the inner circumferential surface of the nozzle when the cold spray method is used under high temperature conditions, The cohesive energy of the nozzle body material is controlled.
  • the likelihood of nozzle clogging is influenced by the particle size of the film forming raw material used in the cold spray method.
  • Japanese Patent No. 6404532 no verification has been made regarding the blockage of the inner circumferential surface of the nozzle in consideration of the particle size of the film-forming raw material.
  • the present disclosure has been made in view of the above problems.
  • the purpose is to provide a nozzle and a film forming method that can suppress clogging of the inner circumferential surface of a passage while taking into account the particle size of the film forming raw material.
  • the nozzle according to the first aspect of the present disclosure is a nozzle used in a thermal spraying method.
  • the nozzle includes a nozzle pipe through which powder serving as a film-forming raw material and operating gas pass.
  • the nozzle pipe has an inner circumferential surface with a surface roughness Sa of 25% or less of the cumulative particle size D10 of the particle size distribution of the powder.
  • the nozzle according to the second aspect of the present disclosure is a nozzle used in a thermal spraying method.
  • the nozzle includes a nozzle pipe through which powder serving as a film-forming raw material and operating gas pass.
  • the nozzle pipe has an inner peripheral surface with a surface roughness Sa of 2 ⁇ m or less.
  • a powder serving as a film forming raw material is prepared.
  • the powder is sprayed onto the surface of the substrate by a cold spray method using a nozzle pipe through which the powder and working gas are passed.
  • the nozzle pipe has an inner circumferential surface with a surface roughness Sa of 25% or less of the cumulative particle size D10 of the particle size distribution of the powder.
  • a nozzle that can suppress clogging of the inner peripheral surface of the passage while taking into consideration the particle size of the film forming raw material.
  • FIG. 1 is a schematic diagram showing the configuration of a film forming apparatus according to the present embodiment.
  • FIG. 2 is a perspective view showing an exploded state of each member constituting the nozzle of FIG. 1;
  • FIG. 2 is a schematic diagram showing a first example of the configuration of a nozzle constituting the film forming apparatus of FIG. 1.
  • FIG. 4 is a schematic diagram showing the external appearance of the nozzle pipe in FIG. 3.
  • FIG. 5 is a schematic cross-sectional view of a region V surrounded by a dashed line in FIG. 4.
  • FIG. It is a graph showing the particle size distribution according to the particle size of the powder and the cumulative proportion of the powder.
  • FIG. 2 is a schematic diagram showing a second example of the configuration of a nozzle constituting the film forming apparatus of FIG. 1.
  • FIG. 2 is a schematic diagram showing a third example of the configuration of a nozzle that constitutes the film forming apparatus of FIG. 1.
  • FIG. FIG. 3 is a schematic diagram showing the external appearance of a nozzle pipe as a comparative example.
  • 10 is a schematic cross-sectional view of a first example of a region A surrounded by a dashed line in FIG. 9.
  • FIG. 10 is a schematic cross-sectional view of a second example of a region A surrounded by a dashed line in FIG. 9.
  • FIG. 3 is a flowchart showing a film forming method according to the present embodiment.
  • FIG. 2 is a table showing the test results of Example 1, that is, the presence or absence of blockage at the end of the nozzle pipe after film formation. It is a table showing the test results of Example 2, that is, the presence or absence of blockage at the end of the nozzle pipe.
  • FIG. 2 is a schematic diagram showing a fourth example of the configuration of a nozzle constituting the film forming apparatus of FIG. 1.
  • FIG. 1 is a schematic diagram showing the configuration of a film forming apparatus according to this embodiment.
  • a film forming apparatus 100 mainly includes a spray gun 2 including a nozzle 2b, a powder supply section 3, a gas supply section 4, and a mask jig 1.
  • the spray gun 2 mainly includes a spray gun main body 2a, a nozzle 2b, a heater 2c, and a temperature sensor 9.
  • a nozzle 2b is connected to a first end, which is the distal end side, of the spray gun main body 2a.
  • a pipe 6 is connected to a second end, which is the rear end side, of the spray gun main body 2a.
  • the pipe 6 is connected to the gas supply section 4 via a valve 7.
  • Gas supply section 4 supplies operating gas to spray gun 2 via piping 6. By opening and closing the valve 7, the supply state of the operating gas from the gas supply unit 4 to the spray gun 2 can be controlled.
  • a pressure sensor 8 is installed in the pipe 6. The pressure sensor 8 measures the pressure of the working gas supplied from the gas supply section 4 to the pipe 6.
  • the operating gas supplied from the second end of the spray gun body 2a into the interior of the spray gun body 2a is heated by the heater 2c.
  • the heater 2c is arranged on the second end side of the spray gun main body 2a.
  • the operating gas flows along the arrow 31 inside the spray gun main body 2a.
  • a temperature sensor 9 is connected to the connection between the nozzle 2b and the spray gun main body 2a. The temperature sensor 9 measures the temperature of the operating gas flowing inside the spray gun main body 2a.
  • a pipe 5 is connected to the nozzle 2b. Piping 5 is connected to powder supply section 3.
  • the powder supply unit 3 supplies powder, which is a film forming raw material, to the nozzle 2b of the spray gun 2 via the pipe 5.
  • the mask jig 1 is placed between the base material 20 and the spray gun 2.
  • a through hole 13 is formed in the mask jig 1 .
  • the through hole 13 defines a film forming area on the surface of the base material 20.
  • operating gas is supplied from the gas supply section 4 to the spray gun 2 via the pipe 6 as shown by an arrow 30.
  • the working gas is supplied to the nozzle 2b.
  • working gas for example nitrogen, helium, dry air or a mixture thereof can be used.
  • the pressure of the working gas is, for example, about 1 MPa.
  • the flow rate of the working gas is, for example, 300 L/min or more and 500 L/min or less.
  • the operating gas supplied to the second end of the spray gun main body 2a is heated by the heater 2c.
  • the heating temperature of the working gas is appropriately set depending on the composition of the film-forming raw material, and can be, for example, 100° C.
  • the operating gas flows from the spray gun body 2a to the nozzle 2b.
  • Powder 10 which serves as a film-forming raw material, is supplied to the nozzle 2b from the powder supply section 3 via the pipe 5 as shown by an arrow 32.
  • the powder 10 for example, aluminum powder, aluminum oxide powder, or a mixed material of tin powder and zinc powder can be used.
  • the particle size of the powder 10 is, for example, 10 ⁇ m or more and 20 ⁇ m or less.
  • the powder 10 supplied to the nozzle 2b is injected toward the base material 20 from the tip of the nozzle 2b together with the operating gas.
  • a mask jig 1 is arranged on the surface of the base material 20.
  • the injected powder 10 reaches the surface of the base material 20 through the through hole 13 of the mask jig 1.
  • FIG. 2 is a perspective view showing an exploded state of each member constituting the nozzle of FIG. 1.
  • FIG. FIG. 3 is a schematic diagram showing a first example of the configuration of a nozzle constituting the film forming apparatus of FIG. 1.
  • nozzle 2b includes a nozzle holder 21 and a nozzle pipe 23.
  • the spray gun main body 2a in FIG. 1 is connected to the right side of the nozzle 2b in FIG. 3.
  • the operating gas flows through the nozzle 2b from the right side to the left side (same as in FIG. 1).
  • the nozzle holder 21 has a first portion 21A extending along the left-right direction in which the operating gas flows within the spray gun 2, and a second portion 21B extending in the vertical direction intersecting (for example, orthogonal to) the first portion 21A. ing.
  • the second portion 21B is not limited to extending perpendicularly to the first portion 21A, but may extend in a direction having some error with respect to the vertical direction.
  • the nozzle holder 21 is made up of a first part 21A and a second part 21B.
  • the first portion 21A is a region into which the operating gas from the spray gun main body 2a flows toward the nozzle pipe 23 side.
  • the second portion 21B is a region into which the powder 10 from the powder supply section 3 and piping 5 flows and flows toward the first portion 21A.
  • the pipe 5 (see FIG. 1) is connected to the second portion 21B of the nozzle holder 21, and further extends in the vertical direction within the second portion 21B.
  • a portion of the piping 5 that is adjacent to an intersection 21C with a cavity (described later) in the first portion 21A and that is particularly present in the nozzle holder 21 in FIG. 3 will be hereinafter referred to as a piping 5A.
  • the piping 5A is a hollow portion extending vertically within the second portion 21B.
  • the pipe 5A extends in a vertical direction intersecting the left-right direction (first direction) in which the operating gas flows within the spray gun 2.
  • the piping 5A is connected to a cavity in the first portion 21A, which will be described later.
  • a cavity extending along the left-right direction in FIG. 3 extends inside the first portion 21A.
  • the cavity is designed as a passage for the working gas and the powder 10.
  • the cavity may extend obliquely with respect to the outer edge of the first portion 21A that extends in the left-right direction.
  • the inner diameter of the cavity may gradually increase and decrease.
  • the cavity includes a throat portion 21D, an expanded portion 21E, and a reduced portion 21F.
  • the portion having the smallest inner diameter is referred to as a throat portion 21D.
  • the throat portion 21D is formed on the upstream side of the working gas (on the right side in FIG.
  • the portions other than the throat portion 21D that is, the portions extending in an inclined manner such that the inner diameter of the cavity gradually increases as the distance from the throat portion 21D increases are referred to as an expanded portion 21E and a contracted portion 21F.
  • the passage on the downstream side (left side in FIG. 3) of the throat part 21D is the expanded part 21E, and the passage on the upstream side of the throat part 21D is the reduced part 21F.
  • the cavity (throat part 21D, expansion part 21E, and contraction part 21F) in the first part 21A and the cavity (piping 5A) in the second part 21B intersect at an intersection 21C in the nozzle holder 21.
  • the working gas flowing through the cavity of the first portion 21A and the powder 10 flowing through the cavity of the second portion 21B meet at the intersection 21C.
  • a working gas containing a film forming raw material flows on the downstream side of the intersection 21C in the first portion 21A.
  • a nozzle pipe 23 is connected to the nozzle holder 21 on the downstream side of the intersection 21C in the first portion 21A.
  • a part of the nozzle pipe 23 is housed in the nozzle holder 21.
  • FIG. 4 is a schematic diagram showing the appearance of the nozzle pipe in FIG. 3. Note that in FIG. 4, portions that are hidden inside the member and cannot be seen from the outside are indicated by broken lines.
  • FIG. 5 is a schematic cross-sectional view of the region V surrounded by the dashed line in FIG. Note that FIG. 5 shows an aspect of the region hidden inside the member in FIG. 4.
  • the nozzle pipe 23 has one end 23EGa in the extending direction (left-right direction in the figure), and the other end 23EGb on the opposite side to the one end 23EGa. It is.
  • the nozzle pipe 23 has an inner peripheral surface 23if formed along the direction in which the nozzle pipe 23 extends.
  • the nozzle pipe 23 has a cylindrical shape that is hollow inside the inner peripheral surface 23if.
  • the nozzle pipe 23 has an inner circumferential surface 23if with a surface roughness Sa of 25% or less of the cumulative particle diameter D10 of the particle size distribution of the powder 10.
  • the surface roughness Sa of the inner circumferential surface 23if being 25% or less of the cumulative particle diameter D10 of the particle size distribution of the powder 10 means that at least within a part of the inner circumferential surface 23if selected for measurement. This means that the maximum value of the surface roughness Sa is 25% or less of the cumulative particle size D10 of the flowing powder 10.
  • the above-mentioned partial area may be the one end 23EGa side, the other end 23EGb side, or the center of the nozzle pipe 23.
  • the part of the region is, as described below, the effect of suppressing occlusion within the inner circumferential surface 23if can be obtained.
  • the diameter of the inner peripheral surface 23if gradually increases from the one end 23EGa side to the other end 23EGb side as shown in FIG. .
  • the above-mentioned partial region is the region at the end of the one end 23EGa. This is because the possibility of collision between the inner circumferential surface 23if and the powder 10 is higher in a narrow region with a small diameter than in a region with a large diameter, and the possibility of clogging occurring is higher.
  • FIG. 6 is a graph showing the particle size distribution according to the particle size of the powder and the cumulative proportion of the powder.
  • the vertical axis represents the number of particles extracted from the powder 10 passing through the nozzle pipe 23 in descending order of particle size, starting from the smallest particle size. The ratio to the total number of grains included in 10 is shown.
  • the horizontal axis of FIG. 6 indicates the particle size of the largest grain included in the group of powders 10 extracted by the proportion shown on the vertical axis.
  • the cumulative particle size D10 indicates the particle size of the largest particle included in the sampled group when 10% of the particles with the smallest particle size are extracted from the particles contained in the powder 10.
  • the surface roughness Sa of the inner circumferential surface 23if of the nozzle pipe 23 is 3 ⁇ m or less. It is. In addition, it is more preferable that the maximum value of the surface roughness Sa of the entire inner circumferential surface 23if is 25% or less of the cumulative particle size D10 of the particle size distribution of the powder 10, as described above.
  • the surface roughness Sa is determined by the arithmetic mean height of ISO 25178.
  • the nozzle pipe 23 has an inner peripheral surface 23if with a surface roughness Sa of 2 ⁇ m or less.
  • the expression that the surface roughness Sa of the inner peripheral surface 23if is 2 ⁇ m or less means that the maximum value of the surface roughness Sa in at least a part of the area selected for measurement is 2 ⁇ m or less. means.
  • the inner circumferential surface 23if may have a surface roughness Sa of 25% or less of the cumulative particle diameter D10 of the particle size distribution of the powder 10, and an absolute value of the surface roughness Sa of 2 ⁇ m or less.
  • the absolute value of the surface roughness Sa of the inner circumferential surface 23if may be 2 ⁇ m or less without satisfying the condition that the surface roughness Sa is 25% or less of the cumulative grain size D10.
  • the outer peripheral surface of the nozzle pipe 23 has a constant diameter from one end 23EGa to the other end 23EGb.
  • the inner circumferential surface 23if of the nozzle pipe 23 is inclined so that its diameter gradually increases (becomes thicker) from one end 23EGa to the other end 23EGb. It's okay. That is, as shown in FIG. 5, the diameter ⁇ 2 of the inner peripheral surface 23if at the position on the other end 23EGb side may be larger than the diameter ⁇ 1 of the inner peripheral surface 23if at the position on the one end 23EGa side.
  • the inner circumferential surface 23if is parallel to the outer circumferential surface of the nozzle pipe 23 (so that the diameter of the inner circumferential surface 23if is approximately constant throughout: the diameter ⁇ 1 and the diameter ⁇ 2 in FIG. 5 are approximately equal). ) may be extended.
  • the steps formed on the inner peripheral surface 23if of the nozzle pipe 23 have a height of 10 ⁇ m or less.
  • the step is, for example, a step between regions where the position of the inner circumferential surface 23if in the radial direction (vertical direction in FIG. 5) and the position in the extending direction of the nozzle pipe 23 (horizontal direction in FIG. This is the part where the shape changes rapidly.
  • the height of the step means a difference in the radial position of the inner circumferential surface 23if.
  • the step difference is more preferably 5 ⁇ m or less, and even more preferably 2 ⁇ m or less.
  • a step is a portion where the height changes suddenly between a certain position and an adjacent position. In this sense, a step is distinguished from surface roughness Sa caused by a gradual change in height between regions.
  • FIG. 7 is a schematic diagram showing a second example of the configuration of the nozzle constituting the film forming apparatus of FIG. 1.
  • a nozzle 2b shown here has basically the same configuration as the nozzle 2b of the first example shown in FIG. Therefore, in FIG. 7, the same components as those in FIG. 3 are given the same reference numerals, and the description thereof will not be repeated unless there is a particular difference.
  • the length in which the first portion 21A of the nozzle holder 21 extends from the intersection 21C in the direction of flow of the arrow 31 (left side) is shorter than that of the nozzle 2b of FIG. 3. Therefore, in FIG. 7, compared to FIG. 3, the part of the nozzle pipe 23 that fits inside the nozzle holder 21 is shorter, and the part of the nozzle pipe 23 that is arranged outside the nozzle holder 21 is longer.
  • FIG. 8 is a schematic diagram showing a third example of the configuration of the nozzle constituting the film forming apparatus of FIG. 1.
  • a nozzle 2b shown here has basically the same configuration as the nozzle 2b of the first example shown in FIG. Therefore, in FIG. 8, the same components as in FIG. 3 are given the same reference numerals, and the description thereof will not be repeated unless there is a particular difference.
  • the nozzle holder 21 does not have the second portion 21B, but only includes a first portion 21A extending in the left-right direction. Therefore, although the pipe 5A in FIG. 8 is adjacent to the intersection 21C, it is arranged outside the nozzle holder 21.
  • the piping 5A in FIG. 8 extends in the vertical direction intersecting the left-right direction in which the operating gas flows in the spray gun 2, as in FIGS. 3 and 7.
  • the piping 5A is connected to a cavity in the first portion 21A, which will be described later.
  • a guide component 24 may be provided on the outside of the nozzle pipe 23 in the radial direction.
  • the guide component 24 has a cylindrical shape and is arranged so as to surround a region of the nozzle pipe 23 that is particularly relatively close to the one end 23EGa from the outside in the radial direction.
  • the guide component 24 surrounds a curved surface (side surface) extending the outer edge of a region of the nozzle pipe 23 that is relatively close to one end 23EGa, and comes into contact with the nozzle pipe 23 .
  • the end of the guide component 24 inside the nozzle holder 21 is defined as a guide component end 24EG.
  • the guide component end 24EG is connected to a cavity (extended portion 21E) within the first portion 21A.
  • the working gas and film-forming raw material that have merged at the intersection 21C then flow through the nozzle pipe 23 from the right side to the left side in FIGS. 3, 7, and 8.
  • the guide component 24 can be fixed to the nozzle pipe 23.
  • the threaded portion 25 be arranged, for example, on the outside of the guide component 24 in the radial direction.
  • the threaded portion 25 has a male thread and a female thread, which can be fastened together.
  • the male thread of the threaded portion 25 may be fixed, for example, as an annular member on a curved surface extending on the outer edge of the guide component 24, or may be formed directly on the outer edge of the guide component 24.
  • the male thread may be fixed on the curved surface of the outer edge of the nozzle pipe 23, or the male thread may be formed directly on the curved surface.
  • the female thread may be formed on the inner wall of the hole in the first portion 21A of the nozzle holder 21 into which the nozzle pipe 23 is inserted, or may be a nut fixed to the nozzle holder 21.
  • the nozzle pipe 23 is fixed to the nozzle 2b (nozzle holder 21) by the threaded portion 25.
  • the expanded portion 21E is connected to the nozzle pipe 23, and in FIGS. 3, 7, and 8, the inner diameter (diameter of the inner wall surface) of the downstream end of the expanded portion 21E is the outer diameter (diameter of the outer wall surface) of the nozzle pipe 23. It's smaller. Such an embodiment may be adopted.
  • the nozzle pipe 23 is made of stainless steel material such as SUS304, SUS410, and SUS430. However, the nozzle pipe 23 may be made of SKD11 instead of stainless steel material. Alternatively, the nozzle pipe 23 may be made of copper. Guide component 24 is made of copper.
  • the nozzle holder 21 is made of brass.
  • the nozzle holder 21 is a member to which the powder 10 serving as a film forming raw material is supplied from the powder supply section 3 and the piping 5.
  • the nozzle pipe 23 is fitted into the nozzle holder 21 on the downstream side of the intersection 21C.
  • the flow direction of the powder 10 changes from the vertical direction to the horizontal direction at the intersection 21C. In the region adjacent to the change in the flow direction of the powder 10, the powder 10 collides with the inner wall surface of the nozzle pipe 23 rather than the inner wall surface of the cavity of the nozzle holder 21.
  • the material of the nozzle holder 21 does not need to have particularly high hardness. Furthermore, on the upstream side of the intersection portion 21C between the powder 10 and the working gas, there is little possibility of the powder 10 colliding in the first place, so there is no need to make the hardness of the nozzle holder 21 particularly high. From this point of view, brass is used for the nozzle holder 21.
  • a pipe-shaped material such as stainless steel is prepared.
  • the pipe-shaped material may be purchased or processed in-house.
  • the outer peripheral surface is processed by a generally known method such as cutting.
  • a wire for electrical discharge machining is passed through the cavity inside the inner peripheral surface of the pipe-shaped material, and a voltage is applied between the wire and the material. Electric discharge machining is thereby performed.
  • the inner peripheral surface of the cavity is cut by electrical discharge machining. Therefore, by electric discharge machining, the step on the inner circumferential surface can be removed and the surface roughness Sa of the inner circumferential surface can be reduced. As a result, high steps are eliminated, and an inner circumferential surface with a small (smooth) surface roughness Sa is formed.
  • the surface roughness Sa of the inner circumferential surface can be made smaller, and the difference in level can be made smaller.
  • the nozzle pipe 23 thus formed has an inner peripheral surface 23if with a surface roughness Sa of 2 ⁇ m or less.
  • the particle size of the powder 10 flowing through the nozzle pipe 23 thus formed may be 10 ⁇ m or more and 20 ⁇ m or less.
  • the nozzle pipe 23 to be measured is divided, for example, at the central portion in the extending direction.
  • the shape of the inner circumferential surface 23if of the nozzle pipe 23 is measured from the dividing plane (cross section in the extending direction) using a generally known 3D shape measuring machine.
  • the measurement results on the divided plane are obtained as a color map. In the area indicated by the color map, measurement points are not extracted, but the entire shape within the area is measured, and the maximum value of the surface roughness Sa is obtained from the measurement result.
  • the surface roughness Sa of the inner circumferential surface 23if can be accurately measured.
  • the level difference on the inner circumferential surface can also be measured basically in the same manner as above.
  • the nozzle pipe 23 is divided such that a step is included in the dividing surface or an area adjacent thereto (it is even more preferable that the nozzle pipe 23 is divided such that the step is exposed on the dividing surface).
  • the nozzle according to the first aspect of the present disclosure is a nozzle 2b used in thermal spraying.
  • the nozzle 2b includes a nozzle pipe 23 through which powder 10, which is a film forming raw material, and operating gas pass.
  • the nozzle pipe 23 has an inner circumferential surface 23if with a surface roughness Sa (arithmetic mean height) of 25% or less of the cumulative particle diameter D10 of the particle size distribution of the powder 10.
  • FIG. 9 is a schematic diagram showing the appearance of a nozzle pipe as a comparative example.
  • FIG. 10 is a schematic cross-sectional view of a first example of region A surrounded by a dashed line in FIG. Note that FIG. 10 shows an aspect of the region hidden inside the member in FIG. 9. 9 and 10, if the inner circumferential surface 23if is rough and its surface roughness Sa exceeds 25% of the cumulative particle size D10 of the particle size distribution of the powder 10, the particle size will be 10 ⁇ m when performing the cold spray method.
  • the nozzle pipe 23 has surface roughness in at least a portion of the inner circumferential surface 23if (a partial region of the inner circumferential surface 23if selected for measurement, or the entire inner circumferential surface 23if).
  • the maximum value of Sa is 25% or less of the cumulative particle size D10 of the powder 10 flowing therethrough.
  • Example 1 the inventor of this embodiment after intensive research found that the surface roughness Sa of the inner circumferential surface 23if of the nozzle pipe 23 is equal to the cumulative particle diameter D10 of the powder 10 passing through the nozzle pipe 23. It has been found that the blockage within the inner circumferential surface 23if can be suppressed if the amount is 25% or less. This was discovered based on the following facts.
  • the surface roughness Sa of the inner circumferential surface 23if is small (if the inner circumferential surface 23if is smooth), clogging by the powder 10 can be suppressed. Conversely, if the surface roughness Sa of the inner circumferential surface 23if is large (if the inner circumferential surface 23if is rough), clogging by the powder 10 is likely to occur. If the inner circumferential surface 23if is rough, the inner circumferential surface 23if has more unevenness than when it is smooth, and the powder 10 tends to adhere to the unevenness, making it easier to cause blockage.
  • the collision area which is the area of the nozzle surface where the powder 10 collides, becomes larger than the size of the powder 10.
  • the powder 10 that is flown by the working gas is easily accelerated and has a high speed. Therefore, the powder 10 has a large collision energy with the nozzle surface. As described above, the powder 10 having a relatively small particle size tends to easily adhere to the nozzle surface.
  • the collision area is smaller than when the powder 10 with a relatively small particle size collides with the nozzle surface. Further, since the particle size of the powder 10 is large, the powder 10 that is flown by the working gas is difficult to accelerate. Therefore, the powder 10 has less collision energy with the nozzle surface. As described above, the powder 10 having a relatively large particle size tends to be difficult to adhere to the nozzle surface.
  • the particle size of the powder 10 As described above, if the particle size of the powder 10 is small, the powder 10 tends to adhere to the nozzle surface unless the surface roughness Sa is made smaller, and the nozzle pipe 23 is likely to be clogged. On the other hand, if the particle size of the powder 10 is large, even if the surface roughness Sa is large, the powder 10 is less likely to adhere to the nozzle surface and the nozzle pipe 23 is less likely to be clogged. Based on this, a favorable relationship between the powder 10 and the surface roughness Sa was found.
  • the powder 10 with a small particle size aggregates, it is difficult to handle it compared to the powder 10 with a large particle size. For this reason, it is desirable to form a film using powder 10 with as large a particle size as possible. Further, it is difficult to process the surface roughness Sa of the inner peripheral surface 23if to make it excessively small. From this point of view as well, it is preferable to use powder 10 with a particle size as large as possible and to perform film formation using nozzle pipe 23 having inner circumferential surface 23if with relatively large surface roughness Sa. According to the present disclosure, the selectable range of the surface roughness Sa can be further expanded, so that the inner peripheral surface 23if can be processed more easily.
  • the surface roughness Sa of the inner circumferential surface 23if can be designed to a size suitable for the particle size of the powder 10 within the range that can be occluded, so there is a degree of freedom in the design value of the surface roughness Sa. increases.
  • the inner circumferential surface 23 if has a surface roughness Sa below a threshold value obtained in accordance with the particle size, so that the nozzle pipe 23 can be prevented from clogging.
  • a nozzle 2b there is provided a nozzle 2b).
  • a powder 10 serving as a film forming raw material is prepared. The powder 10 is sprayed onto the surface of the base material by a cold spray method using the nozzle pipe 23 through which the powder 10 and working gas are passed.
  • the nozzle pipe 23 has an inner circumferential surface with a surface roughness Sa of 25% or less of the cumulative particle diameter D10 of the particle size distribution of the powder 10. According to the film forming method, the same effects as those of the nozzle 2b according to the first aspect of the present embodiment described above can be obtained.
  • the nozzle pipe 23 may have an inner peripheral surface 23if with a surface roughness Sa of 2 ⁇ m or less.
  • the nozzle according to the second aspect of the present disclosure is a nozzle 2b used in a thermal spraying method.
  • the nozzle 2b includes a nozzle pipe 23 through which powder 10, which is a film forming raw material, and operating gas pass.
  • the nozzle pipe 23 has an inner peripheral surface 23if with a surface roughness Sa (arithmetic mean height) of 2 ⁇ m or less.
  • the powder 10 with a particle size of 10 ⁇ m or more and 20 ⁇ m or less will be applied to the inner circumferential surface 23if during cold spraying. If the nozzle pipe 23 passes through the inner peripheral surface 23if, for example, the end portion of the inner peripheral surface 23if may become clogged, and the nozzle pipe 23 may not be usable for a long time.
  • the nozzle pipe 23 has surface roughness in at least a portion of the inner circumferential surface 23if (a partial region of the inner circumferential surface 23if selected for measurement, or the entire inner circumferential surface 23if).
  • the maximum value of Sa is 2 ⁇ m or less, which is extremely fine.
  • the step formed on the inner peripheral surface 23if of the nozzle pipe 23 may be 10 ⁇ m or less.
  • FIG. 11 is a schematic cross-sectional view of a second example of the area A surrounded by the dashed line in FIG. Note that FIG. 11 shows an aspect of the region hidden inside the member in FIG. 9.
  • the powder 10 film forming raw material having a particle size of 10 ⁇ m or more and 20 ⁇ m or less when performing the cold spray method.
  • the powder passes through the inner circumferential surface 23if, there is a possibility that a blockage occurs within the inner circumferential surface 23if (the region through which the powder 10 and the like flows).
  • the step is as small as 10 ⁇ m or less.
  • the powder 10 film forming raw material
  • the inside of the inner peripheral surface 23if region where the powder 10 etc. flows
  • Powder 10 having a fine particle size flows within the inner circumferential surface 23if at a higher speed than powder 10 having a large particle size.
  • the powder 10 flowing at high speed within the inner circumferential surface 23if is easily affected by the rough surface and steps of the inner circumferential surface 23if, and is easily clogged within the inner circumferential surface 23if.
  • the surface roughness Sa should be 2 ⁇ m or less from the viewpoint of suppressing clogging. It is preferable that the height of the step is 10 ⁇ m or less.
  • the particle size of the powder 10 is relatively large, such as 30 ⁇ m or more (40 ⁇ m or more), clogging may not occur on the inner peripheral surface 23if, which would otherwise occur if the particle size was relatively small, such as 10 ⁇ m or more and 20 ⁇ m or less. be.
  • the numerical range of the surface roughness Sa of the inner circumferential surface 23if in which blockage does not occur changes depending on the particle size.
  • the numerical range of the size of the step on the inner circumferential surface 23if in which blockage does not occur changes depending on the particle size.
  • the likelihood of clogging occurring is determined by the combination of the particle size of the powder 10, the surface roughness Sa of the inner circumferential surface 23if, and the size of the step. Therefore, for example, even if the surface roughness Sa of the inner peripheral surface 23if exceeds 10 ⁇ m, if the particle size of the powder 10 is other than 1 ⁇ m or more and 20 ⁇ m or less (that is, the particle size of the powder 10 is less than 1 ⁇ m or more than 20 ⁇ m). (b), clogging of the nozzle pipe 23 can be suppressed in some cases.
  • nozzle pipes 23 having different surface roughnesses Sa of the inner circumferential surface 23if were prepared, and a test was conducted to confirm the presence or absence of blockage when a film was formed by a cold spray method using each of the nozzle pipes 23.
  • the base material 20 was formed into a film by the film forming apparatus 100 of FIG. 1 equipped with the nozzle 2b of FIG. 3.
  • the nozzle pipe 23 used was made of SUS304 and was formed using the wire electrical discharge machining described above.
  • the nozzle pipe 23 has a constant diameter (thickness) on the outer circumferential surface, and the inner circumferential surface 23if has a tapered shape in which the diameter gradually increases from the one end 23EGa side to the other end 23EGb side. It is.
  • the nozzle pipe 23 was fitted into the nozzle holder 21 shown in FIGS. 2 and 3.
  • the nozzle pipe 23 is attachable to and detachable from the nozzle holder 21.
  • the diameter of the inner peripheral surface of the nozzle holder 21 gradually increases from the throat portion 21D to the expanded portion 21E and the contracted portion 21F. Therefore, the nozzle 2b is a so-called Laval nozzle.
  • the surface roughness Sa of relatively end regions of the inner peripheral surfaces 23if of the four types of nozzle pipes 23 was set to 1.0 ⁇ m, 2.0 ⁇ m, 2.6 ⁇ m, and 4.3 ⁇ m. As described above, the value determined by the arithmetic mean height of ISO 25178 is used as the surface roughness Sa. Specifically, the surface roughness Sa is a value obtained by measuring a measurement range of 3 mm x 5 mm at a measurement magnification of 40 times using a one-shot 3D shape measuring machine (Keyence Corporation VR-5000). be. In addition, in any of the nozzle pipes 23, no step with a height t (see FIG. 11) of at least 10 ⁇ m or more was formed on the inner circumferential surface 23if.
  • FIG. 12 is a flowchart showing the film forming method according to this embodiment.
  • the film forming method shown in FIG. 12 is a film forming method carried out using the mask jig 1 and film forming apparatus 100 shown in FIGS. 1 to 3, and includes a preparation step (S10) and a film forming step. (S20) and a post-processing step (S30).
  • the preparation step (S10) includes a step of arranging the mask jig 1 so as to face the surface of the base material 20 as shown in FIG.
  • the mask jig 1 is arranged so that the first surface of the mask jig 1 faces the surface of the base material 20. Further, in the preparation step (S10), powder 10 that becomes a film forming raw material is prepared.
  • the film forming step (S20) powder serving as a film forming raw material is sprayed onto the surface of the base material 20 through the through hole 13 of the mask jig 1 using the film forming apparatus 100 by a cold spray method. At this time, a nozzle pipe 23 is used that passes the powder 10 and the working gas. As a result, a film made of the film-forming raw material is formed on the surface of the base material 20.
  • the film forming raw material powder 10 was injected from the pipe 5A, that is, from the outside in the radial direction of the nozzle pipe 23 in the direction of the arrow 32, using the nozzle 2b in FIG.
  • the powder 10 was supplied by the powder supply section 3 shown in FIG. 1 using negative pressure.
  • Powder 10 is a mixed powder of aluminum powder and aluminum oxide (Al 2 O 3 ) powder having a particle size of 20 ⁇ m.
  • dry air was used as an operating gas in the film forming apparatus 100, and the pressure thereof was set to 0.8 MPa. Further, the working gas was heated to 270° C. by the heater 2c.
  • the mask jig 1 is removed from the surface of the base material 20. Thereafter, necessary treatments such as processing on the base material 20 are performed. In this way, a film can be formed on the surface of the base material 20.
  • FIG. 13 is a table showing the test results of Example 1, that is, the presence or absence of blockage at the end of the nozzle pipe after film formation.
  • the surface roughness Sa of the inner circumferential surface 23if in a certain region at its end, that is, relatively on the one end 23EGa side, is measured. The presence or absence of occlusion was confirmed.
  • film formation was performed using three types of powder 10 for each of four types of nozzles 2b whose inner circumferential surfaces 23if had different surface roughnesses Sa.
  • the three types of powders 10 have different cumulative particle diameters D10. Specifically, the cumulative particle diameters D10 of the three types of powder 10 were 7.8 ⁇ m, 14.1 ⁇ m, and 18.2 ⁇ m, respectively.
  • the nozzle pipe has a surface roughness Sa of 1.0 ⁇ m and 2.0 ⁇ m on the inner circumferential surface 23if in a certain region at the end of the nozzle pipe 23.
  • surface roughness Sa 1.0 ⁇ m and 2.0 ⁇ m on the inner circumferential surface 23if in a certain region at the end of the nozzle pipe 23.
  • no blockage occurred after the film forming process.
  • nozzle pipes 23 with surface roughness Sa of 2.6 ⁇ m and 4.3 ⁇ m were clogged after the film forming process.
  • the surface roughness Sa of the inner peripheral surface 23if in a certain region of the end of the nozzle pipe 23 is 1.0 ⁇ m, 2.0 ⁇ m, and 2.6 ⁇ m. No clogging occurred in the nozzle pipe 23 after the film forming process. On the other hand, clogging occurred in the nozzle pipe 23 having a surface roughness Sa of 4.3 ⁇ m after the film forming process.
  • the surface roughness Sa of the inner peripheral surface 23if is 1.0 ⁇ m, 2.0 ⁇ m, 2.6 ⁇ m, and 4.3 ⁇ m after the film forming process. No occlusion occurred.
  • the surface roughness Sa of the inner circumferential surface 23if without a step is the cumulative particle size D10 of the particle size distribution of the powder 10. It was confirmed that no occlusion occurs if the amount is 25% or less. This is because the data in FIG. 13 are not shown, for example, in the range where D10 is 7.8 ⁇ m and the surface roughness is less than 2.0 ⁇ m, no blockage occurs.
  • the criteria for determining the presence or absence of blockage on the inner circumferential surface 23if are as follows. After the film forming process (S20) by cold spraying was performed using the film forming apparatus 100 for 24 hours or more, the inner circumferential surface 23if of the nozzle pipe 23 was observed. When no powder 10 was observed to adhere to the inner peripheral surface 23if, it was determined that there was no blockage. If adhesion of the powder 10 to the inner circumferential surface 23if was confirmed during the 24-hour film forming step (S20), it was determined that there was a blockage.
  • copper has a cohesive energy of 100 kcal/g-atom or less, which is smaller than the metal material used for the nozzle body in Patent Document 1 mentioned above.
  • the nozzle pipe 23 is not clogged by providing the features of this embodiment.
  • Patent Document 1 mentioned above describes that the hardness of the nozzle body is preferably 150 HV or more.
  • the nozzle pipe 23 made of copper with a voltage of 100 HV or less was effective in suppressing clogging.
  • nozzle pipes 23 having different surface roughnesses Sa of the inner circumferential surface 23if were prepared, and a test was conducted to confirm the presence or absence of blockage when a film was formed by a cold spray method using each of the nozzle pipes 23.
  • the base material 20 was formed into a film using the film forming apparatus 100 of FIG. 1 equipped with the nozzle 2b of FIG. 3.
  • the nozzle pipe 23 used is made of SUS304 formed in the same manner as in Example 1, and has the same dimensions and shape as in Example 1.
  • the surface roughness Sa of the end region of the inner peripheral surface 23if of the four types of nozzle pipes 23 was set to 1.0 ⁇ m, 2.0 ⁇ m, 2.6 ⁇ m, and 4.3 ⁇ m.
  • no step with a height t (see FIG. 11) of at least 10 ⁇ m or more was formed on the inner circumferential surface 23if.
  • the powder 10 used in the film forming step (S20) is a mixed powder of aluminum powder with an average particle size of 10 ⁇ m and aluminum oxide (Al 2 O 3 ) powder with an average particle size of 20 ⁇ m.
  • the diameters of individual particles of aluminum and aluminum oxide in the powder 10 both have some deviation from the above values.
  • dry air was used as an operating gas in the film forming apparatus 100, and the pressure thereof was set to 0.8 MPa. Further, the working gas was heated to 270° C. by the heater 2c.
  • FIG. 14 is a table showing the test results of Example 2, that is, the presence or absence of blockage at the end of the nozzle pipe.
  • the surface roughness Sa of the inner circumferential surface 23if in a certain region at its end, that is, relatively on the one end 23EGa side, is measured. The presence or absence of occlusion was confirmed.
  • the observation mode of the inner circumferential surface 23if within a certain region of the end of the nozzle pipe 23 is shown in the column of "Map (inner circumferential surface)" in the figure.
  • copper has a cohesive energy of 100 kcal/g-atom or less, which is smaller than the metal material used for the nozzle body in Patent Document 1 mentioned above.
  • the nozzle pipe 23 is not clogged by providing the features of this embodiment.
  • Patent Document 1 mentioned above describes that the hardness of the nozzle body is preferably 150 HV or more.
  • the nozzle pipe 23 made of copper with a voltage of 100 HV or less was effective in suppressing clogging.
  • FIG. 15 is a schematic diagram showing a fourth example of the configuration of the nozzle constituting the film forming apparatus of FIG. 1.
  • nozzle 2b according to the present embodiment may have a configuration that does not include nozzle holder 21 and only includes nozzle pipe 23.
  • the cavity 21C extending along the left-right direction in FIG. 15 formed in the nozzle holder 21 in FIGS. 3, 7, and 8 and the intersection 21C with the pipe 5 are all formed in the nozzle pipe 23.
  • a throat portion 21D, an expanded portion 21E, and a contracted portion 21F similar to those shown in FIGS. 3, 7, and 8 are formed in the cavity inside the nozzle pipe 23.
  • a reduced portion 21F is formed in a region adjacent to one end 23EGa.
  • a portion of the piping 5 that exists inside the nozzle pipe 23 is a piping 5A.
  • an inner circumferential surface 23if is formed particularly on the downstream side (left side in the figure) of the expanded portion 21E.
  • the inner circumferential surface 23if may extend slightly inclined with respect to the extending direction of the outer circumferential surface of the nozzle pipe 23, as in the other examples. Thereby, the diameter of the inner circumferential surface 23if may be maximum at the other end 23EGb. It has an inner peripheral surface with a surface roughness Sa of 2 ⁇ m or less.
  • the step formed on the inner circumferential surface 23if is 10 ⁇ m or less.
  • the nozzle pipe 23 (nozzle 2b) having such a configuration also has the same effects as the examples shown in FIGS. 3, 7, and 8.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

Une buse (2b) utilisée dans un procédé de pulvérisation thermique tel qu'une pulvérisation à froid comprend un tuyau de buse (23) à travers lequel une poudre (10), qui sert de matière première de formation de film, et un gaz de travail passent. Le tuyau de buse (23) a une surface périphérique interne au niveau de laquelle la rugosité de surface Sa a une distribution de taille de particule cumulative D10 de la poudre (10) inférieure à 25 %.
PCT/JP2023/004712 2022-03-29 2023-02-13 Buse et procédé de formation de film WO2023188873A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005089826A (ja) * 2003-09-17 2005-04-07 Toto Ltd 複合構造物作製装置
JP2008231527A (ja) * 2007-03-22 2008-10-02 Shinshu Univ コールドスプレー用粉末及び皮膜形成方法
WO2014073633A1 (fr) * 2012-11-12 2014-05-15 日立金属株式会社 Poudre de pulvérisation à froid et procédé de fabrication d'une cible de pulvérisation cathodique dans lequel la poudre est utilisée
WO2019009206A1 (fr) * 2017-07-05 2019-01-10 プラズマ技研工業株式会社 Pistolet de pulvérisation à froid et dispositif de pulvérisation à froid équipé dudit pistolet
WO2021177437A1 (fr) * 2020-03-05 2021-09-10 タツタ電線株式会社 Buse de pulvérisation, partie pointe de buse et dispositif de pulvérisation thermique

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005089826A (ja) * 2003-09-17 2005-04-07 Toto Ltd 複合構造物作製装置
JP2008231527A (ja) * 2007-03-22 2008-10-02 Shinshu Univ コールドスプレー用粉末及び皮膜形成方法
WO2014073633A1 (fr) * 2012-11-12 2014-05-15 日立金属株式会社 Poudre de pulvérisation à froid et procédé de fabrication d'une cible de pulvérisation cathodique dans lequel la poudre est utilisée
WO2019009206A1 (fr) * 2017-07-05 2019-01-10 プラズマ技研工業株式会社 Pistolet de pulvérisation à froid et dispositif de pulvérisation à froid équipé dudit pistolet
WO2021177437A1 (fr) * 2020-03-05 2021-09-10 タツタ電線株式会社 Buse de pulvérisation, partie pointe de buse et dispositif de pulvérisation thermique

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