WO2016039399A1

WO2016039399A1 - Laminate and laminate manufacturing method

Info

Publication number: WO2016039399A1
Application number: PCT/JP2015/075662
Authority: WO
Inventors: 優瀧本; 真也宮地; 雄一郎山内; 哲也竹川
Original assignee: 日本発條株式会社
Priority date: 2014-09-10
Filing date: 2015-09-09
Publication date: 2016-03-17
Also published as: JPWO2016039399A1

Abstract

Provided are: a laminate formed by cold-spraying a film obtained mainly from aluminum, etc. on a substrate surface obtained from a metal or alloy, wherein the close adhesion and electrical conductivity between the substrate and the film can be improved; and a laminate manufacturing method. A laminate (1) is provided with a substrate (10) obtained from a metal or alloy, and a film (11) formed on the surface of the substrate (10) and having aluminum, etc. as the main component. The laminate is characterized in that: the film (11) contains a non-metal with a higher melting point than the aluminum, etc. in a proportion of not more than 10 volume% and is obtained by laminating the aluminum or aluminum alloy powder, which is the main component of the film, in a flat and/or excavated state with respect to the lamination direction; and the interface between the substrate (10) and the film (11) is plastically deformed.

Description

Laminate and method for producing laminate

The present invention relates to a laminate made of aluminum or an aluminum alloy, and a method for producing the laminate.

In recent years, a cold spray method in which material powder is deposited and coated on a substrate by spraying the material powder on the substrate at a high temperature and high speed has attracted attention as one type of thermal spraying method. In the cold spray method, a base material is injected by injecting it from a Laval nozzle together with an inert gas heated below the melting point or softening point of the material powder, and the material that becomes the coating collides with the base material in the solid state. Since a film is formed on the surface, a metal film having no phase transformation and suppressing oxidation can be obtained.

By using the cold spray method, a laminate is prepared by forming a coating of a metal material having another type of electrical conductivity on the surface of a metal material that is a base having excellent electrical conductivity, and the laminate is used as a conductive member. Although the possibility has been sought, when the aluminum or aluminum alloy film is formed by the cold spray method, the adhesion between the film and the substrate is low due to the presence of the oxide film on the surface of the aluminum or aluminum alloy, and the electric conduction. Only films with a conductivity significantly lower than the bulk electrical conductivity of aluminum or aluminum alloys are obtained.

On the other hand, it is a method for manufacturing electronic parts with a film formed on the surface of the substrate by the cold spray method, which improves the thermal conductivity and electrical conductivity while enhancing the bonding of metal material powder and maintaining the thermal expansion moderately As a method for forming the film, a gas containing oxygen gas is used as the compressed gas, and a hard powder such as ceramics is mixed with the metal material powder to form a film. The ratio of the hard powder in the film formed by the above method is 10 to 10%. A method of 50% by volume is disclosed (for example, see Patent Document 1).

Japanese Patent No. 4645464

In Patent Document 1, when copper is used as a metal material powder together with ceramic powder and a film having a ceramic content of 10 to 50% by volume is formed by a cold spray method, the ceramic is not used. Although it has been confirmed that the thermal conductivity can be improved while reducing the thermal expansion coefficient of the film, the case where aluminum is used as the metal material powder is not described. Further, although Patent Document 1 describes that the electrical conductivity can be improved by containing 10 to 50% by volume of ceramic particles in the film, there is no description of the result indicating that the electrical conductivity has been improved.

The present applicants conducted extensive research on a film having excellent electrical conductivity by a cold spray method using a mixed powder of aluminum powder and ceramic powder as a material powder. As a result, an aluminum film containing ceramics at a predetermined ratio is aluminum. Although an improvement in electrical conductivity was recognized as compared with the film formed only from the powder, it was confirmed that it did not reach the desired standard.

The present invention has been made in view of the above, and in a laminate in which a film mainly composed of aluminum or an aluminum alloy is formed on the surface of a substrate composed of a metal or an alloy by a cold spray method, the substrate and the film It is an object of the present invention to provide a laminate and a method for producing the laminate that can improve the adhesion and electrical conductivity of the laminate.

In order to solve the above-described problems and achieve the object, a laminate according to the present invention includes a base material made of a metal or an alloy, and a film mainly composed of aluminum or an aluminum alloy formed on the surface of the base material. The film contains a non-metal having a melting point higher than that of the aluminum or aluminum alloy in a proportion of 10% by volume or less, and the aluminum or aluminum alloy powder as the main component of the film is flat and / or in the stacking direction. Or it is laminated | stacked in the beaten state, The interface of the said base material and the said membrane | film | coat has deformed plastically, It is characterized by the above-mentioned.

The laminate according to the present invention comprises a base material made of a metal or an alloy, and a film mainly composed of aluminum or an aluminum alloy formed on the surface of the base material, and the electric conductivity of the film is as follows: The electrical conductivity of the bulk material of aluminum or aluminum alloy that is the main component of the coating is 75.0% or more, and the aluminum or aluminum alloy powder that is the main component of the coating is flat and / or wrinkled in the stacking direction. The interface between the base material and the coating film is plastically deformed.

Further, the laminate according to the present invention is characterized in that, in the above invention, the porosity of the film is 5.0% by volume or less.

The laminate according to the present invention is characterized in that, in the above invention, the non-metallic powder is ceramic or glass.

Moreover, the method for producing a laminate according to the present invention is a method for producing a laminate in which a film mainly composed of aluminum or an aluminum alloy is formed on the surface of a base material made of a metal or an alloy, Heat mixed powder of aluminum or aluminum alloy powder in a proportion of 5 to 95% by volume and non-metallic powder of higher melting point than aluminum or aluminum alloy to a temperature lower than the melting point of aluminum or aluminum alloy. A coating forming step of accelerating with the generated gas, spraying and depositing on the surface of the substrate in a solid state, and depositing to form a coating, and the ratio of nonmetal contained in the coating is in the mixed powder It is 1/5 or less of the ratio of the nonmetallic powder contained, and is 10 volume% or less.

Further, the method for producing a laminate according to the present invention is characterized in that, in the above-mentioned invention, the non-metallic powder contained in the mixed powder before spraying on the surface of the base material is spherical.

Moreover, the manufacturing method of the laminated body concerning this invention is that in the said invention, the average particle diameter of the nonmetallic powder contained in the said mixed powder before spraying on the said base material surface is 30 micrometers or more and 500 micrometers or less. Features.

Further, the method for manufacturing a laminate according to the present invention is characterized in that, in the above invention, the non-metallic powder is ceramic or glass.

According to the present invention, a non-metallic spherical powder, for example, a powder of aluminum or the like containing ceramic or glass powder at a predetermined ratio is sprayed by a cold spray method to form a film on a base material such as metal, It becomes possible to produce a laminate having a low non-metal content and excellent electrical conductivity and adhesion between the substrate and the film.

FIG. 1 is a cross-sectional view showing the structure of a laminate according to an embodiment of the present invention. FIG. 2 is an SEM photograph of the cross section of the film of the laminate according to the embodiment of the present invention (500 times). FIG. 3 is a schematic diagram showing an outline of a cold spray apparatus used for forming a film of the laminate according to the embodiment of the present invention. FIG. 4 is an SEM image of spherical zircon (D50 = 106 to 125 μm) used in the embodiment of the present invention. FIG. 5 is a schematic diagram for explaining the adhesion strength test (the Lomulus test). FIG. 6 is a diagram showing the relationship between the type of base material and the adhesion strength of the laminate according to the embodiment of the present invention. FIG. 7 is an SEM image of the vicinity of the interface between the base material and the coating film in the cross section of the laminate using spherical zircon (D50 = 106 to 125 μm). FIG. 8 is an SEM image of the film cross section of a laminate using spherical zircon (D50 = 106 to 125 μm). FIG. 9 is an SEM photograph of spherical alumina (D50 = 35 μm, 66 μm, 120 μm) used in the embodiment of the present invention. FIG. 10 is an SEM image of the film cross section of the laminate using spherical alumina (D50 = 35 μm, 66 μm, 120 μm). FIG. 11 is an SEM photograph of alumina used as a comparative example. FIG. 12 is an SEM image of the vicinity of the interface between the base material and the film of the cross section of the laminate using non-spherical alumina (D50 = 30 μm). FIG. 13 is an SEM image of the film cross section of the laminate using non-spherical alumina (D50 = 30 μm). FIG. 14 is an SEM image of the vicinity of the interface between the base material and the film on the cross section of the laminate using non-spherical alumina (D50 = 57 μm). FIG. 15 is an SEM image of the cross-section of the laminate using non-spherical alumina (D50 = 57 μm). FIG. 16 is an SEM image of the cross section of the laminate using non-spherical alumina (D50 = 106 μm). FIG. 17 is an SEM image of the film cross section of the laminate using non-spherical alumina (D50 = 212 μm). FIG. 18 is an SEM image of the vicinity of the interface between the base material and the film in the cross section of the laminate in which the aluminum film is formed without blending ceramics. FIG. 19 is an SEM image of a cross section of a laminate in which an aluminum film is formed without blending ceramics. FIG. 20 is an SEM image of the film cross section of the laminate using spherical titanium (D50 = 30 μm). FIG. 21 is an SEM image of the film cross section of the laminate using non-spherical titanium (D50 = 30 μm).

Hereinafter, embodiments for carrying out the present invention will be described in detail with reference to the drawings. In addition, this invention is not limited by the following embodiment. The drawings referred to in the following description only schematically show the shape, size, and positional relationship so that the contents of the present invention can be understood. That is, the present invention is not limited only to the shape, size, and positional relationship illustrated in each drawing.

FIG. 1 is a cross-sectional view showing the structure of a laminate according to an embodiment of the present invention. A laminate 1 shown in FIG. 1 includes a base material 10 and a film 11 which is formed on the surface of the base material 10 and is laminated by a cold spray method to be described later, and mainly contains aluminum or an aluminum alloy. The laminated body 1 is not limited to the rectangular flat plate shape as shown in FIG. 1, and may be a cylindrical shape, a polygonal column shape, or the like. If the base material 10 consists of a metal or an alloy, material will not be limited.

In the laminate 1 according to the embodiment of the present invention, the film 11 is made of 5 to 95% by volume of aluminum or aluminum alloy powder, and 5% of non-metallic powder having a melting point higher than that of aluminum or aluminum alloy as the main component of the film 11. Formed by accelerating a mixed powder mixed at a rate of ˜95% by volume together with a gas heated to a temperature lower than the melting point of aluminum or aluminum alloy, and spraying and depositing it on the surface of the substrate 10 in a solid state. Is done.

By mixing the nonmetallic powder with the aluminum or aluminum alloy powder forming the coating 11, when the nonmetallic powder is sprayed onto the surface of the base material, the base material surface is blasted to expose the new surface of the base material. Formation of a metal bond between the base material and aluminum or an aluminum alloy is facilitated, and the adhesion strength at the interface between the base material 10 and the film 11 can be improved. Further, when aluminum or aluminum alloy powder and non-metallic powder collide with the base material 10, plastic deformation occurs at the interface between the base 10 and the coating 11. The adhesion between the base material 10 and the film 11 is improved by the anchor effect caused by plastic deformation at the interface. Furthermore, since the aluminum or aluminum alloy deposited on the base material 10 can be peened by mixing the nonmetallic powder with the aluminum or aluminum alloy powder, the dense film 11 with few pores can be obtained.

The coating 11 is plastically deformed and flattened in the stacking direction when the substantially spherical aluminum or aluminum alloy powder, which is the main component, is sprayed on the substrate 10 (the diameter of the copper powder in the stacking direction is the stacking direction). Smaller than the diameter in the direction perpendicular to the surface) and / or in a rolled state (wound by non-metallic powder). The flattened and / or beaten state of the aluminum or aluminum alloy powder forming the film 11 can be observed, for example, with an optical microscope or a (scanning) electron microscope. FIG. 2 is an SEM photograph of a cross section of the film 11 of the laminate 1 according to the embodiment of the present invention. The film 11 shown in FIG. 2 is formed by using a cold spray device, which will be described later, with a substantially spherical aluminum powder and a non-metallic powder (glass). Due to plastic deformation and peening and blasting effect due to non-metallic material, the layer is flat in the laminating direction (the diameter of the copper powder in the laminating direction is smaller than the diameter in the direction perpendicular to the laminating direction) and / or is crushed (non-metallic) It can be confirmed that they are laminated.

The average particle size of the aluminum or aluminum alloy powder used in this embodiment is 20 μm to 150 μm. When the average particle size is 20 μm to 150 μm, the fluidity is good and it is easy to obtain. The aluminum or aluminum alloy powder is produced, for example, by a gas atomizing method.

The mixing ratio of the aluminum or aluminum alloy powder and the nonmetallic powder in the mixed powder is 5 to 95 vol% for the aluminum or aluminum alloy powder and 5 to 95 vol% for the nonmetallic powder. When the blending ratio of the non-metallic powder is less than 5% by volume, a sufficient blasting effect and peening effect cannot be obtained, so that the laminate having the dense coating 11 with excellent adhesion strength at the interface between the substrate 10 and the coating 11 Can't get body 1. In addition, when the blending ratio of the nonmetallic powder is more than 95% by volume, it is difficult to form the film 11 mainly composed of aluminum or an aluminum alloy. The blending ratio of the non-metallic powder in the mixed powder is preferably 10 to 50% by volume, particularly preferably 30 to 50% by volume.

The mixed powder can be prepared by mixing aluminum or aluminum alloy powder and non-metallic powder with a sieve or the like.

The non-metallic powder sprayed onto the surface of the substrate 10 together with the aluminum or aluminum alloy powder is preferably granular, particularly spherical. Non-spherical non-metallic powders such as rods, plates, scales, polyhedrons, and crushed powders are not preferred because they tend to remain in the film 11. All of the non-metallic powders used are preferably spherical, but at least 50% or more, preferably 70% or more may be spherical.

The mixing ratio of the nonmetal in the film 11 is 1/5 or less of the ratio of the nonmetallic powder contained in the mixed powder and 10 volume% or less. By setting the mixing ratio of the nonmetal in the film 11 as described above, the electrical conductivity of the film 11 can be improved.

The average particle diameter (D50) of the nonmetallic powder sprayed on the surface of the base material 10 together with the aluminum or aluminum alloy powder is preferably 30 to 500 μm. When the average particle diameter (D50) of the non-metallic powder is smaller than 30 μm, the non-metal content in the coating 11 is increased and the peening effect is also decreased. On the other hand, when the average particle diameter (D50) of the non-metallic powder is larger than 500 μm, a gas nozzle of a cold spray apparatus described later is likely to be clogged, and erosion may occur in the base material 10 and the deposited film 11. The average particle size (D50) of the ceramic is particularly preferably 100 to 200 μm.

The non-metallic powder used in the present embodiment is not limited as long as it is spherical and has the above average particle diameter, but the surface of the substrate 10 is blasted to expose the new surface, and aluminum. Alternatively, it is preferable to have a predetermined hardness from the viewpoint of forming a metal bond with an aluminum alloy and peening the deposited aluminum or aluminum alloy to obtain a dense film 11. For example, the hardness of the nonmetallic powder is preferably 500 Hv or more.

From the viewpoint of obtaining the anchor effect on the base material 10 and the peening effect on the film 11, the same effect can be obtained even if a metal or alloy powder having a predetermined hardness is used instead of the non-metal powder. Alternatively, when alloy powder is used, the mixed metal or alloy and aluminum or aluminum alloy, the mixed metal or alloy, the mixed metal or alloy and the substrate 10 form a metal bond, and the mixed metal or alloy forms the coating 11. It is preferable to use non-metallic powder because the ratio remaining in the inside becomes high.

The non-metallic powder used in the present embodiment is not limited as long as it has a spherical shape and has the above average particle diameter, but glass such as soda lime glass and quartz glass, zircon, alumina, Ceramics such as zirconia and aluminum nitride can be used.

In the laminate 1 according to the present embodiment, the electric conductivity of the film 11 is 75.0% or more of the electric conductivity of the bulk material of aluminum or aluminum alloy which is the main component of the film 11. When the electric conductivity of the film 11 is 75.0% or more of the electric conductivity of the bulk material of the main component of the film 11, the laminate 1 can be used as a conductive member. The electric conductivity of the film 11 is preferably 80.0% or more, and particularly preferably 85.0% or more of the electric conductivity of the bulk material of aluminum or aluminum alloy which is the main component of the film 11. The electrical conductivity of the film 11 is expressed as a ratio when the electrical conductivity of A1050 is 100% when aluminum powder having a purity of 99.5% is used as the material of the film 11, for example.

In the laminate 1 according to the present embodiment, the porosity of the film 11 is preferably 5.0% by volume or less. In order to improve the adhesion strength at the interface between the base material 10 and the film 11, the porosity of the film 11 is preferably 5.0% by volume or less, and the porosity of the film 11 is 1.0% by volume. Is more preferable, and 0.5% by volume or less is particularly preferable.

Then, the manufacturing method of the laminated body 1 concerning this Embodiment is demonstrated. In the laminate 1, a mixed powder obtained by mixing 5 to 95% by volume of an aluminum or aluminum alloy powder and 5 to 95% by volume of a non-metallic powder on the surface of the substrate 10 is obtained from the melting point of the aluminum or aluminum alloy. The film 11 can be manufactured by accelerating with a gas heated to a low temperature and spraying and depositing on the surface of the base material 10 in a solid state to form the film 11.

Formation of the film 11 on the surface of the substrate 10 is performed by the cold spray method using the above-described mixed powder. The formation on the film 11 will be described with reference to FIG. FIG. 3 is a schematic diagram showing an outline of the cold spray device 20 used for forming the film 11 of the laminate 1 according to the present embodiment.

The cold spray device 20 contains a gas heater 21 that heats the compressed gas, a powder supply device 23 that contains the powder material to be sprayed onto the base material 10 and supplies the powder material to the spray gun 22, and a compressed gas heated by the spray gun 22. And a gas nozzle 24 for injecting the mixed powder material onto the substrate 10. The powder material here is a mixed powder in which aluminum or aluminum alloy powder is mixed in a proportion of 5 to 95% by volume and nonmetallic powder in a proportion of 5 to 95% by volume.

As the compressed gas, helium, nitrogen, air or the like is used. The supplied compressed gas is supplied to the gas heater 21 and the powder supply device 23 by

valves

25 and 26, respectively. The compressed gas supplied to the gas heater 21 is, for example, 100 ° C. or higher and heated to a temperature not higher than the melting point of aluminum or aluminum alloy, which is a powder material for forming the film 11, and then applied to the spray gun 22. Supplied. The heating temperature of the compressed gas is preferably 100 ° C. or higher and a temperature not higher than the melting point of aluminum or aluminum alloy as a powder material.

The compressed gas supplied to the powder supply device 23 supplies the powder material (a mixed powder of aluminum or aluminum alloy powder and nonmetal powder) in the powder supply device 23 to the spray gun 22 so as to have a predetermined discharge amount. . The heated compressed gas is converted into a supersonic flow (about 340 m / s or more) by a gas nozzle 24 having a tapered wide shape. The gas pressure of the compressed gas is preferably about 1 MPa to 5 MPa, more preferably about 2 MPa to 5 MPa. By setting the pressure of the compressed gas to about 2 MPa to 5 MPa, it is possible to improve the adhesion strength between the base material 10 and the film 11. The powder material supplied to the spray gun 22 is accelerated by the injection of this compressed gas into the supersonic flow, and collides with the base material 10 at a high speed in the solid state to form the film 11. Note that the apparatus is not limited to the cold spray apparatus 20 of FIG. 2 as long as the apparatus can form the coating 11 by colliding a mixed powder of aluminum or aluminum alloy powder and non-metallic powder with the base material 10 in a solid state. Absent.

According to the embodiment described above, a mixed powder obtained by mixing a spherical nonmetallic powder in a predetermined ratio with aluminum or an aluminum alloy powder is sprayed onto the surface of the substrate by a cold spray method, whereby the nonmetallic content is predetermined. Therefore, a laminate having excellent electrical conductivity and adhesion between the substrate and the film can be obtained.

(Example 1)
A mixed powder containing 50% by volume of aluminum powder and 50% by volume of zircon (ZrSiO ₄ ) as a non-metallic powder is formed on the base material 10 of different materials by the method for manufacturing the laminate 1 according to the present embodiment. 3 was sprayed by the cold spray device 3 to form a laminate 1 having a film 11 (thickness 0.5 mm) containing aluminum as a main component, and the adhesion strength was evaluated. The zircon used has a spherical shape as shown in FIG. Further, the adhesion strength at the interface between the substrate 10 and the film 11 was evaluated by an adhesion strength test apparatus 30 shown in FIG. In this method, a stud pin 32 (Φ4.1 mm) is bonded to the film 11 formed on the substrate 10 via the adhesive 33, and from above the stud pin 32 bonded to the film 11 via the adhesive 33, After inserting the support base 31 (Φ7.5 to 9.5 mm) having the hole portion 31a from above, the stud pin 32 is pulled upward in the vertical direction, whereby the adhesion strength between the base material 10 and the film 11 is increased. evaluated. The evaluation was performed based on the tensile stress and the peeled state at the time when the adhesive peeled off.

As the base material 10, aluminum (A1050-H24, A5052-H114, A6061-T6), stainless steel (SUS430, SUS304), Inconel 600, phosphor bronze, brass, nickel-phosphorus plating (C1020-1 / 4H), copper (C1020) -H) was used. Aluminum powder (D50) was applied to each substrate 10 by a cold spray device 20 at a compressed gas: nitrogen, a compressed gas temperature: 150 ° C., a compressed gas pressure: 5 MPa, a working distance (WD): 25 mm, a traverse speed: 400 mm / s. = 30 μm) and a mixed powder containing 50% by volume of spherical zircon powder (D50 = 106 to 125 μm) was sprayed to form the film 11, and the laminate 1 was produced. In addition, what was manufactured by the gas atomizing method was used for the aluminum powder. In FIG. 6, the relationship between the kind of base material 10 of the laminated body 1 concerning Example 1, and adhesive strength is shown.

(Comparative Example 1)
As Comparative Example 1, 100% by volume of aluminum powder (D50 = 30 μm) powder was sprayed on the same base material 10 as in Example 1 to form a film 11 to form a laminate 1. Produced. The results are shown in FIG.

As shown in FIG. 6, a mixed powder obtained by mixing spherical zircon powder with aluminum powder is sprayed onto the base material 10 by a cold spray device 20 to form a film 11. The adhesion strength between the base material 10 and the film 11 was improved from the film 11 formed by 100% by volume.

(Examples 2 to 4)
The substrate 10 (C1020-H) was compressed by a cold spray device 20 with compressed gas: nitrogen, compressed gas temperature: 150 ° C., compressed gas pressure: 5 MPa, working distance (WD): 25 mm, traverse speed: 400 mm / s, The mixing ratio of the spherical zircon powder (D50 = 106 to 125 μm) to the aluminum powder (D50 = 30 μm, purity 99.5%) is 10 volume% (Example 2), 30 volume% (Example 3), 50 The mixed powder changed to volume% (Example 4) was sprayed to form the film 11 (thickness 0.5 mm), and the laminate 1 was produced. About the produced laminated body 1, the zircon content in the membrane | film | coat 11, a porosity, and electrical conductivity were measured. The results are shown in Table 1. FIG. 7 shows an SEM image in the vicinity of the interface between the base material of the laminate and the film produced in Examples 2 to 4, and FIG. 8 shows an SEM image of the film cross section. FIGS. 7 (a) and 8 (a) are examples 2 formed with a mixed powder having a zircon powder ratio of 10% by volume, FIGS. 7 (b) and 8 (b) are 30% by volume. Example 3 formed with the mixed powder, and FIG. 7C and FIG. 8C are Example 4 formed with 50% by volume of the mixed powder. 7 (a) to 7 (c), it was confirmed that the blasting effect on the surface of the substrate 10 was larger as the mixing ratio of zircon in the mixed powder was larger.

The zircon content in the film 11 was calculated from the SEM image of the cross section of the film 11 by performing binary image processing with aluminum as black and zircon as white, and the ratio of zircon in the cross section of the film 11. The porosity of the film 11 is the SEM image of the cross-section of the film 11 by performing image processing for dualizing the pores to be black and the film part such as aluminum and zircon (or alumina) to be white, and the ratio of the pores to the film 11 Calculated by For electrical conductivity, a portion of the film 11 is cut out from the laminate 1 into a 2 mm × 2 mm × 40 mm prismatic shape, and a measurement current (1A) is passed between measurement points where the measurement distance is 23 mm, and the potential is measured by the 4-terminal method. The electric conductivity (%) with respect to the potential of A1050-H24.

(Examples 5 to 7)
Under the same conditions as in Examples 2 to 4, the ceramic powder mixed with the aluminum powder (D50 = 30 μm) was changed to spherical alumina (Al ₂ O ₃ ) to produce a laminate 1. The alumina used was D50 = 35 μm (Example 5), D50 = 66 μm (Example 6), and D50 = 120 μm (Example 7). FIG. 9 shows an SEM photograph of the spherical alumina used. 9A shows alumina with D50 = 350 μm, FIG. 9B shows alumina with D50 = 66 μm, and FIG. 9C shows 120 μm. The mixing ratio of alumina in the mixed powder is 50% by volume in each of Examples 5 to 7. For the laminate 1 according to Examples 5 to 7, the zircon content, porosity, and electrical conductivity in the film 11 were measured. The results are shown in Table 1. FIG. 10 shows SEM images of the film cross-sections of the laminates 1 of Examples 5-7. 10A shows alumina D50 = 35 μm (Example 5), FIG. 10B shows alumina D50 = 66 μm (Example 6), and FIG. 10C shows alumina D50 = 120 μm (Example 7). .

(Comparative Examples 2 to 10)
Under the same conditions as in Examples 2 to 4, the ceramic powder mixed with the aluminum powder (D50 = 30 μm) was changed to non-spherical alumina (Al ₂ O ₃ ) to produce a laminate 1. The alumina to be blended is D50 = 30 μm (Comparative Examples 2 to 4), D50 = 57 μm (Comparative Examples 5 to 7), D50 = 106 to 125 μm (Comparative Example 8), and D50 = 212 to 250 μm (Comparative Example 9). It was used. Laminate 1 was prepared by changing the blending ratio of alumina in the mixed powder to 10% by volume, 30% by volume, and 50% by volume.

FIG. 11 shows a SEM photograph of the used non-spherical alumina (D50 = 57 μm). The alumina (D50 = 30 μm, 106 to 125 μm, 212 to 20 μm) used in the other comparative examples has a pulverized shape similar to the alumina (D50 = 57 μm) shown in FIG. Further, under the same conditions as in Examples 2 to 4, only the aluminum powder was sprayed onto the base material 10 to produce a laminate 1 (Comparative Example 10). For the laminates 1 according to Comparative Examples 2 to 10, the alumina content, the porosity, and the electrical conductivity in the coating film 11 were measured. The results are shown in Table 1.

FIG. 12 shows an SEM image in the vicinity of the interface between the base material 10 and the film 11 in the cross section of the laminate 1 of Comparative Examples 2 to 4, and FIG. 13 shows an SEM image in the cross section of the film 11. FIGS. 12 (a) and 13 (a) show comparative example 2, FIG. 12 (b) and FIG. 13 (b) in which the proportion of alumina (D50 = 30 μm) powder is formed by a mixed powder of 10% by volume. Comparative Example 3 in which the ratio of the alumina (D50 = 30 μm) powder is 30% by volume, and FIGS. 12 (c) and 13 (c) show the ratio of the alumina (D50 = 30 μm) powder. It is the comparative example 4 formed with 50 volume% of mixed powder.

FIG. 14 shows an SEM image in the vicinity of the interface between the base material 10 and the film 11 in the cross section of the laminate 1 of Comparative Examples 5 to 7, and FIG. 15 shows an SEM image of the film cross section. FIGS. 14 (a) and 15 (a) show Comparative Example 5, FIG. 14 (b) and FIG. 15 (b) in which the proportion of alumina (D50 = 57 μm) powder is 10% by volume. Comparative Example 6, in which the proportion of alumina (D50 = 57 μm) powder is 30% by volume, FIG. 14 (c) and FIG. 15 (c) are the proportions of alumina (D50 = 57 μm) powder. It is the comparative example 7 formed with 50 volume% of mixed powder.

16 and 17 show SEM images of the film cross-sections of the laminate 1 of Comparative Example 8 (Alumina D50 = 106 to 125 μm) and Comparative Example 9 (Alumina D50 = 212 to 250 μm). 18 shows an SEM image in the vicinity of the interface between the base material 10 and the film 11 in the cross section of the laminate 1 of Comparative Example 10, and FIG. 19 shows an SEM image in the cross section of the film 11.

As shown in Table 1, the laminates of Examples 2 to 7 using spherical ceramics have a low ceramic content in the film 11 and a high electrical conductivity of 75% or more (compared to A1050). In contrast, Comparative Examples 2 to 9 using non-spherical (pulverized) ceramics have low electrical conductivity. When ceramics which is an insulating material is contained, it is considered that the electric conductivity is lowered. However, even in Comparative Examples 5 and 6 having a low ceramic content, sufficient electric conductivity was not obtained. It is considered that this is because the electrical conductivity is caused not only by the ceramic content but also by the peening effect of the coating 11 by the ceramic. Since the laminate 1 of the present embodiment has a low porosity, a dense film, and a low ceramic content in the film 11, the electrical conductivity of the film 11 can be improved.

(Examples 8 to 14)
Under the same conditions as in Examples 2 to 4, the non-metallic powder mixed with the aluminum powder (D50 = 30 μm) was changed to spherical soda-lime glass to produce a laminate 1. As the soda-lime glass to be blended, those having D50 = 150 to 180 μm (Examples 8 and 9), D50 = 106 to 125 μm (Examples 10 to 12), and D50 = 53 to 63 μm (Examples 13 and 14) were used. . The results are shown in Table 2.

(Comparative Examples 11 to 12)
Under the same conditions as in Examples 2 to 4, laminate 1 was prepared by changing the powder mixed with aluminum powder (D50 = 30 μm) to spherical or non-spherical titanium (Ti). The titanium to be blended was D50 = 30 μm (Comparative Examples 11 and 12), and the laminate 1 was produced with the blending ratio in the mixed powder being 50% by volume. The results are shown in Table 2. 20 shows an SEM image of the cross section of the film 11 of the laminate 1 of Comparative Example 11, and FIG. 21 shows an SEM image of the cross section of the film 11 of the laminate 1 of Comparative Example 12.

As shown in Table 2, the laminates of Examples 8 to 14 using spherical soda lime glass have a low content of soda lime glass in the film 11 and an electric conductivity of 75% or more (compared to A1050). And higher. In particular, in Examples 9 and 12 in which spherical volume soda lime glass having a particle size D50 of 100 or more and 200 or less is mixed by 50% by volume, a laminate having an extremely high electrical conductivity of 90% or more (vs. A1050) is obtained. I was able to get it. Further, Comparative Examples 11 and 12 in which titanium powder was mixed as a mixed powder remained in the film 11 regardless of whether spherical or non-spherical, and no improvement in conductivity was observed.

DESCRIPTION OF SYMBOLS 1 Laminated body 10 Base material 11 Film | membrane 20 Cold spray apparatus 21 Gas heater 22 Spray gun 23 Powder supply apparatus 24 Gas nozzle 30 Adhesion strength test apparatus 31 Support stand 31a Hole part 32 Stud pin 33 Adhesive

Claims

A base material made of metal or alloy;
A film mainly composed of aluminum or aluminum alloy formed on the substrate surface;
With
The film contains a non-metal having a melting point higher than that of the aluminum or aluminum alloy in a ratio of 10% by volume or less, and the aluminum or aluminum alloy powder as the main component of the film was flattened and / or crushed in the stacking direction. Laminated in a state,
A laminate characterized in that an interface between the substrate and the coating is plastically deformed.
A base material made of metal or alloy;
A film mainly composed of aluminum or aluminum alloy formed on the substrate surface;
With
The electrical conductivity of the film is 75.0% or more of the electrical conductivity of the bulk material of aluminum or aluminum alloy which is the main component of the film,
The aluminum or aluminum alloy powder, which is the main component of the film, is laminated in a state of being flattened and / or rolled in the lamination direction, and the interface between the base material and the film is plastically deformed. Laminated body.
The laminate according to claim 1 or 2, wherein the porosity of the film is 5.0% by volume or less.
The laminate according to any one of claims 1 to 3, wherein the non-metallic powder is ceramic or glass.
A method for producing a laminate in which a film mainly composed of aluminum or an aluminum alloy is formed on a surface of a substrate made of a metal or an alloy,
A mixed powder obtained by mixing 5 to 95% by volume of an aluminum or aluminum alloy powder and 5 to 95% by volume of a nonmetallic powder having a melting point higher than that of aluminum or the aluminum alloy is mixed with the surface of the base material. Accelerating with a gas heated to a temperature lower than the melting point, spraying the substrate surface in a solid state in a solid state, and depositing to form a film,
The ratio of nonmetal contained in the film is 1/5 or less of the ratio of nonmetal powder contained in the mixed powder and is 10% by volume or less. Method.
The method for producing a laminate according to claim 5, wherein the non-metallic powder contained in the mixed powder before spraying on the surface of the substrate is spherical.
The method for producing a laminate according to claim 5 or 6, wherein the average particle size of the non-metallic powder contained in the mixed powder before spraying on the surface of the base material is 30 µm or more and 500 µm or less.
The method for producing a laminate according to any one of claims 5 to 7, wherein the non-metallic powder is ceramic or glass.