JP2018178161A - Method of manufacturing quasi-crystal alloy film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a quasicrystal alloy film, capable of preventing a thick quasicrystal alloy film from being peeled from a base material even when the film is formed on the base material.SOLUTION: The method for manufacturing a quasicrystal alloy film comprises: preparing quasicrystal alloy particles having a composition represented by AlCuFe(61.0≤x≤66.0, 22.0≤y≤29.0, 10.0≤z≤13.0 and x+y+z=100.0); supplying the quasicrystal alloy particles to a thermal spray gun to form spray particle on a base material; and thermally spraying the spray particles on the base material. When the spray particles collide on the base material, the spray particle temperature is 944-1340°C and the spray particle speed is 100-405 m/sec. The quasicrystal alloy film having a thickness of 160-290 μm is formed by one thermal spray operation performed in the traveling direction of the thermal spray gun or the base material.SELECTED DRAWING: Figure 4

Description

  The present disclosure relates to a method of manufacturing a quasicrystalline alloy film. In particular, the present disclosure relates to a method of manufacturing a quasi-crystalline alloy film, which is difficult to peel off from the substrate even when the film is formed thick on the substrate.

  Quasicrystalline alloys have attracted attention as materials whose thermal conductivity changes with temperature. A quasicrystalline alloy is an alloy having a quasicrystalline phase. The quasicrystalline phase refers to a phase having long-range order but having no translational symmetry.

  Electrical and thermal conductivity of metals and alloys derives from the periodicity of the crystals. However, because the quasicrystalline phase does not have perfect periodicity, quasicrystalline alloys have low electrical and thermal conductivity at low temperatures.

  For quasi-crystalline alloys, powders of the metal elements that make up the alloy are mixed to form a mixture, and the mixture is heated to cause solid-phase diffusion of the respective metal elements with one another to form a block. A quasicrystalline alloy is obtained.

  As a method of forming a quasicrystal alloy film or a film containing a quasicrystal alloy on the surface of a substrate, hot-dip plating, thermal spraying, sputtering, ion plating, vapor deposition, and electroplating may be used. Can be mentioned.

  For example, in Patent Document 1, forming a film in which particles of a quasi-crystalline alloy are dispersed in a matrix (hereinafter sometimes referred to as "quasi-crystalline alloy particle dispersed film") by thermal spraying on a substrate Is disclosed. Further, Patent Document 1 discloses that particles of a quasi-crystalline alloy are an Al-Fe-Cr-Ti-Co based alloy. Further, Patent Document 1 discloses controlling the pressure and temperature of gas used in the thermal spraying method to form a desired film.

JP 2008-248279 A

  In the quasi-crystal alloy particle dispersion film disclosed in Patent Document 1, the matrix is an aluminum-based alloy or an aluminum supersaturated solid solution. Therefore, even if the quasi-crystalline alloy particle dispersed film is formed thick on the base material, the quasi-crystalline alloy particle dispersed film is less likely to peel off due to the ductility of the matrix.

  In general, quasi-crystalline alloys have lower ductility than conventional alloys. Therefore, when the quasi-crystalline alloy film is formed thick on the substrate by the thermal spraying method, it is difficult to ensure the adhesion between the quasi-crystalline alloy film and the substrate, and the quasi-crystalline alloy film is easily peeled off from the substrate The present inventors found a problem.

  The present disclosure has been made to solve the above problems. That is, the present disclosure aims to provide a method for producing a quasi-crystalline alloy film in which even if a thick quasi-crystalline alloy film is formed on a substrate, the film is not easily peeled off from the substrate.

Means for Solving the Problems In order to achieve the above object, the present inventors have intensively studied and completed the method for producing a quasi-crystalline alloy film of the present disclosure. The summary of the method for producing a quasi-crystalline alloy film of the present disclosure is as follows.
<1> Al _x Cu _y Fe _z (61.0 ≦ x ≦ 66.0, 22.0 ≦ y ≦ 29.0, and 10.0 ≦ z ≦ 13.0, and x + y + z = 100.0) Preparing quasi-crystal alloy particles having the following composition, and supplying the quasi-crystal alloy particles to a thermal spray gun to form thermal spray particles, and thermally spraying the thermal spray particles onto a substrate;
Including
When the thermal spray particles collide with the substrate, the temperature of the thermal spray particles is 944-1340 ° C., and the velocity of the thermal spray particles is 100 to 405 m / sec, and
A single thermal spraying operation performed along the running direction of the thermal spraying gun or the substrate forms a quasi-crystalline alloy film having a thickness of 160 to 290 μm.
Method of manufacturing quasi-crystal alloy film.

  According to the present disclosure, a thick quasi-crystalline alloy film is formed on a substrate by a single thermal spraying operation performed with the temperature and velocity of the thermal spray particles in a predetermined range and along the direction of movement of the thermal spray gun or substrate Even if it is, the film can provide the manufacturing method of the quasi-crystal alloy film which is hard to exfoliate from a substrate.

FIG. 1 is a schematic cross-sectional view showing an example of a thermal spraying apparatus used in the method of manufacturing a quasi-crystalline alloy film of the present disclosure. FIG. 2 is a schematic vertical cross-sectional view showing an example of applying the method of manufacturing a quasi-crystalline alloy film of the present disclosure to members in the vicinity of a combustion chamber of an internal combustion engine. FIG. 3 is a view showing a scanning electron microscope image of quasi-crystal alloy particles used in the method for producing a quasi-crystal alloy film of the present disclosure. FIG. 4 is a graph showing the relationship between the velocity of the thermal spray particles, the temperature of the thermal spray particles, and the film thickness of the quasi-crystalline alloy film for the samples of the example and the comparative example. FIG. 5 is a view showing a scanning electron microscopic image of the cross section of the quasi-crystalline alloy film for the sample of Example 12. FIG. 6 is a view showing a scanning electron microscopic image of the cross section of the quasi-crystalline alloy film for the sample of Comparative Example 5.

  Hereinafter, an embodiment of a method of manufacturing a quasi-crystalline alloy film of the present disclosure will be described in detail. In addition, the embodiment shown below does not limit the manufacturing method of the quasi-crystal alloy film of this indication.

  When a thick quasi-crystalline alloy film is formed on a substrate by a thermal spraying method, the quasi-crystalline alloy film tends to peel off from the substrate because the adhesion between the quasi-crystalline alloy film and the substrate is not sufficient. The reason is considered not to be bound by theory but as follows. Immediately after thermal spraying, the temperature difference between the quasicrystal alloy film and the substrate is large. Therefore, an expansion difference occurs between the quasi-crystal alloy film and the base material. As a result, thermal stress remains in the quasi-crystal alloy film.

  While not being bound by theory, the present inventors have found that the following is effective in order to suppress residual thermal stress in the quasi-crystalline alloy film.

  In order to reduce the temperature difference between the quasi-crystalline alloy film and the substrate immediately after the thermal spraying, it is effective to lower the temperature of the quasi-crystalline alloy film and to raise the temperature of the substrate. By reducing the temperature and velocity when the thermal spray particles collide with the substrate, the temperature of the quasi-crystalline alloy film immediately after thermal spraying can be reduced.

  In addition, regarding the thermal spraying operation (hereinafter, this operation may be referred to as “pass”) performed along the running direction of the thermal spray gun or the substrate, it is more than once forming the quasi-crystalline alloy film in a plurality of passes. If the quasi-crystal alloy film is formed by the above-mentioned pass, the temperature of the base material immediately after the thermal spraying can be raised. This is because when the thermal spray particles collide with the substrate, heat is more easily transmitted from the particles to the substrate when the quasi-crystalline alloy film is formed in one pass. In addition, "one pass" is synonymous with the "pass" defined by the number 4019 in "spraying terms" of Japanese Industrial Standard H8200 (2006). Also, in the present specification, “sprayed particles” refers to “particles of a sprayed material sprayed in a state of being melted or near” as defined in “spraying terms” of Japanese Industrial Standard H8200 (2006). .

  Thus, immediately after the thermal spraying, the temperature of the quasi-crystalline alloy film can be lowered and the temperature of the base material can be raised. Thereby, the temperature difference between the quasi-crystal alloy film and the substrate can be reduced. As a result, generation of thermal stress in the quasi-crystal alloy film can be suppressed, and the quasi-crystal alloy film is less likely to be peeled off from the substrate.

  The constituent requirements of the method for producing a quasi-crystalline alloy film according to the present disclosure based on these findings will be described next.

«Method for producing quasi-crystalline alloy film of the present disclosure»
A method of manufacturing a quasi-crystalline alloy film of the present disclosure includes preparing quasi-crystalline alloy particles, supplying quasi-crystalline alloy particles to a thermal spray gun to form thermal spray particles, and thermally spraying the thermal spray particles onto a substrate. including. Each step will be described below.

<Preparation of quasi-crystalline alloy particles>
First, quasi-crystalline alloy particles are prepared.

The composition of the quasi-crystalline alloy particles is Al _x Cu _y Fe _z (61.0 ≦ x ≦ 66.0, 22.0 ≦ y ≦ 29.0, and 10.0 ≦ z ≦ 13.0, and x + y + z = 100. .0). x, y and z are the contents of Al, Cu and Fe, respectively, and are atomic%.

  While satisfying x + y + z = 100.0, x, y, and z are respectively set to 61.0 ≦ x ≦ 66.0, 22.0 ≦ y ≦ 29.0, and 10.0 ≦ z ≦ 13.0. By making the range, 80% by volume or more of the phases in the particles can be made into a quasi-crystalline phase. From this point of view, x, y and z may be as follows. That is, x may be, for example, 61.5 or more, 62.0 or more, or 62.5 or more, and may be 65.5 or less, 65.0 or less, or 64.5 or less. y may be, for example, 22.5 or more, 23.0 or more, 23.5 or more, 24.0 or more, or 24.5 or more, and 28.5 or less, 28.0 or less, 27.5 or less, It may be 27.0 or less, or 26.5 or less. z may be, for example, 10.2 or more, 10.5 or more, 10.7 or more, or 11.0 or more, and 12.8 or less, 12.5 or less, 12.2 or less, or 12.0 or less It may be.

  In the synthesis of quasi-crystalline alloy particles, small amounts of crystalline and non-crystalline phases are inevitably generated. The quasi-crystalline alloy particles may contain such unavoidable formation phase. In the quasi-crystalline alloy particles, the content of the quasi-crystalline phase is preferably 80% by volume or more, more preferably 90% by volume or more, and still more preferably 95% by volume or more. On the other hand, if the volume of the quasi-crystalline phase is 100% by volume in the quasi-crystalline alloy particles, the production cost will be increased. Therefore, even if the content of the quasi-crystalline alloy phase in the quasi-crystalline alloy particles is 99 volume% or less, 98 volume% or less, or 97 volume% or less, there is substantially no problem in function.

  The quasi-crystalline alloy particles may contain unavoidable impurities other than Al, Cu and Fe. Unavoidable impurities refer to impurities contained in the raw material and the like which can not be avoided or which cause a significant increase in manufacturing cost. 90 mass% or more is preferable, as for the purity of a quasi-crystal alloy particle, 95 mass% or more is more preferable, and 98 mass% or more is still more preferable.

  The particle size of the quasi-crystalline alloy particles may be appropriately determined as long as no inconvenience occurs when thermal spraying the quasi-crystalline alloy particles. The smaller the grain size, the more easily the resulting quasi-crystalline alloy film becomes uniform. On the other hand, as the particle diameter is larger, the supplyability and fluidity of the quasi-crystalline alloy particles are more likely to be deteriorated inside the thermal spraying apparatus.

  When high speed flame spraying (HVOF: High Velocity Oxy-Fuel) method is used as the thermal spraying method, the particle diameter of the quasi-crystalline alloy particles is, for example, 15 μm or more, 20 μm or more, 25 μm or more, 30 μm or more, or 35 μm or more. It may be 200 μm or less, 150 μm or less, 100 μm or less, 70 μm or less, or 50 μm or less. In the present specification, the particle size of quasi-crystalline alloy particles is the average of the projected area equivalent circle diameter for all quasi-crystalline alloy particles, unless otherwise specified.

  The method of synthesizing the quasi-crystalline alloy particles is not particularly limited. For example, synthesizing quasi-crystalline alloy particles by an atomizing method in which a molten metal having the above-described composition is sprayed into a gas phase can be mentioned. When a specific element is worn away by evaporation or the like during holding of the molten metal or during spraying, the raw material may be melted in advance in anticipation of the worn portion. When high-speed flame spraying is used as the thermal spraying method, the quasi-crystalline alloy particles preferably have a spherical or near-spherical shape. From the viewpoint of easily obtaining such a form, the atomizing method is preferable as a method of synthesizing quasi-crystalline alloy particles.

  It is preferable to set conditions of the atomizing method so that the molten metal can be cooled at a speed of 1000 to 10000 K / sec. By cooling the molten metal at such a speed, it is possible to contain 80% by volume or more of the quasi-crystalline phase in the quasi-crystalline alloy particles, and reduce the unavoidable phases (crystalline phase and amorphous phase). be able to. The quasi-crystalline alloy particles may be substantially transformed into a single phase of quasi-crystalline phase by heat treating the quasi-crystalline alloy particles synthesized by the atomizing method. The term "quasicrystal phase single phase" substantially means that the quasicrystal phase is 99% by volume or more. As heat treatment conditions for making a quasi-crystal phase single phase substantially, heat-treating for 48 to 96 hours at 680-720 ° C in inactive gas atmosphere, such as argon gas, is mentioned, for example. The heat treatment temperature may be 690 to 710 ° C., and the heat treatment time may be 60 to 84 hours. The inert gas atmosphere also includes a nitrogen gas atmosphere.

  As another synthesis method of quasi-crystalline alloy particles, for example, Al powder, Cu powder, and Fe powder are mixed to form a mixed powder, and this mixed powder is heated to a temperature at which Al, Cu, and Fe mutually diffuse. There is a method of obtaining a quasi-crystalline alloy mass and grinding the quasi-crystalline alloy mass. This synthetic method tends to reduce the phases (crystal phase and amorphous phase) which are inevitably present, by taking sufficient diffusion time. When a specific element is depleted due to evaporation or the like during diffusion, the mixed powder may be blended in advance in anticipation of the amount of depletion.

  As a method of synthesizing quasi-crystalline alloy particles, in addition to these, for example, quasi-crystalline alloy block obtained by liquid quenching method by single roll method or twin roll method, sputtering method, mechanical alloying method, mechanical grinding method, etc. And the like. When a quasi-crystalline alloy is synthesized by these methods, if the specific element is worn away by evaporation or the like during the synthesis, the composition of the raw material may be determined in advance in anticipation of the worn portion.

<Process of spraying thermal spray particles onto a substrate>
The quasi-crystalline alloy powder is supplied to a thermal spray gun to form thermal spray particles, which are sprayed onto the substrate.

  The thermal spraying method is not particularly limited as long as the temperature and the velocity of the thermal spray particles can be in the range described later. Examples of the thermal spraying method include flame spraying, cold spraying, detonation, arc spraying, plasma spraying, and high speed flame spraying. The high-speed flame spraying method is a method of mixing fuel and oxygen, burning the mixture, and applying high kinetic energy to thermal spray particles for thermal spraying. Therefore, when the high-speed flame spraying method is used, the temperature and the velocity of the sprayed particles can be easily set in the range described later. From the viewpoint of the temperature and velocity of the thermal spray particles, high speed flame spraying is preferred.

  FIG. 1 is a schematic cross-sectional view showing an example of a thermal spraying apparatus used in the method of manufacturing a quasi-crystalline alloy film of the present disclosure. The apparatus shown in FIG. 1 is an example of an apparatus used in the high speed flame spraying method, but is not limited thereto.

  The thermal spray gun 110 comprises a chamber 120 and a barrel 130. The chamber 120 includes a fuel supply port 150 and an oxygen gas supply port 160. The barrel 130 is provided with a raw material particle supply port 170.

  In the thermal spray gun 110, the opposite side of the fuel supply port 150 and the oxygen gas supply port 160 is open, and the opening is opposed to the substrate 140.

  Fuel and oxygen gas are supplied to the inside of the chamber 120 from the fuel supply port 150 and the oxygen gas supply port 160, respectively. Inside the chamber 120, the fuel begins to burn and is introduced into the barrel 130 as hot combustion gases.

  The quasi-crystalline alloy particles 175 are supplied to the inside of the barrel 130 from the raw material particle supply port 170. Thermal spray particles 178 are formed from quasi-crystalline alloy particles 175 within barrel 130. Then, the thermal spray frame 190 is jetted from the tip of the thermal spray gun 110 toward the substrate 140. The thermal spray particles 178 are present in the thermal spray frame 190, and the thermal spray particles 178 collide with the substrate 140 to form a quasi-crystalline alloy film 180.

  Next, the temperature and velocity of the thermal spray particles and the thermal spray operation will be described. Although it demonstrates using FIG. 1, it is not restricted to the case of high-speed flame | frame thermal spraying, It is the same also in the case of other thermal spraying methods.

<Temperature of sprayed particles>
When the thermal spray particles 178 collide with the substrate 140, the temperature of the thermal spray particles 178 is 944-1340 ° C. When the thermal spray particles 178 collide with the base material 140, it refers to immediately before the thermal spray particles 178 collide with the base material 140. The temperature of the thermal spray particles 178 refers to the temperature immediately before the thermal spray particles 178 collide with the substrate 140.

  If the temperature of the thermal spray particles 178 is 944 ° C. or higher, the thermal spray particles 178 can be melted or nearly in the thermal spray frame 190. From this point of view, the temperature of the thermal spray particles 178 may be 970 ° C. or more, 1000 ° C. or more, or 1050 ° C. or more.

  On the other hand, if the temperature of the thermal spray particles 178 is 1340 ° C. or lower, the temperature of the quasi-crystalline alloy film 180 immediately after the thermal spraying can be decreased, and the temperature difference between the quasi-crystalline alloy film 180 and the substrate 140 immediately after the thermal spraying is reduced. Contribute to From the viewpoint of lowering the temperature of the quasi-crystalline alloy film 180 immediately after the thermal spraying, the temperature of the thermal spraying particles 178 may be 1300 ° C. or less, 1250 ° C. or less, 1200 ° C. or less, 1150 ° C. or less, or 1100 ° C. or less.

  In the present specification, the temperature of the thermal spray particles 178 is a numerical value measured using a thermal spray particle temperature / velocity measurement system “SprayWactch (registered trademark)” manufactured by Oseir (Ozaire), but is not limited thereto. Even if the temperature of the thermal spray particles 178 is measured by other measurement means, equivalent numerical values can be obtained. SprayWactch (registered trademark) is an apparatus for measuring the temperature and velocity of the thermal spray particles 178 by continuously photographing the thermal spray frame 190 with a special CCD camera.

<Speed of sprayed particles>
When the thermal spray particles 178 collide with the substrate 140, the velocity of the thermal spray particles 178 is 100 to 405 m / sec. When the thermal spray particles 178 collide with the base material 140, it refers to immediately before the thermal spray particles 178 collide with the base material 140. The velocity of the thermal spray particles 178 refers to the velocity just before the thermal spray particles 178 collide with the substrate 140.

  If the velocity of the thermal spray particles 178 is 100 m / sec or more, the thermal spray particles 178 can be made to collide with the substrate 140. From this point of view, the velocity of the thermal spray particles 178 may be, for example, 110 m / s or more, 130 m / s or more, or 150 m / s or more.

  On the other hand, if the velocity of the thermal spray particles 178 is 405 m / sec or less, the temperature of the quasi-crystalline alloy film 180 immediately after the thermal spraying can be decreased, and the temperature difference between the quasi-crystalline alloy film 180 and the substrate 140 immediately after the thermal spraying is small. Contribute to From the viewpoint of reducing the temperature of the quasi-crystalline alloy film 180 immediately after the thermal spraying, the velocity of the thermal spraying particles 178 is, for example, 350 m / sec or less, 300 m / sec or less, 270 m / sec or less, 250 m / sec or less, or 200 m / sec It may be the following.

  In the present specification, the velocity of the thermal spray particles 178 is a numerical value measured using a thermal spray particle temperature / velocity measurement system “SprayWactch (registered trademark)” manufactured by Oseir (Ozaire), but is not limited thereto. Similar numerical values can be obtained by measuring the velocity of the thermal spray particles 178 by other measurement means. SprayWactch (registered trademark) is an apparatus for measuring the temperature and velocity of the thermal spray particles 178 by continuously photographing the thermal spray frame 190 with a special CCD camera.

Spraying operation
A single thermal spraying operation performed along the direction of movement of the thermal spray gun 110 or the base material 140 forms a quasi-crystalline alloy film 180 having a thickness of 160 to 290 μm. In other words, a quasi-crystalline alloy film 180 having a thickness of 160 to 290 μm is formed on the substrate 140 in one pass.

  By forming the quasi-crystalline alloy film 180 having a thickness of 160 to 290 μm on the base material 140 in one pass, the temperature of the base material 140 immediately after the thermal spraying can be raised. This contributes to reducing the temperature difference between 180 and the substrate 140.

  The thickness of the quasi-crystal alloy film 180 formed in one pass may be, for example, 180 μm or more, 200 μm or more, or 220 μm or more, and may be 290 μm or less, 280 μm or less, or 270 μm or less.

  In thermal spraying, the thermal spray gun 110 may be moved or the base material 140 may be moved as long as the quasi-crystalline alloy film 180 of the above thickness can be formed in one pass. If the quasi-crystalline alloy film 180 can be formed in a single pass, the thermal spray gun 110 is moved to form a quasi-crystalline alloy film 180 at one portion, and the base 140 is moved to form a quasi-crystalline alloy at another portion. The film 180 may be formed.

  The barrel length, oxygen supply rate, fuel supply rate, spray distance, spray gun or substrate feed rate, and quasicrystal alloy particle feed rate are as follows to form a quasi-crystalline alloy film 180 of the above thickness in one pass: It may be as follows.

  The barrel length may be, for example, 40 mm or more, 50 mm or more, or 60 mm or more, and may be 200 mm or less, 180 mm or less, or 150 mm or less.

  The oxygen supply rate may be, for example, 500 liters / minute or more, 600 liters / minute or more, or 700 liters / minute or more, 1500 liters / minute or less, 1200 liters / minute or less, or 1000 liters / minute under standard conditions. It may be less than a minute.

  The fuel supply rate may be, for example, 0.20 liter / min or more, 0.25 liter / min or more, or 0.30 liter / min or more for kerosene, 0.80 liter / min or less, 0. 0 or less. It may be up to 60 liters per minute, or up to 0.50 liters per minute.

  The spraying distance may be, for example, 250 mm or more, 300 mm or more, or 400 mm or more, and may be 1100 mm or less, 1000 mm or less, or 900 mm or less. The spraying distance refers to the distance from the tip of the spraying gun 110 to the surface of the substrate 140.

  The thermal spray gun or substrate feeding speed may be, for example, 20 mm / sec or more, 30 msec or more, or 40 mm / sec or more, 500 mm / sec or less, 250 mm / sec or less, 150 mm / sec or less, or 100 mm / sec or less It may be.

  The quasi-crystal alloy particle feed rate may be, for example, 10 g / min or more, 15 g / min or more, or 20 g / min or more, and may be 70 g / min or less, 50 g / min or less, or 40 g / min or less.

  The base material 140 is not particularly limited as long as the quasi-crystal alloy film 180 can be formed while satisfying the structural requirements described above. As the base material 140, a metal material etc. are mentioned, for example. Metallic materials also include alloys. Examples of the metal material include cast iron, steel, aluminum, or an aluminum alloy.

  The substrate 140 may not be flat, and may be, for example, a curved surface. The base material 140 may be, for example, the surface of a member that constitutes a combustion chamber of an internal combustion engine. FIG. 2 is a schematic vertical cross-sectional view showing an example of applying the method of manufacturing a quasi-crystalline alloy film of the present disclosure to members in the vicinity of a combustion chamber of an internal combustion engine.

  The internal combustion engine 90 includes a cylinder block 10, a cylinder head 20, a piston 30, and a valve 40. Further, a cylinder bore 12 is formed in the cylinder block 10. The combustion chamber 50 is formed by being surrounded by the inner wall of the cylinder bore 12, the cylinder head 20, the piston 30, and the valve 40.

  The quasi-crystalline alloy film 60 may be formed on the inner wall of the combustion chamber 50 using the manufacturing method of the present disclosure. In FIG. 2, the thickness of the quasi-crystalline alloy film 60 is drawn in an exaggerated manner so that the quasi-crystalline alloy film 60 can be identified. The actual thickness of the quasi-crystalline alloy film 60 is 160 to 290 μm.

  Assuming that the surface of the substrate is the inner wall surface 15 of the cylinder bore 12 of the internal combustion engine 90, the desired quasi-crystalline alloy film 60 can be obtained by applying the manufacturing method of the present disclosure.

  Similarly, assuming that the surface of the substrate is the surface 22 facing the combustion chamber 50 of the cylinder head 20 of the internal combustion engine 90, the desired quasi-crystal alloy film 60 can be obtained by applying the manufacturing method of the present disclosure.

  Similarly, assuming that the surface of the base is the surface 32 facing the combustion chamber 50 of the piston 30 of the internal combustion engine 90, the desired quasi-crystalline alloy film 60 can be obtained by applying the manufacturing method of the present disclosure.

  Hereinafter, the method for producing the quasi-crystalline alloy of the present disclosure will be described in more detail by examples and comparative examples. In addition, the manufacturing method of the quasi-crystal alloy of this indication is not limited to the conditions used by the following example.

(Preparation of sample)
A quasicrystal alloy film was formed on an aluminum substrate by high-speed flame spraying using the thermal spraying apparatus shown in FIG. 1 and used as samples of Examples or Comparative Examples. The composition of the quasi-crystalline alloy particles was Al _63.00 Fe _11.85 Cu _25.15 . Incidentally, before thermal spraying, the quasi-crystalline alloy particles were heat-treated at 700 ° C. for 72 hours in an argon gas atmosphere to substantially make the inside of the particles a quasi-crystalline phase single phase. In addition, the quasi-crystal alloy particles had a spherical or nearly spherical shape, as shown by the scanning electron microscope image in FIG. Moreover, the particle size of quasicrystal alloy particle was 25-53 micrometers. The spraying conditions are shown in Table 1.

  The results are shown in FIG. FIG. 5 is a view showing a scanning electron microscopic image of the cross section of the quasi-crystalline alloy film for the sample of Example 12. As shown in FIG. 5, the aluminum base 140 and the quasi-crystalline alloy film 180 were in close contact with each other, and peeling did not occur. The same applies to the samples of the other examples. The size of the plot in FIG. 4 relatively represents the thickness of the quasi-crystalline alloy film of each sample. The inner part shown by the broken line in FIG. 4 shows a region where peeling of the quasi-crystalline alloy film has occurred when the quasi-crystalline alloy film is formed by the conventional thermal spraying method (spraying condition).

  FIG. 6 is a view showing a scanning electron microscopic image of the cross section of the quasi-crystalline alloy film for the sample of Comparative Example 5. There is a gap 185 between the aluminum base 140 and the quasi-crystalline alloy film 180, and the portion of the quasi-crystalline alloy film 180 opposite to the aluminum base 140 is missing, and the quasi-crystalline alloy film 180 becomes thinner. Peeling of the quasi-crystalline alloy film 180 is observed. The same applies to the sample of Comparative Example 6. Although peeling did not occur in the samples of Comparative Examples 1 to 4, the quasi-crystalline alloy film 180 was thin.

  From the above results, the effects of the method for producing a quasi-crystalline alloy film of the present disclosure can be confirmed.

DESCRIPTION OF SYMBOLS 10 cylinder block 12 cylinder bore 15 cylinder bore inner wall surface 20 cylinder head 22 cylinder head surface facing combustion chamber 30 piston 32 surface facing piston combustion chamber 40 valve 50 combustion chamber 60 quasicrystal alloy film 70 cooling circuit 90 internal combustion engine 110 thermal spraying Gun 120 chamber 130 barrel 140 base material 150 fuel supply port 160 oxygen gas supply port 170 raw material particle supply port 175 quasi crystal alloy particle 178 thermal spray particle 180 quasi crystal alloy film 185 gap 190 thermal spray frame

Claims (1)

A composition represented by Al _x Cu _y Fe _z (61.0 ≦ x ≦ 66.0, 22.0 ≦ y ≦ 29.0, and 10.0 ≦ z ≦ 13.0, and x + y + z = 100.0) Preparing quasi-crystalline alloy particles having the following formula, and supplying the quasi-crystalline alloy particles to a thermal spray gun to form thermal spray particles, and thermally spraying the thermal spray particles onto a substrate:
Including
When the thermal spray particles collide with the substrate, the temperature of the thermal spray particles is 944-1340 ° C., and the velocity of the thermal spray particles is 100 to 405 m / sec, and
A single thermal spraying operation performed along the running direction of the thermal spraying gun or the substrate forms a quasi-crystalline alloy film having a thickness of 160 to 290 μm.
Method of manufacturing quasi-crystal alloy film.