JPH01287263A - Thermal spraying powder combined with metal powder and ceramic powder for intermediate layer between metal and ceramic and its production - Google Patents

Abstract

PURPOSE:To obtain the title powder capable of giving an intermediate layer having excellent adhesive property and stress relaxation to an adhered article of metal and ceramic, by subjecting metal powder and specific ceramics powder to mixing in a powder colliding device, and diffusing and adhering the ceramics material to the surface of the metal powder. CONSTITUTION:A stator 2 and a high-speed rotary disk 3 having plural colliding pins 4 are disposed in a casing 1. The powder of iron metals such as stainless steel and heat resisting steel and nonferrous metals such as Al alloy and copper alloy and the ceramics powder such as Y2O3, partially stabilized ZrO2 or Al2O3 finer than said metal powder are mixed at 1-20mol% ratio and the mixture is charged through a raw material feed port into the device. The rotary disk 3 is rotated at a high speed and the raw materials are repeatedly circulated in a circulation circuit 5, by which the powerful collision is given to the materials. The powder of the above-mentioned ceramics is fixed to the outside circumferences of the metal powder and both the powders are diffused to each other, by which the combined material of the metal and ceramics having the characteristics such as ductility and toughness intrinsic to the metals and having the excellent heat resistance, heat insulating property, wear resistance, corrosion resistance, and mechanical characteristics provided by the formation of the intermediate ceramics layer is developed.

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a composite spherical powder of metal and ceramics, and in particular, to forming an intermediate layer to improve bonding properties or alleviate thermal stress at the interface when coating a base metal with ceramics, etc. The present invention relates to a composite thermal spraying powder of metal powder and ceramic powder for use, and a method for producing the same. [Prior art and the problem that the ribs are intended to solve] Conventionally, by coating metal materials with ceramics, it is possible to improve the properties such as ductility and toughness of the base metal material, as well as heat insulation, heat resistance, and wear resistance. and corrosion resistance, etc.
Attempts to create mechanically superior composite materials have attracted attention in various fields, and various joined bodies and thermal spraying methods have been developed. In particular, conventional surface coating methods, such as the thermal spraying method for ceramics, are simply mechanically interlocked, or even when forming a reaction layer on the joint surface, they do not take sufficient consideration to the characteristics of the material, so it is difficult to combine them. In some cases, the difference in coefficient of thermal expansion was large, causing thermal stress and strain at the interface, and this did not provide an essential solution to bondability. Therefore, in order to improve the bonding strength between the base metal and the coating ceramic, an intermediate layer, which is a composite of an oxide and the metal-based powder, is interposed between the metal material and the coating ceramic. A method for solving the above-mentioned drawbacks has been devised (for example, Japanese Patent Application Laid-Open No. 62-222052). In this method, at the interface between the metal material and the intermediate layer, the metal and the metal of the same type existing in the intermediate layer are combined, or when the metal to be joined and the metal existing in the intermediate layer are different types, the interface is formed. Bonding is achieved by forming an intermetallic compound in consideration of strength, and on the other hand, the composition of the intermediate layer is selected to provide high bonding strength due to the reaction layer and anchoring effect at the interface between the intermediate layer and the coating ceramic material. Looking at the thermal spraying treatment methods for forming the intermediate layer that contributes to the improvement of bonding strength, there is a mixed thermal spraying method in which a mixed powder of two or more types is supplied onto the surface of the base metal while being mixed at the tip of a thermal spray nozzle. There is also an individual thermal spraying method in which a plurality of thermal spray powders forming an intermediate layer are individually supplied to the tip of a thermal spray nozzle. However, in the former case, segregation tends to occur due to differences in the specific gravity and particle size of the mixed powder at the supply source, and in the latter case, differences in fluidity due to the powder material, particle size, shape, etc. (
In particular, ceramic powder alone has extremely poor fluidity.)
Therefore, it was not possible to secure the desired blending ratio to the thermal spray supply nozzle, and it was not possible to quantitatively form the composite intermediate layer. Therefore, in order to solve these drawbacks, the present invention fixes ceramic powder on metal powder and makes it spherical by mechanical impact means, and at the same time forms a diffusion layer at the interface of both powders to form a composite. The object of the present invention is to provide a composite thermal sprayed powder for forming an intermediate layer with excellent fluidity in which the components of the powder are kept at a predetermined blending ratio, and a method for producing the same. [Means and effects for solving the problem] In order to achieve the above object, the mixing ratio due to segregation in the supply source of the plurality of thermal sprayed powders forming the intermediate layer or the difference in fluidity of each powder. In order to eliminate fluctuations in the temperature, a powder of a predetermined component at a predetermined ratio that constitutes the intermediate layer is selected in advance, and ceramics are applied to the surface of the main component metal powder regardless of shape (hereinafter referred to as "inconstant humidity powder"). By adhering fine particles to the adhering composite powder and applying a continuous impact action to the adhering composite powder using a rotary disk or the like having a large number of impact pins (hereinafter referred to as "mechanical impact means", e.g., JP-A-62-221434), a sphere is formed. The object of the present invention is to provide a composite spherical powder in which a ceramic powder is immobilized on the main component metal powder at the same time as the main component metal powder, and a diffusion layer is formed at the interface between the metal powder and the ceramic powder, and a method for producing the same. Alternatively, after adhering a predetermined ratio of ceramic powder to the surface of the main component metal which has been sphericalized in advance, the ceramic powder is fixed to the main component metal powder by mechanical impact means to form a diffusion layer. The present invention provides a composite powder and a method for producing the same. [Function] According to the composite spherical powder configured as described above, various selected main component metal powders and ceramic powders are used to improve the bondability between the base metal and the dissimilar coating material and to alleviate thermal stress. A desired blending ratio of the composite body can be secured. This fixes the fine powder of the coating material to the powder of the main component of the base metal in advance at a predetermined ratio and forms a diffusion layer. This takes advantage of the fact that fluctuations in the blending ratio due to differences in fluidity are eliminated. In addition, the composite thermal sprayed powder is made by applying an impact or striking action to the individual surfaces of the composite powder using mechanical impact means to forcibly apply a composite powder in which ceramic powder is attached to the main component metal powder. It can be produced by a so-called dry method of immobilization. Furthermore, the diffusion layer of the powder prevents the composite powder from separating or peeling and is firmly bonded, so it also contributes to the bonding properties of the thermally sprayed intermediate layer and allows the desired intermediate layer to be formed. Can be provided. In addition, by selecting amorphous powder as the base metal powder, it is possible to freely select the blending ratio of the components, and the spheroidization process and fixation process, which were conventionally performed separately, can be performed simultaneously. It is possible to provide a composite thermal sprayed powder for forming an intermediate layer that is inexpensive and has excellent bonding strength and fluidity, and a method for producing the same. [Example] Hereinafter, a composite spherical powder of metal powder and ceramic powder according to the present invention and a method for manufacturing the same will be described in detail. The powder according to the present invention is a composite thermal sprayed powder for forming an intermediate layer, in which an oxide powder or a coated ceramic main component powder is immobilized on a metal powder whose main component is a metal material serving as a base material.
A uniform intermediate layer is formed by thermally spraying the powder onto the surface of a metal material, and at this interface (base metal/intermediate layer), the same kind of metals present in the intermediate layer coalesce, or dissimilar metals In between, they are combined by forming intermetallic compounds. Furthermore, coating ceramic powder is thermally sprayed onto the metal material onto which the intermediate layer (sprayed base) has been thermally sprayed, and a chemical reaction layer is generated and an anchoring effect is used at the interface between the composite intermediate layer and the coating ceramic to achieve good bonding properties. It forms a ceramic coating of metal. The metal material used as the base material is not particularly limited, but may be, for example, a ferrous material (SIIS, heat-resistant steel, etc.), a non-ferrous material (A + gold alloy, Cu alloy, etc.), or a heat-resistant metal material. For example, the composite intermediate layer subjected to thermal spray base treatment is made of the main component metal (A1 alloy) of the base metal.
IJA (Y2031~20Mo1%) alone or IJA (Y2031-20Mo1%) alone or with IJA and a part of the coating ceramic component added, or a lower oxide added to the main component of the base metal (in this case, (contains no non-ferrous materials) or active metals (Ti, Nb, At, Cu
etc.), ittria alone or a mixture of ittria and a part of a ceramic component are selected in consideration of the base metal and the coating ceramic, and the material is thermally sprayed on the processed surface under predetermined conditions. There are, for example, the following two methods for producing the composite thermal spray powder for the intermediate layer selected in this way. (1) A composite powder is prepared by using a non-uniform powder as the main component metal powder and a ceramic powder is adhered to the surface thereof, and at the same time, the composite powder is spheroidized by mechanical impact means,
A method for producing a composite thermal sprayed powder in which a ceramic powder is immobilized on the surface or inside of a metal powder to form a diffusion layer at the interface; (2) using spheroidized particles as the main component metal powder; A method of producing a composite thermal sprayed powder in which a composite powder is prepared by adhering ceramic powder to the surface of the composite powder, and the ceramic powder is fixed on the main component metal surface by mechanical impact means to form a diffusion layer at the interface. There are two methods. FIG. 1 is a conceptual diagram showing the above manufacturing method. When non-constant humidity powder is used, it has a larger surface area than spherical wet powder, so it is possible to widen the range of the blending ratio of ceramic powder. FIG. 2 shows an embodiment of a mechanical impact means for producing the composite powder of the present invention, and is an apparatus having an impact impact means (hereinafter referred to as "powder impact apparatus"). The powder impact device includes 1 casing, 2 stators, 3 a rotary disk that is located inside the casing 1 and rotates at high speed, 4 a plurality of impact pins (blades) radially provided around the outer periphery of the rotary disk 3, and 5 is a circulation circuit in which one end opens in a part of the inner wall of the stake 2 and the other end opens near the center of the rotary disk 3 to form a closed circuit, 6 is a raw material input port, and 7 is a part of the stator. It consists of a cut-out valve for discharging processed powder. The operation is a batch operation, and the composite powder, in which a predetermined mixing ratio of ceramic powder is attached to the surface of the main component metal powder using a mixer, etc., is fed into the machine from the input port 6 and rotated at a high speed. While being dispersed by the action of the rotary disk 3, it is carried toward the outer circumference of the rotary disk, receives an impact action from the impact pin 4 and the stator 2, and then passes through the circulation circuit 5 from the outer circumference and is thrown into the machine again, where it is subjected to the same effect. By repeatedly receiving the powder, it is uniformly fixed and sphericalized in a short time, and the discharge lower is opened to collect the processed product.By using a powder processing device with such an impact impact means, ceramics are added to the main component metal. The powder is firmly fixed, and the fixed composite powder is spheroidized. When the composite spherical powder is fixed and spheroidized, the impact force causes the diffusion of the ceramic powder at the main component metal interface. The diffusion layer integrates the individual composites, prevents separation or peeling during thermal spraying, and also contributes to improving the bonding properties of the intermediate layer after thermal spraying. Hereinafter, examples of composite thermal sprayed powder for forming an intermediate layer produced using this powder processing apparatus are shown in Table 1 and further explained. Table 1 shows the composition of the composite thermal sprayed powder, and The operating and processing conditions for manufacturing as well as fluidity (JIS Z 2502 "Metal Powder Fluidity Test Method"), which is one index representing the fluidity of the product, are shown. Flow rate indicates the time required for a given amount of powder to flow out of an orifice. Therefore, the lower the fluidity, the better the fluidity. If the fluidity is very poor, it may not flow out from the orifice and measurement may not be possible. Furthermore, since the fluidity largely depends on the specific gravity of the substance, it is difficult to compare different types of materials, but the composite spheroidization process allows substances that cannot flow alone to maintain fluidity. The fluidity of irregular shaped products of Δ1 alloy, SUS, and Cu is unmeasurable and 36.37, respectively, and the fluidity of spherical powder obtained by spheroidizing these metal powders is 58.1, respectively.
4.16, which is almost the same value as the fluidity of the present composite spherical powder shown in Table 1. This indicates that by making the ceramic powder, which does not flow by itself, into a composite spheroid as described above, the fluidity was improved to the level of a single metal powder. 3 to 9 are photographs of composite powders according to examples of the present invention. [Example 1] The following is an example of a composite powder in which the surface area of the main component metal is expanded to make it easier to control the amount ratio of ceramics. In this case, after directly mixing an appropriate amount of ceramic powder with the amorphous main component metal powder, spheroidization and compounding are simultaneously performed by mechanical impact means, which saves labor in the second step. T-1 in Table 1 contains amorphous A1 alloy powder with an average grain size of 39 μm as the main component metal, and an average grain size of 35 μm as the ceramic 7x.
The composite powder was treated by mixing 5 mol% of μm ¥203 powder, and the fluidity of this composite powder was 56. It can be seen that, like the above, it has excellent fluidity. Figures 3(a'), (a), and (b) are SEM images of the amorphous A1 alloy powder used as the raw material. A scanning electron microscopy (SEM) image of a cross section of the composite powder, and a SEM image and an X-ray image of the cross section taken with an X-ray microanalyzer (EPMA) are shown in FIG. 3 ((C)). As shown in the figure, ¥203 is rolled up inside the wet powder and fixed. A diffusion layer is formed at the interface between the A1 alloy powder and the Y2O3 powder, resulting in a strong bond. The composite powder was sprayed on the A1 alloy round bar shape, and then PS
When Z powder was sprayed and the bonding strength was measured, it was 4kg/
Tensile strengths of greater than 282 mm2 were obtained, with failure occurring primarily between the adhesive and the 282 surface. A1 alloy powder and Y2
Thermal sprayability and fluidity (J
IS Z 2502) were both found to be excellent. [Example 2] In T-2 of Table 1, amorphous A1 alloy powder with an average grain size of 39 μm was used as the main component metal, and an average grain size of 19 μm was used as the ceramic.
5 m of ZrCh and Y203 powder with an average particle size of 3.5 μm
The fluidity of this composite powder was 54 when mixed in mol%. FIGS. 4(a) and 4(b) show SEM images of the appearance and cross section of the composite spherical powder. [Example 3] In T-3 of Table 1, amorphous SUS powder with an average particle size of 58 μm was used as the main component metal, and an average particle size of 3.5 μm was used as the ceramic.
μm Y2O3 powder and average particle size 11, 4 μm Al2
Approximately 5 mol% of O3 was mixed with metal powder and post-treated, and the fluidity of this composite powder was 30. FIGS. 5(a) and 5(b) show SEM images of the appearance and cross section of the composite spherical powder. The same ceramic entrainment effect as seen in the A1 alloy powder occurs in the SUS powder, resulting in a strong composite. [Example 4] In T-4 in Table 1, amorphous SUS powder with an average particle size of 58 μm as the main component metal and 4 mol% of partially stabilized zirconia (PSZ) powder as the ceramic were mixed and post-treated. The fluidity of this composite powder was very good, and the fluidity was improved to 17. FIG. 6(a) shows an SEM image of the appearance of the composite spherical powder. [Example 5] T-5 in Table 1 was mixed with amorphous copper powder with an average particle size of 62 μm as the main component metal and partially stabilized zirconia (PSZ) powder as the ceramic, and was post-treated. The fluidity of the powder was 14. FIG. 7(a) shows a SEM image of the appearance of the composite spherical powder. [Example 6] T-6 in Table 1 contained amorphous copper powder with an average particle size of 62 μm as the main component metal and an average particle size of 1 as the ceramic.
．． The composite powder was post-treated by mixing 45 mol% of 1-+m Al2O3, and the fluidity of this composite powder was 6. FIGS. 8(a) and 8(b) show SEM images of the appearance and cross section of the composite spherical powder. The same ceramic entrainment effect as seen in the A1 alloy powder occurs in the Cu powder, resulting in a strong composite. [Example 7] As shown in T-7 in Table 1, A1 alloy powder with an irregular shape as the main component metal was pre-spheroidized and had an average particle size of 43.
A1 alloy ball diameter powder of μm was used as a raw material. The A1 concerned
After mixing Y2O3 powder with an average particle size of 3.5 μm into the alloy powder at a predetermined ratio (4.5 mol%), using mechanical impact means, the rotary plate outer peripheral speed], OOm/s, processing time 5m1
treated with n. S of the external shape and cross section of this composite powder processed product
EM images are shown in FIGS. 9(a) and 9(b), and SEM and X-ray images of the cross section are shown in FIG. 9(C). The core of the spherical powder is surrounded by A1, the outer periphery is surrounded by Y and O, and it can be seen that a composite of A1 alloy powder and Y2O3 powder has been established. Figure 3 (
Shown in d). A diffusion phenomenon of A1 and Y was observed between the outer periphery of the A1 nucleus and ¥203 as described above, and ¥203 on the Δ1 alloy was observed.
It was found that they were strongly bonded. The fluidity of the composite powder was 57 as shown in Table 1, and it was found to be a powder with good fluidity. The fluidity of conventional ceramic powder is psz <granulated product)
Therefore, the composite powder with excellent fluidity according to the present invention could not be provided by the individual thermal spraying method. In addition, main component metals (excluding non-ferrous metals) powders and lower oxides (e.g. FeO, etc.) or active metals (Ti, Nb
etc.) and ittria to produce a composite powder using mechanical impact means, diffusion and entrainment phenomena occur between the main component metal and the oxide, resulting in a strong bond and a composite powder with excellent fluidity. It turns out that you can get . The composite powder of active metal and ittria is carbide-based (SiC
etc.) and nitrides (Si3N4).It is suitable as an intermediate layer (base) when materials with strong covalent bonds such as Ceramifux are thermally sprayed as a coating Ceramifux. Example Table 1 Production Example 1 of Composite Thermal Sprayed Powder for Forming Intermediate Layer (Effects of the Invention) As explained above, according to the composite spherical powder of metal powder and ceramic powder of the present invention and the method for producing the same, In order to improve bondability and alleviate thermal stress when bonding a different type of coating material such as Ceramifux to a base metal, we adopted a composite powder with an intermediate layer that corresponds to the base metal and coating material. The fine oxide powder is immobilized on the component metal powder by mechanical impact means and made into spheres, and at that time a diffusion layer is formed at the interface, resulting in a stable blending ratio of the components and appropriate fluidity as a powder. Provides a composite thermal spray powder for forming an intermediate layer using a composite spherical powder of metal powder and ceramic powder, which does not cause troubles such as clogging, separation, and segregation that tend to occur during conventional thermal spray processing, and a method for manufacturing the same. can do.

[Brief explanation of the drawing]

Figure 1 is a conceptual diagram of manufacturing composite thermal spray powder, where a is spherical metal powder, a' is amorphous metal powder, b is ceramic powder, and C is ceramic powder attached to metal powder. Composite powder, d, d" represents a state in which ceramic powder is firmly fixed to metal powder. Figure 2 shows an example used to produce a composite thermal sprayed powder for forming an intermediate layer. A powder impact device having a certain impact impact means. Figures 3 to 9 are scanning electron microscopy (SEM) images of composite thermal sprayed powders based on the examples in Table 1. (a) shows the surface of the treated product; b) is the cross section (3.4
．． 5. 8. Figure 9). 3 and 9 (C) are images observed by an X-ray microanalyzer, where the symbol Y on the left represents yttrium, 0 represents oxygen, and A1 represents aluminum. Figure 3 (a'') is an 88M image of the amorphous A1 alloy powder. Patent applicant: Nara Kikai Seisakusho Co., Ltd. Agent: Shin Matsubara, 2 Patent attorney: Kiyoshi Muraki Kawamo
Atsushi Nishima - Figure 4, Figure 5, Figure 6, Figure 8, Figure 7.
Kunio Ogawa, Commissioner of the Japan Patent Office1, Indication of the case 1988 Patent - No. 1.140002 Name of the invention Composite thermal sprayed powder for forming an intermediate layer of metal powder and ceramic powder and its manufacturing method3, Relationship with the case of the person making the amendment Patent applicant name: Nara Kikai Seisakusho Co., Ltd. 4, agent (Y1O2) Address: 5, Ichibancho Central Building, 22-1 Ichibancho, Chiyotsu-ku, Tokyo Date of amendment order: 6 , "Detailed explanation of the invention j, brief explanation of the drawings" of the specification to be amended
Column 7 Contents of the amendment [1] On page 14, line 16 of the specification, "...was. Same as above, fluidity..." was changed to "...and fluidity..."・Correct to "." (2) Page 14, line 18 of the specification r(a), (b)
Delete J. (3) From page 14, line 19 to page 15, line 3 of the specification, ``compounded...shown in Figure 3(C)'' was replaced with ``(
(a) is a scanning electron microscopy (SEM) image of the outer diameter of the spherical powder, and (b) is a SEM image of the cross section of the composite spherical powder. (C) SE of the above cross section by X-ray microanalyzer (EPMΔ)
These are an M image and an X-ray image. ”. (4) Change "46" on page 17, line 14 of the specification to r6.4.
6". (5) Delete "The magnification is not shown in..." written in lines 15 to 16 of page 18 of the specification. (6) Page 18, line 17 of the specification “A1 and Y as above”
are corrected to [A1 and Y2O3 as in Example 1]. (7) In the correspondence diagram of implementation number T-1 described in Table 1 on page 20 of the specification, "(a) to (d) J is replaced with "(a'), (a) to
(C)”. (8) Insert "r (Figures 3, 4, 5, 6, 7, 8, 9)" after "...surface of treated product" on page 22, line 6 of the specification. (9) Specification page 22, line 11 “Amorphous A1 alloy powder”
is corrected to "amorphous A1 alloy raw material powder". 1. Indication of the case Patent Application No. 114000 of 1988 2. Name of the invention Composite thermal sprayed powder for forming an intermediate layer of metal powder and ceramic powder and its manufacturing method 3. Person making the amendment Relationship with the case Patent Applicant Name Nara Kikai Seisakusho Co., Ltd. (1) The entire specification is amended as shown in the attached sheet. (2) Figures 1.2.3 of the drawings are corrected as shown in the attached sheet. Description 1. Name of the invention Composite thermal sprayed powder for forming an intermediate layer of metal powder and ceramic powder and its manufacturing method 2. Claims (1) Main component metal powder in a predetermined quantitative ratio and ceramic powder are bonded and sphericalized by mechanical impact means, and a diffusion layer is formed at the interface between the two powders. body. (2) The composite thermal spraying for forming an intermediate layer of metal powder and ceramic powder according to claim 1, wherein the main component metal powder is an irregular shape or a sphere made of a ferrous material, a nonferrous alloy material, and a heat-resistant metal material. powder. (3) Ceramic powder is made of metal as its main component.
JA (Y2031-20 mol%) alone or partially stabilized zirconia (PSZ 1-20 mol%) with addition of ittria and a part of the ceramic component for coating
<li7. +Shimmy 1-(81203 1~20
mol%), or lower oxides (10~
80 mol%), or partially stabilized Zinicomia (PSZ) in which yttria alone or yttria and a part of the coating ceramic component are added to the active metal.
2. The composite thermal sprayed powder for forming an intermediate layer of metal powder and ceramic powder according to claim 1, wherein the content is 1% to 2%). (4) A predetermined amount of ceramic powder is attached to the surface of the amorphous main component metal powder, and the composite powder is made into a sphere by mechanical impact means, and at the same time, the ceramic powder is fixed to the metal powder. A composite thermal sprayed powder for forming an intermediate layer of metal powder and ceramic powder, characterized in that a diffusion layer is formed at the interface between the two powders. (5) A predetermined northernmost ceramic powder is attached to the surface of the spherical main component metal powder, and the ceramic powder is fixed to the main component metal powder by mechanical impact means, and at this time, both of the above-mentioned A composite thermal sprayed powder for forming an intermediate layer between metal powder and ceramic powder, which is characterized by forming a diffusion layer at the powder interface. (6) For forming an intermediate layer between metal powder and ceramic powder according to any one of claims 1, 4, or 5, wherein the mechanical impact means impacts the outer surface of the composite powder with an impact pin of a rotary disk. Manufacturing method for composite thermal spray powder. 3. Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a composite spherical powder of metal and ceramics, and in particular, when coating a base metal with ceramics, etc. The present invention relates to a composite thermal sprayed powder of metal powder and ceramic powder for forming an intermediate layer for stress relaxation, and a method for producing the same. [Prior art and problems to be solved by the invention] Conventionally, by coating metal materials with ceramics, the characteristics such as ductility and toughness of the metal material as the base material are improved, such as heat insulation, heat resistance, wear resistance and Adds corrosion resistance, etc.
Attempts to create mechanically superior composite materials have attracted attention in various fields, and various joined bodies and thermal spraying methods have been developed. In particular, conventional surface coating methods, such as the thermal spraying method for ceramics, are simply mechanically interlocked, or even when forming a reaction layer on the joint surface, they do not take sufficient consideration to the characteristics of the material, so it is difficult to combine them. In some cases, the difference in coefficient of thermal expansion was large, causing thermal stress and strain at the interface, and this did not provide an essential solution to bondability. Therefore, in order to improve the bonding strength between the base metal and the coating ceramic, an intermediate layer, which is a composite of an oxide and the metal-based powder, is interposed between the metal material and the coating ceramic. A method for solving the above-mentioned drawbacks has been devised (for example, Japanese Patent Application Laid-Open No. 62-222052). In this method, at the interface between the metal material and the intermediate layer, the metal and the metal of the same type existing in the intermediate layer are combined, or when the metal to be joined and the metal existing in the intermediate layer are different types, the interface is formed. Bonding is achieved by forming an intermetallic compound in consideration of strength, and on the other hand, the composition of the intermediate layer is selected to provide high bonding strength due to the reaction layer and anchoring effect at the interface between the intermediate layer and the coating ceramic material. Looking at the thermal spraying treatment methods for forming the intermediate layer that contributes to the improvement of bonding strength, there is a mixed thermal spraying method in which a mixed powder of two or more types is supplied onto the surface of the base metal while being mixed at the tip of a thermal spray nozzle. There is also an individual thermal spraying method in which a plurality of thermal spray powders forming an intermediate layer are individually supplied to the tip of a thermal spray nozzle. However, in the former case, segregation tends to occur due to differences in the specific gravity and particle size of the mixed powder at the supply source, and in the latter case, differences in fluidity due to the powder material, particle size, shape, etc.
In particular, ceramic powder alone has extremely poor fluidity.)
Therefore, it was not possible to secure the desired blending ratio to the solvent supply nozzle, and it was not possible to quantitatively form the composite intermediate layer. Therefore, in order to solve these drawbacks, this method uses mechanical impact to immobilize ceramic powder on metal powder and make it spherical, and at the same time forms a diffusion layer at the interface of both powders. It is an object of the present invention to provide a composite thermal sprayed powder for forming an intermediate layer with excellent fluidity in which the components of the composite powder are kept at a predetermined blending ratio, and a method for producing the same. [Means and effects for solving the problem] In order to achieve the above object, the mixing ratio due to segregation in the supply source of the plurality of thermal sprayed powders forming the intermediate layer or the difference in fluidity of each powder. In order to eliminate fluctuations in the temperature, a powder of a predetermined component at a predetermined ratio that constitutes the intermediate layer is selected in advance, and ceramics are applied to the surface of the main component metal powder regardless of shape (hereinafter referred to as "inconstant humidity powder"). By depositing a number of fine particles and applying a continuous impact to the adhered composite powder using a rotary disk or the like having a large number of impact pins (hereinafter referred to as "mechanical impact means", for example, JP-A-62-221434), The object of the present invention is to provide a composite spherical powder in which a ceramic powder is fixed to a main component metal powder at the same time as it is sphericalized, and a diffusion layer is formed at the interface between the metal powder and the ceramic powder, and a method for producing the same. Alternatively, after adhering a predetermined ratio of ceramic powder to the surface of the main component metal which has been sphericalized in advance, the ceramic powder is fixed to the main component metal powder by mechanical impact means to form a diffusion layer. The present invention provides a composite powder and a method for producing the same. [Function] According to the composite spherical powder configured as described above, various selected main component metal powders and ceramic powders are used to improve the bondability between the base metal and the dissimilar coating material and to alleviate thermal stress. A desired blending ratio of the composite body can be secured. This fixes the fine powder of the coating material to the powder of the main component of the base metal in advance at a predetermined ratio and forms a diffusion layer. This takes advantage of the fact that fluctuations in the blending ratio due to differences in fluidity are eliminated. In addition, the composite thermal sprayed powder is a composite powder in which ceramic powder is attached to a metal powder as a main component, and a mechanical impact means is applied to the surface of the composite powder by applying an impact or impact action to the surface of the composite powder. It can be produced by a so-called dry method in which it is immobilized on. Furthermore, the diffusion layer of the powder prevents the composite powder from separating or peeling and is firmly bonded, so it also contributes to the bonding properties of the thermally sprayed intermediate layer and allows the desired intermediate layer to be formed. Can be provided. In addition, by selecting amorphous powder as the base metal powder, it is possible to freely select the blending ratio of the components, and the spheroidization process and fixation process, which were conventionally performed separately, can be performed simultaneously. It is possible to provide a composite thermal sprayed powder for forming an intermediate layer that is inexpensive and has excellent bonding strength and fluidity, and a method for producing the same. [Example] Hereinafter, a composite spherical powder of metal powder and ceramic powder according to the present invention and a method for manufacturing the same will be described in detail. The powder according to the present invention is a composite thermal sprayed powder for forming an intermediate layer, in which an oxide powder or a coated ceramic main component powder is immobilized on a metal powder whose main component is a metal material serving as a base material,
A uniform intermediate layer is formed by thermally spraying the powder onto the surface of a metal material, and at this interface (base metal/intermediate layer), the same kind of metals present in the intermediate layer coalesce, or dissimilar metals In between, they are combined by forming intermetallic compounds. Furthermore, coating ceramic powder is thermally sprayed onto the metal material onto which the intermediate layer (sprayed base) has been thermally sprayed, and a chemical reaction layer is generated and an anchoring effect is used at the interface between the composite intermediate layer and the coating ceramic to achieve good bonding properties. It forms a ceramic coating of metal. The metal material used as the base material is not particularly limited, but for example, it is a ferrous material (SUS, heat-resistant steel, etc.), a non-ferrous material (IE) (A1 alloy, Cu alloy, etc.), a heat-resistant metal material, and has a predetermined function. For example, the composite intermediate layer that is subjected to thermal spraying undercoating as described above is made by adding ittria (Y2031 to 20Mo1%) alone or adding ittria and a part of the coating ceramic component to the main component metal (A1 alloy) of the base metal. Alternatively, lower oxides are added to the main component of the base metal (in this case, non-ferrous materials are not included),
Alternatively, activated gold (Ti, Nb, AI, Cu, etc.) is selected from yttria alone or yttria and a part of ceramic components added, taking into account the base metal and the coating ceramic, and the surface treated as described above. Thermal spraying is carried out under specified conditions. There are, for example, the following two methods for producing the composite thermal spray powder for the intermediate layer selected in this way. (1) Using amorphous powder as the main component metal powder and adhering ceramic powder to its surface, a composite powder is made, and at the same time, the composite powder is spheroidized by mechanical firing means, and the metal powder is (2) A method of manufacturing a composite thermal sprayed powder in which ceramic powder is fixed on the surface or inside of a body and a diffusion layer is formed at the interface. A method of manufacturing a composite thermal sprayed powder in which a composite powder is made by adhering ceramic powder to a metal, and the ceramic powder is fixed on the surface of the main component metal by mechanical impact means to form a diffusion layer at the interface. There are two methods. FIG. 1 is a conceptual diagram showing the above manufacturing method. When using amorphous powder, its surface area is larger than that of wet powder, so the blending ratio of ceramic powder can be widened. FIG. 2 shows an embodiment of the mechanical impact means for producing the composite powder of the present invention, and is a device having impact impact means (hereinafter referred to as "powder impact device"). The powder impact device includes 1 casing, 2 stators, 3 a rotary disk that is located inside the casing 1 and rotates at high speed, 4 a plurality of impact pins (blades) radially provided around the outer periphery of the rotary disk 3, and 5 has one end opened in a part of the inner wall of the stator 2,
A circulation circuit whose other end opens near the center of the rotary disk 3 to form a closed circuit, 6 is a raw material input port, and 7 is an on-off valve for discharging treated powder provided by cutting out a part of the stator. has been done. The operation is a batch operation, and the composite powder, in which a predetermined mixing ratio of ceramic powder is adhered to the surface of the main component metal powder using a mixer, etc., is fed into the machine from the input port 6, and then the composite powder is fed into the machine through the input port 6, and the composite powder is fed into the machine through the input port 6, and then While being dispersed by the action of the disc 3, it is carried toward the outer circumference of the rotary disc, receives impact from the impact pin 4 and the stator 2, passes through the circulation circuit 5 from the outer periphery, is thrown into the machine again, and undergoes the same action repeatedly. As a result, uniform immobilization and spheroidization are achieved in a short time, and the processed product is recovered by opening the discharge lower. By using a powder processing apparatus having such an impact means, the ceramic powder is firmly fixed to the main component metal, and the fixed composite powder is spheroidized. When the composite spherical powder is immobilized and sphericalized, a diffusion layer of ceramic powder is formed at the main component metal interface due to the impact force. The diffusion layer integrates the individual composites, prevents them from separating or peeling during thermal spraying, and further contributes to improving the bondability of the intermediate layer after thermal spraying. Examples of composite thermal sprayed powder for forming an intermediate layer produced using the powder processing apparatus of this invention are shown in Table 1 and further comments are given below. Table 1 shows the composition of the composite thermal spray powder, the operating treatment conditions for manufacturing, and the fluidity (JIS Z 2502 "Metal powder fluidity test method"), which is an indicator of the fluidity of the product. show. Flow rate indicates the time required for a given amount of powder to flow out of an orifice. Therefore, the lower the fluidity, the better the fluidity. If the fluidity is very poor, it may not flow out from the orifice and measurement may not be possible. Furthermore, since the fluidity largely depends on the specific gravity of the substance, it is difficult to compare different types of materials, but the composite spheroidization process allows substances that cannot flow alone to maintain fluidity. The fluidity of irregularly shaped products of He1 alloy, SUS, and Cu is unmeasurable and 36.37, respectively, and the fluidity of spherical powder obtained by spheroidizing these metal powders is 58.1, respectively.
4.16, which is almost the same value as the fluidity of the present composite spherical powder shown in Table 1. This indicates that by making the ceramic powder, which does not flow by itself, into a composite spheroid as described above, the fluidity was improved to the level of a single metal powder. 3 to 9 are photographs of composite powders according to examples of the present invention. [Example 1] The following is an example of a composite powder in which the surface area of the main component metal is expanded to make it easier to control the amount ratio of ceramics. In this case, an appropriate amount of ceramic powder is directly mixed with the amorphous main component metal powder, and then spheroidization and compounding are simultaneously performed by mechanical impact means, which saves labor in the process. T-1 in Table 1 contains amorphous A1 alloy powder with an average grain size of 39 μm as the main component metal, and an average grain size of 3.0 μm as the ceramic.
The composite powder was treated by mixing 5 mol% of 5 μm Y2O3 powder, and the fluidity of this composite powder was 56, indicating that it has excellent fluidity. Figure 3(a) shows the S of the amorphous A1 alloy powder used as a raw material.
This is an EM image. (b) is a scanning electron microscope (SE) of the spherical powder outer diameter.
M) image, (C) is an 8EM image of the cross section of the composite spherical powder. (d) is an X-ray microanalyzer (EP) of the above cross section.
These are a SEM image and an X-ray image obtained by MA). As seen in the figure, Y203 is wrapped and fixed inside the spherical pine. A diffusion layer was formed at the interface between the A1 alloy powder and the ¥203 powder, resulting in a strong bond. The composite powder was sprayed on the A1 alloy round bar shape, and then PS
When we thermally sprayed the Z-shaped body and measured the bonding strength, it was 4 kg/
Tensile strengths of more than mm2 were obtained, and fractures occurred mainly between the adhesive and the 282 surface. A1 alloy powder and Y20
Thermal sprayability and fluidity (JI
S Z 2502) were both found to be excellent. [Example 2] At T=2 in Table 1, amorphous A1 alloy powder with an average particle size of 39 μm was used as the main component metal, and an average particle size of 1.9 was used as the ceramic.
5μm ZrO2 and average particle size 3.5μm Y2O3 powder
The fluidity of this composite powder was 54 when mixed in mol%. FIGS. 4(a) and 4(b) show SEM images of the appearance and cross section of the composite spherical powder. [Example 3] In T-3 of Table 1, amorphous SUS powder with an average particle size of 58 μm was used as the main component metal, and an average particle size of 3.5 μm was used as the ceramic.
μm Y2O3 powder and average particle size 11,4 pm A
Approximately 5 mol% of I203 was mixed with metal powder and post-treated, and the fluidity of this composite powder was 30. FIGS. 5(a) and 5(b) show SEM images of the appearance and cross section of the composite spherical powder. The same ceramic entrainment effect as seen in the A1 alloy powder occurs in the SUS powder, resulting in a strong composite. [Example 4] In T-4 in Table 1, amorphous SUS powder with an average particle size of 58 μm as the main component metal and 4 mol% of partially stabilized zirconia (PSZ) powder as the ceramic were mixed and post-treated. The fluidity of this composite powder was very good, and the fluidity was improved to 17. FIG. 6(a) shows an SEM image of the appearance of the composite spherical powder. [Example 5] T-5 in Table 1 was mixed with amorphous copper powder with an average particle size of 62 μm as the main component metal and partially stabilized zirconia (PSZ) powder as the ceramic, and was post-treated. The fluidity of the powder was 14. FIG. 7(a) shows a SEM image of the appearance of the composite spherical powder. [Example 6] T-6 in Table 1 contained amorphous copper powder with an average particle size of 62 μm as the main component metal and an average particle size of 11.4 as the ceramic.
The composite powder was post-treated by mixing 5.45 mol% of Δ1203 of μm, and the fluidity of this composite powder was 16. FIGS. 8(a) and 8(b) show SEM images of the appearance and cross section of the composite spherical powder. The same ceramic entrainment effect as seen in the A1 alloy powder occurs in the Cu powder, resulting in a strong composite. [Example 7] As shown in T-7 in Table 1, A1 alloy powder with an irregular shape as the main component metal was pre-spheroidized and had an average particle size of 43.
A1 alloy ball diameter powder of μm was used as a raw material. The A1 concerned
After mixing Y2O3 powder with an average particle size of 3.5 μm into the alloy powder at a predetermined ratio (4.5 mol%), mechanical shock was applied to the rotary plate at a peripheral speed of 100 m/s for a processing time of 3 m/s.
treated with n. S of the external shape and cross section of this composite powder processed product
EM images are shown in FIGS. 9(a) and 9(b), and SEM and X-ray images of the cross section are shown in FIG. 9(C). The core of the spherical powder is A1,
It can be seen that the outer periphery is surrounded by Y and O, and a composite of A1 alloy powder and Y2O3 powder is established. Similar to Example 1, a diffusion phenomenon of A1 and Y2O3 was observed between the outer periphery of the A1 nucleus and Y2O3, and it was found that Y2O3 was firmly bonded to the A1 alloy. The fluidity of the composite powder was 57 as shown in Table 1, indicating that it was a powder with good fluidity. The fluidity of conventional ceramic individual powder is psz <granulated product)
Therefore, the composite powder with excellent fluidity according to the present invention could not be provided by the individual thermal spraying method. In addition, main component metals (excluding non-ferrous metals) powders and lower oxides (e.g. FeO, etc.) or active metals (Ti, Nb
etc.) and ittria to produce a composite powder using mechanical impact means, diffusion and entrainment phenomena occur between the main component metal and the oxide, resulting in a strong bond and a composite powder with excellent fluidity. It turns out that you can get . The composite powder of active metal and ittria is carbide-based (SiC
etc.) and nitrides (SI3N4) etc.) It is suitable as an intermediate layer (base) when coating materials with strong covalent bonds, such as ceramics, as a coating ceramic. Examples [Effects of the Invention] As explained above, according to the composite spherical powder of metal powder and ceramic powder of the present invention and the method for producing the same, when a dissimilar coating material such as ceramics is bonded to a base metal, In order to improve bondability and alleviate thermal stress, we selected a composite powder for the intermediate layer that corresponds to the base metal and coating material, and added fine oxide powder to the base metal powder by mechanical impact. Because it is fixed, sphericalized, and a diffusion layer is formed at the interface, it is possible to ensure a stable blending ratio of ingredients and appropriate fluidity as a powder, eliminating the problems of clogging, separation, and other problems that tend to occur during conventional thermal spraying. It is possible to provide a composite thermal spray powder for forming an intermediate layer using a composite spherical powder of metal powder and ceramic powder that does not cause problems such as segregation, and a method for producing the same.

[Brief explanation of the drawing]

Figure 1 is a conceptual diagram of manufacturing composite thermal spray powder (1) (a
) is amorphous metal powder, (2) (a) is spherical metal powder,
(1) (b) and (2) et al.) are ceramic powders;
(1) (C) and (2) (C) are composite powders with ceramic powder attached to metal powder, (1) (d) and (2) (d) are composite powders with ceramic powder attached to metal powder. It represents a state in which the is firmly fixed. FIG. 2 shows a powder impacting device having an impact impacting means, which is an embodiment used for producing a composite thermal sprayed powder for forming an intermediate layer. Figures 3 to 9 show particle structure photographs and X-ray photographs of composite thermal spray powders based on the examples in Table 1, and Figure 3 (a
) is a photograph of the particle structure of irregularly shaped A1 alloy raw material powder, Figure 3, etc.)
Figures 4 to 9 (a) are photographs of particle structures subjected to composite processing, Figure 3 (C), Figure 4 (0)), Figure 5 (b), and Figure 8.
FIG. 9(b) and FIG. 9(b) are cross-sectional views of grain structure photographs. Further, FIG. 3(d) and FIG. 9(C) are X-ray photographs, and the symbol Y in the upper left indicates the component of yttrium, 0 indicates oxygen, and A1 indicates the component of aluminum. Patent applicant Nara Kikai Seisakusho Co., Ltd. Agent Patent attorney Shin Matsubara 2 Same person Kiyoshi Muraki Usage
Same as above Atsushi Shima - (a) (1) (a) 1 Figure, ) (C) ((
1) -An et al. - Procedural amendment written spontaneously) 1. Display of the case 1988 Patent Application No. 114000 2 Name of the invention Composite thermal sprayed powder for forming an intermediate layer of metal powder and ceramic powder and its manufacturing method 3 Person making the amendment Relationship to the case Name of patent applicant Name: Nara Kikai Seisakusho Co., Ltd. 6, Specification subject to amendment 1, Name of the invention: Composite thermal sprayed powder for forming an intermediate layer of metal powder and ceramic powder and its manufacturing method 2, Claims (" ) A metal powder characterized in that a main component metal powder with a predetermined m ratio and a ceramic powder are bonded and sphericalized by mechanical impact means, and a diffusion layer is formed at the interface between the two powders. and composite thermal sprayed powder for forming an intermediate layer of ceramic powder. (2) The composite thermal spraying for forming an intermediate layer of metal powder and ceramic powder according to claim 1, wherein the main component metal powder is an irregular shape or a sphere made of a ferrous material, a nonferrous alloy material, and a heat-resistant metal material. powder. (3) Ceramic powder has the main component metal (Ittria) (
Partially stabilized zirconia (PSZ 0.1-20 mol%) or alumina (Al2O20, 1-20 mol%) alone or with hyttria and a part of the coating ceramic component added
, or a lower oxide (1 to 80 mol%
), or partially stabilized zirconia (PSZ 0.1 to 20
The composite thermal sprayed powder for forming an intermediate layer of gold fi% powder and ceramic powder according to claim 1, which is (mol%). (4) A predetermined amount of ceramic powder is attached to the surface of the amorphous main component metal powder, and the composite powder is made into a sphere by mechanical impact means, and at the same time, the ceramic powder is fixed to the metal powder. A method for producing a composite thermal sprayed powder for forming an intermediate layer of metal powder and ceramic powder, characterized in that a diffusion layer is formed at the interface between the two powders. (5) A predetermined ratio of ceramic powder is adhered to the surface of the spherical main component metal powder, and the ceramic powder is immobilized on the main component metal powder by mechanical impact means. A method for producing a composite thermal spray powder for forming an intermediate layer between metal powder and ceramic powder, which is characterized by forming a diffusion layer at the powder interface. (6) For forming an intermediate layer between metal powder and ceramic powder according to any one of claims 1, 4, or 5, wherein the mechanical impact means impacts the outer surface of the composite powder with an impact pin of a rotary disk. Manufacturing method for composite thermal spray powder. 3. Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a composite spherical powder of metal and ceramics, and in particular, when coating a base metal with ceramics, etc. The present invention relates to a composite thermal sprayed powder of metal powder and ceramic powder for forming an intermediate layer for stress relaxation, and a method for producing the same. [Prior art and problems to be solved by the invention] Conventionally, by coating metal materials with ceramics, the characteristics such as ductility and toughness of the metal material as the base material are improved, such as heat insulation, heat resistance, wear resistance and Adds corrosion resistance, etc.
Attempts to create mechanically superior composite materials have attracted attention in various fields, and various joined bodies and thermal spraying methods have been developed. In particular, conventional surface coating methods, such as the thermal spraying method for ceramics, are simply mechanically interlocked, or even when forming a reaction layer on the joint surface, they do not take sufficient consideration to the characteristics of the material, so it is difficult to combine them. In some cases, the difference in coefficient of thermal expansion was large, causing thermal stress and strain at the interface, and this did not provide an essential solution to bondability. Therefore, in order to improve the bonding strength between the base metal and the coating ceramic, an intermediate layer, which is a composite of an oxide and the metal-based powder, is interposed between the metal material and the coating ceramic. A method has been devised to solve the above drawbacks (for example, JP-A-62-222052). In this method, at the interface between the metal material and the intermediate layer, the metal and the similar metal present in the intermediate layer are combined, or If the metal to be bonded and the metal present in the intermediate layer are different types, they are bonded by forming an intermetallic compound in consideration of strength at the interface, while at the interface between the intermediate layer and the coating ceramic material, a reaction layer and a The composition of the intermediate layer with high bonding strength is selected due to the anchoring effect. Looking at the thermal spraying method for forming the intermediate layer that contributes to improving the bonding strength, two or more types of There are two methods: a mixed thermal spraying method in which a mixed powder is supplied to the tip of a thermal spray nozzle while being mixed, and an individual thermal spraying method in which a plurality of thermal spraying powders forming an intermediate layer are individually supplied to the tip of a thermal spraying nozzle.However, in the former case, The latter tends to cause segregation due to differences in specific gravity and particle size of the mixed powder at the supply source, and in the latter case, differences in fluidity due to powder material, particle size, shape, etc.
In particular, ceramic powder alone has extremely poor fluidity.)
Therefore, it was not possible to secure the desired blending ratio to the thermal spray supply nozzle, and it was not possible to quantitatively form the composite intermediate layer. Therefore, in order to solve these drawbacks, the present invention fixes ceramic powder on metal powder and makes it spherical by mechanical impact means, and at the same time forms a diffusion layer at the interface of both powders to form a composite. The object of the present invention is to provide a composite thermal sprayed powder for forming an intermediate layer with excellent fluidity in which the components of the powder are kept at a predetermined blending ratio, and a method for producing the same. [Means and actions for solving the problem] In order to achieve the object described in item 1, it is possible to solve the problem by segregation in the supply source of the plurality of thermal sprayed powders forming the intermediate layer or by differences in fluidity of each powder. In order to eliminate variations in the mixing ratio,
Selecting a powder of a predetermined component in a predetermined ratio of amounts constituting the intermediate layer,
Ceramic fine particles are attached to the surface of the main component metal powder regardless of shape (hereinafter referred to as "inconstant moisture powder"), and the attached composite powder is continuously subjected to impact action using a rotary disk or the like having a large number of impact pins. (hereinafter referred to as "mechanical impact means", e.g., Japanese Patent Application Laid-Open No. 62-221.434),
The object of the present invention is to provide a composite spherical powder in which a ceramic powder is fixed to a main component metal powder at the same time as it is sphericalized, and a diffusion layer is formed at the interface between the metal powder and the ceramic powder, and a method for producing the same. Alternatively, after adhering a predetermined ratio of ceramic powder to the surface of the main component metal which has been sphericalized in advance, the ceramic powder is fixed to the main component metal powder by mechanical impact means to form a diffusion layer. The present invention provides a composite powder and a method for producing the same. [Function] According to the composite spherical powder configured as described above, various selected main component metal powders and ceramic powders are used to improve the bondability between the base metal and the dissimilar coating material and to alleviate thermal stress. A desired blending ratio of the composite body can be secured. This fixes the fine powder of the coating material to the powder of the main component of the base metal in advance at a predetermined ratio and forms a diffusion layer. This takes advantage of the fact that fluctuations in the blending ratio due to differences in fluidity are eliminated. In addition, the composite thermal sprayed powder is a composite powder in which ceramic powder is attached to a metal powder as a main component, and a mechanical impact means is applied to the surface of the composite powder by applying an impact or impact action to the surface of the composite powder. It can be produced by a so-called dry method in which it is immobilized on. Furthermore, the diffusion layer of the powder prevents the composite powder from separating or peeling and is firmly bonded, so it also contributes to the bonding properties of the thermally sprayed intermediate layer and allows the desired intermediate layer to be formed. Can be provided. In addition, by selecting amorphous powder as the main component powder of the base metal, the blending ratio of the components can be freely selected, and the spheroidization process and immobilization process, which were conventionally performed separately, can be performed at the same time. It is possible to provide a composite thermal sprayed powder for forming an intermediate layer that is inexpensive and has excellent bonding strength and fluidity, and a method for producing the same. [Example] Hereinafter, a composite spherical powder of metal powder and ceramic powder according to the present invention and a method for manufacturing the same will be described in detail. The powder according to the present invention is a composite thermal sprayed powder for forming an intermediate layer, in which an oxide powder or a coated ceramic main component powder is immobilized on a metal powder whose main component is a metal material serving as a base material,
A uniform intermediate layer is formed by spraying the powder onto the surface of a metal material, and at this interface (base metal/intermediate layer), the same kind of metals present in the intermediate layer coalesce, or dissimilar metals In between, they are combined by forming intermetallic compounds. Furthermore, coating ceramic powder is thermally sprayed onto the metal material onto which the intermediate layer (sprayed base) has been thermally sprayed, and a chemical reaction layer is generated and an anchoring effect is used at the interface between the composite intermediate layer and the coating ceramic to achieve good bonding properties. It forms a ceramic coating of metal. The metal material used as the base material is not particularly limited, but includes, for example, ferrous materials (SUS, heat-resistant steel, etc.), non-ferrous materials (A1 alloy, Cu alloy, etc.), and heat-resistant metal materials. The composite intermediate layer to be subjected to thermal spraying surface treatment is, for example, one in which yttria (Y2O20, 1 to 2Q mol%) is added alone to the main component metal (A1 alloy) of the base metal, or yttria and a part of the coating ceramic component are added. Alternatively, lower oxides are added to the main component of the base metal (in this case, non-ferrous materials are not included), or active metals (Ti, Nb, AI, Cu, etc.) are combined with ittria alone or in combination with ittria and a ceramic component. The base metal and the coating ceramic are selected from among those with a certain amount added, and the material is thermally sprayed on the processed surface under predetermined conditions. There are, for example, the following two methods for producing the composite thermal spray powder for the intermediate layer selected in this way. (1) A composite powder is prepared by using a non-uniform powder as the main component metal powder and a ceramic powder is adhered to the surface thereof, and at the same time, the composite powder is spheroidized by mechanical impact means,
A method for producing a composite thermal sprayed powder in which a ceramic powder is immobilized on the surface or inside of a metal powder to form a diffusion layer at the interface; (2) using spheroidized particles as the main component metal powder; A method of producing a composite thermal sprayed powder in which a composite powder is prepared by adhering ceramic powder to the surface of the composite powder, and the ceramic powder is fixed on the main component metal surface by mechanical impact means to form a diffusion layer at the interface. There are two methods. FIG. 1 is a conceptual diagram showing the above manufacturing method. When using variable humidity powder, its surface area is larger than that of spherical powder, so it is possible to widen the range of the blending ratio of ceramic powder. FIG. 2 shows an embodiment of the mechanical impact means for producing the composite powder of the present invention, and is a device having impact impact means (hereinafter referred to as "powder impact device"). The powder impact device includes 1 casing, 2 stators, 3 a rotary disk that is located inside the casing 1 and rotates at high speed, 4 a plurality of impact pins (blades) radially provided around the outer periphery of the rotary disk 3, and 5 has one end opened in a part of the inner wall of the stator 2,
A circulation circuit whose other end opens near the center of the rotary disk 3 to form a closed circuit, 6 is a raw material input port, and 7 is an on-off valve for discharging treated powder provided by cutting out a part of the stator. has been done. The operation is a batch operation, and the composite powder, in which a predetermined mixing ratio of ceramic powder is adhered to the surface of the main component metal powder using a mixer, etc., is fed into the machine from the input port 6, and then the composite powder is fed into the machine through the input port 6, and the composite powder is fed into the machine through the input port 6, and then While being dispersed by the action of the disc 3, it is carried towards the outer circumference of the rotary disc, receives impact from the impacting pins 4 and the stator 2, and then passes through the circulation circuit 5 from the outer periphery and is thrown into the machine again, where it undergoes the same action. By repeating the process, uniform fixation and spherical formation are achieved in a short period of time, and the processed product is recovered by the discharge lower. By using a powder processing apparatus having such an impact means, the ceramic powder is firmly fixed to the main component metal, and the fixed composite powder is spheroidized. When the composite spherical powder is immobilized and sphericalized, a diffusion layer of ceramic powder is formed at the main component metal interface due to the impact force. The diffusion layer integrates the individual composites, prevents them from separating or peeling during thermal spraying, and further contributes to improving the bondability of the intermediate layer after thermal spraying. Examples of composite thermal sprayed powder for forming an intermediate layer produced using this powder processing apparatus are shown in Table 1 and will be further described below. Table 1 shows the composition of the composite thermal spray powder, the operating and processing conditions of the manufacturing tank, and the fluidity (JIS Z 2502 "Metal powder fluidity test method"), which is an indicator of the fluidity of the product. show. Flow rate indicates the time required for a given amount of powder to flow out of an orifice. Therefore, the lower the fluidity, the better the fluidity. If the fluidity is very poor, it may not flow out from the orifice and measurement may not be possible. Furthermore, since the fluidity largely depends on the specific gravity of the substance, it is difficult to compare different types of materials, but the composite spheroidization process allows substances that cannot flow alone to maintain fluidity. The fluidity of irregular shaped products of A1 alloy, SUS, and Cu is unmeasurable and 36.37, respectively, and the fluidity of spherical powder obtained by spheroidizing these metal powders is 58.1.
4.16, which is almost the same value as the fluidity of the present composite spherical powder shown in Table 1. This indicates that by making the ceramic powder, which does not flow by itself, into a composite spheroid as described above, the fluidity was improved to the level of a single metal powder. 3 to 9 are photographs of composite powders according to examples of the present invention. [Example 1] The following is an example of a composite powder in which the surface area of the main component metal is expanded to make it easier to control the amount ratio of ceramics. In this case, an appropriate amount of ceramic powder is directly mixed with the amorphous main component metal powder, and then spheroidization and compounding are simultaneously performed by mechanical impact means, which saves labor in the process. T-1 in Table 1 contains amorphous A1 alloy powder with an average grain size of 39 μm as the main component metal, and an average grain size of 35 μm as the ceramic.
The composite powder was treated by mixing 5 mol% of μmY2O3 powder, and the fluidity of this composite powder was 56, indicating that it has excellent fluidity. Figure 3(a) shows the S of the amorphous A1 alloy powder used as a raw material.
This is an EM image. ) is a scanning electron microscope (SEM) with a spherical powder appearance.
) image, and (C) is an 8EM image of the cross section of the composite spherical powder. (
d) is an X-ray microanalyzer (EPM) of the above cross section.
SEM image and X-ray image by Δ). As seen in the figure, Y2O3 is immobilized inside the spherical pine. A diffusion layer is formed at the interface between the A1 alloy powder and the Y2O3 powder, resulting in a strong bond. The composite powder was sprayed on the A1 alloy round bar shape, and then PS
When Z powder was sprayed and the bonding strength was measured, it was 4kg/
A tensile strength of +nm2 or more was obtained, and fracture occurred mainly between the adhesive and the 282 surface. A1 alloy powder and Y2
Thermal sprayability and fluidity (J
I322502) were both found to be excellent. [Example 2] T-2 in Table 1 contains amorphous A1 alloy powder with an average particle size of 39 μm as the main component metal and an average particle size of 1.9 as the ceramic.
The composite powder was treated by mixing 5 mol% of Z r O2 with a particle diameter of 3.5 μm and Y203 powder with an average particle size of 3.5 μm, and the fluidity of this composite powder was 54. FIGS. 4(a) and 4(b) show SEM images of the appearance and cross section of the composite spherical powder. [Example 3] In T-3 of Table 1, amorphous SUS powder with an average particle size of 58 μm was used as the main component metal, and an average particle size of 3.5 μm was used as the ceramic.
μm Y2O3 powder and A1゜0 with average particle size 11.4μm
About 5 mol % of 3 was mixed with metal powder and post-treated, and the fluidity of this composite powder was 30. FIGS. 5(a) and 5(b) show SEM images of the appearance and cross section of the composite spherical powder. The same ceramic entrainment effect as seen in the A1 alloy powder occurs in the SUS powder, resulting in a strong composite. [Example 4] In T-4 in Table 1, amorphous SUS powder with an average particle size of 58 μm as the main component metal and 4 mol% of partially stabilized zirconia (PSZ) powder as the ceramic were mixed and post-treated. The fluidity of this composite powder was very good, and the fluidity was improved to 17. FIG. 6(a) shows an SEM image of the appearance of the composite spherical powder. [Example 5] T-5 in Table 1 was mixed with amorphous copper powder with an average particle size of 62 μm as the main component metal and partially stabilized zirconia (PSZ) powder as the ceramic, and was then processed. The fluidity of this composite powder was 14. FIG. 7(a) shows a SEM image of the appearance of the composite spherical powder. [Example 6] In T-6 of Table 1, amorphous copper powder with an average particle size of 62 μm was used as the main component metal, and an average particle size of 11.4 μm was used as the ceramic.
The composite powder had a fluidity of 16. FIGS. 8(a) and 8(b) show SEM images of the appearance and cross section of the composite spherical powder. The same ceramic entrainment effect as seen in the A1 alloy powder occurs in the Cu powder, resulting in a strong composite. [Example 7] As shown in T-7 in Table 1, Δ1 alloy powder with an irregular shape as the main component metal was pre-spheroidized and had an average particle size of 43.
A Δ1 alloy ball diameter powder of μm was used as a raw material. The A1 concerned
After mixing ¥203 powder with an average particle size of 3.5 μm into the alloy powder at a predetermined ratio (4.5 mol%), using a mechanical impact means, the rotary plate outer peripheral speed was 100 m/s and the processing time was 5 m1n.
, processed. SE of the external shape and cross section of this composite powder processed product
The M image is shown in FIGS. 9(a) and 9(b), the cross-sectional SEM image and the
A line image is shown in FIG. 9(C). The core of the spherical powder is A1, the outer periphery is surrounded by Y and ○, and it can be seen that a composite of A1 alloy powder and ¥203" powder has been established. Example between the outer periphery of A1 core and ¥203" Similar to No. 1, a diffusion phenomenon of A1 and ¥203 was observed, and it was found that ¥203 was firmly bonded to the A1 alloy. The fluidity of the composite powder was a value of 57 as shown in Table 1. It was found that the powder has good elasticity and fluidity.The fluidity of conventional individual ceramic powders is that of PSZ (granulated product).
Therefore, the composite powder with excellent fluidity according to the present invention could not be provided by the individual thermal spraying method. In addition, main component metals (excluding non-ferrous metals) powders and lower oxides (e.g. FeO, etc.) or active metals (Ti, Nb
etc.) and ittria to produce a composite powder using mechanical impact means, diffusion and entrainment phenomena occur between the main component metal and the oxide, resulting in a strong bond and a highly fluid composite powder. It turned out that a powder was obtained. The composite powder of active metal and ittria is carbide-based (SiC
etc.) and nitrides (313N4). Suitable for use as an intermediate layer base when thermally spraying materials with strong covalent bonds such as ceramics as coating ceramics. Example Table 1 Example of manufacturing a composite thermal sprayed powder for forming an open layer [Effects of the invention] As explained above, according to the composite spherical powder of metal powder and ceramic powder of the present invention and the method for manufacturing the same, In order to improve bonding performance and alleviate thermal stress when a dissimilar coating such as ceramics 4) J is bonded to a base metal, we adopted a composite powder as an intermediate layer that corresponds to the base metal and coating material. Fine oxide powder is immobilized on the main component metal powder by mechanical impact means,
By forming spheres and forming a diffusion layer at the interface, it is possible to ensure a stable blending ratio of ingredients and appropriate fluidity as a powder, eliminating problems such as clogging, separation, and segregation that tend to occur during conventional thermal spraying. It is possible to provide a composite thermal spraying powder for forming an intermediate layer using a composite spherical powder of metal powder and ceramic powder that does not cause trouble, and a method for producing the same. In order to evaluate the performance of the thermally sprayed coating made of the composite spherical powder, the applicant investigated
On an A1 board (base material) with a width of 5 cm and a thickness of Q, 5 cm,
A sample was prepared by plasma spraying the thermal spray powder of the present invention or a commercially available intermediate layer forming powder, and then a commercially available ceramic on top of it under the spraying conditions shown in Table 2, and heating/cooling was repeated under the conditions shown in Table 3. The thermal shock resistance was repeatedly measured. In FIG. 10, 8 is a Δ1 substrate, 9 is an intermediate layer, and 10 is a ceramic layer. The thickness of the sprayed intermediate layer is 0.1 mm, and the thickness of the ceramic layer is 0.3 mm.
The width and length of both the intermediate layer and the ceramic layer are 5 cm. The apparatus used for the thermal shock resistance test is shown in FIG. 1st
In Fig. 1, 11 is a sample nozzle 12 for repeated thermal shock resistance measurement on which the intermediate layer and ceramic layer shown in Fig. 10 have been thermally sprayed, 13 is a natural gas flow rate adjustment valve, and 14 is an oxygen flow rate adjustment valve. , 15 is a compressed air pipe for cooling the sprayed layer, 16 is a compressed air pipe for cooling the base material, and 17 is a pipe inserted into the hole in the center of the sprayed coating on the back side of the AI board to measure the temperature of the sample. It is a type thermocouple. In addition, 18 is a natural gas supply source, 19 is an oxygen supply source, 2
0 is a compressed air supply source for cooling. Table 2: Sample thermal spraying conditions Table 3: Thermal shock resistance test conditions Table 4 shows the results of the thermal shock resistance test. In this test, as shown in Table 4, composite thermal spray powder 3 of the present invention with different blending ratios of yttria was used for the intermediate layer.
Two types of commercially available spherical thermal sprayed powder (granulated product) and a commercially available spherical thermal sprayed powder (granulated product) were used as the ceramic layer phase. In this table, the number of repeated hot/cool cycles until peeling is the number of times hot/cool cycles are repeated until the sprayed coating starts peeling off. The numerical values listed in this table are the average values of the results obtained twice under the same conditions. In E-2, 3, and 4, no peeling of the sprayed coating occurred even after repeating the heating/cooling cycle 2000 times. When the composite thermal sprayed powder of the present invention is used for the intermediate layer, the bondability is much better than when a commercially available intermediate layer thermal sprayed powder is used, or when nothing is thermally sprayed as the intermediate layer.
The number of repetitions of heating and cooling cycles until peeling was 3 to 7 times more than when a commercially available intermediate layer thermal spray powder was used and when no intermediate layer was thermally sprayed. In this way, the intermediate layer (thermal spray base) is formed by applying a solvent to the composite thermal spraying powder for forming the intermediate layer, which is forcibly fixed by mechanical impact means, using ceramic powder as the main component of the base metal powder. It was possible to alleviate thermal stress and greatly improve the bonding properties of ceramics. Table 4: Jijuen I Impact Test Junkichi

[Brief explanation of the drawing]

Figure 1 is a conceptual diagram of manufacturing composite thermal spray powder (1) (a
) is an amorphous metal powder, (2) (a) is a spherical metal powder, (
1) (b) and (2) (b) is ceramic powder, (], ) (C) and (2) (C) is composite powder (1) ( d) and (2) (d) represents a state in which ceramic powder is firmly fixed to metal powder. FIG. 2 shows an example of fl? used to produce a composite thermal spray powder for forming an intermediate layer. '11 Powder impact device with impact means. 3 to 9 show particle structure photographs and X-ray photographs of composite thermal sprayed powders based on the examples shown in Table 1,
Figure 3(a) is a photograph of the particle structure of the amorphous A1 alloy raw material powder;
Figure 3 (b) and Figures 4 to 9 (a) are photographs of the particle structure after composite processing, Figure 3 (C), Figure 4 (b), Figure 5 (b), Figure 8 ( b) and FIG. 9 Q:1) are cross-sectional views of grain structure photographs. Also, Fig. 3 (d,), Fig. 9 (C
) is an X-ray photograph, and the symbol Y in the upper left indicates the component of yttrium, 0 indicates oxygen, and A1 indicates the component of aluminum. FIG. 10 shows a sample on which a sprayed coating was formed to confirm the effects of the present invention, and FIG. 11 shows an apparatus used for a thermal shock resistance test of the sample. Explanation of symbols 1...Casing 2...Stake-3...
Turntable 4...Impact pin (blade) 5...
・Circulation circuit 6... Raw material input lower... Processed powder... A1 substrate 9... Intermediate layer 1
0... Ceramic layer 11... Sample 1
2... Gas burners 15, 16... Compressed air piping for cooling 17... K type couple 18... Natural gas supply source 19... Oxygen supply source 20... Compressed air supply source Patent applicant Nara Kikai Seisakusho Co., Ltd. Agent
Patent attorney Shin Matsubara 2 Same as Kiyoshi Muraki Replaced
Same as above Atsushi Shima -dof

Claims (6)

[Claims] (1) A metal characterized in that main component metal powder and ceramic powder in a predetermined quantitative ratio are bonded and sphericalized by mechanical impact means, and a diffusion layer is formed at the interface between the two powders. Composite thermal spray powder for forming an intermediate layer between powder and ceramic powder. (2) The composite thermal spraying for forming an intermediate layer of metal powder and ceramic powder according to claim 1, wherein the main component metal powder is an irregular shape or a sphere made of a ferrous material, a nonferrous alloy material, and a heat-resistant metal material. powder. (3) Ceramic powder has yttria (
Y_2O_31-20 mol%) alone or partially stabilized zirconia (PSZ 1-20 mol%) or alumina (Al_2O_31-20 mol%) to which yttria and a part of the coating ceramic component are added, or a lower oxide (10-80 mol%) to the main component metal. %), or partially stabilized dicomia (PSZ 1 to 20 mol%) prepared by adding yttria alone or yttria and a part of a coating ceramic component to an active metal. Composite thermal spray powder for forming an intermediate layer. (4) Attach a predetermined amount of ceramic powder to the surface of the amorphous main component metal powder, turn the composite powder into a sphere by mechanical impact means, and simultaneously fix the ceramic powder to the metal powder. A composite thermal sprayed powder for forming an intermediate layer of metal powder and ceramic powder, characterized in that a diffusion layer is formed at the interface between the two powders. (5) A predetermined ratio of ceramic powder is adhered to the surface of the spherical main component metal powder, and the ceramic powder is fixed to the main component metal powder by mechanical impact means, and at this time, both of the above-mentioned A composite thermal sprayed powder for forming an intermediate layer between metal powder and ceramic powder, which is characterized by forming a diffusion layer at the powder interface. (6) For forming an intermediate layer between metal powder and ceramic powder according to any one of claims 1, 4, or 5, wherein the mechanical impact means impacts the outer surface of the composite powder with an impact pin of a rotary disk. Manufacturing method for composite thermal spray powder.