JP2013199011A - Wear resistant and heat resistant fiber-reinforced composite material and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fiber-reinforced composite material excellent in wear resistance, heat resistance and surface smoothness formed with a thermal-sprayed film having favorable adhesive strength without providing an undercoat layer or a topcoat layer penetrated with ceramic particles, and a method for producing the same.SOLUTION: A wear resistant fiber-reinforced composite material 1 with a thermal-sprayed film layer 4 on the outermost layer includes: a fiber-reinforced plastic substrate layer 2; a glass fiber-reinforced plastic layer 3 laminated on the outer layer of the fiber-reinforced plastic substrate layer 2; and a thermal-sprayed film layer 4 covered on the outer layer of the glass fiber-reinforced plastic layer 3 by thermal spray, wherein the thermal-sprayed film layer 4 has a lower thermal-sprayed film layer 5 covered on the surface of the glass fiber-reinforced plastic layer 3 by the thermal spray and an upper thermal-sprayed film layer 6 covered on the surface of the lower thermal-sprayed film layer 5 by the thermal spray to form the surface layer of the fiber-reinforced composite material, and wherein the porosity of the lower thermal-sprayed film layer 5 is larger than that of the upper thermal-sprayed film layer 6.

Description

  The present invention generally relates to fiber reinforced composite materials such as carbon fiber reinforced plastics and aramid fiber reinforced plastics, and in particular, structures such as roll materials and plate materials having excellent wear resistance in which ceramics, cermets, metals, etc. are sprayed on the surface. The present invention relates to a fiber-reinforced composite material having wear resistance and heat resistance used as a body, and further having surface smoothness, and a method for producing the same.

  Conventionally, a structure such as a roll material or a plate material has been manufactured using a fiber reinforced composite material such as carbon fiber reinforced plastic or aramid fiber reinforced plastic, and in particular, a structure manufactured using these fiber reinforced composite materials. In order to improve the wear resistance and heat resistance of the body surface, it has been proposed to thermally spray ceramics, cermet, metal, etc. on the surface.

  Patent Document 1 discloses wear resistance and surface smoothness in which an undercoat layer made of an organic polymer material and an inorganic material is provided on the surface of a roll of plastic or fiber reinforced plastic, and a ceramic film is formed thereon by spraying ceramics. Describes an excellent roller.

  Further, Patent Document 2 has a structure in which a mixture of a resin of the same type as the base resin and ceramic particles is provided as an intermediate layer on the surface of the fiber reinforced plastic base material, and a thermal spray coating layer made of carbide cermet is provided as a top coat. A plastic matrix composite having excellent surface properties such as wear resistance is described.

  However, the rollers and plastic matrix composite materials described in the above-mentioned patent documents require heating (baking) to mold the fiber reinforced plastic in the production thereof, and in addition, an undercoat layer (Patent Document 1) or an intermediate layer In order to form (patent document 2), it is necessary to heat (baking) again, and a plurality of steps are required until thermal spraying is performed. In addition, at least twice heating (baking) is essential, which requires high energy costs and high costs.

  Accordingly, as described in Patent Document 3, the present applicant has proposed an abrasion-resistant fiber-reinforced composite material that can be used as a fiber-reinforced plastic roll, a plate material, and the like. Referring to FIGS. 2A, 2B, and 2C attached to the present application, the wear-resistant fiber reinforced composite material 1 includes a fiber reinforced plastic base layer 2 and a fiber reinforced plastic base layer 2. The glass fiber reinforced plastic layer 3 laminated on the surface layer and the thermal spray coating layer 4 coated on the surface layer of the glass fiber reinforced plastic layer 3 by thermal spraying.

  A fiber reinforced composite material 1 described in Patent Document 3 is formed by laminating a glass fiber reinforced plastic layer 3 on a surface layer of a fiber reinforced plastic base material 2, and simultaneously heat-curing the fiber reinforced plastic as a base material when molding, and the surface layer is made of glass. By forming the fiber reinforced plastic layer 3 and then performing thermal spraying after blasting, an undercoat layer as described in Patent Documents 1 and 2 or a topcoat layer in which ceramic particles are eroded is provided. The sprayed coating layer 4 having good adhesive strength can be formed.

No. 4-7378 Japanese Patent No. 4436957 Japanese Patent Application No. 2010-225867

  The fiber reinforced composite material 1 described in Patent Document 3 is excellent in wear resistance and heat resistance in which a thermal spray coating layer 4 having good adhesive strength is formed as a surface layer.

  As a result of conducting many research experiments to improve the wear resistance, heat resistance, and surface smoothness of the fiber reinforced composite material 1, these properties of the fiber reinforced composite material 1 are It has been found that this is largely related to the “porosity” of the coating layer 4.

  In the present specification and claims, “porosity” refers to pores measured based on the measurement of porosity by image processing described in “Thermal Spray Engineering Handbook” (page 600, published in January 2010). The rate was calculated. That is, the mirror-polished sample cross section was observed with an optical microscope, the image was binarized, and the porosity was calculated from the ratio of the area in the entire black region.

  That is, by controlling the porosity of the sprayed coating layer of the fiber reinforced composite material 1, the abrasion resistance and heat resistance of the fiber reinforced composite material 1, and also superfinish polishing (hereinafter referred to as “SF polishing”) finish. It has been found that surface smoothness can be dramatically increased by processing, and a fiber-reinforced composite material with stable quality can be provided.

  The present invention is based on such novel findings of the present inventors.

  The object of the present invention is to provide a wear resistance, a heat resistance, and a surface smoothness in which a thermal spray coating having a good adhesive strength is formed without providing an undercoat layer or a topcoat layer in which ceramic particles are eroded. It is providing the fiber reinforced composite material excellent in the, and its manufacturing method.

  Another object of the present invention is to provide a roll-shaped carbon fiber reinforced composite material having a particularly excellent abrasion resistance, heat resistance and surface smoothness on which a sprayed coating is formed, and a method for producing the same.

The above object is achieved by the wear-resistant and heat-resistant fiber-reinforced composite material having the thermal spray coating according to the present invention and the method for producing the same. In summary, the first aspect of the present invention is a wear-resistant, heat-resistant fiber-reinforced composite material having a thermal spray coating layer as an outermost layer,
A fiber reinforced plastic base layer, a glass fiber reinforced plastic layer laminated on the surface of the fiber reinforced plastic base layer, and a thermal spray coating layer coated on the surface of the glass fiber reinforced plastic layer by thermal spraying,
The thermal spray coating layer is formed by coating the surface of the glass fiber reinforced plastic layer by thermal spraying and the surface of the lower thermal spray coating layer by thermal spraying to form a surface layer of the fiber reinforced composite material. An upper thermal spray coating layer, and the porosity of the lower thermal spray coating layer is greater than the porosity of the upper thermal spray coating layer,
This is a wear-resistant and heat-resistant fiber-reinforced composite material.

  In the first aspect of the present invention, according to one embodiment, the porosity of the lower spray coating layer is 10% or more and 30% or less, and the porosity of the upper spray coating layer is 1% or more and less than 10%. It is said.

In the first aspect of the present invention, according to another embodiment, the thermal spray material for forming the lower thermal spray coating layer has a linear expansion coefficient of 3 × 10 ^{−6 to} 12 × 10 ⁻⁶ (1 / ° C.). It is.

  In the first aspect of the present invention, according to another embodiment, the lower sprayed coating layer has a coating thickness of 0.02 to 1.0 mm.

  In the first aspect of the present invention, according to another embodiment, the upper sprayed coating layer has a coating thickness of 0.03 to 1.0 mm, a Vickers hardness HV of 400 to 1200, and an average surface roughness. Ra is 0.05-1.0 micrometer.

  In the first aspect of the present invention, according to another embodiment, the thermal spray material forming the lower thermal spray coating layer and the upper thermal spray coating layer is granular ceramics, cermet or metal, or a mixture thereof.

  In the first aspect of the present invention, according to another embodiment, the fiber reinforced composite material is formed in a roll shape. According to another embodiment, the fiber reinforced composite material has a flat plate shape.

In the first aspect of the present invention, according to another embodiment, the reinforcing fiber of the fiber-reinforced plastic base layer is an inorganic fiber such as carbon fiber, glass fiber, or basalt fiber; boron fiber, titanium fiber, steel fiber, or the like. Metal fibers; organic fibers such as aramid, PBO (polyparaphenylene benzbisoxazole), polyamide, polyarylate, polyester, etc .;
As the resin of the fiber reinforced plastic base layer and the glass fiber reinforced plastic layer, a room temperature curing or thermosetting epoxy resin, vinyl ester resin, MMA resin, acrylic resin, unsaturated polyester resin, or phenol resin Or nylon or vinylon is used.

The second aspect of the present invention is a method for producing a wear-resistant, heat-resistant roll-shaped fiber reinforced composite material,
(A) In order to form the fiber reinforced plastic base material layer to be a roll base material on a mandrel, a predetermined reinforcing fiber is wound using a predetermined resin to form a reinforcing fiber layer to be a base material, and subsequently, A step of laminating a glass fiber layer by winding a glass fiber using a predetermined resin to form the glass fiber reinforced plastic layer on the reinforcing fiber layer to be the base material,
(B) a step of simultaneously heat-curing the resin of the reinforcing fiber layer and the glass fiber layer as the base material,
(C) a step of roughening the surface of the glass fiber reinforced plastic layer formed by curing the resin of the glass fiber layer;
(D) a step of spraying a predetermined thermal spray material on the surface of the roughened glass fiber reinforced plastic layer to form a lower thermal spray coating layer;
(E) a step of spraying a predetermined thermal spray material on the surface of the lower thermal spray coating layer to form an upper thermal spray coating layer so that the porosity is smaller than the porosity of the lower thermal spray coating layer;
A method for producing a wear-resistant, heat-resistant roll-shaped fiber reinforced composite material characterized by comprising:

  In the second aspect of the present invention, according to one embodiment, the reinforcing fibers of the reinforcing fiber layer serving as the base material are carbon fibers.

  In the second aspect of the present invention, according to another embodiment, in the step (a), the glass fiber is wound around the mandrel in the same angular direction.

The third aspect of the present invention is a method for producing a wear-resistant, heat-resistant roll-shaped fiber reinforced composite material,
(A) A prepreg to be a base material using a predetermined reinforcing fiber for forming the fiber reinforced plastic base material layer to be a roll base material is wound around a mandrel, and subsequently, on the prepreg to be the base material A step of winding and laminating a glass fiber prepreg for forming the glass fiber reinforced plastic layer,
(B) a step of simultaneously heat-curing the resin of the prepreg serving as the substrate and the glass fiber prepreg,
(C) a step of roughening the surface of the glass fiber reinforced plastic layer formed by curing the glass fiber prepreg;
(D) a step of spraying a predetermined thermal spray material on the surface of the roughened glass fiber reinforced plastic layer to form a lower thermal spray coating layer;
(E) a step of spraying a predetermined thermal spray material on the surface of the lower thermal spray coating layer to form an upper thermal spray coating layer so that the porosity is smaller than the porosity of the lower thermal spray coating layer;
A method for producing a wear-resistant, heat-resistant roll-shaped fiber reinforced composite material characterized by comprising:

  In the third aspect of the present invention, according to one embodiment, the reinforcing fiber of the prepreg serving as the base material is a carbon fiber.

  In the third aspect of the present invention, according to another embodiment, the glass fiber prepreg is a UD-shaped prepreg formed by aligning glass fibers in one direction, or using a glass fiber woven fabric. It is the formed glass cloth prepreg.

  In the second and third aspects of the present invention, according to one embodiment, in the step (c), the surface of the glass fiber reinforced plastic layer is roughened to an average roughness Ra of 2 to 10 μm by blasting. Is processed.

  In the second and third aspects of the present invention, according to another embodiment, the porosity of the lower sprayed coating layer is 10% or more and 30% or less, and the porosity of the upper sprayed coating layer is 1% or more. Less than 10%.

In the second and third aspects of the present invention, according to another embodiment, the thermal spray material for forming the lower thermal spray coating layer has a linear expansion coefficient of 3 × 10 ^{−6 to} 12 × 10 ⁻⁶ (1 / ° C).

  In the second and third aspects of the present invention, according to another embodiment, the lower sprayed coating layer has a coating thickness of 0.02 to 1.0 mm.

  In the second and third aspects of the present invention, according to another embodiment, the upper sprayed coating layer has a coating thickness of 0.03 to 1.0 mm, a Vickers hardness HV of 400 to 1200, Average roughness Ra is 0.05-1.0 micrometer.

  In the second and third aspects of the present invention, according to another embodiment, the thermal spray material forming the lower thermal spray coating layer and the upper thermal spray coating layer is granular ceramic, cermet, metal, or a mixture thereof. .

  According to the present invention, without providing an undercoat layer or a topcoat layer in which ceramic particles are eroded, a thermal spray coating having a good adhesive strength is formed. Abrasion resistance, heat resistance, and surface smoothness Can be obtained. In particular, according to the present invention, a roll-shaped carbon fiber reinforced composite material having excellent abrasion resistance, heat resistance, and surface smoothness on which a sprayed coating is formed, and a method for producing the same are obtained.

It is the schematic explaining the cross-section of the fiber reinforced composite material which concerns on this invention. FIG. 2A is a schematic diagram for explaining a cross-sectional structure of a fiber-reinforced composite material in the prior art, and FIG. 2B is a roll-shaped example of the fiber-reinforced composite material shown in FIG. FIG. 2C is a diagram for explaining a method for producing a fiber-reinforced composite material, and FIG. 2C is a diagram for explaining a method for producing a plate-like fiber-reinforced composite material, which is an example of a fiber-reinforced composite material in the prior art.

  Hereinafter, the fiber reinforced composite material having the thermal spray coating according to the present invention and excellent in abrasion resistance, heat resistance and surface smoothness and the production method thereof will be described in more detail with reference to the drawings.

Example 1
FIG. 1 shows a schematic cross-sectional configuration of a fiber-reinforced composite material 1 having a thermal spray coating layer 4 according to the present invention, which has abrasion resistance, heat resistance, and excellent surface smoothness by performing SF polishing. Indicates. The fiber reinforced composite material 1 of the present invention includes a fiber reinforced plastic base layer 2, a glass fiber reinforced plastic layer 3 laminated on the surface layer of the fiber reinforced plastic base layer 2, and a surface layer of the glass fiber reinforced plastic layer 3. And a thermal spray coating layer 4 coated by thermal spraying. According to the characteristic configuration of the present invention, the thermal spray coating layer 4 is composed of a lower thermal spray coating layer 5 and an upper thermal spray coating layer 6.

  Next, each layer will be described in more detail.

  As the reinforcing fiber of the fiber reinforced plastic to be the fiber reinforced plastic base layer 2, carbon fiber is most preferable, but various other fibers can be used. For example, as the reinforcing fiber, in addition to carbon fiber, inorganic fiber such as glass fiber and basalt fiber; metal fiber such as boron fiber, titanium fiber, and steel fiber; and further, aramid, PBO (polyparaphenylene benzbisoxazole) Organic fibers such as polyamide, polyarylate, and polyester can be used alone or in a mixture of plural kinds.

  In addition, as the matrix resin impregnated in the reinforcing fiber in the fiber reinforced plastic base layer 2 and the glass fiber reinforced plastic layer 3, a thermosetting resin or a thermoplastic resin can be used. As the thermosetting resin, , Room temperature curable or thermosetting epoxy resin, vinyl ester resin, MMA resin, acrylic resin, unsaturated polyester resin, phenol resin, etc. are preferably used, and thermoplastic resins such as nylon, vinylon, etc. Can be suitably used. The resin impregnation amount is 30 to 70% by weight, preferably 40 to 60% by weight.

  The fiber reinforced plastic base layer 2 usually has a layer thickness t2 of 1 to 30 mm, and the glass fiber reinforced plastic layer 3 usually has a layer thickness t3 of 0.5 to 5 mm, and is appropriately selected according to the application. The

  The thermal spray coating layer 4 is composed of a lower thermal spray coating layer 5 coated on the surface of the glass fiber reinforced plastic layer 3 by thermal spraying, and an upper thermal spray coating layer 6 sprayed on the surface of the lower thermal spray coating layer 5. .

  Here, according to the present invention, the porosity of the lower sprayed coating layer 5 is made larger than the porosity of the upper sprayed coating layer 6. Next, the lower sprayed coating layer 5 and the upper sprayed coating layer 6 will be described in more detail.

(Lower spray coating layer)
According to the present embodiment, the lower sprayed coating layer 5 has a coating thickness t5 of 0.02 to 1.0 mm, and the porosity of the lower sprayed coating layer 5 is larger than that of the upper sprayed coating layer 6. % Or more and 30% or less. When the film thickness t5 is less than 0.02 mm, the concave portion of the glass fiber reinforced plastic layer 3 is not completely filled, and a portion where the glass fiber reinforced plastic layer 3 is exposed cannot be obtained, and sufficient adhesion cannot be obtained. 200 ° C. cannot be achieved. Moreover, when it exceeds 1.0 mm, there exists a problem of high cost. Further, when the porosity is less than 10%, the residual stress of the sprayed coating becomes large, and there is a problem that the coating is cracked at a use temperature of 200 ° C. If the porosity exceeds 30%, the adhesion in the lower sprayed coating layer 5 is lowered, and there is a problem that the coating is cracked during polishing. The optimum specifications of the lower sprayed coating layer 5 are such that the coating thickness t5 is 0.05 to 0.1 mm and the porosity is 15 to 20%.

  Further, as the thermal spray material for forming the lower thermal spray coating layer 5, granular ceramics, cermet, metal, or a mixture thereof can be used. Specifically, as ceramics, alumina, titania, zirconia, magnesia, chromia, cermets include tungsten carbide + cobalt, tungsten carbide + nickel chrome, chromium carbide + nickel chrome, etc., and metals include cobalt compounds, molybdenum, Nickel, nickel chromium, or the like may be used alone or as a mixture thereof. As the particle size of the thermal spray material, an average particle size of 5 to 100 μm can be suitably used.

Further, the spray material to form a lower sprayed coating layer 5, the linear expansion coefficient is as indicating material properties within the scope of ^{3 × 10 -6 ~12 × 10 -6} (1 / ℃). If the linear expansion coefficient is less than 3 × 10 ⁻⁶ (1 / ° C.) or exceeds 12 × 10 ⁻⁶ (1 / ° C.), the difference in linear expansion from the glass fiber reinforced plastic layer 3 is large. There are problems such as cracking and peeling of the film. For optimum use, the material of the lower sprayed coating layer 5 has a linear expansion coefficient of 7 × 10 ⁻⁶ to 10 × 10 ⁻⁶ (1 / ° C.).

(Top sprayed coating layer)
According to the present embodiment, the upper sprayed coating layer 6 has a coating thickness t6 of 0.03 to 1.0 mm, and the porosity of the upper sprayed coating layer 6 is smaller than that of the lower sprayed coating layer 5. % Or more and less than 10%. Furthermore, the surface roughness is 0.05 to 1.0 μm in terms of average roughness Ra, and the surface hardness is 400 to 1200 in terms of Vickers hardness HV.

  When the film thickness t6 is less than 0.03 mm, there is a problem that the polishing margin is small and sufficient surface smoothness cannot be obtained, and when it exceeds 1.0 mm, there are problems that the film is cracked and the cost is increased. Furthermore, when the porosity is less than 1%, the residual stress of the upper thermal spray coating becomes large, and there is a problem that it breaks at the interface between the lower thermal spray coating layer 5 and the upper thermal spray coating layer 6 at a use temperature of 200 ° C. When the porosity exceeds 10%, in order to make the surface roughness Ra 1.0 μm or less, there is a problem that it takes time for SF polishing, that is, super-finish polishing, resulting in high cost.

  Regarding the surface roughness, if the average roughness Ra is less than 0.05 μm, there is a problem that it takes time for SF polishing, that is, super-finish polishing, resulting in high costs, and if it exceeds 1.0 μm, the surface irregularities are large. Thus, sufficient surface smoothness cannot be obtained, and when used for a film transporting roll or the like, there is a problem that the film is damaged and cannot be actually used.

  Further, regarding the surface hardness, there is a problem that sufficient wear resistance cannot be obtained when the Vickers hardness HV is less than 400, and an expensive thermal spray material is used for the specification exceeding 1200, and the cost is high. There is a problem of becoming.

  As the optimum specifications, the film thickness t6 is 0.1 to 0.3 mm, the porosity is 1 to 3%, the surface roughness Ra is 0.05 to 0.15 μm, and the surface hardness HV is 600 to 1000. The

  Further, as the thermal spray material for forming the upper thermal spray coating layer 6, the same thermal spray material as that for the lower thermal spray coating layer 5 can be used. That is, granular ceramics, cermet, metal, or a mixture thereof can be used. Specifically, as ceramics, alumina, titania, zirconia, magnesia, chromia, cermets include tungsten carbide + cobalt, tungsten carbide + nickel chrome, chromium carbide + nickel chrome, etc., and metals include cobalt compounds, molybdenum, Nickel, nickel chrome, etc. may be used alone or in combination. As the particle size of the thermal spray material, an average particle size of 5 to 100 μm can be suitably used.

The thermal spray material for forming the upper thermal spray coating layer 6 has a linear expansion coefficient in the range of 3 × 10 ^{−6 to} 12 × 10 ⁻⁶ (1 / ° C.), like the thermal spray material of the lower thermal spray coating layer 5. It is supposed to exhibit certain material properties. By using a material having the same linear expansion coefficient as the thermal spray material for the upper thermal spray coating layer 6 and the lower thermal spray coating layer 5, problems such as cracking and peeling of the coating under a high temperature environment of 200 ° C. are avoided. can do. As the optimum use, the material of the upper thermal spray coating layer 6 is set to have a linear expansion coefficient of 7 × 10 ⁻⁶ to 10 × 10 ⁻⁶ (1 / ° C.), like the material of the lower thermal spray coating layer 5.

  The fiber reinforced composite material 1 having the above-described configuration is heated at the same time as the fiber reinforced plastic base layer 2 and the glass fiber reinforced plastic layer 3 laminated on the surface layer are molded. (Baked) to cure. Thereafter, the surface of the glass fiber reinforced plastic layer 3 is blasted, and then the thermal spray material is sprayed at a predetermined thickness to form the thermal spray coating layer 4 composed of the lower thermal spray coating layer 5 and the upper thermal spray coating layer 6. Is done.

  The fiber-reinforced composite material 1 according to the present invention is formed into a roll shape or a plate shape. For example, the wear-resistant roll-shaped fiber reinforced composite material is used in a high-temperature environment such as 150 to 200 ° C. The wear-resistant plate-like fiber reinforced composite material is effectively used as a plate-like guide member at the time of manufacturing a film or a sheet, as a roll in various industrial machine devices such as a roll for film conveyance.

  Next, the manufacturing method of the fiber reinforced composite material of the present invention will be described in more detail.

(Molding of fiber reinforced plastic substrate and glass fiber reinforced plastic layer)
The case of the fiber reinforced composite material roll which is one Example of the fiber reinforced composite material of this invention is demonstrated. Moreover, as a reinforced fiber of the fiber reinforced plastic layer 2 used as a base material, it demonstrates as what uses a carbon fiber.

  The carbon fiber reinforced composite roll (hereinafter referred to as “CFRP roll”) of the present embodiment can be suitably produced by using a filament winding method or a sheet winding method well known to those skilled in the art.

(Filament winding method)
A case where a CFRP roll is produced by a filament winding method will be described with reference to FIG. In this embodiment, first, carbon fibers are wound around the mandrel 100 using a predetermined resin, and the reinforcing fiber layer 2A serving as a base for the fiber reinforced plastic base layer 2 serving as a roll base, that is, in this embodiment. Then, a carbon fiber layer (carbon fiber layer to be a base material) 2A for the carbon fiber reinforced plastic base material layer 2 is formed.

  Subsequently, the glass fiber layer 3A for the glass fiber reinforced plastic layer 3 is laminated on the carbon fiber layer 2A serving as the base material by winding the glass fiber using a predetermined resin. At this time, the glass fiber can be directly wound on the carbon fiber layer 2A as the base material, but the glass cloth is produced by cutting a glass cloth, which is a glass fiber fabric made of glass fiber, into a predetermined width. A method of winding a tape may be used.

  The resin used at the time of winding the glass fiber is preferably the same or the same resin as that used at the time of winding the carbon fiber. It is also effective to add inorganic powder used for thermal spraying such as alumina to the resin. The addition amount is 30 to 70% by weight based on the resin amount.

  In addition, when glass fiber is wound around the outermost layer of the carbon fiber layer 2A as a base material by the filament winding method, if a plus or minus helical winding is performed, a resin-only part is created at the intersection of the fibers. Therefore, when a thermal spray material is sprayed, a portion where sufficient adhesion strength cannot be obtained is generated. Therefore, it is desirable to wind only in the plus direction or in the same angular direction only in the minus direction.

  Next, taping is performed from the top of the glass fiber layer 3A, and the carbon fiber layer 2A and the glass fiber layer 3A as the base material are wound up, and then the mandrel 100 and the carbon fiber layer 2A as the base material are loaded into the curing furnace. The resin of the glass fiber layer 3A is cured. Thereby, the roll base tube 1A which consists of a laminated body of the carbon fiber plastic base material layer 2 and the glass fiber reinforced plastic layer 3 is shape | molded.

  Then, after removing the tape, the surface of the glass fiber reinforced plastic layer 3 is ground to adjust the roll diameter to a predetermined dimension. The roll surface having a predetermined diameter, that is, the surface of the glass fiber reinforced plastic layer 3 is blasted to have a predetermined roughness. At this time, the surface roughness of the glass fiber reinforced plastic layer 3 is 2 to 10 μm, and optimally 4 to 8 μm, in terms of an average roughness Ra. If it is less than 2 μm, the adhesion is weak, and if it exceeds 10 μm, the substrate is damaged.

  Thus, before spraying, the roll surface is polished and blasted to make the roll surface a predetermined rough surface, whereby the glass portion 30 (see FIG. 1A) of the glass fiber is formed on the roll surface layer. This is because the exposed ceramic film, cermet, metal, or mixture thereof of the sprayed coating layer 4 (that is, the lower sprayed coating layer 5) adheres to the glass portion 30 and exhibits sufficient adhesiveness (adhesive strength). Presumed.

  Next, a sprayed material is sprayed on the roughened surface to form a lower sprayed coating layer 5 on the roll surface.

(Sheet winding method)
The sheet winding method is carried out in the same manner as the filament winding method except that a sheet-like prepreg fiber sheet is used.

  That is, when the CFRP roll is manufactured by the sheet winding method, the carbon fiber reinforced plastic base material layer 2 is first formed on the mandrel 100 with a predetermined laminated structure. After the carbon fiber prepreg 2A is wound, the glass fiber prepreg 3A for forming the glass fiber reinforced plastic layer 3 is wound around the outermost layer of the carbon fiber prepreg 2A. The glass fiber prepreg 3A may be a glass cloth prepreg or a UD-shaped prepreg in which glass fibers are aligned in one direction. The resin of the glass fiber prepreg 3A is preferably the same or the same resin as the resin used for the carbon fiber prepreg 2A.

  Next, taping is performed, and after the carbon fiber prepreg 2A and the glass fiber prepreg 3A are wound up, the mandrel is placed in a curing furnace, the carbon fiber prepreg 2A and the glass fiber prepreg 3A are cured, and the carbon fiber reinforced plastic base A roll base tube 1A composed of the material layer 2 and the glass fiber reinforced plastic layer 3 is produced. Thereafter, similarly to the filament winding method, after removing the tape, the surface of the glass fiber reinforced plastic layer 3 is polished, and the roll diameter is adjusted to a predetermined dimension. The roll surface having a predetermined diameter, that is, the surface of the glass fiber reinforced plastic layer 3 is blasted to have a predetermined roughness.

  Next, the surface is sprayed using a predetermined spraying material to form the sprayed coating layer 4 (that is, the lower sprayed coating layer 5) on the roll surface.

  The fiber-reinforced composite material 1 of the present invention is not limited to the above-described roll-shaped structure, and is a fiber-reinforced composite material having a flat or complex structure as illustrated in FIG. You can also.

  Also in this case, a glass fiber prepreg 3A is laminated on the outermost layer of the prepreg 2A serving as a structure base material, the resin is cured, and a plate-like material 1A comprising the fiber reinforced plastic layer 2 and the glass fiber reinforced plastic layer 3 is obtained. Is made. Thereafter, the surface of the cured glass fiber reinforced plastic layer 3 is ground, and the surface of the glass fiber reinforced plastic layer 3 is blasted to have a predetermined roughness.

  Next, the surface is sprayed using a predetermined spraying material to form the sprayed coating layer 4 on the roll surface.

(Formation of sprayed coating layer)
(A) Formation of lower sprayed coating layer The surface of the roughened glass fiber reinforced plastic layer 3 is made of a predetermined sprayed material using a plasma spraying apparatus so that the thickness t5 is 0.02 to 1.0 mm. The lower sprayed coating layer 5 is formed (coated) by thermal spraying. At this time, the porosity of the lower sprayed coating layer 5 is set to 10% or more and 30% or less. The method is not particularly limited, but can be achieved, for example, by appropriately adjusting the spraying distance.
(B) Formation of upper thermal spray coating layer A predetermined thermal spray material is sprayed on the surface of the lower thermal spray coating layer 5 using a plasma spraying apparatus so that the thickness t6 becomes 0.03 to 1.0 mm. Upper sprayed coating layer 6 is formed (coated). At this time, the porosity of the upper sprayed coating layer 6 is set to be 1% or more and less than 10%. The method is not particularly limited, but can be achieved, for example, by appropriately adjusting the spraying distance.

  After the thermal spray coating treatment, if necessary, a thermal spray coating polishing treatment and then a thermal spray coating sealing treatment step can be provided.

In this example, polishing treatment was performed after the thermal spray coating treatment, and then sealing treatment was performed. Examples of the sealing agent include a silane-based sealing agent (for example, Permeate (trade name) manufactured by D & D Co., Ltd.), and the sealing agent is applied to the sprayed coating at 10 to 30 g / m ² . After application, in order to accelerate the curing, it is cured for about 30 minutes to 3 hours in a high temperature furnace (50 to 100 ° C.).

  After the sealing treatment, the surface of the sprayed coating is subjected to SF polishing. As a result, the upper sprayed coating layer 6 having a thickness of 0.03 to 1.0 mm is formed with a surface roughness (average roughness) Ra of 0.05 to 1.0 μm.

  Next, in order to prove the performance of the fiber reinforced composite material of the present invention, a fiber reinforced composite material roll having a configuration according to the present invention is produced, and an experimental example compared with a comparative example is described.

Experimental example 1
A CFRP roll having a configuration according to the present invention was produced by a filament winding method.

  As the carbon fiber, a monofilament average diameter of 7 μm and a bundle of 12,000 fibers, that is, a PAN-based carbon fiber strand (“TR50” (trade name) manufactured by Mitsubishi Rayon Co., Ltd.) is used, and the resin is an epoxy resin (Nippon Steel Materials). "HP100" manufactured by Co., Ltd.), a carbon fiber layer 2A as a base material is 5 mm at an angle of 90 ° (circumferential direction), ± 45 °, ± 15 ° on a mandrel having an outer diameter of 88 mm and a length of 2 m. It wound so that it might become thickness (fiber volume content Vf = 57%).

  Subsequently, the same resin is used on the carbon fiber layer 2A as the base material, and TEX1174 g / km, that is, E glass fiber strand (“RS110QL” manufactured by Nitto Boseki Co., Ltd. (trade name) is used as the glass fiber. The glass fiber was wound at the same angle of + 60 ° so as to be 2 mm thick (Vf = 57%). In terms of the resin impregnation amount, the carbon fiber layer 2A serving as the base material was 32% by weight, and the glass fiber layer 3A was 21% by weight.

  Thereafter, taping was performed using a PET tape having a width of 25 mm and a thickness of 0.1 mm, and then the mandrel 100 around which the carbon fiber layer 2A and the glass fiber layer 3A as a base material impregnated with the resin were wound was placed in a heating and curing furnace. After charging, the temperature was increased to 180 ° C. at a temperature increase rate of 2 ° C./minute, held for 3 hours, and then cooled, and the cured reinforcing fiber plastic molded product (element tube) 1A was removed from the mandrel 100. Thereby, the inner diameter of the glass fiber reinforced plastic layer 3 formed on the surface layer is 88 mm, the thickness (t2) of the carbon fiber reinforced plastic base layer 2 is 5 mm, the thickness (t3) of the glass fiber reinforced plastic layer 3 is 2 mm, A carbon fiber reinforced plastic tube (element tube) 1A having a length of 1800 mm was obtained.

  The roll base tube 1A was axially mounted and polished so that the roll diameter was 100 mm, and the ground surface of the glass fiber reinforced plastic layer 3 was exposed.

  Next, the surface of the glass fiber reinforced plastic layer 3 was roughened by blasting. The surface roughness Ra was 7.6 μm.

In order to form the lower spray coating layer 5 on the roughened glass fiber reinforced plastic layer 3, plasma spraying was performed using alumina / titania which is ceramic particles as a spraying material. The linear expansion coefficient of alumina and titania, which is a thermal spray material, was 8.5 × 10 ⁻⁶ (1 / ° C.).

  The thickness (t5) of the lower sprayed coating layer 5 thus formed was 0.1 mm. Further, the thermal spraying was performed with the spraying distance set to 150 mm so that the porosity of the lower sprayed coating layer 5 was 15%.

Further, in order to form the upper sprayed coating layer 6 on the lower sprayed coating layer 5 thus formed, plasma spraying was performed using alumina / 40% titania which is ceramic particles as a spraying material. The linear expansion coefficient of alumina and 40% titania as the thermal spray material was 8.7 × 10 ⁻⁶ (1 / ° C.).

  The thickness (t6) of the upper sprayed coating layer 6 thus formed was 0.2 mm. Further, the thermal spraying was performed with the spraying distance set to 70 mm so that the porosity of the upper sprayed coating layer 6 was 5%.

  The total film thickness (t5 + t6) of the lower sprayed coating layer 5 and the upper sprayed coating layer 6 was 0.3 mm by the said thermal spraying.

Alumina / titania particles and alumina / 40% titania, which are the thermal spraying materials used in the thermal spraying to form the lower thermal spray coating layer 5 and the upper thermal spray coating layer 6, are “K-13” manufactured by Showa Denko K.K. (Trade name) and “K-40M” (trade name), and the plasma spraying apparatus was “9MB plasma spraying” (trade name) manufactured by SULZER METCO Corporation. The spraying conditions are: Gas used: N ₂ / H ₂ , Flow rate N ₂ : 35 to 40 L / min, H ₂ : 10 to 15 L / min, Gas ratio used: N ₂ : H ₂ = 3: 1, Voltage: 70 to It was 76V, powder supply amount: 5-10 g / min.

Polishing treatment was performed after thermal spraying, and then sealing treatment was performed. The sealant was Permite (trade name) manufactured by D & D Co., Ltd., which was applied at 30 g / m ² on the sprayed coating and then cured at 80 ° C. for 30 minutes.

  After the sealing treatment, the surface of the sprayed coating was subjected to SF polishing.

  The surface roughness of the thermal spray coating was measured with a contact-type surface roughness meter after SF polishing. As a result, the surface roughness (average roughness) Ra was 0.1 μm. The surface hardness was measured with a Vickers hardness tester. The Vickers hardness HV was 630.

  Furthermore, a heat resistance test was performed. The test conditions were kept in a furnace at 180 ° C. for 2 hours, and then taken out from the furnace, and the cracking and peeling of the sprayed coating were visually confirmed. There were no problems such as cracking or peeling of the film, and a good film could be obtained. When the roll was cut after the heat resistance test and the porosity was measured, the porosity of the lower sprayed coating layer 5 was 19%, and the porosity of the upper sprayed coating layer 6 was 3%.

Comparative Example 1
For comparison, a roll base tube 1A was obtained in which the surface of the glass fiber reinforced plastic layer 3 was roughened by blasting using the same materials and production conditions as in Experimental Example 1. The surface roughness Ra was 7.6 μm.

Next, in order to form the lower sprayed coating layer 5 on the roughened glass fiber reinforced plastic layer 3, as a thermal spray material, a linear expansion coefficient is 17.3 × 10 ⁻⁶ (1 / ° C.). No. 80Ni-20Cr was used, and plasma spraying was performed under the same thermal spraying conditions as in Experimental Example 1.

  As a result, 80Ni-20Cr particles sprayed by thermal spraying bounced from the glass fiber reinforced plastic layer 3, and a sufficient film thickness could not be obtained.

Comparative Example 2
For comparison, a roll base tube 1A was obtained in which the surface of the glass fiber reinforced plastic layer 3 was roughened by blasting using the same materials and production conditions as in Experimental Example 1. The surface roughness Ra was 7.6 μm.

Next, in order to form the lower sprayed coating layer 5 on the roughened glass fiber reinforced plastic layer 3, the thermal expansion material has a linear expansion coefficient of 8.5 × 10 ⁻⁶ (1 / ° C.). The plasma spraying was performed under the same spraying conditions as in Experimental Example 1 except that the alumina-titania was used and the spraying distance was 70 mm so that the porosity was 5%.

Thereafter, in the same manner as in Experimental Example 1, in order to form the upper sprayed coating layer 6 on the lower sprayed coating layer 5, plasma spraying was performed using alumina / 40% titania which is ceramic particles as a spraying material. The linear expansion coefficient of alumina and 40% titania as the thermal spray material was 8.7 × 10 ⁻⁶ (1 / ° C.).

  The thickness (t5) of the upper sprayed coating layer 6 thus formed was 0.2 mm. Further, the thermal spraying was performed with the spraying distance set to 70 mm so that the porosity of the upper sprayed coating layer 6 was 5%.

  Due to the above thermal spraying, the total film thickness of the lower thermal spray coating layer 5 and the upper thermal spray coating layer 6 was 0.3 mm.

  This film was polished in the same manner as in Experimental Example 1, and then sealed and SF polished. The roll was subjected to a heat resistance test in the same manner as in Experimental Example 1 to confirm cracking and peeling of the film. As a result, cracking and peeling of the film were confirmed on the entire roll surface. When the roll was cut after the heat resistance test and the porosity was measured, the porosity of the lower sprayed coating layer 5 was 6%, and the porosity of the upper sprayed coating layer 6 was 3%.

  Table 1 summarizes the test results of Experimental Example 1 and Comparative Examples 1 and 2.

  As will be understood from the above, according to the present invention, without providing an undercoat layer or a topcoat layer into which ceramic particles have been eroded, wear resistance in which a sprayed coating having good adhesive strength is formed, A fiber-reinforced composite material excellent in heat resistance and surface smoothness can be obtained. In particular, according to the present invention, it is possible to obtain a roll-shaped carbon fiber reinforced composite material having a thermal spray coating and excellent wear resistance, heat resistance and surface smoothness.

DESCRIPTION OF SYMBOLS 1 Fiber reinforced composite material 1A Roll-shaped element | tube, plate-shaped raw material 2 Fiber reinforced plastic base material layer 2A Reinforcement fiber layer used as a base material, prepreg used as a base material 3 Glass fiber reinforced plastic layer 3A Glass fiber layer, glass fiber prepreg 4 Thermal spray coating layer 5 Lower thermal spray coating layer 6 Upper thermal spray coating layer 30 Glass portion

Claims (21)

A wear-resistant, heat-resistant fiber-reinforced composite material with a thermal spray coating layer on the outermost layer,
A fiber reinforced plastic base layer, a glass fiber reinforced plastic layer laminated on the surface of the fiber reinforced plastic base layer, and a thermal spray coating layer coated on the surface of the glass fiber reinforced plastic layer by thermal spraying,
The thermal spray coating layer is formed by coating the surface of the glass fiber reinforced plastic layer by thermal spraying and the surface of the lower thermal spray coating layer by thermal spraying to form a surface layer of the fiber reinforced composite material. An upper thermal spray coating layer, and the porosity of the lower thermal spray coating layer is greater than the porosity of the upper thermal spray coating layer,
A wear- and heat-resistant fiber-reinforced composite material.   The porosity of the lower sprayed coating layer is 10% or more and 30% or less, and the porosity of the upper sprayed coating layer is 1% or more and less than 10%. Wear resistant, heat resistant fiber reinforced composite material. The thermal spray material for forming the lower thermal spray coating layer has a linear expansion coefficient of 3 × 10 ^{−6 to} 12 × 10 ⁻⁶ (1 / ° C.), according to claim 1 or 2. Abrasion and heat resistant fiber reinforced composites.   The wear-resistant and heat-resistant fiber-reinforced composite material according to any one of claims 1 to 3, wherein the lower sprayed coating layer has a coating thickness of 0.02 to 1.0 mm.   The upper sprayed coating layer has a coating thickness of 0.03 to 1.0 mm, a Vickers hardness HV of 400 to 1200, and an average surface roughness Ra of 0.05 to 1.0 μm. The wear-resistant and heat-resistant fiber-reinforced composite material according to any one of claims 1 to 4.   The thermal spray material for forming the lower thermal spray coating layer and the upper thermal spray coating layer is granular ceramics, cermet, metal, or a mixture thereof. Abrasion and heat resistant fiber reinforced composites.   The wear-resistant and heat-resistant fiber-reinforced composite material according to any one of claims 1 to 6, wherein the fiber-reinforced composite material has a roll shape.   The wear-resistant and heat-resistant fiber-reinforced composite material according to any one of claims 1 to 6, wherein the fiber-reinforced composite material has a flat plate shape. Reinforcing fibers of the fiber-reinforced plastic base layer are inorganic fibers such as carbon fibers, glass fibers, and basalt fibers; metal fibers such as boron fibers, titanium fibers, and steel fibers; aramid, PBO (polyparaphenylene benzbisoxazole), Organic fibers such as polyamide, polyarylate, and polyester; are used alone or in a hybrid mixed with multiple types,
As the resin of the fiber reinforced plastic base layer and the glass fiber reinforced plastic layer, a room temperature curing or thermosetting epoxy resin, vinyl ester resin, MMA resin, acrylic resin, unsaturated polyester resin, or phenol resin Or nylon or vinylon is used, The abrasion-proof and heat-resistant fiber-reinforced composite material of any one of Claims 1-8 characterized by the above-mentioned. A method for producing a wear-resistant, heat-resistant roll-shaped fiber reinforced composite material,
(A) In order to form the fiber reinforced plastic base material layer to be a roll base material on a mandrel, a predetermined reinforcing fiber is wound using a predetermined resin to form a reinforcing fiber layer to be a base material, and subsequently, A step of laminating a glass fiber layer by winding a glass fiber using a predetermined resin to form the glass fiber reinforced plastic layer on the reinforcing fiber layer to be the base material,
(B) a step of simultaneously heat-curing the resin of the reinforcing fiber layer and the glass fiber layer as the base material,
(C) a step of roughening the surface of the glass fiber reinforced plastic layer formed by curing the resin of the glass fiber layer;
(D) a step of spraying a predetermined thermal spray material on the surface of the roughened glass fiber reinforced plastic layer to form a lower thermal spray coating layer;
(E) a step of spraying a predetermined thermal spray material on the surface of the lower thermal spray coating layer to form an upper thermal spray coating layer so that the porosity is smaller than the porosity of the lower thermal spray coating layer;
A process for producing a wear-resistant, heat-resistant roll-shaped fiber-reinforced composite material comprising:   The method for producing a wear-resistant, heat-resistant roll-shaped fiber-reinforced composite material according to claim 10, wherein the reinforcing fibers of the reinforcing fiber layer serving as the base material are carbon fibers.   The manufacture of the wear-resistant and heat-resistant roll-shaped fiber-reinforced composite material according to claim 10 or 11, wherein the glass fiber is wound around the mandrel in the same angular direction in the step (a). Method. A method for producing a wear-resistant, heat-resistant roll-shaped fiber reinforced composite material,
(A) A prepreg to be a base material using a predetermined reinforcing fiber for forming the fiber reinforced plastic base material layer to be a roll base material is wound around a mandrel, and subsequently, on the prepreg to be the base material A step of winding and laminating a glass fiber prepreg for forming the glass fiber reinforced plastic layer,
(B) a step of simultaneously heat-curing the resin of the prepreg serving as the substrate and the glass fiber prepreg,
(C) a step of roughening the surface of the glass fiber reinforced plastic layer formed by curing the glass fiber prepreg;
(D) a step of spraying a predetermined thermal spray material on the surface of the roughened glass fiber reinforced plastic layer to form a lower thermal spray coating layer;
(E) a step of spraying a predetermined thermal spray material on the surface of the lower thermal spray coating layer to form an upper thermal spray coating layer so that the porosity is smaller than the porosity of the lower thermal spray coating layer;
A process for producing a wear-resistant, heat-resistant roll-shaped fiber-reinforced composite material comprising:   14. The method for producing a wear-resistant, heat-resistant roll-shaped fiber-reinforced composite material according to claim 13, wherein the reinforcing fibers of the prepreg serving as the base material are carbon fibers.   The glass fiber prepreg is a UD-shaped prepreg formed by aligning glass fibers in one direction or a glass cloth prepreg formed using a glass fiber fabric. Or 14. A method for producing a wear-resistant, heat-resistant roll-shaped fiber-reinforced composite material according to 14.   The surface of the glass fiber reinforced plastic layer in the step (c) is roughened to an average roughness Ra of 2 to 10 μm by blasting. The manufacturing method of the abrasion-resistant and heat-resistant roll-shaped fiber reinforced composite material as described in a term.   The porosity of the lower sprayed coating layer is 10% or more and 30% or less, and the porosity of the upper sprayed coating layer is 1% or more and less than 10%. The method for producing a wear-resistant, heat-resistant roll-shaped fiber-reinforced composite material according to any one of the items. 18. The thermal spray material for forming the lower thermal spray coating layer has a linear expansion coefficient of 3 × 10 ^{−6 to} 12 × 10 ⁻⁶ (1 / ° C.). The manufacturing method of the abrasion-resistant and heat-resistant roll-shaped fiber reinforced composite material as described in a term.   The wear resistant and heat resistant roll-like fiber reinforced composite according to any one of claims 10 to 18, wherein the lower sprayed coating layer has a coating thickness of 0.02 to 1.0 mm. A method of manufacturing the material.   The upper sprayed coating layer has a coating thickness of 0.03 to 1.0 mm, a Vickers hardness HV of 400 to 1200, and an average surface roughness Ra of 0.05 to 1.0 μm. The manufacturing method of the abrasion-proof and heat-resistant roll-shaped fiber reinforced composite material of any one of Claims 10-19.   The thermal spray material for forming the lower thermal spray coating layer and the upper thermal spray coating layer is a granular ceramic, a cermet metal, or a mixture thereof. A method for producing an abrasion- and heat-resistant roll-shaped fiber-reinforced composite material.

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