WO2014167658A1 - Metal-coated resin structure and method for producing same - Google Patents
Metal-coated resin structure and method for producing same Download PDFInfo
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- WO2014167658A1 WO2014167658A1 PCT/JP2013/060771 JP2013060771W WO2014167658A1 WO 2014167658 A1 WO2014167658 A1 WO 2014167658A1 JP 2013060771 W JP2013060771 W JP 2013060771W WO 2014167658 A1 WO2014167658 A1 WO 2014167658A1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C24/00—Coating starting from inorganic powder
- C23C24/02—Coating starting from inorganic powder by application of pressure only
- C23C24/04—Impact or kinetic deposition of particles
Definitions
- the present invention relates to a structure in which a resin is coated with a metal and a manufacturing method thereof.
- the windmill blade surface in wind power generation equipment is generally made of lightweight and high strength glass fiber reinforced plastic (hereinafter referred to as GFRP).
- GFRP is a glass fiber fabric impregnated with a resin, and is electrically insulating. Almost one third of the damage / failure factors of this windmill blade are due to lightning strikes.
- One of the measures to prevent lightning strikes is to ground the lightning current by coating the entire blade with metal to provide electrical conductivity.
- Patent Document 1 discloses a film forming method by a cold spray method. Here, the density of the powder deposition layer of the coating material is improved by irradiating the powder path from the spray nozzle to the substrate with laser light to heat the powder.
- the base material is a material mainly composed of an organic material such as a resin
- the base material when the particle heated to a high temperature by the laser beam collides with the base material, the base material depends on the temperature of the particle. There is a problem that the base material is worn out due to semi-melting and decomposition of the substrate.
- An object of the present invention is to form a metal film on a substrate with reduced wear.
- the metal-coated resin structure of the present invention includes a base material containing a filler containing a metal component and a resin, an intermediate layer containing the metal component contained in the filler and covering the base material, A metal film covering the intermediate layer, wherein the metal component is continuously distributed from the base material to the intermediate layer.
- a method of manufacturing a metal-coated resin structure includes a step of irradiating a base material including a filler containing a metal component and a resin, a step of accelerating a metal powder forming a metal film with a gas flow, and the laser And spraying the accelerated metal powder onto the surface of the base material irradiated with the material.
- the metal-coated resin structure manufacturing apparatus includes a laser head that irradiates a base with a laser, and a spray nozzle that sprays metal powder accelerated by a gas flow onto the surface of the base that has been irradiated with the laser. It is characterized by providing.
- a metal film can be formed on a substrate with reduced wear.
- Sectional drawing of the structure concerning this invention Sectional drawing showing the manufacturing method of the structure concerning this invention.
- the metal-coated resin structure of the present invention provides conductivity by covering the surface of a base material mainly composed of an organic material with a metal film.
- Grounding can prevent damage from lightning. It can also be an effective preventive measure against ultraviolet deterioration, which is one of the main causes of organic material deterioration.
- a filler containing a metal component is mixed with the base material, an intermediate layer mainly containing the metal component is provided between the base material and the metal film, and the metal component of the intermediate layer is the filler contained in the base material. It is a metal component.
- the metal component contained in the filler continuously exists from the base material to the intermediate layer, and the base material has a structure in which the metal component contained in both the base material and the intermediate layer is bonded metallurgically. And the intermediate layer can be firmly bonded.
- the composition of the metal component from the surface layer to the intermediate layer of the substrate is inclined.
- middle layer has the structure
- coat can also be couple
- the base material includes at least a resin and a filler, and may further include a curing agent, a catalyst, glass fiber, carbon fiber, and the like.
- the filler contains a metal component, and for example, SiO 2 , TiO 2 , Sb 2 O 3 and the like are suitable. In the present invention, Si is also classified as a metal.
- the intermediate layer mainly contains a metal component contained in the filler, and the metal film contains a typical metal having an atomic number of 12 or more and a melting point of 420 ° C. or more, a transition metal, or an alloy thereof.
- the structure of the metal-coated resin structure is formed by the production method of the present invention described later, and a layer (intermediate layer) mainly composed of metal components, that is, Si, Ti, Sb, etc. is generated from the filler in the substrate. And covering the resin substrate surface. Since this intermediate layer is harder than the resin base material, it is possible to prevent the base material from being worn even when the metal powder collides at high speed when forming the metal film, while maintaining the soundness of the base material. It promotes adhesion and deposition of metal powder, that is, formation of a film.
- the metal powder is deposited in a flat shape by colliding with the substrate at a high speed, and the intermediate layer and the metal film are not only metallurgically bonded but also mechanically bonded.
- the metal film can be densely and firmly bonded even in the in-plane direction.
- the proportion of the metal component in the intermediate layer is preferably about 70% by volume or more. Thereby, a strong film can be formed while preventing the wear of the substrate due to metal powder collision.
- the base material and the intermediate film are first firmly bonded, and the intermediate layer and the metal film are firmly bonded, so that the base material and the metal film are bonded. Can be indirectly and firmly bonded.
- the amount of oxygen contained in the metal film is preferably 2500 ppm or less. When the amount of oxygen is larger than this, the surface oxidation of the metal particles constituting the metal film is large, the bonding between the particles becomes weak, the film becomes brittle and causes breakage, and corrosion tends to progress.
- the thickness of the metal film and the intermediate layer is preferably 150 ⁇ m or more. If the film is thinner than this, the film will be easily peeled off due to deformation of the resin base material in the usage environment, and if the intermediate layer is thinner than this, the effect of preventing the wear of the base material when forming the above film Decreases.
- the manufacturing method of the metal-coated resin structure is to first irradiate the surface of the substrate with laser.
- a microwave or an electron beam may be used.
- the filler contained in the surface layer of the substrate is decomposed and the organic component is volatilized, and the metal component contained in the filler is exposed to the surface layer to form an intermediate layer.
- the metal component is contained in both the base material and the intermediate layer, the metal component is continuously distributed from the base material to the intermediate layer. It bonds firmly and allows metal coating through the intermediate layer.
- the metal powder constituting the metal film is accelerated by a high-speed gas flow and collides with the intermediate layer to be deposited.
- This can be realized by a technique called cold spray or kinetic spray.
- Cold spray is a method in which powder particles are plastically deformed and deposited and deposited on a substrate by colliding the particles with a substrate at high speed using an ultra-high-speed carrier gas. Even when sprayed directly onto the resulting substrate, it does not deposit and a metal film cannot be obtained. This is because when hard metal particles collide with the base material compared to the organic material, the base material is scraped off and worn out. Therefore, as described above, when the surface of the substrate is irradiated with a laser, the surface of the substrate is covered with a relatively hard metal-rich layer, thereby suppressing the wear of the substrate and forming a coating.
- the continuous construction of the above process is an apparatus comprising a laser head for irradiating a laser to a substrate and a spray nozzle for accelerating and spraying metal powder with a high-speed gas flow onto the surface irradiated with the laser
- the laser is irradiated above the base material so that the laser head scans and moves on the same track before the spray nozzle.
- the metal powder can be accurately injected at the position.
- the metal-coated resin structure can also be obtained by moving the substrate side instead of the laser head and the spray nozzle. That is, what is necessary is just to inject a metal powder after irradiating a laser to a board
- Metal-coated resin structures are used for lightweight and conductive structures such as wind turbine blades for wind power generation, aircraft bodies, and automobile bodies, and for members that require lightweight and corrosion resistance, such as automobile fuel tanks. By doing so, those functions are effectively exhibited. Moreover, it becomes possible to provide abrasion resistance to machine parts, such as resin gears, for example, by using a metal having excellent abrasion resistance as a coating.
- FIG. 1 A structure having the cross-sectional structure in FIG. 1 in which the surface of the epoxy resin was coated with Al or Cu under the conditions shown in Table 1 was manufactured.
- 1 is a base material mainly composed of an organic material
- 2 is an intermediate layer mainly composed of a metal component contained in the organic material
- 3 is a metal film.
- No. 1 and No. 2 are comparative examples
- No. 3 to No. 8 are examples according to the present invention.
- FIG. 2 Schematic diagram of the structure manufacturing method is shown in FIG.
- 4 is a laser
- 5 is a metal powder as a raw material for the metal film 3.
- the method of forming the intermediate layer is as follows.
- the surface of the epoxy resin substrate 1 (diameter 40 mm ⁇ thickness 5 to 10 mm) containing a filler, a curing agent, etc. was irradiated with a laser beam (Yb fiber laser) 4 while scanning under the conditions shown in Table 1.
- Yb fiber laser Yb fiber laser
- FIG. 3A is a scanning electron micrograph of a cross section
- FIG. 3B is a distribution of Si in FIG. 3A obtained by an energy dispersive X-ray analyzer.
- the metal component content and thickness of the intermediate layer 2 shown in Table 1 are representative values obtained from fluorescent X-ray analysis and cross-sectional structure, respectively.
- Sample Nos. 1 and 2 were samples in which the intermediate layer 2 was not formed as a comparative example.
- the metal powder 5 used as a raw material was an Al or Cu spherical powder having a particle size of 20 to 45 ⁇ m. Compressed air of 0.6 MPa was used as the carrier gas, and the injection distance shown in Table 1 (distance from the tip of the cold spray nozzle to the film forming surface) and the carrier gas temperature, No. 1 and 2 were applied to the substrate 1, In No. 3 to No. 8, the metal powder 5 was injected into the intermediate layer 2 almost vertically for 4 passes (4 times). In this way, a structure in which the resin base material 1 is coated with the metal film 3 is obtained by the method shown in FIG.
- the thickness and oxygen amount of the metal film 3 shown in Table 1 are representative values obtained by a cross-sectional structure and an infrared absorption method, respectively.
- Comparative Example No. 1 did not form the intermediate layer 2, so that the surface of the resin base material 1 was worn out by the collision of the metal powder 5, and the metal film 3 could not be formed. Therefore, in No. 2, the temperature of the carrier gas was increased to 200 ° C. to try to form the metal film 3, but the wear of the base material 1 was further increased, and similarly, the metal film 3 could not be formed.
- Table 2 shows the results of evaluating the electrical conductivity and corrosion depth of Sample Nos. 3 to 8 from which the metal film 3 was obtained.
- the electrical conductivity (IACS%) is a relative value expressed by assuming that the electrical conductivity of annealed pure copper is 100%, and the corrosion depth is the maximum value obtained from the cross-sectional structure after spraying 5% salt water for 24 hours.
- the intermediate layer 2 is sufficiently thick, so even if the metal powder 5 collides, the intermediate layer 2 is hardly destroyed and a sufficiently thick metal Film 3 could be formed. Therefore, the denseness of the metal film 3 was high, and the corrosion depth could be reduced. And since the electrical conductivity of the metal film 3 also shows a relatively high value, it is considered that the progress of corrosion is suppressed by the formation of the dense metal film 3.
- the substrate 1 mainly composed of a resin containing a filler is irradiated with a laser 4 or the like, a relatively hard intermediate layer 2 mainly composed of a metal component is formed, and the metal powder 5 is sprayed thereon at a high speed.
- the base material 1 can be coated with the metal film 3 excellent in conductivity and corrosion resistance without being damaged.
- the same intermediate layer 2 can be formed even if the filler contained in the substrate 1 is Sb 2 O 3 , Al (OH) 3 or the like containing a metal component.
- the intermediate layer 2 and the metal film 3 can be formed by the same method.
- the metal film 3 may be another transition metal, and the film can be made of a low melting point glass by the same method.
- sample Nos. 3 to 8 can be continuously manufactured using the apparatus shown in FIG. In FIG. 4, 6 is a spray nozzle and 7 is a laser head.
- Trial manufacture of No.4-9 structures by prototyping a device in which the spray nozzle 6 moves on the same track at the same scanning speed in advance of the laser head 7 by controlling both the nozzle and the head in cooperation. It was. As a result, it was confirmed that structures substantially equivalent to the structure and film characteristics shown in Tables 1 and 2 were obtained, and that these structures could be manufactured almost continuously by the manufacturing apparatus according to the present invention. The same effect can be obtained by integrating or connecting the spray nozzle 6 and the laser head 7.
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Abstract
A metal-coated resin structure including: a base material containing a resin and a filler, the filler containing a metal component; an intermediate layer containing the metal component contained in the filler, and covering the base material; and a metal coating covering the intermediate layer. The metal component is continuously distributed from the base material to the intermediate layer. A method for manufacturing a metal-coated resin structure, having: a step for irradiating a base material containing a resin and a filler containing a metal component with laser; a step for using a gas flow to cause metal particles for forming a metal coating to accelerate; and a step for spraying the accelerated metal particles onto the surface of the base material irradiated with the laser, and causing the metal particles to adhere and accumulate. A device for manufacturing a metal-coated resin structure, provided with a laser head for irradiating a base material with laser, and a spray nozzle for spraying metal particles accelerated by a gas flow onto the surface of the base material irradiated with the laser.
Description
本発明は、樹脂が金属で被覆された構造体とその製法に関する。
The present invention relates to a structure in which a resin is coated with a metal and a manufacturing method thereof.
風力発電設備における風車のブレード表面は、一般に軽量で強度の高いガラス繊維強化プラスチック(Glass-Fiber Reinforced Plastics;以下、GFRP)からなっている。GFRPはガラス繊維繊布に樹脂を含浸したもので、電気的に絶縁性を有する。この風車ブレードの破損・故障要因のほぼ1/3は落雷によるもので、落雷防止策の一つとして、ブレード全面に金属を被覆して導電性をもたせ、落雷電流をアースする方法があり、例えば特許文献１には、コールドスプレー法による皮膜形成方法が開示されている。ここでは、スプレーノズルから基材に至る粉末の経路にレーザ光を照射して粉末を加熱することにより、皮膜材料の粉末堆積層の密度を向上させている。
The windmill blade surface in wind power generation equipment is generally made of lightweight and high strength glass fiber reinforced plastic (hereinafter referred to as GFRP). GFRP is a glass fiber fabric impregnated with a resin, and is electrically insulating. Almost one third of the damage / failure factors of this windmill blade are due to lightning strikes.One of the measures to prevent lightning strikes is to ground the lightning current by coating the entire blade with metal to provide electrical conductivity. Patent Document 1 discloses a film forming method by a cold spray method. Here, the density of the powder deposition layer of the coating material is improved by irradiating the powder path from the spray nozzle to the substrate with laser light to heat the powder.
しかし、上記特許文献のものでは、基材が樹脂のような有機材料を主成分とする材質の場合、レーザ光により高温に加熱された粒子が基材に衝突すると、粒子の温度によっては基材の半溶融や分解が生じて、基材が損耗するという課題がある。
However, in the above-mentioned patent document, when the base material is a material mainly composed of an organic material such as a resin, when the particle heated to a high temperature by the laser beam collides with the base material, the base material depends on the temperature of the particle. There is a problem that the base material is worn out due to semi-melting and decomposition of the substrate.
本発明の目的は、損耗が低減された基材上に金属皮膜を形成することにある。
An object of the present invention is to form a metal film on a substrate with reduced wear.
上記目的を達成するため、本発明の金属被覆樹脂構造体は、金属成分を含むフィラーと樹脂とを含む基材と、前記フィラーに含まれる前記金属成分を含み前記基材を覆う中間層と、前記中間層を覆う金属皮膜とを有し、前記金属成分が前記基材から前記中間層にかけて連続的に分布することを特徴とする。
In order to achieve the above object, the metal-coated resin structure of the present invention includes a base material containing a filler containing a metal component and a resin, an intermediate layer containing the metal component contained in the filler and covering the base material, A metal film covering the intermediate layer, wherein the metal component is continuously distributed from the base material to the intermediate layer.
また、金属被覆樹脂構造体の製造方法は、金属成分を含むフィラーと樹脂とを含む基材にレーザを照射する工程と、金属皮膜を形成する金属粉末をガス流で加速する工程と、前記レーザが照射された前記基材の面に加速された前記金属粉末を噴射して付着堆積させる工程とを有することを特徴とする。
In addition, a method of manufacturing a metal-coated resin structure includes a step of irradiating a base material including a filler containing a metal component and a resin, a step of accelerating a metal powder forming a metal film with a gas flow, and the laser And spraying the accelerated metal powder onto the surface of the base material irradiated with the material.
また、金属被覆樹脂構造体の製造装置は、基材にレーザを照射するレーザヘッドと、前記レーザが照射された前記基材の面にガス流で加速された金属粉末を噴射するスプレーノズルとを備えることを特徴とする。
The metal-coated resin structure manufacturing apparatus includes a laser head that irradiates a base with a laser, and a spray nozzle that sprays metal powder accelerated by a gas flow onto the surface of the base that has been irradiated with the laser. It is characterized by providing.
本発明によれば、損耗が低減された基材上に金属皮膜を形成することができる。
According to the present invention, a metal film can be formed on a substrate with reduced wear.
本発明の金属被覆樹脂構造体は、有機材料を主成分とする基材の表面を金属皮膜が覆うことにより導電性を付与するもので、風車ブレードや航空機体等に用いた場合、金属皮膜からアース(接地)をとることで落雷による損傷を防ぐことができる。また、有機材料劣化のおもな要因の一つである紫外線劣化に対しても有効な防止策となり得る。
The metal-coated resin structure of the present invention provides conductivity by covering the surface of a base material mainly composed of an organic material with a metal film. When used for a windmill blade, an aircraft body, etc., Grounding can prevent damage from lightning. It can also be an effective preventive measure against ultraviolet deterioration, which is one of the main causes of organic material deterioration.
本発明では、基材に金属成分を含むフィラーを混合し、基材と金属皮膜との間に金属成分を主に含む中間層を設け、中間層の金属成分が、基材に含まれるフィラーの金属成分であることを特徴とする。これにより、基材から中間層に渡ってフィラーに含まれる金属成分が連続的に存在し、基材と中間層の両方に含まれる金属成分が冶金的に結合した組織を有することにより、基材と中間層は強固に結合することができる。特に基材の表層から中間層にかけての金属成分の組成が傾斜している。そして、中間層に存在する金属成分が、金属皮膜を形成する金属粉末とも冶金的に結合した組織を有することで、中間層と金属皮膜も強固に結合することができる。
In the present invention, a filler containing a metal component is mixed with the base material, an intermediate layer mainly containing the metal component is provided between the base material and the metal film, and the metal component of the intermediate layer is the filler contained in the base material. It is a metal component. Thereby, the metal component contained in the filler continuously exists from the base material to the intermediate layer, and the base material has a structure in which the metal component contained in both the base material and the intermediate layer is bonded metallurgically. And the intermediate layer can be firmly bonded. In particular, the composition of the metal component from the surface layer to the intermediate layer of the substrate is inclined. And since the metal component which exists in an intermediate | middle layer has the structure | tissue couple | bonded metallurgically with the metal powder which forms a metal membrane | film | coat, an intermediate | middle layer and a metal membrane | film | coat can also be couple | bonded firmly.
基材は樹脂とフィラーを少なくとも含み、硬化剤、触媒、ガラス繊維、炭素繊維等を更に含んでもよい。フィラーには金属成分が含まれ、たとえばSiO2、TiO2、Sb2O3等が好適である。本発明ではSiも金属に分類する。中間層はフィラーに含まれる金属成分を主に含むものであり、金属皮膜は原子番号が12以上で融点が420℃以上の典型金属、遷移金属、またはそれらの合金が含まれる。
The base material includes at least a resin and a filler, and may further include a curing agent, a catalyst, glass fiber, carbon fiber, and the like. The filler contains a metal component, and for example, SiO 2 , TiO 2 , Sb 2 O 3 and the like are suitable. In the present invention, Si is also classified as a metal. The intermediate layer mainly contains a metal component contained in the filler, and the metal film contains a typical metal having an atomic number of 12 or more and a melting point of 420 ° C. or more, a transition metal, or an alloy thereof.
金属被覆樹脂構造体の構造は、後述する本発明の製法により形成されるものであり、基材中のフィラーから金属成分、すなわちSi、Ti、Sb等を主体とした層（中間層）が生成し、樹脂基材表面を覆う。この中間層は樹脂基材に比べて硬質なため、金属皮膜を構成する際に金属粉末が高速で衝突しても基材の損耗を防止することができ、基材の健全性を維持しながら金属粉末の付着・堆積、すなわち皮膜の形成を助長する。金属粉末は高速で基材に衝突することで扁平形状として堆積し、中間層と金属皮膜とは冶金的な結合だけでなく、機械的な結合も生じる。金属皮膜を形成する金属粉末同士も冶金的・機械的に結合するため、金属皮膜は面内方向においても、緻密で強固に結合することができる。この中間層における金属成分の占める割合は、望ましくは概ね70体積％以上が良い。これにより、金属粉末衝突による基材の損耗を防ぎながら強固な皮膜を形成することができる。
The structure of the metal-coated resin structure is formed by the production method of the present invention described later, and a layer (intermediate layer) mainly composed of metal components, that is, Si, Ti, Sb, etc. is generated from the filler in the substrate. And covering the resin substrate surface. Since this intermediate layer is harder than the resin base material, it is possible to prevent the base material from being worn even when the metal powder collides at high speed when forming the metal film, while maintaining the soundness of the base material. It promotes adhesion and deposition of metal powder, that is, formation of a film. The metal powder is deposited in a flat shape by colliding with the substrate at a high speed, and the intermediate layer and the metal film are not only metallurgically bonded but also mechanically bonded. Since the metal powders forming the metal film are also metallurgically and mechanically bonded, the metal film can be densely and firmly bonded even in the in-plane direction. The proportion of the metal component in the intermediate layer is preferably about 70% by volume or more. Thereby, a strong film can be formed while preventing the wear of the substrate due to metal powder collision.
有機材料と金属材料との間では冶金的あるいは化学的結合が生じないため、樹脂のような有機材料を主成分とする基材の表面に金属を直接被覆することは困難であるが、上記のように基材と金属皮膜との間に中間層を設けることで、まず基材と中間層とが強固に結合し、中間層と金属皮膜とが強固に結合することで、基材と金属皮膜とを間接的に強固に結合することができる。
Since metallurgical or chemical bonding does not occur between the organic material and the metal material, it is difficult to directly coat the metal on the surface of the base material mainly composed of an organic material such as a resin. Thus, by providing an intermediate layer between the base material and the metal film, the base material and the intermediate film are first firmly bonded, and the intermediate layer and the metal film are firmly bonded, so that the base material and the metal film are bonded. Can be indirectly and firmly bonded.
金属皮膜に含まれる酸素量は2500ppm以下が望ましい。酸素量がこれより多いと、金属皮膜を構成する金属粒子の表面酸化が大きく、粒子間の結合が弱くなり、皮膜が脆化して破壊を招くとともに、腐食が進展しやすくなる。また、金属皮膜および中間層の厚さは、いずれも150μm以上であることが好ましい。皮膜がこれより薄いと、使用環境下における樹脂基材の反り等の変形に伴い、皮膜が剥離しやすくなり、中間層がこれより薄いと、上記の皮膜形成時における基材の損耗を防ぐ効果が低下する。
The amount of oxygen contained in the metal film is preferably 2500 ppm or less. When the amount of oxygen is larger than this, the surface oxidation of the metal particles constituting the metal film is large, the bonding between the particles becomes weak, the film becomes brittle and causes breakage, and corrosion tends to progress. The thickness of the metal film and the intermediate layer is preferably 150 μm or more. If the film is thinner than this, the film will be easily peeled off due to deformation of the resin base material in the usage environment, and if the intermediate layer is thinner than this, the effect of preventing the wear of the base material when forming the above film Decreases.
金属被覆樹脂構造体の製法は、まず、基材の表面にレーザを照射するものである。レーザの他にマイクロ波や電子ビームでもよい。この急速加熱により、基材の表層に含まれるフィラーが分解するとともに有機成分が揮散し、フィラーに含まれる金属成分が表層に露出して中間層を形成する。これにより、金属成分は基材と中間層の両方に含まれることになるため、基材から中間層に渡って連続的に金属成分が分布し、前述のように基材と中間層が比較的強固に結合するとともに、中間層を介した金属被覆を可能にする。
The manufacturing method of the metal-coated resin structure is to first irradiate the surface of the substrate with laser. In addition to the laser, a microwave or an electron beam may be used. By this rapid heating, the filler contained in the surface layer of the substrate is decomposed and the organic component is volatilized, and the metal component contained in the filler is exposed to the surface layer to form an intermediate layer. As a result, since the metal component is contained in both the base material and the intermediate layer, the metal component is continuously distributed from the base material to the intermediate layer. It bonds firmly and allows metal coating through the intermediate layer.
また、中間層を形成した後、金属皮膜を構成する金属の粉末を高速ガス流で加速し、中間層に衝突させて付着堆積させるものである。これは、コールドスプレーやキネティックスプレー等と呼ばれる手法により実現できる。コールドスプレーは、粉末粒子を超高速のキャリアガスを用いて基材に高速で衝突させることにより、粒子を塑性変形させて基材上に付着・堆積させるものであるが、金属粉末を有機材料からなる基材に直接噴射しても堆積せず、金属皮膜は得られない。なぜならば、有機材料に比べて硬質な金属粒子が基材に衝突すると、基材を削り落して損耗させるためである。そこで上記のように、基材表面に対してレーザを照射すると、基材表面が比較的硬質の金属リッチ層で覆われ、基材の損耗を抑制し、皮膜の形成を可能にする。
Also, after the intermediate layer is formed, the metal powder constituting the metal film is accelerated by a high-speed gas flow and collides with the intermediate layer to be deposited. This can be realized by a technique called cold spray or kinetic spray. Cold spray is a method in which powder particles are plastically deformed and deposited and deposited on a substrate by colliding the particles with a substrate at high speed using an ultra-high-speed carrier gas. Even when sprayed directly onto the resulting substrate, it does not deposit and a metal film cannot be obtained. This is because when hard metal particles collide with the base material compared to the organic material, the base material is scraped off and worn out. Therefore, as described above, when the surface of the substrate is irradiated with a laser, the surface of the substrate is covered with a relatively hard metal-rich layer, thereby suppressing the wear of the substrate and forming a coating.
上記プロセスの連続的な施工は、基材にレーザを照射するためのレーザヘッドと、レーザが照射された面に金属粉末を高速ガス流で加速して噴射するためのスプレーノズルとを備えた装置を用いることによって可能となる。レーザヘッドとスプレーノズルを連結または一体化あるいは連携制御することにより、基材の上方において、スプレーノズルよりもレーザヘッドが先行して同一軌道上を走査移動する機構とすれば、レーザが照射された位置に的確に金属粉末を噴射することができる。レーザヘッドとスプレーノズルではなく、基板側が動くことでも金属被覆樹脂構造体は得ることができる。即ち、基板にレーザを照射してから金属粉末を噴射するものであればよい。このプロセスが連続的に行われることにより、上記の金属被覆樹脂構造体が連続して得られ、量産が可能になる。
The continuous construction of the above process is an apparatus comprising a laser head for irradiating a laser to a substrate and a spray nozzle for accelerating and spraying metal powder with a high-speed gas flow onto the surface irradiated with the laser This is possible by using. By connecting, integrating, or controlling the laser head and the spray nozzle together, the laser is irradiated above the base material so that the laser head scans and moves on the same track before the spray nozzle. The metal powder can be accurately injected at the position. The metal-coated resin structure can also be obtained by moving the substrate side instead of the laser head and the spray nozzle. That is, what is necessary is just to inject a metal powder after irradiating a laser to a board | substrate. By performing this process continuously, the above metal-coated resin structure can be obtained continuously and mass production becomes possible.
金属被覆樹脂構造体は、風力発電用風車ブレード、航空機の機体、自動車の車体等の軽量かつ導電性を有することが望ましい構造物や、自動車燃料タンク等の軽量かつ耐食性を必要とする部材に用いることで、それらの機能を有効に発揮する。また、耐摩耗性に優れた金属を皮膜とすることで、例えば樹脂製歯車等の機械部品に耐摩耗性を付与することも可能になる。
Metal-coated resin structures are used for lightweight and conductive structures such as wind turbine blades for wind power generation, aircraft bodies, and automobile bodies, and for members that require lightweight and corrosion resistance, such as automobile fuel tanks. By doing so, those functions are effectively exhibited. Moreover, it becomes possible to provide abrasion resistance to machine parts, such as resin gears, for example, by using a metal having excellent abrasion resistance as a coating.
以下、発明を実施するための形態を実施例によって詳細に説明するが、本発明はこれらの実施例に限定されるものではない。
Hereinafter, modes for carrying out the invention will be described in detail by way of examples, but the present invention is not limited to these examples.
表1に示す条件で、エポキシ樹脂の表面をAlまたはCuで被覆した図1の断面構造を有する構造体を試作した。図1において、１は有機材料を主成分とする基材、2は有機材料に含まれる金属成分を主体とする中間層、3は金属皮膜である。また、表1において、No.1、No.2は比較例、No.3～No.8は本発明に係る実施例である。
A structure having the cross-sectional structure in FIG. 1 in which the surface of the epoxy resin was coated with Al or Cu under the conditions shown in Table 1 was manufactured. In FIG. 1, 1 is a base material mainly composed of an organic material, 2 is an intermediate layer mainly composed of a metal component contained in the organic material, and 3 is a metal film. In Table 1, No. 1 and No. 2 are comparative examples, and No. 3 to No. 8 are examples according to the present invention.
構造体の製造方法の模式図を、図2に示す。図2において、4はレーザ、5は金属皮膜3の原料となる金属粉末である。まず、中間層の形成方法は次のとおりである．フィラーや硬化剤等を含むエポキシ樹脂製の基材1(直径40mm×厚さ5～10mm)の表面に対し、レーザ線(Ybファイバレーザ)4を表1に示す条件で走査しながら照射した。これにより樹脂表層に存在するフィラーは分解し、基材1の表面にフィラーの金属成分を主体とする中間層2が形成される。図3は、中間層2を形成した後の断面組織の例として、表1中の試料No.5の断面を示す。図3の(a)は断面の走査電子顕微鏡写真、(b)はエネルギー分散型X線分析装置で求めた(a)におけるSiの分布である。このように、レーザ4を照射することにより、樹脂基材1の表面に比較的硬質な金属リッチの中間層2を形成することができる。なお、表1に示した中間層2の金属成分含有量および厚さは、それぞれ蛍光X線分析および断面組織から求めた代表値である。また、試料No.1および2は、比較例として中間層2を形成しなかったものである。
Schematic diagram of the structure manufacturing method is shown in FIG. In FIG. 2, 4 is a laser, and 5 is a metal powder as a raw material for the metal film 3. First, the method of forming the intermediate layer is as follows. The surface of the epoxy resin substrate 1 (diameter 40 mm × thickness 5 to 10 mm) containing a filler, a curing agent, etc. was irradiated with a laser beam (Yb fiber laser) 4 while scanning under the conditions shown in Table 1. As a result, the filler present in the resin surface layer is decomposed, and the intermediate layer 2 mainly composed of the metal component of the filler is formed on the surface of the substrate 1. FIG. 3 shows a cross section of Sample No. 5 in Table 1 as an example of the cross-sectional structure after forming the intermediate layer 2. 3A is a scanning electron micrograph of a cross section, and FIG. 3B is a distribution of Si in FIG. 3A obtained by an energy dispersive X-ray analyzer. Thus, by irradiating the laser 4, the relatively hard metal-rich intermediate layer 2 can be formed on the surface of the resin substrate 1. The metal component content and thickness of the intermediate layer 2 shown in Table 1 are representative values obtained from fluorescent X-ray analysis and cross-sectional structure, respectively. Sample Nos. 1 and 2 were samples in which the intermediate layer 2 was not formed as a comparative example.
次に、金属皮膜の形成方法を以下に示す．原料となる金属粉末5には、粒径が20～45μmのAlあるいはCuの球形粉を用いた。キャリアガスには0.6MPaの圧縮空気を用い、表1に示す噴射距離(コールドスプレー用ノズルの先端から皮膜形成面までの距離)およびキャリアガス温度で、No.1および2は基材1に、No.3からNo.8は中間層2に対して金属粉末5をほぼ垂直に4パス(4回重ねて)噴射した。このように、図2に示す方法により、金属皮膜3で樹脂基材1を被覆した構造体が得られる。なお、表1に示した金属皮膜3の厚さおよび酸素量は、それぞれ断面組織および赤外線吸収法により求めた代表値である。
Next, the method of forming the metal film is shown below. The metal powder 5 used as a raw material was an Al or Cu spherical powder having a particle size of 20 to 45 μm. Compressed air of 0.6 MPa was used as the carrier gas, and the injection distance shown in Table 1 (distance from the tip of the cold spray nozzle to the film forming surface) and the carrier gas temperature, No. 1 and 2 were applied to the substrate 1, In No. 3 to No. 8, the metal powder 5 was injected into the intermediate layer 2 almost vertically for 4 passes (4 times). In this way, a structure in which the resin base material 1 is coated with the metal film 3 is obtained by the method shown in FIG. The thickness and oxygen amount of the metal film 3 shown in Table 1 are representative values obtained by a cross-sectional structure and an infrared absorption method, respectively.
得られた構造体のうち、比較例No.1は中間層2を形成していないため、金属粉末5の衝突によって樹脂基材1の表面が損耗し、金属皮膜3は形成できなかった。そこでNo.2では、キャリアガスの温度を200℃に高めて金属皮膜3の形成を試みたが、基材1の損耗はさらに大きくなり、同様に金属皮膜3の形成はできなかった。
Among the obtained structures, Comparative Example No. 1 did not form the intermediate layer 2, so that the surface of the resin base material 1 was worn out by the collision of the metal powder 5, and the metal film 3 could not be formed. Therefore, in No. 2, the temperature of the carrier gas was increased to 200 ° C. to try to form the metal film 3, but the wear of the base material 1 was further increased, and similarly, the metal film 3 could not be formed.
金属皮膜3が得られた試料No.3～8について、更に導電率と腐食深さを評価した結果を表2に示す。表2において、導電率(IACS%)は焼きなまし純銅の導電率を100％として表した相対値、腐食深さは5％塩水を24時間噴霧した後の断面組織から求めた最大値である。No.3,4に対してNo.5～8の構造体では、中間層2が十分厚いために、金属粉末5が衝突しても中間層2はほとんど破壊されず、十分な厚さの金属皮膜3を形成できた。従って金属皮膜3の緻密性も高く、腐食深さを低減することができた。そして、金属皮膜3の導電率も比較的高い値を示していることから、緻密な金属皮膜3が形成されたことにより腐食の進展が抑制されたものと思われる。
Table 2 shows the results of evaluating the electrical conductivity and corrosion depth of Sample Nos. 3 to 8 from which the metal film 3 was obtained. In Table 2, the electrical conductivity (IACS%) is a relative value expressed by assuming that the electrical conductivity of annealed pure copper is 100%, and the corrosion depth is the maximum value obtained from the cross-sectional structure after spraying 5% salt water for 24 hours. In the structures Nos. 5 to 8 compared to Nos. 3 and 4, the intermediate layer 2 is sufficiently thick, so even if the metal powder 5 collides, the intermediate layer 2 is hardly destroyed and a sufficiently thick metal Film 3 could be formed. Therefore, the denseness of the metal film 3 was high, and the corrosion depth could be reduced. And since the electrical conductivity of the metal film 3 also shows a relatively high value, it is considered that the progress of corrosion is suppressed by the formation of the dense metal film 3.
このように、フィラーを含む樹脂を主体とする基材1にレーザ等4を照射すると、金属成分を主体とする比較的硬質な中間層2が形成され、そこに金属粉末5を高速で噴射し、堆積させることにより、基材1を損傷させることなく導電性および耐食性に優れた金属皮膜3で被覆することが可能となる。なお、基材1に含まれるフィラーは金属成分を含むSb2O3、Al(OH)3等でも同様の中間層2を形成することができ、基材1が熱可塑性樹脂のほか、最表面が樹脂で覆われているGFRPや炭素繊維強化プラスチック(Carbon-Fiber Reinforced Plastics)等の場合においても、同様の方法で中間層2および金属皮膜3の形成が可能である。また、金属皮膜3は他の遷移金属でもよく、さらには皮膜を低融点ガラスとすることも同様の方法で可能である。
In this way, when the substrate 1 mainly composed of a resin containing a filler is irradiated with a laser 4 or the like, a relatively hard intermediate layer 2 mainly composed of a metal component is formed, and the metal powder 5 is sprayed thereon at a high speed. By depositing, the base material 1 can be coated with the metal film 3 excellent in conductivity and corrosion resistance without being damaged. In addition, the same intermediate layer 2 can be formed even if the filler contained in the substrate 1 is Sb 2 O 3 , Al (OH) 3 or the like containing a metal component. In the case of GFRP or carbon-fiber reinforced plastics covered with resin, the intermediate layer 2 and the metal film 3 can be formed by the same method. Further, the metal film 3 may be another transition metal, and the film can be made of a low melting point glass by the same method.
試料No.3～8の構造体は、図4に示す装置を用いて連続的に製造することも可能である。図4において、6はスプレーノズル、7はレーザヘッドである。ノズルとヘッドの両者を連携制御して、スプレーノズル6がレーザヘッド7よりも先行して同一軌道上を同じ走査速度で移動する装置を試作し、No.4～9の構造体の作製を試みた。その結果、いずれも表1および2に示した構造・皮膜特性とほぼ同等の構造体が得られ、本発明に係る製造装置によってこれらの構造体がほぼ連続的に製造できることを確認した。なお、スプレーノズル6とレーザヘッド7とを一体化させるか連結させる方法によっても、同様の効果が得られる。
The structures of sample Nos. 3 to 8 can be continuously manufactured using the apparatus shown in FIG. In FIG. 4, 6 is a spray nozzle and 7 is a laser head. Trial manufacture of No.4-9 structures by prototyping a device in which the spray nozzle 6 moves on the same track at the same scanning speed in advance of the laser head 7 by controlling both the nozzle and the head in cooperation. It was. As a result, it was confirmed that structures substantially equivalent to the structure and film characteristics shown in Tables 1 and 2 were obtained, and that these structures could be manufactured almost continuously by the manufacturing apparatus according to the present invention. The same effect can be obtained by integrating or connecting the spray nozzle 6 and the laser head 7.
1…基材、2…中間層、3…金属皮膜、4…レーザ、5…金属粉末、6…スプレーノズル、7…レーザヘッド。
1 ... substrate, 2 ... intermediate layer, 3 ... metal film, 4 ... laser, 5 ... metal powder, 6 ... spray nozzle, 7 ... laser head.
Claims (8)
- 金属成分を含むフィラーと樹脂とを含む基材と、前記フィラーに含まれる前記金属成分を含み前記基材を覆う中間層と、前記中間層を覆う金属皮膜とを有し、前記金属成分が前記基材から前記中間層にかけて連続的に分布することを特徴とする金属被覆樹脂構造体。 A base material containing a filler containing a metal component and a resin, an intermediate layer containing the metal component contained in the filler and covering the base material, and a metal film covering the intermediate layer, wherein the metal component is the A metal-coated resin structure which is continuously distributed from a base material to the intermediate layer.
- 前記基材中の前記金属成分と、前記中間層中の前記金属成分とが、冶金的に結合した組織を有することを特徴とする請求項1に記載の金属被覆樹脂構造体。 2. The metal-coated resin structure according to claim 1, wherein the metal component in the base material and the metal component in the intermediate layer have a metallurgically bonded structure.
- 前記金属皮膜と、前記中間層とが、冶金的または機械的に結合した組織を有することを特徴とする請求項1に記載の金属被覆樹脂構造体。 2. The metal-coated resin structure according to claim 1, wherein the metal film and the intermediate layer have a metallurgical or mechanically bonded structure.
- 前記基材は、硬化剤、触媒、ガラス繊維、炭素繊維の少なくとも1種を含み、前記金属皮膜は、原子番号が12以上で融点が420℃以上の典型金属、遷移金属、またはそれらの合金を含むことを特徴とする請求項1に記載の金属被覆樹脂構造体。 The base material includes at least one of a curing agent, a catalyst, glass fiber, and carbon fiber, and the metal film includes a typical metal having a atomic number of 12 or more and a melting point of 420 ° C. or more, a transition metal, or an alloy thereof. 2. The metal-coated resin structure according to claim 1, further comprising:
- 前記金属皮膜の酸素含有量は2500ppm以下で、前記金属皮膜および前記中間層の厚さはいずれも150μm以上であることを特徴とする請求項1に記載の金属被覆樹脂構造体。 2. The metal-coated resin structure according to claim 1, wherein the oxygen content of the metal film is 2500 ppm or less, and the thickness of each of the metal film and the intermediate layer is 150 μm or more.
- 金属成分を含むフィラーと樹脂とを含む基材にレーザを照射する工程と、金属皮膜を形成する金属粉末をガス流で加速する工程と、前記レーザが照射された前記基材の面に加速された前記金属粉末を噴射して付着堆積させる工程とを有することを特徴とする金属被覆樹脂構造体の製造方法。 A step of irradiating a substrate containing a filler containing a metal component and a resin with a laser, a step of accelerating a metal powder forming a metal film with a gas flow, and a surface of the substrate irradiated with the laser are accelerated. And a step of spraying the metal powder to deposit and deposit the metal powder.
- 基材にレーザを照射するレーザヘッドと、前記レーザが照射された前記基材の面にガス流で加速された金属粉末を噴射するスプレーノズルとを備えることを特徴とする金属被覆樹脂構造体の製造装置。 A metal-coated resin structure comprising: a laser head that irradiates a substrate with a laser; and a spray nozzle that sprays metal powder accelerated by a gas flow onto a surface of the substrate irradiated with the laser. Manufacturing equipment.
- 前記レーザヘッドが前記スプレーノズルに先行して移動し、前記スプレーノズルの軌道が前記レーザヘッドと同じであることを特徴とする請求項6に記載の金属被覆樹脂構造体の製造装置。 7. The apparatus for producing a metal-coated resin structure according to claim 6, wherein the laser head moves in advance of the spray nozzle, and the orbit of the spray nozzle is the same as the laser head.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007246967A (en) * | 2006-03-15 | 2007-09-27 | Mitsubishi Heavy Ind Ltd | Method for imparting electric conductivity to surface of molding and molding having electrically conductive surface |
| JP2009235427A (en) * | 2008-03-25 | 2009-10-15 | Institute Of National Colleges Of Technology Japan | Method for embedding particles in substance surface, and method for surface-oxidizing and surface-nitriding particle and substance |
| JP2011122213A (en) * | 2009-12-11 | 2011-06-23 | Iwate Industrial Research Center | Method for forming film by cold spray method and cold spray apparatus |
-
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007246967A (en) * | 2006-03-15 | 2007-09-27 | Mitsubishi Heavy Ind Ltd | Method for imparting electric conductivity to surface of molding and molding having electrically conductive surface |
| JP2009235427A (en) * | 2008-03-25 | 2009-10-15 | Institute Of National Colleges Of Technology Japan | Method for embedding particles in substance surface, and method for surface-oxidizing and surface-nitriding particle and substance |
| JP2011122213A (en) * | 2009-12-11 | 2011-06-23 | Iwate Industrial Research Center | Method for forming film by cold spray method and cold spray apparatus |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016180160A (en) * | 2015-03-24 | 2016-10-13 | オーエム産業株式会社 | Production method of device |
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