JP4975583B2 - Manufacturing method of fiber reinforced composite material - Google Patents

Description

  The present invention relates to a method for producing a composite material such as a metal film reinforced with fibers.

In recent years, the importance of coating technology has increased rapidly, and various coating methods have been developed.
However, a coating method capable of applying a high-density coating film having a thickness of about several tens to several hundreds of μm at a low temperature has not been known.

Non-Patent Document 1 and Non-Patent Document 2 disclose a supersonic free jet (SFJ) physical vapor deposition (PVD) apparatus.
The SFJ-PVD apparatus includes an evaporation chamber and a film formation chamber.
The evaporation chamber is equipped with an evaporation source material placed on a water-cooled hearth and an electrode made of a refractory metal (specifically tungsten). After the pressure in the evaporation chamber has been reduced to a predetermined pressure once The gas source is replaced with a predetermined gas atmosphere, the evaporation source is the anode (anode), and the highly conductive metal electrode at a certain distance from the anode is the cathode (cathode), and a negative voltage and a positive voltage are applied respectively. The evaporation source material is heated and evaporated by the transfer arc plasma that causes arc discharge between the two electrodes. In the evaporation chamber having a predetermined gas atmosphere, atoms evaporated by heating of the evaporation source are aggregated together to obtain fine particles having a diameter of nanometer order (hereinafter referred to as nanoparticles).

The obtained nanoparticles are transported to the film forming chamber through the transfer pipe on the gas flow generated by the differential pressure (vacuum degree difference) between the evaporation chamber and the film forming chamber. A deposition target substrate is installed in the deposition chamber.
The gas flow due to the differential pressure is accelerated to a supersonic speed of about 3.6 Mach by a specially designed supersonic nozzle (Laval nozzle) attached to the tip of a transfer pipe connected from the evaporation chamber to the deposition chamber. The nanoparticles are accelerated at a high speed in the supersonic free jet stream, and are ejected into the deposition chamber and deposited on the deposition target substrate.

  By using the SFJ-PVD apparatus, it is possible to apply a high-density coating film having a film thickness of about several tens to several hundreds of μm, which has been difficult in the past.

Further, for example, in Patent Document 1, first particles and second particles are generated in two evaporation chambers, and these are mixed using the oscillation phenomenon of the coaxial opposed collision jet described in Non-Patent Document 3 to obtain a supersonic speed. A physical vapor deposition apparatus for performing physical vapor deposition on a substrate in a gas flow is disclosed.
Using the above physical vapor deposition apparatus or the like, for example, as disclosed in Patent Document 2, it has become possible to form a film in which silicon fine particles are dispersed in an aluminum matrix.

By the way, a fiber reinforced composite material film in which fibers such as silicon carbide are arranged in a thin film of metal or the like to improve the strength of the film has been developed.
As a manufacturing method of the above-mentioned fiber reinforced composite material film, a fiber material to be included is arranged on a substrate, a melting method in which a film forming material such as a molten metal is poured from above, or a thermal spraying in which a molten metal material is sprayed A method of forming by the method is known.

However, in the above conventional fiber reinforced composite film manufacturing method, the film forming material in a molten state is brought into contact with the fiber material in a high temperature state, so that the film forming material and the fiber material react chemically or physically. As a result, the fiber strength may not be sufficiently strengthened by the fibers, or the composition of the film itself may not be intended, and it is difficult to suppress the reaction between the film forming material and the fiber material.
JP 2006-111921 A JP 2006-45616 A A. Yumoto, F. Hiroki, I. Shiota, N. Niwa, Surface and Coatings Technology, 169-170, 2003, 499-503 Atsushi Yumoto, Fujio Kashiwagi, Ichiji Shioda, Naoki Niwa: Formation of Ti and Al films by supersonic free jet PVD, Journal of the Japan Institute of Metals, Vol. 65, No. 7 (2001) pp 635-643 Shinjiro Yamamoto, Akira Nomoto, Tadao Kawashima, Nobuaki Nakado: Oscillation Phenomenon of Coaxial Opposing Collision Jet, Oil Pressure and Air Pressure (1975) pp 68-77

  The problem to be solved is that it is difficult to suppress the reaction between the film forming material and the fiber material in the method for producing a fiber reinforced composite material film in which the fiber material is encapsulated in the film forming material.

  The method for producing a fiber-reinforced composite material film of the present invention includes a step of placing a substrate having a fiber material fixed on a surface in a vacuum chamber, and a film-forming material particle by heating an evaporation source of the film-forming material in an inert gas atmosphere. And the film-forming material particles are transferred, placed in a supersonic free jet air stream and ejected into the vacuum chamber, and physically vapor-deposited on the substrate on which the fiber material is fixed, Forming a fiber-reinforced composite material film in which the fiber material is encapsulated in a film made of a film-forming material.

  In the method for producing a fiber-reinforced composite material film of the present invention, a substrate having a fiber material fixed on the surface is placed in a vacuum chamber. On the other hand, film-forming material particles are generated by heating the evaporation source of the film-forming material in an inert gas atmosphere. Next, the film-forming material particles are transferred, placed in a supersonic free jet air stream, ejected into a vacuum chamber, and physically vapor-deposited on a substrate on which a fiber material is fixed, into a film made of the film-forming material. A fiber reinforced composite film containing the fiber material is formed.

In the method for producing a fiber-reinforced composite film of the present invention, preferably, the film forming material is a metal.
Alternatively, preferably, the film forming material is ceramic.
Preferably, in the step of forming the fiber reinforced composite material film, the fiber reinforced composite material film is formed at a film forming temperature of 600 ° C. or lower.
Preferably, in the step of forming the fiber reinforced composite material film, a fiber reinforced composite material film having a thickness of 10 μm or more is formed.

  The method for producing a fiber reinforced composite material film of the present invention can suppress a reaction between the film forming material and the fiber material because a fiber reinforced composite material film in which the fiber material is included in the film forming material can be formed at a low temperature. it can.

  Embodiments of a method for producing a fiber-reinforced composite material film according to the present invention will be described below with reference to the drawings.

Fig.1 (a) is a typical perspective view of the fiber reinforced composite material film | membrane which concerns on this embodiment, FIG.1 (b) is sectional drawing in XX 'in Fig.1 (a), FIG.1 (c). ) Is a cross-sectional view taken along line YY ′ in FIG.
For example, a metal such as titanium, tungsten, aluminum, niobium or silicon, titanium oxide, tungsten oxide, aluminum oxide, niobium oxide or silicon oxide on a substrate 33 made of metal such as titanium or titanium alloy, ceramics, or polymer. A film 1 made of a metal oxide such as, or other ceramics is formed.

Inside the coating 1, for example, fiber materials (2a, 2b) such as silicon carbide (SiC) fiber, tungsten carbide (WC) fiber, and carbon fiber are disposed.
As described above, the fiber-reinforced composite material film according to this embodiment is formed. By adopting a structure in which a fiber material is embedded inside the coating, a composite material film with increased mechanical strength is obtained.

The film thickness of the film 1 is, for example, about several μm to 1000 μm, preferably 10 μm or more, and more preferably 30 μm or more.
The film 1 may have a uniform composition throughout the film, for example, may have a profile such that the composition changes in the thickness direction.

In addition, for example, the fiber material (2a, 2b) is arranged such that the second-layer fiber material 2b is arranged at regular intervals in contact with the first layer on the upper layer of the first-layer fiber material 2a arranged at regular intervals. It becomes the composition.
The fiber material (2a, 2b) has a diameter of about several μm to several hundred μm, for example.

When the fiber material has a plurality of layers as described above as described above, the first layer of fiber material 2a is arranged along the first direction as described above, and the second layer of fiber material 2b. Can be arranged along a second direction perpendicular to the first direction. Alternatively, the first direction and the second direction may be the same direction or other different directions.
The layers of the fiber material (2a, 2n) may be in contact with each other as described above, or may be provided so as not to contact each other.
Or you may be provided with the structure of only one layer.

  Moreover, as said fiber material, it is good also as a structure arrange | positioned in the membrane | film | coat 1 in the state in which the fiber material arranged along the some direction was knitted.

The coating 1 generates film-forming material particles by heating an evaporation source such as a metal or metal oxide in an inert gas atmosphere, transfers the obtained film-forming material particles, and places them on a supersonic free jet stream. The film is formed by ejecting into the vacuum chamber and physically vapor-depositing on the substrate disposed in the vacuum chamber.
By fixing the fiber material to the surface of the substrate 33 before the film formation, the film is formed so that the fiber material is embedded in the film.

  In this embodiment, a supersonic free jet (SFJ) -physical vapor deposition (PVD) in which a film is formed by high-speed deposition of nanoparticles on a substrate as a method for forming the film as described above. : Physical Vapor Deposition) method is used. The SFJ-PVD method can deposit almost all evaporation source materials as nanoparticles and form a thick film.

  Below, the SFJ-PVD apparatus for forming a metal oxide film by said SFJ-PVD method is demonstrated.

FIG. 2 is a schematic configuration diagram of the SFJ-PVD apparatus according to the present embodiment.
The SFJ-PVD apparatus according to this embodiment includes an evaporation chamber 10 and a film forming chamber 30 that is a vacuum chamber for film formation, and both are connected by a transfer pipe 17.

The evaporation chamber 10 is provided with an exhaust pipe 11 connected to the vacuum pump VP1, and the inside of the evaporation chamber 10 is exhausted by the operation of the vacuum pump VP1, for example, an ultra-high vacuum atmosphere of about 10 ⁻¹⁰ Torr. Furthermore, an inert gas such as He, Ar, or N ₂ is supplied at a predetermined flow rate from the gas supply source 13 provided via the mass flow controller 12 as the atmospheric gas in the evaporation chamber 10, and the inside of the evaporation chamber 10 is determined in a predetermined manner. Pressure atmosphere. Or it is good also as an air atmosphere.

In the evaporation chamber 10, a water-cooled copper crucible 14 is provided, in which a metal such as titanium, tungsten, aluminum, niobium or silicon, or titanium oxide, tungsten oxide, aluminum oxide, niobium oxide or oxide. An evaporation source 15 made of a metal oxide such as silicon or other ceramics is contained.
A heating unit 16 such as an arc torch or a plasma torch is provided in the vicinity of the evaporation source 15. The evaporation source 15 is heated and evaporated by the heating unit 16, and has a diameter of nanometer order from atoms evaporated from the evaporation source 15. Film-forming material particles are formed.

On the other hand, the film forming chamber 30 is provided with an exhaust pipe 31 connected to the vacuum pump VP3, and the inside of the film forming chamber 30 is exhausted by the operation of the vacuum pump VP3, for example, an ultrahigh vacuum atmosphere of about 10 ⁻¹⁰ Torr. Is done.

  A stage driven in the XY direction is provided in the film forming chamber 30, and a substrate holder 32 having an electric resistance heating system is connected to the stage, and a film forming substrate 33 is fixed. The temperature of the substrate 33 is measured by a thermocouple (not shown) at a point close to the film formation region of the substrate 33 and is fed back to the electric resistance heating system to be temperature controlled.

Although there is no limitation in particular as a board | substrate of film-forming object, For example, a pure titanium board (JIS grade 1), an A1050 aluminum alloy board, a SUS304 stainless steel board etc. can be used. The substrate is preferably used after being ultrasonically cleaned in acetone before being set in the film forming chamber 30.
The film formation region of the substrate is, for example, 7 mm square.

  A fiber material such as a silicon carbide fiber, a tungsten carbide fiber, or a carbon fiber is fixed to the surface of the substrate 33 in advance at least in the film formation region before film formation. The fiber material can be fixed by, for example, a method of fixing with an adhesive tape or an adhesive, or a method of fixing with a clip material that is physically pressed. Moreover, when the film-forming surface of the substrate 33 faces vertically upward, it is possible to place a weight or the like to press the fiber material.

The other end of the transfer pipe 17 connected to the evaporation chamber 10 is led into the film forming chamber 30, and a supersonic nozzle (Laval nozzle) 35 is provided at the tip of the transfer pipe 17.
A gas flow is generated between the evaporation chamber 10 and the film forming chamber 30 due to a pressure difference between the two chambers, and the film forming material particles generated in the evaporation chamber 10 are transferred together with the atmospheric gas to the film forming chamber 30 through a transfer pipe. And transferred.
The fluid containing the film forming material particles and the atmospheric gas is ejected from the supersonic nozzle 35 toward the substrate 33 in the film forming chamber 30 as a supersonic gas flow (supersonic free jet airflow).

The supersonic nozzle 35 is designed according to the type and composition of the gas and the exhaust capacity of the film forming chamber 30 based on the one-dimensional or two-dimensional compressible fluid dynamics theory, and is connected to the tip of the transfer pipe, or It is formed integrally with the tip portion of the transfer pipe. Specifically, it is a reduction-expansion tube in which the inner diameter of the nozzle is changed, and the gas flow generated by the differential pressure between the evaporation chamber 10 and the film formation chamber 30 is, for example, a Mach number of 1.2 or more, for example, a Mach number. It can be increased to a supersonic speed of 3.6.
The film-forming material particles are accelerated as described above, are ejected into the film-forming chamber 30 by riding on a supersonic gas flow, and are deposited (physical vapor deposition) on the substrate 33 as a film-forming target to form the film 1. .

  In the above film formation, since the fiber material is fixed on the substrate 33 in advance, when the film made of the film forming material is formed as described above, the fiber in which the fiber material is included in the film A reinforced composite film is formed.

A method for forming a fiber-reinforced composite material film according to this embodiment using the SFJ-PVD apparatus will be described.
First, the substrate 33 having a fiber material fixed on the surface is placed in the film forming chamber 30.
Fig.3 (a) is a typical perspective view which shows said process in the manufacturing process of the fiber reinforced composite material film concerning this embodiment, FIG.3 (b) is XX 'in Fig.3 (a). FIG. 3C is a cross-sectional view taken along line YY ′ in FIG.
For example, a fiber material made of silicon carbide fiber or the like is disposed on the substrate 33 made of titanium or the like. Here, for example, the first layer of fiber material 2a is arranged at regular intervals so as to be in contact with the substrate 33, and the second layer of fiber material 2b is arranged at regular intervals in contact with the first layer.

In the present embodiment, the first direction in which the first-layer fiber materials 2a are arranged and the second direction in which the second-layer fiber materials 2b are arranged are orthogonal to each other.
Moreover, in order to fix said fiber material (2a, 2b) to the board | substrate 33, the adhesive tape 3 is used, for example.
The layers of the fiber material (2a, 2n) may be in contact with each other as described above, or may be provided so as not to contact each other.

On the other hand, after the inside of the evaporation chamber 10 is evacuated to a predetermined ultra-high vacuum atmosphere, an inert gas such as He, Ar, or N ₂ is supplied at a predetermined flow rate to obtain a predetermined pressure atmosphere.

  Next, an evaporation source 15 made of a metal such as titanium, a metal oxide, or other ceramics placed in a crucible 14 in the evaporation chamber 10 is heated by a heating unit 16 such as an arc torch or a plasma torch to evaporate. Then, film-forming material particles having a diameter of nanometer order are formed from atoms evaporated from the evaporation source 15.

Further, the film forming chamber 30 is evacuated to a predetermined ultra-high vacuum atmosphere.
A gas flow is generated by the pressure difference between the evaporation chamber 10 and the film forming chamber 30, and the film forming material particles generated in the evaporation chamber 10 are transferred to the film forming chamber 30 through the transfer pipe together with the atmospheric gas. As shown in FIG. 4, which is a schematic perspective view showing a process in the manufacturing process of the fiber-reinforced composite film according to the embodiment, the film-forming material particles are placed on the air flow of the supersonic free jet J from the supersonic nozzle 35. The film is ejected into the film forming chamber 30 and is deposited (physical vapor deposition) on the substrate 33 disposed in the film forming chamber 30.
As described above, as shown in FIG. 1, on the substrate 33, the film 1 which is a fiber reinforced composite material film in which the fiber material is included in the film made of the film forming material particles and the mechanical strength is enhanced. Form.

The method for forming a fiber reinforced composite material film of the present embodiment is preferably formed at a film formation temperature of 600 ° C. or lower in the step of forming the fiber reinforced composite material film. More preferably, the film forming temperature is about room temperature.
Compared with the conventional CVD method or thermal spraying method, the film can be formed by low-temperature treatment, and the formed fiber-reinforced composite material film becomes a film that is not easily broken by stress.

In the method for forming a fiber reinforced composite material film of the present embodiment, the fiber reinforced composite material film having a thickness of 10 μm or more is formed in the step of forming the fiber reinforced composite material film.
Since it is physical vapor deposition, it is possible to realize a high film formation rate as compared with the sputtering method. For example, it is easy to form a thick fiber reinforced composite film of about several μm to 1000 μm, preferably 10 μm or more, more preferably 30 μm or more. Can do.

  As described above, the fiber-reinforced composite film forming method of the present embodiment makes it possible to deposit film-forming material particles by physical vapor deposition, which is a low-temperature treatment, and the mechanical strength is increased by including the fiber material. Furthermore, film-forming material particles that are not easily broken by stress can be formed at a high film formation rate.

By forming the fiber reinforced composite material film by the SFJ-PVD method, the following effects can be obtained.
(1) Since the fiber reinforced composite material film in which the fiber material is encapsulated in the film forming material can be formed at a low temperature, the reaction between the film forming material and the fiber material can be suppressed.
(2) By changing the type and strength of the fiber material to be included, it is possible to cope with fiber reinforced composite material films corresponding to various film thicknesses.

The present invention is not limited to the above description.
For example, the type of the fiber reinforced composite material film is not particularly limited, and films having various compositions can be formed. As a film forming material constituting the film, ceramic materials other than metal oxides can be used in addition to metals and metal oxides. As the fiber material, various fiber materials that can improve the mechanical strength of the film can be used in addition to those exemplified.
In addition, various modifications can be made without departing from the scope of the present invention.

  The method for forming a fiber-reinforced composite material film of the present invention can be applied as a method for forming a film covering various articles.

FIG. 1A is a schematic perspective view of a fiber-reinforced composite film according to an embodiment of the present invention, FIG. 1B is a cross-sectional view taken along line XX ′ in FIG. (C) is sectional drawing in YY 'in Fig.1 (a). FIG. 2 is a schematic configuration diagram of the SFJ-PVD apparatus according to the embodiment of the present invention. Fig.3 (a) is a typical perspective view which shows the process in the manufacturing process of the fiber reinforced composite material film | membrane which concerns on embodiment of this invention, FIG.3 (b) is XX 'in Fig.3 (a). FIG. 3C is a cross-sectional view taken along line YY ′ in FIG. FIG. 4 is a schematic perspective view showing a process in the manufacturing process of the fiber-reinforced composite material film according to the embodiment of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Film | membrane 2a, 2b ... Fiber material 3 ... Adhesive tape 10 ... Evaporation chamber 11 ... Exhaust pipe 12 ... Mass flow control 13 ... Gas supply source 14 ... Crucible 15 ... Evaporation source 16 ... Heating part 17 ... Transfer pipe 30 ... Deposition chamber 31 ... Exhaust pipe 32 ... Stage 33 ... Substrate 35 ... Supersonic nozzle J ... Supersonic free jet

Claims (5)

Placing a substrate having a fiber material fixed on its surface in a vacuum chamber;
Generating film-forming material particles by heating an evaporation source of the film-forming material in an inert gas atmosphere;
The film-forming material particles are transported, placed in a supersonic free jet stream, jetted into the vacuum chamber, and physically vapor-deposited on the substrate on which the fiber material is fixed. Forming a fiber reinforced composite film in which the fiber material is encapsulated. A method for producing a fiber reinforced composite film. The method for producing a fiber-reinforced composite material film according to claim 1, wherein the film-forming material is a metal. The method for producing a fiber-reinforced composite film according to claim 1, wherein the film forming material is ceramic. The method for producing a fiber-reinforced composite material film according to claim 1, wherein in the step of forming the fiber-reinforced composite material film, the fiber-reinforced composite material film is formed at a film forming temperature of 600 ° C or lower. The method for producing a fiber-reinforced composite material film according to claim 1, wherein in the step of forming the fiber-reinforced composite material film, a fiber-reinforced composite material film having a thickness of 10 μm or more is formed.

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