JP4487306B2 - Composite structure forming apparatus and forming method - Google Patents

Description

  The present invention relates to a composite structure forming apparatus for forming a composite structure composed of a base material and a structure by spraying an aerosol containing fine particles onto the base material to form a structure composed of the fine particle material on the base material, and the formation Regarding the method.

  As a method of forming a structure made of a brittle material on the surface of a base material, there are conventional Patent Document 1, Patent Document 2, Patent Document 3 and the like, which are recognized by a name called a fine particle beam deposition method or an aerosol deposition method. ing. This is because an aerosol in which fine particles of a brittle material are dispersed in a gas is sprayed from a nozzle toward the substrate, the fine particles of the brittle material collide with the base material, and the impact of the collision causes the brittle material to be deformed or crushed. It is characterized by directly forming a structure consisting of constituent materials of brittle material fine particles on the material, and in particular a process that can form a structure at room temperature that does not require a heating means, and has a mechanical strength equivalent to a fired body The brittle material structure possessed can be obtained. The apparatus used in this method basically consists of an aerosol generator for generating aerosol and a nozzle for injecting the aerosol toward the base material. When a structure is produced with a larger area than the opening of the nozzle, , Which has a position control device such as an XY stage that relatively moves and swings the substrate and the nozzle, and has a chamber and a vacuum pump when producing under reduced pressure, and a gas for generating aerosol It is common to have a source.

  For the purpose of improving this technique, Patent Document 4 irradiates a flow of fine particles with a high energy beam such as an ion, atom, molecular beam, or low-temperature plasma to activate the fine particles to obtain good film properties and a good substrate. The device has been devised to ensure the adhesion.

  In Patent Document 2, by changing the incident angle of the spray flow of the fine particle material onto the substrate surface, the film of the fine particle material is sufficiently bonded, the structure is dense, the surface is smooth, and the density is uniform. There is a device for manufacturing things.

  In Patent Document 3, after the step of applying internal strain to the brittle material fine particles, the brittle material fine particles collide with the surface of the base material, and the fine particles are recombined with each other by the impact of the collision. A method of forming a composite structure is proposed, in which an anchor portion made of a brittle material that partially penetrates the substrate surface is formed in the portion, and a structure made of a brittle material is formed on the anchor portion. Devises to improve speed.

  Examples of the substrate used in these aerosol deposition methods include metals, glass, ceramics, and certain plastics.

  Patent Document 5 introduced a gas deposition method in which fine particles are aerosolized and then sprayed onto a film forming substrate to form a fine particle film, and then heat treatment at 750 ° C. or higher is performed to increase the density. A method for forming a ceramic film to obtain a fine particle film is described. Here, in order to solve the problem that the film forming substrate itself is distorted due to the stress generated during the film formation or the heat treatment in the subsequent process, the aerosol fine particles are simultaneously applied to the front and back surfaces of the film forming substrate. There is an introduction of a gas deposition film forming method and an apparatus for forming a fine particle film on the front and back surfaces simultaneously.

Japanese Patent No. 3256741 Japanese Patent No. 3338422 Japanese Patent No. 3348154 Japanese Patent No. 3256741 JP 2002-339058 A

  While inventions have been made to improve the quality of these structures, when a dense and strong structure with good adhesion is formed, compressive residual stress is generated in the structure, and therefore the base material There is a problem of causing deformation along the convex shape upward. In particular, when the base material is thin, such as a metal foil or plastic film, and easily bends, when the film is formed on one side, the base material itself curls or swells in a scroll shape, and is handled. The trouble that becomes difficult occurs. This is because the structure is always exposed to the application of compressive impact force during the formation of the structure due to the characteristics of this method of colliding fine particles, and stress is accumulated inside and the structure is forged and expanded. it is conceivable that.

  In addition, even when trying to simultaneously supply aerosol and simultaneously form a fine particle film in Patent Document 5, if a soft and flexible base material such as a metal foil or a plastic film is used, the base material is in a position floating in the air. Due to the collision of high-speed sprayed aerosol, vibration of the substrate, displacement of the position, etc. may occur, and the distance between the substrate and the nozzle may change, which may cause problems in film formation accuracy. is there. Although it is difficult to form a fine particle film on a roll-shaped substrate with the XYZ-θ table introduced as a substrate transport device, the area of the rolled substrate, which is one of the objects of the present invention In the case of using a large material, there is a great concern about this vibration and displacement.

  The present invention has been made in view of the above circumstances, and in forming a structure of a brittle material, the structure is formed without being obstructed by the deformation of the composite structure caused by the residual stress possessed by the structure. Further, the present invention proposes a composite structure forming apparatus and a forming method capable of obtaining a composite structure in a state where deformation due to residual stress is reduced.

In the present invention , an aerosol in which fine particles of brittle material are dispersed in a gas is jetted from a nozzle toward a film-like metal substrate surface to be collided, and a brittle material structure made up of constituent materials of the brittle material fine particles is used as a substrate. A composite structure forming apparatus for forming on one surface of the substrate having a base material transport device for transporting the base material, after the base material transport device forms a brittle material structure on one surface of the base material And a mechanism for applying a tensile stress to the other surface of the base material while transporting the base material so that the other surface of the base material extends and undergoes ductile deformation. I will provide a. In addition, an aerosol in which fine particles of brittle material are dispersed in a gas is jetted from a nozzle toward the surface of a film-like metal base material to be collided. a composite structure forming method for forming on one surface of the timber, after having formed a structure on one side of the substrate, as the other surface of the substrate, extending undergo ductile deformation, Provided is a method for forming a composite structure, wherein a tensile stress is applied to the other surface of the base material while the base material is conveyed .

Applying a tensile stress to the substrate is preferable because a thin film can be prevented from being bent or deformed during film formation. This tensile stress may be a stress within the elastic deformation level of the substrate, or a stress until the substrate is ductile deformed and extended. By forming a structure having internal stress on the base material, the base material is deformed. However, by applying tensile stress to the base material to cause ductile deformation, tensile stress is also applied to the structure. As a result, the stress is offset. As a result, although the base material expands somewhat, product defects such as curling and swelling are resolved.

  As described above, according to the present invention, even when a brittle material structure having compressive residual stress is formed on a film-like base material by the aerosol deposition method, the base material is deformed as much as possible by the stress. It becomes possible to suppress.

  In the aerosol deposition method, an aerosol in which fine particles such as brittle materials are dispersed in a gas is sprayed from a nozzle toward the base material, and the microparticles collide with a base material such as metal, glass, ceramics or plastic, and the impact of this collision It is characterized in that brittle material fine particles are deformed or crushed and joined together to directly form a structure consisting of fine particle constituent materials on the base material, especially at room temperature that does not require heating means A structure can be formed, and a structure having mechanical strength equivalent to that of the fired body can be obtained. The apparatus used in this method basically consists of an aerosol generator for generating aerosol and a nozzle for injecting the aerosol toward the base material. When a structure is produced with a larger area than the opening of the nozzle, In addition, it has a position control means that moves and swings the base material and the nozzle relative to each other, and has a chamber and a vacuum pump for forming a structure when producing under reduced pressure, and also generates aerosol It is common to have a gas source.

  The process temperature of the aerosol deposition method is room temperature, and one feature is that the structure is formed at a temperature sufficiently lower than the melting point of the particulate material, that is, several hundred degrees C. or less.

  In addition, the fine particles used are mainly brittle materials such as ceramics and semiconductors, and fine particles of the same material can be used alone or mixed, and different fine particles of brittle material can be mixed or used in combination. Is possible. Further, it is also possible to mix a part of a metal material or an organic material with brittle material fine particles or to coat the surface of brittle material fine particles. Even in these cases, the main component of structure formation is a brittle material.

  In the structure formed by this method, when crystalline brittle material fine particles are used as a raw material, the brittle material portion of the structure is a polycrystalline body whose crystallite size is smaller than that of the raw material fine particles, and the crystal In many cases, there is substantially no crystal orientation, and it can be said that there is substantially no grain boundary layer consisting of a glass layer at the interface between brittle material crystals, and a part of the structure is an anchor that bites into the substrate surface It is characterized by often forming a layer.

  The structure formed by this method clearly has a sufficient strength unlike a so-called green compact in which fine particles are packed by pressure and keeps a form by physical adhesion.

  In this structure formation, the brittle material fine particles are crushed and deformed by measuring the brittle material fine particles used as raw materials and the crystallite size of the formed brittle material structure by X-ray diffraction. it can. That is, the crystallite size of the structure formed by the aerosol deposition method is smaller than the crystallite size of the raw material fine particles. A new surface in which atoms originally present inside and bonded to other atoms are exposed is formed on the slip surface or fracture surface formed by crushing or deforming fine particles. This active new surface having a high surface energy is considered to be formed by joining the surface of the adjacent brittle material, the new surface of the adjacent brittle material, or the substrate surface. In addition, when hydroxyl groups are present on the surface of the fine particles moderately, a mechanochemical acid-base dehydration reaction occurs due to local shear stress generated between the fine particles or between the fine particles and the structure when the fine particles collide with each other. It can be considered. The addition of continuous mechanical impact force from the outside causes these phenomena to occur continuously, and the progress and densification of joints are performed by repeated deformation and crushing of fine particles, and brittle material structures grow. it is conceivable that.

  Embodiments of the present invention will be described below with reference to the accompanying drawings. FIG. 1 shows a composite structure manufacturing apparatus 10 according to the present invention. A film preparation chamber 102, a structure preparation chamber 105, a film cleaning chamber 115, and a film are provided in a structure preparation chamber 101 that is cut off from the outside environment. A winding chamber 117 is installed. In the film preparation chamber 102, a long film 103 prepared in a roll shape is loaded into a film unwinding device 104, which is a base material transport device, connected to a rotation control device (not shown). As the film 103, a metal foil, a plastic foil, or the like is prepared. The film 103 is inserted into the structure production chamber 105 in such a manner that the end of the film 103 is pulled out, and the shaping rolls 106a, 106b, 106c, 106d connected to a rotation control device (not shown) and the substrate transport connected to a rotation control device (not shown) Substrate transport fixed to cylindrical structure forming rolls 107a and 107b, which are holders, set on cleaning roll 116 in film cleaning chamber 115, and connected to a rotation control device (not shown) in film winding chamber 117 This end is fixed to a take-up roll 118 which is a device. On the other hand, aerosol generators 109a and 109b are disposed through gas cylinders 108a and 108b such as nitrogen and helium, and brittle material particles such as aluminum oxide are loaded in the aerosol generators 109a and 109b. The aerosol generators 109a and 109b have nozzles 111a and 111b through aerosol transport pipes 110a and 110b, with the opening at the tip thereof facing the surface of the film 103 disposed on the structure forming rolls 107a and 107b. The forming rolls 107a and 107b are arranged so as to be paired on the front and back of the base material. The nozzle 111a and the nozzle 111b are arranged on one side of the film 103 and the other side different from the nozzle 103 with the aerosol injection opening facing each other. Further, aerosol recovery ports 112a and 112b are arranged at the tip of the nozzle opening, and these are connected to vacuum pumps 114a and 114b through powder recovery devices 113a and 113b through piping.

  The operation of the composite structure manufacturing apparatus 10 based on the aerosol deposition method will be described below. The gas cylinders 108a and 108b are opened, the gas is sent into the aerosol generators 109a and 109b, and the gas cylinders 108a and 108b are operated to generate an aerosol in which brittle material fine particles and gas are mixed at an appropriate ratio. Further, the vacuum pumps 114 a and 114 b are operated to generate a differential pressure between the aerosol generators 109 a and 109 b and the structure manufacturing chamber 105. Aerosol is accelerated through the aerosol transport pipes 110a and 110b, and sprayed toward different surfaces of the film 103 from the nozzles 111a and 111b. On the other hand, the film 103 is conveyed in such a manner that it is gradually wound around the film take-up roll 118 under the rotation control of the film take-up roll 118 and the film take-up roll 104. The arrow on the illustrated roll indicates the film winding direction. In this manner, a film-like brittle material structure is formed on both surfaces of the film 103 by collision of fine particles while changing the collision position with the aerosol on the film 103. At this time, the film 103 may travel in one direction and be transported, or may be transported by repeatedly proceeding and retreating by rotation control. That is, in order to form a desired formation height, the conveyance speed can be increased or decreased, or the formation speed can be increased by swinging. It is also preferable to further increase the formation height by arranging a plurality of these nozzles. The arrows at the tips of the nozzles 111a and 111b in the figure indicate the flow of the aerosol. The aerosol that has not been used to form the structure is introduced into the aerosol collection ports 112a and 112b at the tip, and the powder collection device 113a. 113b, the brittle material fine particles and the gas are separated, the brittle material fine particles are recovered, and the gas is exhausted to the outside by the vacuum pumps 114a and 114b. In addition, since the collision position of the aerosol to the base material is just on the surface of the base material held in contact with the surface of the structure forming roll, even if a high-speed aerosol flow collides, the foil-shaped base material is bent, There are no problems such as vibration.

  In this way, since structure formation is performed on both surfaces of the film 103 in one step, the difficulty of handling due to film bulging or curling due to the process of forming and removing the structure on only one side is eliminated. In addition, after the film is formed on both sides of the film, the compressive stress of the brittle material structure is canceled, and wrinkles such as swelling and curling can be eliminated.

  Further, the aerosol generator 109a is stopped, the structure is formed only on one side by the nozzle 111b, and the surface of the structure forming roll 107b and the shaping roll 106d is made of rubber, so that the friction of the contact portion with the film 103 is reduced. By increasing the resistance, or by placing a skewer electrode and applying an electrostatic attraction force to a dielectric material such as a plastic film by applying an electric field, we devised to generate an attraction force between the film 103 and the roll, and The rotation control of these rolls is performed by an electromagnetic motor, and while the peripheral speed of the structure forming roll 107b is controlled to be the same as the other rolls, the shaping roll 106d is not loaded and is above the peripheral speed of the structure forming roll 107b. By controlling in advance to rotate and forming the structure while moving the film in this state, The film 106d receives the resistance of the film 103 adhered to the structure forming roll 107b and slows the peripheral speed to the same level as that of the structure forming roll 107b, while applying a tensile stress to the film 103 in the region located between them. Furthermore, it is possible to relieve the compressive stress of the structure by causing the film to stretch between these rolls.

  It is also preferable to promote the stretching by heating the structure forming roll 107b and the shaping roll 106d so that the film 103 easily undergoes plastic deformation.

  The present invention is, for example, used for forming a photocatalytic film such as an insulating film or titania on a metal foil or a plastic film, or a film-like structure of barium titanate, strontium titanate, PZT or a composite oxide thereof on a copper foil. It can be used for the production of a capacitor sheet for a circuit board on which is formed.

Schematic diagram showing a composite structure manufacturing device

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 ... Composite structure preparation apparatus 101 ... Structure preparation chamber 102 ... Film preparation room 103 ... Film 104 ... Film unwinding apparatus 105 ... Structure preparation room 106a, 106b, 106c, 106d ... Shaping roll 107a, 107b ... Structure formation Roll 108a, 108b ... Gas cylinder 109a, 109b ... Aerosol generator 110a, 110b ... Aerosol transport pipe 111a, 111b ... Nozzle 112a, 112b ... Aerosol recovery port 113a, 113b ... Powder recovery device 114a, 114b ... Vacuum pump 115 ... Film cleaning Chamber 116 ... Cleaning roll 116
117 ... film winding chamber 118 ... winding roll

Claims (2)

An aerosol in which fine particles of brittle material are dispersed in a gas is jetted from a nozzle toward the surface of a film-like metal base material to be collided, and a brittle material structure made of the constituent material of the brittle material fine particles is applied to one of the base materials . A composite structure forming apparatus to be formed on the surface of the substrate having a base material transport device for transporting the base material, the base material transport device forming a brittle material structure on one surface of the base material And a mechanism for applying a tensile stress to the other surface of the base material while transporting the base material so that the other surface of the base material undergoes ductile deformation and extends later. A composite structure forming apparatus. The aerosol in which the fine particles of the brittle material are dispersed in the gas is jetted from the nozzle toward the surface of the film-like metal base material to be collided, and by this impact, the brittle material structure made of the constituent material of the brittle material fine particles is A method of forming a composite structure formed on one surface of a base material, wherein after the structure is formed on one surface of the base material, the other surface of the base material undergoes ductile deformation and extends As described above , a tensile stress is applied to the other surface of the base material while the base material is being conveyed .

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