CN1899795A - Device for preparing ordered micro structure resin base composite material film - Google Patents

Abstract

The invention is a device for preparing ordered microstructure resin matrix composite film. It consists of tension control system (1), composite material coating system (2), magnetic field treatment system (3), heat treatment system (4), speed-regulating DC servo motor (5) and base (6). The device is fixed on the base (6) sequentially. The device drives the bottom film (7) to move through the speed-regulating DC servo motor (5). First, the pre-prepared resin-based composite material liquid or The melt is coated on the base film, and then passes through the magnetic field treatment system (3) to order the microstructure in the composite material, and heats the composite material during the magnetic field treatment to pre-cure the composite material, and finally passes through the heating treatment system to make the composite material Completely cured, finally forming an ordered microstructure resin matrix composite. The device is used for continuously preparing resin-based composite material films with ordered magnetic response microstructures. Wherein, the ordering includes the ordering of the array perpendicular to the film plane and the ordering of the orientation (the longitudinal direction of the film and the transverse direction of the film) parallel to the film plane; the microstructure includes functional groups or chain segments in the resin macromolecules, Crystal structure, addition of fine particles, etc. Compared with the existing preparation methods of ordered microstructured resin-based composite membranes, this device is characterized in that it can prepare array-ordered composite membranes whose microstructures are perpendicular to the membrane plane, and can also prepare arrayed composite membranes whose microstructures are parallel to the membrane plane. The planar orientation-ordered composite material film can be prepared both batchwise and continuously, and the operation is simple and the film forming is convenient.

Description

A device for preparing ordered microstructured resin-based composite film

technical field

The invention relates to a continuous preparation device for a resin-based composite film with an ordered magnetic response microstructure. Wherein, the ordering includes the ordering of the array perpendicular to the film plane and the ordering of the orientation (the longitudinal direction of the film and the transverse direction of the film) parallel to the film plane; the microstructure includes functional groups or chain segments in the resin macromolecules, Crystal structure, addition of fine particles, etc.

Background technique

Magnetic composite material refers to a permanent magnetic composite obtained by mixing, molding, and curing permanent magnetic powder as a functional body with a binder. Because it can produce large, medium and small products with precise size, low shrinkage rate, thin wall and complex shape at one time, it can also be conveniently processed by secondary cutting, and has good impact resistance and tensile strength. Therefore, permanent magnetic composite materials It has attracted the attention of all countries. Under the action of an external magnetic field, ordering the internal microstructure of the composite material can improve various properties of the existing composite material, especially the magnetic and electrical properties. Due to the application of a magnetic field during the molding process, the magnetic particles are rotated in the same direction as the magnetic field, and arranged into an ordered chain of magnetic particles, which remains in this state after the sample is solidified. The magnetic or electrical properties produced by each particle can be directly transmitted to the connected particles, thereby improving the magnetic and electrical properties of the material; while the magnetic particle chains are blocked by the binder to limit the generation of eddy current effects, thus Expand the application of composite materials under high frequency conditions. In addition, due to the magnetic loss of magnetic particles to electromagnetic waves, they have a good absorption effect on electromagnetic waves, so the application of magnetic composite materials in the field of wave absorption is also a research hotspot of magnetic functional composite materials. Therefore, in view of the development trend of aerospace resin-based composites, it is necessary to carry out research on microstructure-ordered polymer-based composites.

Recently, a domestic patent (publication number CN 1740228A) discloses a method for preparing aligned composite materials using a magnetic field. In this method, magnetically responsive particles (iron powder, carbon nanotubes, etc.) are added to a thermosetting resin matrix (epoxy resin, unsaturated polyester), and then a curing agent is added. Put into a magnetic field and solidify at room temperature, and finally obtain a composite material with aligned microparticles. The resistivity of the aligned iron powder/unsaturated polyester prepared by this method is only 4.5×10 ^-3 O.cm. However, the method for preparing the ordered microstructure composite material in this method is to put the composite material into a mold, and then place the mold in a magnetic field to solidify at room temperature, which is a batch method, so the composite material preparation efficiency is low; and, the The composite material prepared by the method is limited by the mold size and cost, and the size range of the composite material is very narrow. At the same time, due to the limitation of the preparation process of this method, the resin matrix of the prepared ordered microstructure composite material is almost all thermosetting, and does not involve the preparation of thermoplastic resin-based composite materials. This device not only provides a method for continuously preparing ordered microstructure resin-based composite membranes, which improves the preparation efficiency of composite materials; but also can prepare arrays with microstructures perpendicular to the membrane plane and parallel to the membrane as required. Orientation ordering of the plane (longitudinal direction of the film or transverse direction of the film) composite film, and the size of the film is controllable in a wide range. In addition, this device also specially provides components for preparing thermoplastic resin-based composite material films, which realizes the preparation of ordered microstructure thermoplastic resin-based composite materials, thereby greatly broadening the application range of ordered microstructure composite materials.

Contents of the invention

The invention provides a continuous preparation device for a resin-based composite material film with an ordered magnetic response microstructure. The purpose of the present invention is to overcome the technical deficiencies of the existing ordered microstructure resin-based composite film preparation device, and develop a device capable of continuously preparing ordered microstructure resin-based composite film. The array-ordered composite film whose structure is perpendicular to the film plane can also be prepared with an orientation-ordered composite film whose microstructure is parallel to the film plane; it can be prepared batchwise or continuously, and the operation is simple and the molding is convenient.

The preparation device drives the movement of the bottom film through the speed-regulating motor, first passes through the composite material coating system, and coats the pre-prepared composite material on the bottom film, and then passes through the magnetic field processing system to order the microstructure in the composite material, And finally form an ordered microstructure resin matrix composite film. The microstructure in this preparation device includes ① functional groups or segments with magnetic response in resin macromolecules, crystal structure, etc.; ② added microparticles with magnetic response: except iron powder, ferrite, neodymium iron boron (NbFeB), In addition to magnetic particles such as dysprosium iron (Terfenol-D), it also includes carbon nanotubes, carbon black, carbon fibers, graphite and other particles capable of forming magnetic orientation. The resin substrates that can be used in this preparation device include: epoxy resin, unsaturated polyester, phenolic resin, urea-formaldehyde resin, melamine resin, silicone resin, polyurethane, thermosetting polyimide and other thermosetting resins and polyethylene, polypropylene, polypropylene, etc. Butene, polyisobutylene, polystyrene, polyvinyl chloride, polyvinyl alcohol, polyacrylonitrile, polyoxymethylene, polyphenylene ether, polyphenylene sulfide, polysulfone, polycarbonate, polymethyl methacrylate, polyacrylic acid Thermoplastic resins such as methyl ester, nylon, polyethylene terephthalate, thermoplastic polyimide, and liquid crystal materials with anisotropic structure. The size range of the composite film prepared by the device is: width 1mm-2000mm; thickness 10 ² nm-10 ⁶ nm; length can be selected arbitrarily according to needs.

The invention consists of a tension control system (1), a composite material coating system (2), a magnetic field processing system (3), a heating system (4), an ultra-low speed DC servo motor (5) and a base (6). (See Figure 1 and Figure 2)

The tension control system (1) mainly includes a height-adjustable tension adjustment cylinder, which can adjust the tension and height of the base film (7) to meet the height requirements of the magnetic field processing system and heating system.

Composite material film coating system (2) consists of composite material film thickness control board (9), thermosetting composite material raw material casting and extrusion tank (10), thermoplastic composite material raw material casting and extrusion tank (11), heating sheet (12) , supporting plate (13) and residual material recovery tank (14) form. Wherein the thermoplastic composite raw material casting extrusion tank (11) is provided with a heating jacket, which can heat the raw material tank to melt the composite material. The temperature control range of the heating mantle and the heating sheet is 0°C to 400°C. According to the different composite materials used, the coating system of this preparation device can be divided into:

1 Thermosetting composite material coating system (see Figure 3): firstly, the thermosetting composite material liquid prepared in advance according to the formula is introduced into the raw material casting extrusion tank (10), and the composite material is coated on the base film by casting extrusion (7), adjusting the height of the thickness control plate (9) (see Figure 5) can control the thickness of the composite material film, so that the thickness of the composite material film can be adjusted between 10 ² nm to 10 ⁶ nm, and the redundant Composite material flows in the residual material recovery groove (14) under supporting plate (13).

2. Thermoplastic composite material coating system (see Figure 4): First, introduce the thermoplastic composite material particles mixed in advance according to the formula into the raw material casting extrusion tank (11), and heat the thermoplastic composite material in the tank through the heating jacket, so that Composite material is melted, then heats up by heating plate, makes the temperature of base film (7) reach the fusing temperature of composite material, so that the composite material that is coated on the base film can still keep molten state; Lay on the bottom film (7), adjust the height of the thickness control plate (9) (see Figure 5) to control the thickness of the composite material film, so that the thickness of the composite material film can be controlled between 10 ² nm and 10 ⁶ nm Tune. Unnecessary composite material flows in the residual material recovery groove (14) under supporting plate (13).

The magnetic field treatment system (3) consists of a transparent heat shield (15), a heat reflection device (16), a heating element (17) with a controller, a magnet bracket (18) and a magnet (permanent magnet, electromagnet or super electromagnet ) (19); the transparent heat shield (15) mainly enables the magnetic field processing system to be carried out in a relatively stable environment, and at the same time facilitates the observation of the change of the composite material film during the magnetic field processing. The heat reflection device (16) mainly reflects the heat of the heating component to the composite material film in parallel, so that the composite material film is heated as evenly as possible. The function of the heating part (17) is related to the composite material used: for the thermosetting composite composite material, the heating part is mainly a pre-cured composite material film, and the temperature control range is between 30 and 80 °C to fix the ordered microstructure in the In the composite material matrix; for thermoplastic composite materials, the temperature of the heating part is kept near the melting temperature of the composite material, and the cooling rate of the molten thermoplastic composite material is delayed to ensure that the composite material has a low enough viscosity so that it can be fully active in the magnetic field Sequential arrangement. The temperature of the heating part is adjusted by the current controller and can be controlled within the range of 0-400°C. The magnet (19) can generate a uniform magnetic field around the composite material film, so that the microstructures in the composite material are ordered and arranged. Through different combinations of magnets (19), magnets with different magnetic field strengths and magnetic field directions can be obtained, and the control of the ordering direction and response time of the microstructure in the composite material can be achieved, and the ordering and ordering of the microstructure perpendicular to the film plane can be obtained. Orientation-Ordered Composite Films Parallel to the Film Plane. Fig. 6 and Fig. 7 are schematic diagrams of the magnetic field treatment system for ordering composite film arrays, and Fig. 8 and Fig. 9 are schematic diagrams of magnetic field treatment systems for longitudinal alignment ordering and transverse alignment ordering of composite film respectively. The magnet combination used in the preparation device can provide a magnetic field of 0.1-30T.

The heat treatment system (4) (see Fig. 7) consists of a transparent heat shield (15), a heat reflection device (16), a heating component (17) with a controller and a supporting plate (13). The transparent heat shield (15) mainly keeps the thermal atmosphere of the whole heating system. The heat reflection device (16) mainly reflects the heat of the heating component to the composite material film in parallel, so that the composite material film is heated as evenly as possible. The temperature of the heating part can be changed in the range of 0-400°C through the current controller to meet the needs of different composite materials.

The speed-regulating DC servo motor (5) is composed of a DC servo motor and a control power supply. The servo motor (5) drives the movement of the base film (7), thereby driving the operation of the composite material in the whole device. The rotational speed range of the speed-regulating DC servo motor (5) used in the device is 0-100r/min, which can well control the running speed of the composite material film to meet the time required for film coating, magnetic field treatment and heat treatment. The servo motor (5) is provided with a take-up shaft (8), and the servo motor (5) drives the base film to move through the take-up shaft (8), and the finally formed composite material film will also be wound on the take-up shaft.

The bottom film (7) mainly carries the composite material film, and drives the composite material film to pass through film coating, magnetic field treatment, heat treatment, and finally form. The final composite film can be used directly, or can be used as a functional film separately from the base film. Base film (7) material comprises polyethylene film, polypropylene film, polybutene film, polyisobutylene film, polystyrene film, polyvinyl chloride film, polyvinyl alcohol film, polyacrylonitrile film, polyoxymethylene film, polystyrene film Ether film, polyphenylene sulfide film, polysulfone film, polycarbonate film, polymethyl methacrylate film, polymethyl acrylate film, nylon film, polyethylene terephthalate film, thermoplastic polyimide Various polymer films such as films and thermosetting polyimide films, and non-magnetic metal films or sheets such as inorganic cellophane or inorganic glass sheets, copper or aluminum, etc.

Compared with the existing experimental device, the present invention has the following characteristics.

1. The device of the present invention can continuously prepare resin-based composite membranes with ordered microstructures, overcome the shortcomings of existing preparation techniques, and greatly improve the efficiency of preparing resin-based composite membranes with ordered microstructures.

2. The device of the present invention can design different magnets (permanent magnets, electromagnets or super-strong electromagnets) to combine according to the needs, so that the arrays perpendicular to the membrane plane can be ordered, and the longitudinal and transverse orientations parallel to the membrane plane can be ordered. The three kinds of ordered microstructure composite membranes have a large degree of design freedom, and the size of the prepared composite membranes can be adjusted in a wide range, which greatly increases the application prospects of the ordered microstructure resin-based composite membranes.

3. The device of the present invention designs a composite material coating system, a magnetic field treatment system, a heat treatment system, and a motor drive system according to needs, and the mutual cooperation between the functions of each system provides a smooth preparation for the smooth preparation of an ordered microstructured resin-based composite material film. a strong guarantee.

4. The device of the present invention introduces a bottom film, and the composite material is driven to run in the whole device through the bottom film, so as to realize the continuous preparation of a composite material film with an ordered microstructure. And the final composite material film can be used directly, and can also be used as a functional film separately from the base film, which greatly increases the application range of the prepared composite material film. The choice of bottom film material is very wide, including polyethylene film, polypropylene film, polybutylene film, polyisobutylene film, polystyrene film, polyvinyl chloride film, polyvinyl alcohol film, polyacrylonitrile film, polyoxymethylene film , polyphenylene ether film, polyphenylene sulfide film, polysulfone film, polycarbonate film, polymethyl methacrylate film, polymethyl acrylate film, nylon film, polyethylene terephthalate film, thermoplastic polyester Various polymer films such as imide film and thermosetting polyimide film, as well as inorganic cellophane or inorganic glass sheet, non-magnetic metal film or sheet such as copper or aluminum, etc.

5. According to the characteristics of thermosetting and thermoplastic composite materials, the device of the present invention designs two coating systems and heat treatment methods, which greatly increases the range of materials prepared by the device. At the same time, a heating device is introduced in the process of ordering the magnetic field, which shortens the preparation time of the composite material, especially the thermosetting composite material, and improves the preparation efficiency of the composite material.

6. The device of the present invention has simple operation, good ordering effect and convenient molding.

7 The resin-based functional composite material with ordered microstructure prepared by the device of the present invention has broad application prospects in the fields of aerospace, electronic information, transportation, construction and chemical industry.

Description of drawings

Fig. 1 is a structural representation (side view) of the present invention

Fig. 2 is a structural representation (top view) of the present invention

Figure 3 is a schematic diagram of the thermosetting composite coating system structure (side view)

Figure 4 is a schematic diagram of the thermoplastic composite film coating system (side view)

Figure 5 is a schematic diagram of the cross-sectional structure of the baffle in the coating system

Figure 6 is a structural schematic diagram of the composite film array ordering magnetic field processing system (top view)

Figure 7 is a schematic structural diagram of the composite material array ordered magnetic field processing system (side view)

Figure 8 is a structural schematic diagram of the magnetic field treatment system for the orientation ordering (longitudinal direction of the film) of the composite material film (top view)

Figure 9 is a structural schematic diagram of the magnetic field treatment system for the orientation ordering (transverse direction of the film) of the composite material film (top view)

Figure 10 is a structural schematic diagram of the heat treatment system

In the figure: 1 tension control system, 2 composite material coating system, 3 magnetic field processing system, 4 heat treatment system, 5 speed regulating DC servo motor, 6 base, 7 base film, 8 motor take-up shaft, 9 composite material film thickness Control panel, 10 thermosetting composite raw material casting and extrusion tank, 11 thermoplastic composite material raw material casting and extrusion tank, 12 heating plate, 13 pallet, 14 residual material recovery tank, 15 transparent heat shield, 16 heat reflection device, 17 temperature-controllable heating tubes, 18 magnet supports, 19 magnets (permanent magnets, electromagnets or super-strong electromagnets).

Detailed ways

Example 1:

Weigh ferrite:epoxy resin:tetraethylenepentamine (curing agent) in a mass ratio of 1:10:2, mix, then ultrasonically disperse, and vacuum degas to obtain a ferrite/epoxy resin composite material liquid. The liquid is introduced into the thermosetting composite raw material casting extrusion groove in the coating system, and the composite material is extruded and coated on the base film. Start the DC servo motor with a speed of 2r/min, the motor drives the bottom film to move, adjust the height of the thickness control plate, and control the thickness of the composite film. When the composite material enters the magnetic field processing system, it is heated with a heating tube, and the temperature of the heating tube is controlled at about 40°C, so that the epoxy resin is gradually pre-cured during the process of ordering the ferrite. When the composite came out of the magnetic field, the epoxy crosslinked enough to hold the ordered ferrites in place. Then the composite material enters the heating treatment system, and the temperature of the heating tube is controlled at about 80°C to completely cure the epoxy resin and finally form a solid composite material film. Finally, the composite material film is wound on the take-up shaft of the servo motor. 11 to 13 are the ordered optical micrographs of the ferrite/epoxy composite film under different magnetic field directions.

Example 2:

Dissolve 5g of polyvinyl alcohol (PVA) with a degree of polymerization of 1750 in 50ml of water at 85°C, add 1g of ferrite, stir, then transfer the composite material solution to a thermoplastic raw material casting extrusion tank at a temperature of 85°C, At this point, heat the heating plate to 85°C, then extrude the composite material and coat it on the bottom film, start the DC servo motor at a speed of 2r/min, the motor drives the bottom film to move, adjust the height of the thickness control board, and control the thickness of the composite film . When the composite material enters the magnetic field treatment system, it is heated and dried with a heating tube, and the temperature is controlled at about 60°C, so that the composite material still has a certain fluidity, so that the ferrite can be well ordered in the magnetic field system. After the composite material comes out of the magnetic field, it is cooled and dried at room temperature, so that the ordered ferrite is fixed in it. Finally, the composite material film is wound on the take-up shaft of the servo motor.

Claims (7)

1. A device for preparing an ordered microstructure resin-based composite film, characterized in that: the device contains: a tension control system (1), a composite coating system (2), a magnetic field processing system (3), a temperature-controlled heating The processing system (4), the speed-regulating DC servo motor (5) and the base (6), each system is fixed on the base (6) in sequence. 2. The device for preparing resin-based composite film with ordered microstructure according to claim 1, characterized in that: the tension control system (1) mainly includes a height-adjustable tension adjustment cylinder. 3. ordered microstructure resin-based composite material film preparation device according to claim 1, is characterized in that: composite material film coating system (2) is made of composite material film thickness control plate (9), thermosetting composite material raw material casting Extrusion tank (10), thermoplastic composite raw material casting extrusion tank (11), heating sheet (12), supporting plate (13) and residual material recovery tank (14); wherein thermoplastic composite material raw material casting extrusion The tank (11) is equipped with a heating jacket, which can heat the composite material in the tank to melt the composite material; the temperature control range of the heating jacket and the heating sheet is 0°C to 400°C. 4. ordered microstructure resin matrix composite film preparation device according to claim 1, is characterized in that: magnetic field treatment system (3) is made of transparent heat shield (15), heat reflector (16), band controller The heating part (17), the magnet bracket (18) and the magnet (permanent magnet, electromagnet or super electromagnet) (19); the temperature of the heating part (17) is adjusted by the current controller, and can be 0～400 ℃ Change within a certain range; through different combinations of magnets (19), magnets with different magnetic field strengths and magnetic field directions can be obtained, and the control of the ordering direction and response time of the microstructure in the composite material can be achieved, and an array of microstructures perpendicular to the film plane can be obtained The ordered composite film is ordered and aligned in an orientation parallel to the plane of the film (machine direction of the film or transverse direction of the film). The magnetic field intensity provided by the combination of magnets (19) ranges from 0.1T to 30T. 5. ordered microstructure resin-based composite film preparation device according to claim 1, is characterized in that: heat treatment system (4) is made of transparent heat shield (15), heat reflector (16), band controller The heating part (17) and the supporting plate (13) are composed; the temperature of the heating part (17) is regulated by a current controller, and can be varied within the range of 0-400°C. 6. The ordered microstructure resin-based composite film preparation device according to claim 1, characterized in that: the speed-regulating DC servo motor (5) is made up of a DC servo motor and a control power supply, and has a take-up shaft (8 ); the rotational speed range of the servo motor (5) is 0 to 100r/min; the servo motor (5) drives the movement of the composite material film through the take-up shaft (8) to control the movement speed of the composite material film, thereby controlling the coating film of the composite material, After the magnetic field treatment and heat treatment time, the finally formed composite material film will also be wound on the take-up shaft. 7. The ordered microstructure resin-based composite film preparation device according to claim 1, characterized in that: the composite material is coated on the base film (7), and the base film drives it to form an ordered structure in a magnetic field , and solidified (or cooled) into shape, the final composite material film can be used directly, or can be used as a functional film separately from the bottom film; the bottom film (7) materials include polyethylene film, polypropylene film, polybutene film, Polyisobutylene film, polystyrene film, polyvinyl chloride film, polyvinyl alcohol film, polyacrylonitrile film, polyoxymethylene film, polyphenylene ether film, polyphenylene sulfide film, polysulfone film, polycarbonate film, polyformaldehyde film Various polymer films such as methyl acrylate film, polymethyl acrylate film, nylon film, polyethylene terephthalate film, thermoplastic polyimide film and thermosetting polyimide film, as well as inorganic cellophane or inorganic Glass flakes, non-magnetic metal films or flakes such as copper or aluminum, etc.

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