JPS6311983B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a novel organic fiber/inorganic composite material mainly consisting of a sheet material made of organic fibers and a thermally sprayed inorganic material. The present invention is a novel composite material that combines the strength, lightness, bulkiness, and flexibility of organic fiber materials with the heat resistance, fire resistance, chemical resistance, light resistance, and electrical conductivity of inorganic materials, as well as a method for producing the same. Therefore, it has the potential to be accepted as a new material in a wide range of fields.

Many composite materials of organic fiber materials and inorganic materials have been known. However, most of them have an adhesive on the material interface, have an inorganic material bonded with an organic substance, or have an inorganic substance mixed inside the fiber, and the heat resistance, fire resistance, Currently, when utilizing properties such as chemical resistance, light resistance, and electrical conductivity, these properties are not fully demonstrated due to the limitations of the properties of the adhesive and fiber materials that exist outside the adhesive layer or inorganic material. It is.

Plating and vapor deposition are known methods for producing composite materials in which organic fiber materials and metal are in direct contact, but these metal films are generally extremely thin and generally have poor protective effect on organic fiber materials. For this reason, these metal films generally have low strength and durability. Also, plating and vapor deposition take time,
Because they consume a lot of energy, they are generally expensive and can only be used for very limited purposes. Furthermore, as a method for manufacturing a composite material in which an organic fiber material and ceramics are in direct contact, a method is known in which ceramics are produced by coating with various inorganic compounds and heat-treating the material. The disadvantage of this method is that the inorganic compound cannot be uniformly coated without using a solvent such as water, so the coating solution inevitably has low viscosity and high permeability. Therefore, when applied to one side of an organic fiber material, it tends to penetrate too deeply and make the organic fiber material extremely hard and brittle. Furthermore, when coated on both sides, it becomes a nearly one-piece sheet-like product, which has poor flexibility and has almost no advantage of the presence of organic fibers. Another drawback is that the heat treatment temperature for turning the coating layer into ceramic is generally high and takes a long time, so that there are few organic fiber materials that can be used. In addition, many coating liquids are strongly alkaline, so
Another drawback is that many fiber materials cannot be used due to lack of alkali resistance.

As a highly efficient technique for coating inorganic materials, thermal spraying is known as a high-efficiency coating method in which the coated material is made of high-temperature fine particles that can be fused and is sprayed onto the workpiece together with a high-temperature fluid to create molded products. It is widely used as a surface processing technology. Recently, it has been used for surface processing of ceramics and other materials, but it is difficult for heat transfer to occur during processing for materials with low thermal conductivity and low heat resistance, such as organic fiber materials. The temperature of the object to be sprayed rises due to the heat brought in by the spraying material.
It has been said that fibers deteriorate and do not bond properly. Also, if you try to avoid this by lowering the temperature of the spray fluid or spraying from a distance,
It has been said that the thermal spray particles no longer integrate and bond with the fiber material. Therefore, it is a well-established theory that thermal spray materials cannot be processed unless they have a melting point lower than the softening point or thermal decomposition temperature of the fiber material.

As an example of thermal spraying processing for organic fibers, it is known that lead is thermally sprayed onto cotton cloth to produce radiation shielding work clothes. In addition, JP-A-52-66798 discloses that epoxy resin prepolymer, polyethylene, polypropylene, nylon 11
An example is disclosed in which the powder is thermally sprayed as powder for thermal spraying. In all of these examples, the melting point of the organic fiber is higher than that of the thermal spray material, and although the maximum temperature of the plasma is around 10,000℃,
The practical thermal spray processing temperature has been thought to be slightly lower than the melting point or pyrolysis temperature of the organic fiber.
The present inventor accidentally found out that this established theory was wrong while researching thermal spraying technology, and arrived at the present invention. In addition, Japanese Patent Application Laid-Open No. 48-52644 describes that when copper is sprayed directly onto a hard vinyl chloride plate,
It is stated that a thermal sprayed coating with a weak bonding force can be obtained, but a thermal sprayed coating with a strong bonding force can be obtained by coating a thermosetting resin on a hard vinyl chloride plate and thermally spraying copper while it is in a semi-cured state. This method is considered to be an advantageous method for joining plastic sheets and metal, but for joining cloth foil and metal, it requires laminating the cloth foil and metal film, which is costly in terms of quality and cost. Since there is not much difference in terms of performance, lamination is considered to be more advantageous due to its greater process flexibility.
However, if we provide an intermediate layer that has better heat resistance and chemical resistance than thermosetting resin, we believe that a new product can be obtained because the presence of the intermediate layer will have a greater protective effect on the organic fibers in the fabric. It will be done. For example, if a metal (alloy) with a slightly lower melting point than the organic fiber is used as the intermediate layer, when a high melting point metal is sprayed, the latent heat of melting absorbs the heat brought in by the sprayed material and exhibits a protective effect. While considering thermal spraying using such an intermediate layer, due to an experimental error, a metal with a higher melting point than the organic fiber was sprayed on the part without the intermediate layer, and that part peeled off more than the part with the intermediate layer. It was found that the strength was large, and from this we learned that the conventional theory was wrong.

As a result of various studies, the present invention aims to shorten the contact time per time with the high temperature fluid used for thermal spraying.
By cooling as quickly as possible after contact, inorganic materials such as metals and ceramics with a melting point much higher than that of the organic fibers are thermally sprayed onto the sheet-like material mainly composed of organic fibers, forming a cloth-like, film-like or It was found that a thin plate-like composite material could be obtained.
If the thickness of the molded product produced by thermal spraying is insufficient, this operation may be repeated.

The contact time between the high-temperature fluid used for thermal spraying and the sheet material mainly composed of organic fibers is 1 second or less per time, preferably 1/10 to 1/10000 seconds. Specifically, the thermal spray gun, the sheet material, or both are moved, and the relative velocity thereof, that is, the relative velocity between the feeding speed of the sheet material and the central axis of the high temperature fluid is set to 0.1 m/sec or more and 100 m/sec or less. Specific devices include a device that sprays by moving the thermal spray gun back and forth at a fairly high speed in a direction almost orthogonal to the sheet while slowly feeding the fabric, and a device that connects the sheets like an endless belt and runs the thermal spray gun in a circular manner at high speed. A device that sprays by slowly moving the sheet, a device that moves the sheet back and forth between a reversible take-up device and an unwinding device, and a device that sprays the sheet using a slowly moving thermal spray gun, or a device that sprays the sheet by moving it slowly on a flat table or on a specific surface. According to the present invention, there is provided an apparatus for producing patterned composite materials or composite materials having a three-dimensional shape by fixing the spray gun on a table having the shape of , and moving the spray gun at high speed according to a predetermined pattern. It is effective against

In carrying out the present invention, after the sheet material to be thermally sprayed and the high-temperature fluid used for thermal spraying are separated, they are rapidly cooled in as short a time as possible. Cooling is carried out by spraying a gas or a gas in which various liquids and solids are dispersed onto the thermally sprayed molding. Preferably, air or an inert gas is blown. The flow rate is 1
m/sec or more, preferably 10 m/sec or more and the sound speed or less. It is preferable that cooling is also performed from the back side of the sheet-like material. For cooling from the back side, it is preferable to use a solid cooling device provided with an internal heat removal mechanism, such as a rotating roller or a plate-like cooling device of various shapes. This is because by bringing the sheet material into close contact with a solid cooling device, it is possible to prevent the sheet material from undulating due to the fluid flow for thermal spraying and cooling, thereby making the thermal spraying non-uniform.

In the present invention, since the sheet material to be thermally sprayed is porous, a portion of the thermal spray material passes through the sheet material and comes out to the back side. The equipment that cools the sheet material to be thermally sprayed from the back side must be maintained under conditions that will not allow the thermal spraying material to adhere.To do this, the surface must be smoothed to a certain level of gloss and the surface temperature must be kept below 200℃, preferably Keep below 100℃. The cooling device is preferably attached with an auxiliary device for bringing the sheet material to be thermally sprayed into close contact with the cooling device, and further preferably with a device for scraping off the thermally sprayed material when it adheres.

A feature of the composite material of the present invention is that a sheet-like material mainly made of organic fibers and a thermally sprayed material made of inorganic materials are integrated in a multilayered structure, and the bonding force between the two components is determined by the bonding force on the surface of the organic fibers and This appears to be due to the entangled structure at the interface of both components. Such structures can be formed even under conditions where there are significant discontinuities in the inorganic moldings, and the presence of such discontinuities makes it possible to create highly flexible and durable fabric foils. A shaped composite material is formed.
Furthermore, by forming an inorganic molded article with good continuity, it is possible to make it a strong barrier against substances with high photothermochemical reactivity. Additionally, if the porosity of the sheet material is large, the inorganic molding can be formed to cover the back of the sheet, and the entire surface can be covered with the spray molding without spraying from both sides. can.

The composite material of the present invention is produced by thermally spraying an inorganic material onto a sheet material mainly composed of organic fibers and solidifying the material.
Manufactured by forming a molded article. here,
The inorganic material is formed into fine particles at a temperature that can be melted or sintered in plasma or flame generated by electric discharge or the like, and then carried by the plasma stream or high-temperature air stream and collided with the sheet-like material. The relative velocity between the sheet material and the central axis of the high-temperature fluid used for thermal spraying is 0.1.
m/sec to 100 m/sec, and immediately after the sheet-like material is separated from the high-temperature fluid, it is rapidly cooled. As a result, the sheet-like material can be taken out of the high-temperature fluid used for thermal spraying before deterioration due to heat progresses. Cooling of the sheet-like material can also be added at a stage before it comes into contact with the hot fluid. This cooling increases the heat capacity of the sheet-like material and suppresses deterioration. This operation is repeated until the amount of spraying reaches a desired value, and the inorganic material is formed in the form of a film, sponge, or scale on the sheet-like material. Here, the inorganic fine particles carried by the plasma flow or high-temperature air flow are melted entirely, their surface layer, or their binder component, and are accelerated to near-sonic or supersonic speeds and collide with the sheet-like object. The particles are compressed to the fiber surface by their own momentum and form a film, and some of the particles pierce and adhere to the fiber surface. In addition, a part of the particles penetrates into the sheet-like material through the gaps between the fibers and fuses with subsequent particles to form a network structure. Particles pressed onto the surface of organic fibers soften and melt the surface area of the organic fiber due to the amount of heat they possess, but by cooling this at a sufficient rate, the core of the fiber softens. We have discovered that it is possible to mold inorganic materials without any process. Inorganic particles can be formed into a continuous film, an intermittent film, or a layered film by selecting thermal spraying conditions. Furthermore, by incorporating particles that do not melt during thermal spraying, a sintered body-like molded product or a sponge-like molded product can be obtained. FIG. 1 shows a microscopic photograph of the surface of a typical thermal spray molded product of the present invention. It can be seen that it is a layered product of scale-like film-like material. Figure 2 shows a microscopic photograph of the material sprayed very thinly so that the fibers are visible. Although the fibers were vinylon, no deformation due to heat was observed, indicating that the fibers did not soften to the center.

Thermal spraying may be carried out on one side or both sides of a sheet material mainly made of organic fibers. When double-sided, the spray materials can be the same or different. Although it is simple and cost-effective to use only one type of thermal spraying material, there are cases where one type cannot satisfy the required function, and it is sometimes preferable to use two or more types. For thermal spraying of two or more types of materials, it is possible to thermally spray them sequentially in a multilayered form, or by thermally spraying a mixture near the boundary between two types of materials, the composition can be formed so that the composition gradually changes from one to the other. It is possible.

In the case of multi-layer thermal spraying, it is possible to thermally spray materials with extremely high melting points at a high rate by sequentially spraying materials with high melting points. In particular, when metal is thermally sprayed, as the thermal spray coating becomes thicker, it becomes easier to rapidly cool the coating, and as a result, subsequent thermal spraying tends to become more efficient. In addition, when spraying in multiple layers,
By thermally spraying materials with higher hardness in sequence, it is possible to suppress the phenomenon of cracking in the thermally sprayed coating. When spraying materials with low elongation such as ceramics, first spray a soft metal such as aluminum, then spray a hard metal on top of that, and then spray ceramics on top of that to prevent cracks in the ceramic layer. can be significantly reduced. Furthermore, when thermal spraying is performed in a multilayered manner, a metal having a high infrared reflectance can be thermally sprayed on the outermost layer to form a heat insulating material that is mainly effective by reflecting infrared rays. Preferred metals for this purpose include aluminum and silver.

The sheet-like material mainly composed of organic fibers, which is a component of the composite material of organic fibers and inorganic materials of the present invention, includes woven or knitted materials made of natural and artificial organic fibers,
It is a flat-shaped object such as non-woven fabric, braided fabric, or paper, and includes those that are brushed, flocked, flocked, resin coated, etc. This may contain some inorganic fibers, adhesive resins, fillers, adhesives, and various finishing agents.

The thermally sprayed inorganic material, which is one component of the organic fiber and inorganic composite material of the present invention, is a thermally sprayed inorganic material whose melting point is higher than the melting point or thermal decomposition temperature of the other component, the organic fiber. . here,
Inorganic materials include metals, ceramics, and cermets, which are composite materials of metals and ceramics.
More specifically, they include metals, alloys, carbon, boron, silicon, oxides, carbides, nitrides, borides, and mixtures of two or more substances selected from these groups.

As the thermal spraying method in the present invention, any conventionally known method can be applied, but there is a method in which the thermal spraying material is introduced in powder form into a plasma jet, and a method in which the thermal spraying material is introduced in the form of a rod into a flame or arc discharge. A method of introducing a thermal spraying material and then crushing and melting it, and a method of introducing a thermal spraying material in powder form into a flame and thermally spraying are preferred for producing the organic fiber and inorganic composite material of the present invention. .

The surface of the spray molded product obtained by the method of the present invention has a highly uneven surface as shown in FIG.
It does not have a strong luster and has a so-called satin-like appearance. If the spray molded product has malleability, the surface can be easily smoothed. Smoothening of the surface can be achieved by applying strong pressure to a smooth surface. Pressure treatment is preferably carried out between rollers made of a hard material having a smooth surface. Materials that are malleable at temperatures that do not degrade the organic fibers can be selected from metals and alloys. If the material of each layer has ductility, smoothing treatment is possible even for multi-layer thermal sprayed molded products. Even in the case of a material that is not malleable, if a malleable material is first thermally sprayed and smoothed and then thermally sprayed on top of that, the smoothness will be improved. however,
Please note that the smoothing process narrows the temperature conditions that allow thermal spraying, making thermal spraying difficult.

Because of the severe irregularities on the surface of the thermal spray molded product, the wear resistance and bending resistance of the composite material of the present invention cannot necessarily be said to be sufficient. To improve this, it is effective to apply a thin layer of organic polymer to the surface.
Various organic polymers can be used, but
Many are easy to use for polyurethane, acrylamide, silicone, and epoxy resins. When these resins are used in large quantities, they can improve the surface gloss, but they have the disadvantage of decreasing air permeability and fire resistance.

In addition to the surface irregularities, the thermal spray molded product of the present invention has pores in the direction that penetrates the film, and has air permeability. Although this contributes little to the air permeability of the composite material of the present invention, it has a negative effect on the chemical resistance. The organic polymer coating described above is effective in filling such pores. In addition, coating with an inorganic compound that produces ceramics through surface processing by plasma polymerization or heat treatment, and coating with glass having a low melting point are also effective. However, it seems that extremely high corrosion resistance cannot be obtained because it is necessary to process the organic fibers under conditions that avoid deterioration.

The composite condition of the present invention is manufactured by thermally spraying fine particles onto a highly insulating and flexible material using a high-temperature fluid. Because conventional thermal spray processing is performed on relatively hard materials with good thermal conductivity, the processing equipment is not configured to be suitable for manufacturing the composite materials of the present invention. Although there are no special requirements regarding the spray material and the interior of the spray gun, what happens after it leaves the spray gun is completely different. Several examples of apparatus suitable for manufacturing the composite material of the present invention will now be described. Note that the composite material manufacturing apparatus of the present invention is not limited to these examples.

FIG. 3 shows a schematic diagram of essential parts of an example of an apparatus suitable for manufacturing the composite material of the present invention. A sheet 2 mainly made of organic fibers is sent out from an unwinding device 7, passed around a cooling roller 5, and wound up by a winding device 8. The tentering device and tension adjusting device are omitted in the figure. The thermal spraying material is pulverized and melted by a thermal spraying gun 3 (the thermal spraying material supply device and the gas and power supply devices are omitted) that reciprocates in a direction perpendicular to the drawing, and is thermally sprayed onto the sheet 2 to be formed. When the sheet 2 reaches a position immediately after it exits the thermal spraying hot fluid stream 1, cooling gas is blown onto the sheet 2 from a cooling gas blowing device 4 to cool the sheet 2. The thermal spray material that has passed through the sheet is prevented from being deposited on the cooling roller 5 by a scraping device 6, and is removed to the outside by a dust collection device (not shown). By providing two or more such combinations of rollers and guns, thermal spraying from both sides of the sheet or lamination of two or more types of materials can be performed. In order to make the thickness of the spray molded product uniform, it is preferable to move the spray gun quickly to increase the number of times the spray coatings overlap. It is also preferable to arrange a large number of thermal spray guns side by side for this purpose. The feeding and taking-off of the sheet 2 need not be the drum type shown, and any type can be used.

As another example, it is also preferable to adopt a method in which the unwinding device 7, the cooling drum 5, and the winding device 8 are made reversible at the same time in the apparatus shown in FIG. 3, and the sheet 2 is thermally sprayed while being reciprocated. In this case, the moving speed of the thermal spray gun 3 is low, and the moving speed of the sheet 2 is high. It is necessary to take measures to prevent the sheet 2 from being damaged by the sprayed high temperature fluid flow 1 when the running direction of the sheet 2 changes. For example, the direction of the thermal spray gun 3 may be changed only at that time, or a shield plate or the like may be placed between the thermal spray gun 3 and the cooling roller 5. The advantages of this device are that the moving speed of the thermal spray gun 3 is low and does not require strain, and that a thick thermal spray film can be easily obtained. The disadvantages are that the thermal spray molding is likely to be damaged, and that the thermal spraying efficiency tends to differ between the forward and return passes, resulting in striped thickness unevenness in the thermal spray molding.

FIG. 4 shows another example of an apparatus suitable for manufacturing the composite material of the present invention. In this example, the sheet 2 is connected at both ends to form an endless belt, and the cooling roller 5
and the feed rollers 7 and 8 to run it. A slowly moving thermal spray gun 3 forms a thermal spray molding, and a cooling gas blowing device 4 cools the thermal spray molding. Although the number of feed rollers is two in the figure, it is possible to select an arbitrary number of one or more depending on the length of the sheet 2. The advantage of this method is that small-scale equipment can be manufactured at low cost and the spray moldings are relatively uniform. The disadvantage of this method is that it takes a long time to complete the composite material and then reapply the sheet 2 for further processing.

FIG. 5 shows yet another example of an apparatus suitable for manufacturing the composite material of the present invention. In this example, the entire apparatus for moving the sheet material to be thermally sprayed is rotated around the A-A' axis, and a cylindrical cooling device 9 coaxial with the rotating shaft is installed approximately in the center, and the length of the sheet 2 is mounted on the surface of the cylindrical cooling device 9, which is coaxial with the rotating shaft. The sheet 2 is rolled up into a cylindrical shape with the horizontal direction as the axis, fed out from the unwinding device 7, and slid onto the cylindrical cooling device 9 to be moved to the winding device 8.
Wind it up. The device for moving the sheet material to be thermally sprayed has a cylindrical cooling device 9 whose surface velocity is 0.1 to 100.
Rotate at m/sec. The thermal spray material is liquefied and atomized by a thermal spray gun 3 and sprayed onto the sheet 2 . In this example, the thermal spray gun 3 is fixed. The thermal spraying hot fluid stream 1 is directed to the vicinity where the sheet 2 leaves and a cooling fluid is injected to rapidly cool the sheet 2. Although one thermal spray gun 3 and one cooling gas blowing device 4 are shown in FIG. 5, it is also possible to use a large number of them in parallel. The advantages of this method are that it enables high-speed and uniform processing, and that raw materials and products can be easily attached and detached. On the other hand, the disadvantages of this method are that the equipment is expensive and that both sides cannot be processed in one go.

In the present invention, the relative speed between the sheet 2 and the thermal spray gun 3 must be maintained at 0.1 to 100 m/sec in any case. If it is less than 0.1 m/sec, cooling will be insufficient no matter how you change the thermal spraying conditions, and deterioration of the organic fibers cannot be avoided. On the other hand, 100
It is difficult to move the spray gun at speeds close to m/s, and the only method that can be implemented is to rotate the cooling roller at high speed as shown in Figure 3.
If the speed exceeds m/sec, it becomes difficult for spray particles to stick due to centrifugal force. The relative speed between the sheet 2 and the thermal spray gun 3 is preferably 0.5 to 20 m/sec. Relative speed is 0.5m/
If the time is less than 1 second, the spraying material and spraying conditions are severely limited, which is disadvantageous in terms of cost. If the speed is 20 m/sec or more, the length of the sheet 2 that runs when the equipment starts up increases the speed becomes significantly longer, and extremely complicated spraying amount control is required to maintain the uniformity of the sprayed molded product in this area. There are drawbacks that make it necessary. The relative speed between the sheet 2 and the thermal spray gun 3 is more preferably 1 to 5 m/sec. When the relative speed exceeds 1 m/sec, many types of thermal spray materials can be sprayed under conditions where the thermal spray gun reaches its maximum capacity, and even if the relative speed is increased beyond this point, the production rate will not increase. 5
The thermal spray gun can be moved up to m/sec, and any of the above-mentioned types of thermal spray processing equipment can be operated at speeds below this speed.

The heat resistance of the composite material of the present invention is comparable to that of thermally sprayed inorganic materials for very short periods of time. Therefore, it exhibits excellent performance as clothing and flexible materials used in work that involves occasional exposure to sparks, or as clothing and flexible materials used in work where there is a risk of short-term contact with flames. Specifically, these include work clothes in front of a furnace, curtains to prevent sparks, gloves to prevent sparks, shoes to prevent sparks, furnace cloth for gases containing sparks, welding work clothes, apron for welding, arm clippers for welding, and firefighting work. Used for clothing, fire hoses, sanding work clothes, sanding aprons, sanding arm clippers, dustproof covers for sanding, flame-retardant curtains, automobile racer clothes, tank rider clothes, flamethrower work clothes, etc. Furthermore, the composite material of the present invention has excellent dimensional stability near the softening point of organic fibers, expanding the conditions under which organic fibers can be used. It also prevents clothing from melting and deteriorating due to frictional heat generation. Specifically, surface materials for ironing boards and insulation materials,
It is used to prevent friction melting on motocross pants, the knees and heel of children's clothing, and to prevent friction melting on athletic clothing that may slip on the floor.

The composite material of the present invention includes metals with high infrared reflectivity,
For example, by disposing silver, aluminum, or an alloy based on these on the surface of the sprayed layer, it has the ability to block heat supplied or dissipated by infrared and visible light.
The organic fiber layer is flexible and has excellent heat retention properties, forming an excellent heat insulating material. Specific uses include:
Tents, blackout curtains, blinds, firefighting uniforms, insulation materials, insulation materials, overlays for insulation materials and insulation materials,
These products include carpet linings with heaters, sheets for use in agriculture to prevent soil temperature rise, weed control sheets, sheets to improve utilization by reflecting sunlight, sheets to prevent soil moisture evaporation, and sheets to prevent water evaporation in reservoirs.

The composite material of the present invention includes a substance with high infrared absorption rate,
For example, carbon, graphite, various black metal oxides,
By thermally spraying various black pigments together with a binder if necessary, it is possible to impart the ability to efficiently convert infrared rays and visible light into heat, resulting in good durability. Specifically, it is used for heat absorption plates in solar water heaters and solar heating devices, and is lighter and cheaper than conventional products.

The composite material of the present invention exhibits extremely high light resistance because it can utilize the excellent light blocking performance of metals. Specifically, by thermally spraying metal onto both sides of an organic fiber sheet material, it can be used for tents, cheesecloth, curing sheets, scour prevention sheets for waterways, etc., and has significantly superior weather resistance compared to conventional organic fiber materials. Show your gender.

The composite material of the present invention exhibits a wide range of electrical conductivity by disposing a semiconductor or metal in the sprayed layer. Materials made of aluminum, copper, nickel, stainless steel, etc. exhibit high electrical conductivity and are used in fabric-like conductive materials, electromagnetic shielding materials, electromagnetic wave reflecting materials, etc. Specifically, conductive work clothes, anti-static work clothes, dust-proof work clothes, electromagnetic wave leakage prevention structures,
It can be used for parabolic antenna materials, flexible waveguides for microwaves, etc. As a structure for preventing electromagnetic wave leakage, a molded product made of plastic and a laminated structure has excellent properties as it has both insulation properties.

The composite material of the present invention, in which an alloy or semiconductor having high electrical resistance is arranged in a sprayed layer, exhibits excellent performance as an electrical resistance heating element. In conventional flexible surface heating elements, a material with poorer heat deterioration resistance than organic fiber materials is placed around the conductive material. The disadvantage was that the lifespan was extremely short. In the case of the composite material of the present invention, the life of the heating element is long, the life difference with the surface fiber material is reduced, and flexibility, folding durability, etc. are significantly improved. Furthermore, since the light resistance is greatly improved, it can be embedded in concrete or asphalt and used for melting snow and ice on roads, airports, etc.

The composite material of the present invention, in which electrically insulating ceramics are arranged in a sprayed layer, has notable uses as an insulator. The composite material of the present invention, which uses fibers that are difficult to carbonize as organic fibers, is formed into various shapes and then incinerated to form an extremely heat-resistant and lightweight insulating layer around the metal conductive material. can. Something similar is formed when organic fibers are extracted with solvents. Even if a ceramic thin plate is made and molded, it is difficult to deform it uniformly, so processing such as wrapping it around an electric wire is impossible, but the composite material of the present invention can be deformed to a large extent under limited conditions.

The composite material of the present invention, in which ceramics are arranged in a sprayed layer, from which organic fibers are removed, is porous;
Due to its large surface irregularities, it exhibits excellent performance as an extremely lightweight heat insulating material and overfill material.

The composite material of the present invention, in which a hard material such as ceramics or cermet is disposed in the sprayed layer, exhibits excellent performance as a sheet-like abrasive material. When producing a sheet-like abrasive material by applying powdered abrasive material to cloth, the cloth is usually first coated with a filler coating, then a primary adhesive layer is coated, and then a powdered abrasive material is coated with a secondary adhesive layer. Apply an abrasive. In order to use the composite material of the present invention as an abrasive, a highly malleable metal such as aluminum, cobalt, nickel, or copper may be sprayed onto an organic fiber sheet material, and then ceramics or cermets may be sprayed thereon. If the particle size of the abrasive is small, it is better to add calendering in the middle. In the conventional method, pretreatment for abrasive coating requires four steps including drying, whereas with the composite material of the present invention, only one or two steps are required.

When the thermal spray layer contains large amounts of copper, tin, and cadmium, the composite material of the present invention is used underwater,
It is characterized by significantly less adhesion of marine organisms. A net made of the composite material of the present invention exhibits excellent antifouling performance as a fish tank used in the sea.

When the sprayed layer contains large amounts of boron and cadmium, the present invention exhibits excellent performance as a neutron shielding material. Specific applications include work clothes used in areas around nuclear reactors where thermal neutrons may be leaking.

In the present invention, the unique color of the sprayed material can be used to spray the material into a specific shape to provide a decorative effect. To spray a specific shape, you can move the spray gun around that shape, but you can also cut out the specific shape from a heat-resistant sheet of material, cover the parts you don't want to spray with the sheet of material, and make sure the spray flame comes in contact with the shape. It is preferable not to do so.

Certain forms of thermal spraying can also be implemented as antistatic treatments. To suppress static electricity, it is not necessary to provide a conductive layer on the entire surface of the composite material;
The conductive layer may be provided in a striped, lattice, or other pattern at cm intervals. In contrast to providing a conductive layer over the entire surface, the advantage of providing a conductive layer locally in a specific pattern is that the material is lighter and more flexible.

The composite material of the present invention can be manufactured by forming a sheet and then thermally spraying an inorganic material.
In particular, when making clothing, it is difficult for a needle to pass through the sprayed layer, so it is better to spray it after sewing to make a better product. However, since cooling after thermal spraying is very difficult, it is necessary to adjust the cooling device for each size of clothing, which is disadvantageous in terms of cost. When thermal spraying is applied after clothing has been sewn, it is also preferable to perform the thermal spraying locally, particularly in areas where fire resistance is required.

The present invention will be explained below with reference to Examples.

Example 1 Cloth made of vinylon spun yarn (fabric weight 220 g/m ² , plain weave,
Alumina-titania-based ceramics thermal spray powder (Meteco) was applied using a plasma spraying system 7M equipment manufactured by Metco (USA) with a density of 42 pieces/inch x 42 pieces/inch).
130SF (melting point 1840°C) was spray molded to a thickness of approximately 25 μm. Thermal spraying conditions were a voltage of 50 volts, a current of 160 amperes, and an argon flow rate of 2 normal cubic meters/hour.
Cloth feeding speed 2.2 m/sec (one time contact time with spray fluid flame 0.014 sec), spray gun moving speed (perpendicular to cloth feeding direction) 0.05 m/sec, spacing between spray gun and cloth 120-140 mm, thermal spraying The number of times was 16. Cooling air was sent at a flow rate of 12 m/sec toward the point where the fabric escaped from the spray fluid flame to rapidly cool it.

The surface condition of the fabric thus obtained is good;
The texture is slightly harder than the raw material vinylon cloth, but it does not show any roughness. When expressing the stiffness of a cloth by the distance that a horizontally protruding cloth hangs from the tip of the support base to a line drawn diagonally downward at 45 degrees, a value of 10 cm is obtained, compared to 7 cm for the vinylon cloth used as the raw material.
It was found that the thermal spraying had made it a little harder.
However, this value is not so large that it poses a particular problem as a characteristic of the cloth.

The abrasion resistance of this fabric was examined using a taper type abrasion tester. Assuming that the end point of wear is the point at which 1/2 of the cloth surface becomes vinylon fiber, the wear wheel CS-17 and the load are
When a wear test was conducted at 500g, the wear life was
It was 300 times.

The peeling resistance of the ceramic layer was investigated. I repeated pasting and peeling off the sellotape 20 times, but
No substantial peeling was observed.

In order to investigate the wash resistance of this fabric, synthetic detergent was washed using a commercially available electric washing machine (Hitachi PF2500 Aozora).
I washed it in a 0.5% solution for 10 minutes, but there was no substantial change.

A steel ball weighing 4 g was heated to 500°C and placed on top of this cloth, but no substantial change was observed. Furthermore, when a burning cigarette (highlight) was left on this cloth, slight yellowing and hardening of the vinylon fibers occurred, but no deformation of the cloth occurred. This change was determined to be the same or slightly smaller than that of Nomex (registered trademark of Dupont) cloth with a similar weight.

Example 2 The same vinylon cloth as in Example 1 was coated with a diameter of 4.8 mm using a frame spray gun model 12E made by Metco, USA.
Thermal spraying was carried out by supplying aluminum wire of mm.
Thermal spraying conditions were: oxygen flow rate 2.2 normal cubic meters/hour, acetylene flow rate 1.0 normal cubic meters/hour, wire feed rate 7 kg/hour, cloth feed rate 2.2
The moving speed of the spray gun was 0.1 m/sec, the distance between the spray gun and the cloth was 200 mm, and the number of sprays was 6 times. Cooling air was sent at a flow rate of 10 m/sec toward the point where the cloth escaped from the spray flame to cool the cloth.

The average thickness of the aluminum film on the fabric thus obtained was about 35 μm, and the surface had an appearance similar to that of a metal material with a matte finish. The texture is a little harder and a little rougher than the raw vinylon cloth, but it's not uncomfortable. When we express the hardness of the cloth by the distance that the horizontally protruding cloth hangs from the tip of the support base to a line drawn 45 degrees downward, we obtain a value of 18 cm, compared to 7 cm for the vinylon cloth used as the raw material, indicating that it has become considerably harder due to thermal spraying. I found out that but,
This value is not so large that it poses a problem when worn for work clothes or the like.

The abrasion resistance of this fabric was examined using a taper type abrasion tester. 1/2 of the cloth surface as the end point of wear
As the point where becomes vinylon fiber, wear ring CS-17,
When a wear test was conducted under a load of 500g, the wear life was 1000 cycles.

In order to examine the peeling resistance of the aluminum layer, cellophane tape was applied and peeled 20 times, but no substantial peeling was observed.

In order to examine the washing resistance of this fabric, synthetic detergent was used in a commercially available electric washing machine (Hitachi PF2500 Aozora).
Washing in a 0.5% solution for 10 minutes resulted in no substantial change.

A steel ball weighing 4 g was heated to 500°C and placed on top of this cloth, but no substantial change was observed. A cigarette (highlight) was also left burning on the cloth, but no substantial change occurred.
Further, when the flame of a commercially available gas lighter was adjusted to a flame length of 2 cm and then brought into contact with this cloth and heated for 1 minute, only slight hardening of the vinylon fibers was observed and no deformation of the cloth occurred. This change was judged to be slight compared to Nomex cloth of similar weight.

The electrical resistance of this cloth, 10 cm wide and 30 cm long, was approximately 5 ohms. This cloth had almost the same radio wave shielding ability as aluminum foil with a thickness of 50 μm.

Example 3 In place of the vinylon cloth in Example 1, fabrics made of cotton, wool, polyester, nylon, and acrylic spun yarns having approximately the same weight were used and treated under the same conditions as in Example 1. When we adjusted the distance between the thermal spray gun and the cloth, we found that there was a suitable distance for each material.
All the thermal spray coatings obtained at that distance showed excellent wear resistance and peeling resistance. In addition, the resulting fabric exhibited flexibility and breathability within a range that allowed it to be used as clothing. The resulting fabric had excellent heat resistance and flame resistance.

Comparative Example 1 In Example 1, the cloth feeding was stopped and the distance between the thermal spray gun and the cloth was adjusted to perform the treatment, but at a distance where the vinylon fibers did not melt, a thermal spray coating was not formed, but a thermal spray coating was formed. Melting of vinylon fibers occurred under these conditions.

When the speed of the thermal spray gun is increased to 0.1 m/sec, conditions are created in which vinylon fibers do not melt and an initial coating is formed. At this time, the rate of scattering of the sprayed material was large and the growth of the film was slow.

Example 4 In place of the vinylon cloth in Example 2, fabrics made of cotton, wool, polyester, nylon, and acrylic spun yarns with approximately the same weight were used and treated under the same conditions as in Example 2. A thermal sprayed coating with excellent peeling resistance was obtained. In addition, the obtained fabric exhibited flexibility and breathability within a range suitable for use as clothing, and had excellent heat resistance and flame resistance.

Example 5 Fabric weight 80-100 instead of vinylon cloth in Example 2
When treated under the same conditions as in Example 2 using long fiber cloths of polyester, nylon, vinylon, and acrylic of g/m ² , thermal spray coatings with excellent abrasion resistance and peeling resistance were obtained in all cases.

Example 6 Instead of the vinylon cloth in Example 2, cheesecloth (density 8
When the fabric was treated under the same conditions as in Example 2, the aluminum thermal spray coating covered the back surface of the cloth and exhibited excellent light resistance and radio wave shielding properties.

Example 7 Instead of the alumina-titania ceramic powder of Example 1, alumina (Meteco 105SF), chromium oxide (Meteco 106F), zirconia (Meteco
201NS), molybdenum (Meteco 63), 17% cobalt-tungsten carbide cermet (Meteco
73FNS-1), a uniform and good sprayed coating was formed in all cases.

Example 8 Instead of the aluminum wire in Example 2, zinc,
When we sprayed copper, nickel, carbon steel (Meteco Splastel #10), and stainless steel (SUS304), good sprayed coatings were formed in all cases.

Example 9 The same thermal spray gun was used to supply stainless steel wire (SUS304) to the aluminum sprayed vinylon cloth obtained in Example 2, and thermal spraying was performed. The spray conditions were the same as for aluminum. The thickness of the obtained stainless steel film was 10 μm on average.

The surface had the appearance of a satin-finished metal material, but the texture was rough and hard, like a file. The fabric was slightly stiffer than that obtained in Example 2, but remained flexible enough to be used in clothing. The wear life of the stainless steel film was 800 cycles using a Taber abrasion tester.

[Brief explanation of the drawing]

FIG. 1 is an electron micrograph of the surface of the composite material of the present invention. FIG. 2 is an electron micrograph showing the morphology of inorganic particles attached to fibers when a very small amount of thermal spraying was performed. FIG. 3 is a schematic diagram of main parts of a processing apparatus used in carrying out the present invention. FIG. 4 is a schematic diagram of main parts of another embodiment of a processing apparatus used in carrying out the present invention. FIG. 5 is a schematic diagram of the main parts of a processing apparatus according to still another embodiment.

Claims (1)

[Claims] 1. When forming a molded article on a sheet-like material mainly consisting of organic fibers by thermally spraying fusible particles of an inorganic substance having a melting point higher than the melting point of the organic fibers using a high-temperature fluid, The relative velocity between the central axis of the object and the high temperature fluid is 0.1 to 100 m/
A method for producing a composite material of organic fibers and inorganic materials, characterized in that the sheet-like material is rapidly cooled immediately after leaving the high-temperature fluid.