JPS6094677A - Organic fiber composite material that reduces aquatic biofouling - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] The present invention is a rope for use underwater, especially in the ocean.

This invention relates to organic fiber composite materials with reduced aquatic biofouling that are useful as fibrous structures such as nets.

Among the lil fibrous structures used underwater are fixed nets.

A fixed net fishing rope, for aquaculture, and a connection for the aquaculture corner.

Trade ropes, ropes for aquaculture rafts, nets for seaweed cultivation.

There are many materials that are used continuously for long periods of time, such as restraining ropes for various floating structures, sheets for preventing scour, and sheets for preventing wave erosion. This is because shellfish such as shellfish and various other organisms attach to them, and their amount increases over time.

Since water flow resistance increases and if left untreated, it will be damaged, so removing these attached organisms is essential for maintenance and requires a large amount of cost.In order to prevent such attached organisms, A method has been proposed in which metals that are toxic to aquatic organisms are twisted in the form of wire rods or foils, but the metals in such twisted products are subjected to continuous stress from waves underwater, causing stress corrosion cracking. to cause it to fall off,
The effect is not permanent, and the effect is lost long before the life of the fibrous structure is reached, so it is not practical and fC.

In addition, there are methods of coating the surface of pongee structures with plastics mixed with metals or their compounds that are toxic to aquatic organisms, and methods of coating fibrous structures with metals that are toxic to aquatic organisms using adhesives. Methods of attaching the seams are also being considered, but since fibers and plastics are generally inferior in light resistance and wave resistance, the range of options is limited, and no preferred material has been found to date. .

Possible ways to solve these problems include not interposing a layer of organic material between the fiber and metal, and if possible, using a processing method that allows reprocessing of the structure in use. .

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 preservation effects on organic fiber materials. Due to this, these metal films generally have low strength and durability. Furthermore, plating and vapor deposition are time-consuming and consume a large amount of energy, so they are generally expensive and cannot be used to prevent attachment of aquatic organisms.

The present invention is characterized by comprising a thermally sprayed product containing a metal or alloy that is toxic to aquatic organisms, and a fibrous structure mainly composed of organic fibers having a lower melting point than the metal or alloy. Underwater Materials 3 - This is an organic fiber composite material that reduces the adhesion of substances, and its purpose is to make it possible to omit the binder layer between the metal material and the fiber material, and to reduce the molding cost of the metal material per weight. The goal is to reduce

Thermal spraying is performed by forming the fibrous structure into a sheet.

If necessary, the sheet-like material is further processed to return to its original shape.

Conventionally, as a highly efficient technique for coating inorganic materials, the coating material is made of high-temperature fine particles that can be fused, and the material is coated with 1.
A thermal spraying method is known in which molded products are made by spraying hot fluid with hot fluid, and it is widely used as a surface processing technique for metal materials in particular. Recently, it has been used for surface processing of ceramics and other materials, but heat transfer occurs during processing for materials with low thermal conductivity and low heat resistance, such as organic fiber materials. It has been said that the heat brought in by the thermal spraying material increases the temperature of the object to be thermally sprayed, causing deterioration of the fibers and resulting in poor bonding.

In order to avoid this, the temperature of the thermal spray fluid is lowered,
It was said that if the spray was applied from a distance, the spray particles would not be integrated and would not bond with the fiber material. For this reason, it is believed that thermal spraying 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 on organic fibers, lead is sprayed onto cotton cloth to make radiation shielding work clothes. Furthermore, Japanese Patent Application Laid-open No. 1SZ-SA79S discloses an example in which an evo medium resin prepolymer, polyethylene, polypropylene, and nylon 11 are thermally sprayed as powder for thermal spraying onto vinylon cloth and cotton cloth by thermal spraying using a plasma jet. ing. In all of these examples, the melting point of the organic fiber is higher than that of the thermal spray material, and the maximum temperature of the plasma is around 10,000°C.
The practical thermal spray processing temperature has been thought to be slightly lower than the melting point or pyrolysis temperature of the organic fiber.

While researching thermal spray technology, the present inventor happened to discover that this well-established theory was incorrect, and arrived at the present invention. Furthermore, JP-A-48-52644 discloses that when steel is sprayed directly onto a hard vinyl chloride plate, a sprayed coating with a weak bonding force of 5- is obtained; It is said that if copper is shot in a semi-hardened state, a stratodermal gland with strong bonding strength can be obtained.

This method is considered to be an advantageous method for joining plastic sheets and metal, but for joining cloth foil and metal, the process is more flexible than lining processing of cloth foil and metal film. It is generally considered that linate processing with a larger value is more advantageous. However, if a thermosetting intermediate layer has excellent heat and chemical resistance, the presence of the intermediate layer will have a strong film-retaining effect on the major fibers in the fabric.
It is thought that something standard can be obtained.

For example, if a metal (alloy) with a melting point slightly lower than that of organic fibers is used as the intermediate layer, when the metal at the melting point is sprayed, the heat accumulated by the melting material absorbs and retains the heat brought in by the sprayed material.
Show action. During the study of thermal spraying using such an intermediate layer, organic fibers and high melting point metals were sprayed from an experimental chair onto the area where the intermediate layer was not present, and that area became the area where the intermediate layer was present. It was found that the strong detachment earthquake was larger than that of the earthquake, and from this 6- we learned that the conventional theory was incorrect.

As a result of various studies, the inventor of the present invention found that by shortening the time of contact with the high-temperature fluid used for thermal spraying, and by cooling it as rapidly as possible after contact, the present inventors discovered that It was found that composite materials in the form of threads, ropes, fabrics, membranes, or thin plates can be obtained by thermal spraying metals or inorganic materials such as ceramics, which have a melting point much higher than that of the organic fibers. If the thickness of the molded product produced by zero thermal spraying is insufficient, this operation may be repeated.

When thermal spraying is applied to a fibrous structure, the structure is formed into a sheet shape. Sheet-like materials include woven materials, knitted materials, non-woven fabrics, paper-like materials, fibers, threads, nets, and ropes arranged in a substantially parallel manner, and those obtained by compressing these materials into a flat surface using pressure. (Hereinafter, such a structure will be referred to as a sheet-like product.) After thermal spraying, the sheet-like product can be used as it is or after passing through a commonly used fiber processing process. You can solve the situation and use the previous set one by one. It is also possible to spirally wind a single thread or rope around a roller or the like in parallel, spray it, and then unwind it. In the case of netting, it can be processed into a flat shape by stretching it in the direction of the grain. It is also possible to thermally spray a sheet material, slit it into a tape shape, heat it, or make it into a rope shape. The sheet-like material can be subjected to various treatments that can be applied to ordinary fibrous materials before, after, or at the same time as thermal spraying.

The contact time between the high-temperature fluid used for thermal spraying and the sheet-like material mainly composed of organic fibers is 1 second or less per blast, preferably 1 second.
/10 to 1/10000 seconds 0 Specifically, the thermal spray gun, the sheet-shaped object, or both are moved, and their relative speeds, i.e., the relative speed of the feeding speed of the sheet-shaped object and the central axis of the high-temperature fluid for thermal spraying. is 0.1 m/sec or more and 100 m/sheet or less. Specific devices include a device that sprays by moving the thermal spray gun back and forth at high speed in a direction almost perpendicular to the sheet while feeding the cloth slowly, and a device that sprays by connecting the sheets into an endless belt and running them in a ring at high speed. A device that sprays by slowly moving a gun, or a device that sprays by using a slowly moving spray gun that moves the sheet back and forth between a reversible winding device and an unwinding device, or a device that sprays yarn or - onto a roller. A device that rotates a parallel spiral spiral at high speed and sprays while slowly moving the thermal spray gun in a direction almost perpendicular to the thread or rope.The thread or rope is hung on a nelson roller and the roller is rotated at high speed. It is possible to use a device that sprays one or more thermal spray glasses either in a fixed state or while moving them.In carrying out the present invention, it is necessary to spray as quickly as possible after the sheet-like material to be sprayed and the high-temperature fluid used for spraying are separated. Cool rapidly over time. Cooling is preferably 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 velocity is at least 1 m/sec, preferably at least 10 m/sec and at most the speed of sound. 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 equipped with an internal heat removal mechanism, such as a 101-turn roller or a plate-like cooling device of various shapes.

This is because by closely adhering to a solid cooling device, it is possible to prevent the sheet-like material from being undulated by the fluid flow for thermal spraying and cooling, resulting in uneven thermal spraying.

Since the sheet material to be thermally sprayed in the present invention is porous, a portion of the thermal spray material may pass through the sheet material and come out to the back side. The equipment that cools the sheet material to be thermally sprayed from the back side needs to be maintained under conditions where the thermal spraying material does not adhere to it.To do this, the surface must be smoothed to a certain level of gloss, and the surface temperature must be kept below 200°C, preferably. 10
Maintain below 0℃. 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.

The moldiness of the composite material of the present invention is that the fibrous structure mainly composed of organic fibers and the thermally sprayed molded product mainly composed of gold 114 are integrated in a multilayered manner, and the bond between the two components. The force appears to be due to the bonding force on the organic fiber surface and the entangled structure at the interface between the two components. Such structures can be formed even under conditions where there are significant discontinuities in the metal-based moldings, and the presence of such discontinuities results in highly flexible and durable structures. A composite material is formed. In addition, by changing the continuity of the metal-based molded product, it is possible to change the elution into water and chemical reactivity, and it is possible to create a layer that changes the sustainability of the underwater biofouling prevention effect. .

In the thermal spraying process of metal materials when manufacturing the composite material of the present invention, raw materials are formed into fine particles at a temperature that can be melted or sintered in plasma generated by flame or electric discharge, and then exposed to a plasma stream or high-temperature air stream. The object is placed on the object and collided with the sheet-like object. Then, the relative velocity between the central axis of the sheet-like material and the high-temperature fluid used for thermal spraying is set to 0.1 m/sec or more and 100 m/sec or less, and the sheet-like material is rapidly cooled immediately after it is separated from the high-temperature fluid.

As a result, the sheet-like material can be removed from 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. Due to this cooling, the heat of the sheet material is
G wrinkles increase and deterioration is suppressed. This operation is repeated until the amount of irradiation reaches a desired value, and the metal material is formed into a film, a sponge, or a piece on the sheet material.

Here, the metal fine particles carried by the plasma flow or the high-temperature air current are melted in their entirety, the surface layer of the particles, 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 movement and form a film, and some of them pierce the fiber surface and become fixed. A part of the particles penetrates into the sheet 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 can be prevented from softening. It has been found that it is possible to form a metal spray coating. Metal 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.

Thermal spraying may be carried out on one side or both sides of a sheet material mainly made of organic fibers. If double-sided, the sprayed materials may be the same or different. Although it is simple and cost-effective to use only one type of thermal spraying material, the toxicity of metals varies markedly depending on the species of living organisms, so it may not be possible to obtain a sufficient adhesion prevention function with type-M. It may be preferable to use more than one species. When spraying two or more materials, they may be sprayed in parallel or sequentially in multiple layers. By spraying the mixture near the boundary between the two materials, the composition can be gradually changed from one to the other. It is also possible to mold it so that it changes from one to the other.

If the sheet material is shaped like a lined string or rope, it is possible to spray from three or more directions by changing the way the sheet is lined up. Since a material such as a rope cannot sufficiently spread the sprayed particles, it is necessary to spray from many directions in order to obtain a uniform sprayed product.

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 flame or plasma jet, and a method in which the thermal spraying material is introduced into a flame or an arc discharge. The method of introducing a rod-shaped thermal spray material, crushing it, melting it, and thermal spraying is preferable for producing the composite material of the present invention.In producing the composite material of the present invention, the relative speed of the sheet material and the spray gun is Even in the case of 0.1~Zoom
/second. If it is less than 0.1 m/sec, cooling will be insufficient no matter how you change the thermal spraying conditions, and the deterioration of the organic fibers cannot be prevented. On the other hand, at speeds close to 100 m/s, it is difficult to move the thermal spray gun, and the only method that can be used is to rotate a cooling roller with a sheet-like material on it at high speed.14- However, if the relative speed exceeds 100 m/s, The force makes it difficult for spray particles to stick together. The relative speed between the sheet material and the thermal spray gun is preferably 0.5 to 20 m/sec. If the relative velocity is 0.5 m/sec or less, there are strong limitations on the metal material to be sprayed and the spraying conditions, which is disadvantageous in terms of cost.
If the speed is 20 m/sec or more, the length that the sheet-like object travels during the speed increase process at startup of the device becomes significantly longer.
In order to maintain the uniformity of the sprayed molded product in this part, it is necessary to perform extremely complicated spraying amount control, resulting in a drawback that the cost of the equipment becomes extremely high. The relative speed between the sheet material and the thermal spray gun is more preferably 1 to 5 m/sec. 1m/
When the speed exceeds 2 seconds, many types of thermal spray metal materials can be sprayed under the conditions where the spray gun reaches its maximum capacity, and even if the relative speed is increased further, the production rate on a weight basis of the thermal spray material will not increase. .

The spray gun can be moved up to 5 m/sec, and below this speed many types of spray processing equipment can be used, making production extremely easy. Particularly in the case of thermal spraying on fabrics and papers, processing can be performed without stopping except when changing the supply of sheet-like materials, resulting in extremely low costs.

Metals that are toxic to aquatic organisms used in the composite material of the present invention include steel, tin, cadmium, amlm
, bismuth, antimony, nickel, chromium, manganese, molybdenum, mercury, and helium are known, but extremely toxic substances such as mercury and beryllium are difficult to control in the amount released, and they are not permanent. It is difficult to use because there is a concern that it may cause environmental pollution. Copper, tin, lead,
Relatively weakly toxic metals such as manganese and molybdenum can be used under conditions with high elution rates, or moderately toxic metals such as cadvalam, lead, antimony, and nickel can be used under conditions that slightly suppress the elution rate. It is preferable to use

Conditions that result in a large elution amount include conditions where each piece is larger than a rolled foil or thin wire, for example, when molded into a twisted structure with stacked roof tiles like a thermal spray molded product, or when a metal with a low ionization tendency is used. They can be placed in such a way that they are in contact with the metal to form a battery to accelerate elution, or they can be made into an alloy to increase the elution rate.

Conditions that suppress the elution rate include coating the surface with a synthetic resin, glass, ceramic, etc., or contacting a metal with a high ionization tendency, and preferentially bathing the metal with a high ionization tendency to form a battery. This can be done by suppressing the elution of the target metal by making it elute, or by creating an alloy to reduce the elution rate. Tar, a synthetic resin that is less susceptible to deterioration due to waves, can be used to suppress the elution rate by surface coating.

Pitch or a mixture of these is highly effective. Synthetic resins include polyurethane, polyacryland, silicone, epoxy, and polyvinyk:f-
acrylic acid, acrylic ester, and maleic acid-based resins are easy to use. It is preferable to use these as a copolymer, and it is also preferable to use them in a dark color. The coating with these resins not only suppresses the elution of metal, but also prevents the film of the sprayed metal from being damaged by waves.
It has the effect of preventing peeling and falling off.

17- Next, the present invention will be explained by examples.

Implementation 911 Rope made of vinylon spun yarn (diameter: 32 mm, weight: 760 tons/
3 folded twisted cloves) were wound in a spiral on iron rollers (nine rolls with a mirror finish on the surface) with diameters of 50 scratches and lengths of 6 m, so that the ropes of adjacent windings were substantially in close contact with each other. In this state, both ends were tied together. This roller was rotated at a surface speed of 140 m/min and the steel was thermally sprayed using an oxygen-acetylene flame type spray gun to obtain an oxygen flow rate of 1.3 NtIi'.
/hour acetylene flow rate 1.2 N27 hours, compressed air flow rate 1
．． 6 N♂/hour, copper wire supply t10.5 Kp1 hour, thermal spray gun running speed 0, 8 m 7 minutes. The cooling air flows at a distance of 101 m from the center of the spray flame at a velocity of 8 m/se.
The shortest distance between the rope and the thermal spray gun, which cooled the rope immediately after spraying with e, was about 1000 mm.

The thermal spraying gun is moved back and forth parallel to the axis of the roller once to perform thermal spraying. After nine, the rope is re-wound and thermal sprayed again. This is repeated and the thermal spraying process is performed four times from different directions by 9G each, and the rope is then thermally sprayed. 1m length 2518-ff) Double injection molding was formed.

The adhesion between the static injection-molded vIJ film and the rope is good, and it hardly peels off even if the adhesive tape is pasted and peeled off repeatedly. Furthermore, even if you try to separate the thermally sprayed film by cutting it open with a knife, the fibers will break and remain on the film.

When the ropes after thermal spraying were immersed in the sea, even for a year, there was very little adhesion of seaweed, and in particular, almost no adhesion of shellfish such as Fujibo. On the other hand, when the rope was immersed in the sea before thermal spraying, so much algae had adhered to it that the rope's twists could no longer be seen after two months.

Example 2 The same vinylon rope as in Example 1 was wound around the same metal roller as in Example 1, and thermal spraying was performed. The thermal spray gun uses a direct current arc discharge using a supplied metal wire as a consumable electrode. Metal: Aluminum ia * Zinc 8
Uses 7% alloy wire.

Arc current 100 amps Arc voltage 28 volts, metal wire feed rate 14? / Tokito.

The shortest path between the rope and the thermal spray gun is 5100 □, the roller surface speed is 140 m/min, the gun travel speed is 0.8 m/min, and the rope is re-wound and sprayed diagonally.
The sprayed product was sprayed from four different directions to obtain a sprayed product of 42 f/m.

The adhesion between the thermal spray molding and the rope was as good as in Example 1. Furthermore, when the ropes after thermal spraying were thrown into the sea and the amount of biofouling was examined, the amount of biofouling was extremely low.

Example 3 The same vinylon lobe as in Example 1 was wound around the same metal roller as in Example 1, and molybdenum powder (Met
CO663) was sprayed.Thermal spraying conditions were voltage: 50 volts, current: 160 amperes, and argon flow rate: 2. ONd1
time, roller surface speed 132 m/min (one time contact time with oblique plasma flame 0.014 sec), spray gun moving speed 3 m/sec, minimum distance between the spray gun tip and rope 120 m/min, old spray gun is roller It was made to reciprocate 8 times in a direction parallel to the axis.

For oblique spraying, the rope was re-wound on a roller and processed four times from different directions by 90 degrees, after which a thermally sprayed wIJ film of υ28f per 1m of rope was formed.

The adhesion between the thermal spray molding and the rope was as good as in Example 1. When the rope was thrown into the sea after being shot, and the amount of biofouling was examined, the amount of biofouling was extremely low.

Example 4 A rope was made by changing the fibers in the surface layer of the vinylon rope of Example 1. Copper was thermally sprayed under the same conditions as in p1. Ropes with approximately the same thickness were made using 100% cotton, wool, rayon, polyester, nylon, and acrylic as spun yarns for the surface layer.

Thermal spray processability was not much different from that of vinylon, and no deterioration during processing was observed, except for polyester nylon, which suffered from a decrease in strength.

The amount of biofouling on the thermally sprayed rope in the sea was small, and the value was not much different from that in Example 1.

Example 5 A 2l-5JllQI2O vinylon rope was made by changing the fibers in the surface layer, and an alloy of Al1=Um13TiZinc871 was thermally sprayed under the same conditions. Multifilament yarns of rayon, polyester, nylon, vinylon, and polypropylene, as well as split yarns of polypropylene and polyethylene were used to replace the vinylon spun yarn in the surface layer to create ropes with approximately the same thickness.

The adhesion efficiency during thermal spraying is 10 to 2 compared to vinylon spun yarn.
0'% low and 9 showed almost no deterioration during processing and only slight dimensional change.

The amount of biofouling on the thermally sprayed rope in the sea was small (the value was not much different from that in Example 2).

Example 6 The steel plate of Example 1 was sprayed with zinc, cadmium-containing zinc, tin, lead, 10% bismuth-containing lead, antimony-containing lead, nickel, chromium, and manganese. In either case, a good film is formed on the thermally sprayed molded product, and the effect of preventing the adhesion of underwater organisms is excellent.

22-

Claims (2)

[Claims] (1) An aquatic organism characterized by consisting of a thermally sprayed molded product containing a metal or alloy that is toxic to aquatic organisms and a fibrous structure whose main component is an organic fiber having a lower melting point than the metal or alloy. Organic fiber composite material with reduced adhesion (2) In the preceding paragraph, an organic fiber composite material with reduced aquatic biofouling, characterized in that the organic fibers at the time of forming the thermally sprayed molded product are in the form of a sheet.