JPH03146770A - Production of hybrid yarn - Google Patents

Abstract

PURPOSE:To obtain hybrid yarn suitable as a material for fiberreinforced metal by precoating continuous inorganic yarn and/or a material lying between matters with an organic substance and by attaching the material lying between matters, comprising scaly metal particles to the surface of the continuous inorganic yarn. CONSTITUTION:Continuous inorganic yarn 1 (e.g. alumina yarn or silica yarn) and/or material lying between matters is previously immersed in a solution dissolving an organic substance such as lubricant, e.g. natural paraffin or microwax, coated with the organic substance and the continuous inorganic yarn is introduced to an emulsion 3 containing the material lying between matters, comprising scaly metal particles such as aluminum paste or copper paste and a binder such as polyethylene oxide by pulleys 5, 6, 7 and 8. Then the continuous inorganic yarn is sent through a drying furnace 11, brought into contact with opening rollers 16 and 17 and the yarn bundle is opened to give uniformly opened hybrid yarn without causing breakage of yarn. The yarn is used as a reinforcing material to give FRM having excellent mechanical properties.

Description

[Detailed description of the invention] (Industrial application field) The present invention relates to fiber reinforced metal (hereinafter referred to as FRM).

), and relates to a method for producing reinforcing fibers that can be suitably used as materials for

(Prior art) In recent years, alumina fiber, silica fiber, silicon carbide fiber, boron fiber, silicon nitride fiber,
FRM using carbon fiber etc. and aluminum, magnesium, titanium, copper etc. as matrix metal
has been developed and is beginning to be used in many industrial fields, such as various mechanical parts and structural materials.

Although FRM is expected to provide the mechanical properties indicated by the convergence law, in reality, predetermined mechanical properties are not obtained due to contact between continuous inorganic fibers and unevenness of the fibers.

As a solution to these problems, Japanese Patent Laid-Open No. 61-26666
Publication No. 6 discloses that inclusions such as short fibers, whiskers, or powder made of at least one kind of heat-resistant substances such as ceramics such as silicon carbide, silicon nitride, and aluminum, carbon, and metals are added to the surface of the fibers. JP-A No. 61-295346 discloses an FRM reinforced with the attached hybrid fibers. These publications state that by using the above-mentioned hybrid fibers, FRMs in which fibers are uniformly dispersed can be manufactured.

(Problems to be Solved by the Invention) The above-mentioned publication describes a method for producing hybrid fibers in which a continuous inorganic fiber bundle is immersed in a suspension of inclusions using, for example, an apparatus as shown in FIG. Hereinafter, this method may be referred to as the "suspension immersion method."

) are listed.

A continuous inorganic fiber bundle 1 is unwound from a bobbin 2 and passed through a treatment bath 4 containing a suspension 3 of inclusions on a pulley 5.6.
．． 7 and 8 and pass through.

During this time, inclusions adhere to the surfaces of the fibers constituting the continuous inorganic fiber bundle 1.

The continuous inorganic fiber bundle 1 with inclusions attached thereto is transferred to a pressure roller 9.
10 to squeeze out the liquid contained in the continuous inorganic fiber bundle 1, and then dry it in a drying oven 11 and wind it around a bobbin 12.

When the above method is carried out continuously, the inclusions are
．． 7.8 and the pressure roller 9.10, and when the continuous inorganic fiber bundle 1 comes into contact with the inclusions that are fixed to the pulley and the roller, the two may rub against each other or cross the fibers in the longitudinal direction. A force is applied in this direction, causing damage or breakage of the continuous inorganic fiber bundle 1. Damage or breakage of this continuous inorganic fiber can be easily determined by the fuzziness of the resulting hybrid fiber. It is extremely difficult to mold damaged or broken hybrid fibers into a preform of a desired shape, such as a fabric, and the FRM obtained using this preform does not exhibit the desired strength.

The applicant has diligently considered the above issues, and
We proposed a solution to this problem in Japanese Patent Application No. 1983-327710.

The specification attached to Japanese Patent Application No. 63-327710 states that (1) a continuous inorganic fiber bundle is immersed in a suspension of inclusions selected from the group consisting of powder of a heat-resistant substance, short fibers, and whiskers; When producing a hybrid fiber in which inclusions are attached to the surface of the continuous inorganic fibers constituting the fiber bundle, the hybrid fiber is characterized in that at least one of the continuous inorganic fibers and the inclusions is coated with an organic substance in advance. (2) immersing a continuous inorganic fiber bundle in a suspension of inclusions selected from the group consisting of powder of a heat-resistant substance, short fibers, and whiskers; Discloses a method for producing a hybrid fiber, characterized in that an organic substance is dissolved in the suspension when producing a hybrid fiber having inclusions attached to its surface, and (3) a continuous inorganic fiber having inclusions attached thereto. A method for producing the hybrid fiber according to (1) or (2) above is described, which is characterized in that the hybrid fiber is fiber-woven, and by these means, the fiber can be produced without damage or breakage due to inclusions such as metal or ceramic. Hybrid fibers that are uniformly opened can be obtained.

(Means for Solving the Problems) An object of the present invention is to further improve the above-mentioned proposed method, and by using scale-like metal particles as inclusions, fiber bundles can be opened more easily. The object of the present invention is to provide a method for producing a hybrid fiber that is uniformly spread and that allows easier control of the spread width.

According to the present invention, a continuous inorganic fiber bundle is immersed in a suspension containing inclusions selected from the group consisting of scaly metal particles, and the inclusions are attached to the surface of the continuous inorganic fibers constituting the fiber bundle. Provided is a method for producing a hybrid fiber characterized in that the continuous inorganic fibers and/or inclusions are coated with an organic substance in advance.

Further, according to the present invention, a continuous inorganic fiber bundle is immersed in a suspension of inclusions selected from the group consisting of scaly metal particles, and inclusions are formed on the surface of the continuous inorganic fibers constituting the fiber bundle. There is provided a method for producing a hybrid fiber, characterized in that an organic substance is dissolved in the suspension when producing the attached hybrid fiber.

Furthermore, according to the present invention, there is provided a method for producing the above-mentioned hybrid fiber, which comprises opening continuous inorganic fibers to which inclusions are attached.

The present invention will be explained in detail with reference to the drawings.

FIG. 2 or 3 is a schematic diagram of an apparatus preferably used in the method for producing hybrid fibers of the present invention.

The continuous inorganic fiber bundle 1 is unwound from the bobbin 2.

When the continuous inorganic fiber bundle 1 is not bundled with the sizing agent, the electric furnace 15 is not operated and the fiber bundle 1 is passed through without operation.
can be directly supplied to the treatment bath 4. When the fiber bundle 1 is bundled with a sizing agent, the fiber bundle 1 may be passed through an electric furnace 15 in operation to decompose and remove the sizing agent in order to cause inclusions to adhere to the surface of the continuous inorganic fibers. preferable.

Examples of the fibers constituting the continuous inorganic fiber bundle l include silicon carbide fibers, silicon nitride fibers, boron nitride fibers, aluminum nitride fibers, silica fibers, poron fibers, aluminum fibers, carbon fibers, and polymeclocarbosilane. 5i-Ti or Zr-C-0 based inorganic fibers (manufactured by Ube Industries@, Tyranno Fiber: registered trademark) obtained by In some cases, it is composed of a combination of the above-mentioned fibers.

Further, as the continuous inorganic fiber bundle l in the present invention, the inorganic fibers described in the claims of the specification attached to Japanese Patent Application No. 1-206640 and Japanese Patent Application No. 1-224511 filed by the applicant of the present application can also be suitably used.

The inorganic fibers described in the text attached to Japanese Patent Application No. 1-206640 are: i) a radial structure, an onion structure, a random structure derived from a polycyclic aromatic compound in a mesophase state constituting the polymer; a carbonaceous material exhibiting at least one type of crystal orientation selected from the group consisting of a core sial structure, a skin onion structure, and a mosaic structure; +i) an optically isotropic polycyclic aromatic compound containing an organic solvent insoluble component constituting the polymer; non-oriented crystalline carbon and/or amorphous carbon derived from a compound, and ji) an amorphous phase consisting essentially of Si, C and O;
Or, it is an aggregate consisting of crystalline ultrafine particles substantially made of β-3iC with a particle size of 500 Å or less and amorphous Sin (Q<χ≦2), and the proportion of the constituent elements is Si; 30 ~70% by weight, C;
The present invention is a high-strength, high-modulus inorganic fiber characterized by being a 5i-C-0 material containing 20-60% by weight and O; 0.5-10% by weight.

The above fiber has i) a bonding unit (Si-CH,) or a bonding unit (Si-CH,);
CH2) and a bonding unit (Si-5i), and has a side chain group selected from the group consisting of a hydrogen atom, a lower alkyl group, a phenyl group, and a silyl group in the side chain of a silicon atom, and a bonding unit (SiCHz) The total number of bonding units (Si-
At least a part of the silicon atoms of the organosilicon polymer in which the ratio of the total numbers of 3i) is in the range of 1:0 to 20 are connected to an aromatic ring of petroleum-based or coal-based pitch or a heat-treated product thereof and a silicon-carbon linking group. 100 parts by weight of a random copolymer bonded via 50000
A first step of heating and/or heating-melting the silicon-containing polycyclic aromatic polymer at a temperature in the range of 200 to 500''C, a spinning dope of the silicon-containing polycyclic aromatic polymer; a second step of preparing and spinning the yarn, and a third step of infusibleizing the spun yarn under tension or no tension.
and a fourth step of firing the infusible spun fibers at a temperature in the range of 800 to 3000° C. in vacuum or in an inert gas atmosphere.

In addition, the inorganic fiber described in the specification attached to Japanese Patent Application No. 1-224511 has a) a radial structure, an onion structure, or a random structure derived from a polycyclic aromatic compound in a mesophase state constituting the polymer. , a carbonaceous substance exhibiting at least one type of crystalline arrangement selected from the group consisting of a coa-radial structure, a skin-onion structure, and a mosaic structure; b) an optically isotropic polycyclic aromatic substance containing an organic solvent-insoluble component constituting the polymer; C) ■ an amorphous substance consisting essentially of Si, M, C and O, and/or ■ substantially β -3iC, MC, a solid solution of β-3iC and MC, and an aggregate of crystalline ultrafine particles with a particle size of 500λ or less consisting of MC+-x, and amorphous 5iOy and MO, and the proportion of the constituent elements is St. ; 5-70% by weight, M: 0.5
~45% by weight, C; 20-40% by weight and 0; O, 01
~30% by weight of SiM-C-0 material (in the above formula:
M is at least one element selected from Ti, Zr, and Hf, and O<x<1.0<y≦2, O<z≦2. ) is a high-strength, high-modulus inorganic fiber.

The above fiber has: 1) a bonding unit (Si CHz) or a bonding unit (Si
It mainly consists of CH2) and bonding units (Si-3i),
The side chain of the silicon atom has a hydrogen atom, a lower alkyl group, a phenyl group, or a silyl group, and the silicon atom of the main skeleton consisting of the above bonding unit has at least M (M is at least one selected from the group consisting of titanium, zirconium, and hafnium). is one type of element) is bonded to at least a portion of the silicon atoms directly or through an oxygen atom. or a heat-treated product thereof, which is a random copolymer bonded to the carbon of the aromatic ring of a polycyclic aromatic compound obtained from pitch containing an organic solvent-insoluble content; and 2) petroleum-based or coal-based pitch. A polycyclic aromatic compound consisting of mesophase or both phases of a mesophase and an optically isotonic phase, obtained from A first step of obtaining a polycyclic aromatic polymer containing a metal-containing polycyclic aromatic polymer, a second step of preparing a spinning stock solution of the metal-containing polycyclic aromatic polymer and spinning the spinning stock, and undying the spun yarn under tension or under no tension. Melting third
and a fourth step of firing the infusible spun fibers at a temperature in the range of 800 to 3000°C in vacuum or in an inert gas atmosphere.

Furthermore, the above-mentioned Japanese Patent Application No. 1-206640 and Japanese Patent Application No. 1
The description of the specification attached to No.-224511 is incorporated herein by reference.

The continuous inorganic fiber bundle 1 is guided by pulleys 5, 6, 7 and 8 and passes through a treatment bath 4 containing a suspension 3 of inclusions.

The scaly metal particles constituting the inclusions in the hybrid fiber of the present invention include Ag, Ti, Cu, Ni, and Co.
, Zr5Si, Cr, Zn, W, M.

These scaly metal particles can be used alone or in combination of two or more types.

The average particle size of the scaly metal particles is preferably in the range of 0.5 to 20 μm, and the average thickness of the scaly metal particles is generally 0.5 to 20 μm. It is in the range of ■~2.0μ.

If the above average particle size is too large, the scaly metal particles cannot be sufficiently interposed between the fibers and cannot work effectively during fiber opening. has no effect.

The concentration of inclusions in suspension 3 is not particularly limited, and is 0.3
The content is generally about 300 wt%, preferably 0.3 to 30 wt%.

In the first aspect of the attachment of inclusions to the fiber bundle 1 in the present invention, at least one of the continuous inorganic fibers passing through the treatment bath 4 and the inclusions is coated with an organic substance in advance.

The organic substance used in the coating may be any organic substance as long as it has the effect of alleviating forces such as friction and compression between the fiber bundle and inclusions and eliminating damage and breakage of the fibers. A lubricant having lubricating properties is effectively used to reduce friction and eliminate fiber damage and breakage. By coating the surface of at least one of the fibers and the attached material with a lubricant, the sliding between the two becomes good, and it becomes possible to eliminate breakage and breakage of the brittle and easily damaged fibers.

Examples of lubricants include natural paraffin, microwax, synthetic paraffin wax, polyethylene wax, fluorocarbon oil, higher fatty acids, oxyfatty acids, fatty acid amides, bisfatty acid amides, fatty acids, lower alcohol esters, polyhydric alcohol esters of fatty acids, and Hoechst wax. , natural waxes, aliphatic alcohols, etc.

The lubricant may be used alone or in combination with a binder, a plasticizer, etc.

The amount of the lubricant applied is preferably in the range of 0.5 to 20.0 parts by weight per 100 parts by weight of the object to be coated.

``If the amount of lubricant is too small relative to the object to be coated, it will not be effective, and if it is too large, there will be no benefit from adding more and it is not economical.

As a lubricant coating method, general coating methods such as a method of immersing a fiber bundle or an inclusion in a solution containing a lubricant and a method of spraying a fiber bundle with a solution containing a lubricant are used.

The thickness of the coating layer depends on whether the fibers or inclusions are coated, their diameter and thickness, etc.
A thickness of μm or less is sufficient.

A commercially available scaly metal paste can be used as is as the inclusion whose surface is coated with a lubricant.

Examples of the commercially available metal pastes include aluminum paste, copper paste, silver paste, nickel paste, and alloy pastes thereof.

It is preferable that a binder is dissolved in the suspension 3 to promote attachment of inclusions to the inorganic fibers, and examples of the binder include polyethylene oxide, ethyl cellulose, and the like.

The concentration of the binder in the suspension is suitably 0.1 to 0.2% by weight.

In the second embodiment of the attachment of inclusions to the fiber bundle 1 according to the present invention, the continuous inorganic fiber bundle 1 is immersed in a medium in which inclusions are suspended and organic matter is dissolved.

Specific examples of the medium in which inclusions are suspended and optionally organic substances are dissolved include alcohols such as methanol and ethanol, and organic solvents such as benzene, toluene, and xylene.

Note that water can also be used as a solvent for suspending only inclusions. In the first and second aspects of the invention, there are no particular restrictions on the method of immersing the continuous inorganic fibers in a suspension of inclusions, optionally in a medium in which inclusions are suspended and organic matter is dissolved. Any method known per se can be used.

In addition, in order to uniformly suspend inclusions in the treatment bath 4,
The magnetic cooler 13 can rotate the stirrer piece 14 to stir the suspension.

The fiber bundle 1 that has passed through the treatment bath 4 and has inclusions attached thereto is directly passed through a drying oven 11, as shown in FIG. 2 or 3, to evaporate and remove the medium.

There are no particular restrictions on the method of opening the fiber bundle of hybrid fibers obtained by the above method, but in order to spread the fibers uniformly, a group of rollers (one
6, 17, 18 and 19) is preferred.

This roller group C (hereinafter referred to as opening rollers) is installed just before the winding drum 12, and flattens the fiber bundle by ironing the fiber bundle up and down and changing the tension applied to the fiber bundle. The number of opening rollers may be selected depending on the number of reinforcing fibers used.

When FRM is manufactured using hybrid fibers uniformly spread to any width as described above, the fibers are more uniformly dispersed in the matrix, and the fibers have excellent mechanical properties.
Furthermore, FRMs with a wide range of fiber contents (V,) can be obtained.

The above-mentioned hybrid fiber uniformly spread to an arbitrary spread width can also be used for fiber reinforced plastic (FRP) in the same way as FRM.

FR using the hybrid fiber obtained by the method of the present invention
There are no particular restrictions on the method of manufacturing M, but in particular, a method of manufacturing a prepreg sheet by a thermal spraying method and using this to manufacture an FRM by a diffusion bonding method produces an FRM with excellent mechanical properties. It can be suitably used for.

(Effects of the Invention) According to the present invention, when manufacturing FRM using hybrid fibers in which scale-like metal particles are attached to the fibers, the fiber bundles required when manufacturing a prepreg sheet by a thermal spraying method can be uniformly distributed. In the opening process, the fibers are not damaged or broken by metal particles, and the opening width can be controlled arbitrarily, so that an FRM having a wide range of vf values in which the fibers are uniformly dispersed in the matrix can be obtained.

(Example) The invention will be explained in further detail by the following examples.

Example 1 Aluminum rice husks with an average diameter of 10 μm and an average thickness of lum were dispersed in a toluene solution containing 8 wt% stearic acid, and the aluminum powder was dried after filtration to obtain scaly aluminum powder coated with stearic acid on the surface of the aluminum powder. Ta.

The coating amount of stearic acid determined by dry weight was 5.0 wt%.

5 g of this flaky aluminum powder was placed in a treatment tank containing a mixed solution of 200 d of water and 1,800 d of ethanol, and suspended with stirring. Next, polyethylene oxide as a binder was dissolved in this suspension to a concentration of 0.1% by weight.

In this example, hybrid fibers were produced in the following manner using the apparatus shown in FIG.

The average diameter is 11 μm and the tensile strength is 314 kg/mm.”
+7) S i -T i -C-0@Vi (Ube Industries ■
While unwinding the fiber bundle 1 consisting of 800 Tyranno fibers (registered trademark) from the bobbin 2, the fiber bundle 1 is passed through the suspension at 3 m/m.
The sample was passed through while immersed at a speed of 1.5 in. Boo'J 5.6.
7 and 8, the fiber bundle 1 was immersed in the treatment bath 4 and then passed through the drying oven 11 to be dried.

Thereafter, the fiber bundle 1 was brought into contact with opening rollers 16 and 17, and the fiber bundle 1 was opened and wound around the drum 12. At that time, the opening width is 4
It was ffII11. No fuzz was observed in the fibers wound on the drum, and the tensile strength after opening was 309.
kg/m+n'', and it was found that the strength of the fibers was hardly reduced.

Comparative Example 1 Using silicon carbide powder with an average particle size of 0.2 μm, the same operation as in Example 1 was performed. In order to make the opening width 411IT11, in addition to opening rollers 16 and 17, 18. 19
I had to make contact with him.

[Brief explanation of the drawing]

FIG. 1, FIG. 2, and FIG. 3 are schematic diagrams of an example of a manufacturing apparatus used for manufacturing hybrid fibers. l--Continuous inorganic fiber 3-Suspension 5.6.7.
8--Pulley 11--Drying oven

Claims (3)

[Claims] (1) Hybrid fiber in which a continuous inorganic fiber bundle is immersed in a suspension containing inclusions selected from the group consisting of scaly metal particles, and the inclusions are attached to the surface of the continuous inorganic fibers constituting the fiber bundle. 1. A method for producing hybrid fibers, characterized in that continuous inorganic fibers and/or inclusions are coated with an organic substance in advance. (2) A continuous inorganic fiber bundle is immersed in a suspension of inclusions selected from the group consisting of scaly metal particles to produce a hybrid fiber with inclusions attached to the surface of the continuous inorganic fibers constituting the fiber bundle. A method for producing a hybrid fiber, characterized in that an organic substance is dissolved in the suspension. (3) The method for producing a hybrid fiber according to claim 1 or 2, which comprises opening continuous inorganic fibers to which inclusions have adhered.