JPH0791728B2 - Woven cloth - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention provides a reinforcing member such as a fiber reinforced resin (FRP), a fiber reinforced metal (FRM), a pneumatic tire, or a magnetic shield property for an aircraft. Further, the present invention relates to a woven fabric that is adopted as a garment material having high strength as a constituent member thereof, and particularly to a novel high-strength metal ultrafine wire having a novel fibrous fine metal structure in at least one of warp threads and weft threads. Woven fabric with various structures.

[Conventional technology]

For example, reinforcing fibers such as FRP and FRM have conventionally been glass fibers, carbon fibers, aramid fibers, etc. These single fibers or a plurality of sizing-treated composite yarns are woven. The woven fabric is generally used as a reinforcing member for FRP and the like. On the other hand, high-strength metal wires such as piano wires have a large wire diameter and it is difficult to perform a yarn-sizing process.
In addition, since it is difficult to cut the weft threads when making a woven cloth, a woven cloth made of high-strength fine metal wires has not been manufactured so far.

[Problems to be Solved by the Invention] By the way, as a woven fabric for reinforcement such as FRP, it is necessary to increase the strength of the woven fabric as much as possible in view of its use. For that purpose, the warp yarns constituting the woven fabric are required. ， It is necessary to greatly improve the tensile strength of the weft. Further, in order to facilitate the woven process, it is required that the wire diameter be as small as possible to facilitate the sizing treatment. In order to meet such requirements, it is expected that the metal extra fine wire will have high strength and excellent toughness. However, as described above, the conventional piano wire has a large wire diameter and is difficult to perform the sizing treatment, and the tensile strength is not so high as compared with aramid fiber or the like,
We cannot meet the above requests.

The present invention has been made in order to meet the above-mentioned conventional requirements, and by making the wire diameter as small as possible and improving the tensile strength, a woven fabric that is easy to be woven and has extremely high strength can be obtained. It is intended to be provided.

[Means for solving problems]

In order to achieve the above object, the inventors of the present invention have conducted extensive studies on a metal structure capable of significantly improving the tensile strength of a warp or weft for a woven fabric, and have found the following points. That is, Fe-C
-Si-Mn-based iron-based alloys and wire rods with a composite metallographic structure in which the low-temperature transformation-forming phase consisting of acicular martensite, bainite, or a mixed structure of these is uniformly dispersed in the ferrite phase It is excellent, and if a wire with such a metal structure is used, the wire diameter is 160 μm due to cold drawing.
The following ultrafine wires can be easily and surely obtained. When such a wire rod is subjected to strong working by cold drawing to a working strain of 4 or more, a uniform fibrous fine metallographic structure in which the composite structure in which the ferrite phase and the low temperature transformation forming phase are combined extends in one direction. It was found that the ultrafine wire formed and having such a metallographic structure has a dramatically improved tensile strength of 300 to 600 kg f / mm ² and a toughness comparable to that of conventional piano wire and stainless wire.

Such a fibrous fine metallic structure is a completely new structure which has not been known so far. From the viewpoint that the fibrous fine metallographic structure is a main factor for improving the tensile strength, the inventors further conducted research on the strengthening mechanism, and as a result, the metallographic structure having the ultrahigh strength as described above. Found that the distance between the fibers is 50 to 1000Å and the fibrous composite structure is composed of ultrafine cells of 5 to 100Å.

Therefore, the present invention is a woven fabric obtained by weaving warp yarns and weft yarns, in which at least one of the warp yarns and the weft yarns is formed by subjecting a wire rod to strong working by cold drawing, and producing 5 to 100Å Of ultrafine cells are arranged in one direction in a fibrous form, and a fibrous fine metallographic structure in which the distance between the fibers is 50 to 1000Å is formed. Wire diameter is 160 μm or less, tensile strength is 300 to 600 kg.
It is characterized in that it is an ultrahigh-strength metal ultrafine wire of f / mm ² or a composite yarn obtained by subjecting a plurality of the metal ultrafine wires to sizing treatment.

In the woven fabric according to the present invention, either one of the warp yarns and the weft yarns, for example, when the weft yarns are made of metal ultrafine wires, carbon fibers, aramid fibers, and glass fibers conventionally used may be used for the warp yarns. Alternatively, the metal ultrafine wire of the present invention may be mixed with carbon fiber or the like to form a yarn.

Here, a method for producing an ultrahigh-strength metal ultrafine wire for warp or weft in the woven fabric of the present invention will be described.

First, C: 0.01 to 0.50% by weight, Si: 3.0% or less, Mn: 5.0
% Or less, wire diameter 3.5 mm consisting of balance Fe and unavoidable impurities
After heating the following wire to a temperature in the range of 700-1100 ℃,
After cooling (this heating or cooling may be carried out multiple times), a low temperature transformation forming phase consisting of martensite, bainite or a mixed structure thereof, which may partially contain retained austenite, is added to the ferrite phase. 15-75 by volume
A wire having a composite structure uniformly dispersed in the range of 10% is manufactured. Incidentally, such a manufacturing method is disclosed in JP-A-62-20
It is described in Japanese Patent No. 824.

Then, the composite textured wire thus obtained is subjected to a strong working to a working strain of 4 or more, preferably 5 or more by cold wire drawing to compound the ferrite phase and the low temperature transformation forming phase,
A fine fibrous structure extending continuously in one direction is formed as a metal structure. By increasing the degree of processing in this way, the fibrous structure is further miniaturized and the fiber spacing is narrowed, and finally the cell size and fiber spacing produced by processing as described above are 5 to 100Å, 50 to It has a fine fibrous microstructure of 1000Å. It should be noted that in a fine wire obtained by wire drawing with a working strain of less than 4, the fibrous structure is in the middle of its development and its structure is incomplete, and therefore its strength is also small.

FIG. 8 is a comparison of the tensile strength and toughness of the ultrahigh-strength metal ultrafine wire for warp and weft in the woven fabric of the present invention with that of a conventional aramid fiber and the like.
It can be seen that the tensile strength and toughness are dramatically improved compared to aramid fibers and the like. Further, FIG. 9 is a scanning electron micrograph of the metal ultrafine wire for warp and weft of the present invention which has been strongly processed to a processing strain of 5 or more (area reduction rate 99.5%) by the above-mentioned method. A fibrous fine metallic structure extending is observed. FIG. 10 is a photograph of the above fibrous structure observed by an ultra-high voltage electron microscope (3MV). In the internal microstructure, 20-50Å ultrafine cells are observed.

Next, the reasons for setting various conditions in the above manufacturing method will be described.

C: In order to obtain the fibrous fine metallic structure according to the present invention and the above tensile strength, it is necessary to regulate the amount of C added, and as a result of experiments, it was found that the range of 0.01 to 0.50% is appropriate. .

Si: Si is effective as a strengthening element for the ferrite phase,
If added in excess of 3.0%, the transformation temperature will shift to the extremely high temperature side and decarburization of the wire surface will easily occur.
The upper limit of addition is 3.0%.

Mn: Mn has the effect of strengthening the ultrafine wire and enhancing the quenching of both phases, but even if added in excess of 5.0%, this effect saturates, so the upper limit of addition is 5.0%.
And

Further, elements whose content is preferably controlled, elements which may be added, and inevitable impurities are described.

H is a harmful element that embrittles steel, and its effect increases as the strength increases, so in the present invention, H
The amount should be regulated to 1 PPM or less, particularly preferably 0.5 PPM. As a method of reducing the amount of H, means such as degassing treatment with molten steel, hot rolling on wire rods, cooling control after heat treatment, and low temperature dehydrogenation control are effective.

In the present invention, in order to refine the metal structure of the ultrafine wire, N
At least one element selected from b, V and Ti can be added. These elements are used for the refinement of the structure.
Both require 0.005% or more addition, but even if added too much, the effect is saturated and it is economically disadvantageous, so the upper limit is made 0.5%.

Inevitable impurities include S, P, N, Al, and the like.

S is preferably 0.005% or less in order to reduce the amount of MnS, whereby the ductility can be further improved. On the other hand, by adding rare earth elements such as Ca and Ce, M
It is also preferable to adjust the shape of the nS inclusions.

PHF.Since it is an element with remarkable grain boundary segregation, its content is 0.
It is preferably set to 01%.

N is an element that is most easily aged when it exists in a solid solution state, and it aged during processing to impair the workability, or aged after processing to deteriorate the ductility of the ultrafine wire obtained by wire drawing, It is preferably 0.003% or less.

Al forms oxide inclusions, and since these inclusions are difficult to deform and hinder the workability of the wire, it is usually preferable to set it to 0.01% or less. Also, as the Si / Al ratio in the ultrafine wire increases, silicate inclusions increase, and especially when the amount of Al is small, the silicate inclusions increase rapidly, which not only deteriorates the wire drawability but also causes wire drawing. The characteristics of the obtained ultrafine wire are deteriorated. Therefore, in the present invention, the Si / Al ratio is preferably 1000 or less, particularly preferably 250 or less.

The reason why the volume fraction of the low-temperature transformation forming phase in the ferrite phase in the composite structure of the wire is within the range of 15 to 75% is as follows. If it is less than 15%, it will be 16 due to cold drawing of the wire with such a composite structure.
Although an ultrafine wire of 0 μm or less can be obtained, the obtained ultrafine wire does not have a fibrous fine metallographic structure as described above, the fibrous structure is incomplete, and the tensile strength is 30%.
It will be 0 kg f / mm ² or less. On the other hand, when the volume fraction of the low-temperature transformation forming phase in the ferrite phase is more than 75%, the wire rod is easily broken during wire drawing, and even if the wire can be drawn without breaking, the obtained ultrafine wire is As in the case of the above 15% or less, it does not have a fine fibrous structure, the fibrous structure is incomplete, and the tensile strength is low at 300 kg f / mm ² or less.

Regarding the volume fraction of the wire, the wire diameter and the volume fraction of the wire are regulated by the form of the low temperature transformation generation phase, that is, whether the phase is mainly needle-like or mainly lumpy. It In addition, needle-shaped (elongated here)
Or acicular) means that the particles have directionality,
The term “globular” means that the particles do not have directionality.

That is, when 80% or more of the low-temperature transformation-producing phase is acicular, the low-temperature transformation-producing phase has a volume fraction of 50% or less and a wire diameter of 3.5 m.
If it is m or less and 80% or more is lumpy, the volume fraction should be 50% or less and the wire diameter should be 2.0 mm or less. When the low-temperature transformation-producing phase has a mixed structure of needles and lumps, the volume fraction should be 75% or less and the wire diameter should be 3.5 mm or less. The lower limit of the wire diameter that the wire should have is not particularly limited, but is usually 0.3 mm in view of the current processing technology.

[Action]

According to the woven fabric of the present invention, the metal ultrafine wire adopted for the warp and the weft has a processing cell of 5 to 100 Å produced by the strong working of cold drawing and is arranged in a fiber in one direction, and the fiber is It has a fibrous fine metallic structure with a spacing of 50 to 1000Å and, as explained in the strengthening mechanism above, 300 to 600 kg f / m.
It has an ultra high strength of m ² . Therefore, the tensile strength of the woven fabric can be dramatically improved.

Further, the metal ultrafine wire for woven fabric of the present invention has excellent cold workability, and a wire having a diameter of 160 μm or less can be easily and surely obtained by appropriately selecting the wire diameter and the workability of the wire. Therefore, for example, if a wire diameter of 10 to 100 μm is adopted, the combined yarn-sizing process is easy, and even when used for the weft yarn, the wire diameter is small and the weft yarn can be easily cut. Is high.

Further, the woven fabric of the present invention is capable of so-called hybrid weaving in which metal ultrafine wires and conventional carbon fibers or the like are mixed and woven,
Therefore, it is possible to manufacture a composite woven fabric that brings out the advantages of each fiber. For example, a woven fabric that has the light weight of carbon fiber and the high strength, high toughness and electromagnetic shielding property of the metal ultrafine wire of the present invention is possible. Becomes

〔Example〕

 Embodiments of the present invention will be described below with reference to the drawings.

1 and 2 are views for explaining a woven fabric according to an embodiment of the present invention.

In the figure, 1 is a woven fabric having a plain weave structure in which a warp yarn 2 and a weft yarn 3 are interwoven, and the warp and weft yarns 2 and 3 are
20 to 50 fine metal wires 4 each having a thickness of 10 to 100 μm are combined and subjected to a sizing treatment. The outer surface of each metal fine wire 4 is plated with Ni. This is mainly for improving the focusing property in the sizing process. That is, if not plated,
Since the metal ultrafine wire 4 is iron-based, by using a water-soluble epoxy-based sizing agent in the sizing treatment, rust is generated to impair the focusing property, and the adhesive force with the matrix resin is reduced. . It should be noted that it is effective not only to apply Ni plating but also to apply Cu, plus or the like plating.

Each of the metal fine wires 4 in this embodiment has a weight percentage of C: 0.01 to 0.
50%, Si: 3.0% or less, Mn: 5.0% or less, the remaining Fe and unavoidable impurities with a wire diameter of 2.5 mm or less are cold-drawn and strongly processed to a wire diameter of 160 μm or less. ,
The processing cells produced by the strong processing form a fibrous fine metal structure in which fibers are arranged in one direction in a fibrous shape, and the size and the fiber interval of the processing cells are 5 to 100Å, 50 to 10 respectively.
It is an ultra-high-strength ultrafine metal wire with a strength of 00Å and a strength of 300 to 600 kg f / mm ² .

As described above, since the metal ultrafine wire 4 of this embodiment can have a very small diameter, the composite yarn-sizing treatment is easy, and the workability in the case of weaving is high, and the conventional piano wire or the like is used. It is possible to realize a woven fabric with metal fine wires, which was difficult with. Further, since the outer surface of the metal ultrafine wire 4 of this embodiment is plated with Ni, it is possible to prevent rust from being generated by the water-soluble sizing agent, and improve the focusing property by the sizing treatment. It is also easy to woven fabric.

The woven fabric 1 of this embodiment is used for reinforcing FRP, FRM, pneumatic tires, etc. In this case, the metal fine wire 4 has a strength of 300 to 600 kg f / mm ^{2, which} is a conventional value. Compared to aramid fiber etc., it is dramatically improved, so it is FRP
And the like can be improved. Further, in the case of obtaining the same level of strength as the conventional one, the amount of reinforcing fiber required is greatly reduced, and the weight reduction can be achieved accordingly.

Next, the wire diameter of the present invention is 160 μm or less, and the tensile strength is 300 to 600 kg.
An experimental example in which the thin metal wire 4 of f / mm ² is manufactured will be described.

Experimental Example 1 First, the wire diameter shown in Table 2 having the chemical composition shown in Table 1
A 0.9 to 2.5 mm wire rod is continuously heated and quenched at a temperature of 890 ° C, and then continuously heated and cooled at 810 ° C, both of which have a ferrite phase and a martensite phase partially containing retained austenite. A composite textured wire having a phase structure was obtained.
Then, this composite structure wire rod was drawn into an ultrafine wire of the wire system shown in Table 2 by cold drawing. In Table 2, steel numbers 1 to 9 can be adopted as the metal extra fine wire 4 for the woven fabric of the present invention. For comparison, a wire rod having the chemical composition shown in Steel No. 10 in Table 1 was subjected to lead patenting and wire drawing four times to obtain a high carbon steel piano ultrafine wire. The tensile strength of these ultrafine wires was measured, and the metallographic structure was observed with an ultrahigh voltage electron microscope (3MV).

The results are shown in Table 2. As is clear from this table, the fiber spacing is 90 to 650Å, the cell size is 20 to 90Å, and the tensile strength is 3
30~538kg an f / mm ^2, the tensile strength is found that has greatly improved over 318kg f / mm ² of the comparative example according to conventional methods. Further, in this case, the higher the degree of processing, the narrower the fiber spacing and the smaller the cell size, and the tensile strength is improved accordingly.

Experimental Example 2 C: 0.18%, Si: 0.9%, Mn: 1.5%, S: 0.002%, N:% by weight
A wire rod with a wire diameter of 2.5 mm having a chemical composition of 0.002% and Al: 0.003% is reheated and quenched at 900 ° C, and subsequently heated to 800 ° C
It was adjusted and cooled to form a composite structure of the ferrite phase and the low temperature transformation generating phase, and the low temperature transformation generating phase was mainly formed into a needle shape with a volume fraction of 35%. This wire material was subjected to wet continuous drawing to obtain ultrafine wires having wire diameters of 100, 50 and 25 μm. In addition to measuring the characteristics of this ultra-thin wire, an ultra-high voltage electron microscope (3M
V) was used to observe the metallographic structure. For comparison, the same measurement was performed for piano wire (0.82% C), stainless wire (SUS304), amorphous wire (Fe-Si-B system), tangs wire and aramid wire.

The results are shown in Table 3. As is clear from the table, the extra fine wire for a woven fabric according to the present invention has a tensile strength of 300 kg f / mm ² or more and is excellent in toughness. The ultrafine wire of the present invention had a uniform fiber structure extending in the drawing direction, the fiber interval was 100 to 200Å, and the cell size was 30 to 90Å.

Further, with respect to the metal ultrafine wire 4 for a woven fabric of the present invention, the strength change after holding in a high temperature environment, the properties of the tensile fracture portion, the bent portion, the fatigue characteristic, and the stress reclamation characteristic were also measured.

FIG. 3 shows the results of measuring the tensile strength after heating the ultrafine wire of 50 μm shown in Table 3 above to a temperature of room temperature to 450 ° C. for 30 minutes in the air (curve A). The piano wire (100μ
m) and the amorphous line (50 μm) also show the results measured under the same conditions (curves B and C). As is clear from this figure, the ultrafine wire of the present invention shows no strength reduction up to 400 ° C.

FIG. 4 and FIG. 5 are an enlarged view of the tensile fracture portion and the bent portion of the ultrafine wire of 50 μm shown in Table 3 above. As is clear from FIG. 4, the material was fractured after being greatly squeezed (the squeeze reduction ratio in this case was 50% or more), and as is clear from FIG. 5, cracks were observed even after bending (kink) deformation. It does not occur, and it can be understood from these points that it is tough.

FIG. 6 shows the fatigue characteristics of the ultrafine wire of 100 μm shown in Table 1 above in the Hunter fatigue test. The ratio of fatigue limit strength (10 ⁷ times evaluation) to tensile strength (strength ratio) is 0.38, which shows excellent fatigue resistance. Also, the seventh
The figure shows the stress relaxation characteristics of an ultrafine wire with a diameter of 60 μm manufactured under the same conditions when an initial stress of 85% of the tensile strength was applied, and the stress loss was 2% or less.
It is clear from FIGS. 6 and 7 that the metal fine wire for woven fabric of the present invention has high reliability under dynamic and static (repeating, fluctuating) stress loads.

In the above embodiment, both the warp yarns and the weft yarns are made of the metal ultrafine wire 4.
Although the woven fabric of the present invention may be made of a single metal thin wire, the warp yarn or the weft yarn may be made of a metal ultrafine wire, and the other is conventionally used. Carbon fibers or the like may be used, and the metal ultrafine wire of the present invention may be mixed with carbon fibers or the like to form a yarn. In the case of such a composite woven fabric, the advantages of each fiber can be combined.

〔The invention's effect〕

As described above, according to the woven fabric of the present invention, as warp yarns and weft yarns, processed cells of 5 to 100Å are arranged in a fibrous shape, and the fiber intervals form a line forming an ultrafine grain metallographic structure of 50 to 1000Å. Since the ultra-high-strength metal ultrafine wire with a diameter of 160 μm or less and a tensile strength of 300 to 600 kg f / mm ² is adopted, the strength of the woven fabric can be made much higher than before, and as a result, this was used as a reinforcing member.
This has the effect of significantly improving the strength of FRP and the like.

[Brief description of drawings]

1 and 2 are views for explaining a woven fabric according to an embodiment of the present invention. FIG. 1 is a plan view thereof, FIG. 2 is a sectional view thereof, and FIGS. It is a figure for demonstrating the characteristic of the metal ultrafine wire of this invention, FIG. 3 is a characteristic view which shows the strength change after a high temperature environment hold | maintenance, FIG. 4 is an enlarged view of a tensile fracture part, FIG. Enlarged view showing the processed part, FIG. 6 is a view showing fatigue characteristics, FIG. 7 is a view showing stress relaxation characteristics, FIG. 8 is a characteristic view of tensile strength and toughness, FIG. 9, FIG.
The figure is a micrograph showing the metal structure of the metal fine wire for woven fabric of the present invention. In the figure, 1 is a woven fabric, 2 and 3 are warp and weft yarns (warp and weft), and 4 is a fine metal wire.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location D02G 3/02 D03D 1/00 A // C21D 8/06 A 7217-4K (56) References Special features Kai 62-20824 (JP, A) JP 63-288242 (JP, A) JP 61-70040 (JP, A) JP 49-57157 (JP, A) JP 52-37985 (JP JP, B1)

Claims (1)

[Claims] 1. A woven fabric obtained by weaving warp yarns and weft yarns, wherein at least one of the warp yarns and the weft yarns is formed by subjecting a wire rod to a strong working by cold drawing, and Ultra fine cells of ~ 100Å are arranged in one direction in a fibrous form and have a fibrous fine metallographic structure in which the fiber intervals are 50 ~ 1000Å, wire diameter 160 μm or less, tensile strength 300 to 600 kg f /
A woven fabric characterized by being a super-high-strength metal ultrafine wire of mm ² or a plurality of outer ultrafine wires combined and subjected to a sizing treatment.