JPS62297425A - Fiber-reinforced metal and its production - Google Patents

Abstract

PURPOSE:To provide a fiber-reinforced metal which has overall excellent mechanical characteristics by consisting the same of continuous inorg. fibers consisting of Si, Ti or Zr, C and O and an Al alloy base material contg. a prescribed ratio of Ni and incorporating the needle-like phase of said alloy into said Al base material. CONSTITUTION:The continuous inorg. fibers which consist of an amorphous material substantially composed of Si, M, C and O, or solid soln. such as beta-SiC, MC (M is Ti or Zr) and/or respective ultrafine crystalline particles and aggregate, etc., consisting of amorphous SiO2 and MO2 and consist of Si, Ti, or Zr, C and O are prepd. Such continuous inorg. fibers and the Al alloy member contg. 0.5-6wt% Ni are combined by a casting method, more particularly high-pressure casting method and are solidified in a short period. The combined material is cooled from the direction orthogonal with the continuous fibers in the stage of such solidification, by which the fine needle-like crystalline material is crystallized in entanglement with said fibers in the direction perpendicular to the fibers among the continuous fibers, by which the excellent inter- layer shearing strength is imparted. As a result, the fiber-reinforced metal (FRM) having high strength is obtd.

Description

Detailed Description of the Invention 3. Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a fiber-reinforced metal and a method for producing the same, and more particularly to an aluminum alloy reinforced with continuous fibers and a method for producing the same.

(Prior art and its problems) Fiber reinforced metals (FRM) have excellent strength and rigidity, and have recently been used as various mechanical parts and structural materials.

Among these, FRM, which is made by reinforcing an aluminum alloy matrix with continuous fibers such as ceramic or carbon, is light, has high rigidity, and has good strength at high temperatures.

Further, if a casting method such as a high-pressure solidification casting method is adopted as a manufacturing method for FRM, parts with complicated shapes such as automobile parts and precision machine parts can be easily manufactured.

However, when manufacturing FRM using the above-mentioned reinforcing fibers by high-pressure coagulation casting, it is difficult for the continuous fibers to be uniformly dispersed in the base material, so it is necessary to mix 40 to 60% continuous fibers by weight. However, if a large amount of continuous fibers is mixed in, the fibers will come into contact with each other, making it impossible to obtain strength that satisfies the composite law. Furthermore, this fiber-reinforced metal has a problem to be solved in that its strength in a direction perpendicular to the length direction of the continuous fibers is low.

In addition, the composition of the alloy matrix is important for the compatibility between fibers and the matrix, but the proposed combination of reinforcing fibers and alloy matrix does not cause the fibers to deteriorate during the production of fiber-reinforced metals. Raise the desired 14. A composite material with the following properties cannot be obtained.

(Technical Means for Solving the Problems) The object of the present invention is to provide an overall excellent machine by not causing fiber deterioration during FRM production and by crystallizing acicular microcrystals in the base material. An object of the present invention is to provide a fiber-reinforced metal having excellent characteristics and a method for producing the same.

The fiber-reinforced metal of the present invention is (i) an amorphous material consisting essentially of Si, M, C and 0, or (ii) substantially consisting of β-3i C% MC% β-5iC
A solid solution of MC and/or MCt- has a particle size of 500 Å.
Each of the following crystalline ultrafine particles and amorphous SiO2 and MO
or (iii) a mixed system of the amorphous material of (i) above and the crystalline ultrafine particle aggregate of (ii) above, (However, M in the above formula represents Ti or Zr. , X is a number greater than 0 and less than 1), a continuous inorganic fiber made of silicon, titanium or zirconium, carbon and oxygen;
It consists of an aluminum alloy base material containing 0.5 to 6% nickel by weight, and is characterized by containing an acicular phase of the alloy in the alloy base material.

The continuous inorganic 13N fiber in the present invention can be prepared, for example, according to the following method described in European Patent No. 30145 and European Patent No. 37209.

(1) It has a main chain skeleton mainly composed of structural units of the formula + S 1-CH2 with a number average molecular weight of about 500 to 10,000, and the silicon atoms in the formula are substantially composed of hydrogen atoms, lower alkyl groups, and phenyl groups. A side chain group selected from the group consisting of 21
[1i1 polycarbosilane, and (2) a metalloxane bonding unit with a number average molecular weight of about 500 to 10,000 → M O+ (M: Ti or Zr
) and a main chain skeleton consisting of +5i-0 siloxane bonding units, and the ratio of the total number of siloxane bonding units of the metalloxane bonding units is within the range of 30=1 to l:30, and the siloxane bonding units Most of the silicon atoms of the metalloxane bonding unit have one (or two) side chain groups selected from the group consisting of lower alkyl groups and phenyl groups, and most of the total bent atoms of the metalloxane bonding unit have as side chain groups. A polymetallosiloxane having one or two lower alkyl groups has a ratio of 1 + Si - CH2 ÷ total number of structural units of the polymetallosiloxane to +M-0± total number of bonding units of the polycarbosilane of 100:1. The resulting mixture is heated in an organic solvent in an atmosphere inert to the reaction to remove at least one of the silicon atoms of the polycarbosilane. The number average molecular weight of the crosslinked polycarbosilane portion and the polymetallosiloxane portion is approximately 1000 by bonding the polymetallosiloxane with at least a portion of the silicon atoms and/or metal atoms through oxygen atoms. A first step of producing an organometallic polymer of ~50,000, a second step of preparing and spinning a spinning dope of the polymer, a third step of infusibleizing the spun fibril under tension or no tension, and The melted spun fibers are heated for 80 minutes in a vacuum or in an inert gas atmosphere.
From the fourth step of firing at a temperature in the range of 0 to 1800°C, inorganic fibers consisting essentially of Si, Ti or Zr, C and O can be produced.

In addition, as an alternative method, the main chain skeleton mainly represented by the formula % formula % (wherein R in the formula represents a hydrogen atom, a lower alkyl group, or a phenyl group) and a number average molecular weight of 200 to 1
0000 polycarbosilane, and the formula MX& (where M in the formula represents Ti or Zr, and X has 1 carbon number
Indicates an alkoxy group, phenoxy group or acetylacetoxy group having ~20 groups. ), the organometallic compound represented by : In addition to the quantitative ratio within the range of 1, at least a portion of the silicon atoms of the polycarbosilane are converted into metal atoms and oxygen atoms of the organometallic compound by a heating reaction in an atmosphere inert to the reaction. with a number average molecular weight of about 700 to
a first step of producing toooooo organometallic polymer; a second step of preparing and spinning a spinning dope of the organometallic polymer; a third step of infusibleizing the spun fibers under tension or no tension; From the fourth step of firing the melted spun fibers at a temperature in the range of 800 to 1800°C in vacuum or in an inert gas atmosphere, substantially S
Alternatively, inorganic fibers made of Zr, C, and O can be produced.

The proportion of each element in the continuous inorganic fiber is Si: 30 to 60% by weight, Ti or Zr: 0.5 to 35% by weight.
% by weight, particularly preferably 1-10% by weight, C: 25-4
0% by weight, ○: 0.01 to 30% by weight.

Continuous inorganic fibers can be used by aligning the fibers themselves in the axle direction or multi-axis direction, or by making them into various types of fabrics such as hand weaving, satin weaving, mock-sailing weaving, twill weaving, bag weaving, tangle weaving, spiral weaving, and three-dimensional weaving. There are two ways to use it: one method is to use it as an ice cream, and the other is to use it as a joseopdofaihar.

The alloy base material in the present invention is a binary alloy containing aluminum and nickel in an amount of 0.5 to 6% by weight, preferably 2 to 5% by weight, or a ternary alloy further containing manganese in an amount of 0.1 to 2ffiff1%. When these alloys are used, fine whisker-like second F phases of 0.5 μm or less are crystallized during solidification, and the whisker-like second phase crystallizes more efficiently by high-pressure casting.

By combining the alloy matrix of the present invention and continuous fibers, crystallized substances are crystallized in the alloy matrix between the continuous fibers in the form of fine needles or whiskers. Therefore, since contact between continuous fibers is reduced and the continuous fibers are not deteriorated, a high-strength FRM can be obtained. ~ Casting is preferable as a method for compositing continuous fibers and alloy matrix, and high-pressure solidification casting is particularly effective because it solidifies in a short time and produces fine needle-like crystallized substances. be. The pressure during solidification is several hundred kg/cI.
Grade A is easy to use. In addition, by cooling from the direction perpendicular to the continuous fibers during cargo storage, fine needle-shaped crystallized substances become entangled between the continuous fibers in a direction perpendicular to the continuous fibers and crystallize. It exhibits excellent glabella shear strength by acting as a bridge between the two.

(Example) The present invention will be explained below by way of examples.

Production method of continuous inorganic fiber [1] 3 parts by weight of polyborosiloxane was added to 100 parts by weight of polydimethylsilane synthesized by dechlorination condensation of dimethyldichlorosilane with metallic sodium, and 3 parts by weight of polyborosiloxane was added to 350 parts by weight in nitrogen.
Titanium is added to polycarbosilane, which is obtained by thermal condensation at °C and has a main chain skeleton mainly composed of carbosilane units of the formula +5i-CH2÷, and has a hydrogen atom and a methyl group on the silicon atom of the carbosilane unit. By adding alkoxide and crosslinking polymerization at 340°C in nitrogen, 100 parts of carbosilane units and 1 part of titanoxane of formula +Ti-0+
A polytitanocarbosilane consisting of 0 parts was obtained. This polymer was melt-spun and treated in the air at 190°C to make it infusible.
Furthermore, the fiber diameter was 13 μm, the tensile strength was 310 kg/Tsuru 2, and the tensile modulus was 1.
A continuous inorganic fiber [I] of 5 t/mm2 and containing 3% by weight of titanium element mainly composed of silicon, titanium, carbon and oxygen was obtained.

This fiber is composed of an amorphous substance consisting of S t s T i s C and O, a solid solution of β-SiC and TiC, and a Ti
It consisted of a mixed system of 50 crystalline ultrafine particles with a grain size of C1-su (Q<x<1) and an aggregate of amorphous SiO2 and TiO2.

Manufacturing method of continuous inorganic fiber [II] Polyzirconocarbosilane was prepared in exactly the same manner as above except that 10 g of zirconium ethoxide was added to 80 g of polycarbosilane obtained in the same manner as above.

This polymer was dissolved in benzene, dry spun, infusible at 170°C in air, and subsequently heated at 1200°C in nitrogen.
'c fired, fiber diameter 10μ, tensile strength 350k
g/m2, elastic modulus of 18t/mu2, zirconium element base consisting mainly of silicon zirconium, carbon S and oxygen ff
Amorphous continuous inorganic fiber [11F] with 14.5f=ff1% was obtained.

Example 1 Inorganic fiber El] was cut into 150 m lengths, weighed to a volume fraction of 50%, and filled into a steel pipe. This is 72
After preheating for 15 minutes in a nitrogen gas atmosphere at 0'C, 2
Placed in a mold heated to 50°C, A1-5 at 720°C
%Ni alloy molten metal is poured and punched at 250℃ for 500k.
It was pressurized to g/cIiI and coagulated. This is designated as sample A. FRMs of an A2-2% Cu-2% Ni alloy base material and a pure AN base material were also created in the same manner. Sample B
and C.

As a result of observing the cross section of FRM sample A taken from the ingot with a scanning electron microscope, it was found that there were fine Al3 particles in the gaps between the fibers.
Ni whiskers were relatively uniformly distributed. Furthermore, two-point bending tests and AE measurements were conducted using these FRMs.

The bending strength is pure, l! 150k for FRM (sample C)
g / Seal 12, but the number of AE events leading up to destruction was significantly higher. Also, Al-'1%Cu-2%
For Ni combined CuM (sample B), the number of AE events is the same as that for sample C.
The bending strength was significantly smaller, although it decreased compared to the above.

In contrast, in the case of AA-5%NiFRM (sample A), the bending strength was 140 kg/mu2, and sample C
The number of AE events was also significantly reduced, indicating a reduction in microscopic destruction.

Example 2 The same method as Example 1 was repeated except that inorganic fiber [II] was used instead of inorganic fiber [I], and Al-5%N
iFRM was manufactured.

This FRM had the same internal structure and strength as Sample A in Example 1.

(Effects of the invention) The fiber-reinforced metal of the present invention has strength comparable to that when pure aluminum is used, and has less microscopic fracture when stress is applied than when pure aluminum is used. This shows a significant decrease in the amount of carbon dioxide, showing overall excellent properties.

In addition, according to the manufacturing method of the present invention, when manufacturing fiber-reinforced metal using a high-pressure casting method, pressure is applied with a cold punch from a direction perpendicular to the longitudinal direction of the continuous fibers, and the continuous fibers are pressed at right angles to the longitudinal direction of the fibers. Since a temperature gradient is generated in the direction, the acicular phase of the alloy can be crystallized in the alloy matrix in the direction perpendicular to the length direction of the fibers, making it possible to obtain fiber reinforced gold mud with excellent overall properties. .

Claims (5)

[Claims] (1) (i) an amorphous material consisting essentially of Si, M, C and O, or (ii) essentially β-SiC, MC, β-SiC and MC
Solid solution of and/or particle size of MC_1_-_x is 500 Å
Each of the following crystalline ultrafine particles and amorphous SiO_2 and M
an aggregate consisting of O_2, or (iii) a mixed system of the amorphous substance of (i) above and the crystalline ultrafine particle aggregate of (ii) above, (However, M in the above formula represents Ti or Zr. , x is a number greater than 0 and less than 1), a continuous inorganic fiber made of silicon, titanium or zirconium, carbon and oxygen;
A fiber-reinforced metal comprising an aluminum alloy base material containing 0.5 to 6% nickel by weight, and containing an acicular phase of the alloy in the alloy base material. (2) The aluminum alloy base material has a weight ratio of nickel of 0.
Fiber reinforced metal according to claim 1, characterized in that it contains 5-6% manganese and 0.1-2% manganese. (3) In compositing continuous fibers and alloy matrix,
The fiber-reinforced metal according to claim 1, characterized in that a high-pressure solidification casting method is used. (4) (i) an amorphous material consisting essentially of Si, M, C and O, or (ii) essentially β-SiC, MC, β-SiC and MC
Solid solution of and/or particle size of MC_1_-_x is 500 Å
Each of the following crystalline ultrafine particles and amorphous SiO_2 and M
an aggregate consisting of O_2, or (iii) a mixed system of the amorphous substance of (i) above and the crystalline ultrafine particle aggregate of (ii) above, (However, M in the above formula represents Ti or Zr. , x is a number greater than 0 and less than 1), a continuous inorganic fiber made of silicon, titanium or zirconium, carbon and oxygen;
When forming a composite with an aluminum alloy base material containing 0.5 to 6% nickel by weight, the continuous fibers are cooled in a direction perpendicular to the length direction of the continuous fibers during solidification, and needles are inserted into the alloy base material. A method for producing a fiber-reinforced metal, characterized by crystallizing a phase in a direction perpendicular to the longitudinal direction of the continuous fibers. (5) The aluminum alloy base material has a weight ratio of nickel of 0.
Fiber reinforced metal according to claim 1, characterized in that it contains 5-6% manganese and 0.1-2% manganese.