JPH08199317A - High strength and high rigidity aluminum-base alloy - Google Patents

Abstract

PURPOSE: To produce an Al-base alloy having high strength and high rigidity by preparing an Al-base alloy constituted from Al, V, Mo or the like shown by a specified formula and allowing quasi-crystal phases to lie in the alloy structure. CONSTITUTION: An Al-base alloy having a compsn. shown by the general formula of Al100-(a+b) Qa Mb [in the formula, Q denotes one or >= two kinds of metallic elements selected from V, Mo, Fe, W, Nb and Pd, M denotes one or >= two kinds of metallic elements selected from Mn, Fe, Co, Ni and Cu and (a) and (b) satisfy, by atomic%, 1<=a<=10, 0<b<5 and 3<=a+b<12[ is prepd. The cooling rate of the molten metal of the same Al-base alloy is controlled to form a mixed structure of Al phases and quasi-crystal phases in the alloy structure. Thus, the Al-base alloy excellent in corrosion resistance can be obtd.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an aluminum base alloy having high specific strength and high rigidity.

[0002]

2. Description of the Related Art Al-based conventional aluminum-based alloys are
Cu-based, Al-Si-based, Al-Mg-based, Al-Cu-Si
System, Al-Cu-Mg system, Al-Zn-Mg system, and other alloys of various component types are known, and all of these systems are lightweight and have excellent corrosion resistance. Depending on the material characteristics, it is widely used for mechanical structural members such as vehicles, ships, and aircraft, or as exterior materials for construction, sashes, roofing materials, structural materials for LNG tanks, and the like.

However, conventional aluminum-based alloys are
Compared with Fe-based materials, they generally have the drawbacks of low hardness and low heat resistance. Further, among those in which the strength is increased by adding an element such as Cu, Mg or Zn, there are some which have a drawback in corrosion resistance.

On the other hand, recently, by refining and solidifying an aluminum-based alloy from a molten state, the structure is refined,
Attempts have also been made to exhibit excellent properties in terms of both mechanical strength and corrosion resistance. Against this background, as disclosed in Japanese Patent Application Laid-Open No. 1-275732, AlM ₁ X system (M ₁ is V, Cr, Mn, F) having a specific composition ratio.
e, Co, Ni, Cu, Zr and other elements, and X is
Rare earth elements such as La, Ce, Sm, Nd, Y, Nb,
Ta, Mm (Misch metal), etc. are shown. Patent application has been made for an aluminum-based alloy having a composition of (1) and having an amorphous structure or an amorphous structure and a fine crystalline structure.

[0005]

The aluminum-based alloy of the above patent application is useful as a high hardness material, a high strength material, a high electrical resistance material, a wear resistant material, a brazing material, etc. It is also excellent as a heat-resistant material because it can be extruded or pressed using the plastic phenomenon. However, the aluminum-based alloy contains a large amount of expensive rare earth elements and highly active metal elements such as Y, and thus has a drawback of high cost. That is, since it is necessary to use expensive raw materials, and also to use raw materials having high activity and difficulty in handling, there is a problem that the scale of manufacturing equipment becomes large, the cost becomes high, and the labor cost is also high. is there. Further, the aluminum-based alloy having the above composition tends to be insufficient in terms of oxidation resistance and corrosion resistance.

The present invention has been made in view of the above circumstances, and has a composition that does not contain a highly active element such as a rare earth element or Y, realizes low cost and low activation, and has high strength, high rigidity, and An object of the present invention is to provide an aluminum-based alloy having excellent corrosion resistance.

[0007]

In order to solve the above-mentioned problems, the invention according to claim 1 has the general formula Al _{100- (} a + b ₎ QaMb (wherein Q is V, Mo, Fe,
One or more metal elements selected from W, Nb and Pd are shown, and M is Mn, Fe, Ni, Co and C.
One or more metal elements selected from u are shown. ), And a and b showing composition ratios are
It satisfies the relations of 1 ≦ a ≦ 10, 0 <b <5, 3 ≦ a + b ≦ 12 in atomic%, and has a quasicrystalline phase in the alloy structure.

In order to solve the above-mentioned problems, the invention according to claim 2 has the composition and composition ratio according to claim 1, and has a mixed phase structure of an aluminum phase and a quasi-crystalline phase, and a metal solid solution consisting of an aluminum matrix and a quasi-phase. It has at least one structure of a mixed phase structure of a crystalline phase, a mixed phase structure of a quasicrystalline phase and a stable or metastable intermetallic compound phase, a solid solution of an aluminum matrix, and a mixed phase structure of an amorphous phase and a quasicrystalline phase. It will be.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Next, the reasons for limiting the composition of each component of the present invention alloy will be explained. The content of Al (aluminum) in atomic% is 88 ≦ Al ≦ 97, preferably 92 ≦
Al ≦ 97, particularly preferably 94 ≦ Al ≦ 97. This is because if it is less than 88 atom%, it becomes brittle, and if it exceeds 97 atom%, the strength and hardness are reduced. V (vanadium), Mo (molybdenum), Fe
(Fe), W (tungsten), Nb (niobium), Pd
The content of one or more selected from (palladium) is 1 atom% or more and 10 atom% or less, preferably 2 atom% or more and 8 atom% or less, particularly preferably 2 atom%
It is 6 atomic% or less. This means that their content is 1
If it is less than 10% by atom, no quasicrystalline phase is formed and the strength is remarkably reduced. Because.

The content of one or more selected from Mn (manganese), Fe (iron), Co (cobalt), Ni (nickel), and Cu (copper) is less than 5 atomic%.
Preferably 1 to 3 atomic%, particularly preferably 1 to 2 atomic%.
Is. This is because when the content of these exceeds 5 atom%, intermetallic compounds are formed and coarsened (particle size of 500 nm or more).
However, it is significantly brittle and the strength is reduced.

Fe and S are unavoidable impurities.
i, Cu, Zn, Ti, O, C, N, etc., and the total content thereof is 0.3% by weight or less, preferably 0.15.
It is not more than wt%, particularly preferably not more than 0.10 wt%. This is because if it exceeds 0.3% by weight, the quenching effect is reduced and the quasicrystal forming ability is reduced. Among the unavoidable impurities, it is preferable that O is 0.1% by weight or less and C and N are 0.03% by weight or less.

The aluminum-based alloy can be manufactured by rapidly solidifying the molten alloy having the above composition by a liquid quenching method. The liquid quenching method refers to a method of rapidly cooling a molten alloy, for example, a single roll method, a twin roll method,
The spinning liquid spinning method and the like are particularly effective, and a cooling rate of about 10 ⁴ to 10 ⁶ K / sec can be easily obtained by these methods. In order to manufacture a ribbon material by this single roll method, twin roll method, etc., in a storage container such as a quartz tube containing molten metal,
Approximately 300 to 10,000 rp through the nozzle hole at the tip of the quartz tube
Diameter 30 ~ 300mm rotating at constant speed in the range of m
The molten metal is ejected onto a roll made of, for example, copper or copper alloy. As a result, the width is about 1 to 300 mm and the thickness is about 5
Various ribbon materials of 500 μm can be easily obtained.

On the other hand, in order to produce a fine wire material by the rotating submerged spinning method, a depth held by a centrifugal force in a hollow drum rotating at about 50 to 500 rpm through a nozzle hole and a back pressure of argon gas. A fine wire material can be easily obtained by jetting a molten metal into a solution refrigerant layer of about 1 to 10 cm. At this time, the angle formed by the molten metal ejected from the nozzle and the refrigerant surface is
About 60 to 90 degrees, the relative velocity ratio between the ejected molten metal and the solution refrigerant surface is preferably about 0.7 to 0.9. Further, instead of the above method, a thin film of the aluminum-based alloy having the above composition can be obtained by a film forming method such as a sputtering method, and the molten metal is rapidly cooled by various atomizing methods such as a high pressure gas atomizing method and a spray method. Thus, the aluminum-based alloy powder having the above composition can be obtained.

An example of the microstructure of the aluminum-based alloy obtained by the above method is shown below. (1) Mixed phase structure of aluminum phase and quasicrystalline phase. (2) A mixed phase structure of a metal solid solution composed of an aluminum matrix and a quasicrystalline phase. (3) A mixed phase structure of a quasicrystalline phase and a stable or metastable intermetallic compound phase. (4) A mixed phase structure of a metal solid solution composed of an aluminum matrix, an amorphous phase and a quasi-crystalline phase. The fine crystalline phase referred to in the present invention is a crystalline phase in which the average of the maximum diameters of crystal grains is 1 μm or less. Any of the structures described in (1) to (4) above can be obtained by controlling the cooling rate of the molten alloy.

Properties of Alloys in Various Structures The alloys in mixed phase structure shown in (1) and (2) have high strength and good bending ductility. The alloy in the mixed phase structure state shown in (3) has higher strength than the alloys in the mixed phase structure state shown in (1) and (2), but the ductility is inferior. However, it has high strength. The alloy in the mixed phase structure state shown in (4) has high strength, high toughness, and high ductility.

Each of the above-mentioned tissue states can be easily known by a usual X-ray diffraction method or observation with a transmission electron microscope.
When a quasicrystal is present, it exhibits a gentle peak peculiar to the quasicrystal phase. Any of the multiphase microstructure states described in (1) to (3) above can be obtained by controlling the cooling rate of the molten alloy. The textured alloy described in (4) above is A
Arbitrary alloys can be obtained by rapidly cooling an alloy melt having an l-rich structure (for example, Al ≧ 92 atomic%).

Since the aluminum alloy of the present invention exhibits a superplastic phenomenon in the vicinity of the crystallization temperature (crystallization temperature ± 50 ° C.) or in the high temperature range within the stable temperature range of the fine crystal phase, it is easily extruded or pressed. Processing such as hot forging can be performed. Therefore, by extruding, pressing, hot forging the aluminum-based alloy of the above composition obtained in the form of ribbon, wire, plate or powder,
A bulk material can be easily obtained. Further, since the aluminum-based alloy having the above composition has a high degree of viscosity,
It will be bendable.

If the rare earth element is contained, the passivation film on the surface of the alloy is likely to be nonuniform due to the activity of the rare earth element, and there is a drawback that corrosion from that portion to the inside proceeds. Since the alloy having the above structure does not contain a rare earth element, the problem in that respect has been solved.

Next, with respect to the aluminum-based alloy having the above composition, a case of manufacturing a bulk (lump) member will be described. The aluminum-based alloy according to the present invention precipitates a fine crystalline phase when heated and crystallizes, and also precipitates an aluminum matrix (α phase), and when heated to a temperature higher than that, an intermetallic compound also precipitates. By utilizing the properties, bulking having high strength and ductility can be performed. Specifically, the ribbon alloy produced by the quenching method is crushed by a ball mill, and is vacuum hot pressed under a vacuum (for example, 10 ⁻³ Torr) at a temperature slightly lower than the crystallization temperature (for example, at about 470 K). An extruding billet having a diameter of several tens of millimeters and a length of several tens of millimeters is prepared by pressing.
This billet can be set in a container of an extruder, held at a temperature slightly higher than the crystallization temperature for several tens of minutes, and then extruded to obtain an extruded material having a desired shape such as a round bar. (Operation of the present invention) V, Mo, Fe, W, Nb, P on Al
By adding a predetermined amount of any one of d, the quasi-crystal phase forming ability is improved, and the strength, hardness and toughness of the alloy are improved. Furthermore, by adding Mn, Fe, Co, Ni, and Cu in a predetermined amount, the quenching effect is improved, the thermal stability of the structure is improved, and the strength and hardness are improved.

[0020]

EXAMPLE A molten alloy having a predetermined composition was manufactured in a high frequency melting furnace, and this was applied to a quartz tube 1 having a small hole 5 (hole diameter: 0.2 to 0.5 mm) at the tip as shown in FIG. After charging and melting by heating, the quartz tube 1 is placed directly above the copper roll 2, the roll 2 is rotated at a high speed at 4000 rpm, and the quartz tube 1 is supplied with an argon gas pressure (0.7 kg / cm ³ ). Then, the molten metal was sprayed from the small holes 5 of the quartz tube 1 onto the surface of the roll 2 to be rapidly cooled and rapidly solidified to obtain an alloy ribbon 4. Depending on the manufacturing conditions, a large number of alloy ribbon samples (width 1 mm, thickness 20) having compositions (atomic%) shown in Tables 1 to 24
μm) was prepared, and the hardness (Hv) and the tensile breaking strength (σ _f : MPa) of each ribbon sample were measured, and Table 1 to Table 24
The results shown in are obtained. The hardness is a value measured by a micro Vickers hardness meter (DPN: Diamond Pyramid Number).
Furthermore, for each ribbon sample, make 180
As a result of a 180 degree close contact bending test in which the end portions are brought into close contact with each other by bending, the one showing ductility that does not break is shown by Duc, and the broken one is shown by Bri.

[0021]

[Table 1]

[0022]

[Table 2]

[0023]

[Table 3]

[0024]

[Table 4]

[0025]

[Table 5]

[0026]

[Table 6]

[0027]

[Table 7]

[0028]

[Table 8]

[0029]

[Table 9]

[0030]

[Table 10]

[0031]

[Table 11]

[0032]

[Table 12]

[0033]

[Table 13]

[0034]

[Table 14]

[0035]

[Table 15]

[0036]

[Table 16]

[0037]

[Table 17]

[0038]

[Table 18]

[0039]

[Table 19]

[0040]

[Table 20]

[0041]

[Table 21]

[0042]

[Table 22]

[0043]

[Table 23]

[0044]

[Table 24]

From the results shown in Tables 1 to 24, Al-V binary system, Al-Mo binary system, Al-W binary system, Al-Fe binary system, Al-Nb binary system, or Al-Pd2 system.
Mn, Fe, Co, N as element M for the original alloy
In alloys containing one of i and Cu, atomic%
With Al _bal QaMb, 1 ≦ a ≦ 10, 0 <b <5, 3 ≦ a + b
≦ 12, Q = V, Mo, Fe, W, Nb, Pd, M = M
By satisfying the relationship of n, Fe, Co, Ni, and Cu, it has been revealed that an aluminum-based alloy having high yield strength, high hardness, and strong bending resistance can be obtained.

In the samples according to the present invention shown in Tables 1 to 9, the usual aluminum-based alloy has Hv: 50-1.
Approximately 00DPN, but 295-375DPN
And shows extremely high hardness. Next, regarding the tensile breaking strength (σf), the value of a usual age hardening type aluminum-based alloy (Al-Si-Fe system) is 200 to 600MP.
In contrast to a, the sample of the present invention has 630 to 135
It was in the range of 0 MPa, which proved to be extremely excellent. Regarding tensile strength, JIS standard 600
In the 0-based or 7000-based aluminum-based alloy, the pressure is about 250 to 300 MPa, the Fe-based structural steel sheet is about 400 MPa, and the Fe-based high-tensile steel sheet is 800 MPa.
Considering that it is about 980 MPa, it is clear that the aluminum-based alloy according to the present invention is extremely excellent.

FIG. 2 shows Al₉₄V_FourFe₂Alloy composition
The X-ray diffraction pattern of the material is shown in FIG. Al₉₅Mo₃Ni₂Become
The X-ray diffraction pattern of the alloy sample having the composition is shown in FIG. Al₉₁N
b₆Co₃Showing the X-ray diffraction pattern of alloy samples of different composition
In these figures, the three alloy samples show fine fcc structure.
Mixed phase structure of Al crystal phase and fine icosahedral quasicrystal and
It has become. In the figure, (11
1), (200), (220), and (311)
Is a crystal peak of Al of the fcc structure, (2111
The peaks shown in 11) and (221001) are regular icosahedrons.
It is a gentle peak of a quasicrystal. Figure 5 shows Al₉₄V_FourN
i₂Alloy composition of the following composition at a heating rate of 0.67 k / s
The DSC (differential scanning calorimetry) curve when heated is shown.
Things. In this figure, on the high temperature side
When the crystal phase changes to a stable crystal phase, a gentle heat generation
Is appearing.

[0048]

INDUSTRIAL APPLICABILITY As described above, the aluminum-based alloy according to the present invention is useful as a high hardness material, a high strength material, and a high rigidity material, and has excellent characteristics that it can be machined because it is strong against bending. Have. From the above, the aluminum-based alloy according to the present invention is used as a structural member for aircraft, vehicles, ships, etc., or a structural member for an engine part, or as a building exterior material, sash, roof material, and further, seawater equipment. It can be widely used as a member for a reactor, a member for a nuclear reactor, and the like.

[Brief description of drawings]

FIG. 1 is a configuration diagram showing an example of a single roll device used when a ribbon is produced by rapidly solidifying the alloy of the present invention.

FIG. 2 is a diagram showing an X-ray diffraction analysis result of an alloy having a composition of Al ₉₄ V ₄ Fe ₂ .

FIG. 3 is a view showing an X-ray diffraction analysis result of an alloy having a composition of Al ₉₅ Mo ₃ Ni ₂ .

FIG. 4 is a diagram showing an X-ray diffraction analysis result of an alloy having a composition of Al ₉₁ Nb ₆ Co ₃ .

FIG. 5 is a diagram showing thermal characteristics of an alloy having a composition of Al ₉₄ V ₄ Ni ₂ .

[Explanation of symbols]

1 ... Quartz tube, 2 ... Roll, 3 ... Molten metal, 4 ... Thin strip, 5
... Nozzle holes.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Akihisa Inoue Kawauchi Muzen, Aoba-ku, Sendai City, Miyagi Prefecture 11-806 (72) Inventor Hisami Kimura 44, Fujiwara Bridge, Watarihama, Watari-gun, Miyagi Prefecture (72) Invention Yuma Horio 10-1 Nakazawa-machi, Hamamatsu City, Shizuoka Prefecture Yamaha Stock Company

Claims (2)

[Claims] 1. The general formula Al _{100- (} a + b ₎ QaMb (wherein Q represents one or more metal elements selected from V, Mo, Fe, W, Nb and Pd, M
Indicates one or more metal elements selected from Mn, Fe, Co, Ni and Cu. ), The composition ratios a and b are atomic% and 1 ≦ a ≦ 10, 0 <b <
5, a high-strength and high-rigidity aluminum-based alloy, which satisfies the relationship of 5 and 3 ≦ a + b ≦ 12 and has a quasicrystalline phase in the alloy structure. 2. The composition and the composition ratio according to claim 1,
Mixed phase structure of aluminum phase and quasicrystalline phase, mixed phase structure of metal solid solution consisting of aluminum matrix and quasicrystalline phase,
High strength and high characteristics characterized by having at least one structure of a mixed phase structure of a quasicrystalline phase and a stable or metastable intermetallic compound phase, a metal solid solution consisting of an aluminum matrix, and a mixed phase structure of an amorphous phase and a quasicrystalline phase Rigid aluminum base alloy.