JP2703480B2 - High strength and high corrosion resistance aluminum base alloy - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aluminum-based alloy having high specific strength and excellent corrosion resistance.

[0002]

2. Description of the Related Art Conventional aluminum-based alloys include Al-
Cu-based, Al-Si-based, Al-Mg-based, Al-Cu-Si
Alloys of various component systems such as Al-Cu-Mg system and Al-Zn-Mg system are known, and any of these systems is lightweight and excellent in corrosion resistance. Depending on the material properties, it is widely used for mechanical structural members of vehicles, ships, aircrafts, etc., or as exterior materials for buildings, sashes, roofing materials, structural materials for LNG tanks, and the like.

However, conventional aluminum-based alloys are:
In general, it has the disadvantages of lower hardness and lower heat resistance than Fe-based materials. Further, some of the alloys whose strength is increased by adding elements such as Cu, Mg or Zn have a defect in corrosion resistance.

[0004] On the other hand, recently, the structure of the aluminum-based alloy has been refined by rapidly solidifying it from a molten metal state.
Attempts have also been made to exhibit properties that are superior in both mechanical strength and corrosion resistance. Against this background, as disclosed in Japanese Patent Application Laid-Open No. 1-275732, an AlM ₁ X-based material having a specific composition ratio (M ₁ is V, Cr, Mn, F
e, elements such as Co, Ni, Cu, and Zr, and X represents
Rare earth elements such as La, Ce, Sm, Nd, Y, Nb,
Ta, Mm (mish metal) and the like are shown. ), Wherein an aluminum-based alloy having an amorphous structure or an amorphous and fine crystalline structure has been applied for a patent.

[0005]

The aluminum-based alloy of the patent application is useful as a high-hardness material, a high-strength material, a high-resistance material, a wear-resistant material, a brazing material, and the like. Extrusion and press working are also possible utilizing the plastic phenomenon, and are excellent as heat-resistant materials. However, the above-mentioned aluminum-based alloy has a disadvantage that the cost is high because it contains a large amount of expensive rare earth elements and highly active metal elements such as Y. In other words, it is necessary to use expensive raw materials, and it is necessary to use raw materials having high activity and difficulties in handling, so that the scale of the manufacturing equipment is increased, the cost is increased, and labor costs are increased. 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-mentioned circumstances, and has a composition not containing a highly active element such as a rare earth element or Y, thereby realizing low cost and low activation, and having high strength and excellent corrosion resistance. It is an object to provide an aluminum-based alloy.

[0007]

According to a first aspect of the present invention, there is provided an image forming apparatus comprising: a general formula AlxCoyMz (where M is one selected from the group consisting of Fe and Cu);
This indicates two or more metal elements selected from Mn, Fe, and Cu . X), which has a composition represented by
y and z are x + y + z = 100 in atomic%, 50 ≦ x ≦ 95,
It is characterized by satisfying a relationship of 0.5 ≦ y ≦ 35 and 0.5 ≦ z ≦ 20.

According to a second aspect of the present invention, to solve the above-mentioned problem, a general formula AlaFebLc (where L is Mn,
One or more metal elements selected from Cu. A) having a composition represented by
b, c are a + b + c = 100 in atomic%, 50 ≦ a ≦ 95,
It satisfies the relationship of 0.5 ≦ b ≦ 35 and 0.5 ≦ c ≦ 20.

According to a third aspect of the present invention, there is provided a composition having a composition represented by the general formula: AldCoeMnf.
And d, e, and f indicating the composition ratio are d + e + f = 10 in atomic%.
0, 50 ≦ d ≦ 95, 20 ≦ e ≦ 35, 5 ≦ f <20
It is characterized by satisfying the relationship .

[0010]

By adding a predetermined amount of Co or Fe to Al, the quenching effect is improved, an amorphous phase or a fine crystalline phase is easily obtained, and the thermal stability of the structure is improved. Also,
Strength and hardness are also improved. Further, Mn and F are not used for Al-Co binary alloys or Al-Fe binary alloys.
By adding a predetermined amount of e and Cu, strength and hardness are improved .

Next, the reasons for limiting the composition of each component of the alloy of the present invention will be described. The Al (aluminum) content is
Atomic% is in the range of 50 ≦ Al ≦ 95.
If it is less than atomic%, it will become brittle, and if it exceeds 95 atomic%, the strength and hardness will decrease.

The content of Co (cobalt) or Fe (iron) is in the range of 0.5 atomic% to 35 atomic%, but if it is less than 0.5 atomic%, strength and hardness are not improved and If it exceeds 35 at%, the material becomes brittle, and the strength and toughness decrease. In addition, when Fe is added to the Al-Co binary alloy, embrittlement starts when it exceeds 20 atomic%. The content of Mn (manganese) and Cu (copper) is expressed in terms of atomic% as 0.5 ≦ Mn ≦ 20 or 0.5 ≦ Cu ≦
If it is less than 0.5%, the strength and hardness will not be improved, and if it is more than 20% by atom, it will be brittle and the toughness will be reduced.

Further, Mn is used for Al—Co binary alloy.
, 20 ≦ Co ≦ 35, 5 ≦ Mn <20
%, Preferably within this range.
Excellent tensile strength and excellent resistance to fracture even in bending tests
Bending characteristics can be compatible.

The aluminum-based alloy can be produced by rapidly solidifying a 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,
Spinning in a rotating liquid is particularly effective, and in these methods, a cooling rate of about 10 ⁴ to 10 ⁶ K / sec can be easily obtained. In order to manufacture a ribbon material by the single roll method, the twin roll method, or the like, a container such as a quartz tube containing molten metal is used.
About 300 to 10000 rp through the nozzle hole at the tip of the quartz tube
30-300mm diameter rotating at a constant speed in the range of m
For example, a molten metal is jetted onto a copper or copper roll. Thereby, the width is about 1-300mm and the thickness is about 5-500μ.
m can be easily obtained.

On the other hand, in order to produce a thin wire material by the spinning method in a rotating liquid, a depth held by a centrifugal force through a nozzle hole in a hollow drum rotating at about 50 to 500 rpm under argon gas back pressure. The thin wire material can be easily obtained by ejecting the molten metal into the solution refrigerant layer of about 1 to 10 cm. At this time, the angle between the molten metal ejected from the nozzle and the refrigerant surface is
It is preferable that the relative speed ratio between the molten metal jet and the solution refrigerant surface is about 0.7 to 0.9 degrees. 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 spraying method or a spray method. Thus, an aluminum-based alloy powder having the above composition can be obtained.

An example of the structure of the aluminum-based alloy obtained by the above method is shown below. (1) Amorphous phase. (2) A mixed phase structure of an amorphous phase and a fine crystalline phase of Al. (3) A mixed phase structure of an amorphous phase and a stable or metastable intermetallic compound phase. (4) A mixed phase structure of Al and a stable or metastable intermetallic compound phase or an amorphous phase. (5) A solid solution containing Al as a mother phase. The fine crystalline phase referred to in the present invention is a crystalline phase in which the average of the maximum diameter of the crystal grains is 1 μm or less.

The alloy in the structural state (amorphous phase) shown in (1) has high strength, good bending ductility, and high toughness. (2)
The alloys having the microstructures shown in (3) and (3) are (1)
Is 1.2 to 1.2 more than the alloy in the structure state (amorphous phase) shown in
1.5 times higher strength. The alloys in the structural state (mixed phase structure or solid solution) shown in (4) and (5) are (1) to
It has higher toughness and higher strength than the alloy having the structure shown in (3).

Each of the above-mentioned tissue states can be easily known by ordinary X-ray diffraction or observation with a transmission electron microscope.
In the case of the amorphous phase, a halo pattern peculiar to the amorphous phase is shown. In the case of a mixed phase structure of the amorphous phase and the fine crystalline phase, the halo pattern and the diffraction peak caused by the fine crystalline phase are different. A synthesized diffraction pattern is shown. In the case of a mixed phase structure of an amorphous phase and an intermetallic compound phase, a halo pattern and a diffraction peak resulting from the intermetallic compound phase are synthesized. Any of the microstructures described in the above (1) to (3) can be obtained by controlling the cooling rate of the molten alloy.
Any of the microstructures described in the above (4) to (5) can be obtained by quenching a molten alloy having an Al-rich microstructure (for example, Al ≧ 92 atomic%).

Next, when heated, the amorphous structure is decomposed into crystals at a specific temperature or higher (this temperature is called a crystallization temperature). By utilizing the thermal decomposition of the amorphous phase, it is possible to obtain a composite of a finely crystalline aluminum solid solution phase and an intermetallic compound that differs depending on the alloy composition.

The aluminum alloy of the present invention exhibits a superplastic phenomenon in the vicinity of the crystallization temperature (crystallization temperature ± 100 ° C.) or in a high temperature range within the stable temperature range of the fine crystal phase.
Extrusion, pressing, hot forging, and other processing can be easily performed. Therefore, a bulk material can be easily obtained by extruding, pressing, and hot-forging an aluminum-based alloy having the above composition obtained in the form of a ribbon, wire, plate, or powder at the above-mentioned temperature. . Further, since the aluminum-based alloy having the above composition has a high viscosity,
It can be bent by 80 degrees.

Incidentally, the amorphous phase or the alloy having a mixed phase structure of the amorphous phase and the fine crystal phase includes structural non-uniformity such as crystal grain boundaries and segregation such as a crystalline alloy, and chemical non-uniformity. It has no corrosion resistance and exhibits high corrosion resistance due to passivation caused by the formation of an aluminum oxide film. In addition, when a rare earth element is contained, the passivation film on the alloy surface tends to cause non-uniformity due to the activity of the rare earth element, and there is a disadvantage that corrosion proceeds from that portion to the inside. Since the alloy does not contain a rare earth element, the problem in that respect has been solved.

Next, a description will be given of a case where a bulk member is manufactured for the aluminum-based alloy having the above composition. The aluminum-based alloy according to the present invention, when heated, precipitates and crystallizes a fine crystalline phase, precipitates an aluminum matrix (α phase), and when heated to a higher temperature, also precipitates an intermetallic compound. Utilizing the properties, bulking with high strength and ductility can be performed. Specifically, the ribbon alloy produced by the quenching method is pulverized by a ball mill, and is vacuum-pressed by a vacuum hot press (for example, 10 ⁻³ Torr) at a temperature slightly lower than the crystallization temperature (for example, at about 470 K). An extruded billet with a diameter of several tens of mm and a length of several tens of mm is produced by compacting.
The billet is set in a container of an extruder, and is 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.

[0023]

EXAMPLE A molten alloy having a predetermined composition was produced by a high-frequency melting furnace, and this was converted into a quartz tube 1 having small holes 5 (pore 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 a roll 2 made of copper, and the roll 2 is rotated at a high speed of 4000 rpm, and an argon gas pressure (0.7 kg / cm ³ ) is applied to the quartz tube 1. The molten metal was sprayed from the small holes 5 of the quartz tube 1 onto the surface of the roll 2 and rapidly cooled to solidify rapidly to obtain an alloy ribbon 4. According to the manufacturing conditions, a number of alloy ribbon samples (width 1 mm, thickness 20 μm) having the compositions (atomic%) shown in Tables 1 to 3
X-ray diffraction and TEM for each sample
(Transmission electron microscope) was observed, and the results shown in Tables 1 to 3 were obtained.

[0024]

[Table 1]

[0025]

[Table 2]

[0026]

[Table 3]

From the above measurement results, as shown in the column of the structure state in Tables 1 to 3, an amorphous (Amo) single phase structure or
Crystal structure of intermetallic compound phase or solid solution (Co
m) or a mixed phase structure (fcc-Al + Amo) of an amorphous phase and a fine crystal phase of aluminum having an fcc structure, and a structure in which the amorphous phase and the crystal structure are mixed are obtained. Was confirmed.

Next, the hardness (Hv) and the tensile strength at break (σ _f : MPa) of each ribbon sample were measured, and the results shown in Tables 1 to 3 were obtained. The hardness is a value measured by a micro Vickers hardness tester (DPN: Diamond Pyramid Number). Further, for each of the ribbon samples, as a result of performing a 180-degree close-contact bending test in which each of the ribbon samples was bent at 180 degrees so as to have a U-shape and the ends were brought into close contact with each other, those showing ductility to the extent of not breaking are shown in Tables 1 to 3. Duc is shown, and the broken one is shown by Bri.

From the results shown in Tables 1 to 3, from the results shown in FIG.
For elementary alloys, M is one of Mn, Fe, and Cu
In an alloy containing one or more kinds, 50 ≦ Al ≦ 95, 0.5 ≦ Co ≦ 35, 0.5 ≦ M in atomic%.
It has been clarified that by satisfying the relationship of ≦ 20, it is possible to obtain an aluminum-based alloy which has a high proof stress, a high hardness, and can be processed to be strong in bending. Furthermore, from the results shown in Tables 1 to 3, it can be seen from the results shown in Tables 1 to 3 that in alloys obtained by adding one or more of Mn and Cu as the element L to the Al-Fe binary alloy, 50 ≦ Al
By satisfying the relationships of ≦ 95, 0.5 ≦ Fe ≦ 35, and 0.5 ≦ L ≦ 20, the proof stress is high, the hardness is high,
It became clear that it was possible to obtain an aluminum-based alloy that was strong in bending and could be processed.

In the samples according to the present invention shown in Tables 1 to 3, the normal aluminum-based alloy has a Hv of 50 to 100.
Although it is about DPN, it shows an extremely high hardness of 165 to 387 DPN. Next, the tensile breaking strength (σ
Regarding f), the value of a normal age hardening type aluminum-based alloy (Al-Si-Fe-based) is 200 to 600 MPa, while that of the sample of the present invention is 760 to 1270 M
It became Pa range, and it became clear that it was extremely excellent. Regarding the tensile strength, in the case of JIS-based 6000 or 7000-based aluminum-based alloys,
About 250-300 MPa, about 400 MPa for Fe-based structural steel sheets, and 800-9 for Fe-based high-tensile steel sheets.
Considering that the pressure is about 80 MPa, it is clear that the aluminum alloy according to the present invention is extremely excellent.

FIG. 2 shows an X-ray diffraction pattern of an alloy sample having a composition of Al ₈₉ Co ₈ Mn _{3. In} this figure, a broad pattern without a crystal peak was observed, and the alloy sample was amorphous. It shows that it has a single-phase structure. FIG. 3 shows an X-ray diffraction pattern of an alloy sample having a composition of Al ₉₀ Co ₆ Fe ₄ .
It shows that it has a mixed phase structure with a fine Al crystal phase having an fcc structure. In the figure, (111), (20)
What is indicated by 0) is a crystal peak of Al having the fcc structure.

[0032] Figure 4 shows a DSC (differential scanning calorimetry) curve when heated alloy samples Al ₉₀ Co ₉ Cu ₁ having a composition at a heating rate of 0.67k / s, 5 Al ₉₀ C ₉ 9 shows a DSC curve when an alloy sample having a composition of Mn ₁ is heated at a heating rate of 0.67 k / s. As is clear from FIGS. 4 and 5, the broad peak on the low temperature side is the Acc of the fcc structure.
1 shows the crystallization peak of the particles, and the sharp peak on the high temperature side shows the crystallization peak of the compound. Having such two peaks means that if heat treatment such as quenching is performed at an appropriate temperature, the volume fraction of Al particles dispersed in the amorphous matrix can be controlled. It is clear that the mechanical properties can be improved. Furthermore, Ti and
When a predetermined amount of Zr is added, the quenching effect is improved and the amorphous phase
And a fine crystalline phase are easily obtained,
Stability is improved. Ti (titanium), Zr (zirconia
Um) content is less than or equal to 1/2 of the element M or the element L.
If the ratio is less than 0.5 atomic%, the rapid cooling effect is
In the case where the alloy structure contains crystalline
Crystal grains are not refined. Further, the content is 10 atomic%.
If it exceeds, the material becomes brittle and the toughness decreases. In addition, melting point rises
And dissolution becomes difficult. Also, the viscosity of the molten metal increases,
It becomes difficult to eject from a nozzle used during manufacturing. What
Note that the element M is converted to T within a range of more than half the content of the element M.
When substituted with i or Zr, hardness, strength and toughness decrease.
Would.

[0033]

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 material having high corrosion resistance. Further, the heat treatment can improve the mechanical properties, and has excellent properties such as being able to be machined because it is strong against bending. From the above, aluminum-based alloy according to the present invention, aircraft, vehicles,
As a structural member of a ship or the like, or a structural member of an engine part, or a building exterior material, sash, or roofing material,
Furthermore, it can be widely used as a member for seawater equipment, a member for a nuclear reactor, and the like.

[Brief description of the drawings]

FIG. 1 is a configuration diagram showing an example of a single roll device used for producing a ribbon by rapidly solidifying an 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 ₈₉ Co ₈ Mn ₃ .

FIG. 3 is a view showing an X-ray diffraction analysis result of an alloy having a composition of Al ₉₀ Co ₆ Fe ₄ .

FIG. 4 is a view showing thermal characteristics of an alloy having a composition of Al ₉₀ Co ₉ Cu ₁ .

FIG. 5 is a diagram showing thermal characteristics of an alloy having a composition of Al ₉₀ Co ₉ Mn ₁ ;

[Explanation of symbols]

 1 Quartz tube 2 Roll 3 Molten 4 Thin strip 5 Nozzle hole

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Akihisa Inoue 11-806 Kawauchi Residence No. Kawauchi, Aoba-ku, Aoba-ku, Sendai City, Miyagi Prefecture (72) Inventor Hiroma Horio 10-1 Nakazawacho, Hamamatsu-shi, Shizuoka Yamaha In-company (56) References JP-A-6-256875 (JP, A) JP-A-1-316434 (JP, A) JP-A-62-37335 (JP, A) JP-A-3-257133 (JP, A) )

Claims (3)

(57) [Claims] 1. A general formula AlxCoyMz (where M is, Fe, 1 kind or Mn is selected from among Cu, Fe, show two or more metal elements selected from among Cu.) Composition represented by X, y, and z indicating the composition ratio are x + y + z = 100 and 5 in atomic%.
A high-strength, high-corrosion-resistant aluminum-based alloy, characterized by satisfying the following relationships: 0 ≦ x ≦ 95, 0.5 ≦ y ≦ 35, and 0.5 ≦ z ≦ 20. 2. A composition having a composition represented by the general formula AlaFebLc (where L represents one or more metal elements selected from Mn and Cu), and a, b indicating a composition ratio , C are a + b + c = 100, 5 in atomic%
A high-strength, high-corrosion-resistant aluminum-based alloy characterized by satisfying a relationship of 0 ≦ a ≦ 95, 0.5 ≦ b ≦ 35, and 0.5 ≦ c ≦ 20. 3. A composition having a composition represented by the general formula: AldCoeMnf , wherein d, e, and f representing composition ratios are atoms.
% + D + e + f = 100, 50 ≦ d ≦ 95, 20 ≦ e ≦ 3
5. A high-strength, high-corrosion-resistant aluminum-based alloy characterized by satisfying a relationship of 5, 5 ≦ f <20 .