JP2583718B2 - High strength corrosion resistant 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, and more particularly to an aluminum-based alloy having an amorphous structure or a structure in which fine crystals are dispersed in an amorphous material.

[0002]

2. Description of the Related Art Conventional aluminum-based alloys include Al-
Cu-based, Al-Si-based, Al-Mg-based, Al-Cu-Si-based, A
Alloys of various component systems such as l-Cu-Mg system and Al-Zn-Mg system are known, and any of these systems is lightweight and has excellent corrosion resistance. Depending on the machine, structural members of vehicles, ships, aircraft, etc., or building exterior materials, sashes, roofing materials, LN
It is widely used as a structural material for G tanks.

However, conventional aluminum-based alloys are:
In general, there are disadvantages that the hardness is lower and the heat resistance is lower than Fe-based materials. Some of the elements whose strength is increased by adding an element 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 AlMX-based alloy having a specific composition ratio (M is V, Cr, Mn, Fe, C
O, Ni, Cu, Zr and the like are shown, and X is La, Ce,
Rare earth elements such as Sm and 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. Therefore, the present inventors have conducted intensive research on an aluminum-based alloy capable of exhibiting the same excellent properties as an aluminum-based alloy having the above composition.
The present invention has been reached.

The present invention has been made in view of the above circumstances, and realizes low cost and low activation by minimizing the content of expensive elements such as rare earth elements or highly active elements such as Y. It is another object of the present invention to provide an aluminum-based alloy having high strength and excellent corrosion resistance.

[0007]

According to a first aspect of the present invention, there is provided an image forming apparatus, comprising: a compound represented by the general formula: AlxMyRz (where M is at least one selected from Ti, Cu, and Nb ); Metal elements or Ti, Cu, Nb
One or more metal elements selected from the group consisting of Ni and Ni , and R represents one or more elements or a mixture of Y, Ce, La, Nd and Mm (mish metal) Is shown. X, y, and z, which have a composition represented by the following composition ratio, are x + y + z = 100 in atomic% and 64.5 ≦ x
≤95, 0.5≤y≤35, and 0 <z <0.5, and mainly consist of amorphous or a mixed structure of amorphous and fine crystalline.

According to a second aspect of the present invention, in order to solve the above-mentioned problems, the mixed structure according to the first aspect has an aluminum phase, a stable or metastable intermetallic compound phase, or a metal of an aluminum matrix. Of the solid solution
At least one is mainly used.

[0009]

The aluminum-based alloy according to the present invention has the general formula
AlxMyRz (where Al represents aluminum, M
Is, Ti (titanium), Cu (copper), one or more metal elements selected from among Nb (niobium), there have
Is one or two selected from Ti, Cu and Nb
The above metal elements and Ni (nickel) are shown, and R is Y
One or two or more elements selected from (yttrium), Ce (cerium), La (lanthanum), Nd (neodymium), and Mm (mish metal). X), y, and z, which have the composition shown in ()) and indicate the composition ratio, are atomic%.
X + y + z = 100, 64.5 ≦ x ≦ 95, 0.5 ≦ y ≦ 3
It satisfies the relationship of 5, 0 <z <0.5 and is mainly composed of amorphous or a mixed structure of amorphous and fine crystalline.

[0010] The microcrystalline material of the mixed structure is mainly composed of at least one of a fine crystal phase of aluminum, a stable or metastable intermetallic compound phase, and a metal solid solution comprising an aluminum matrix. is there. The crystal grain size of these fine crystalline materials is about 30 to 50 nm.

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 diameter rotating at a constant speed in a range of about 300 to 10000 rpm through a nozzle hole formed in a storage container such as a quartz tube containing a molten metal. The molten metal is jetted onto a roll of copper or copper of 30 to 300 mm. As a result, various kinds of ribbon materials having a width of about 1 to 300 mm and a thickness of about 5 to 500 μm can be easily obtained.

On the other hand, in order to produce a thin wire material by spinning in a rotating liquid, a depth held by centrifugal force through a nozzle hole in a hollow drum rotating at about 50 to 500 rpm under argon gas back pressure. A thin wire material can be easily obtained by jetting a molten metal into a solution refrigerant layer of about 1 to 10 cm and rapidly cooling it. At this time, the angle between the molten metal jetted from the nozzle hole and the refrigerant surface is preferably about 60 to 90 degrees, and the relative speed ratio between the jetted molten metal and the solution refrigerant surface is about 0.7 to 90 degrees.
It is preferably 0.9. 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 and a spraying method. Thus, an aluminum-based alloy powder having the above composition can be obtained.

Whether or not the quenched aluminum-based alloy thus obtained is amorphous, or a composite of amorphous and microcrystalline or microcrystalline, can be easily known by ordinary X-ray diffraction. it can. That is, in the case of amorphous, a halo pattern peculiar to amorphous is shown in the obtained X-ray diffraction pattern, and in the case of a complex of amorphous and fine crystalline, the halo pattern and fine crystalline are caused. In the case of a fine crystalline material, a synthesized diffraction pattern of a peak caused by an intermetallic compound that varies depending on the aluminum solid solution (α phase) and the alloy composition is shown.
These amorphous materials, a composite of amorphous and fine crystalline materials, or fine crystalline materials can be obtained by the above-mentioned single roll method, twin roll method, spinning in a rotating liquid, sputtering, various atomizing methods, spraying methods, mechanical methods. It can be obtained by an alloying method or the like. Further, by selecting appropriate production conditions as needed, a mixed phase of amorphous and fine crystals can be obtained.

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.

On the other hand, in the above composition ratio, the atomic% of Al
In the range of 64.5 to 95 and the atomic% of the element M in the range of 0.5 to 3
The reason why the atomic% of the element R is limited to the range of 0 to 0.5 in the range of 5 is that if the composition of each element is out of these ranges, it becomes difficult to become amorphous or to exceed the solid solubility limit. In order to make it difficult to form a supersaturated solid solution, an industrial quenching means utilizing the liquid quenching method or the like is required to provide an amorphous, composite of amorphous and fine crystalline having the properties of the present invention. Alternatively, a microcrystalline aluminum-based alloy cannot be obtained. When the composition is out of the above-mentioned composition range, the amorphous phase obtained by the quenching method is crystallized by a suitable heat treatment or temperature control in a powder molding process using a conventional powder metallurgy technique to form a microcrystalline composite. It becomes difficult to obtain an amorphous phase for obtaining a body.

The element M is one or more metal elements selected from Ti, Cu, and Nb ;
One or more selected from i, Cu, Nb
And the effect of increasing the crystallization temperature of the amorphous phase together with the element R. Here, the hardness and strength of the amorphous phase are shown here. The effect of remarkably improving is important. On the other hand, under the conditions for producing fine crystals, it has the effect of stabilizing the fine crystal phase, forms a stable or metastable intermetallic compound with aluminum and other additional elements, and forms an aluminum matrix (α phase). It is uniformly and finely dispersed in the alloy to remarkably improve the hardness and strength of the alloy, and suppresses coarsening of fine crystals at a high temperature to impart heat resistance. If the atomic percentage of the element M is less than 0.5%, the strength and hardness decrease, which is not preferable. If the atomic percentage exceeds 35%, an intermetallic compound is easily formed, which is not preferable.

The element R represents one or more elements selected from Y, Ce, La, Nd, and Mm (mish metal). Here, the misch metal is a general term for a complex containing a main element of La and Ce and a rare earth element other than La and Ce and unavoidable impurities (Si, Fe, Mg, etc.). The element R has an effect of improving the crystallization temperature of the amorphous phase and increasing the crystallization temperature of the amorphous phase, in addition to improving the ability to form an amorphous phase. Thereby, the corrosion resistance can be remarkably improved, and the amorphous phase can be stably present at a high temperature. Further, under the conditions for producing a microcrystalline alloy, the alloy has the effect of coexisting with the element M and stabilizing the microcrystalline phase. On the other hand, if the atomic percentage of the element R exceeds 0.5%, the alloy is liable to be oxidized, and the production cost is undesirably increased.

The aluminum-based alloy of the present invention exhibits a superplastic phenomenon in the vicinity of the crystallization temperature (crystallization temperature ± 100 ° C.) or in the high temperature range within the stable temperature range of the fine crystal phase. Processing such as processing and hot forging can be 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 180 degrees.

The above-mentioned alloys based on aluminum-based amorphous or a mixed composition of amorphous and fine crystals include structural non-uniformities such as crystal grain boundaries and segregation such as crystalline alloys, and chemical non-uniformities. 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 included, 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 contains only a trace amount of a rare earth element, the problem in that respect is also solved, and corrosion inside the alloy does not progress.

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. Bulking can be performed using the properties. In particular,
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 T
orr) at a temperature slightly lower than the crystallization temperature (eg, 47
Approximately tens of mm in diameter and several tens in length
Make an extruded billet of mm. 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.

[0021]

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 to apply an argon gas pressure (0.7 kg / cm ³ ) to the quartz tube 1. The molten metal was sprayed onto the surface of the roll 2 from the small hole 5 of the quartz tube 1 to rapidly solidify it to obtain an alloy ribbon 4. Under the above manufacturing conditions, a number of alloy ribbon samples (width 1 mm, thickness 20 μm) having the composition (atomic%) shown in FIGS. 2 and 3 were prepared.
As a result of subjecting each sample to X-ray diffraction and TEM (transmission electron microscope) observation, as shown in the column of the structure state in FIGS. 2 and 3, an amorphous (Amorphous) single-phase structure or an intermetallic structure was obtained. It has been confirmed that a crystal structure composed of a compound or a solid solution (Crystalline) or a two-phase structure (fcc-Al + Amo) in which aluminum having an fcc structure is dispersed as fine crystal particles in an amorphous matrix is obtained. Was.

Next, the hardness (Hv) and the tensile strength at break (σ _f : MPa) of each ribbon sample were measured, and the results shown in FIGS. 2 and 3 were obtained. The hardness is a value measured by a micro Vickers hardness tester (DPN: Diamond Pyramid Number). Further, each of the ribbon samples was subjected to a 180-degree adhesion bending test in which each of the ribbon samples was bent at 180 degrees so as to form a U-shape and the ends thereof were adhered to each other. Duc is shown, and the broken one is shown by Bri.

From the results shown in FIG. 2 and FIG.
4.5 ≦ Al ≦ 95, 0.5 ≦ M ≦ 35, 0 <R <0.5
It has been clarified that by satisfying the following relationship, it is possible to obtain an aluminum-based alloy which has a high proof stress, a high hardness, and a high bending resistance.

In the samples according to the present invention shown in FIGS. 2 and 3, the ordinary aluminum-based alloy has a Hv of 50 to 100.
It shows an extremely high hardness of about 260 to 340 DPN, which is about 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, whereas that of the sample of the present invention is in the range of about 800 to 1250, It turned out to be excellent.
Regarding the tensile strength, in the case of a 6000 or 7000 aluminum alloy based on JIS, 250 tensile strength is required.
About 300 MPa, and 400 for Fe-based structural steel sheets.
Approx.MPa, 800 ~ 980MPa with Fe-based high-tensile steel plate
Considering the degree, the aluminum alloy according to the present invention is clearly excellent.

FIG. 4 shows an X-ray diffraction pattern of an alloy sample having a composition of Al ₈₈ Ni _11.6 Ce _0.4 . In this figure, a broad pattern without a crystal peak is observed.
This shows that the alloy sample has an amorphous single-phase structure. FIG. 5 shows an X-ray diffraction pattern of an alloy sample having a composition of Al _89.7 Ni ₅ Fe _0.5 Ce _0.3 . In this figure, two phases in which fine Al particles having a nanoscale fcc structure are dispersed in an amorphous phase are shown. It shows that it has a structure. In the figure, those indicated by (111) and (200) are crystal peaks of Al having the fcc structure.

[0026] Figure 6 shows an Al _89.6 Ni ₅ Co ₅ DSC of when the alloy samples of Ce _0.4 a composition was heated at a heating rate of 0.67k / s (differential scanning calorimetry) curve, FIG. 7 Al ₈₈
9 shows a DSC curve when an alloy sample having a composition of Ni _11.6 Y _0.4 is heated at a temperature rising rate of 0.67 k / s. As is clear from FIGS. 6 and 7, the broad peak on the low temperature side indicates the crystallization peak of Al particles having the fcc structure, and the sharp peak on the high temperature side indicates 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.

[0027]

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. Further, the alloy according to the present invention
In addition to having the above excellent material properties, rare earth elements and Y
A composition containing only a very small amount of highly active elements, lower cost,
Low activation can be realized.

[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 shows the results of measuring the properties of the obtained alloy samples.

FIG. 3 shows the results of measuring the properties of the obtained alloy samples.

FIG. 4 is a view showing an X-ray diffraction analysis result of an alloy having a composition of Al ₈₈ Ni _11.6 Ce _0.4 .

FIG. 5 is a view showing an X-ray diffraction analysis result of an alloy having a composition of Al _89.7 Ni ₅ Fe ₅ Ce _0.3 .

FIG. 6 is a diagram showing the thermal characteristics of an alloy having a composition of Al _89.6 Ni ₅ Co ₅ Ce _0.4 .

FIG. 7 is a view showing thermal characteristics of an alloy having a composition of Al ₈₈ Ni _11.6 Y _0.4 .

[Explanation of symbols]

1 quartz tube, 2 rolls, 3
Molten metal, 4 ribbons, 5 nozzle holes,

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Akihisa Inoue 11-806 Kawauchi Residence, Kawauchi, Aoba-ku, Sendai City, Miyagi Prefecture (72) Inventor Hiroma Horio 10-1 Nakazawacho, Hamamatsu-shi, Shizuoka Yamaha In-company (56) References JP-A-3-260037 (JP, A) JP-A-4-41654 (JP, A)

Claims (2)

(57) [Claims] 1. A general formula AlxMyRz (where M is, Ti, Cu, 1 kind or 2 or more metal elements selected from among Nb, or,, Ti, Cu, N
one or more metal elements selected from b
And Ni , and R represents one or more elements or a mixture selected from among Y, Ce, La, Nd, and Mm (mish metal). X, y, z indicating the composition ratio are x + y + z = 100, 6 in atomic%.
4.5 ≦ x ≦ 95, 0.5 ≦ y ≦ 35, 0 <z <0.5, and mainly composed of amorphous or a mixed structure of amorphous and fine crystalline A high-strength corrosion-resistant aluminum-based alloy characterized by the following: 2. The fine crystalline material of the mixed structure according to claim 1,
Aluminum phase, stable or metastable intermetallic phase,
Alternatively, a high-strength corrosion-resistant aluminum-based alloy characterized by mainly comprising at least one of a metal solid solution comprising an aluminum matrix.