JP2892270B2 - Method for producing alloy having fine crystal structure and fine crystalline alloy - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to an amorphous alloy,
The present invention relates to a method for producing an alloy having a fine crystal structure composed of ultrafine crystal grains of sub-nanometers to tens of nanometers, and a microcrystalline alloy.

[0002]

2. Description of the Related Art Conventionally, a method of producing a fine crystalline structure of several tens of nanometers to several microns by heat-treating an amorphous alloy is disclosed in, for example, Japanese Patent Application Laid-Open No. 5-134.
No. 6 is known.

[0003] Japanese Patent Application Laid-Open No. 5-1346 discloses an alloy having an average crystal grain size of 0.01 (μm) to 80 (μm). It is disclosed that an alloy having an amorphous structure is manufactured by a rapid solidification method, and the alloy is heated and decomposed to control the average crystal grain size as described above. .

[0004]

As described above, it has recently been known that a fine crystal structure of several tens of nanometers to several microns can be obtained by heat treatment, and research on a strength material utilizing these has been advanced. Has been successful.
Thereby, further improvement in mechanical performance and chemical characteristics can be expected by making the crystal grains finer, but it is difficult to stably obtain a finer crystal structure with the current technology.

The present invention provides a fine crystalline alloy having improved mechanical properties, chemical properties, and the like by further refining the fine crystal structure of an Al-based alloy and stably presenting the same, and having the above-mentioned excellent properties. It is an object of the present invention to provide a method for producing an alloy having a fine crystal structure that can easily produce an alloy.

[0006]

SUMMARY OF THE INVENTION The present invention provides at least two
An alloy composition that can produce an alloy containing an amorphous phase with at least one kind of element has a content of 0.1% or more at least one of the elements constituting the alloy.
An amorphous alloy is prepared by adding an additive element which forms a solid solution of at least 01 at%, and is subjected to a heat treatment at a temperature from the crystallization temperature (Tx) -100 (K) to the crystallization temperature (Tx) +100 (K). A method for producing an alloy having a fine crystal structure, characterized by producing an alloy having a crystal structure composed of fine crystal grains by applying.

The main metal element of the amorphous alloy is A
l, Ga, Ge, L in which the above-mentioned additional element is dissolved in Al
Suitable is at least one element selected from i, Mg, Mn, Sc, V, Ag, and Cu.

The present invention provides a method of obtaining a fine crystal structure by crystallization of an amorphous alloy, which has not been clarified, and provides a method of controlling the crystal grain size by changing the type and amount of an additive element. It is made possible.

In an amorphous alloy containing an amorphous phase, an element which forms a solid solution with one or more of the elements constituting the alloy in an amount of 0.01 at% or more, preferably an element which forms a solid solution with 0.1 to 15 at% is used.
% (Tx-100) K to (Tx + 100)
By performing the heat treatment at the temperature of K (Tx = crystallization temperature), a fine crystal structure of sub-nanometers to several tens of nanometers can be obtained. As described above, a fine crystal structure can be obtained by adding an element that forms a solid solution to the amorphous alloy because the addition of the additional element forms a portion having a different solute element concentration in the matrix, Fluctuations occur. Due to such concentration fluctuations, a large number of portions having different crystallization temperatures are formed in the parent phase, a large number of nuclei are generated during the heat treatment, and the crystal grains are refined. Therefore, it is appropriate that the amount added corresponds to the amount of solid solution at the heat treatment temperature.
Even if the elements which are solid-solubilized completely are replaced up to 100%, there is an effect of miniaturization, but if replaced by 15% or more, the properties of the mother phase itself change remarkably, so the replacement amount is up to 0.01 to 15%. did. Based on such a rule, the crystal grains were refined and the mechanical strength was greatly improved.

[0010] Additional elements (Ga, Ge, Li, Mg, M
More preferred ranges of n, Sc, V, Ag, and Cu) are G
a: 0.01 to 10 at%, Ge: 0.01 to 3 at%
%. , Li: 0.01 to 10 at%, Mg: 0.01 to
15 at%, Mn: 0.01 to 1 at%, Sc: 0.0
1 to 0.5 at%, V: 0.01 to 1 at%, Ag:
0.01 to 15 at%, Cu: 0.01 to 15 at%
It is.

The composition from which an amorphous alloy can be produced is more preferably a composition containing a rare earth element. A specific example thereof is described in JP-A-1-275732.

That is, the general formula Al _a M _b X _c [where M:
V, Cr, Mn, Fe, Co, Ni, Cu, Zr, T
i, Mo, W, Ca, Li, Mg, one or more metal elements selected from Si, X: Y, La, Ce,
One or more elements selected from the group consisting of Sm, Nd, Hf, Nb, Ta, and Mm [Misch metal];
b and c are atomic percentages, such as 50 ≦ a ≦ 95 0.5 ≦ b ≦ 35 0.5 ≦ c ≦ 25].

The heat treatment temperature is a crystallization temperature (Tx) -10.
It is necessary that the temperature be from 0 (K) to the crystallization temperature (Tx) +100 (K), and the crystallization temperature (Tx) −100 (K)
When the heating is performed at a temperature lower than the above, it is difficult to obtain a fine crystal structure intended for the present invention even if heating is performed for a long time, and the crystallization temperature (T
x) When the temperature is higher than +100 (K), crystallization and crystal growth progress in a short time, and it is difficult to obtain a fine crystal structure intended for the present invention.

The heat treatment time is preferably from 10 seconds to 6 hours. If the heat treatment time is less than 10 seconds, the fine crystal structure of the present invention can be obtained by heating at a temperature of Tx + 100K or at a temperature exceeding Tx + 100K. This is because an alloy having a fine crystal structure can be obtained by heating at a temperature of Tx-100K for more than 6 hours, but it is uneconomical when industrially performed. .

Further, by obtaining an alloy consisting of average grain size 10 n m or less fine crystal grains can provide is the object mechanical properties, excellent alloy chemical properties of the present invention.

[0016]

The present invention will be specifically described below with reference to examples.

A molten alloy having various component compositions capable of producing an alloy containing an amorphous phase is produced by a high frequency melting furnace, and various additions are made to one or more of the elements constituting the component composition when the molten alloy is in an equilibrium state. Add a predetermined amount of element.

Next, this is charged into a quartz tube having a small hole at the tip and heated and melted.
Installed just above a 0 mm roll, and rotate at 5000 rpm
Under high-speed rotation, the molten alloy in the quartz tube is ejected from the small holes of the quartz tube under argon pressure (0.7 kg / cm ² ), and is brought into contact with the surface of the roll to rapidly solidify to obtain a ribbon. That is, a ribbon is produced by a single roll method.

Under the above manufacturing conditions, alloy ribbons having the compositions shown in Tables 1 and 2 were obtained. After confirming that each of the test ribbons is an alloy containing an amorphous phase by X-ray diffraction or the like, differential scanning calorimetry was performed, and the crystallization temperature (based on the obtained differential calorimetric analysis curve) was determined. Tx) was determined, and the heat treatment temperature was determined based on the obtained crystallization temperature (Tx). Each of the test ribbons was heat-treated at the temperatures and times shown in Tables 1 and 2. The sample after the heat treatment was observed by TEM, and the tensile strength of the sample was measured. The results are shown in the right columns of Tables 1 and 2.

In addition, Table 1 shows, for comparison, the results obtained from the samples subjected to the same heat treatment without adding the additive element of the present invention.

According to Tables 1 and 2, it can be seen that a fine crystal structure is obtained with the alloy of the present invention, and an alloy having excellent strength is obtained by the structure.

Table 1 shows the results obtained by examining the case where a part of the composition composed of Al ₈₇ Ni ₁₀ Ce ₃ was replaced by the various additive elements of the present invention. Table 2 shows the part of the alloy element composed of the various compositions. Is a result obtained by examining the case where is replaced with various additional elements of the present invention.

[0023]

[Table 1]

[0024]

[Table 2]

[0025]

As described above, according to the production method of the present invention, an ultrafine crystal structure can be easily obtained, and the ultrafine crystals can be stably present.

Further, according to the alloy of the present invention, since it has an ultrafine crystal structure, it is possible to provide an alloy having excellent properties such as mechanical properties and chemical properties.

Continued on the front page (72) Inventor Akihisa Inoue 11-806 Kawauchi House, Kawauchi Muban, Aoba-ku, Sendai, Miyagi Prefecture Inventor Hideo Fukui 3-15-15, Wakabayashi, Wakabayashi-ku, Sendai, Miyagi B-102 (56) References JP-A-5-320837 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C22F 1/00 C22C 21/00 C22F 1/04

Claims (3)

(57) [Claims] 1. A method according to claim 1, wherein Al is the main metal element, and other than the main metal element.
Are transition elements and rare earth elements (however,
Excluding) at least 0.01 at% of Ga, Ge which forms a solid solution with at least one of the elements constituting the alloy in an alloy composition capable of producing an alloy containing an amorphous phase with at least two or more of these elements. , Li, Mg, Mn, Sc, V, Ag, C
0.1 at least one kind of additive elements selected from u
at% to 15 at%, to prepare an amorphous alloy, which is converted from the crystallization temperature (Tx) -100 (K) to the crystallization temperature (T
x) a method for producing an alloy having a fine crystal structure, characterized by producing an alloy having a crystal structure composed of fine crystal grains having an average particle diameter of 10 nm or less by performing a heat treatment at a temperature up to +100 (K). . 2. The method for producing an alloy having a fine crystal structure according to claim 1, wherein the time of the heat treatment is from 10 seconds to 6 hours. 3. The main metal element is Al, and the auxiliary metal element is at least one or more elements selected from transition elements and rare earth elements (excluding the following additional elements) .
The additive element added at 1 at% to 15 at% is Ga, G
e, having a composition comprising at least one or more elements selected from Li, Mg, Mn, Sc, V, Ag, and Cu;
A microcrystalline alloy having a fine crystal structure having an average crystal grain size of 10 nm or less.