(57) High strength magnesium-based alloy materials having a microcrystalline composite
structure, the alloy materials consisting of a composition represented by the general
formula (I): Mg
aNd
bZn
c, wherein a, b and c are, in atomic %, 80 ≦ a ≦ 99, 1 ≦ b ≦ 12 and 0 ≦ c ≦ 12; or
the general formula (II): Mg
a'Nd
b'Zn
c', wherein a', b' and c' are, in atomic %, 95 < a' ≦ 99, 1 ≦ b' ≦ 3 and 0 ≦ c' ≦ 3.
The alloy materials have superior mechanical properties as high specific strength
materials and plastic working materials and are produced by rapidly solidifying a
molten alloy represented by the general formula (I) or (II) so as to form a fine-grained
matrix phase; and subjecting the resultant rapidly solidified alloy to plastic working
at a prescribed heating temperature for work hardening, thereby forming a microcrystalline
composite structure having a dispersion of the fine intermetallic compounds in the
matrix.
BACKGROUND OF THE INVENTION
1. Field of the Invention
[0001] The present invention relates to high strength magnesium-based alloy materials having
superior mechanical properties and a method for producing the same.
2. Description of the Prior Art
[0002] As conventional magnesium-based alloys, there are known Mg-Al, Mg-Al-Zn, Mg-Th-Zr,
Mg-Th-Zn-Zr, Mg-Zn-Zr, Mg-Zn-Zr-RE (RE: rare earth element), etc. and these known
alloys have been extensively used as light-weight structural component materials in
a wide variety of applications, according to their properties. Further, as rapidly
solidified materials, there are known alloys disclosed in Japanese Patent Laid-open
No. 3-47,941.
[0003] However, under the present circumstances, known various types of magnesium-based
alloys, as set forth above, have a low hardness and strength. Although the alloys
disclosed in Japanese Patent Laid-open No. 3-47,941 have superior hardness and tensile
strength, they still leave some room for further improvement in thermal stability
and ductility. Further, in the Japanese Patent specification, there is no specific
mention about Mg-Nd-Zn alloys, which are contemplated by the present invention, and
most of the alloys disclosed therein are alloys including Mg in an amount of 70-80
atomic %.
SUMMARY OF THE INVENTION
[0004] In view of the foregoing, it is an object of the present invention to provide magnesium-based
alloy materials which have an advantageous combination of properties of high hardness,
strength and thermal resistance and which are useful as lightweight and high strength
materials (i.e., high specific strength materials) and have a superior ductility.
[0005] According to the present invention, there is provided a high strength magnesium-based
alloy material having a microcrystalline composite structure, the alloy material consisting
of a composition represented by the general formula (I): Mg
aNd
bZn
c, wherein a, b and c are, in atomic %, 80 ≦ a ≦ 99, 1 ≦ b ≦ 12 and 0 ≦ c ≦ 12.
[0006] The present invention also provides a high strength magnesium-based alloy material
having a microcrystalline composite structure, the alloy material consisting of a
composition represented by the general formula (II): Mg
a'Nd
b'Zn
c', wherein a', b' and c' are, in atomic %, 95 < a' ≦ 99, 1 ≦ b' ≦ 3 and 0 ≦ c' ≦ 3.
[0007] The aforesaid high strength magnesium-based alloy materials are produced by a method
comprising:
rapidly solidifying a molten alloy so as to form a fine-grained matrix phase, the
molten alloy consisting of the composition represented by the above-defined general
formula (I) or (II); and
subjecting the resultant rapidly solidified alloy to plastic working at a prescribed
heating temperature for work hardening, thereby forming a microcrystalline composite
structure having a uniform dispersion of very fine intermetallic compounds in the
matrix.
[0008] The matrix in the composite structure consists of an Mg matrix having a hexagonal
close-packed (hcp) structure and intermetallic compounds consisting of a non-equilibrium
phase having a face-centered cubic (hcp) structure and/or other intermetallic compound
phases, such as an Mg₁₂Nd phase, are finely and uniformly dispersed throughout the
matrix .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0009] As described above, the present invention provides the above-defined high strength
magnesium-based alloy materials consisting of a composition represented by the general
formula (I) or (II). In the above-defined general formula (I), the ranges of a, b
and c are so limited that the above-defined alloy can be obtained with the aforesaid
microcrystalline composite structure by industrial rapid cooling techniques, such
as liquid quenching.
[0010] The reason why the ranges of a', b' and c' of the general formula (II) are limited
as defined above is that since a large amount of intermetallic compounds are formed
with a small amount of Nd, the rapidly solidified material obtained from the alloy
composition has a high strength on a higher Mg content side as compared with the rapidly
solidified material represented by the general formula (I) and is useful as a high
specific strength material. Further, the addition of solute elements can be saved.
[0011] As a further important reason, in the above-defined compositional ranges, fine hcp-Mg
precipitates as a host matrix, and finer intermetallic compounds of a non-equilibrium
fcc phase formed from, at least, Mg and Nd and/or Mg₁₂Nd phase, etc. are uniformly
and finely distributed throughout the hcp-Mg matrix. Especially, when the intermetallic
compounds comprising the non-equilibrium fcc phase, which is formed from, at least,
Mg and Nd and which has a good compatibility with the matrix of hcp-Mg, are uniformly
and finely dispersed in the matrix, the Mg matrix is strengthened and the strength
of the alloy is outstandingly improved. However, when the Mg content is 95 atomic
% or less, a very high ductility as obtained in the case of Mg contents exceeding
95 atomic % cannot be expected because the proportion of the intermetallic compounds
dispersed in the matrix becomes excessive with respect to the entire alloy.
[0012] In the magnesium-based alloys of the present invention, Nd makes it possible to form
the above-mentioned composite structure having a dispersion of intermetallic compounds
consisting of a non-equilibrium fcc phase, which is formed from, at least, Nd and
Mg, and/or other intermetallic compounds, such as an Mg₁₂Nd phase, while suppressing
the grain growth of the matrix phase. Since the intermetallic compounds can be formed
in large quantities in the presence of a small amount of Nd, it is possible to obtain
alloys having a high strength on an Mg-rich side so that high specific-strength materials
can be obtained.
[0013] Another alloying element Zn transforms the non-equilibrium phase to a more stable
non-equilibrium phase of fcc structure so that the intermetallic compounds having
a good compatibility with the magnesium matrix (α phase) uniformly and finely disperse
in the matrix. As a result, the hardness and strength of the resultant alloys are
improved and a high thermal resistance is imparted to the alloys by suppressing coarsening
of the microcrystalline structure of the alloys at high temperatures.
[0014] In the production of the high strength magnesium-based alloy materials of the present
invention, a molten alloy having the above-defined composition is rapidly solidified
so as to obtain a fine-grained matrix phase. In the rapidly solidification step, a
cooling rate of 10²-10⁶ K/sec is particularly effective. The resultant rapidly solidified
alloy is heated to a prescribed temperature and subjected to plastic working. As a
result, it is possible to obtain magnesium alloy materials having a microcrystalline
composite structure composed of an hcp Mg matrix and, homogeneously distributed in
the matrix, intermetallic compounds consisting of a non-equilibrium fcc phase and/or
other intermetallic compound phases, such as an Mg₁₂Nd phase formed of Mg and Nd.
The non-equilibrium fcc phase may be formed either during rapid solidification or
during plastic working. The plastic working is preferably performed at a temperature
of 50 to 500°C. A temperature lower than 50°C cannot provide a sound material due
to an excessive deformation resistance. On the other hand, a temperature exceeding
500°C causes a considerable grain growth, thereby lowering the strength.
[0015] The magnesium matrix and the intermetallic compounds formed by the above production
method have a grain size ranging from 200 nm to 600 nm and a particle size ranging
from 10 nm to 400 nm, respectively.
[0016] Further, by controlling the matrix grain size and the intermetallic compound particle
size of the inventive alloys to the above-defined ranges, the alloys may have superior
properties as superplastic working materials.
[0017] The present invention will be illustrated in more detail by the following examples.
Examples
[0018] A molten alloy having a given composition was prepared using a high-frequency melting
furnace. The molten alloy was subjected to a single-roller melt-spinning technique,
which is one of the rapid solidification techniques, at a cooling of 10²-10⁶ K/sec
and a rapidly solidified material comprising a fine-grained matrix phase.
[0019] The thus obtained rapidly solidified material was subjected to hot-extrusion at a
temperature of 320°C under an applied pressure of 1240-1628 MPa, while suppressing
the grain growth of the matrix phase. The thus obtained extruded material had a microcrystalline
composite structure having a dispersion of fine intermetallic compounds.
[0020] According to the processing conditions as set forth above, test samples (extruded
materials) having the compositions (by atomic %) given in Table 1 were produced. Comparative
extruded materials having compositions falling outside the compositional range of
the present invention were produced under the same processing conditions as described
above. The comparative materials are disclosed in Japanese Patent Application Laid-Open
No. 3-47,941 hereinbefore described.
[0021] Each test sample was subjected to X-ray diffraction and measured for its mechanical
properties, i.e., tensile strength (σ
B), plastic elongation (ε
f), Young's modulus (E), specific strength (σ
B/
ρ). The results are shown on the right-hand column of Table 1. The specific strength
was obtained by dividing tensile strength by density for each sample. Further, the
test samples were observed by a transmission electron microscope (TEM). The results
of the TEM observation were as follows:
Mg₉₇Nd₃ comprised an hcp-Mg matrix having a grain size of 200 nm to 600 nm and,
homogeneously distributed in the matrix, an intermetallic compound of Mg₁₂Nd formed
of Mg and Nd and having a particle size of 250 nm to 400 nm.
[0022] Mg₉₆Nd₃Zn₁ was composed of an hcp-Mg matrix having a grain size of 200 nm to 300
nm and, homogeneously distributed in the matrix, non-equilibrium fcc phase intermetallic
compounds formed of Mg and Nd and/or Zn with a particle size of 10 nm to 200 nm.
Table 1
No. |
Mg |
Nd |
Zn |
Phase |
σB (MPa) |
Ef (%) |
E (MPa) |
σB/ρ |
1 |
97 |
3 |
- |
Mg+unknown +Mg₁₂Nd |
562 |
0.44 |
38 |
285 |
2 |
96 |
3 |
1 |
Mg+non-equilibrium fcc |
617 |
3.7 |
37 |
307 |
3 |
95.5 |
2.5 |
2 |
Mg+non-equilibrium fcc |
611 |
4.7 |
39 |
306 |
4 |
95 |
3 |
2 |
Mg+non-equilibrium fcc |
633 |
1.0 |
39 |
310 |
Comparative Test Sample |
1 |
Mg 90 |
Cu 5 |
La 5 |
Mg+Mg₂Cu +Mg₉La |
872 |
0.1 |
47 |
382 |
2 |
Mg 80 |
Cu 10 |
Y 10 |
Mg+Mg₂Cu +Mg₂₄Y₅ |
901 |
0.05 |
52 |
360 |
[0023] As is evident from Table 1, every test sample of the present invention exhibited
superior mechanical properties, i.e., a tensile strength of not less than 500 MPa,
a plastic elongation of not less than 0.4%, a Young's modulus of at least 37 GPa and
a specific strength of not less than 280 MPa. Particularly, since the magnesium-based
alloys of the present invention are superior in plastic elongation over the comparative
test samples, they can be successfully subjected to various working operations and
exhibit a sufficient durability to permit a high degree of working (plastic working).
When the Mg content exceeded 95 atomic % in the Mg-Nd-Zn alloys, the plastic elongation
surprisingly increased, although any significant change was hardly detected in the
tensile strength, Young's modulus and specific strength.
[0024] Since the magnesium-based alloys of the present invention have high levels of strength
and heat-resistance, they are very useful as high strength materials and high heat-resistant
materials. The magnesium-based alloys are also useful as high specific-strength materials
because of their high specific strength. Still further, since the alloys exhibit superior
elongation at room temperature and Young's module at room temperature, they can be
successfully subjected to various working operations and exhibit a sufficient durability
to permit a high degree of working (plastic working).
1. A high strength magnesium-based alloy material having a microcrystalline composite
structure, the alloy material consisting of a composition represented by the general
formula (I): MgaNdbZnc, wherein a, b and c are, in atomic %, 80 ≦ a ≦ 99, 1 ≦ b ≦ 12 and 0 ≦ c ≦ 12.
2. A high strength magnesium-based alloy material having a microcrystalline composite
structure, the alloy material consisting of a composition represented by the general
formula (II): Mga'Ndb'Znc', wherein a', b' and c' are, in atomic %, 95 < a' ≦ 99, 1 ≦ b' ≦ 3 and 0 ≦ c' ≦ 3.
3. A high strength magnesium-based alloy material as claimed in Claim 1 or 2, wherein
the magnesium-based alloy material has a microcrystalline composite structure consisting
of an Mg matrix having a hexagonal close-packed structure, and, homogeneously and
finely distributed in the matrix, intermetallic compounds consisting of a non-equilibrium
phase having a face-centered cubic structure and/or an Mg₁₂Nd phase.
4. A high strength magnesium-based alloy material as claimed in Claim 3, wherein the
intermetallic compounds contain at least an intermetallic compound consisting of a
non-equilibrium phase having a face-centered cubic structure.
5. A method for producing a high strength magnesium-based alloy material, comprising:
rapidly solidifying a molten alloy so as to form a fine-grained matrix phase, the
molten alloy consisting of a composition represented by the general formula (I): MgaNdbZnc, wherein a, b and c are, in atomic %, 80 ≦ a ≦ 99, 1 ≦ b ≦ 12 and 0 ≦ c ≦ 12; and
subjecting the resultant rapidly solidified alloy to plastic working at a prescribed
heating temperature for work hardening, thereby forming a microcrystalline composite
structure having a dispersion of fine intermetallic compounds in the matrix.
6. A method for producing a high strength magnesium-based alloy material, comprising:
rapidly solidifying a molten alloy so as to form a fine-grained matrix phase, the
molten alloy consisting of a composition represented by the general formula (II):
Mga'Ndb'Znc', wherein a', b' and c' are, in atomic %, 95 < a' ≦ 99, 1 ≦ b' ≦ 3 and 0 ≦ c' ≦ 3;
and
subjecting the resultant rapidly solidified alloy to plastic working at a prescribed
heating temperature for work hardening, thereby forming a microcrystalline composite
structure having a dispersion of fine intermetallic compounds in the matrix.
7. A method as claimed in Claim 5 or 6, wherein the prescribed heating temperature ranges
from 50 to 500°C.