Field of the Invention
The present invention relates to a high strength and high
toughness metal and a method of producing the same, more particularly, a high strength
and high toughness metal, in which the high strength and high toughness property
can be achieved by containing a specific rare-earth element at a specific rate,
and a method of producing the same.
Background of the Invention
A magnesium alloy has come quickly into wide use as materials
of a housing of a mobile-phone and a laptop computer or an automotive member because
of its recyclability.
For these usages, the magnesium alloy is required to have
a high strength and high toughness property. Thus, a producing method of a high
strength and high toughness metal has been studied in many ways from a material
aspect and a manufacture aspect.
In a manufacture aspect, as a result of promoting nanocrystallizing,
a rapid-solidified powder metallurgy method (a RS-P/M method) has been developed
to obtain a magnesium alloy having a strength of about 400MPa as much as about two
times that of a casting material.
As a magnesium alloy, a Mg-Al based, a Mg-Al-Zn based,
a Mg-Th-Zn based, a Mg-Th-Zn-Zr based, a Mg-Zn-Zr based, a Mg-Zn-Zr-RE (rare-earth
element) based alloys are widely known. When a magnesium alloy having the aforesaid
composition is produced by a casting method, a sufficient strength cannot be obtained.
On the other hand, when a magnesium alloy having the aforesaid composition is produced
by the RS-P/M method, a strength higher than that by the casting method can be obtained;
however, the strength is still insufficient. Alternatively, the strength is sufficient
while a toughness (a ductility) is insufficient. So, it is troublesome to use a
magnesium alloy produced by the RS-P/M method for applications requiring a high
strength and high toughness.
For a high strength and high toughness magnesium alloy,
Mg-Zn-RE (rare-earth element) based alloys have been proposed (for instance, referring
to Patent Literatures 1, 2 and 3) .
- Patent Literature 1: Patent Number 3238516 (Fig.1),
- Patent Literature 2: Patent Number 2807374,
- Patent Literature 3:
Japanese patent Application Laid Open 2002-256370
(Claims and Embodiments),
Disclosure of Invention
Problems to be resolved by the Invention
However, in a conventionally Mg-Zn-RE based material, a
high strength magnesium alloy is obtained by, for instance, heat-treating an amorphous
alloy material for forming a fine-grained structure. In this case, depending on
a preconceived idea in which adding a substantial amount of zinc and rare-earth
element is a requirement for obtaining the amorphous alloy material, a magnesium
alloy containing relatively a large amount of zinc and rare-earth element has been
used.
The Patent Literatures 1 and 2 disclose that a high strength
and high toughness alloy can be obtained. However, practically, there are no alloys
having enough strength and toughness for putting in practical use. And, currently,
applications of a magnesium alloy have expanded, so an alloy having a conventionally
strength and toughness is insufficient for such applications. Therefore, a higher
strength and higher toughness magnesium alloy has been required.
The present invention has been conceived in view of the
above problems. An object of the present invention is to provide a high strength
and high toughness metal having a strength and a toughness both being on a sufficient
level for the alloy to be practically used for expanded applications of a magnesium
alloy and a method of producing the same.
In order to solve the above-mentioned problems, a high
strength and high toughness metal according to the present invention comprises a
magnesium alloy having a crystal structure having an hcp-Mg phase and a long-period
stacking ordered structure phase,
wherein at least a part of said long-period stacking ordered structure phase exists
in a lamellar form with a 2H structure Mg phase.
In the high strength and high toughness metal according
to the present invention, a plastically worked product produced by subjecting a
magnesium alloy to a plastic working has a crystal structure having an hcp-Mg phase
and a long-period stacking ordered structure phase,
wherein at least a part of said long-period stacking ordered structure phase exists
in a lamellar form with a 2H structure Mg phase.
And, in the high strength and high toughness metal according
to the present invention, at least a part of said lamellar structure existing in
a lamellar form is preferably flexed or bend. A lamellar structure is a structure
in which a long-period stacking ordered structure phase and a 2H structure Mg phase
are alternatively stacked.
A high strength and high toughness metal according to the
present invention comprises a magnesium alloy having a crystal structure having
an hcp-Mg phase and a long-period stacking ordered structure phase,
wherein at least a part of said long-period stacking ordered structure phase is
flexed or bend.
In the specification, a magnesium alloy shows an alloy
which consists primarily of magnesium.
In the high strength and high toughness metal according
to the present invention, a plastically worked product produce by subjecting a magnesium
alloy to a plastic working has a crystal structure having an hcp-Mg phase and a
long-period stacking ordered structure phase,
wherein at least a part of said long-period stacking ordered structure phase is
flexed or bend.
And, in the high strength and high toughness metal according
to the present invention, said magnesium alloy before subjecting to a plastic working
may have a crystal structure having a long-period stacking ordered structure phase
in which flexure or bend is not formed.
And, in the high strength and high toughness metal according
to the present invention, a part of a region where said long-period stacking ordered
structure phase is flexed or bend is preferable to contain random grain boundaries.
And, in the high strength and high toughness metal according
to the present invention, said long-period stacking ordered structure phase is preferable
to have a dislocation density one-digit smaller than said hcp-Mg phase.
In the high strength and high toughness metal according
to the present invention, said magnesium alloy may contain Zn in an amount of "a"
atomic% and Y in an amount of "b" atomic%,
wherein "a" and "b" satisfy the following expressions (1) to (3):
and
And, in said magnesium alloy, part other than Zn and Y
preferably consists of Mg.
In the high strength and high toughness metal according
to the present invention, said magnesium alloy may contain Zn in an amount of "a"
atomic% and at least one element selected from the group consisting of Dy, Ho and
Er in a total amount of "b" atomic%, wherein "a" and "b" satisfy the following expressions
(1) to (3):
and
And, in said magnesium alloy, part other than Zn, Dy, Ho
and Er preferably consists of Mg.
In the high strength and high toughness metal according
to the present invention, said magnesium alloy may contain Zn in an amount of "a"
atomic% and at least one element selected from the group consisting of Dy, Ho and
Er in a total amount of "b" atomic%, wherein "a" and "b" satisfy the following expressions
(1) to (3):
and
And, in said magnesium alloy, part other than Zn, Dy, Ho
and Er preferably consists of Mg.
In the high strength and high toughness metal according
to the present invention, said magnesium alloy may contain at least one element
selected from the group consisting of Y, Gd, Tb, Tm and Lu in a total amount of
"y" atomic%, wherein "y" satisfies the following expressions (4) to (5):
and
In the high strength and high toughness metal according
to the present invention, said magnesium alloy may contain at least one element
selected from the group consisting of Yb, Sm and Nd in a total amount of "c" atomic%,
wherein "c" satisfies the following expressions (4) to (5):
and
In the high strength and high toughness metal according
to the present invention, said magnesium alloy may contain at least one element
selected from the group consisting of La, Ce, Pr, Eu and Mm in a total amount of
"c" atomic%, wherein "c" satisfies the following expressions (4) to (5):
and
In the high strength and high toughness metal according
to the present invention, said magnesium alloy may contain at least one element
selected from the group consisting of Yb, Sm and Nd in a total amount of "c" atomic%
and at least one element selected from the group consisting of La, Ce, Pr, Eu and
Mm in a total amount of "d" atomic%, wherein "c" and "d" satisfy the following expressions
(4) to (6):
and
In the high strength and high toughness metal according
to the present invention, said magnesium alloy may contain Zn in an amount of "a"
atomic% and Y in an amount of "b" atomic%, wherein "a" and "b" satisfy the following
expressions (4) to (6):
and
And, in said magnesium alloy, part other than Zn and Y
preferably consists of Mg.
In the high strength and high toughness metal according
to the present invention, said magnesium alloy may contain Zn in an amount of "a"
atomic% and at least one element selected from the group consisting of Dy, Ho and
Er in a total amount of "b" atomic%, wherein "a" and "b" satisfy the following expressions
(1) to (3):
and
And, in said magnesium alloy, part other than Zn, Dy, Ho
and Er preferably consists of Mg.
In the high strength and high toughness metal according
to the present invention, said magnesium alloy may contain Zn in an amount of "a"
atomic% and at least one element selected from the group consisting of Dy, Ho and
Er in a total amount of "b" atomic%, wherein "a" and "b" satisfy the following expressions
(1) to (3):
and
And, in said magnesium alloy, part other than Zn, Dy, Ho
and Er preferably consists of Mg.
In the high strength and high toughness metal according
to the present invention, said magnesium alloy may contain at least one element
selected from the group consisting of Y, Gd, Tb, Tm and Lu in a total amount of
"y" atomic%, wherein "y" satisfies the following expressions (4) to (5):
and
In the high strength and high toughness metal according
to the present invention, said magnesium alloy may contain at least one element
selected from the group consisting of Yb, Sm and Nd in a total amount of "c" atomic%,
wherein "c" satisfies the following expressions (4) to (5):
and
In the high strength and high toughness metal according
to the present invention, said magnesium alloy may contain at least one element
selected from the group consisting of La, Ce, Pr, Eu and Mm in a total amount of
"c" atomic%, wherein "c" satisfies the following expressions (4) to (5):
and
In the high strength and high toughness metal according
to the present invention, said magnesium alloy may contain at least one element
selected from the group consisting of Yb, Sm and Nd in a total amount of "c" atomic%
and at least one element selected from the group consisting of La, Ce, Pr, Eu and
Mm in a total amount of "d" atomic%, wherein "c" and "d" satisfy the following expressions
(4) to (6):
and
In the high strength and high toughness metal according
to the present invention, said magnesium alloy may contain Zn in an amount of "a"
atomic% and at least one element selected from the group consisting of Gd, Tb, Tm
and Lu in a total amount of "b" atomic%, wherein "a" and "b" satisfy the following
expressions (1) to (3):
and
And, in said magnesium alloy, part other than Zn and Gd
preferably consists of Mg.
In the high strength and high toughness metal according
to the present invention, said magnesium alloy may contain Zn in an amount of "a"
atomic% and at least one element selected from the group consisting of Gd, Tb, Tm
and Lu in a total amount of "b" atomic%, wherein "a" and "b" satisfy the following
expressions (1) to (3):
and
And, in said magnesium alloy, part other than Zn and Gd
preferably consists of Mg.
In the high strength and high toughness metal according
to the present invention, said magnesium alloy may contain at least one element
selected from the group consisting of Yb, Sm and Nd in a total amount of "c" atomic%,
wherein "c" satisfies the following expressions (4) to (5):
and
In the high strength and high toughness metal according
to the present invention, said magnesium alloy may contain at least one element
selected from the group consisting of La, Ce, Pr, Eu and Mm in a total amount of
"c" atomic%, wherein "c" satisfies the following expressions (4) to (5):
and
In the high strength and high toughness metal according
to the present invention, said magnesium alloy may contain at least one element
selected from the group consisting of Yb, Sm and Nd in a total amount of "c" atomic%
and at least one element selected from the group consisting of La, Ce, Pr, Eu and
Mm in a total amount of "d" atomic%, wherein "c" and "d" satisfy the following expressions
(4) to (6):
and
In the high strength and high toughness metal according
to the present invention, said magnesium alloy contains Zn in an amount of "a" atomic%
and at least one element selected from the group consisting of Gd, Tb, Tm and Lu
in a total amount of "b" atomic%, wherein "a" and "b" satisfy the following expressions
(1) to (3):
and
And, in said magnesium alloy, part other than Zn, Gd, Tb,
Tm and Lu preferably consists of Mg.
In the high strength and high toughness metal according
to the present invention, said magnesium alloy may contain Zn in an amount of "a"
atomic% and at least one element selected from the group consisting of Gd, Tb, Tm
and Lu in a total amount of "b" atomic%, wherein "a" and "b" satisfy the following
expressions (1) to (3):
AND
And, in said magnesium alloy, part other than Zn, Gd, Tb,
Tm and Lu preferably consists of Mg.
In the high strength and high toughness metal according
to the present invention, said magnesium alloy may contain at least one element
selected from the group consisting of Yb, Sm and Nd in a total amount of "c" atomic%,
wherein "c" satisfy the following expressions (4) to (5):
AND
In the high strength and high toughness metal according
to the present invention, said magnesium alloy may contain at least one element
selected from the group consisting of La, Ce, Pr, Eu and Mm in a total amount of
"c" atomic%, wherein "c" satisfy the following expressions (4) to (5):
and
In the high strength and high toughness metal according
to the present invention, said magnesium alloy may contain at least one element
selected from the group consisting of Yb, Sm and Nd in a total amount of "c" atomic%
and at least one element selected from the group consisting of La, Ce, Pr, Eu and
Mm in a total amount of "d" atomic%, wherein "c" and "d" satisfy the following expressions
(4) to (6):
and
In the high strength and high toughness metal according
to the present invention, said magnesium alloy may contain at least one element
selected from the group consisting of Dy, Ho and Er in a total amount of larger
than 0 atomic% to 1.5 atomic% or less.
In the high strength and high toughness metal according
to the present invention, said magnesium alloy may contain Y in an amount of larger
than 0 atomic% to 1.0 atomic% or less.
And, in the high strength and high toughness metal according
to the present invention, said magnesium alloy preferably contains at least one
element selected from the group consisting of Gd, Tb, Tm and Lu in a total amount
of less than 3 atomic%.
In the high strength and high toughness metal according
to the present invention, said magnesium alloy may be produced by the following
manner: a mineral ore containing rare-earth elements is refined to prepare a rare-earth
alloy containing plural rare-earth elements; and the rare-earth alloy is used as
a part of starting material for casting to produce said magnesium alloy which contains
the rare-earth elements in a total amount of 6.0 atomic% or less.
In the high strength and high toughness metal according
to the present invention, said magnesium alloy may contain at least one element
selected from the group consisting of Al, Th, Ca, Si, Mn, Zr, Ti, Hf, Nb, Ag, Sr,
Sc, B and C in a total amount of larger than 0 atomic% to 2.5 atomic% or less.
In the high strength and high toughness metal according
to the present invention, said magnesium alloy may contain at least one precipitate
selected from the group consisting of precipitate comprising compound of Mg and
rare-earth element, precipitate comprising compound of Mg and Zn, precipitate comprising
compound of Zn and rare-earth element and precipitate comprising compound of Mg,
Zn and rare-earth element.
In the high strength and high toughness metal according
to the present invention, said magnesium alloy preferably has a grain size of 100nm
to 500 µm.
A high strength and high toughness metal according to the
present invention has a composition of general formula of Mg(100-x-y)YxZny(1<x<5,0.3<y<6;
x and y represent atomic%) and having a crystal structure of an average grain size
of 1 µm or smaller. And, said Mg(100-x-y)YxZnyis
produced in the following manner:amineralore containing rare-earth elements is refined
to prepare a rare-earth alloy containing plural rare-earth elements; the rare-earth
alloy is used as a part of starting material and made into liquid form; the rare-earth
alloy in liquid form is rapidly solidified into powder, thin band or thin wire;
and the powder, thin band or thin wire is solidified so as to be applied with shear.
In the high strength and high toughness metal according
to the present invention, said rare-earth alloy preferably contains at least one
element selected from the group consisting of Y, Gd, Tb, Dy, Ho, Er, Tm and Lu in
a total amount of 50 atomic% or larger and at least one rare-earth element other
than Y, Gd, Tb, Dy, Ho, Er, Tm and Lu in a total amount of less than 50 atomic%.
A method of producing a high strength and high toughness
metal according to the present invention comprises a step for preparing a magnesium
alloy having a crystal structure having an hcp-Mg phase and a long-period stacking
ordered structure phase, wherein at least a part of said long-period stacking ordered
structure phase exists in a lamellar form with a 2.H structure Mg phase; and a step
for subjecting said magnesium alloy to a plastic working to produce a plastically
worked product which keeps a lamellar structure existing in a lamellar form.
A method of producing a high strength and high toughness
metal according to the present invention comprises a step for preparing a magnesium
alloy having a crystal structure having an hcp-Mg phase and a long-period stacking
ordered structure phase ; and a step for subjecting said magnesium alloy to a plastic
working to produce a plastically worked product in which at least a part of said
long-period stacking ordered structure phase is flexed or bend.
In the method of producing a high strength and high toughness
metal according to the present invention, said step for preparing a magnesium alloy
may be a step for producing a magnesium alloy casting product which contains Zn
in an amount of "a" atomic% and Y in an amount of "b" atomic%, wherein "a" and "b"
satisfy the following expressions (1) to (3):
and
And, in said magnesium alloy, part other than Zn and Y
preferably consists of Mg.
In the method of producing a high strength and high toughness
metal according to the present invention, said step for preparing a magnesium alloy
may be a step for producing a magnesium alloy casting product which contains Zn
in an amount of "a" atomic% and at least one element selected from the group consisting
of Dy, Ho and Er in a total amount of "b" atomic%, wherein "a" and "b" satisfy the
following expressions (1) to (3):
and
And, in said magnesium alloy, part other than Zn, Dy, Ho
and Er preferably consists of Mg.
And, each element of Y, Dy, Ho and Er is a rare-earth element
which forms a crystal structure of long-period stacking ordered structure phase
in the magnesium alloy casting product.
In the method of producing a high strength and high toughness
metal according to the present invention, said step for preparing a magnesium alloy
may be a step for producing a magnesium alloy casting product which contains Zn
in an amount of "a" atomic% and at least one element selected from the group consisting
of Dy, Ho and Er in a total amount of "b" atomic%, wherein "a" and "b" satisfy the
following expressions (1) to (3):
and
And, in said magnesium alloy, part other than Zn, Dy, Ho
and Er preferably consists of Mg.
In the method of producing a high strength and high toughness
metal according to the present invention, said magnesium alloy may contain at least
one element selected from the group consisting of Y, Gd, Tb, Tm and Lu in a total
amount of "y" atomic%, wherein "y" satisfies the following expressions (4) to (5):
and
In the method of producing a high strength and high toughness
metal according to the present invention, said magnesium alloy may contain at least
one element selected from the group consisting of Yb, Sm and Nd a total amount of
"c" atomic%, wherein "c" satisfies the following expressions (4) to (5):
and
In the method of producing a high strength and high toughness
metal according to the present invention, said magnesium alloy may contain at least
one element selected from the group consisting of La, Ce, Pr, Eu and Mm in a total
amount of "c" atomic%, wherein "c" satisfies the following expressions (4) to (5):
and
In the method of producing a high strength and high toughness
metal according to the present invention, said magnesium alloy may contain at least
one element selected from the group consisting of Yb, Sm and Nd in a total amount
of "c" atomic% and at least one element selected from the group consisting of La,
Ce, Pr, Eu and Mm in a total amount of "d" atomic%, wherein "c" and "d" satisfy
the following expressions (4) to (6):
and
A method of producing a high strength and high toughness
metal according to the present invention comprises a step for preparing a magnesium
alloy having a crystal structure having an hcp-Mg phase and a long-period stacking
ordered structure phase, wherein at least a part of said long-period stacking ordered
structure phase exists in a lamellar form with a 2H structure Mg phase; a step for
cutting said magnesium alloy to form a chip-shaped cutting product; and a step for
subjecting said chip-shaped cutting product to a plastic working to solidify and
thereby to produce a plastically worked product keeping said lamellar structure
existing in a lamellar form.
A method of producing a high strength and high toughness
metal according to the present invention comprises a step for preparing a magnesium
alloy having a crystal structure having an hcp-Mg phase and a long-period stacking
ordered structure phase; a step for cutting said magnesium alloy to produce a chip-shaped
cutting product; and a step for subjecting said chip-shaped cutting product to a
plastic working to solidify and thereby to produce a plastically worked product
in which at least a part of said long-period stacking ordered structure phase is
flexed or bend.
In the method of producing a high strength and high toughness
metal according to the present invention, said step for preparing a magnesium alloy
may be a step for producing a magnesium alloy casting product which contains Zn
in an amount of "a" atomic% and Y in an amount of "b" atomic%, wherein "a" and "b"
satisfy the following expressions (1) to (3):
and
And, in said magnesium alloy, part other than Zn and Y
preferably consists of Mg.
In the method of producing a high strength and high toughness
metal according to the present invention, said step for preparing a magnesium alloy
may be a step for producing a magnesium alloy casting product which contains Zn
in an amount of "a" atomic% and at least one element selected from the group consisting
of Dy, Ho and Er in a total amount of "b" atomic%, wherein "a" and "b" satisfy the
following expressions (1) to (3):
and
And, in said magnesium alloy, part other than Zn, Dy, Ho
and Er preferably consists of Mg.
In the method of producing a high strength and high toughness
metal according to the present invention, said step for preparing a magnesium alloy
may be a step for producing a magnesium alloy casting product which contains Zn
in an amount of "a" atomic% and at least one element selected from the group consisting
of Dy, Ho and Er in a total amount of "b" atomic%, wherein "a" and "b" satisfy the
following expressions (1) to (3):
and
And, in said magnesium alloy, part other than Zn, Dy, Ho
and Er preferably consists of Mg.
In the method of producing a high strength and high toughness
metal according to the present invention, said magnesium alloy may contain at least
one element selected from the group consisting of Y, Gd, Tb, Tm and Lu in a total
amount of "y" atomic%, wherein "y" satisfies the following expressions (4) to (5):
and
In the method of producing a high strength and high toughness
metal according to the present invention, said magnesium alloy may contain at least
one element selected from the group consisting of Yb, Sm and Nd in a total amount
of "c" atomic%, wherein "c" satisfies the following expressions (4) to (5):
and
In the method of producing a high strength and high toughness
metal according to the present invention, said magnesium alloy may contain at least
one element selected from the group consisting of La, Ce, Pr, Eu and Mm in a total
amount of "c" atomic%, wherein "c" satisfies the following expressions (4) to (5)
:
and
In the method of producing a high strength and high toughness
metal according to the present invention, said magnesium alloy may contain at least
one element selected from the group consisting of Yb, Sm and Nd in a total amount
of "c" atomic% and at least one element selected from the group consisting of La,
Ce, Pr, Eu and Mm in a total amount of "d" atomic%, wherein "c" and "d" satisfy
the following expressions (4) to (6):
and
In the method of producing a high strength and high toughness
metal according to the present invention, said step for preparing a magnesium alloy
may be a step for producing a magnesium alloy casting product which contains Zn
in an amount of "a" atomic% and at least one element selected from the group consisting
of Gd, Tb, Tm and Lu in a total amount of "b" atomic%, wherein "a" and "b" satisfy
the following expressions (1) to (3):
and
And, the method may further comprise a step for subj ecting
said magnesium alloy to a heat treatment between said step for producing a magnesium
alloy casting product and said step for producing a plastically worked product.
And, in said magnesium alloy, part other than Zn, Gd, Tb,
Tm and Lu preferably consists of Mg.
In the method of producing a high strength and high toughness
metal according to the present invention, said step for preparing a magnesium alloy
may be a step for producing a magnesium alloy casting product which contains Zn
in an amount of "a" atomic% and at least one element selected from the group consisting
of Gd, Tb, Tm and Lu an a total amount of "b" atomic%, wherein "a" and "b" satisfy
the following expressions (1) to (3):
and
And, the method may further comprise a step for subjecting
said magnesium alloy to a heat treatment between said step for producing a magnesium
alloy casting product and said step for producing a plastically worked product.
And, in said magnesium alloy, part other than Zn, Gd, Tb,
Tm and Lu preferably consists of Mg.
In the method of producing a high strength and high toughness
metal according to the present invention, said magnesium alloy may contain at least
one element selected from the group consisting of Yb, Sm and Nd in a total amount
of "c" atomic%, wherein "c" satisfies the following expressions (4) to (5):
and
In the method of producing a high strength and high toughness
metal according to the present invention, said magnesium alloy may contain at least
one element selected from the group consisting of La, Ce, Pr, Eu and Mm in a total
amount of "c" atomic%, wherein "c" satisfies the following expressions (4) to (5):
and
In the method of producing a high strength and high toughness
metal according to the present invention, said magnesium alloy may contain at least
one element selected from the group consisting of Yb, Sm and Nd in a total amount
of "c" atomic% and at least one element selected from the group consisting of La,
Ce, Pr, Eu and Mm in a total amount of "d" atomic%, wherein "c" and "d" satisfy
the following expressions (4) to (6) :
and
In the method of producing a high strength and high toughness
metal according to the present invention, said step for preparing a magnesium alloy
may be a step for producing a magnesium alloy casting product which contains Zn
in an amount of "a" atomic% and at least one element selected from the group consisting
of Gd, Tb, Tm and Lu in a total amount of "b" atomic%, wherein "a" and "b" satisfy
the following expressions (1) to (3) :
and
And, the method may further comprise a step for subjecting
said magnesium alloy to a heat treatment between said step for producing a magnesium
alloy casting product and said step for producing a chip-shaped cutting product,
or, between said step for producing a chip-shaped cutting product and said step
for producing a plastically worked product.
And, in said magnesium alloy, part other than Zn, Gd, Tb,
Tm and Lu preferably consists of Mg.
In the method of producing a high strength and high toughness
metal according to the present invention, said step for preparing a magnesium alloy
may be a step for producing a magnesium alloy casting product which contains Zn
in an amount of "a" atomic% and at least one element selected from the group consisting
of Gd, Tb, Tm and Lu in a total amount of "b" atomic%, wherein "a" and "b" satisfy
the following expressions (1) to (3):
and
And, the method may further comprise a step for subj ecting
said magnesium alloy to a heat treatment between said step for producing a magnesium
alloy casting product and said step for producing a chip-shaped cutting product,
or, between said step for producing a chip-shaped cutting product and said step
for producing a plastically worked product.
And, in said magnesium alloy, part other than Zn, Gd, Tb,
Tm and Lu preferably consists of Mg.
In the method of producing a high strength and high toughness
metal according to the present invention, said magnesium alloy may contain at least
one element selected from the group consisting of Yb, Sm and Nd in a total amount
of "c" atomic%, wherein "c" satisfies the following expressions (4) to (5) :
and
In the method of producing a high strength and high toughness
metal according to the present invention, said magnesium alloy may contain at least
one element selected from the group consisting of La, Ce, Pr, Eu and Mm in a total
amount of "c" atomic%, wherein "c" satisfies the following expressions (4) to (5):
and
In the method of producing a high strength and high toughness
metal according to the present invention, said magnesium alloy may contain at least
one element selected from the group consisting of Yb, Sm and Nd in a total amount
of "c" atomic% and at least one element selected from the group consisting of La,
Ce, Pr, Eu and Mm in a total amount of "d" atomic%, wherein "c" and "d" satisfy
the following expressions (4) to (6) :
and
In the method of producing a high strength and high toughness
metal according to the present invention, said magnesium alloy preferably contain
at least one element selected from the group consisting of Gd, Tb, Tm and Lu in
a total amount of less than 3 atomic%.
In the method of producing a high strength and high toughness
metal according to the present invention, said step for preparing a magnesium alloy
may be a step for preparing a magnesium alloy is a step for producing a magnesium
alloy casting product which contains at least one element selected from the group
consisting of Yb, Sm and Nd in a total amount of "c" atomic%, wherein"c" satisfies
the following expressions (4) to (5):
and
In the method of producing a high strength and high toughness
metal according to the present invention, said step for preparing a magnesium alloy
may be a step for preparing a magnesium alloy is a step for producing a magnesium
alloy casting product which contains at least one element selected from the group
consisting of La, Ce, Pr, Eu and Mm in a total amount of "c" atomic%, wherein "c"
satisfies the following expressions (4) to (5):
and
In the method of producing a high strength and high toughness
metal according to the present invention, said step for preparing a magnesium alloy
may be a step for preparing a magnesium alloy is a step for producing a magnesium
alloy casting product which contains at least one element selected from the group
consisting of La, Ce, Pr, Eu and Mm in a total amount of "c" atomic%, wherein "c"
satisfies the following expressions (4) to (5):
and
In the method of producing a high strength and high toughness
metal according to the present invention, said step for preparing a magnesium alloy
may be a step for producing a magnesium alloy casting product which contains at
least one element selected from the group consisting of Yb, Sm and Nd in a total
amount of "c" atomic% and at least one element selected from the group consisting
of La, Ce, Pr, Eu and Mm in a total amount of "d" atomic%, wherein "c" and "d" satisfy
the following expressions (4) to (6):
and
In the method of producing a high strength and high toughness
metal according to the present invention, said step for preparing a magnesium alloy
may be a step for preparing a magnesium alloy is a step for producing a magnesium
alloy casting product which contains at least one element selected from the group
consisting of Yb, Tb, Sm and Nd in a total amount of "c" atomic% and at least one
element selected from the group consisting of La, Ce, Pr, Eu and Mm in a total amount
of "d" atomic%, wherein "c" and "d" satisfy the following expressions (4) to (6)
:
and
In the method of producing a high strength and high toughness
metal according to the present invention, said step for preparing a magnesium alloy
may be a step for preparing a magnesium alloy is a step for producing a magnesium
alloy casting product which contains at least one element selected from the group
consisting of Al, Th, Ca, Si, Mn, Zr, Ti, Hf, Nb, Ag, Sr, Sc, B and C in a total
amount of larger than 0 atomic% to 2.5 atomic% or less.
In the method of producing a high strength and high toughness
metal according to the present invention, said step for subjecting a magnesium alloy
to a heat treatment is preferable to be a step for subjecting said magnesium alloy
to a heat treatment at temperatures of 300°C to 550°C for 10 minutes or
more to shorter than 24 hours.
In the method of producing a high strength and high toughness
metal according to the present invention, said step for producing a magnesium alloy
casting product comprises:
- a step for refining a mineral ore containing rare-earth elements to prepare
a rare-earth alloy containing plural rare-earth elements;
the rare-earth alloy is used as a part of starting material for casting to produce
said magnesium alloy which contains the rare-earth elements in a total amount of
6.0 atomic% or less.
In the method of producing a high strength and high toughness
metal according to the present invention, said magnesium alloy before subjecting
to said plastic working preferably have a grain size of 100nm to 500 µm.
In the method of producing a high strength and high toughness
metal according to the present invention, said magnesium alloy after subjecting
to said plastic working has an hcp-Mg phase having a dislocation density preferably
one-digit larger than a long-period stacking ordered structure phase.
In the method of producing a high strength and high toughness metal according to
the present invention, said magnesium alloy is plastically worked at 250°C
or higher. It is because a plastic working is difficult that said magnesium alloy
is plastically worked at temperature less than 250°C.
In the method of producing a high strength and high toughness
metal according to the present invention, said plastic working is carried out by
at least one process in rolling, extrusion, ECAE, drawing, forging, cyclic working
of these workings and FSW.
Mm (misch metal) is a mixture or an alloy of a number of
rare-earth elements consisting of Ce and La mainly, and is a residue generated by
refining and removing useful rare-earth element, such as Sm and Nd, from mineral
ore. Its composition depends on a composition of the mineral ore before the refining.
In the high strength and high toughness metal according
to the present invention, said magnesium alloy may contain at least one element
selected from the group consisting of Al, Th, Ca, Si, Mn, Zr, Ti, Hf, Nb, Ag, Sr,
Sc, B and C in a total amount of larger than 0 atomic% to 2.5 atomic% or less. This
can improve various properties other than strength and toughness which are being
kept high.
In the high strength and high toughness metal according
to the present invention, said crystal grain having said long-period stacking ordered
structure phase preferably has a volume fraction of 5% or more, more preferably
10% or more.
In the high strength and high toughness metal according
to the present invention, said crystal structure of long-period stacking ordered
structure phase preferably has a grain size of 100nm to 500µm.
In the high strength and high toughness metal according
to the present invention, said plastically worked product may contain at least one
kind of precipitate selected from the group consisting of precipitate comprising
compound of Mg and rare-earth element, precipitate comprising compound of Mg and
Zn, precipitate comprising compound of Zn and rare-earth element and precipitate
comprising compound of Mg, Zn and rare-earth element. And, the precipitate preferably
has a total volume fraction of larger than 0% to 40% or less. And, said plastically
worked product has an hcp-Mg phase.
In the high strength and high toughness metal according
to the present invention, said plastic working is preferably carried out by at least
one process in rolling, extrusion, ECAE, drawing and forging.
And, each element of Yb, Sm and Gd is a rare-earth element
which does not form a crystal structure of long-period stacking ordered structure
phase in the magnesium alloy casting product when the element forms a ternary alloy
with Mg and Zr. And, the element has a solid solubility limit in magnesium.
And, each element of La, Ce, Pr, Eu and Mn is a rare-earth
element which does not form a crystal structure of long-period stacking ordered
structure phase in the magnesium alloy casting product when the element forms a
ternary alloy with Mg and Zr. And, the element has little solid solubility limit
in magnesium.
According to the method of producing a high strength and
high toughness metal according to the present invention, by subjecting to a plastic
working, the magnesium alloy casting product can have improved hardness and yield
strength compared with the magnesium alloy casting product before subjecting to
the plastic working.
And, the method of producing a high strength and high toughness
magnesium alloy according to the present invention preferably may further comprise
a step for subjecting the magnesium alloy casting product to a homogenizedheat treatment
between said step for producing a magnesium alloy casting product and said step
for producing a plastically worked product. In this case, the homogenized heat treatment
is preferably carried out under a condition of a temperature of 400°C to 550°C
and a treating period of 1 minute to 1500 minutes.
And, the method of producing a high strength and high toughness
metal according to the present invention may further comprise a step for subjecting
the plastically worked product to a heat treatment after said step for producing
a plastically worked product . In this case, the heat treatment is preferably carried
out under a condition of a temperature of 150°C to 450°C and a treating
period of 1 minute to 1500 minutes.
In the method of producing a high strength and high toughness
metal according to the present invention, said plastic working is preferably carried
out by at least one process in rolling, extrusion, ECAE, drawing and forging. In
this case, each process may be carried out solely or in a combination thereof.
In the high strength and high toughness metal according
to the present invention, said step for producing a plastically worked product by
a plastic working may be a step for producing a plastically worked product by extruding
the magnesium alloy casting product and solidifying. And, the extrusion may be carried
out under a condition of an extrusion temperature of 250°C to 500°C and
a reduction rate of a cross section of 5% or more.
In the high strength and high toughness metal according
to the present invention, said step for producing a plastically worked product by
said plastic working may be a step for producing a plastically worked product by
rolling the magnesium alloy casting product and solidifying. And, the rolling may
be carried out under a condition of a rolling temperature of 250°C to 500°C
and a rolling reduction of 5% or more.
In the high strength and high toughness metal according
to the present invention, said step for producing a plastically worked product by
said plastic working may be a step for producing a plastically worked product by
subjecting the magnesium alloy casting product to ECAE and solidifying. And, the
ESAE working may be carried out under a condition of a temperature of 250°C
to 500°C and a number of passes of the ECAE working may be set to 1 or more.
In the high strength and high toughness metal according
to the present invention, said step for producing a plastically worked product by
said plastic working may be a step for producing a plastically worked product by
drawing the magnesium alloy casting product and solidifying. And, the drawing may
be carried out under a condition of a temperature of 250°C to 500°C and
a reduction rate of a cross section of 5% or more.
In the high strength and high toughness metal according
to the present invention, said step for producing a plastically worked product by
said plastic working may be a step for producing a plastically worked product by
forging the magnesium alloy casting product and solidifying. And, the forging may
be carried out under a condition of a temperature of 250°C to 500°C and
a processing rate of 5% or more.
And, the method of producing a high strength and high toughness
metal according to the present invention may further comprise a step for subjecting
a plastically worked product to a heat treatment after said step for producing a
plastically worked product. This can improve the plastically worked product in hardness
and yield strength than that before the heat treatment.
In the method for producing a high strength and high toughness
metal according to the present invention, the heat treatment for a plastically worked
product may be carried out under a condition of a temperature of 150°C to 450°C
and a period of 1 minute to 1500 minutes.
In the method of producing a high strength and high toughness
metal according to the present invention, said magnesium alloy casting product may
contain at least one element selected from the group consisting of Al, Th, Ca, Si,
Mn, Zr, Ti, Hf, Nb, Ag, Sr, Sc, B and C in a total amount of larger than 0 atomic%
to 2.5 atomic% or less.
The method of producing a high strength and high toughness
metal according to the present invention comprises a mineral ore containing rare-earth
elements is refined to prepare a rare-earth alloy containing plural rare-earth elements;
the rare-earth alloy is used as a part of starting material and made into liquid
having a composition of general formula of Mg(100-x-y)YxZny(1<x<5,
0.3<y<6; x and y represent atomic%) ;
said liquid is rapidly solidified into powder, thin band or thin wire; and
said powder, thin band or thin wire is solidified so as to be applied with shear.
In the method of producing a high strength and high toughness
metal according to the present invention, said rare-earth alloy preferably contains
at least one element selected from the group consisting of Y, Gd, Tb, Dy, Ho, Er,
Tm and Lu in a total amount of 50 atomic% or more and at least one rare-earth element
other than Y, Gd, Tb, Dy, Ho, Er, Tm and Lu in a total amount of less than 50 atomic%.
In the high strength and high toughness metal according
to the present invention, said long-period stacking ordered structure phase may
have a density modulation. The density modulation shows a phenomenon in which a
concentration of solute element changes periodically every atomic layer.
As mentioned above, the present invention can provide a
high strength and high toughness metal having a strength and a toughness both being
on a sufficient level for an alloy to be practically used for expanded applications
of a magnesium alloy.
Brief Description of the Drawings
- Fig.1 is photographs showing crystal structures according to Example 1 and Comparative
examples 1 and 2.
- Fig.2 is a photograph showing a crystal structure according to Examples 2 to
4
- Fig.3 is a photograph showing a crystal structure according to Examples 5 to
7.
- Fig.4 is photographs showing crystal structures according to Examples 8 and
9.
- Fig.5 is a photograph showing a crystal structure according to Examples 10 to
12.
- Fig.6 is photographs showing crystal structures according to Comparative examples
3 to 9.
- Fig.7 is a photograph showing a crystal structure according to the reference
example.
- Fig. 8 is a view showing a composition range of a magnesium alloy according
first embodiment of the present invention.
- Fig. 9 is a view showing a composition range of a magnesium alloy according
seventh embodiment of the present invention.
- Fig.10 is a photograph showing a crystal structure according to Example 13.
- Fig.11 is a photograph showing a crystal structure of a casting material of
Example 29.
- Fig.12 is a photograph showing a crystal structure of a casting product which
is not subjected to a heat treatment.
- Fig.13 is a photograph showing a crystal structure of a casting product after
subjecting to a heat treatment at a temperature of 200°C.
- Fig. 14 is a photograph showing a crystal structure of a casting product after
subjecting to a heat treatment at a temperature of 300°C.
- Fig.15 is a photograph showing a crystal structure of a casting product after
subjecting to a heat treatment at a temperature of 500°C.
- Fig.16(A) is a photograph showing a crystal structure of a magnesium alloy of
Example 73 before subjecting to a heat treatment; and Fig.16(B) a photograph showing
a crystal structure of a magnesium alloy of Example 73 after subjecting to a heat
treatment.
- Fig.17(A) is a photograph showing a crystal structure of a magnesium alloy of
Example 66 before subjecting to a heat treatment; and Fig. 17(B) a photograph showing
a crystal structure of a magnesium alloy of Example 66 after subjecting to a heat
treatment.
- Fig. 18(A) is a photograph showing a crystal structure of a magnesium alloy
of Example 67 before subjecting to a heat treatment; and Fig.18(B) a photograph
showing a crystal structure of a magnesium alloy of Example 67 after subjecting
to a heat treatment.
- Fig.19(A) is a photograph showing a crystal structure of a magnesium alloy of
Example 68 before subjecting to a heat treatment; and Fig. 19(B) a photograph showing
a crystal structure of a magnesium alloy of Example 68 after subjecting to a heat
treatment.
- Fig.20 is a SEM photograph showing a crystal structure of a magnesium alloy
of Example 66.
- Fig.21 is a SEM photograph showing a crystal structure of a magnesium alloy
of Example 67.
- Fig.22 is a SEM photograph showing a crystal structure of a magnesium alloy
of Example 68.
- Fig.23 is a SEM photograph showing a crystal structure of a magnesium alloy
of Example 73.
- Fig.24 is a drawing showing a composition range of a magnesium alloy of Embodiment
13 according to the present invention.
- Fig.25 is a drawing showing a composition range of a magnesium alloy of Embodiment
14 according to the present invention.
- Fig. 26 is a drawing showing an X-ray diffraction pattern of Mg-Zn-Gd based
casting extruded product.
- Fig.27 is a photograph showing a crystal structure of extruded product of Mg96.5-Zn1-Gd2.5
casting product (Example 68) after subjecting to a heat treatment.
- Fig.28 is a photograph showing a crystal structure of extruded product of Mg96-Zn2-Gd2
casting product (Example 21) .
- Fig.29 is a drawing showing a system for producing rapid-solidified powder and
for producing an extruded billet by a gas atomizing method.
- Fig.30 is a drawing showing a process in which a billet is heated and pressed
for solidification-forming.
- Fig.31(A) is a photograph showing a crystal structure of a casting material
of MgZn2Y2Zr0.2 of Example 43; Fig. 31 (B) is a
photograph showing a crystal structure of a casting material of MgZn2Y2.
Detailed Description of Best Mode of the Invention
Hereinafter, preferred embodiments of the present invention
will be described.
The inventors, back to basics, have studied a strength
and a toughness of a binary magnesium alloy at the first step. Then, the study is
expanded to a multi-element magnesium alloy. As a result, it is found that a magnesium
alloy having a sufficient strength and toughness property is an Mg-Zn-RE (rare-earth
element) based magnesium alloy. In addition, it is also found that a nonconventional
high strength and high toughness property can be obtained under conditions in which
the rare-earth element is at least one element selected from the group consisting
of Y, Dy, Ho and Er, a content of Zn is small as 5.0 atomic% or less and a content
of the rare-earth element is small as 5.0 atomic% or less, unlike in conventional
technique.
A plastic working for a metal having a long period stacking
ordered structure phase allows flexing or bending at least a part of the long period
stacking ordered structure phase. As a result, a high strength, high ductile and
high toughness metal can be obtained.
Furthermore, it is found that subj ecting a casting alloy,
which forms a long period stacking ordered structure phase, to a plastic working
or to a heat treatment after a plastic working can provide a high strength, high
ductile and high toughness magnesium alloy. In addition, an alloy composition capable
of forming a long period stacking ordered structure and providing a high strength,
high ductile and high toughness property by subjecting to a plastic working or to
a heat treatment after a plastic working can be also found.
And, it is found that even if an alloy does not have long-period
stacking ordered structure phase just after casting, subjecting the alloy to a heat
treatment can form long-period stacking ordered structure phase in the alloy. In
addition, an alloy composition capable of providing a high strength, high ductility
and high toughness property by subjecting to a plastic working or to a heat treatment
after a plastic working is also found.
Beside, it is also found that by producing a chip-shaped
casting product by cutting a casting alloy, which forms a long period stacking ordered
structure, and then subjecting the chip-shaped casting product to a plastic working
or a heat treating after a plastic working, a higher strength, higher ductile and
higher toughness magnesium alloy can be obtained as compared with a case not containing
the step for cutting into a chip-shaped casting product. And, an alloy composition
can be found, which can form a long period stacking ordered structure and provide
a high strength, high ductile and high toughness property after subjecting a chip-shaped
casting product to a plastic working or to a heat treatment after a plastic working.
(Embodiment 1)
A magnesium alloy according to Embodiment 1 of the present
invention is a ternary or more alloy essentially containing Mg, Zn and rare-earth
element, in which the rare-earth element is one or more elements selected from the
group consisting of Y, Dy, Ho and Er.
A composition range of the Mg-Zn-Y alloy according to the
embodiment is shown in Fig. 8 at a range bounded by a line of A-B-C-D-E. When a
content of Zn is set to "a" atomic% and a content of one or more of the rare-earth
elements is set to "b" atomic%, "a" and "b" satisfy the following expressions (1)
to (3):
and
When a content of Zn exceeds 5 atomic%, a toughness (or
a ductility) tends to be decreased particularly. And, when a total content of Y
exceeds 5 atomic%, a toughness (or a ductility) tends to be decreased particularly.
When a content of Zn is less than 0.5 atomic% or a content
of Y is less than 1.0 atomic%, at least either one of strength or toughness deteriorates.
Accordingly, a lower limit of a content of Zn is set to 0.5 atomic% and a lower
limit of a content of Y is set to 1.0 atomic%.
When a content of Zn is 0.5 to 1.5 atomic%, a strength
and a toughness are remarkably increased. In a case of a content of Zn of near 0.5
atomic%, although a strength tends to decrease when a content of rare-earth element
decreases, the strength and the toughness can be maintained at a higher level than
that of a conventional alloy. Accordingly, in a magnesium alloy according to the
embodiment, a content of Zn is set to a maximum range within 0.5 atomic% to 5.0
atomic%.
A ratio of Y to Zn in content is preferably 1:1 or approximately
equal to the same. This ratio can improve the high strength and high toughness property.
The magnesium alloy containing one or more rare-earth elements
selected from the group consisting of Dy, Ho and Er has the following composition
range. When a content of Zn is set to "a" atomic% and a content of one or more of
the rare-earth elements is set to "b" atomic%, "a" and "b" satisfy the following
expressions (1) to (3):
and
The magnesium alloy containing one or more rare-earth elements
selected from the group consisting of Dy, Ho and Er may contain at least one element
selected from the group consisting of Y, Gd, Tb, Tm and Lu in a total amount of
"y" atomic%, wherein "y" satisfies the following expressions (4) to (5):
and
When a content of Zn exceeds 5 atomic%, a toughness (or
a ductility) tends to decrease particularly. And, when a total content of one or
more rare-earth elements exceeds 5 atomic%, a toughness (or a ductility) tends to
decrease particularly.
When a content of Zn is less than 0.2 atomic% or a total
content of the rare-earth elements is less than 0.2 atomic%, at least strength or
toughness becomes insufficient. Accordingly, a lower limit of content of Zn is set
to 0.2 atomic% and a lower limit of total content of the rare-earth elements is
set to 0.2 atomic%.
When a content of Zn is 0.2 to 1.5 atomic%, the strength
and the toughness increase remarkably. In a case where a content of Zn is near 0.2
atomic%, although the strength tends to decrease when a content of rare-earth element
decreases, the strength and the toughness can be maintained at a higher level than
that of a conventional alloy. Accordingly, in a magnesium alloy according to the
embodiment, a maximum range of content of Zn is 0.5 atomic% to 5.0 atomic%.
In a Mg-Zn-RE based magnesium alloy according to the embodiment,
part other than Zn and the rare-earth element having the aforesaid content ranges
is magnesium; however, the magnesium alloy may contain impurities of such a content
that characteristic of the alloy is not influenced.
The magnesium alloy containing one or more rare-earth elements
selected from the group consisting of Dy, Ho and Er has the composition range represented
by the aforesaid expressions (1) to (3); however, the composition range preferably
satisfies the following expressions (1') to (3') :
and
And, in the magnesium alloy, a ratio of Dy to Zn in content
is more preferably set to 2:1 or approximately equal to the same. And, a ratio of
Er to 2n in content is more preferably set to 2:1 or approximately equal to the
same. The ratios can further improve the high strength and high toughness property.
(Embodiment 2)
A magnesium alloy according to Embodiment 2 of the present
invention is a quaternary alloy or more alloy essentially containing Mg, Zn and
rare-earth element, in which the rare-earth element is one or more elements selected
from the group consisting of Y, Dy, Ho and Er and the forth element is one or two
or more elements selected from the group consisting of Yb, Sm and Nd.
The magnesium alloy in the embodiment has the following
composition range. When a content of Zn is set to "a" atomic%, a content of Y is
set to "b" atomic% and a total content of one or two or more forth elements is set
to "c" atomic%, "a", "b" and "c" satisfy the following expressions (1) to (5):
and
Causes for setting a content of Zn to 5 atomic% or less,
setting a content of Y to 5 atomic% or less, setting a content of Zn to 0.5 atomic%
or more and setting a content of Y to 1.0 atomic% or more are the same as the Embodiment
1. In this embodiment, an upper limit of a content of the forth element is set to
3.0 atomic% because the forth element has a small solid solubility limit. And, the
reason for containing the forth element is because of effects for forming a fine-grained
structure and for precipitating an intermetallic compound.
The magnesium alloy containing one or more rare-earth elements
selected from the group consisting of Dy, Ho and Er has the following composition.
When a content of Zn is set to "a" atomic%, a total content of one or more rare-earth
elements is set to "b" atomic% and a total content of one or two or more forth elements
is set to "c" atomic%, "a", "b" and "c" satisfy the following expressions (1) to
(5):
and
The reason that a content of Zn is set to 5 atomic% or
less, a total content of one or more rare-earth elements is set to 5 atomic% or
less, a content of Zn is set to 0.2 atomic% or more and a total content of the rare-earth
element is set to 0.2 atomic% or more are the same as Embodiment 1. In this embodiment,
an upper limit of content of the forth element is set to 3.0 atomic% because the
forth element has a small solid solubility limit. And, the reason for containing
the forth element is because of effects for forming a fine-grained structure and
for precipitating an intermetallic compound.
The Mg-Zn-Y base magnesium alloy according to the embodiment
may contain impurities of such a content that characteristic of the alloy is not
influenced.
The magnesium alloy containing one or more rare-earth elements
selected from the group consisting of Dy, Ho and Er has the composition range represented
by the aforesaid expressions (1) to (5); however, the composition range preferably
satisfies the following expressions (1') to (5') :
and
(Embodiment 3)
A magnesium alloy according to Embodiment 3 of the present
invention is a quaternary alloy or more alloy essentially containing Mg, Zn and
rare-earth element, in which the rare-earth element is one or more elements selected
from the group consisting of Y, Dy, Ho and Er and the forth element is one or two
ormore elements selected from the group consisting of La, Ce, Pr, Eu and Mm. Mm
(misch metal) is a mixture or an alloy of multiple rare-earth elements consisting
of Ce and La mainly, and is a residue generated by refining and removing useful
rare-earth element, such as Sm and Nd, from mineral ore. Its composition depends
on a composition of the mineral ore before the refining.
The magnesium alloy according to the embodiment has the
following composition. When a content of Zn is set to "a" atomic%, a content of
Y is set to "b" atomic% and a total content of one or two or more forth element
is set to "c" atomic%, "a", "b" and "c" satisfy the following expressions (1) to
(5) :
and
Causes for setting a content of Zn to 5 atomic% or less,
setting a total content of one or two or more rare-earth elements to 5 atomic% or
less, setting a content of Zn to 0.5 atomic% or more and setting a total content
of one or two or more rare-earth elements to 1.0 atomic% or more are the same as
the Embodiment 1. In this embodiment, an upper limit of a content of the forth element
is set to 2.0 atomic% because the forth element has a small solid solubility limit.
And, the reason for containing the forth element is because of effects for forming
a fine-grained structure and for precipitating an intermetallic compound.
The magnesium alloy containing one or more rare-earth elements
selected from the group consisting of Dy, Ho and Er has the following composition.
When a content of Zn is set to "a" atomic%, a total content of one or more rare-earth
element is set to "b" atomic% and a total content of one or two or more forth elements
is set to "c" atomic%, "a", "b" and "c" satisfy the following expressions (1) to
(5) :
and
The reason that a content of Zn is set to 5 atomic% or
less, a total content of one or more rare-earth elements is set to 5 atomic% or
less, a content of Zn is set to 0.2 atomic% or more and a total content of the rare-earth
element is set to 0.2 atomic% or more are the same as Embodiment 1. In this embodiment,
an upper limit of content of the forth element is set to 2.0 atomic% because the
forth element has little solid solubility limit. And, the reason for containing
the forth element is because of effects for forming a fine-grained structure and
for precipitating an intermetallic compound.
The Mg-Zn-RE base magnesium alloy according to the embodiment
may contain impurities of such a content that characteristic of the alloy is not
influenced.
The magnesium alloy containing one or more rare-earth elements
selected from the group consisting of Dy, Ho and Er has the composition range represented
by the aforesaid expressions (1) to (5); however, the composition range preferably
satisfies the following expressions (1') to (5'):
and
(Embodiment 4)
A magnesium alloy according to Embodiment 4 of the present
invention is a quintet alloy or more alloy essentially containing Mg, Zn and rare-earth
element, in which the rare-earth element is one or more elements selected from the
group consisting of Y, Dy, Ho and Er, the forth element is one or two or more elements
selected from the group consisting of Yb, Sm and Nd and the fifth element is one
or two or more elements selected from the group consisting of La, Ce, Pr, Eu and
Mm.
The magnesium alloy according to the embodiment has the
following composition range. When a content of Zn is set to "a" atomic%, a content
of Y is set to "b" atomic%, a total content of one or two or more forth elements
is set to "c" atomic% and a total content of one or two or more of fifth elements
is set to "d" atomic%, "a", "b", "c" and "d" satisfy the following expressions (1)
to (6):
and
In this embodiment, the reason that a total content of
Zn, Y, the forth element and the fifth element is set to 6.0 atomic% or less is
because of increasing in weight and manufacturing cost and decreasing in toughness
if the content exceeds 6.0 atomic%. And, the reason that a content of Zn is set
to 0.5 atomic% or more and a total amount of Y, the forth element and the fifth
element is set to 1.0 atomic% or more is because a strength deteriorates if concentration
of these elements are low. And, the reason for containing the forth and fifth elements
is because of effects for forming a fine-grained structure and for precipitating
an intermetallic compound.
The magnesium alloy containing one or more rare-earth elements
selected from the group consisting of Dy, Ho and Er has the following composition.
When a content of Zn is set to "a" atomic%, a content of one or more rare-earth
elements is set to "b" atomic%, a total content of one or two or more forth elements
is set to "c" atomic% and a total content of one or two or more of fifth elements
is set to "d" atomic%, "a", "b", "c" and "d" satisfy the following expressions (1)
to (6):
and
In this embodiment, the reason that a total content of
rare-earth elements, forth elements and fifth elements is set to 6.0 atomic% or
less is because of increasing in weight and manufacturing cost and decreasing in
toughness if the content exceeds 6.0 atomic%. And, the reason that a total content
of rare-earth elements, forth elements and fifth elements is set to 0.2 atomic%
or more is because the strength becomes insufficient if the content is less than
0.2 atomic%. And, the reason for containing the forth and fifth elements is because
of effects for forming a fine-grained structure and for precipitating an intermetallic
compound.
The Mg-Zn-RE base magnesium alloy according to the embodiment
may contain impurities of such a content that characteristic of the alloy is not
influenced.
The magnesium alloy containing one or more rare-earth elements
selected from the group consisting of Dy, Ho and Er has the composition range represented
by the aforesaid expressions (1) to (6); however, the composition range preferably
satisfies the following expressions (1') to (6'):
and
(Embodiment 5)
A magnesium alloy according to the fifth embodiment of
the present invention is a magnesium alloy having any compositions of the magnesium
alloys described in the Embodiments 1 to 4 to which Me is added. Me is at least
one element selected from the group consisting of Al, Th, Ca, Si, Mn, Zr, Ti, Hf,
Nb, Ag, Sr, Sc, B, C, Sn, Au, Ba, Ge, Bi, Ga, In, Ir, Li, Pd, Sb and V. A content
of Me is set to larger than 0 atomic % to 2.5 atomic% or less. An addition of Me
can improve characteristics other than the strength and the toughness which are
being kept high. For instance, a corrosion resistance and an effect for forming
a fine-grained crystal structure are improved.
(Embodiment 6)
A method of producing a magnesium alloy according to the
sixth embodiment of the present invention will be described.
A magnesium alloy having any one composition in the magnesium
alloys according to the Embodiments 1 to 5 was melted and cast to prepare a magnesium
alloy casting product. A cooling rate at the casting was 1000K/sec or less, more
preferably 100K/sec or less. As the magnesium alloy casting product, a product cut
from an ingot into a specific shape is used.
Next, the magnesium alloy casting product may be subjected
to a homogenized heat treatment. In this case, a heating temperature is preferably
400°C to 550°C and a treating period is preferably 1 minute to 1500 minutes
(or 24 hours) .
Then, the magnesium alloy casting product is plastically
worked. As the plastic working method, extrusion, ECAE (Equal Channel Angular Extrusion),
rolling, drawing, forging, cyclic process thereof, FAW (Friction Stir Welding) and
the like may be employed.
When the plastic working method is an extrusion, an extrusion
temperature is preferably set to 250°C to 500°C and a reduction rate of
a cross section due to the extrusion is preferably set to be 5% or more.
The ECAE working is carried out such that a sample is rotated
every 90° in the length direction thereof every pass for introducing a strain
therein uniformly. Specifically, a forming die having a forming pore of a L-shaped
cross section is employed, and the magnesium alloy casting product as a forming
material is forcibly poured in the forming pore. And, the magnesium alloy casting
product is applied with stress at a portion at which the L-shaped forming pore is
curved at 90° thereby to obtain a compact excellent in strength and toughness.
A number of passes of the ECAE working is preferably set to 1 to 8, more preferably,
3 to 5. A temperature of the ECAE working is preferably set to 250°C to 500°C.
When the plastic working method is an extrusion, an extrusion
temperature is preferably set to 250°C to 500°C and a rolling reduction
is preferably set to 5% or more.
When the plastic working method is a drawing, a drawing
temperature is preferably set to 250°C to 500°C and a reduction rate of
a cross section is preferably set to 5% or more.
When the plastic working method is a forging, a forging
temperature is preferably set to 250°C to 500°C and a processing rate
is preferably set to 5% or more.
The plastically worked product in which a magnesium alloy
casting product is plastically worked in the aforesaid manner has a crystal structure
of long-period stacking ordered structure phase under room temperatures. And, a
volume fraction of the crystal grain having long-period stacking ordered structure
phase is of 5% or more (preferably, 10% or more). And, the magnesium alloy has a
crystal grain size of 100nm to 500 µm. At least a part of the long period stacking
ordered structure phase is flexed or bend. And, the plastically worked product may
contain at least one kind of precipitation selected from the group consisting of
a compound of Mg and rare-earth element, a compound of Mg and Zn, a compound of
Zn and rare-earth element and a compound of Mg, Zn and rare-earth element. The precipitation
preferably has a total volume fraction of higher than 0 to 40% and below. The plastically
worked product has an hcp-Mg phase. The plastically worked product after subjecting
to the plastic working has Vickers hardness and yield strength higher than the casting
product before subjecting to the plastic working.
The plastically worked product after subjecting to the
plastic working may be subjected to a heat treatment. The heat treatment is preferably
carried out at a temperature of 400°C or more to lower than 550°C and
a treating period of 1 minutes to 1500 minutes (or 24 hours). Theplasticallyworked
product subjected to the heat treatment is improved in Vickers hardness and yield
strength as compared with that before the heat treatment. And, the plastically worked
product after subjecting to the heat treatment has a crystal structure of long-period
stacking ordered structure phase under room temperatures similar to the product
before subjecting to the heat treatment. And, the crystal grain having long-period
stacking ordered structure phase has a volume fraction of 5% or more (preferably,
10% or more). And, the magnesium alloy has a crystal grain size of 100nm to 500
µm. At least a part of the long period stacking ordered structure phase is
flexed or bend. And, the plastically worked product may contain at least one kind
of precipitation selected from the group consisting of a compound of Mg and rare-earth
element, a compound of Mg and Zn, a compound of Zn and rare-earth element and a
compound of Mg, Zn and rare-earth element. The precipitation preferably has a total
volume fraction of higher than 0 to 40% and below. And, the said plastically worked
product contains hcp-Mg.
According to the Embodiments 1 to 6, a high strength and
high toughness metal having a strength and a toughness both being on a level for
an alloy to be practically used for expanded applications of a magnesium alloy,
for example, a high technology alloy requiring a high strength and toughness, and
a method of producing the same can be provided.
And, when the magnesium alloy having each composition of
Embodiments 1 to 4 added with Zr in an amount of larger than 0 atomic% to 2.5 atomic%
or less is melted and cast to produce a magnesium alloy casting product, the magnesium
alloy casting product has the following characteristics: precipitation of a compound
such as Mg3Zn3RE2 is suppressed; formation of long-period
stacking ordered structure phase is promoted; and the crystal structure is made
into fine structure. Accordingly, it becomes easy to plastically work the magnesium
alloy casting product. And, the plastically worked product subjected to the plastic
working has a larger amount of long-period stacking ordered structure phase and
has a finer-grained crystal structure than a plastically worked product of a magnesium
alloy which is not added with Zr. The large amount of long-period stacking ordered
structure phase can improve the strength and the toughness.
The long-period stacking ordered structure phase has a
density modulation. The density modulation shows a phenomenon in which a concentration
of solute element changes periodically every atomic layer.
(Embodiment 7)
A magnesium alloy according to Embodiment 7 is applied
for a number of chip-shaped casting products each having a side length of several
mm or less produced by cutting a casting product. The magnesium alloy is a ternary
or more alloy essentially containing Mg, Zn and rare-earth element, wherein the
rare-earth element is one or more elements selected from the group consisting of
Y, Dy, Ho and Er.
A composition range of the Mg-Zn-Y alloy according to the
embodiment is shown in Fig.9 at a range bounded by a line of A-B-C-D-E. When a content
of Zn is set to "a" atomic% and a content of Y is set to "b" atomic%, "a" and "b"
satisfy the following expressions (1) to (3):
and
When a content of Zn is more than 5 atomic%, a toughness
(or a ductility) tends to decrease particularly. And, when a content of Y is more
than 5 atomic%; a toughness (or a ductility) tends to decrease particularly.
And, when a content of Zn is less than 0.25 atomic% or
a content of Y is less than 0.5 atomic%, either one of strength or toughness deteriorates.
Accordingly, a lower limit of a content of Zn is set to 0.25 atomic% and a lower
limit of a content of rare-earth element is set to 0.5 atomic%. The reason that
each of the lower limits of the contents of Zn and rare-earth element can be decreased
to a half of that of the first embodiment is for employing a chip-shaped casting
product.
When a content of Zn is 0.5 to 1.5 atomic%, a strength
and a toughness are remarkably increased. In a case of a content of Zn of near 0.5
atomic%, although a strength tends to decrease when a content of rare-earth element
decreases, the strength and the toughness can be maintained at a higher level than
that of a conventional alloy. Accordingly, in the magnesium alloy according to the
embodiment, a content of Zn is set to a maximum range within 0.25 atomic% to 5.0
atomic%.
The magnesium alloy containing one or more rare-earth elements
selected from the group consisting of Dy, Ho and Er has the following composition.
When a content of Zn is set to "a" atomic% and a total content of one or more rare-earth
elements is set to "b"atomic%, "a" and "b" satisfy the following expressions (1)
to (3):
and
And, the magnesium alloy containing one or more rare-earth
elements selected from the group consisting of Dy, Ho and Er may contain at least
one kind of element selected from the group consisting of Y, Gd, Tb, Tm and Lu in
a total amount of "y" atomic%, wherein "y" satisfies the following expressions (4)
to (5):
and
When a content of Zn is 5 atomic% or more, a toughness
(or a ductility) tends to decrease particularly. And, when a total content of one
or more rare-earth elements is 5 atomic% or more, a toughness (or a ductility) tends
to decrease particularly.
And, when a content of Zn is less than 0.1 atomic% or a
total content of rare-earth elements is less than 0 . 1 atomic%, either one of strength
or toughness deteriorates. Accordingly, a lower limit of content of Zn is set to
0.1 atomic% and a lower limit of total content of rare-earth elements is set to
0.1 atomic%. The reason that the lower limits of contents of Zn and rare-earth element
can be decreased to a half of that of Embodiment 1 is for employing a chip-shaped
casting product.
When a content of Zn is 0.5 to 1.5 atomic%, a strength
and a toughness are remarkably increased. In a case where a content of Zn is near
0.5 atomic%, although a strength tends to decrease when a content of rare-earth
element decreases, the strength and the toughness can be maintained at a higher
level than that of a conventional alloy. Accordingly, in the magnesium alloy according
to the embodiment, a maximum range of content of Zn is 0.1 atomic% to 5.0 atomic%.
In the Mg-Zn-RE based magnesium alloy according to the
present invention, part other than Zn and rare-earth elements each having the aforesaid
range consists of magnesium; however, the magnesium alloy may contain impurities
of such a content that characteristic of the alloy is not influenced.
The magnesium alloy containing one or more rare-earth elements
selected from the group consisting of Dy, Ho and Er has the composition range represented
by the aforesaid expressions (1) to (3); however, the composition range preferably
satisfies the following expressions (1') to (3'):
and
(Embodiment 8)
A magnesium alloy according to Embodiment 8 of the present
invention is applied for a number of chip-shaped casting products having a side
length of several mm or less produced by cutting a casting product. The magnesium
alloy is a quaternary alloy or more alloy essentially containing Mg, Zn and rare-earth
element, wherein the rare-earth element is one or more elements selected from the
group consisting of Y, Dy, Ho and Er and the forth element is one or two or more
elements selected from the group consisting of Yb, Sm and Nd.
In a composition range of the Mg-Zn-Y alloy according to
the embodiment, when a content of Zn is set to "a" atomic%, a content of Y is set
to "b" atomic% and a total content of one or two or more forth elements is set to
"c" atomic%, "a", "b" and "c" satisfy the following expressions (1) to (5) :
and
Causes for setting a content of Zn to 5 atomic% or less,
setting a total content of one or two or more rare-earth elements to 5 atomic% or
less, setting a content of Zn to 0.25 atomic% or more and setting a content of Y
to 0.5 atomic% or more are the same as the Embodiment 7. In this embodiment, an
upper limit of a content of the forth element is set to 3.0 atomic% because the
forth element has a small solid solubility limit. And, the reason for containing
the forth element is because of effects for forming a fine-grained structure and
for precipitating an intermetallic compound.
The magnesium alloy containing one or more rare-earth elements
selected from the group consisting of Dy, Ho and Er has the following composition.
When a content of Zn is set to "a" atomic%, a total content of one or more rare-earth
element is set to "b" atomic% and a total content of one or more forth elements
is set to "c" atomic%, "a", "b" and "c" satisfy the following expressions (1) to
(5):
and
The Mg-Zn-RE base magnesium alloy according to the embodiment
may contain impurities of such a content that characteristic of the alloy is not
influenced.
The magnesium alloy containing one or more rare-earth elements
selected from the group consisting of Dy, Ho and Er has the composition range represented
by the aforesaid expressions (1) to (3); however, the composition range preferably
satisfies the following expressions (1') to (3') :
and
(Embodiment 9)
A magnesium alloy according to Embodiment 9 of the present
invention is applied for a number of chip-shaped casting products having a side
length of several mm or less produced by cutting a casting product. The magnesium
alloy is a quaternary alloy or quintet or more alloy essentially containing Mg,
Zn and rare-earth element, wherein the rare-earth element is one or more elements
selected from the group consisting of Y, Dy, Ho and Er and the forth element is
one or two ormore elements selected from the group consisting of La, Ce, Pr, Eu
and Mm.
In a composition range of the Mg-Zn-RE alloy according
to the embodiment, when a content of Zn is set to "a" atomic%, a content of Y is
set to "b" atomic% and a total content of one or two or more forth elements is set
to "c" atomic%, "a", "b" and "c" satisfy the following expressions (1) to (5):
and
Causes for setting a content of Zn to 5 atomic% or less,
setting a total content of one or more rare-earth elements to 5 atomic% or less,
setting a content of Zn to 0.25 atomic% or more and setting a content of Y to 0.5
atomic% or more are the same as the Embodiment 7. In this embodiment, an upper limit
of a content of the forth element is set to 2.0 atomic% because the forth element
has a small solid solubility limit. And, the reason for containing the forth element
is because of effects for forming a fine-grained structure and for precipitating
an intermetallic compound.
The magnesium alloy containing one or more rare-earth elements
selected from the group consisting of Dy, Ho and Er has the following composition.
When a content of Zn is set to "a" atomic%, a total content of one ormore rare-earth
element is set to "b" atomic% and a total content of one or more forth elements
is set to "c" atomic%, "a", "b" and "c" satisfy the following expressions (1) to
(5):
and
The Mg-Zn-RE base magnesium alloy according to the embodiment
may contain impurities of such a content that characteristic of the alloy is not
influenced.
The magnesium alloy containing one or more rare-earth elements
selected from the group consisting of Dy, Ho and Er has the composition range represented
by the aforesaid expressions (1) to (3); however, the composition range preferably
satisfies the following expressions (1') to (3'):
and
(Embodiment 10)
A magnesium alloy according to Embodiment 10 of the present
invention is applied for a number of chip-shaped casting products having a side
length of several mm or less produced by cutting a casting product. The magnesium
alloy is a quintet alloy or more alloy essentially containing Mg, Zn and rare-earth
element, wherein the rare-earth element is one or more elements selected from the
group consisting of Y, Dy, Ho and Er, the forth element is one or two or more elements
selected from the group consisting of Yb, Sm and Nd and the fifth element is one
or two or more elements selected from the group consisting of La, Ce, Pr, Eu and
Mm.
In a composition range of the Mg-Zn-Y alloy according to
the embodiment, when a content of Zn is set to "a" atomic%, a content of Y is set
to "b" atomic%, a total content of one or two or more forth elements is set to "c"
atomic% and a total content of one or two or more of fifth elements is set to "d"
atomic%, "a", "b", "c" and "d" satisfy the following expressions (1) to (6):
and
Causes for setting a total content of Zn, y, the forth
element and the fifth element to less than 6.0 atomic% and setting a total content
of Zn, Y, the forth element and the fifth element to higher than 1.0 atomic% are
the same as the
Embodiment 4.
The magnesium alloy containing one or more rare-earth elements
selected from the group consisting of Dy, Ho and Er has the following composition.
When a content of Zn is set to "a" atomic%, a total content of one or more rare-earth
element is set to "b" atomic%, a total content of one or more forth elements is
set to "c" atomic% and a total content of one or more forth elements is set to "d",
"a", "b", "c" and "d" satisfy the following expressions (1) to (4):
and
The Mg-Zn-RE base magnesium alloy according to the embodiment
may contain impurities of such a content that characteristic of the alloy is not
influenced.
The magnesium alloy containing one or more rare-earth elements
selected from the group consisting of Dy, Ho and Er has the composition range represented
by the aforesaid expressions (1) to (3); however, the composition range preferably
satisfies the following expressions (1') to (3') :
and
(Embodiment 11)
A magnesium alloy according to the eleventh embodiment
of the present invention is a magnesium alloy having any composition of the magnesium
alloys described in the Embodiments 7 to 11 to which Me is added. Me is at least
one element selected from the group consisting of Al, Th, Ca, Si, Mn, Zr, Ti, Hf,
Nb, Ag, Sr, Sc, B and C. A content of Me is set to larger than 0 atomic% to 2.5
atomic% or less. An addition of Me can improve characteristics other than the strength
and the toughness which are being kept high. For instance, a corrosion resistance
and an effect for forming fine-grained crystal structure are improved.
(Embodiment 12)
A method of producing a magnesium alloy according to the
twelve embodiment of the present invention will be described.
A magnesium alloy having any composition in the magnesium
alloys according to Embodiments 7 to 11 was melted and cast to prepare a magnesium
alloy casting product. A cooling rate at the casting was 1000K/sec or less, more
preferably 100K/sec or less. For the magnesium alloy casting product, products cut
from ingot into a specified shape was employed.
Next, the magnesium alloy casting product may be subjected
to a homogenized heat treatment. In this case, a heating temperature is preferably
set to 400°C to 550°C and a treating period is preferably set to 1 minute
to 1500 minutes (or 24 hours).
Then, the magnesium alloy casting product was cut into
a number of chip-shaped casting products each having a side length of several mm
or less.
And, the chip-shaped casting products may be preformed
by a press or a plastic working method and then subjected to a homogenized heat
treatment. In this case, a heating temperature is preferably set to 400°C to
550°C and a treating period is preferably set to 1 minute to 1500 minutes (or
24 hours). And, the preformed product may be subjected to a heat treatment under
a condition of a temperature of 150°C to 450°C and a treating period of
1 minute to 1500 minutes (or 24 hours) .
The chip-shaped casting products are usually employed as
a material for thixocasting.
And, a mixture of the chip-shaped casting product and ceramic
particles may be preformed by a press or a plastic working and then subjected to
a homogenized heat treatment. And, before the performing of the chip-shaped casting
products, a forced straining working may be carried out additionally.
Then, the chip-shaped casting products were plastically
worked. For a method of the plastic working, various methods may be employed as
with the Embodiment 6.
The plastically worked product subjected to the plastic
working has a crystal structure of a hcp structured magnesium phase and a long period
stacking ordered structure phase at room temperatures. At least a part of the long
period stacking ordered structure phase is flexed or bend. The plastically worked
product subjected to the plastic working is improved in Vickers hardness and yield
strength as compared with the casting product before the plastic working.
The plastically worked product after subjecting the chip-shaped
casting product to the plastic working may be subjected to a heat treatment. The
heat treatment is preferably carried out at a temperature of 400°C or more
to lower than 550°C and a treating period of 1 minute to 1500 minutes (or 24
hours). The plastically worked product subj ected to the heat treatment is improved
in Vickers hardness and yield strength as compared with that before the heat treatment.
And, the plastically worked product subjected to the heat treatment, as with that
before the heat treatment, has a crystal structure of a hcp structured magnesium
phase and a long period stacking ordered structure phase at room temperatures. At
least a part of the long period stacking ordered structure phase is flexed or bend.
According to the Embodiment 12, since a casting product
is cut into chip-shaped casting products, a fine-grained structure crystal can be
obtained. As a result, it becomes possible to produce a plastically worked product
having a higher strength, a higher ductility and a higher toughness than that according
to the Embodiment 6. In addition, a magnesium alloy according to the embodiment
can have a high strength and a high toughness if densities of Zn and rare-earth
element are lower than those of the magnesium alloys according to Embodiments 1
to 6.
According to Embodiments 7 to 12, a high strength and high
toughness metal having a strength and a toughness both being on a level for an alloy
to be practically used for expanded applications of a magnesium alloy, for example,
a high technology alloy requiring a high strength and toughness property, and a
method of producing the same can be provided.
The long-period stacking ordered structure phase may have
a density modulation. The density modulation shows a phenomenon in which a concentration
of solute element changes periodically every atomic layer.
(Embodiment 13)
A magnesium alloy according to Embodiment 13 of the present
invention is a ternary or more alloy essentially containing Mg, Zn, and Gd or Tb
or Tm or Lu. The magnesium alloy contains Zn in an amount of "a" atomic%, at least
one element selected from the group consisting of Gd, Tb, Tm and Lu and a residue
consisting of Mg, wherein "a" and "b" satisfy the following expressions (1) to (3):
and
more preferably the following expressions (1') to (3') :
and
The composition range is shown in Fig.24 at a range bounded
by a line of A-B-C-D-E.
And, a preferable upper limit of content of Gd is less
than 3 atomic% in viewpoint of economical efficiency and increasing of gravity.
In the magnesium alloy, a ratio of Gd to Zn in content
is 2:1 or approximately equal to the same. The ratio can improve the high strength
and toughness property.
The magnesium alloy may contain at least one element selected
from the group consisting of Yb, Sm and Nd in a total amount of "c" atomic%, wherein
"c" satisfies the following expressions (4) to (5):
and
These elements can provide effects for forming a fine-grained
structure and for precipitating an intermetallic compound.
The magnesium alloy may contain at least one element selected
from the group consisting of La, Ce, Pr, Eu and Mm in a total amount of "c" atomic%,
wherein "c" satisfies the following expressions (4) to (5) :
and
These elements can provide effects for forming a fine-grained
structure and for precipitating an intermetallic compound.
The magnesium alloy may contain at least one element selected
from the group consisting of Yb, Sm and Nd in a total amount of "c" atomic% and
at least one element selected from the group consisting of La, Ce, Pr, Eu and Mm
in a total amount of "d" atomic%, wherein "c" and "d" satisfy the following expressions
(4) to (6):
and
These elements can provide effects for forming a fine-grained
structure and for precipitating an intermetallic compound.
The magnesium alloy may contain at least one elements selected
from the group consisting of Dy, Ho and Er in a total amount of larger than 0 atomic%
to 1.5 atomic% or less. And, the magnesium alloy may contain Y in an amount of larger
than 0 atomic% to 1.0 atomic% or less. These rare-earth elements can promote formation
of long-period stacking ordered structure phase.
The magnesium alloy may contain at least one element selected
from the group consisting of Al, Th, Ca, Si, Mn, Zr, Ti, Hf, Nb, Ag, Sr, Sc, B and
C in a total amount of larger than 0 atomic% to 2.5 atomic% or less. These elements
can improve characteristics other than the strength and the toughness which are
being kept high. For instance, a corrosion resistance and an effect for forming
a fine-grained crystal structure are improved.
The magnesium alloy having the aforesaid composition is
melted and cast to produce a magnesium alloy casting product. The casting is carried
out under a condition of a cooling rate of 1000K/s or less, more preferably 100K/s
or less. As the magnesium alloy casting product, a product cut from an ingot into
a specific shape is employed. The magnesium alloy casting product does not have
long-period stacking ordered structure phase formed therein.
Then, the magnesium alloy casting product is subjected
to a heat treatment. The heat treatment is preferably carried out under a condition
of a temperature of 300°C to 550°C and a period of 10 minutes to shorter
than 24 hours. The heat treatment forms long-period stacking ordered structure phase
in the magnesium alloy.
Next, the magnesium alloy casting product is plastically
worked at a temperature of 300°C to 450°C. As the plastic working method,
extrusion, ECAE (Equal Channel Angular Extrusion), rolling, drawing, rolling, forging,
cyclic process thereof, FAW (Friction Stir Welding) and the like accompanied with
plastic deformation may be employed.
The plastically worked product subjected to the plastic
working in the aforesaid manner has a crystal structure in which at least a part
of long-period stacking ordered structure phase is bend or flexed at room temperatures.
The magnesium alloy has a crystal grain size of 100nm to 500 µm. And, the plastically
worked product may contain at least one kind of precipitation selected from the
group consisting of a compound of Mg and rare-earth element, a compound of Mg and
Zn, a compound of Zn and rare-earth element and a compound of Mg, Zn and rare-earth
element. The plastically worked product has an hcp-Mg phase. The plastically worked
product after subjecting to the plastic working has higher Vickers hardness and
yield strength than the casting product before subjecting to the plastic working.
The long-period stacking ordered structure phase may have
a density modulation. The density modulation shows a phenomenon in which a concentration
of a solute element changes periodically every atomic layer.
(Embodiment 14)
A magnesium alloy according to Embodiment 14 of the present
invention is applied for a number of chip-shaped casting products having a side
length of several mm or less produced by cutting a casting product. The magnesium
alloy is a ternary or more alloy essentially containing Mg, Zn, and Gd or Tb or
Tm or Lu. The magnesium alloy contains Zn in an amount of "a" atomic%, at least
one element selected from the group consisting of Gd, Tb, Tm and Lu in a total amount
of "b" atomic% and a residue consisting of Mg, wherein "a" and "b" satisfy the following
expressions (1) to (3):
and
more preferably the following expressions (1') to (3') :
and
The composition range is shown in Fig.25 at a range bounded
by a line of A-B-C-D-E.
And, a preferable upper limit of content of Gd is less
than 3 atomic% in viewpoint of economical efficiency and increasing of gravity.
The magnesium alloy may contain at least one element selected
from the group consisting of Yb, Sm and Nd in a total amount of "c" atomic%, wherein
"c" satisfies the following expressions (4) to (5):
and
These elements can provide effects for forming a fine-grained
structure and for precipitating an intermetallic compound.
The magnesium alloy may contain at least one element selected
from the group consisting of La, Ce, Pr, Eu and Mm in a total amount of "c" atomic%,
wherein "c" satisfies the following expressions (4) to (5):
and
These elements can provide effects for forming a fine-grained
structure and for precipitating an intermetallic compound.
The magnesium alloy may contain at least one element selected
from the group consisting of Yb, Sm and Nd in a total amount of "c" atomic% and
at least one element selected from the group consisting of La, Ce, Pr, Eu and Mm
in a total amount of "d" atomic%, wherein "c" and "d" satisfy the following expressions
(4) to (6):
and
These elements can provide effects for forming a fine-grained
structure and for precipitating an intermetallic compound.
The magnesium alloy may contain at least one element selected
from the group consisting of Dy, Ho and Er in a total amount of larger than 0 atomic%
to 1.5 atomic% or less. And, the magnesium alloy may contain Y in an amount of larger
than 0 atomic% to 1.0 atomic% or less. These rare-earth elements can promote formation
of long-period stacking ordered structure phase.
The magnesium alloy may contain at least one element selected
from the group consisting of Al, Th, Ca, Si, Mn, Zr, Ti, Hf, Nb, Ag, Sr, Sc, B and
C in a total amount of larger than 0 atomic% to 2.5 atomic% or less. These elements
can improve characteristics other than the strength and the toughness which are
being kept high. For instance, a corrosion resistance and an effect for forming
a fine-grained crystal structure are improved.
The magnesium alloy having the aforesaid composition is
melted and cast to produce a magnesium alloy casting product and cut from an ingot
into a specific shape as the same manner as Embodiment 13.
Then, the magnesium alloy casting product is subjected
to a heat treatment. The heat treatment is carried out under the same condition
as Embodiment 13. The heat treatment may be carried out after producing a chip-shaped
cutting product.
And, the magnesium alloy casting product is cut into a
chip-shaped cutting product. The cutting is carried out in the same manner as Embodiment
7.
Then, the cutting product is plastically worked at temperature
of 300°C to 450°C for solidification-forming to form a plastically worked
product in which a part of long-period stacking ordered structure phase is bend
or flexed. And, before the solidification-forming, a boll milling working or repeatedly
working may be added. And, after the solidification-forming, a plastic working or
blast working may be subjected, or a heat treatment at 180°C to 450°C
for 10 minutes to shorter than 24 hours may be added. The magnesium alloy casting
product may be compounded with ceramic particles or fiber. And, the chip-shaped
cutting product may be mixed with ceramic particles or fiber.
The solidification-forming product subjected to the plastic
working has a crystal structure in which at least a part of long-period stacking
ordered structure phase is bend or flexed at room temperatures. The magnesium alloy
has a crystal grain size of 100nm to 500µm. And, the plastically worked product
may contain at least one kind of precipitation selected from the group consisting
of a compound of Mg and rare-earth element, a compound of Mg and Zn, a compound
of Zn and rare-earth element and a compound of Mg, Zn and rare-earth element. The
plastically worked product has an hcp-Mg phase. The plastically worked product after
subj ecting to the plastic working has higher Vickers hardness and yield strength
than the casting product before subjecting to the plastic working.
According to Embodiments 13 and 14, a high strength and
high toughness magnesium alloy having a strength and a toughness both being on a
level to be practically used for expanded applications of a magnesium alloy, for
example, a high technology alloy requiring a high strength and toughness property,
and a method of producing the same can be provided.
The long-period stacking ordered structure phase may have
a density modulation. The density modulation shows a phenomenon in which a concentration
of solute element changes periodically every atomic layer.
(Embodiment 15)
A method for producing a magnesium alloy according to Embodiment
15 will be explained.
The method for producing a magnesium alloy according to
the embodiment has the same processes as Embodiment 6 except for the process for
producing a magnesium alloy casting product. The processes other than the process
for producing a magnesium alloy casting product will be not explained.
Hereinafter, the method for producing a magnesium alloy
casting product will be explained.
First, a mineral ore containing rare-earth elements is
refined or smelted to prepare a rare-earth alloy containing plural kinds of rare-earth
elements. As the rare-earth alloy, an alloy containing large amount of rare-earth
element which forms long-period stacking ordered structure phase, such as ion absorbing
ore or xenotime, may be employed.
The ion absorbing ore contains Y2O3
in an amount of about 64.1 wt%. And, the xenotime contains Y2O3
in an amount of about 55.0 to 60.8wt%.
A process for getting an objective metal component out
of a natural mineral ore is referred to as a smelting process. And, a process for
increasing purity of a crude metal obtained by the smelting process or adjusting
the components is referred to as a refining process. A high purity rare-earth element
is obtained by conventionally known smelting process and refining process. The rare-earth
alloy used in the embodiment is a rare-earth metal, an intermediate product, at
a stage before a final product of high purity rare-earth element is extracted. The
rare-earth alloy is more economical in product cost than the final product of the
high purity rare-earth elements. That is because a separation process is omitted
and a residue of the mineral ole from which marketable expensive rare-earth elements
are extracted is used. The rare-earth alloy may be a residue of the mineral ore
from which Nd, Ce, light rare-earth element and the like are extracted.
The rare-earth alloy preferably contains at least one rare-earth
element selected from the group consisting of Y, Dy, Ho and Er, which form long-period
stacking ordered structure phase, in a total amount of 50 atomic% or more, preferably
66 atomic% or more, a residue consisting of another rare-earth element (rare-earth
element which does not form long-period stacking ordered structure phase, for instance,
rare-earth elements other than Y, Dy, Ho, Er, Gd, Tb, Tm and Lu) and unavoidable
impurity.
Then, the rare-earth alloy, Mg and Zn are used as a starting
material such that a magnesium alloy contains rare-earth elements having any one
of compositions of Embodiments 1 to 5 , and are melted and cast to produce a magnesium
alloy casting product. As the rare-earth alloy, an alloy obtained by mixing plural
kinds of rare-earth elements may be employed.
The casting is carried out at a cooling rate of 1000K/s
or less, more preferably 100K/s or less. As the magnesium alloy casting product,
a product cut from an ingot into a specific shape is employed.
Gd, Tb, Tm and Lu are rare-earth elements which form long-period
stacking ordered structure phase by subjecting to a heat treatment; Y, Dy, Ho and
Er are rare-earth elements which form long-period stacking ordered structure phase
without subjecting to a heat treatment.
According to Embodiment 15, the same effect as Embodiment
6 can be obtained.
According to the present embodiment, since the rare-earth
alloy is used as a part of the starting material in the aforesaid manner, material
cost of the rare-earth element can decrease.
(Embodiment 16)
A method for producing a magnesium alloy according to Embodiment
16 will be explained.
The method for producing a magnesium alloy according to
the embodiment has the same processes as Embodiment 12 except for the process for
producing a magnesium alloy casting product. The process for producing a magnesium
alloy casting product is the same process as Embodiment 15.
According to the embodiment, the same effect as Embodiment
12 can be obtained.
According to the present embodiment, material cost of the
rare-earth element can decrease similar to Embodiment 1.5.
(Embodiment 17)
A method for producing a magnesium alloy according to Embodiment
17 will be explained.
The method for producing a magnesium alloy according to
the embodiment has the same processes as Embodiment 13 except for the process for
producing a magnesium alloy casting product. The processes other than the process
for producing a magnesium alloy casting product will be not explained.
Hereinafter, the method for producing a magnesium alloy
casting product will be explained.
First, a mineral ore containing rare-earth elements is
refined or smelted to prepare a rare-earth alloy containing plural kinds of rare-earth
elements.
As the same manner as Embodiment 15, the rare-earth alloy
is a rare-earth metal, an intermediate product, at a stage before a final product
of high purity rare-earth element is extracted. The rare-earth alloy is more economical
in product cost than the final product of the high purity rare-earth elements. That
is because a separation process is omitted and a residue of the mineral ole from
which marketable expensive rare-earth elements are extracted is used. The rare-earth
alloy may be a residue of the mineral ore from which Nd, Ce, light rare-earth element
and the like are extracted.
The rare-earth alloy preferably contains at least one rare-earth
element selected from the group consisting of Gd, Tb, Tm and Lu, which form long-period
stacking ordered structure phase, in a total amount of 50 atomic% or more, preferably
66 atomic% or more and a residue consisting of another rare-earth element (rare-earth
element which does not form long-period stacking ordered structure phase, for instance,
rare-earth elements other than Y, Dy, Ho, Er, Gd, Tb, Tm and Lu) and unavoidable
impurity.
Then, the rare-earth alloy, Mg and Zn are used as a starting
material such that a magnesium alloy contains rare-earth elements having the composition
of Embodiment 13, and are melted and cast to produce a magnesium alloy casting product.
As the rare-earth alloy, an alloy obtained by mixing plural kinds of intermediate
products may be employed.
According to the embodiment, the same effect as Embodiment
13 can be obtained.
According to the present embodiment, since the rare-earth
alloy is used as a part of the starting material in the aforesaid manner, material
cost of the rare-earth element can decrease.
(Embodiment 18)
A method for producing a magnesium alloy according to Embodiment
1.8 will be explained.
The method for producing a magnesium alloy according to
the embodiment has the same processes as Embodiment 14 except for the process for
producing a magnesium alloy casting product. The process for producing a magnesium
alloy casting product is the same process as Embodiment 17.
According to the embodiment, the same effect as Embodiment
14 can be obtained.
According to the present embodiment, material cost of the
rare-earth element can decrease similar to Embodiment 17.
(Embodiment 19)
A method for producing a magnesium alloy according to Embodiment
19 will be explained.
For producing rapid solidified powder and solidification-forming
of the same, a closed P/M processing system is employed. The employed system is
shown in Figs. 29 and 30. Fig.29 shows processes for producing rapid solidified
powder by a gas atomizing method and extruding the produced powder to form a billet.
Fig. 30 shows a process for extruding the formed billet. Referring to Figs. 29 and
30, the processes for producing rapid solidified powder and solidification-forming
of the same will be explained in detail.
In Fig. 29, a magnesium alloy powder having an objective
composition ratio is produced using a high-pressure gas atomizer 100. That is, first,
the alloy having the objective composition ratio is melted in a crucible 116 in
a melting room 119 using an induction coil 114. The employed alloy is prepared in
the same manner as a process for preparing materials before melting in Embodiment
15. That is, a mineral ore containing rare-earth elements is smelted or refined
into a rare-earth alloy containing plural kinds of rare-earth elements. In the embodiment,
the magnesium alloy has a composition of general formula of Mg(100-x-y)YxZny
(1<x<5, 0.3<y<6; x and y represent atomic%).
Then, putting up a stopper 112, the melted alloy is injected.
And, to the injected alloy, a high-pressure inactive gas (for example, helium gas
and argon gas) is splayed from a nozzle 132 to form a powder of the alloy. The nozzle
and the like are heated by a heater 131. The atomizer room 130 is checked by an
oxygen analyzer 162 and a vacuum gage 164.
The produced alloy powder is collected in a hopper 220
of a vacuum globe box 200 through a cyclone classifier 140. Subsequent treatments
are carried out in the vacuum globe box 200. Then, in the vacuum globe box 200,
the alloy powder is passed through sieves 230, of which sieve opening becomes finer
from top to bottom, thereby to obtain a powder having an objective grain size. In
the embodiment, a powder having a grain size of 32µm or less is obtained. And,
thin band or thin wire can be obtained exchanged for the powder.
In order to produce a billet using the alloy powder, a
preliminary compression is carried out using a vacuum hot press apparatus 240 capable
of pressurizing with a pressure of 30 ton.
A copper can 254 is filled with the alloy powder using
the hot press apparatus 240 and then closed with a cap 252. The cap 252 and the
can 254 are weld by a welding machine 256 while rotating on a rotary table 258 to
form a billet 260. The billet 260 is checked for leakage using a vacuum pump connected
thereto via a valve 262. When leakage does not occur, the valve 262 is closed and
the alloy billet 260 together with the container having the closed valve 262 is
get out from the vacuum globe box 200 through an entrance box 2.80.
As shown in Fig.30, the billet 260 is connected to a vacuum
pump for outgassing while being pre-heated in a heating furnace (referring to Fig.
30 (a)). Then, the cap of the billet 260 is compressed and then spot-welded by using
a spot welding machine 340 thereby to isolate the billet 260 from outside (referring
to Fig.30(b)). And, the billet is subjected to an extruding machine 400 together
with the container to form into a final shape (referring to Fig.30(c)). The extruding
machine 400 has characteristics of a main pressure (on a side of a main stem 450)
of 100 ton and a back pressure (on a side of back stem 470) of 20 ton, and can set
an extrusion temperature by heating the container 420 with a heater 410.
The rapid solidified powder of the embodiment is produced
by a high pressure He gas atomizing method as mentioned above. And, a copper can
is filled with the produced powder having a grain size of 32 µm or less and
vacuumed to form a billet. Then, the billet is extruded at extrusion temperature
of 623 to 723K and at an extrusion ratio of 10:1 to solidification form. The extrusion
forming adds pressure and shear to the powder, resulting in obtaining a powder having
compact structure and closed bonding between particles. The forming by rolling or
forging also adds shear to the powder.
According the present embodiment, a high strength and high
toughness magnesium alloy can be provided. The magnesium alloy has a fine grain
structure having an average grain size of 1µm or less.
And, according to the embodiment, material cost of the
rare-earth element can decrease as with Embodiment 15.
(Example)
Hereinafter, preferred examples of the present invention
will be described.
In Example 1, a ternary alloy containing 97 atomic% of
Mg, 1 atomic% of Zn and 2 atomic% of Y is employed.
In Example 2, a ternary Mg97Zn1Dy2
alloy is employed.
In Example 3, a ternary Mg97Zn1Ho2
alloy is employed.
In Example 4, a ternary Mg97Zn1Er2
alloy is employed.
In Example 5, a quaternary Mg96.5Zn1Y1Dy1.5
alloy is employed.
In Example 6, a quaternary alloy containing 96.5 atomic%
of Mg, 1 atomic% of Zn, 1 atomic% of Y and 1 . 5 atomic% of Gd is employed.
In Example 7, a quaternary Mg96.5Zn1Y1Er1.5
alloy is employed.
Each of the magnesium alloy of Examples 5 and 7 is an alloy
to which rare-earth element which forms a long-period stacking ordered structure
phase is added. The magnesium alloy according to Example 6 is an alloy to which
rare-earth element, which forms a long period stacking ordered structure, and another
rare-earth element, which does not form a long period stacking ordered structure,
are added in combination.
In Example 8, a quaternary alloy containing 97.5 atomic%
of Mg, 1 atomic% of Zn, 2 atomic% of Y and 0.5 atomic% of La is employed.
In Example 9, a quaternary alloy containing 97.5 atomic%
of Mg, 0.5 atomic% of Zn, 1.5 atomic% of Y and 0.5 atomic% of Yb is employed.
Each of the magnesium alloys according to Examples 8 and
9 is an alloy to which a rare-earth element, which forms a long period stacking
ordered structure, and another rare-earth element, which does not form a long period
stacking ordered structure, are added in combination.
In Example 10, a quaternary Mg96.5Zn1Y1.5Dy1
alloy is employed.
In Example 11, a quaternary alloy containing 96. 5 atomic%
of Mg, 1 atomic% of Zn, 1.5 atomic% of Y and 1 atomic% of Gd is employed.
In Example 12, a quaternary Mg96.5Zn1Y1.5Er1
alloy is employed.
In Example 13, a ternary alloy containing 96 atomic% of
Mg, 1 atomic% of Zn and 3 atomic% of Y is employed.
In Comparative example 1, a ternary alloy containing 97
atomic% of Mg, 1 atomic% of Zn and 2 atomic% of La is employed.
In Comparative example 2, a ternary alloy containing 97
atomic% of Mg, 1 atomic% of Zn and 2 atomic% of Yb is employed. In Comparative example
3, a ternary alloy containing 97 atomic% of Mg, 1 atomic% of Zn and 2 atomic% of
Ce is employed.
In Comparative example 4, a ternary alloy containing 97
atomic% of Mg, 1 atomic% of Zn and 2 atomic% of Pr is employed.
In Comparative example 5, a ternary alloy containing 97
atomic% of Mg, 1 atomic% of Zn and 2 atomic% of Nd is employed.
In Comparative example 6, a ternary alloy containing 97
atomic% of Mg, 1 atomic% of Zn and 2 atomic% of Sm is employed.
In Comparative example 7, a ternary alloy containing 97
atomic% of Mg, 1 atomic% of Zn and 2 atomic% of Eu is employed.
In Comparative example 8, a ternary alloy containing 97
atomic% of Mg, 1 atomic% of Zn and 2 atomic% of Tm is employed.
In Comparative example 9, a ternary alloy containing 97
atomic% of Mg, 1 atomic% of Zn and 2 atomic% of Lu is employed.
For a reference example, a binary alloy containing 98 atomic%
of Mg and 2 atomic% of Y is employed.
(Structure of Casting Material)
First, ingots having compositions according to Examples
1 to 13, Comparative examples 1 to 9 and the reference example were prepared by
high frequency melting under an Ar gas environment. Then, a sample 10mm in diameter
and 60mm in length was cut out from each of the ingots. And, a structure of each
of the casting samples was observed using SEM and XRD. Photographs of the observed
structures are shown in Figs.1 to 7.
Fig.1 is photographs showing crystal structures according
to Example 1 and Comparative examples 1 and 2. Fig. 2 is a photograph showing a
crystal structure according to Examples 2 to 4. Fig.3 is a photograph showing a
crystal structure according to Examples 5 to 7. Fig. 4 is a photograph showing a
crystal structure according to Examples 8 and 9. Fig.5 is a photograph showing a
crystal structure according to Examples 10 to 12. Fig.6 is photographs showing crystal
structures according to Comparative examples 3 to 9. Fig.7 is a photograph showing
a crystal structure according to the reference example. Fig.10 is a photograph showing
a crystal structure according to Example 13.
As shown in Figs. 1 to 5, the magnesium alloys according
to Examples 1 to 13 have a long period stacking ordered structure crystal formed
therein. On the contrary, as shown in Fig. 1 and Figs. 6 and 7, the magnesium alloys
according to Comparative examples 1 to 9 and the reference example do not have a
long period stacking ordered structure crystal formed therein.
From the observation of Examples 1 to 13 and Comparative
examples 1 to 9, the following facts are confirmed.
In the Mg-Zn-RE ternary casting alloy, a long period stacking
ordered structure is formed therein if RE is Y, Dy, Ho and Er; however, it is not
formed if RE is La, Ce, Pr, Nd, Sm, Eu, Gd and Yb. Gd is slightly different from
La, Ce, Pr, Nd, Sm, Eu and Yb in behavior. So, although a long period stacking ordered
structure is not formed if Gd is added alone (Zn is necessarily added), when Gd
is added together with Y, Dy, Ho and Er which is an element for forming a long period
stacking ordered structure, a long period stacking ordered structure is formed if
an addition amount is 2.5 atomic% (referring to Examples 6 and 11).
And, when each of Yb, Tb, Sm, Nd and Gd is added to a Mg-Zn-RE
(RE=Y, Dy, Ho, Er) alloy at an addition amount of 5.0 atomic% or less, a formation
of a long period stacking ordered structure is not inhibited. When each of La, Ce,
Pr, Eu and Mm is added to a Mg-Zn-RE (RE=Y, Dy, Ho, Er) alloy at an addition amount
of 5.0 atomic% or less, a formation of a long period stacking ordered structure
is not inhibited.
The casting material according to Comparative example 1
has a particle diameter of about 10 to 30µm, the casting material according
to Comparative example 2 has a particle diameter of about 30 to 100 µm and
the casting material according to Example 1 has a particle diameter of about 20
to 60µm. From the observation of these casting materials, a large quantity
of crystallization is formed at grain boundaries. And, from the observation of a
crystal structure of the casting material according to Comparative example 2, fine
precipitation is formed in its particle.
(Vickers Hardness of Casting Material)
Each of the casting materials according to Example 1 and
Comparative examples 1 and 2 was evaluated in Vickers hardness according to a Vickers
hardness test. As a result, the casting material of Comparative example 1 has a
Vickers hardness of 75Hv, the casting material of Comparative example 2 has a Vickers
hardness of 69Hv and the casting material of Example 1 has a Vickers hardness of
79Hv.
(ECAE Working)
Each of the casting materials of Example 1 and Comparative
Examples 1 and 2 was subjected to an ECAE working at 400°C. The ECAE working
was carried out such that the sample was rotated every 90° in the length direction
thereof every pass for introducing strain therein uniformly. A number of the pass
was 4 times and 8 times. And, a working rate was constant at 2mm/sec.
(Vickers Hardness of ECAE Worked Material)
Each of the casting material subj ected to the ECAE working
was evaluated in Vickers hardness according to a Vickers hardness test. As a result
of 4 times of the ECAE working, the casting material of Comparative Example 2 has
a Vickers hardness of 76Hv. On the contrary, the casting material of Example 1 has
a Vickers hardness of 96Hv. So, each of the casting material subjected to the ECAE
working is improved in Vickers hardness to 10 to 20% higher than that before the
ECAE working. The casting material subjected to the ECAE working for 8 times shows
little difference in hardness from the casting material subjected to the ECAE working
for 4 times.
(Crystal Structure of ECAE Worked Material)
Composition of each of the casting sample subjected to
the ECAE working was observed using SEM and XRD. In the casting materials of Comparative
examples 1 and 2, crystallization formed at grain boundaries is decoupled into order
of several microns to be dispersed uniformly therein. On the contrary, in the casting
materials of Example 1, crystallization formed at grain boundaries is not decoupled
and is applied with shear while matrix and consistency being maintained. The casting
material subjected to the ECAE working for 8 times shows little difference in structure
from the casting material subjected to the ECAE working for 4 times.
(Tensile Strength of ECAE Worked Material)
The ECAE worked casting materials were evaluated in tensile
strength according to a tensile strength test. The tensile strength test was carried
out under an initial strain rate of 5×10-4/sec in the parallel direction
to a pushing direction. In a case of 4 times of the ECAE working, the casting materials
according to Comparative examples 1 and 2 have a yield strength of 200Mpa or lower
and an elongation of 2 to 3%. On the contrary, the casting materials according to
Example 1 have a yield strength of 260Mpa and an elongation of 15%. This shows an
excellent performance as compared with a casting material having a yield strength
10OMPa under proof stress of 0.2% and an elongation of 4%.
(Heat Treatment of ECAE Worked Material)
The casting material subjected to the ECAE working for
4 times was maintained at a constant temperature of 225°C and then a relation
between the retention period and change in hardness was evaluated. As a result,
in the casting material of Example 1, the heat treatment of 225°C further improves
hardness such that a yield strength according to a tensile test can increase to
300MPa.
When a treating temperature of the ECAE working for the
casting material of Example 1 decreases down to 375°C (that is, when the casting
material of Example 1 is subjected to the ECAE working for 4 times at a temperature
of 375°C, not 400°C), the ECAE worked product of Example 1 have a yield
strength of 300MPa and an expansion of 12%. And, a heat treatment of the ECAE worked
casting material at 225°C can improve a yield strength according to a tensile
test up to 320MPa.
(Extrusion of Casting Alloy of Example 13)
The casting alloy of Example 13 is a ternary alloy containing
96 atomic% of Mg, 1 atomic% of Zn and 3 atomic% of Y. which has a long period stacking
ordered structure. The casting alloy was extruded at a condition of a temperature
of 300°C, a cross section reduction rate of 90% and an extrusion speed of 2.5mm/sec.
The resultant extruded magnesium alloy has a yield strength of 420MPa and an expansion
of 2% at room temperatures.
(Property of Extruded Casting Alloys of Examples 13 to 34 and
Comparative Examples 11 to 13)
Mg-Zn-Y alloys having compositions shown in Tables 1 and
2 were cast to form casting products of the alloys. And, the each casting products
were extruded at extrusion temperatures and extrusion rates shown in Tables 1 and
2. The extruded casting products were evaluated in 2% proof stress (yield strength),
tensile strength and elongation according to a tensile test at temperatures shown
in Tables 1 and 2. Also, hardness (Vickers hardness) of the extruded product was
evaluated. The measurements are shown in Tables 1 and 2.
Table 1
Mg-Zn-Y alloy
Composition (atomic%)
Extrusion temperature (°C)
Extrusion ratio
Test temperature (°C )
0.2% proofstress (MPa)
Tensil strength (MPa)
Elongation (%)
Hardness (Hv)
Mg
zn
y
Example 13
96
1
3
300
10
room temperature
418
1
Example 14
97.5
1
1.5
350
10
room temperature
367
380
1.3
Example 15
97
1
2
350
10
room temperature
375
420
4
97
Example 16
97
1
2
400
10
room temperature
330
385
7
91
Example 17
96.5
1
2.5
350
10
room temperature
335
380
7
Example 18
96
1
3
350
10
room temperature
335
408
8
Example 19
96.5
1.5
2
350
10
room temperature
389
399
0.7
Example 20
96.5
1.5
2
400
10
room temperature
360
434
5
Example 21
96
2
2
350
10
room temperature
389
423
5
Example 22
96
2
2
400
10
room temperature
326
361
4
Example 23
95.5
2.5
2
350
10
room temperature
385
415
3.7
Example 24
95.5
2.5
2
400
10
room temperature
345
369
6
Example 25
94
3
3
450
10
room temperature
430
487
7.5
Example 26
94
3
3
450
10
200
287
351
21.1
Example 27
93.5
3.5
3
350
10
room temperature
425
490
7.5
Example 28
94
2.5
3.5
450
10
room temperature
360
442
9
Example 29
93.5
3
3.5
450
10
room temperature
440
492
6
Table 2
Mg-Zn-Y alloy
composition (atomic%)
Extrusion temperature (°
C)
Extrusion ratio
Test temperature (° C)
0.2% proof stress (MPa)
Tensil strength (MPa)
Elongation (%)
Mg
Zn
Y
Example 30
93.5
2.5
4
450
10
room temperature
370
450
6
Example 31
93.5
2.5
4
450
10
200
286
385
18.1
Example 32
97
1
2
350
2.5
room temperature
273
325
0.5
Example 33
97.5
0.5
2
350
10
room temperature
310
350
6
Example 34
97.5
0.5
2
400
10
room temperature
270
300
2
Comparative Example 11
97
1
2
350
1
room temperature
77
100
1.5
Comparative Example 12
96
2
2
350
1
room temperature
80
104
1.5
Comparative Example 13
95
4
1
400
10
room temperature
260
325
9.8
*Extrusion ratio of 1 shows
a hot pressed material at 1GPa.
Tables 1 and 2 show results of the tensile test and the
hardness test at room temperatures of the Mg-Zn-Y alloy casting products prepared
by changing addition amounts of Z and Y, to which an extrusion was subjected under
conditions of temperatures, extrusion rates shown in Tables 1 and 2 and an extrusion
speed of 2.5mm/sec.
The extrusion rate of 1 shown in Table 2 means hot press
in which pressure of 1GPa is applied for 60 seconds and a working rate is 0.
The magnesium alloy casting product having a composition
of Example 29 is shown in Fig. 11
(Property of Extruded Casting Alloys of Examples 35 to 40 and
Comparative Examples 14 to 18)
Ternary magnesium alloys having compositions shown in Table
3 were cast to form casting products of the alloys. And, the casting products were
extruded at extrusion temperatures and extrusion rates shown in Table 3. The extruded
casting products were evaluated in 0.2% proof stress (yield strength), tensile strength
and elongation according to a tensile test at temperatures shown in Table 3. Also,
hardness (Vickers hardness) of the extruded product was evaluated. The measurements
are shown in Table 3.
Table 3
Mg-Zn-X alloy
Composition (atomic%)
Extrusion temperature (°C)
Extrusion ratio
Test temperature (°C)
0.2% proof stress (MPa)
Tensil strength (MPa)
Elongation (%)
Hardness (Hv)
Example 35
Mg-1Zn-2Dy
350
10
room temperature
350
385
7.5
93
Example 36
Mg-1Zn-2Dy
400
10
room temperature
325
365
6.5
94
Example 37
Mg-1Zn-2Y(H.T)
350
10
room temperature
355
410
6
94
Example 38
Mg-1Zn-2Dy(H.T)
350
10
room temperature
350
385
4
96
Example 39
Mg-1Zn-2Er-(H.T)
350
10
room temperature
355
380
3
90
Example 40
Mg-1Zn-2Ho(H.T)
350
10
room temperature
350
385
3
93
Comparative Example 14
Mg-1Zn-2La
350
10
room temperature
-
210
0
-
Comparative Example 15
Mg-1Zn-2La
400
10
room temperature
240
245
0.5
83
Comparative Exampke 16
Mg-1Zn-2Yb
350
10
room temperature
-
300
0
84
Comparative Example 17
Mg-1Zn-2Yb
400
10
room temperature
250
260
7
81
Comparative Exampke 18
Mg-1Zn-2Srn(H.T)
350
10
room temperature
-
350
0
95
*(H.T): Extruded castnig product
after heat treatment at 500° C for 10 hours.
Mg97-Zn1-RE2 casting product
was extruded at various extrusion temperatures, an extrusion rate of 10 and an extrusion
speed of 2.5mm/s. And, the extruded casting products were evaluated in tensile strength
and hardness (Vickers hardness) under room temperatures. The results are shown in
the table. In the table, alloys noted with (H.T) shows are those which are subjected
to a homogenized heat treatment at 500°C for 10 hours before the extrusion
working.
(Property of Extruded Casting Alloys of Examples 41 to 46)
casting material of a magnesium alloy having compositions
shown in Table 4 were prepared. And, the casting materials were extruded at an extrusion
temperatures and an extrusion rates shown in Table 4. The extruded casting materials
were evaluated in a 2% proof stress (a yield strength), a tensile strength and an
elongation according to a tensile test at temperatures shown in Table 4. The measurements
are shown in Table 4.
Table 4
Mg-Zn-Y-X based alloy
Compositions (atomic%)
Extrusion temperature (°C)
Extrusion ratio
Test temperature Test temperature (°C)
0.2% proof stress (MPa)
Tensil strength (MPa)
Elongation (%)
Example 41
Mg-2Zn-2Y-0.2Zr
350
10
room temperature
405
465
8.5
Example 42
Mg-2Zn-2Y-0.2Zr
400
10
room temperature
425
471
8.5
Example 43
Mg-2Zn-2Y-0.2Zr
350
10
room temperature
418
469
6
Example 44
Mg-2Zn-2Y-1.3Ca
350
10
room temperature
a406
417
1.3
Example 45
Mg-2Zn-2Y-1Si
350
10
room temperature
370
409
6
Example 46
Mg-2Zn-2Y-0.5Ag
350
10
room temperature
401
441
6
Examples 41 and 42 in Table 4 are Mg-Zn-Y-X based alloy
casting products which were extruded at various extrusion temperatures, an extrusion
rate of 10 and an extrusion speed of 2. 5mm/s. And, the extruded casting products
were evaluated according to a tensile test and a hardness test under room temperatures.
The results are shown in Table 4. Examples 43 to 46 in Table 4 are Mg-Zn-Y-X based
alloy casting products which were subjected to a heat treatment at 500°C for
10 hours and then extruded at a temperature of 350°C, an extrusion rate of
10 and an extrusion speed of 2.5mm/s. And, the extruded casting products were evaluated
according to a tensile strength and a hardness test under room temperatures. The
results are shown in Table 4.
Fig.31(A) is a photograph showing a crystal structure of
Mg-Zn2-Y2-Zr0.2 casting product of Example 43 and
Fig. 31 (B) is a photograph showing a crystal structure of Mg-Zn2-Y2
casting product
As can be seen in Figs. 31 (A) and 31(B), the casting product
of Example 43, to which Zn is added, has the following characteristics; precipitate
of compound such as Mg3Zn3RE2 is suppressed; formation
of long-period stacking ordered structure phase is promoted; and the crystal is
made into a fine grained structure. And, as shown in Table 4, the magnesium alloy
to which Zr is added has higher yield strength without losing ductility compared
with the magnesium alloy to which Zr is not added. This is because formation of
long-period stacking ordered structure phase is promoted.
(Property of Extruded Casting Alloys of Examples 47 to 62)
Each of ingots of the Mg-Zn-Y alloys having compositions
shown in Table 5 was melt using a high frequency melting furnace at an Ar gas environment
and then cut into a number of chip-shaped casting products. And, after charging
the chip-shaped casting products in a can made of copper, the can containing the
casting product chips was subjected to a heat vacuum degasification at 150°C
and sealed. Then, the can in which the chip-shaped casting products were contained
was extruded at extrusion temperatures and extrusion ratios shown in Table 5. Then,
the resultant extruded materials were evaluated in a 0.2% proof strength (a yield
strength), a tensile strength and an elongation by a tensile test at temperatures
shown in Table 5. Also, a hardness (a Vickers hardness) of each of the extruded
materials was evaluated. The measurements are shown in Table 5.
Table 5
Mg-Zn-Y alloy chip
Composition (atomic%)
Extrusion temperature (°
C)
ratio
Test temperature (°C)
0.2% proof stress (MPa)
Tensil (MPa)
Elongation strength (%)
Hardness (%) (Hv)
Mg
Zn
Y
Example 47
97.5
1
1.5
350
10
room temperature
450
483
1
113
Example 48
97.5
1
1.5
400
10
room temperature
390
420
6
108
Example 49
97
1
2
350
10
room temperature
442
464
5
105
Example 50
97
1
2
400
10
room temperature
400
406
10
112
Example 51
96.5
1
2.5
350
10
room temperature
373
401
13
105
Example 52
96.5
1
2.5
400
10
room temperature
371
394
14
105
Example 53
96
1
3
350
10
room temperature
400
424
6.5
115
Example 54
96
1
3
400
10
room temperature
375
417
8
113
Example 55
96
1
3
350
5
room temperature
440
452
0.5
122
Example 56
96
1
3
350
15
room temperature
362
408
4.5
113
Example 57
97.5
0.5
2
350
10
room temperature
332
355
10
Example 58
97.5
0.5
2
400
10
room temperature
330
360
11
103
Example 59
96.5
1.5
2
350
10
room temperature
490
500
3
Example 60
96.5
1.5
2
400
10
room temperature
445
455
7
112
Example 61
96
2
2
350
10
room temperature
497
500
4
114
Example 62
96
2
2
400
10
room temperature
433
450
9
103
Table 5 shows results of the tensile test and ha hardness
test at room temperatures of the Mg-Zn-Y alloy casting materials prepared by changing
addition amounts of Z and Y, to which an extrusion was subjected at a temperature
and a extrusion rate shown in Table 5 and at an extrusion speed of 2.5mm/sec for
solidification.
(Structures of Casting Products and Materials subjected to Heat
Treatment after Extrusion Working)
First, an ingot having a composition according to Example
68 (Mg96.5Zn1Gd2.5) was prepared by high frequency
melting under an Ar gas environment. Then, the ingot was cut into samples 10mm in
diameter and 60mm in length. And, a structure of the sample was observed using SEM
(Scanning Electron Microscope) . And, the samples were subjected to a heat treatment
at each temperature of 200°C, 300°C and 500°C. Then, a structure
of each sample was observed using SEM. Photographs of the observed structures are
shown in Figs.12 to 15. Fig.12 is a photograph showing a crystal structure of a
casting product which is not subjected to the heat treatment. Fig.13 is a photograph
showing a crystal structure of a casting product which is subjected to the heat
treatment at 200°C. Fig.14 is a photograph showing a crystal structure of a
casting product which is subjected to the heat treatment at 300°C. Fig. 15
is a photograph showing a crystal structure of a casting product which is subjected
to the heat treatment at 500°C.
As shown in Fig. 12, the casting product before subjecting
to the heat treatment does not have long-period stacking ordered structure phase
formed therein; as shown in Figs.13 to 15, the casting products, which are subjected
to the heat treatment, have long-period stacking ordered structure phase formed
therein.
Next, an ingot having each composition according to Example
73 (Mg97.5Zn0.5Gd2), Example 66 (Mg97
Zn1Gd2), Example 67 (Mg96.75Zn1Gd2.25)
and Example 68 (Mg96.5Zn1Gd2.5) was prepared by
high frequency melting under an Ar gas environment. Then, each ingot was cut into
samples 10mm in diameter and 60mm in length. The samples were subjected to a heat
treatment at 773K. And, a structure of the samples were observed using SEM. Photographs
showing a structure of each sample are shown in Figs.16 to 19.
Fig. 16 (a) is a photograph showing a crystal structure
of a magnesium alloy of Example 73 before subjecting to the heat treatment; and
Fig. 16 (b) is a photograph showing a crystal structure of a magnesium alloy of
Example 73 after subjecting to the heat treatment. Fig.17(a) is a photograph showing
a crystal structure of a magnesium alloy of Example 66 before subjecting to the
heat treatment; and Fig. 17 (b) is a photograph showing a crystal structure of a
magnesium alloy of Example 66 after subjecting to the heat treatment. Fig. 18(a)
is a photograph showing a crystal structure of a magnesium alloy of Example 67 before
subjecting to the heat treatment; and Fig.18(b) is a photograph showing a crystal
structure of a magnesium alloy of Example 67 after subjecting to the heat treatment.
Fig.19(a) is a photograph showing a crystal structure of a magnesium alloy of Example
68 before subjecting to the heat treatment; and Fig.19 (b) is a photograph showing
a crystal structure of a magnesium alloy of Example 68 after subjecting to the heat
treatment.
As shown in the figures, it is found that by subjecting
the casting product having no long-period stacking ordered structure phase formed
therein to a heat treatment, a long-period stacking ordered structure phase is formed
in the product.
(Structures of Extruded Products of Casting Products after Subjecting
to Heat Treatment)
Alloys of Examples 66, 67, 68 and 73 in which casting products
are subjected to a heat treatment at 500°C were extruded at a temperature of
350°C and at an extrusion ratio of 10. Then, a structure of each extruded product
was observed using SEM. Photographs of the observed structures are shown in Figs.20
to 23. Fig.20 is a photograph showing a crystal structure of the alloy of Example
66. Fig.21 is a photograph showing a crystal structure of the alloy of Example 67.
Fig. 22 is a photograph showing a crystal structure of the alloy of Example 68.
Fig.23 is a photograph showing a crystal structure of the alloy of Example 73.
As shown in Figs. 20 to 23, it is found that the magnesium
alloy after subjecting to the extrusion working has long-period stacking ordered
structure phase a part of which is bend or flexed. And, it is also found that the
long-period stacking ordered structure phase has a dislocation density at least
one-digit smaller than the hcp-Mg phase.
And, as shown in Fig.26, it is also found that the magnesium
alloy contains Mg3Gd compound.
And, as shown in Fig.27, it is found that the hcp-Mg phase
in the magnesium alloy does not have twin crystal or has twin crystal smaller than
the hcp-Mg phase in a conventionally magnesium alloy which subjected to a plastic
working. So, it seems that the magnesium alloy hardly causes twin crystal transformation
at the transformation.
And, the magnesium alloys of Examples have a crystal size
of 100nm to 500 µm. When the alloy has a small crystal size as less than 100nm,
a long-period stacking ordered structure phase is not bend.
(Mechanical Property of Extruded Products of Casting Products
after Subjecting to Heat Treatment)
An ingot having each composition according to Examples
63 to 76 shown in Table 6 was prepared by high frequency melting under an Ar gas
environment. Then, each of the ingots was cut into a sample 10mm in diameter and
60mm in length. And, the samples were subjected to a heat treatment at 773K (500°C)
for 10 hours. And then, the samples were extruded at 623K and an extrusion ratio
of 10. The extruded casting products were evaluated in yield strength, maximum strength
and elongation according to a tensile test at room temperatures. The measurements
are shown in Table 6.
Table 6
Composition (atomic%)
Yield strength (MPa)
Maximum strength (Mpa)
Elongation (%)
Example 63
Mg98Zn1Gd1
329
332
3.9
Example 64
Mg97.5Zn1Gd1.5
301
334
10.6
Example 65
Mg98.25Zn1Gd1.75
332
355
7.5
Example 66
Mg97Zn1Gd2
369
405
9.4
Example 67
Mg96.75Zn1Gd2.25
329
379
7.3
Example 68
Mg96.5Zn1Gd2.5
351
391
7.2
Example 69
Mg96Zn1Gd3
368
411
6.5
Example 70
Mg95.5Zn1Gd3.5
375
406
6.4
Example 71
Mg95Zn1Gd4
382
397
3.9
Example 72
Mg94.5Zn1Gd4.5
356
409
3.5
Example 73
Mg97.5Zn0.5Gd2
309
353
7.9
Example 74
Mg96.5Zn1.5Gd2
306
340
9.4
Example 75
Mg96Zn2Gd2
283
319
14
Example 76
Mg95.5Zn2.5Gd2
269
300
13.3
Extrusion temperature: 623K
Extrusion ratio: 10
Test temperature: room temperature
The extruded products of Examples 63, 66, 69, 71, 73 and
75 were evaluated in yield strength, maximum strength and elongation according to
a tensile test at 473K. The measurements are shown in Table 7.
Table 7
Composition (atomic%)
Yield strength (MPa)
Maximum strength (Mpa)
Elongation (%)
Example 63
Mg98Zn1Gd1
243
258
13
Example 66
Mg97Zn1Gd2
297
337
12,7
Example 69
Mg96Zn1Gd3
323
370
9.4
Example 71
Mg95Zn1Gd4
324
357
17.2
Example 73
Mg97.5Zn0.5Gd2
278
320
4.4
Example 75
Mg96Zn2Gd2,
241
286
8.2
Extrusion temperature: 623K
Extrusion ratio: 10
Test temperature: 473K
An ingot having a composition according to Comparative
Example 19 shown in Table 8 was prepared by high frequency melting under an Ar gas
environment. Then, the ingot cut into a sample 10mm in diameter and 60mm in length.
The sample was evaluated in yield strength, maximum strength and elongation according
to a tensile test at room temperatures. The measurements are shown in Table 8.
Table 8
Composition (atomic%)
Yield strength (MPa)
Maximum strength (Mpa)
Elongation (%)
Comparative Example 19
Mg97Zn1Gd2
288
323
7.7
Extrusion temperature: 623K
Extrusion ratio: 10
Test temperature: room temperature
The magnesium alloy of Comparative Example 19 has the same
composition as the magnesium alloy of Example 66 . However, the magnesium alloy
of Comparative Example 19 which was subjected to an extrusion working, without subjecting
to a heat treatment, after casting has yield strength of 288Mpa, maximum strength
of 323Mpa and elongation of 7.7%; the magnesium alloy of Example 66 which was subjected
to a heat treatment after casting and then an extrusion working has yield strength
of 369MPa, maximum strength of 405MPa and elongation of 9.4%. The results show that
the heat treatment increased yield strength by 5%, maximum strength by 25% and elongation
by 22%. So, by subjecting the magnesium alloy to a heat treatment so as to form
a long-period stacking ordered structure phase and then to an extrusion working
so that a part of the long-period stacking ordered structure phase is bend or flexed,
a high strength and high toughness magnesium alloy can be obtained.
The bend or flexed long-period stacking ordered structure
phase contains random grain boundaries which improve strength of the magnesium alloy
and prevents grain boundary slipping at high temperature. Accordingly, as shown
in Table 7, a high strength can be achieved at high temperatures.
And, it is probable that a high density dislocation of
a hcp structured magnesium phase strengthens a magnesium alloy; while a small density
dislocation of a long period stacking ordered structure phase improves ductility
and strength of the magnesium alloy.
The above results show that in another metal, not only
a magnesium alloy, formation of a long-period stacking ordered structure phase in
the metal and subjecting the metal to a plastic working such that at least a part
of the long-period stacking ordered structure phase is bend or flex can make the
alloy to have a high strength and a high toughness.
As shown in Table 6, Mg-Zn-Gd alloys of Examples 63 to
74 have yield strength larger than that of Comparative Example 19, for example 290MPa
or more, and elongation of 3% or more. Examples shown in Table 7 have yield strength
of 200MPa or more at 473K. Accordingly, the alloys of Examples 63 to 74 have sufficient
mechanical strength for putting into practical use. So, when a magnesium alloy has
the following compositions, the magnesium alloy can have high strength and high
toughness.
The high strength and high toughness magnesium alloy contains
Zn in an amount of '"a" atomic%, Gd in an amount of "b" atomic% and a residue consisting
of Mg, wherein "a" and "b" satisfy the following expressions (1) to (3):
and
more preferably the following expressions (1') to (3'):
and
The high strength and high toughness magnesium alloy may
contain at least one element selected from the group consisting of Yb, Tb, Sm and
Nd in a total amount of "c" atomic%, wherein "c" satisfies the following expressions
(4) to (5) :
and
Containing these elements can make the magnesium alloy
to have a fine-grained structure and promote precipitation of intermetallic compounds.
The high strength and high toughness magnesium alloy may
contain at least one element selected from the group consisting of La, Ce, Pr, Eu
and Mm in a total amount of "c" atomic%, wherein "c" satisfies the following expressions
(4) to (5):
and
Containing these elements can make the magnesium alloy
to have a fine-grained structure and promote precipitation of intermetallic compounds.
The high strength and high toughness magnesium alloy may
contain at least one element selected from the group consisting of Yb, Tb, Sm and
Nd in a total amount of "c" atomic% and at least one element selected from the group
consisting of La, Ce, Pr, Eu and Mm in a total amount of "d" atomic%, wherein "c"
and "d" satisfy the following expressions (4) to (6):
and
Containing these elements can make the magnesium alloy
to have a fine-grained structure and promote precipitation of intermetallic compounds.
The high strength and high toughness magnesium alloy may
contain at least one element selected from the group consisting of Al, Th, Ca, Si,
Mn, Zr, Ti, Hf, Nb, Ag, Sr, Sc, B and C in a total amount of larger than 0 atomic%
to 2.5 atomic% or less.
These elements can improve characteristics other than the
strength and the toughness which are being kept high. For instance, a corrosion
resistance and an effect for forming a fine-grained crystal structure are improved.
(Structures of Extruded Products of Casting Products after Subjecting
to Heat Treatment)
Mg96.5-Zn1-Gd2.5 casting
product (Example 68) was subjected to a heat treatment at a temperature of 500°C
and then extruded at temperature of 350°C, an extrusion ratio of 10 and an
extrusion speed of 2.5m/s. The extruded product was observed using TEM (transmission
electron microscope) . The observed crystal structure of the extruded product is
shown in photograph of Fig.27.
As shown in Fig.27, in the magnesium alloy after subjecting
to an extrusion working, a structure in which a part of long-period stacking ordered
structure phase is bend or flexed continuously at any angle is observed.
(Structure of Casting Product after subjecting to Extrusion
Working)
Mg96-Zn2-Y2 casting product
(Example 21) was extruded at a temperature of 350°C, an extrusion ratio of
10 and an extrusion speed of 2.5m/s. The extruded product was observed using SEM.
The observed crystal structure of the extruded product is shown in photograph of
Fig.28.
As shown in Fig.28, in the magnesium alloy after subjecting
to an extrusion working, a structure in which a part of long-period stacking ordered
structure phase is bend or flexed continuously at any angle is observed. And, at
least a part of the long-period stacking ordered structure phase exists in a layer
(lamellar) form with a 2H structure Mg phase. The 2H structure shows a hexagonal
close-packed structure (HCP) . The long-period stacking ordered structure phase
is a structure in which base atomic layers in the HCP structure are repeatedly arranged
in the normal direction to the base with long period. Original HCP magnesium metal
has two periodic structure (2H) .
The present invention is not limited solely to the embodiments
specifically exemplified above and various variations may be contained without departing
from the scope of the invention.
The long-period stacking ordered structure phase may have
a density modulation. The density modulation shows a phenomenon in which a concentration
of solute element changes periodically every atomic layer.