JPH0499244A - High strength magnesium base alloy - Google Patents

Abstract

PURPOSE:To manufacture an Mg base alloy excellent in corrosion resistance as well as hardness and strength by superrapidly cooling the molten metal of an alloy having a specified compsn. essentially consisting of Mg. CONSTITUTION:The molten metal 3 of an Mg base alloy having a compsn. expressed by general formulae [I] to [IV] [in the formulae, X denotes >= two kinds among Cu, Ni, Sn and Zn, M denotes one or >= two kinds among Al, Si and Ca and Ln denotes one or >= two kinds among Y, La, Ce, Nd and Sm or misch metal, and as for the value of (a) to (e), by atomic %, 40<=a<=95, 5<=b<=60, 1<=c<=35, 1<=d<=25 and 3<=e<=25 are regulated] is poured into a silica tube 1, is dropped from a small opening 5 at the lower part on a rapidly rotating cooling roll 2 made of copper and is solidified into the shape of a thin sheet 4. The Mg base alloy constituted of a crystalline phase of which various intermetallic compounds are finely dispersed into an Mg matrix and an amorphous phase contg. Mg and other incorporated elements and excellent in hardness, strength and corrosion resistance can be manufactured.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a magnesium-based alloy that has excellent hardness and strength as well as excellent corrosion resistance.

[Prior Art] Conventionally, this type of amorphous alloy has been disclosed in Japanese Patent Application No. 1-179.
The amorphous magnesium-based alloy described in No. 139 has been applied for, but all of them are aimed at forming an amorphous single phase in order to promote high strength.

[Problems to be Solved by the Invention] However, the amorphous magnesium-based alloy described in the above-mentioned Japanese Patent Application No. 1-179] is an excellent alloy exhibiting high strength and high hardness, and has high strength. Although it is an excellent material,
By focusing on the ratio of amorphous phase to crystalline phase in the alloy material, there is still room for further improvement in strength and hardness.

In view of the above, an object of the present invention is to provide a magnesium-based alloy that further improves hardness and strength by focusing on the amorphous phase and the crystalline phase.

[Means for Solving the Problems] The present invention has the following general formula: M g -X b [However, X; Cu SN t s S n SZ
two or more elements selected from n, a and b have a composition shown in atomic percent as follows: 40≦a≦95 5≦b≦60], and the matrix element and/or the above elements are present in the matrix of Mg. A high-strength magnesium-based alloy consisting of a crystalline phase formed by finely dispersing various intermetallic compounds and an amorphous phase containing Mg elements and M elements and forming a matrix, A high-strength magnesium alloy characterized in that the crystalline phase and the amorphous phase contain a large volume fraction of the crystalline phase.

Or general formula: Mg, a, cSd has a composition expressed as 40≦a≦95 1≦C≦35 1≦d≦25 in atomic percent, and contains various metals composed of the matrix element and/or the above elements in the Mg matrix. A crystalline phase composed of finely dispersed intermediate compounds and M
A high-strength magnesium-based alloy consisting of an amorphous phase containing G element and M element and constituting a matrix, the crystalline phase and the amorphous phase containing a large amount of the crystalline phase in terms of volume ratio. A high-strength magnesium alloy that is characterized by its properties.

or general formula +Mg, )(, ln.

[However, X: one or more elements selected from Cu, Ni, Sn, and Zn; Ln: Y.

Mitsushmetal (Mm) is an aggregate of one or more elements selected from La, Ce, Nd, and Sm, or rare earth elements aSc, e is atomic percent 40≦a≦95 1≦C≦35 3≦ e≦25], and a crystalline phase composed of a matrix element and/or various intermetallic compounds composed of the above elements finely dispersed in a matrix of Mg;
A high-strength magnesium-based alloy consisting of an amorphous phase containing G element and M element and constituting a matrix, the crystalline phase and the amorphous phase containing a large amount of the crystalline phase in terms of volume ratio. A high-strength magnesium alloy that is characterized by its properties.

Furthermore, the general formula + M, g, X eMa L n
.

[However, X: one or more elements selected from Cu, Ni, and 5nSZn, M: one or more elements selected from Al, Sl, and Ca, L n : Y s
1 selected from L a SCe SN d % S m
Mitsushmetal (M m ), which is a species or an aggregate of two or more elements or rare earth elements, has a composition shown as follows: 40≦a≦95 1≦C≦35 1≦d≦25 3≦e≦25], A crystalline phase constituted by finely dispersing matrix elements and/or various intermetallic compounds constituted by the above elements in a matrix of Mg;
A high-strength magnesium-based alloy consisting of an amorphous phase containing G element and M element and constituting a matrix, the crystalline phase and the amorphous phase containing a large amount of the crystalline phase in terms of volume ratio. This is a high-strength magnesium alloy that is characterized by its properties.

Among the elements shown in the above composition, La5Ce, Nd, Sm
Mitsushmetal (
Mm).

In addition, Mm here is Ce40~50%, L a 2
0-25%, the remainder consisting of other rare earth elements, with acceptable impurities (Mg, AISS i.

It is a complex containing Fe, etc.). Mm can be substituted with one of the other Ln elements at a ratio of approximately 1:1 (atomic %), is inexpensive, and has a great economical effect as a source of the actual alloying element Ln.

The magnesium-based alloy of the present invention can be obtained by rapidly solidifying a molten alloy having the above composition using a liquid quenching method. This liquid quenching method refers to a method of rapidly cooling a molten alloy, and for example, a single roll method, a twin roll method, a spinning method in a rotating liquid, etc. are particularly effective. A cooling rate on the order of seconds is obtained. To produce a ribbon material by this single roll method, double roll method, etc., a diameter of approximately 300 to 1100 D is passed through the nozzle hole.
Diameter 30-30 rotating at a constant speed in the range of Orp.
The molten metal is spouted onto a roll made of copper or steel, for example, 00a+a+.

This makes the width about 1 to '300 tatr and the thickness about 5
Various ribbon materials with a length of ~50071 m can be easily obtained. In addition, in order to produce a fine wire material by spinning in a rotating liquid, about 50~
A fine wire material can be easily obtained by spouting the molten metal into a solution refrigerant layer with a depth of about 1 to 10 cm held by centrifugal force in a drum rotating at 500 rpm. At this time, the angle between the molten metal spouted from the nozzle and the surface of the solution refrigerant is approximately 60
~90 degrees, the relative velocity ratio between the jetted molten metal and the solution refrigerant surface is approximately 0.
It is preferable that it is 7-0.9.

The alloy of the present invention is produced using the same method as above, only the cooling rate is slightly higher than the above, to first obtain an amorphous alloy, which is then heated near the crystallization temperature (crystallization temperature ±100°C) to crystallize it. It can also be obtained by converting In some alloys, crystallization can be performed at a temperature lower than 100° C. below the crystallization temperature.

In addition, a thin film can be obtained by a sputtering method, and a rapidly cooled powder can be obtained by various atomizing methods such as a high-pressure gas blowing method, a spray method, a mechanical alloying method, a mechanical blinding method, etc., without using the above-mentioned method.

In the magnesium-based alloy of the present invention represented by the general formula of claim (1) above, a is 40 to 95 in atomic percent.
% range and b to a range of 5 to 60%, respectively, because if it deviates from these ranges, it becomes difficult to form a supersaturated solid solution exceeding the solid solubility limit, and it becomes difficult to become amorphous. In addition, it is impossible to obtain an alloy having the characteristics of the present invention using industrial quenching means such as the above-mentioned liquid quenching.

In the magnesium-based alloy of the present invention represented by the general formula of claim (2) above, a is in the range of 40 to 95% in atomic %, C is in the range of 1 to 35%, and d is in the range of 1 to 25%. The reason for this limitation is that if it deviates from these ranges, it becomes difficult to form a supersaturated solid solution that exceeds the solid solubility limit, and it becomes difficult to become amorphous. This is because it becomes impossible to obtain an alloy having the characteristics of the present invention.

Further, in the magnesium-based alloy of the present invention represented by the general formula of claim (3) above, a is 96 and a is 40 to 95.
%, C to 1 to 35%, and e to 3 to 25%.As mentioned above, if it deviates from these ranges, it becomes difficult to form a supersaturated solid solution that exceeds the solid solubility limit. This is because the alloy becomes difficult to partially become amorphous, making it impossible to obtain an alloy having the characteristics aimed at by the present invention by industrial quenching means such as the liquid quenching described above.

Further, in the magnesium-based alloy of the present invention represented by the general formula of claim (4) above, a is 40 to 95% in atomic %.
, C 1-35%, d i -25%, e 3-25%
The reason for limiting each range to these ranges is that, as mentioned above, if it deviates from the range, it becomes difficult to form a supersaturated solid solution that exceeds the solid solubility limit, and it becomes difficult to become amorphous. This is because an alloy having the desired characteristics of the present invention cannot be obtained using industrial quenching means.

Element X is an element selected from CuSNi and 5nSZn, and under the conditions for producing the alloy of the present invention, it has an excellent effect of stabilizing the fine crystalline phase and improving the ability to form an amorphous phase. In addition, it has the effect of improving strength while maintaining malleability.

In addition, the M element is an element selected from AI, Si, and Ca, and in the fine crystalline phase of the present invention, it forms a stable or metastable intermetallic compound with the magnesium element and other additive elements, and the M element is an element selected from AI, Si, and Ca. It is uniformly and finely dispersed in the matrix (α phase), significantly improving the hardness and strength of the alloy, and suppressing the coarsening of fine crystals at high temperatures.
Provides heat resistance. The amorphous phase provides amorphous stability at relatively high temperatures. Among the above elements, A
I, Ca elements have the effect of improving corrosion resistance, and S
The i element has the effect of improving the flowability of the molten alloy.

The Ln element is Mm, which is an element selected from Y, La, Ce, Nd, and Sm, or an aggregate of rare earth elements.
- Further stabilizes the microstructure by adding it to the M system,
Enables greater hardness improvement. In the amorphous phase, by making it coexist with the above-mentioned X element, it exhibits the effect of improving the ability to form a more excellent amorphous phase.

The magnesium-based alloy of the present invention has a temperature near the crystallization temperature (Tx
Since it exhibits a superplastic phenomenon at temperatures (±100°C), it can be easily processed by extrusion, press working, hot forging, etc.

Therefore, the magnesium-based alloy of the present invention obtained in the form of a ribbon, wire, plate or powder has a TX ±1.00
Bulk materials can be manufactured by subjecting the material to extrusion, press working, hot forging, etc. in the temperature range of °C.

Furthermore, the magnesium-based alloys of the present invention have a high degree of viscosity and some are highly bendable.

[Example] Melted alloy 3 having a predetermined composition using a high-frequency melting furnace
A small hole 5 (hole diameter:
(1.5 m5), and after heating and melting, the quartz tube 1 was placed directly above the copper roll 2,
Under high-speed rotation at a rotational speed of 500 rpm, the molten alloy 3 in the quartz tube 1 was heated under pressure of argon gas (0.7 kg/c+n2
) is injected from the small hole 5 of the quartz tube 1 and brought into contact with the surface of the copper roll 2 to rapidly solidify the alloy ribbon 4.
get.

7 having the composition (atomic %) shown in the table under the above manufacturing conditions
A variety of alloy thin strips (width: 1 .mu.m, thickness: 2 .mu.m) were obtained, and the hardness and tensile strength of each sample strip were measured, and the results shown in the right column of the table were obtained.

As a result of observing the alloy ribbon obtained above using a TEM, it was confirmed that it was composed of a fine crystalline phase and an amorphous phase, and contained a large amount of the fine crystalline phase in terms of volume percentage.

Hardness (Hv) is a measured value (D P N) using a micro Vickers hardness meter with a load of 25 g.

As shown in the table, all samples have hardness Hv (DPN
) is 185 or more, which is 2.0 to 3.0 times the hardness Hv (DPN) of commercially available magnesium-based alloys of 60 to 90, and in terms of tensile strength, all samples of the present invention show 630 MPa or more. , which is about 1.5 times higher than that of the highest of conventional magnesium-based alloys, which is 400 MPa. From these facts, the alloy of the present invention is a material with excellent hardness and strength. I understand.

Table [Effects of the Invention] As described above, the magmedium-based alloy of the present invention has a 2.
．． It has a hardness of 0 times or more and a tensile strength of 1.5 times or more, and can be processed such as extrusion, so it can exhibit excellent effects in a variety of industrial applications.

[Brief explanation of drawings]

FIG. 1 is an explanatory diagram of a single roll device used to rapidly solidify the alloy of the present invention to form a ribbon. 1... Quartz tube, 2... Copper roll, 3... Molten alloy, 4... Quenched ribbon, 5... Small hole patent applicant Yoshida Kogyo Co., Ltd. agent Patent attorney Takeshi Komatsu

Claims (4)

[Claims] (1) General formula: Mg_aX_b [However, X: two or more elements selected from Cu, Ni, Sn, and Zn, a and b are atomic percentages of 40≦a≦95 5≦b≦60] and a crystalline phase composed of finely dispersed matrix elements and/or various intermetallic compounds composed of the above elements in a Mg matrix;
A high-strength magnesium-based alloy consisting of an amorphous phase containing G element and M element and constituting a matrix, the crystalline phase and the amorphous phase containing a large amount of the crystalline phase in terms of volume ratio. A high-strength magnesium alloy that is characterized by its properties. (2) General formula: Mg_aX_cM_d [However, X: one or more elements selected from Cu, Ni, Sn, and Zn; M: one or more elements selected from Al, Si, and Ca; a, c, and d have a composition shown in atomic percent as follows: 40≦a≦95 1≦c≦35 1≦d≦25], and various elements constituted by the matrix element or/and the above elements in the Mg matrix. A crystalline phase composed of finely dispersed intermetallic compounds and M
A high-strength magnesium-based alloy consisting of an amorphous phase containing G element and M element and constituting a matrix, the crystalline phase and the amorphous phase containing a large amount of the crystalline phase in terms of volume ratio. A high-strength magnesium alloy that is characterized by its properties. (3) General formula: Mg_aX_cLn_e [However, X: one or more elements selected from Cu, Ni, Sn, and Zn, Ln: Y, La, Ce, Nd,
Misch metal (Mm) is an aggregate of one or more elements selected from Sm or rare earth elements, a, c, and e are atomic percentages of 40≦a≦95 1≦c≦35 3≦e≦ 25] A crystalline phase consisting of a matrix element and/or various intermetallic compounds constituted by the above elements finely dispersed in an Mg matrix;
A high-strength magnesium-based alloy consisting of an amorphous phase containing G element and M element and constituting a matrix, the crystalline phase and the amorphous phase containing a large amount of the crystalline phase in terms of volume ratio. A high-strength magnesium alloy that is characterized by its properties. (4) General formula: Mg_aX_cM_dLn_e [however,
X: One or two selected from Cu, Ni, Sn, and Zn
More than one element, M: one or more elements selected from Al, Si, Ca, Ln: Y, La, Ce, Nd,
Misch metal (Mm), which is an aggregate of one or more elements selected from Sm or rare earth elements, is represented by 40≦a≦95 1≦c≦35 1≦d≦25 3≦e≦25] A crystalline phase composed of finely dispersed matrix elements and/or various intermetallic compounds composed of the above elements in a Mg matrix;
A high-strength magnesium-based alloy consisting of an amorphous phase containing G element and M element and constituting a matrix, the crystalline phase and the amorphous phase containing a large amount of the crystalline phase in terms of volume ratio. A high-strength magnesium alloy that is characterized by its properties.