KR20170102187A - A tin-containing amorphous alloy composition - Google Patents

Abstract

The present invention provides a composite metal or an amorphous alloy containing a soft crystalline metal particle in an amorphous metal matrix, and tin of a predetermined concentration. The present invention also provides a method of improving workability of the amorphous alloy containing low purity substance without reduction of mechanical and thermal properties of the amorphous alloy by adding tin.

Description

[0001] A TIN-CONTAINING AMORPHOUS ALLOY COMPOSITION [0002]

The present invention relates to a composite metal comprising an amorphous alloy or ductile crystalline metal particles in an amorphous metal matrix; Particularly those materials having a tin-containing composition.

Bulk-solidifying amorphous alloy composites have been found in a variety of alloy systems. Such materials are typically prepared by quenching the molten alloy at ambient temperature above the melting temperature. Generally, a cooling rate of less than or equal to 10 < ⁵ > C / sec is used to obtain an amorphous structure. By the early nineteenth century, the processability of conventional amorphous alloys was fairly limited, and conventional amorphous alloys were very thin foils or strips, either in powder form, or with critical dimensions less than 100 micrometers, . However, at the beginning of the 19th century, new types of Zr-based and Ti-based amorphous alloys were developed. These alloys had a critical cooling rate of less than 10 ³ ° C / second, in some cases as low as 10 ° C / second, which was much lower than that of the alloy systems discovered up to that time. Bulk solid amorphous alloys have a unique combination of very high strength, high specific strength, high elastic strain limit, and other engineering properties.

Other types of flexible composite metals include soft crystalline metal particles in the amorphous metal matrix (in-situ complex amorphous alloy), improved toughness and high plastic strain to failure. Crystalline dendritic structures can stabilize the shear band and crack growth in the matrix and increase the strain to failure magnitude of the composite.

Amorphous alloys and in-situ complex amorphous alloys usually require high purity components to achieve optimal mechanical and thermal properties. High purity requirements also do not limit the number of remelting and regeneration steps that the alloy may be subjected to. This will not only increase manufacturing costs, but also increase waste and environmental pollution. Accordingly, there is a need to develop a new class of engineering alloys that exhibit the same thermal and mechanical properties (e.g., high yield strength, high hardness, high ductility and toughness), but reduce manufacturing costs and environmental impact.

The present invention relates to an amorphous alloy and an in-situ compound amorphous alloy to which a small amount of Sn is added, and the alloy can be produced using a low purity constituent element.

In one embodiment of the invention, about 0.5 to 4.5 atomic percent of tin is added to the amorphous alloy or in-situ compound amorphous alloy.

In another embodiment of the present invention, the alloy has a composition according to the following formula:

Zr _a M _b N _c Sn _d

Wherein M is selected from the group consisting of one or more transition metal elements, N is one of Al or Be, a, b, c, and d represent atomic percentages, a is about 30 to 70, 60, c is about 5 to 30, and d is about 0.1 to 5. In this embodiment, the alloy may take one of the following combinations of materials: M is a combination of Ni and Cu, N is Al; M is a combination of Ni and Cu, N is Be; M is a combination of Ni and Cu, N is a combination of Al and Be; M is Cu, N is Be; M is Cu, N is a combination of Al and Be; M is a combination of Ti, Cu and Nb; N is Be; M is a combination of Ti, Nb, Cu and Ni; N is Be; M is a combination of Ti, V, Cu and Ni; N is Be; M is a combination of Ti, Ta, Cu and Ni; N is Be; M is a combination of Ti, Mo, Cu and Ni; N is Be; M is a combination of Ti, W, Cu and Ni, and N is Be.

In another embodiment of the present invention, the alloy has a composition according to the following formula:

Ti _a M _b N _c Sn _d

Wherein M is selected from the group consisting of one or more transition metal elements, N is one of Al or Be, a, b, c, and d represent atomic percentages, a is about 30 to 70, 60, c is about 5 to 30, and d is about 0.1 to 5. In this embodiment, the alloy may be formed such that M is a combination of Zr and V and N is Be.

In another embodiment of the present invention, the alloy has a composition according to the following formula:

Ti _a M _b N _c Sn _d

Wherein M is selected from the group consisting of one or more transition metal elements, N is at least one of Al and Be; a, b, c, and d represent atomic percentages, where a is about 30 to 70, b is about 25 to 60, c is about 5 to 30, and d is about 0.1 to 5.

In another embodiment of the present invention, the constituents of the amorphous alloy may have a purity of less than 98.75%.

In another embodiment of the present invention, the amorphous alloy may also contain at least 200 ppm of oxygen impurities.

The present invention relates to a process for the production of polyurethane foam which has excellent mechanical properties such as high yield strength, high hardness, high ductility and toughness, but which can be formed using low purity components, To a new class of tin-containing engineering alloys.

Bulk solid amorphous alloys are a family of recently discovered amorphous alloys and can be cooled substantially slower than a cooling rate of less than about 500 K / sec and still retain substantially the amorphous atomic structure. Thus, they can be made to a thickness of at least 1.0 mm, which is typically thicker than a typical amorphous alloy, which is limited to a thickness of 100 micrometers and requires a cooling rate of 10 ⁵ K / sec or more. U.S. Patent 5,288,344; 5,368,659; 5,618,359; 5,735,975; 5,797,443; 6,325,868; 6,682,611; And 6,709,536 are hereby incorporated by reference and disclose such bulk coagulation type associations.

Surprisingly, it has been found that up to about 5% tin addition can dramatically improve the ability to form high quality bulk coagulated amorphous alloys from low purity components. More particularly, in one preferred embodiment, the amorphous alloy of the present invention can be defined by the following formula

Zr _a M _b N _c Sn _d

Wherein M is selected from the group consisting of one or more transition metal elements, N is one of Al or Be, a, b, c, and d represent atomic percentages, a is about 30 to 70, 60, c is about 5 to 30, and d is about 0.1 to 5.

More preferably, the alloy of the present invention comprises one of the following combinations of constituents:

M is a combination of Ni and Cu, N is Al;

M is a combination of Ni and Cu, N is Be;

M is a combination of Ni and Cu, N is a combination of Al and Be;

M is Cu and N is Be;

M is Cu; N is a combination of Al and Be;

M is a combination of Ti, Cu and Nb; N is Be;

M is a combination of Ti, Nb, Cu and Ni; N is Be;

M is a combination of Ti, V, Cu and Ni; N is Be;

M is a combination of Ti, Ta, Cu and Ni; N is Be;

M is a combination of Ti, Mo, Cu and Ni; N is Be;

M is a combination of Ti, W, Cu and Ni, and N is Be.

In an alternative preferred embodiment, the amorphous alloy may be prepared according to the following formula:

Ti _a M _b N _c Sn _d

Wherein M is selected from the group consisting of one or more transition metal elements, N is one of Al or Be, a, b, c, and d represent atomic percentages, a is about 30 to 70, 60, c is about 5 to 30, and d is about 0.1 to 5. More preferably, the alloy is formed such that M is a combination of Zr and V, and N is Be.

In another alternative preferred embodiment, the amorphous alloy can be prepared according to the following formula:

Ti _a M _b N _c Sn _d

Wherein M is selected from the group consisting of one or more transition metal elements, N is at least one of Al and Be; a, b, c, and d represent atomic percentages, where a is about 30 to 70, b is about 25 to 60, c is about 5 to 30, and d is about 0.1 to 5.

In any of the above embodiments, the composition of the amorphous alloy may have a purity of less than 98.75%. In addition, the amorphous alloy may contain at least 200 ppm of oxygen impurities.

The Zr-based or Ti-based Sn-containing alloys of the present invention can be prepared in any conventional manner. In one embodiment, the ingot can be prepared by arc-melting or inductively melting the component metal and then casting to the appropriate shape and size. Although the ingot is mentioned in the above embodiments, any suitable shape, size, molding and melting technique may be used with the present invention. Although any suitable purity of zirconium or titanium may be used, in one embodiment of the present invention the zirconium purity is about 98%. Similarly, any suitable form and content of tin additive may be used in the present invention; However, in a preferred embodiment of the present invention, the tin content is 0.5 to 4.5 atomic percent.

The present specification will be better understood with reference to the following data graphs, which represent representative embodiments of the invention and should not be construed as a complete description of the scope of the invention:
Figure 1 provides a plot of data on the characteristics of exemplary amorphous alloys made in accordance with the present invention.

To investigate the effect of tin addition on the thermal properties of alloys in a Zr-Cu-Ni-Al alloy system,

(Zr _50.75 Cu _36.25 Ni ₄ Al ₉ ) _100-x Sn _x

Composites according to the above formula were prepared by direct casting to a copper mold. It has been determined that a completely amorphous phase can be obtained for an alloy of about 0 to 5 x. As shown in the data plot below, the values of T _g and T _x moved slightly to the right and then to the left, shifting to the right again as more annotations were added. ΔT drops noticeably only after a tin of 1.5 atomic percent is added to the system. Although T _g , T _x , and ΔT vary, the amorphous phase formation and critical cooling rate of the alloy do not change appreciably. Zr-Ti-Cu-Ni-Be, Zr-Ti-Cu-Ni-Be and Zr-Ti-Cu-Ni-Be having low purity components, A completely amorphous monolithic in-situ composite alloy was introduced into a Ti-Nb-Cu-Ni-Be glass forming alloy system and was obtained using up to 5 atomic percent tin. The results of adding Sn to a series of Zr-Cu-Ni-Al alloys are summarized in Table 1 below.

Table 1: Properties of representative tin-containing Zr-Cu-Ni-Al amorphous alloys Sn content (%) T _g (° C) T _x (° C) ΔT
(° C) ? H _x (J / g) T _s (° C) T _l (° C) ? H _f (J / g) 0.0 413.7 497.3 83.6 49.44 746.3 887.3 161.332 0.5 426.2 509.8 83.6 57.21 767.9 890.7 143.984 1.0 430.4 509.9 79.5 58.64 713.8 892.3 147.71 1.5 433.9 499.5 65.6 63.66 713.4 894.8 137.109 2.0 430.5 493.7 63.2 54.55 711.3 898.3 129.23 2.5 428.5 489.5 61 50.27 706.1 901.3 124.592 3.0 432.5 494.4 61.9 46.07 708.2 897.4 133.51 3.5 439.4 501.6 62.2 42.32 709.5 966.1 135.32 4.0 442.9 507.8 64.9 39.76 711 937.9 121.33 4.5 445.7 510.6 64.9 39.28 712.3 956.9 117.64 5.0 447.9 513.3 65.4 39.93 717.1 971.2 105.45

Although specific embodiments are disclosed herein, those skilled in the art will recognize that alternative Zr-based or Ti-based Sn-containing alloys and methods of making such alloys within the scope of the following claims may be designed in a literal or equivalent manner, something to do.

Claims (1)

3. The amorphous alloy according to claim 1,

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