CN105132837A - A low-cost bulk amorphous alloy - Google Patents

Abstract

The invention relates to the technical field of bulk amorphous alloy manufacturing, in particular to a low-cost bulk amorphous alloy, the composition of which is: Zr _a (Hf,Ti) _b Al _c ( _{Cux Ni y ) d} (Ag,Re) _e (Li,Na,K,Si,Mg,Ca) _f O _g , where a, b, c, d, e, f, g are the atomic percentage content of each element in the amorphous alloy , respectively: 45≤a≤70, 5≤b≤10, 3≤c≤15, 20≤d≤40, 0≤e≤3, 0≤f≤10, 0.05≤g≤1, and 0.2≤x /y≤5, 0.1≤e+f≤10, Re is one or several kinds of rare earth elements. The invention provides a low-cost bulk amorphous alloy, which greatly reduces the sensitivity of the formula to oxygen content, and can still form a relatively large bulk amorphous alloy that can be used in industrial applications at a relatively high oxygen content. .

Description

A low-cost bulk amorphous alloy

technical field

The invention relates to the technical field of bulk amorphous alloy manufacturing, in particular to a low-cost bulk amorphous alloy.

Background technique

Due to its special structure, Zr-based amorphous alloy has many excellent properties, such as: high strength (≥1500MPa), high hardness (about HRC50), high elastic limit (about 2%), excellent corrosion resistance and Liquid near-net formability, etc., have important application prospects in the fields of consumer electronics, medical and health care, aerospace and transportation.

For Zr-based amorphous alloys, a variety of alloy components have been developed, such as the Zr-Ti-Cu-Ni-Be alloy system developed in the United States, with a critical cooling rate of 1K/s, strong amorphous formation ability, and manufacturable The ability is strong, but the existence of toxic element Be in the alloy system restricts its wide application. The Zr-Al-Ni-Cu alloy system developed in Japan can form an amorphous size up to φ30mm, but the preparation conditions required for this alloy system are relatively harsh, requiring high-purity raw materials and high-vacuum preparation technology.

The GFA and toughness of existing Zr-based alloys are particularly sensitive to the oxygen content in the alloy. Due to the strong binding force between zirconium and oxygen, zirconia or zirconium/oxygen clusters are easy to form in the alloy melt, which can be used as the core of heterogeneous nucleation, reducing the GFA of the alloy, and at the same time, tiny crystals are formed in the alloy Become the source of micro-cracks, so that the toughness of the alloy also decreases. Since a certain amount of oxygen will inevitably be introduced into Zr-based amorphous alloys under ordinary laboratory or industrial production conditions, expensive high-purity raw materials must be used in the production process, and high vacuum is required in the melting and die-casting processes. The degree of vacuum is often required to be above 10 ^-2 Pa or even 10 ^-3 Pa to prevent the decrease of amorphous GFA caused by the increase of oxygen content in the alloy. High-purity raw materials (above 99.9%) and harsh protective atmosphere result in very high preparation costs of Zr-based amorphous alloys, which cannot meet large-scale mass production. When the more common industrial-grade raw materials in the market are used, parts and products with a certain size of amorphous structure cannot be prepared, and at the same time, the toughness of the alloy will be greatly reduced, resulting in a significant decrease in the reliability of the final product, which seriously restricts its production and application.

Contents of the invention

The technical problem to be solved by the present invention is: in order to solve the problem that the amorphous alloy system in the prior art is highly sensitive to oxygen content and difficult to form massive amorphous in the industrial continuous production process, the present invention provides a A low-cost bulk amorphous alloy greatly reduces the sensitivity of the formulation to oxygen content, and can still form bulk bulk amorphous alloys that can be used in industrial applications at a relatively high oxygen content.

The technical solution adopted by the present invention to solve its technical problems is:

A low-cost bulk amorphous alloy, the composition of the amorphous alloy is: Zr _a (Hf, Ti) _b Al _c ( _{Cux Ni y ) d} (Ag, Re) _e (Li, Na, K, Si ,Mg,Ca) _f O _g , where a, b, c, d, e, f, g are the atomic percentages of each element in the amorphous alloy, respectively: 45≤a≤70, 5≤b≤ 10, 3≤c≤15, 20≤d≤40, 0≤e≤3, 0≤f≤10, 0.05≤g≤1, and 0.2≤x/y≤5, 0.1≤e+f≤10, Re One or more of La, Ce, Po, Ho, Er, Nd, Gd, Dy, Sc, Eu, Tm, Tb, Pr, Sm, Yb, Lu, Y elements.

Preferably, the Re is a combination of one or more of La, Ce, Po, Ho, Er, Nd, Gd, Dy, Sc, Eu, Tm, Tb, Pr, Sm, Yb, Lu elements and Y .

Specifically, the content of Ti in all atomic percentages is not less than 5.

Specifically, the atomic percentages of the elements in the amorphous alloy are: 50≤a≤60, 5≤b≤7, 7≤c≤12, 25≤d≤35, 0.1≤e≤1.5, 0.5≤f≤10, 0.05≤g≤1.

The beneficial effects of the present invention are: the present invention provides a low-cost bulk amorphous alloy, which greatly reduces the sensitivity of the formula to the oxygen content, and can still form a larger limit amorphous size at a higher oxygen content. The bulk amorphous alloy with relatively excellent toughness and low cost is very suitable for industrial production; Li, Na, K, Si, Mg, Ca and other elements are introduced into the bulk amorphous alloy of the present invention, and the atomic size of these elements It is small, which is conducive to the accumulation of atoms in the microscopic form, and can effectively inhibit the crystallization of the metal liquid during the cooling process. At the same time, the affinity with O atoms in the molten state is higher than that of Zr, and it is easy to form low-density oxides floating on the surface. The surface of the molten metal is decomposed in a vacuum atmosphere, thereby fundamentally increasing the forming ability of the amorphous alloy, so that the selection range of the raw materials required for the production of the amorphous alloy is wider, and it can be used without selecting high-purity raw materials. Under certain conditions, it has good amorphous forming ability, and at the same time reduces the production process conditions and greatly reduces the production cost.

Description of drawings

Fig. 1 is a schematic diagram of the structure of a test sample prepared by utilizing a low-cost bulk amorphous alloy of the present invention;

Fig. 2 is the test instrument used for the test sample used in the present invention.

Detailed ways

The preparation technology of bulk amorphous alloy in the present invention is as follows:

The raw materials Hf, Al, Cu, Ni, Ag, Re, Li, Na, K, Si, Mg, and Ca used in this example are metals of industrial grade purity, Zr and Ti metals are sponge zirconium, sponge titanium, Hf You can also choose sponge zirconium containing a certain amount of Hf. O can be oxygen brought in by metal oxides or other impurities. After the raw materials are prepared according to the atomic percentage, the master alloy ingot is prepared by arc melting or induction melting under the protection of argon. In order to ensure the uniformity of the smelted alloy ingot, when the master alloy ingot is arc smelted, it needs to be turned over 3 to 4 times, and then cast through a Cu mold, the induction heating temperature is about 1000 ℃, and the vacuum degree is 10 ^-1 ~ 10 ^-2 Pa.

Specific examples are shown in the following table:

Toughness test method:

Prepare at least 20 test samples (as shown in Figure 1) for each formula master alloy using a vacuum die-casting machine, load a specific weight counterweight on the middle plate of the sample, use the reserved hole to lock, and the counterweight The weight is combined with the actual application of the product. This patent preferably uses 200g counterweight, and the test sample is subjected to a drop test on a 1-meter drum (as shown in Figure 2). Put the test sample into the drum 1 and open it from the control box 2. The test instrument records the ratio of broken test samples to the total test samples after the drum 1 rotates 100 times. The lower the ratio of broken test pieces to the total test pieces, the better the toughness of the formulation.

Inspired by the above-mentioned ideal embodiment according to the present invention, through the above-mentioned description content, relevant workers can make various changes and modifications within the scope of not departing from the technical idea of the present invention. The technical scope of the present invention is not limited to the content in the specification, but must be determined according to the scope of the claims.

Claims (4)

1. A low-cost bulk amorphous alloy is characterized in that, the composition of the amorphous alloy is: Zr _a (Hf, Ti) _b Al _c ( _{Cux Ni y ) d} (Ag, Re) _e (Li ,Na,K,Si,Mg,Ca) _f O _g , where a, b, c, d, e, f, g are the atomic percentages of each element in the amorphous alloy, respectively: 45≤a≤ 70, 5≤b≤10, 3≤c≤15, 20≤d≤40, 0≤e≤3, 0≤f≤10, 0.05≤g≤1, and 0.2≤x/y≤5, 0.1≤e +f≤10, Re is one or more of La, Ce, Po, Ho, Er, Nd, Gd, Dy, Sc, Eu, Tm, Tb, Pr, Sm, Yb, Lu, Y elements. 2. A low-cost bulk amorphous alloy as claimed in claim 1, characterized in that: said Re is La, Ce, Po, Ho, Er, Nd, Gd, Dy, Sc, Eu, Tm, Tb , Pr, Sm, Yb, Lu elements or a combination of Y. 3. A low-cost bulk amorphous alloy according to claim 1, characterized in that: said Ti accounts for at least 5 atomic percent. 4. A low-cost bulk amorphous alloy according to claim 1, characterized in that: the atomic percentages of the elements in the amorphous alloy are respectively: 50≤a≤60, 5≤b≤ 7, 7≤c≤12, 25≤d≤35, 0.1≤e≤1.5, 0.5≤f≤10, 0.05≤g≤1.