WO2018107830A1

WO2018107830A1 - Highly plastic zirconium-based bulk amorphous alloy with no beryllium or nickel, and method for preparing same

Info

Publication number: WO2018107830A1
Application number: PCT/CN2017/101424
Authority: WO
Inventors: 吕昭平; 曹迪; 王辉; 吴渊; 刘雄军
Original assignee: 北京科技大学
Priority date: 2016-12-12
Filing date: 2017-09-12
Publication date: 2018-06-21
Also published as: CN106756647B; CN106756647A

Abstract

Disclosed are a highly plastic zirconium-based bulk amorphous alloy with no beryllium or nickel, and a method for preparing same. The alloy has the components in atom percent as follows: Zr: 38-50％, Hf: 2-15％, Cu: 20-30％, Fe: 5-10％, Al: 10-15％, Co: 0-5％, Ag: 0-5％, and Nb: 0-5％; and the alloy is prepared by arc melting/copper mold suction casting. The amorphous alloy contains no metal elements such as Be and Ni, thus improving the biocompatibility of the Zr-based alloy; the alloy has a high amorphous forming ability, which allows a Zr-based bulk amorphous alloy with a critical size of no less than 5mm to be prepared by a copper mold suction casting method; the alloy has a high hardness, the Vickers hardness thereof always being more than 540Hv; the alloy has a plastic deformation ability of more than 3%; and the alloy has a wide super-cooled liquid region range, the maximum being 92K. The alloy has a wide application prospect in the field of complex and precise medical devices and parts, artificial joints and bones and other biomedical materials.

Description

High-plasticity zirconium-based bulk amorphous alloy without niobium and nickel and preparation method thereof

Technical field

The invention belongs to a bulk amorphous alloy, in particular to a high plasticity Zr-based bulk amorphous alloy which does not contain metal elements Be and Ni, and has a critical dimension of not less than 5 mm and a plastic deformation capacity of not less than 3%.

technical background

Amorphous alloys (metal glass) are metal materials that have emerged in recent years as a new generation of structural and functional applications. Different from the long-range ordered arrangement of atoms in traditional metal materials, the atoms of amorphous alloys are randomly arranged, do not have long-range order, and do not have defects such as grain boundaries and dislocations in their microstructure. Amorphous alloys exhibit excellent properties such as high strength, high hardness, high elastic limit, low modulus, and corrosion resistance that cannot be achieved by conventional crystalline alloys. In addition, the amorphous alloy exhibits a high viscous flow in the supercooled liquid region, exhibiting superplastic deformation characteristics. This property of the amorphous alloy enables it to be accurately press molded in the supercooled liquid region. These superior properties make amorphous alloys have broad application prospects in many fields.

In recent years, researchers have obtained bulk amorphous materials in more than ten kinds of alloy systems such as Zr-based, Pd-based, La-based, Mg-based, Fe-based, and Ni-based. Compared with alloys of other systems, Zr-based bulk amorphous alloys have attracted much attention due to their excellent amorphous forming ability. Recently developed Zr-Ti-Cu-Ni-Be, Zr-Ti-Cu-Ni-Al, Zr-Cu-Ni-Al, Zr-Cu-Al-Be and other Zr amorphous alloys have high strength (2GPa). High toughness (K _IC ~ 60MPam ^1/2 ), high elastic limit (2%) and low elastic modulus (50-100GPa). However, in the Zr-based bulk amorphous alloy system with high amorphous forming ability, in order to improve the amorphous forming ability, Be or Ni is often indispensable in the alloy system. However, there is a sudden catastrophic fracture of the material after the inclusion of Be and the elastic limit. It can be seen that the biocompatibility and room temperature brittleness of Zr-based amorphous alloys limit their practical applications. Therefore, it is necessary to develop a new high-plastic Zr-based amorphous alloy containing no Be and Ni elements with strong amorphous forming ability. To broaden the application of bulk amorphous alloys in the biomedical field.

Summary of the invention

The invention develops a high-plastic zirconium-based bulk amorphous alloy without nickel and nickel, and aims to remove not only the Be and Ni elements which have toxic side effects on the human body, but also has good biocompatibility and strong amorphous forming ability and The plastic deformation ability is good to obtain a good comprehensive effect of the amorphous alloy in terms of safety, processability and economy.

The technical proposal of the invention is: a high-plastic zirconium-based bulk amorphous alloy without niobium and nickel, the atomic percentage of the amorphous alloy expressing Zr _a Hf _b Cu _c Fe _d Al _e L _f , and the components: 38≤a≤50, 2≤b≤15, 20≤c≤30, 5≤d≤10, 10≤e≤15, 0≤f≤5, and a+b+c+d+e+f=100 Wherein L is one or more of J or K, and J is at least one of Mn, Co, Zn, Au, Ag, Pd, Pt, Cd, Ru, Re, Os, Ir; K is V, At least one of Ta, Nb, Cr, W, Mo, and Y.

Further, when L is Ag, a=39, b=14, c=26, d=8, e=12, f=1, Zr ₃₉ Hf ₁₄ Cu ₂₆ Fe ₈ Al ₁₂ Ag ₁ alloy can form bulk amorphous The critical dimension is not less than 5 mm, the Vickers hardness is not less than 558 Hv, the plastic strain is not less than 3%, and the width of the supercooled liquid region is not less than 53K.

Further, when L is a combination of Co and Nb, a=38, b=14, c=26, d=8, e=12, f=2, Zr ₃₈ Hf ₁₄ Cu ₂₆ Fe ₈ Al ₁₂ (CoNb) ₂ The critical dimension of the alloy capable of forming bulk amorphous is not less than 5 mm, the Vickers hardness is not less than 572 Hv, the plastic strain is not less than 4%, and the width of the supercooled liquid region is not less than 64K.

Further, the atomic percentage expression of the amorphous alloy is Zr _a Hf _b Cu _c Fe _d Al _e , and each component: 38≤a≤50, 2≤b≤15, 20≤c≤30, 5≤d≤ 10, 10 ≤ e ≤ 15, and a + b + c + d + e = 100.

When a=40, b=14, c=26, d=8, e=12, the critical dimension of Zr ₄₀ Hf ₁₄ Cu ₂₆ Fe ₈ Al ₁₂ alloy capable of forming bulk amorphous is not less than 5 mm, and Vickers hardness is not Below 551 Hv, the plastic strain is not less than 5%, and the width of the supercooled liquid region is not less than 91K.

Another object of the present invention is to provide a method for preparing the above alloy, which specifically comprises the following steps:

Step 1. The metal Zr, Hf, Cu, Fe, Al, Ag, Nb, Co having a purity of 99.0 wt% to 99.99 wt% is converted into mass according to the atomic percentage of the above expression;

Step 2. The surface of the raw material in the step 1 is removed, and the raw materials are washed with industrial ethanol and weighed according to the respective required qualities;

Step 3. The raw materials processed in the step 2 are stacked in a non-consumable vacuum electric arc furnace or a cold heading suspension furnace in the order of melting point for melting. After the mother alloy is sufficiently smelted uniformly, the alloy is suction-cast into water-cooled copper molds of different sizes using a vacuum suction casting apparatus to obtain an amorphous alloy material.

The beneficial effects of the invention are:

(1) The alloy does not contain Be and Ni elements harmful to living organisms, and is excellent in biocompatibility.

(2) The alloy has a strong amorphous forming ability, and the amorphous alloy prepared by the copper mold suction casting method has a critical dimension of not less than 5 mm, and can satisfy the dimensional requirements in the field of amorphous alloy processing.

(3) The alloy has good plastic deformation ability, and the plastic strain at break is more than 3%, and the maximum is up to 18%.

(4) The alloy has high hardness and its Vickers hardness is higher than 540 Hv.

(5) The alloy has a wide temperature range of supercooled liquid phase, not less than 53K, and up to 92K, which is advantageous for superplastic forming.

Figure 1 is an XRD pattern of a Zr-Hf-Cu-Fe-Al bulk amorphous alloy prepared in Example 1 of the present invention;

Figure 2 is a graph showing the compressive stress-strain curve of a Zr-Hf-Cu-Fe-Al bulk amorphous alloy prepared in Example 1 of the present invention.

Figure 3 is an XRD pattern of Zr-Hf-Cu-Fe-Al-L1 and Zr-Hf-Cu-Fe-Al-L2 bulk amorphous alloys prepared in Examples 2 and 3 of the present invention.

Figure 4 is a Vickers hardness of a Zr-Hf-Cu-Fe-Al-L1 bulk amorphous alloy prepared in Example 2 of the present invention.

detailed description

The technical solution of the present invention will be further described below in conjunction with specific implementation examples.

Example 1: Preparation and properties of Zr-Hf-Cu-Fe-Al bulk amorphous alloy

The Zr _a Hf _b Cu ₂₆ Fe ₈ Al ₁₂ amorphous alloy composition was designed, wherein a = 46, 44, 42, 40; b = 54-a. An alloy of Zr ₄₆ Hf ₈ Cu ₂₆ Fe ₈ Al ₁₂ , Zr ₄₄ Hf ₁₀ Cu ₂₆ Fe ₈ Al ₁₂ , Zr ₄₂ Hf ₁₂ Cu ₂₆ Fe ₈ Al ₁₂ and Zr ₄₀ Hf ₁₄ Cu ₂₆ Fe ₈ Al ₁₂ was obtained.

As shown in FIG. 1, Zr ₄₆ Hf ₈ Cu ₂₆ Fe ₈ Al ₁₂ , Zr ₄₄ Hf ₁₀ Cu ₂₆ Fe ₈ Al ₁₂ , Zr ₄₂ Hf ₁₂ Cu ₂₆ Fe ₈ Al ₁₂ and Zr ₄₀ Hf ₁₄ Cu ₂₆ Fe ₈ Al ₁₂ alloy The XRD pattern of the 5mm sample has only a typical diffuse scattering peak of the amorphous state, indicating that the 5mm alloy is amorphous, and the alloy has strong amorphous forming ability.

The compressive stress-strain curve of the alloy is shown in Figure 2. It can be seen that the alloy does not immediately undergo catastrophic fracture after reaching the yield strength, but undergoes a plastic deformation (> 5%), wherein the Zr ₄₀ Hf ₁₄ Cu ₂₆ Fe ₈ Al ₁₂ alloy has the largest plastic deformation ability. The plastic deformation before fracture reached 18%, indicating that the bulk amorphous alloy of the alloy system has good plastic deformation ability. See Table 1 for the relevant plastic deformation capability data.

Example 2: Preparation and properties of Zr-Hf-Cu-Fe-Al-L1 bulk amorphous alloy

Designing _a composition of Zr _a Hf _b Cu ₂₆ Fe ₈ Al ₁₂ L1 _g amorphous alloy, wherein L1 is one of Ag, Co, Nb, a=39; b=14; g=1 or a=39,46; b =6; g=2. The alloy composition is prepared as Zr ₄₆ Cu ₂₆ Fe ₈ Al ₁₂ Hf ₆ Ag ₂ , Zr ₄₆ Cu ₂₆ Fe ₈ Al ₁₂ Hf ₆ Co ₂ , Zr ₄₆ Cu ₂₆ Fe ₈ Al ₁₂ Hf ₆ Nb ₂ , Zr ₃₉ Cu ₂₆ Fe ₈ Al ₁₂ Hf ₁₄ Ag ₁ and Zr ₃₉ Cu ₂₆ Fe ₈ Al ₁₂ Hf ₁₄ Nb ₁ .

Figure 3 shows the XRD pattern of a 5 mm sample of Zr _a Hf _b Cu ₂₆ Fe ₈ Al ₁₂ L1 _g alloy. The XRD pattern of the 5 mm sample has only a typical diffuse scattering peak, indicating that the 5 mm alloy is amorphous. The alloy has a strong amorphous forming ability.

As shown in Fig. 4, the Vickers hardness of Zr _a Hf _b Cu ₂₆ Fe ₈ Al ₁₂ L1 _g alloy, the hardness of the amorphous alloy is more than 550Hv, and the highest hardness value of Zr ₃₉ Cu ₂₆ Fe ₈ Al ₁₂ Hf ₁₄ Nb ₁ The alloy reached 573 Hv. See Table 1 for the relevant hardness values.

Example 3: Preparation of Zr-Hf-Cu-Fe-Al-L2 bulk amorphous alloy and two of its properties, a = 38; b = 14; g = 2 or a = 46; b = 6 ;g=2, the two elements in L2 have the same atomic fraction. The alloy composition was prepared as Zr ₄₆ Cu ₂₆ Fe ₈ Al ₁₂ Hf ₆ Nb ₁ Co ₁ and Zr ₃₈ Cu ₂₆ Fe ₈ Al ₁₂ Hf ₁₄ Nb ₁ Ag ₁ .

The XRD pattern of the 5 mm sample of Zr _a Hf _b Cu ₂₆ Fe ₈ Al ₁₂ L2 _g alloy in Example 3 is shown in Fig. 3, in which only the amorphous diffuse scattering peak is typical, indicating that the 5 mm alloy is amorphous phase, the alloy Has a strong amorphous forming ability.

Table 1: Composition, mechanical properties and thermodynamic parameters of a non-Be non-Ni high plasticity Zr-based bulk amorphous alloy of the present invention

Claims

A high-plastic zirconium-based bulk amorphous alloy free of nickel and nickel, characterized in that the atomic percentage of the amorphous alloy expresses Zr a Hf b Cu c Fe d Al e L f , and the content of each component is: 38≤a≤50, 2≤b≤15, 20≤c≤30, 5≤d≤10, 10≤e≤15, 0≤f≤5, and a+b+c+d+e+f=100 Wherein L is one or more of J or K, and J is at least one of Mn, Co, Zn, Au, Ag, Pd, Pt, Cd, Ru, Re, Os, Ir; K is V, At least one of Ta, Nb, Cr, W, Mo, and Y.
The zirconium-based bulk amorphous alloy according to claim 1, wherein the atomic percentage expression of the amorphous alloy is Zr a Hf b Cu c Fe d Al e , and the content of each component is: 38 ≤ a ≤ 50, 2 ≤ b ≤ 15, 20 ≤ c ≤ 30, 5 ≤ d ≤ 10, 10 ≤ e ≤ 15, and a + b + c + d + e = 100.
The zirconium-based bulk amorphous alloy according to claim 1, wherein L is a combination of Co and Nb, a = 38, b = 14, c = 26, d = 8, and e = 12, f = 2, Zr 38 Hf 14 Cu 26 Fe 8 Al 12 (CoNb) 2 alloy can form bulk amorphous with a critical dimension of not less than 5 mm, Vickers hardness of not less than 572 Hv, plastic strain of not less than 4%, and supercooled liquid The phase zone width is not less than 64K.
The zirconium-based bulk amorphous alloy according to claim 2, wherein the amorphous alloy a = 40, b = 14, c = 26, d = 8, e = 12, Zr 40 Hf 14 Cu 26 Fe The critical dimension of 8 Al 12 alloy capable of forming bulk amorphous is not less than 5 mm, the Vickers hardness is not less than 551 Hv, the plastic strain is not less than 5%, and the width of the supercooled liquid region is not less than 91K.
The zirconium-based bulk amorphous alloy according to claim 1, wherein the amorphous alloy: L is Ag, a = 39, b = 14, c = 26, d = 8, and e = 12, f = 1, Zr 39 Hf 14 Cu 26 Fe 8 Al 12 Ag 1 ; The alloy can form bulk amorphous with a critical dimension of not less than 5 mm, a Vickers hardness of not less than 558 Hv, a plastic strain of not less than 3%, and a supercooled liquid region width Not less than 53K.
A method of preparing a zirconium-based bulk amorphous alloy according to any one of claims 1 to 5, which comprises the following steps:

Step 1. The metal raw material metal having a purity of 99.0 wt% to 99.99 wt% is converted into mass according to the atomic percentage of the expression;

Step 2. The surface of the metal raw material in the step 1 is removed, and the raw materials are washed with industrial ethanol, and weighed according to the respective required qualities;

Step 3. The metal raw materials processed in step 2 are stacked in a non-consumable vacuum electric arc furnace or a cold heading suspension furnace in the order of melting point. After the mother alloy is fully melted uniformly, the alloy is sucked and cast using vacuum suction casting equipment. Zirconium-based bulk amorphous alloy materials were obtained in water-cooled copper molds of different sizes.
The method according to claim 6, wherein the amorphous alloy material has a critical dimension of not less than 5 mm and a Vickers hardness of more than 540 Hv.
A zirconium-based bulk amorphous alloy material prepared by the method of claim 6 is applied in the field of biomedical materials such as sophisticated medical zero devices, artificial joints, and human bones.