Zr-based amorphous alloy and manufacturing method thereof

Abstract

A Zr-based amorphous alloy and a manufacturing method thereof, wherein the Zr-based amorphous alloy includes a composition of (Zr.sub.aHf.sub.bCu.sub.cNi.sub.dAl.sub.e).sub.100-XO.sub.x, wherein a, b, c, d, e, x are atomic percentages, and 49≤a≤55, 0.05≤b≤1, 31≤c≤38, 3≤d≤5, 7≤e≤10.5, and 0.05≤x≤0.5, wherein based on the volume of the alloy, the Zr-based amorphous alloy is cast into a rod-shaped sample having a diameter of 12-16 mm and a length of 60 mm, an amorphous content of 40%-95%, a strength of above 1800 MPa, and a fracture toughness of higher than 90 KPam.sup.1/2.

Claims

1. A Zr-based amorphous alloy, wherein the Zr-based amorphous alloy composition is (Zr.sub.49.3Hf.sub.0.7Cu.sub.37.8Ni.sub.4.2Al.sub.8).sub.99.5O.sub.0.5, wherein the Zr-based amorphous alloy has a seize reaching diameter of Φ16 mm with a length of 60 mm, a strength above 1800 MPa, and a fracture toughness higher than 90 KPam.sup.1/2.

2. A method for manufacturing a Zr-based amorphous alloy characterized in that, a raw material is heated and smelted by induction melting, a power is increased during smelting and the melting temperature is controlled, and the melting temperature is 1400-1600° C., and a holding time is not less than 180 seconds at a highest temperature, and the melt is poured into a mold by flip casting, and a casting temperature is higher than 1100° C., wherein the Zr-based amorphous alloy composition is (Zr.sub.aHf.sub.bCu.sub.cNi.sub.dAl.sub.e).sub.100-xO.sub.x wherein a, b, c, d, e, x represent atomic unit and 49≤a≤55, 0.05≤b≤1, 31≤c≤38, 3≤d≤5, 7≤e≤10.5, 0.05≤x≤0.5.

3. The method for manufacturing a Zr-based amorphous alloy according to claim 2, wherein the raw material has a purity of no less than 97% and an oxygen content of not higher than 2 at %.

4. The method for manufacturing a Zr-based amorphous ally according to claim 2, wherein a crucible used in the smelting process is one of a quartz crucible, a graphite crucible, a calcium oxide crucible and a multiple crucible.

5. The method for manufacturing a Zr-based amorphous alloy according to claim 2, characterized in that, the Zr-based amorphous alloy is smelted under vacuum, and the degree of vacuum required is from 0.5 to 500 Pa.

6. The method for manufacturing a Zr-based amorphous alloy according to claim 2, wherein a smelting protective gas is argon.

7. The method for manufacturing a Zr-based amorphous alloy according to claim 2, wherein the Zr-based amorphous alloy composition is (Zr.sub.aHf.sub.bCu.sub.cNi.sub.dAl.sub.e).sub.100-xO.sub.x wherein a, b, c, d, e, x represent atomic unit, and 52.5≤a≤54, 0.3≤b≤0.6, 33≤c≤35.5, 3.2≤d≤4, 8≤e≤10, 0.05≤x≤0.2.

8. The method for manufacturing a Zr-based amorphous alloy according to claim 2, wherein the Zr-based amorphous alloy composition is (Zr.sub.aHf.sub.bCu.sub.cNi.sub.dAl.sub.e).sub.100-xO.sub.x wherein a, b, c, d, e, x represent atomic unit and 50.5≤a≤52, 0.4≤b≤0.8, 36≤c≤37.5, 3≤d≤4.5, 8≤e≤10, 0.05≤x≤0.3.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a XRD diffraction pattern of the amorphous alloy described in Example 1.

(2) FIG. 2 shows the thermodynamic parameter of the amorphous alloy described in Example 1.

(3) FIG. 3 is a graph showing the mechanical properties of the amorphous alloy described in Example 1.

(4) FIG. 4 is a XRD diffraction pattern of the amorphous alloy described in Example 2.

(5) FIG. 5 shows the thermodynamic parameter of the amorphous alloy described in Example 2.

(6) FIG. 6 is a graph showing the mechanical properties of the amorphous alloy described in Example 2.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

(7) The invention is described in detail below with reference to the preferred embodiments of the invention.

(8) The raw materials used in the following examples have a purity of more than 97%, a oxygen content of less than 2 at. %, and the argon has a purity of more than 97%.

Example 1

(9) Composition: (Zr.sub.54Hf.sub.0.5Cu.sub.32.9Ni.sub.3.6Al.sub.9).sub.99.95 O.sub.0.05

(10) Placing the raw material in a graphite crucible, vacuuming to 5 Pa, and then smelting the raw material under an argon atmosphere, increasing slowly the power to rise the melting temperature to 1400° C., and then keeping warm for 300 s (the holding time is 300 seconds), and then reducing slowly the power and lowering the temperature to 1200° C. After the temperature is lowered to 1200° C., casting the melt raw material into a copper mold, so as to obtain a rod-shaped sample having a size of Φ12×60 mm, and its amorphous content is 95% by volume. It is analyzed by an XRD diffractometer to determine whether it is amorphous, and its structure is confirmed to be an amorphous structure as shown in FIG. 1. The thermodynamic parameters are measured by DSC, as shown in FIG. 2, the rod-shaped sample has a T.sub.g of 687K and a T.sub.x of 763K. The mechanical properties are tested by a mechanical property testing machine, as shown in FIG. 6, the 2 mm bar compressive has a strength reaching 1941 MPa, a Vickers hardness reaching 544, and a fracture toughness reaching 90 KPam.sup.1/2.

Example 2

(11) Composition: (Zr.sub.50.5Hf.sub.0.5Cu.sub.36.45Ni.sub.4.05Al.sub.8.5).sub.99.9 O.sub.0.1

(12) Placing the raw material in a quartz crucible, vacuuming to 5 Pa, and then smelting the raw material under an argon atmosphere. Increasing slowly the power to rise the melting temperature to 1500° C., and then keeping warm for 240 s (the holding time is 240 seconds), and then reducing slowly the power and lowering the temperature to 1150° C. After the temperature is lowered to 1150° C., casting the melt raw material into a copper mold, so as to obtain a rod-shaped sample having a size of Φ16×60 mm, and its amorphous content is 99% by volume. It is analyzed by an XRD diffractometer to determine whether it is amorphous, and its structure is confirmed to be an amorphous structure as shown in FIG. 4. The thermodynamic parameters are measured by DSC, as shown in FIG. 5, which has a T.sub.g of 690K and a T.sub.x of 767K. The mechanical properties are tested by a mechanical property testing machine. As shown in FIG. 6, the 2 mm bar compressive has a strength reaching 1890 MPa, a Vickers hardness reaching 550, and a fracture toughness reaching 93 KPam.sup.1/2.

Example 3

(13) Composition: (Zr.sub.52.7Hf.sub.0.3Cu.sub.34.2Ni.sub.3.8Al.sub.9).sub.99.7O.sub.0.3

(14) Placing the raw material in a graphite crucible, vacuuming to 15 Pa, and then smelting the raw material under a vacuum atmosphere. Increasing slowly the power to rise the melting temperature to 1600° C., and then keeping warm for 240 s (the holding time is 240 seconds), and then reducing slowly the power and lowering the temperature to 1100° C. After the temperature is lowered to 1100° C., casting the melt raw material into a copper mold, so as to obtain a rod-shaped sample having a size of Φ12×60 mm, and its amorphous content is 90% by volume.

Example 4

(15) Composition: (Zr.sub.50.6Hf.sub.0.4Cu.sub.35.1Ni.sub.3.9Al.sub.10).sub.99.8O.sub.0.2

(16) Placing the raw material in a graphite crucible, vacuuming to 0.5 Pa, and then smelting the raw material under an argon atmosphere. Increasing slowly the power to rise the melting temperature to 1400° C., and then keeping warm for 180 s (the holding time is 180 seconds), and then reducing slowly the power and lowering the temperature to 1200° C. After the temperature is lowered to 1200° C., casting the melt raw material into a copper mold, so as to obtain a rod-shaped sample having a size of Φ16×60 mm, and its amorphous content is 90% by volume.

Example 5

(17) Composition: (Zr.sub.53.7Hf.sub.0.3Cu.sub.34.2Ni.sub.3.8Al.sub.8).sub.99.9O.sub.0.1

(18) Placing the raw material in a calcium oxide crucible, vacuuming to 10 Pa, and then smelting the raw material under an argon atmosphere. Increasing slowly the power to rise the melting temperature to 1500° C., and then keeping warm for 240 s (the holding time is 240 seconds), and then reducing slowly the power and lowering the temperature to 1150° C. After the temperature is lowered to 1150° C., casting the melt raw material into a copper mold, so as to obtain a rod-shaped sample having a size of Φ12×60 mm, and its amorphous content is 80% by volume.

Example 6

(19) Composition: (Zr.sub.54.1Hf.sub.0.9Cu.sub.31.5Ni.sub.3.5Al.sub.10).sub.99.85O.sub.0.15

(20) Placing the raw material in a calcium oxide crucible, vacuuming to 10 Pa, and then smelting the raw material under an argon atmosphere. Increasing slowly the power to rise the melting temperature to 1500° C., and then keeping warm for 240 s (the holding time is 240 seconds), and then reducing slowly the power and lowering the temperature to 1150° C. After the temperature is lowered to 1150° C., casting the melt raw material into a copper mold, so as to obtain a rod-shaped sample having a size of Φ12×60 mm, and its amorphous content is 70% by volume.

Example 7

(21) Composition: (Zr.sub.54.9Hf.sub.0.1Cu.sub.34.2Ni.sub.3.8Al.sub.7).sub.99.7O.sub.0.3

(22) Placing the raw material in a calcium oxide crucible, vacuuming to 50 Pa, and then smelting the raw material under an argon atmosphere. Increasing slowly the power to rise the melting temperature to 1600° C., and then keeping warm for 240 s (the holding time is 240 seconds), and then reducing slowly the power and lowering the temperature to 1200° C. After the temperature is lowered to 1200° C., casting the melt raw material into a copper mold, so as to obtain a rod-shaped sample having a size of Φ12×60 mm, and its amorphous content is 70% by volume.

Example 8

(23) Composition: (Zr.sub.50.2Hf.sub.0.8Cu.sub.37.8Ni.sub.4.2Al.sub.7).sub.99.9O.sub.0.1

(24) Placing the raw material in a calcium oxide crucible, vacuuming to 5 Pa, and then smelting the raw material under an argon atmosphere. Increasing slowly the power to rise the melting temperature to 1400° C., and then keeping warm for 300 s (the holding time is 300 seconds), and then reducing slowly the power and lowering the temperature to 1200° C. After the temperature is lowered to 1200° C., casting the melt raw material into a copper mold, so as to obtain a rod-shaped sample having a size of Φ16×60 mm, and its amorphous content is 50% by volume.

Example 9

(25) Composition: (Zr.sub.49.3Hf.sub.0.7Cu.sub.37.8Ni.sub.4.2Al.sub.8).sub.99.5O.sub.0.5

(26) Placing the raw material in a calcium oxide crucible, vacuuming to 10 Pa, and then smelting the raw material under an argon atmosphere. Increasing slowly the power to rise the melting temperature to 1600° C., and then keeping warm for 180 s (the holding time is 180 seconds), and then reducing slowly the power and lowering the temperature to 1150° C. After the temperature is lowered to 1150° C., casting the melt raw material into a copper mold, so as to obtain a rod-shaped sample having a size of Φ 16×60 mm, and its amorphous content is 40% by volume.

Example 10

(27) Composition: (Zr.sub.49.4Hf.sub.0.6Cu.sub.35.55Ni.sub.3.95Al.sub.10.5).sub.99.6O.sub.0.4

(28) Placing the raw material in a calcium oxide crucible, vacuuming to 1 Pa, and then smelting the raw material under an argon atmosphere. Increasing slowly the power to rise the melting temperature to 1500° C., and then keeping warm for 180 s (the holding time is 180 seconds), and then reducing slowly the power and lowering the temperature to 1100° C. After the temperature is lowered to 1100° C., casting the melt raw material into a copper mold, so as to obtain a rod-shaped sample having a size of Φ16×60 mm, and its amorphous content is 50% by volume.

(29) The above embodiments are merely illustrative of the technical concept and the features of the invention and the purpose of the invention is to enable those skilled in the art to understand the invention and to implement the invention, and the scope of the invention is not limited thereto. Equivalent variations or modifications made in accordance with the spirit of the invention are intended to be included within the scope of the invention.