CN1151308C - A multi-element titanium-based alloy that can form an amorphous structure - Google Patents

Abstract

The invention provides a class of multi-component titanium-based alloys capable of forming an amorphous structure. The expression of the alloy composition is: Ti _a M _b ( _Cux Ni _1-x ) _c R _d Z _e (a, b, c , d, e are atomic percent, x is atomic fraction). M is the element Mg, R is the element Al, and Z is the element Sn or at least one of Sn and B and Si elements. a=37-77%, b=0-27%, c=20-50%, d=0-17%, e=1-15%, a+b+c+d+e=100%. x=0.35～0.75. According to the above alloy composition, the mixture prepared from element powder is used as the starting material, which can be alloyed by mechanical grinding, and the powder with amorphous structure can be formed by solid state reaction, and the volume percentage of the amorphous phase is not less than 50%. According to the above alloy composition, the element block material is used as the starting material, and the master alloy ingot is formed by pre-melting, and the debris of the master alloy ingot after mechanical crushing can be mechanically ground to form an amorphous powder, and the amorphous phase The volume percentage is not less than 50%.

Description

A multi-element titanium-based alloy that can form an amorphous structure

Technical field:

The invention relates to a class of multi-component titanium-based alloys capable of forming an amorphous structure.

Background technique:

Compared with conventional polycrystalline metal materials, the main structural feature of amorphous alloys (also known as metallic glasses) is that the atomic arrangement has no long-term order and no grain boundaries. Therefore, it has excellent properties such as high strength, corrosion resistance, and isotropy. It has broad application prospects in the fields of automobiles, aircraft, micro-machines, microelectronics, sporting goods, precision instruments, anti-theft equipment, energy conversion, and medical materials. At present, the preparation methods of amorphous alloys mainly include: melt quenching, sputtering deposition, electrochemical deposition, gas ultrasonic atomization, ion beam irradiation, multilayer film diffusion annealing, mechanical grinding and other methods. Due to the restriction of the alloy's intrinsic amorphous formation ability, most of the available amorphous metal materials are limited to powder, ribbon, filament, film and other forms. For a few alloys with strong intrinsic amorphous ability, the critical cooling rate for forming an amorphous structure by liquid cooling can be lower than 500°C/s, and the method of melt casting can be used to directly form bulk materials with a thickness of millimeters or parts.

Amorphous alloy is a material in a metastable state, which can be transformed into a material with a crystal structure under the action of external environments such as temperature, pressure, and magnetic field (called crystallization transition), which will be accompanied by changes in alloy properties. The intrinsic amorphous-forming ability and thermal stability of an alloy depend directly on the chemical composition of the alloy. Generally, the diversification of alloy composition (that is, composed of a variety of alloying elements) can improve the intrinsic amorphous forming ability and thermal stability of the alloy. The key to forming an amorphous structure by cooling an alloy melt is to supercool the melt below the glass transition temperature (expressed as T _g ) of the alloy, so as to avoid crystallization and freeze into a solid material. Some amorphous alloys have better thermal stability before heating to undergo crystallization transformation, forming a relatively stable supercooled liquid, which can be observed in thermal analysis. Obvious glass transition (that is, transition from amorphous solid to It is a supercooled liquid, usually accompanied by a sudden change in viscosity and specific heat), which can form a wide range of supercooled liquid temperature (expressed as ΔT _x , ΔT _x is defined as the crystallization transition of amorphous alloy during continuous heating The difference between the initial temperature T _x and the glass transition temperature T _g , that is, ΔT _x =T _x −T _g ). In this temperature range, the viscosity of amorphous alloys drops sharply and can exhibit superplasticity, which provides opportunities for the processing and forming of amorphous alloys. Utilizing this feature can realize near-net-shape processing, and can make amorphous alloys into parts with complex shapes, or use hot pressing, hot isostatic pressing, warm extrusion, and sintering of amorphous alloy powders or thin strips. Powder metallurgy techniques such as forging are consolidated into bulk materials. It has been found that about dozens of alloy systems that can form an amorphous state have the above characteristics, and the ΔT _x value can exceed 30 °C or even greater than 100 °C, such as Mg-Ln-TM, Ln-Al-TM, Zr- Al-TM, Zr-(Ti, Nb, Pd)-Al-TM, Zr-Ti-TM-Be, Fe-(Al, Ga)-(P, C, B, Si), Co-Cr-(Al , Ga)-(P, C, B, Si), Pd-Cu-Ni-P, Pd-Ni-Fe-P, (Fe, Co, Ni)-(Zr, Nb, Ta)-B, Fe- Co-(Zr, Nb)-(Mo, W)-B, Co-Fe-(Zr, Nb, Ta)-B (Ln is a lanthanide metal, TM is a transition metal) and other alloy systems.

Compared with iron-based, zirconium-based and palladium-based amorphous alloys, titanium-based amorphous alloys have the characteristics of low density, high strength and corrosion resistance. The main element titanium has a density of 4.5 g/cm ³ , a melting point of 1668°C, a thermal conductivity of 0.036 cal/cm·s·degree, and a linear expansion coefficient of 9.0×10 ^-6 °C ^-1 . The tensile strength of the amorphous Ti ₅₀ Cu ₂₅ Ni ₂₅ alloy formed by the melt quenching method can reach 1800MPa, which is twice that of the industrial titanium alloy Ti-6Al-4V, Ti-13V-11Cr-3Al and Ti-2Al- 1.5 times that of 11.5V-2Sn-11.3Zr (Transage 129). It has been found that an amorphous structure can be formed in certain composition ranges of binary alloys such as Ti-Be, Ti-Cu, Ti-Ni, Ti-Mn, Ti-Si, Ti-V, Ti-Zr. Based on these alloys, the formation ability and thermal stability of titanium-based amorphous alloys will be further improved by adding a variety of alloy elements, and its application range will be expanded.

Technical content of the invention:

The invention provides a class of multi-element titanium-based alloys capable of forming an amorphous structure, and the expression of the alloy composition is:

(1) Ti _a M _b ( _Cux Ni _1-x ) _c Z _e ,

a, b, c, e are atomic percentages, and x is the atomic fraction.

M is the element Mg, and Z is at least one element among the elements B, Ge, Si, C, and Sn.

a=37-77%, b=0.5-27%, c=20-50%, e=1-15%, a+b+c+e=100%. x=0.35～0.75.

(2) Ti _a M _b ( _Cux Ni _1-x ) _c Z _e ,

a, b, c, e are atomic percentages, and x is the atomic fraction.

M is at least one element among elements Mg, Ca, Mn, Nb, Fe, V, Mo, and Zr, and Z is at least one element among elements Sn or Sn and B and Si elements.

(3) a=37-77%, b=0.5-27%, c=20-50%, e=1-15%, a+b+c+e=100%. x=0.35～0.75. Ti _a ( _Cux Ni _1-x ) _c R _d Z _e ,

a, c, d, and e are atomic percentages, and x is the atomic fraction.

R is the element Al,

Z is at least one element among elements B, Ge, Si, C, and Sn.

a=37-77%, c=20-50%, d=0.5-17%, e=1-15%, a+c+d+e=100%.

x=0.35～0.75.

(4) Ti _a (Cux _{Ni 1-x} ) _c R _d Z _e ,

a, c, d, and e are atomic percentages, and x is the atomic fraction.

R is at least one of the elements Al, Ag, Co, Fe, Pd, Zn,

Z is element Sn or at least one of Sn and B and Si elements.

a=37-77%, c=20-50%, d=0.5-17%, e=1-15%, a+c+d+e=100%. x=0.35～0.75.

(5) Ti _a M _b ( _Cux Ni _1-x ) _c R _d Z _e ,

a, b, c, d, e are atomic percentages, and x is the atomic fraction.

M is the element Mg, R is the element Al,

Z is at least one element among elements B, Ge, Si, C, and Sn.

a=37-77%, b=0.5-27%, c=20-50%, d=0.5-17%, e=1-15%, a+b+c+d+e=100%. x=0.35～0.75.

(6) Ti _a M _b ( _Cux Ni _1-x ) _c R _d Z _e ,

a, b, c, d, e are atomic percentages, and x is the atomic fraction.

M is at least one element among elements Mg, Ca, Mn, Nb, Fe, V, Mo, Zr, R is at least one element among elements Al, Ag, Co, Fe, Pd, Zn,

Z is element Sn or at least one of Sn and B and Si elements.

a=37-77%, b=0.5-27%, c=20-50%, d=0.5-17%, e=1-15%, a+b+c+d+e=100%. x=0.35～0.75.

Among the above alloys, a, b and e are preferably selected as a=37-70%, b=0.5-20%, e=1-12%.

Among the preparation methods of many amorphous alloys, the mechanical grinding method has the following characteristics: (1) The range of alloy composition forming the amorphous structure is wide, while the amorphous alloy formed by cooling of the melt is usually limited to a narrow range. The composition range close to the eutectic point of the alloy; (2) Alloy elements with large melting point difference and liquid phase immiscibility can be formed into complex alloys through solid state reaction; (3) The preparation technology is simple, easy to industrialize, and the powder output can be reduced It can reach the kilogram level and meet a wide range of practical needs. The amorphous alloy powder obtained by this method can be prepared into bulk materials or parts through various powder metallurgy techniques according to requirements.

The present invention also provides the preparation method of above-mentioned amorphous alloy, namely:

According to the alloy composition given by the expression, the commercially available element powder mixture is used as the starting material, alloyed by mechanical grinding, and the powder with amorphous structure is formed by solid state reaction, and the volume percentage of the amorphous phase is not less than 50%. The volume percentage of the amorphous phase can be estimated from the release heat of crystallization transition of the amorphous phase obtained from x-ray diffraction spectrum, electron microscope observation and differential scanning calorimetry (DSC) analysis.

Or, according to the alloy composition given by the expression, the element block material is used as the starting material, and the master alloy ingot is formed by pre-smelting, and the debris of the master alloy ingot is mechanically crushed and mechanically ground to form an amorphous structure. For powder, the volume percentage of amorphous phase is not less than 50%. The volume percentage of the amorphous phase can be estimated from the release heat of crystallization transition of the amorphous phase obtained from x-ray diffraction spectrum, electron microscope observation and differential scanning calorimetry (DSC) analysis.

In the process of mechanical grinding, in order to avoid cold welding, agglomeration, and adhesion of powder or alloy debris on the ball milling tool, a small amount of hydrocarbons such as methanol, ethanol, stearic acid, and vacuum grease can be added as process control agents. Grinding has no effect on the structure of the final product.

Among the titanium-based amorphous alloys provided by the present invention, some alloys have strong amorphous forming ability and good thermal stability. Transformation, the formed supercooled liquid temperature range exceeds 50 ℃. This provides an opportunity for the processing and forming of amorphous alloys. Utilizing this feature can realize near-net-shape processing, making amorphous alloy powder into parts with complex shapes, or using powder metallurgy technologies such as hot pressing, hot isostatic pressing, warm extrusion, and sintering forging. Consolidation into bulk materials such as plates and rods.

Description of drawings:

Fig. 1 is the x-ray diffraction spectrum of seven kinds of alloy powders formed by mechanical grinding, which confirms that the alloy has an amorphous structure.

Wherein a) Ti ₄₅ Mg ₅ Cu ₂₀ Ni ₂₄ Si ₄ B ₂ (Example 1),

b) Ti ₆₄ V ₁₀ Fe ₁ Cu ₇ Ni ₁₂ Si ₄ B ₂ (Example 3),

c) _{Ti50Cu16Ni20Al8Si4B2 ( Example 5 ) ,}

_d ) _{Ti50Cu18Ni22Al4Sn3Si2B1 ( Example 7 ) ,}

_e ) _{Ti50Cu15Ni18Co10Pd1Si4B2 ( Example 9 ) ,}

_f ) _{Ti50Nb5Cu13Ni20Co6Si4B2 ( Example 11 ) ,}

g) Ti ₄₅ Zr ₅ Cu ₁₉ Ni ₂₃ Fe ₁ Co ₁ Si ₄ B ₂ (Example 13)

Figure 2 is the thermal analysis curves of seven alloy powders formed by mechanical grinding (heating rate is 40K/min).

Wherein a) Ti ₄₅ Mg ₅ Cu ₂₀ Ni ₂₄ Si ₄ B ₂ (Example 1),

b) Ti ₆₄ V ₁₀ Fe ₁ Cu ₇ Ni ₁₂ SiB ₂ (Example 3),

c) _{Ti50Cu16Ni20Al8Si4B2 ( Example 5 ) ,}

_d ) _{Ti50Cu18Ni22Al4Sn3Si2B1 ( Example 7 ) ,}

_e ) _{Ti50Cu15Ni18Co10Pd1Si4B2 ( Example 9 ) ,}

_f ) _{Ti50Nb5Cu13Ni20Co6Si4B2 ( Example 11 ) ,}

g) Ti ₅ Zr ₅ Cu ₁₉ Ni ₂₃ Fe ₁ Co ₁ Si ₄ B ₂ (Example 13)

Detailed ways:

Example 1 Ti ₄₅ Mg ₅ Cu ₂₀ Ni ₂₄ Si ₄ B ₂ alloy (alloy composition is atomic percentage, at.%, the same below).

Using commercially available metal element titanium, magnesium, copper, nickel powder and metalloid element silicon, boron powder as starting materials, the purity of the element powder is higher than 99.5% (weight percentage, wt.%, the same below), and the particle size is -200 Or -325 mesh, prepared as a powder mixture with a nominal composition of Ti ₄₅ Mg ₅ Cu ₂₀ Ni ₂₄ Si ₄ B ₂ . The powder mixture and GCr15 steel balls are filled in a quenched stainless steel ball mill tank under the atmosphere of high-purity Ar gas (99.99%) according to the weight ratio of balls and materials of 5:1. The closed ball mill jar was installed on a SPEX 8000 high-energy vibratory ball mill for grinding. After 48 hours of mechanical grinding, the powder mixture was confirmed to be an amorphous structure by X-ray diffraction, that is, an amorphous Ti ₄₅ Mg ₅ Cu ₂₀ Ni ₂₄ Si ₄ B ₂ alloy was formed, and the volume percentage of the amorphous phase was not less than 50%. The particle size of the powder is about 20-100 microns. The thermal analysis (differential scanning calorimeter, DSC, the same below) curve of the ball-milled powder can observe the endothermic phenomenon caused by glass transition and the exothermic reaction caused by crystallization. The X-ray diffraction spectrum and thermal analysis results of Ti ₄₅ Mg ₅ Cu ₂₀ Ni ₂₄ Si ₄ B ₂ alloy powder samples formed by mechanical grinding for 48 hours are shown in Fig. 1(a) and Fig. 2(a), respectively. Structural characteristics (amorphous, crystalline or amorphous + crystalline) and thermal analysis results of Ti ₄₅ Mg ₅ Cu ₂₀ Ni ₂₄ Si ₄ B ₂ amorphous alloy powder, namely glass transition temperature (T _g ), crystallization initiation temperature ( T _x ) and the subcooled liquid temperature region width (ΔT _x ) are listed in Table 1.

Example 2 Ti ₄₀ Mn ₁₀ Cu ₁₈ Ni ₂₆ Si ₄ B ₂ alloy.

Commercially available metal elements titanium, manganese, copper, nickel powder and metalloid element silicon, boron powder are used as starting materials, the purity of the element powder is higher than 99.5%, the particle size is -200 or -325 mesh, and the nominal composition is formulated as Ti ₄₀ Mn ₁₀ Cu ₁₈ Ni ₂₆ Si ₄ B ₂ powder mixture. The mechanical grinding process is the same as in Example 1. It is confirmed by X-ray diffraction that the element powder mixture after ball milling for 48 hours is basically a typical amorphous structure, that is, an amorphous Ti ₄₀ Mn ₁₀ Cu ₁₈ Ni ₂₆ Si ₄ B ₂ alloy is formed. The particle size of the powder is about 20-100 microns. The structural characteristics and thermal analysis results of the ball-milled powders are listed in Table 1.

Example 3 Ti ₆₄ V ₁₀ Fe ₁ Cu ₇ Ni ₁₂ Si ₄ B ₂ alloy.

The bulk materials (plates, strips, wires, rods or sheets) of commercially available metal elements titanium, vanadium, iron, copper, nickel and metalloid elements silicon and boron are used as starting materials, and the purity is higher than 99.5%. After the nominal composition of ₆₄ V ₁₀ Fe ₁ Cu ₇ Ni ₁₂ Si ₄ B ₂ was prepared, the alloy was arc-melted in a high-purity Ar gas (99.999%) atmosphere to form a master alloy button ingot with a weight of about 50 grams. The scrap of the master alloy ingot after mechanical crushing was used as the starting material for the subsequent mechanical grinding. The master alloy chips and GCr15 steel balls are filled in the quenched stainless steel ball mill tank under the atmosphere of high-purity Ar gas (99.99%) according to the weight ratio of balls and materials of 5:1. The closed ball mill jar was installed on a SPEX 8000 high-energy vibratory ball mill for grinding. After the powder mixture was mechanically ground for 32 hours, it was confirmed by X-ray diffraction that the starting material had transformed into an amorphous structure, that is, an amorphous Ti ₆₅₄ V ₁₀ Fe ₁ Cu ₇ Ni ₁₂ Si ₄ B ₂ alloy was formed. The particle size of the powder is about 20-100 microns. No endothermic phenomenon caused by glass transition was observed on the thermal analysis curve of the ball-milled powder, but exothermic reaction caused by crystallization still appeared, which further confirmed the amorphous nature of the powder. The X-ray diffraction spectrum and thermal analysis results of the Ti ₆₄ V ₁₀ Fe ₁ Cu ₇ Ni ₁₂ Si ₄ B ₂ alloy powder formed by mechanical grinding for 32 hours are shown in Fig. 1(b) and Fig. 2(b), respectively.

The structural characteristics and thermal analysis results of Ti ₆₄ V ₁₀ Fe ₁ Cu ₇ Ni ₁₂ Si ₄ B ₂ amorphous alloy powders are listed in Table 1.

Example 4 Ti ₅₅ Zr ₅ Fe ₂ Cu ₁₃ Ni ₁₉ Si ₄ B ₂ alloy.

Commercially available metal elements titanium, zirconium, iron, copper, nickel, etc. and metalloid elements silicon and boron bulk materials (plates, strips, wires, rods or sheets) are used as starting materials, and the purity is higher than 99.5%. After preparing the alloy with the nominal composition of Ti ₅₅ Zr ₅ Fe ₂ Cu ₁₃ Ni ₁₉ Si ₄ B ₂ , the preparation and mechanical grinding process of the master alloy chips are the same as in Example 3. X-ray diffraction of the powder after ball milling for 48 hours confirmed that the alloy powder transformed into an amorphous structure, that is, an amorphous Ti ₅₅ Zr ₅ Fe ₂ Cu ₁₃ Ni ₁₉ Si ₄ B ₂ alloy was formed. The particle size of the powder is about 20-100 microns. The thermal analysis curve of the ball-milled powder can observe the endothermic phenomenon caused by glass transition and the exothermic reaction caused by crystallization. The structural characteristics and thermal analysis results of the ball-milled powders are listed in Table 1.

Example 5 Ti ₅₀ Cu ₁₆ Ni ₂₀ Al ₈ Si ₄ B ₂ alloy

Using commercially available metal elements titanium, copper, nickel, aluminum powder and metalloid element silicon, boron powder as starting materials, the element powder purity is higher than 99.5%, the particle size is -200 or -325 mesh, and the nominal composition is prepared as Ti ₅₀ Cu ₁₆ Ni ₂₀ Al ₈ Si ₄ B ₂ powder mixture, the powder mechanical grinding process is the same as in Example 1. The powder after ball milling for 48 hours was confirmed to be amorphous by X-ray diffraction. That is, an amorphous Ti ₅₀ Cu ₁₆ Ni ₂₀ Al ₈ Si ₄ B ₂ alloy is formed. The particle size of the powder is about 20-100 microns. The thermal analysis curve of the ball-milled powder can observe the endothermic phenomenon caused by glass transition and the exothermic reaction caused by crystallization. The X-ray diffraction spectrum and thermal analysis results of the Ti ₅₀ Cu ₁₆ Ni ₂₀ Al ₈ Si ₄ B ₂ alloy powder formed by mechanical grinding for 48 hours are shown in Fig. 1(c) and Fig. 2(c), respectively. The structural characteristics and thermal analysis results of Ti ₅₀ Cu ₁₆ Ni ₂₀ Al ₈ Si ₄ B ₂ amorphous alloy powders are listed in Table 1.

Example 6 Ti ₇₀ Cu ₉ Ni ₁₃ Co ₂ Si ₄ B ₂ alloy.

The bulk materials (plates, strips, wires, rods or sheets) of commercially available metal elements titanium, copper, nickel, cobalt and metalloid elements silicon and boron are used as starting materials, and the purity is higher than 99.5%, according to Ti ₇₀ Cu After the nominal composition of ₉ Ni ₁₃ Co ₂ Si ₄ B ₂ is formulated into the alloy, the preparation and mechanical grinding process of the master alloy chips are the same as in Example 3. The alloy powder after ball milling for 48 hours was confirmed to be an amorphous structure by X-ray diffraction, that is, an amorphous Ti ₇₀ Cu ₉ Ni ₁₃ Co ₂ Si ₄ B ₂ alloy was formed. The particle size of the powder is about 20-100 microns. The exothermic reaction due to the crystallization transition of the amorphous phase can be observed in the thermal analysis curve of the ball milled powder. The structural characteristics and thermal analysis results of the ball-milled powders are listed in Table 1.

Example 7 Ti ₅₀ Cu ₁₈ Ni ₂₂ Al ₄ Sn ₃ Si ₂ B ₁ alloy.

Commercially available metal element titanium, copper, nickel, aluminum, tin powder and metalloid element silicon, boron powder are used as starting materials, the purity of the element powder is higher than 99.5%, the particle size is -200 or -325 mesh, and the nominal composition is prepared It is a powder mixture of Ti ₅₀ Cu ₁₈ Ni ₂₂ Al ₄ Sn ₃ Si ₂ B ₁ . The mechanical milling procedure of the powder blend was the same as in Example 1. The powder after ball milling for 48 hours was confirmed to be an amorphous structure by X-ray diffraction, that is, an amorphous Ti ₅₀ Cu ₁₈ Ni ₂₂ Al ₄ Sn ₃ Si ₂ B ₁ alloy was formed. The particle size of the powder is about 20-100 microns. The thermal analysis curve of the ball-milled powder can observe the endothermic phenomenon caused by the glass transition and the exothermic reaction caused by the crystallization transition of the amorphous phase. The X-ray diffraction spectrum and thermal analysis results of the Ti ₅₀ Cu ₁₈ Ni ₂₂ Al ₄ Sn ₃ Si ₂ B ₁ alloy powder sample formed by mechanical grinding for 48 hours are shown in Figure 1(d) and Figure 2(d), respectively. The structural characteristics and thermal analysis results of Ti ₅₀ Cu ₁₈ Ni ₂₂ Al ₄ Sn ₃ Si ₂ B ₁ amorphous alloy powders are listed in Table 1.

Example 8 Ti ₅₀ Cu ₁₃ Ni ₁₈ Al ₁₂ Fe ₁ Si ₄ B ₂ alloy.

The bulk materials (plates, strips, wires, rods or sheets) of commercially available metal elements titanium, copper, nickel, aluminum, iron and metalloid elements silicon and boron are used as starting materials, and the purity is higher than 99.5%. According to Ti After preparing the alloy with the nominal composition of ₅₀ Cu ₁₃ Ni ₁₈ Al ₁₂ Fe ₁ Si ₄ B ₂ , the preparation and mechanical grinding process of the master alloy chips are the same as in Example 3. The powder after ball milling for 48 hours was confirmed to be an amorphous structure by X-ray diffraction, that is, an amorphous Ti ₅₀ Cu ₁₃ Ni ₁₈ Al ₁₂ Fe ₁ Si ₄ B ₂ alloy was formed. The particle size of the powder is about 20-100 microns. The exothermic reaction due to the crystallization transition of the amorphous phase can be observed in the thermal analysis curve of the ball milled powder. The structural characteristics and thermal analysis results of the ball-milled powders are listed in Table 1.

Example 9 Ti ₅₀ Cu ₁₅ Ni ₁₈ Co ₁₀ Pd ₁ Si ₄ B ₂ alloy.

The bulk materials (plates, strips, wires, rods or sheets) of commercially available metal elements titanium, copper, nickel, cobalt, palladium and metalloid elements silicon and boron are used as starting materials, and the purity is higher than 99.5%. After preparing the alloy with the nominal composition of ₅₀ Cu ₁₅ Ni ₁₈ Co ₁₀ Pd ₁ Si ₄ B ₂ , the preparation and mechanical grinding process of the master alloy chips are the same as in Example 3. The powder after ball milling for 48 hours was confirmed to be amorphous by X-ray diffraction, that is, an amorphous Ti ₅₀ Cu ₁₅ Ni ₁₈ Co ₁₀ Pd ₁ Si ₄ B ₂ alloy was formed, and the volume percentage of the amorphous phase was not less than 50%. The particle size of the powder is about 20-100 microns. The exothermic reaction caused by the crystallization transition of the amorphous phase can be observed in the thermal analysis curve of the ball milled powder. The X-ray diffraction spectrum and thermal analysis results of the Ti ₅₀ Cu ₁₅ Ni ₁₈ Co ₁₀ Pd ₁ Si ₄ B ₂ alloy powder sample formed by mechanical grinding for 32 hours are shown in Figure 1(e) and Figure 2(e), respectively. The structural characteristics and thermal analysis results of Ti ₅₀ Cu ₁₅ Ni ₁₈ Co ₁₀ Pd ₁ Si ₄ B ₂ amorphous alloy powders are listed in Table 1.

Example 10 Ti ₄₅ V ₅ Cu ₁₉ Ni ₂₃ Co ₂ Si ₄ B ₂ alloy.

The bulk materials (plates, strips, wires, rods or sheets) of commercially available metal elements titanium, vanadium, copper, nickel, cobalt and metalloid elements silicon and boron are used as starting materials, and the purity is higher than 99.5%. The nominal composition of ₄₅ V ₅ Cu ₁₉ Ni ₂₃ Co ₂ Si ₄ B ₂ was used to prepare the alloy, and the preparation and mechanical grinding process of the master alloy chips were the same as in Example 3. The powder after ball milling for 48 hours was confirmed to be an amorphous structure by X-ray diffraction, that is, an amorphous Ti ₄₅ V ₅ Cu ₁₉ Ni ₂₃ Co ₂ Si ₄ B ₂ alloy was formed. The particle size of the powder is about 20-100 microns. The structural characteristics and thermal analysis results of the ball-milled powders are listed in Table 1.

Example 11 Ti ₅₀ Nb ₅ Cu ₁₃ Ni ₂₀ Co ₆ Si ₄ B ₂ alloy.

The bulk materials (plates, strips, wires, rods or sheets) of commercially available metal elements titanium, niobium, copper, nickel, cobalt and metalloid elements silicon and boron are used as starting materials, and the purity is higher than 99.5%. The nominal composition of ₅₀ Nb ₅ Cu ₁₃ Ni ₂₀ Co ₆ Si ₄ B ₂ formulated the alloy. The preparation and mechanical grinding process of the master alloy chips are the same as in Example 3. The powder after ball milling for 48 hours was confirmed to be an amorphous structure by X-ray diffraction, that is, an amorphous Ti ₅₀ Nb ₅ Cu ₁₃ Ni ₂₀ Co ₆ Si ₄ B ₂ alloy was formed, and the volume percentage of the amorphous phase was greater than 50%. The particle size of the powder is about 20-100 microns. The exothermic reaction caused by the crystallization transition of the amorphous phase can be observed in the thermal analysis curve of the ball milled powder. The X-ray diffraction spectrum and thermal analysis results of Ti ₅₀ Nb ₅ Cu ₁₃ Ni ₂₀ Co ₆ Si ₄ B ₂ alloy powder samples formed by mechanical grinding for 48 hours are shown in Figure 1(f) and Figure 2(f), respectively. The structural characteristics and thermal analysis results of Ti ₅₀ Nb ₅ Cu ₁₃ Ni ₂₀ Co ₆ Si ₄ B ₂ amorphous alloy powders are listed in Table 1.

Example 12 Ti ₅₀ Nb ₁ Fe ₁ Cu ₁₅ Ni ₁₉ Al ₈ Sn ₃ Si ₂ B ₁ alloy.

Using commercially available metal elements titanium, niobium, iron, copper, nickel, aluminum, tin powder and metalloid element silicon, boron powder as starting materials, the element powder purity is higher than 99.5%, and the particle size is -200 or -325 mesh. Prepare a powder mixture whose nominal composition is Ti ₅₀ Nb ₁ Fe ₁ Cu ₁₅ Ni ₁₉ Al ₈ Sn ₃ Si ₂ B ₁ . The mechanical milling procedure of the powder blend was the same as in Example 1. The powder after ball milling for 48 hours was confirmed to be amorphous by X-ray diffraction, that is, an amorphous Ti ₅₀ Nb ₁ Fe ₁ Cu ₁₅ Ni ₁₉ Al ₈ Sn ₃ Si ₂ B ₁ alloy was formed. The particle size of the powder is about 20-100 microns. The structural characteristics and thermal analysis results of the ball-milled powders are listed in Table 1.

Example 13 Ti ₄₅ Zr ₅ Cu ₁₉ Ni ₂₃ Fe ₁ Co ₁ Si ₄ B ₂ alloy.

The commercially available metal elements titanium, zirconium, copper, nickel, iron, cobalt, etc. and the bulk materials (plates, strips, wires, rods or sheets) of metalloid elements silicon and boron are used as starting materials, and the purity is higher than 99.5%. , after preparing the alloy according to the nominal composition of Ti ₄₅ Zr ₅ Cu ₁₉ Ni ₂₃ Fe ₁ Co ₁ Si ₄ B ₂ . The preparation and mechanical grinding process of the master alloy chips are the same as in Example 3. The powder after ball milling for 48 hours is confirmed to be amorphous by X-ray diffraction, that is, an amorphous Ti ₄₅ Zr ₅ Cu ₁₉ Ni ₂₃ Fe ₁ Co ₁ Si ₄ B ₂ alloy is formed, and the volume percentage of the amorphous phase is greater than 50% . The particle size of the powder is about 20-100 microns. The exothermic reaction caused by the crystallization transition of the amorphous phase can be observed in the thermal analysis curve of the ball milled powder. The X-ray diffraction spectrum and thermal analysis results of the ball-milled amorphous powder samples are shown in Fig. 1(g) and Fig. 2(g), respectively. The structural characteristics and thermal analysis results of Ti ₄₅ Zr ₅ Cu ₁₉ Ni ₂₃ Fe ₁ Co ₁ Si ₄ B ₂ amorphous alloy powders are listed in Table 1.

Example 14 Ti ₄₀ Mg ₁₀ Nb ₁ Cu ₁₉ Ni ₂₃ Fe ₁ Co ₁ Sn ₅ alloy.

The bulk materials (plates, strips, wires, rods or sheets) of commercially available metal elements titanium, magnesium, niobium, copper, nickel, iron, cobalt, tin, etc. are used as starting materials, and the purity is higher than 99.5%. Nominal composition of ₄₀ Mg ₁₀ Nb ₁ Cu ₁₉ Ni ₂₃ Fe ₁ Co ₁ Sn ₅ after alloying. The preparation and mechanical grinding process of the master alloy chips are the same as in Example 3. The powder after ball milling for 48 hours was confirmed to be amorphous by X-ray diffraction, that is, an amorphous Ti ₄₀ Mg ₁₀ Nb ₁ Cu ₁₉ Ni ₂₃ Fe ₁ Co ₁ Sn ₅ alloy was formed, and the volume percentage of the amorphous phase was not less than 50 %. The particle size of the powder is about 20-100 microns. The structural characteristics and thermal analysis results of the ball-milled powders are listed in Table 1.

Structural characteristics and thermal analysis results of 14 kinds of mechanically ground alloy powders given in the examples in Table 1 ^*

  (heating rate is 40K/min)

Example Powder T _g T _x ΔT _x

  Alloy composition (at.%)

serial number

Phase Structure (K) (K) (K)

1 Ti ₄₅ Mg ₅ Cu ₂₀ Ni ₂₄ Si ₄ B ₂ Am+Cry 644 761 117

2 Ti ₄₀ Mn ₁₀ Cu ₁₈ Ni ₂₆ Si ₄ B ₂ Am -- 773 --

3 Ti ₆₄ V ₁₀ Fe ₁ Cu ₇ Ni ₁₂ Si ₄ B ₂ Am+Cry -- 774 --

4 Ti ₅₅ Zr ₅ Fe ₂ Cu ₁₃ Ni ₁₉ Si ₄ B ₂ Am+Cry 703 756 53

5 Ti ₅₀ Cu ₁₆ Ni ₂₀ Al ₈ Si ₄ B ₂ Am 721 781 60

6 Ti ₇₀ Cu ₉ Ni ₁₃ Co ₂ Si ₄ B ₂ Am 698 758 60

7 Ti ₅₀ Cu ₁₈ Ni ₂₂ Al ₄ Sn ₃ Si ₂ B ₁ Am 711 775 64

8 Ti ₅₀ Cu ₁₃ Ni ₁₈ Al ₁₂ Fe ₁ Si ₄ B ₂ Am -- 774 --

9 Ti ₅₀ Cu ₁₅ Ni ₁₈ Co ₁₀ Pd ₁ Si ₄ B ₂ Am+Cry -- 753 --

10 Ti ₄₅ V ₅ Cu ₁₉ Ni ₂₃ Co ₂ Si ₄ B ₂ Am -- 757 --

11 Ti ₅₀ Nb ₅ Cu ₁₃ Ni ₂₀ Co ₆ Si ₄ B ₂ Am+Cry -- 752 --

12 Ti ₅₀ Nb ₁ Fe ₁ Cu ₁₅ Ni ₁₉ Al ₈ Sn ₃ Si ₂ B ₁ Am -- 763 --

13 Ti ₄₅ Zr ₅ Cu ₁₉ Ni ₂₃ Fe ₁ Co ₁ Si ₄ B ₂ Am+Crv 700 752 52

14 Ti ₄₀ Mg ₁₀ Nb ₁ Cu ₁₉ Ni ₂₃ Fe ₁ Co ₁ Sn ₅ Am+Cry -- 747 --

^* Am means that the alloy forms a completely amorphous phase, Am+Cry means that the alloy is a mixture of amorphous phase (Am) and crystal phase (Cry); T _g is the glass transition temperature, T _x is the initiation of crystallization transition of the amorphous phase ΔT _x is the width of the supercooled liquid temperature range (ΔT _x =T _x -T _g ).

Claims (9)

1, a kind of multicomponent titanium base alloy that forms amorphous structure is characterized in that the expression formula of alloying constituent is: Ti _aM _b(Cu _xNi _1-x) _cZ _eA wherein, b, c, e are atomic percent, x is an atomic fraction, M is selected from Mg, and Z is selected from least a in B, Ge, Si, C, the Sn element, a=37～77%, b=0.5～27%, c=20～50%, e=1～15%, a+b+c+e=100%, x=0.35～0.75.

2, a kind of multicomponent titanium base alloy that forms amorphous structure is characterized in that the expression formula of alloying constituent is: Ti _aM _b(Cu _xNi _1-x) _cZ _eA wherein, b, c, e is an atomic percent, x is an atomic fraction, and M is selected from least a in Mg, Ca, Mn, Nb, Fe, V, Mo, the Zr element, and Z is selected from least a in Sn or Sn and B, the Si element, a=37～77%, b=0.5～27%, c=20～50%, e=1～15%, a+b+c+e=100%, x=0.35～0.75.

3, a kind of multicomponent titanium base alloy that forms amorphous structure is characterized in that the expression formula of alloying constituent is: Ti _a(Cu _xNi _1-x) _cR _dZ _e, a wherein, c, d, e are atomic percent, x is an atomic fraction, and R is selected from Al, and Z is selected from least a in B, Ge, Si, C, the Sn element, a=37～77%, c=20～50%, d=0.5～17%, e=1～15%, a+c+d+e=100%, x=0.35～0.75.

4, a kind of multicomponent titanium base alloy that forms amorphous structure is characterized in that the expression formula of alloying constituent is: Ti _a(Cu _xNi _1-x) _cR _dZ _e, a wherein, c, d, e are atomic percent, and x is an atomic fraction, R is selected from least a in Al, Ag, Co, Fe, Pd, the Zn element, Z is selected from least a in Sn or Sn and B, the Si element, a=37～77%, c=20～50%, d=0.5～17%, e=1～15%, a+c+d+e=100%, x=0.35～0.75.

5, a kind of multicomponent titanium base alloy that forms amorphous structure is characterized in that the expression formula of alloying constituent is: Ti _aM _b(Cu _xNi _1-x) _cR _dZ _e, a wherein, b, c, d, e are atomic percent, x is an atomic fraction, and M is selected from Mg, and R is selected from Al, and Z is selected from least a in B, Ge, Si, C, the Sn element, a=37～77%, b=0.5～27%, c=20～50%, d=0.5～17%, e=1～15%, a+b+c+d+e=100%.x＝0.35～0.75。

6, a kind of multicomponent titanium base alloy that forms amorphous structure is characterized in that the expression formula of alloying constituent is: Ti _aM _b(Cu _xNi _1-x) _cR _dZ _e, a wherein, b, c, d, e are atomic percent, x is an atomic fraction, and M is selected from least a in Mg, Ca, Mn, Nb, Fe, V, Mo, the Zr element, and R is selected from least a in Al, Ag, Co, Pd, the Zn element, Z is selected from least a in Sn or Sn and B, the Si element, a=37～77%, b=0.5～27%, c=20～50%, d=0.5～17%, e=1～15%, a+b+c+d+e=100%.x＝0.35～0.75。

7, according to the described multicomponent titanium base alloy that forms amorphous structure of one of claim 1～6, it is characterized in that: described a=37～70%.

8, according to claim 1,2, the 5 or 6 described multicomponent titanium base alloys that form amorphous structure, it is characterized in that: described b=0.5～20%.

9, according to the described multicomponent titanium base alloy that forms amorphous structure of one of claim 1～6, it is characterized in that: described e=1～12%.

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