Nickel-based amorphous alloy material as well as preparation method and application thereof

Abstract

The invention relates to the technical field of amorphous alloy materials, in particular to a nickel-based amorphous alloy material and a preparation method and application thereof. The chemical formula of the nickel-based amorphous alloy material is shown as NiaNbbTacPdFee (I), a, b, c, d and e are mass percentage contents of corresponding component atoms respectively, 40 < = a < = 60, 10 < = b < = 30, 10 < = c < = 30, 1 < = d < = 15, 0 < = e < = 15, and a + b + c + d + e = 100. The nickel-based amorphous alloy material provided by the invention is easy to form a completely amorphous structure, has high thermal stability and high-temperature hydrochloric acid corrosion resistance, and can act on a high-corrosion-resistance alloy system to be used in a severe high-temperature hydrochloric acid working condition.

Description

Technical Field

[0001] The present invention relates to the technical field of amorphous alloy materials, and in particular to a nickel-based amorphous alloy material, a preparation method thereof, and an application thereof. Background Art

[0002] Amorphous alloy materials exhibit a series of unique physical, chemical, and mechanical properties, such as high strength, high elasticity, and high corrosion resistance, due to the long-range disorder and short-range order of the internal atomic arrangement. In recent years, the composition design, performance detection, and practical application of amorphous alloy materials have become one of the important research directions in the field of materials science and engineering. However, due to many factors such as raw material purity and cooling rate, it is difficult for metal alloys to form large-sized bulk amorphous materials. Generally, by adding appropriate alloying elements, the glass-forming ability and properties of amorphous alloy materials can be improved.

[0003] Nickel-based alloy materials not only have high high-temperature mechanical properties but also have good chemical stability. As one of the important amorphous alloy systems, nickel-based amorphous alloys have been widely studied, and a series of nickel-based amorphous alloy composition systems with certain glass-forming ability have been developed, such as Ni-Nb, Ni-Pd-P, Ni-Fe, Ni-Nb-Co, Ni-Zr, Ni-Nb-Ta, etc., especially in the field of high-temperature corrosion-resistant alloys, they have a wide application background. At present, the glass-forming ability of nickel-based amorphous alloys is still relatively low, and the high-temperature hydrochloric acid corrosion resistance of the alloys is not strong. Pitting corrosion and uniform corrosion often occur during use, which is not conducive to the engineering application of the alloys. Therefore, the design and development of new amorphous nickel-based alloy materials with both high glass-forming ability and high-temperature hydrochloric acid corrosion resistance have important theoretical value and engineering practical significance. Summary of the Invention

[0004] The purpose of the present invention is to overcome the above technical problems and provide a nickel-based amorphous alloy material, a preparation method thereof, and an application thereof. The nickel-based amorphous alloy material has complete amorphous, high corrosion resistance, and good thermal stability at the same time.

[0005] To achieve the above purpose, in the first aspect of the present invention, a nickel-based amorphous alloy material is provided. The nickel-based amorphous alloy material has a composition shown in formula (I): Ni a Nb b Ta c P d Fe e wherein a, b, c, d, and e are the mass percentage contents of the respective corresponding components. 40 ≤ a ≤ 60, 10 ≤ b ≤ 30, 10 ≤ c ≤ 30, 1 ≤ d ≤ 15, 0 ≤ e ≤ 15, and a + b + c + d + e = 100.

[0006] Preferably, in formula I, 2 ≤ a / c ≤ 4, preferably 3 ≤ a / c ≤ 4.

[0007] Preferably, in formula I, 0.5 ≤ b / c ≤ 1.5, preferably 0.7 ≤ b / c ≤ 1.

[0008] The second aspect of the present invention provides a method for preparing a nickel-based amorphous alloy material, and the preparation method includes:

[0009] (1) In an inert atmosphere, melting alloy raw materials satisfying formula I to obtain an alloy ingot;

[0010] (2) Subjecting the alloy ingot to impurity removal, cleaning, and liquid rapid quenching in sequence to obtain a nickel-based amorphous alloy material;

[0011] Among them, the nickel-based amorphous alloy material has the composition shown in chemical formula Ni a Nb b Ta c P d Fe e (I), where a, b, c, d, and e are the mass percentage contents of the atoms of the corresponding components respectively, 40 ≤ a ≤ 60, 10 ≤ b ≤ 30, 10 ≤ c ≤ 30, 1 ≤ d ≤ 15, 0 ≤ e ≤ 15, and a + b + c + d + e = 100.

[0012] The third aspect of the present invention provides a nickel-based amorphous alloy material prepared by the preparation method provided in the second aspect.

[0013] The fourth aspect of the present invention provides an application of the nickel-based amorphous alloy materials provided in the first aspect and the third aspect in the industrial scenarios of high-temperature chlorine-containing and concentrated hydrochloric acid.

[0014] Compared with the prior art, the present invention has the following advantages:

[0015] (1) For the nickel-based amorphous alloy material provided by the present invention, by defining that Ni, Nb, Ta, Fe, and P satisfy the composition of formula I, especially when controlling the mass content of Ta to be 10 - 30 wt%, it is easy to form a completely amorphous structure, and has high thermal stability and the ability to resist high-temperature hydrochloric acid corrosion, and can be used as a highly corrosion-resistant alloy system in harsh high-temperature hydrochloric acid working conditions;

[0016] (2) The nickel-based amorphous alloy material provided by the present invention has high corrosion resistance, and shows better corrosion resistance than Hastelloy C276 and 304 stainless steel in artificial seawater and high-temperature hydrochloric acid solutions. Especially after being immersed in an 80 °C hydrochloric acid solution with a concentration of 32 wt% for 7 months, the surface still maintains metallic luster and no obvious corrosion is seen. Description of the Drawings

[0017] Figure 1is the TG-DSC curve of the nickel-based amorphous alloy material S1 provided in Example 1, with a heating rate of 20 K / min;

[0018] Figure 2 is the XRD pattern of the nickel-based amorphous alloy material S1 provided in Example 1;

[0019] Figure 3 is the potentiodynamic polarization curve of the nickel-based amorphous alloy material S1, Hastelloy C276 and 304 stainless steel in a 32 wt% hydrochloric acid corrosion solution at 25 °C. The reference electrode is a saturated calomel electrode (SCE), and the potential scanning rate is 1 mV / s;

[0020] Figure 4 is the potentiodynamic polarization curve of the nickel-based amorphous alloy material S1, Hastelloy C276 and 304 stainless steel in a 32 wt% hydrochloric acid corrosion solution at 80 °C. The reference electrode is a saturated calomel electrode (SCE), and the potential scanning rate is 1 mV / s;

[0021] Figure 5 is the corrosion rate curve of the nickel-based amorphous alloy material S1, Hastelloy C276 and 304 stainless steel in a 32 wt% hydrochloric acid solution, based on the JB / T 7901-1999 standard, "Full immersion test for uniform corrosion of metal materials in the laboratory". Detailed implementation mode

[0022] In the ranges disclosed herein, the endpoints and any values are not limited to the exact ranges or values, and these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, the endpoint values of each range, between the endpoint values of each range and individual point values, and between individual point values can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be regarded as specifically disclosed herein.

[0023] The first aspect of the present invention provides a nickel-based amorphous alloy material, and the nickel-based amorphous alloy material has a composition shown in Chemical Formula (I), where a, b, c, d, and e are the mass percentage contents of the corresponding component atoms respectively, 40 ≤ a ≤ 60, 10 ≤ b ≤ 30, 10 ≤ c ≤ 30, 1 ≤ d ≤ 15, 0 ≤ e ≤ 15, and a + b + c + d + e = 100. a Nb b Ta c P d Fe e (I)

[0024] The inventors of the present invention have found through research that: based on a systematic study of the elements Ni, Nb, Ta, Fe, and P, it is found that in the NiNbTaPFe quinary alloy system, when the mass percentage content of tantalum atoms is 10 - 30 wt%, an amorphous structure is easily formed. Compared with pure rare metal tantalum, the amount of high-cost tantalum used in this nickel-based amorphous alloy material is less; combined with specific contents of Ni, Nb, Fe, and P, it is easier to form a completely amorphous structure, and its glass-forming ability is strong; at the same time, this nickel-based amorphous alloy material also has a relatively high glass transition temperature T g and crystallization temperature T x , the larger the value, the more the material can maintain the amorphous state in a high-temperature environment without undergoing solid-liquid transformation, that is, the material can maintain stability in a high-temperature environment, is not easily crystallized or melted, indicating that it has high thermal stability; this nickel-based amorphous alloy material also has a low corrosion rate, indicating that it has high-temperature corrosion resistance and can be applied to industrial scenarios involving high-temperature chlorine-containing and concentrated hydrochloric acid, especially in the fields of petrochemical, chemical, pharmaceutical, and molten salt power generation.

[0025] In the present invention, unless otherwise specified, a, b, c, d, and e are respectively the mass percentage contents of the corresponding component atoms based on the total weight of the nickel-based amorphous alloy material. The Ni content is 40 - 60 wt%, the Nb content is 10 - 30 wt%, the Ta content is 10 - 30 wt%, the Fe content is 0 - 15 wt%, the P content is 1 - 15 wt%, and the total content of Ni, Nb, Ta, P, and Fe is 100 wt%.

[0026] In some embodiments of the present invention, in formula I, 40 ≤ a ≤ 60, for example, 40, 45, 49, 50, 51, 53, 55, 60, and any value within the range composed of any two numerical values, preferably 45 ≤ a ≤ 55, more preferably 49 ≤ a ≤ 51.

[0027] In some embodiments of the present invention, in formula I, 10 ≤ b ≤ 30, for example, 10, 11, 12, 13, 14, 15, 18, 20, 25, 30, and any value within the range composed of any two numerical values, preferably 10 ≤ b ≤ 20, more preferably 10 ≤ b ≤ 15.

[0028] In some embodiments of the present invention, in formula I, 10 ≤ c ≤ 30, for example, 10, 11, 12, 13, 14, 15, 18, 20, 25, 30, and any value within the range composed of any two numerical values, preferably 10 ≤ c ≤ 20, more preferably 10 ≤ c ≤ 15.

[0029] In some embodiments of the present invention, in formula I, 1 ≤ d ≤ 15, for example, 1, 2, 5, 6, 7, 8, 9, 10, 12, 15, and any value within the range composed of any two numerical values, preferably 1 ≤ d ≤ 10, more preferably 5 ≤ d ≤ 10.

[0030] In some embodiments of the present invention, in formula I, 0 ≤ e ≤ 15, for example, 0, 2, 5, 8, 10, 12, 13, 15, and any value within the range composed of any two numerical values, preferably 5 ≤ e ≤ 15, more preferably 10 ≤ e ≤ 15; and a + b + c + d + e = 100 is satisfied.

[0031] In the present invention, when the content of each component in formula I meets the above limitations, on the premise that the nickel-based amorphous alloy material has a completely amorphous structure, it has excellent thermal stability and corrosion resistance.

[0032] In the present invention, there is a wide selection range for the composition of the nickel-based amorphous alloy material, as long as it meets the composition of formula I above. Preferably, the nickel-based amorphous alloy material includes, but is not limited to, Ni 50 Nb 14 Ta 14 P 9 Fe 13 、Ni 50 Nb 17 Ta 13 P 7 Fe 13 、Ni 51 Nb 17 Ta 11 P 7 Fe 14 etc.

[0033] In some embodiments of the present invention, preferably, in formula I, 2 ≤ a / c ≤ 4, for example, 2, 3, 3.2, 3.5, 3.8, 4, and any value within the range composed of any two numerical values, preferably 3 ≤ a / c ≤ 4. Meeting the above limitations further regulates the thermal stability and corrosion resistance of the nickel-based amorphous alloy material.

[0034] In some embodiments of the present invention, preferably, in formula I, 0.5 ≤ b / c ≤ 1.5, for example, 0.5, 0.7, 0.8, 0.9, 1, 1.5, and any value within the range composed of any two numerical values, preferably 0.7 ≤ b / c ≤ 1. Meeting the above limitations further regulates the corrosion resistance, grain refinement, and high-temperature stability of the nickel-based amorphous alloy material.

[0035] In the present invention, the XRD pattern of the nickel-based amorphous alloy material exhibits a typical amorphous hump peak. Preferably, the nickel-based amorphous alloy material has a completely amorphous structure.

[0036] In some embodiments of the present invention, preferably, the nickel-based amorphous alloy material is in the form of a block, a thin strip, a sheet, a wedge shape, or a stepped shape.

[0037] In some embodiments of the present invention, preferably, the nickel-based amorphous alloy material has a length of 50 - 100 cm, a width of 2 - 3 mm, and a thickness of 20 - 50 μm.

[0038] In some embodiments of the present invention, preferably, the supercooled liquid region width ΔT of the nickel-based amorphous alloy material x ≥50 K, preferably 100 - 150 K. For example, 50 K, 70 K, 80 K, 100 K, 110 K, 120 K, 130 K, 140 K, 150 K, and any value within the range composed of any two of these values. In the present invention, when the above-defined range is satisfied, the nickel-based amorphous alloy material has high thermal stability.

[0039] In the present invention, unless otherwise specified, the supercooled liquid region width ΔT x = crystallization temperature T x - glass transition temperature T g .

[0040] In some embodiments of the present invention, more preferably, the glass transition temperature T of the nickel-based amorphous alloy material g ≥800 K. For example, 800 K, 900 K, 980 K, 990 K, 1000 K, and any value within the range composed of any two of these values, preferably 980 - 1000 K.

[0041] In some embodiments of the present invention, more preferably, the crystallization temperature T of the nickel-based amorphous alloy material x ≥850 K. For example, 850 K, 900 K, 1100 K, 1110 K, 1120 K, 1130 K, 1140 K, 1150 K, and any value within the range composed of any two of these values, preferably 1100 - 1150 K.

[0042] In some embodiments of the present invention, preferably, the reduced glass transition temperature of the nickel-based amorphous alloy material is ≥ 0.5 K, for example, 0.5 K, 0.6 K, 0.7 K, 0.8 K, 0.9 K, 1 K, and any value within the range composed of any two of these values, preferably 0.6 - 1 K. Meeting the above limitations, when the temperature is higher than the reduced glass transition temperature, the material presents a flowing liquid state; when the temperature is lower than the reduced glass transition temperature, the material presents a solid state with high stability.

[0043] In some embodiments of the present invention, preferably, in 32 wt% concentrated hydrochloric acid at a temperature of 80 °C, the annual corrosion rate of the nickel-based amorphous alloy material is ≤ 0.2 μm / a, preferably ≤ 0.01 μm / a, and more preferably 0 μm / a.

[0044] The second aspect of the present invention provides a preparation method of a nickel-based amorphous alloy material, and the preparation method includes:

[0045] (1) In an inert atmosphere, melting alloy raw materials satisfying formula I to obtain an alloy ingot;

[0046] (2) Sequentially performing impurity removal, cleaning, and liquid rapid quenching on the alloy ingot to obtain a nickel-based amorphous alloy material;

[0047] Among them, the nickel-based amorphous alloy material has the composition shown in chemical formula Ni a Nb b Ta c P d Fe e (I), where a, b, c, d, and e are the mass percentage contents of the atoms of the corresponding components respectively, 40 ≤ a ≤ 60, 10 ≤ b ≤ 30, 10 ≤ c ≤ 30, 1 ≤ d ≤ 15, 0 ≤ e ≤ 15, and a + b + c + d + e = 100.

[0048] In some embodiments of the present invention, preferably, in step (1), in terms of elements, the mass ratio of nickel, niobium, tantalum, phosphorus, and iron in the alloy raw materials satisfies (40 - 60):(10 - 30):(10 - 30):(1 - 15):(0 - 15); further preferably, in terms of elements, the mass ratio of nickel, niobium, tantalum, phosphorus, and iron in the alloy raw materials satisfies (45 - 55):(10 - 20):(10 - 20):(1 - 10):(5 - 15); more preferably, in terms of elements, the mass ratio of nickel, niobium, tantalum, phosphorus, and iron in the alloy raw materials satisfies (49 - 51):(10 - 15):(10 - 15):(5 - 10):(10 - 15).

[0049] In a specific embodiment of the present invention, by element, the mass ratio of elemental nickel, elemental niobium, elemental tantalum, elemental phosphorus and elemental iron satisfies (40 - 60):(10 - 30):(10 - 30):(1 - 15):(0 - 15); preferably satisfies (45 - 55):(10 - 20):(10 - 20):(1 - 10):(5 - 15); more preferably satisfies (49 - 51):(10 - 15):(10 - 15):(5 - 10):(10 - 15).

[0050] In some embodiments of the present invention, preferably, the melting is carried out in a vacuum arc melting furnace or a levitation induction melting furnace.

[0051] In some embodiments of the present invention, preferably, the conditions of the melting include: the vacuum degree is (3 - 5)×10 - 3 Pa; the arc current is 100 - 150 A; the number of times is 3 - 5 times.

[0052] In the present invention, without special circumstances, the inert atmosphere includes but is not limited to nitrogen atmosphere, helium atmosphere, argon atmosphere, etc.

[0053] In the present invention, in step (2), the way of impurity removal is selected from mechanical grinding; the way of cleaning is selected from ultrasonic vibration cleaning in alcohol.

[0054] In some embodiments of the present invention, preferably, the liquid rapid quenching is carried out in a melt spinning quenching device, including: melting the alloy by induction heating, the induction heating current is 5 - 10 A; adopting the copper mold casting method, directly pouring the metal liquid into the copper mold to make it rapidly cool to form bulk metallic glass, the injection pressure is 0.02 - 0.05 MPa, the copper mold is selected from water-cooled and non-water-cooled methods, the pouring method is selected from differential pressure casting, vacuum suction casting, squeeze casting; or, adjusting the distance between the bottom of the quartz tube and the surface of the copper wheel to be 1 - 2 mm, adjusting the rotation speed of the copper wheel to 30 - 40 m / s; evacuating to make the vacuum degree in the cavity reach 1×10 -2 Pa, filling with inert gas for protection; melting the alloy by induction heating, the induction heating current is 5 - 10 A; setting the injection pressure to 0.02 - 0.05 MPa, and spraying the molten alloy from the small hole at the bottom of the quartz tube onto the high-speed rotating copper wheel by using the inert gas.

[0055] The third aspect of the present invention provides a nickel-based amorphous alloy material prepared by the preparation method provided in the second aspect.

[0056] The fourth aspect of the present invention provides an application of the nickel-based amorphous alloy materials provided in the first aspect and the third aspect in the industrial scenarios of high-temperature chlorine-containing and concentrated hydrochloric acid, preferably in the fields of petrochemical, chemical, pharmaceutical, and molten salt power generation.

[0057] According to a particularly preferred embodiment of the present invention, a nickel-based amorphous alloy material, the nickel-based amorphous alloy material having a chemical formula of Ni a Nb b Ta c P d Fe e (I) shown in the composition, wherein, a, b, c, d, e are the mass percentage contents of the respective corresponding component atoms, 49 ≤ a ≤ 51, 10 ≤ b ≤ 15, 10 ≤ c ≤ 15, 5 ≤ d ≤ 10, 10 ≤ e ≤ 15, and a + b + c + d + e = 100; wherein, in formula I, 3 ≤ a / c ≤ 4, 0.7 ≤ b / c ≤ 1;

[0058] Wherein, the supercooled liquid region width ΔT of the nickel-based amorphous alloy material x is 100 - 150K, the glass transition temperature T g is 980 - 1000K; the crystallization temperature T x is 1100 - 1150K; the reduced glass temperature is 0.6 - 1K; at a temperature of 80 °C and 32 wt% concentrated hydrochloric acid, the annual corrosion rate of the nickel-based amorphous alloy material is 0 μm / a.

[0059] The present invention will be described in detail below through examples.

[0060] The physical property parameters of the nickel-based amorphous alloy materials prepared in Examples 1 - 3 and Comparative Examples 1 - 2 are all listed in Table 1.

[0061] Example 1

[0062] (1) In terms of elements, pure nickel, pure niobium, pure tantalum, pure phosphorus and pure iron with a purity of 99 wt% were mixed in a mass ratio of 50:14:14:9:13 to obtain an alloy raw material;

[0063] In an argon atmosphere, the above alloy raw material was placed in a vacuum arc melting furnace, and the vacuum was pumped to make the vacuum degree in the furnace reach 5×10 -3 Pa, and then argon was filled as a protective gas; the arc current was adjusted to 150A, and the above operation was repeatedly melted 3 times to ensure the uniformity of the alloy composition. After cooling to 25 °C, it was taken out to obtain an alloy ingot;

[0064] (2) The surface impurities of the above alloy ingot were removed by mechanical grinding method, and after being placed in alcohol and ultrasonically vibrated and washed; the alloy ingot was broken and loaded into a quartz tube and suspended in a melt spinning quenching device, and the alloy was melted by induction heating, and the induction heating current was 10A; by using the copper mold casting method, the molten metal was directly poured into the copper mold to rapidly cool to form a bulk metallic glass, and the injection pressure was 0.04MPa to obtain a thin strip-shaped nickel-based amorphous alloy material S1.

[0065] Among them, the TG-DSC curve of the above nickel-based amorphous alloy material S1 with a heating rate of 20 K / min is as Figure 1 shown, and it can be seen from Figure 1 that the glass transition temperature T of the above nickel-based amorphous alloy material S1 g is 988 K, the crystallization temperature T x is 1121 K, and the width of the supercooled liquid region ΔT x is 133 K, indicating excellent thermal stability.

[0066] Among them, the XRD pattern of the above nickel-based amorphous alloy material S1 is as Figure 2 shown, and it can be seen from Figure 2 that the above nickel-based amorphous alloy material S2 exhibits a typical amorphous bread-like peak, indicating a completely amorphous structure.

[0067] Among them, the potentiodynamic polarization curves of the above nickel-based amorphous alloy material S1, Hastelloy C276, and 304 stainless steel in a 32 wt% hydrochloric acid corrosion solution at 25 °C and 80 °C are respectively as Figure 3-4 shown, and it can be seen from Figure 3-4 that the nickel-based amorphous alloy material S1 of Example 1 shows passivation characteristics in solutions at 25 °C and 80 °C, and the pitting potential (E pit ) is higher than that of Hastelloy C276 and 304 stainless steel, and the self-corrosion current density (I corr ) and the passive current density (I pass ) are lower than those of Hastelloy C276 and significantly lower than those of 304 stainless steel. E corr represents the ease of corrosion initiation; E pit is the potential at which the passive film is damaged and pitting occurs; I corr can characterize the corrosion rate of the alloy; I pass indicates the corrosion rate during anodic protection. Therefore, it can be seen from the polarization curve that the above nickel-based amorphous alloy material S1 has better corrosion resistance than Hastelloy C276 and 304 stainless steel in acidic environments at both 25 °C and 80 °C. In a 10 N hydrochloric acid solution at 25 °C, for the nickel-based amorphous alloy material S1 of Example 1, E corr is -497 mV, E pit is 2829 mV, I corr is 1.9×10 -5 A / cm 2 , the corrosion rate is 3.1×10 -6 mm / a, and I pass is 4.3×10 -4 A / cm 2, indicating that the corrosion rate is relatively small during anodic protection in this corrosion solution; in a 32 wt% hydrochloric acid solution at 80 °C, the E of the nickel-based amorphous alloy material S1 corr is -213 mV, and the E pit is 1193 mV, and the I corr is 3.6×10 - 5 A / cm 2 , and the corrosion rate is 5.9×10 -6 mm / a, and the I pass is 1.1×10 -4 A / cm 2 , indicating that the corrosion rate is also relatively small during anodic protection in this corrosion solution.

[0068] Among them, the corrosion rate curves of the above-mentioned nickel-based amorphous alloy material S1, Hastelloy C276, and 304 stainless steel in a hydrochloric acid solution with a mass concentration of 32 wt.% are as Figure 5 shown. It can be seen from Figure 5 that, compared with Hastelloy C276 and 304 stainless steel, the above-mentioned nickel-based amorphous alloy material S1 has the lowest corrosion rate as the immersion time prolongs.

[0069] Example 2

[0070] According to the method of Example 1, the difference is that

[0071] in step (1), the mass ratio of elemental nickel, elemental niobium, elemental tantalum, elemental phosphorus, and elemental iron is adjusted to 50:17:13:7:13 according to the parameters in Table 1;

[0072] Under the same other conditions, the nickel-based amorphous alloy material S2 is obtained.

[0073] Example 3

[0074] According to the method of Example 1, the difference is that

[0075] in step (1), the mass ratio of elemental nickel, elemental niobium, elemental tantalum, elemental phosphorus, and elemental iron is adjusted to 51:17:11:7:14 according to the parameters in Table 1;

[0076] Under the same other conditions, the nickel-based amorphous alloy material S3 is obtained.

[0077] Comparative Example 1

[0078] According to the method of Example 1, the difference is that

[0079] in step (1), the mass ratio of elemental nickel, elemental niobium, elemental tantalum, elemental phosphorus, and elemental iron is adjusted to 52:18:9:7:14 according to the parameters in Table 1;

[0080] Under the same other conditions, the nickel-based amorphous alloy material DS1 was obtained.

[0081] Comparative Example 2

[0082] According to the method of Example 1, the difference is that

[0083] In step (1), according to the parameters in Table 1, the mass ratio of elemental nickel, elemental niobium, elemental tantalum, elemental phosphorus and elemental iron was adjusted to 53:18:7:8:14;

[0084] Under the same other conditions, the nickel-based amorphous alloy material DS2 was obtained.

[0085] Table 1

[0086] Ni, a Nb, b Ta, c P, d Fe, e a / c b / c Example 1 50 14 14 9 13 3.57 1 Example 2 50 17 13 7 13 3.85 1.31 Example 3 51 17 11 7 14 4.64 1.55 Comparative Example 1 52 18 9 7 14 5.78 2 Comparative Example 2 53 18 7 8 14 7.57 2.57

[0087] Continued Table 1

[0088]

[0089]

[0090] Note: The annual corrosion rate refers to the annual corrosion rate of the above nickel-based amorphous alloy material in 32 wt% concentrated hydrochloric acid at a temperature of 80 °C, μm / a.

[0091] It can be seen from the data in Table 1 that compared with Comparative Examples 1-2, the nickel-based amorphous alloy materials prepared in Examples 1-3 satisfy the composition of Formula I, and not only have a completely amorphous structure, but also have high thermal stability and high-temperature corrosion resistance. In particular, by adjusting the subscript of Ta in Formula I, the thermal stability and high-temperature corrosion resistance of the nickel-based amorphous alloy material are further improved.

[0092] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited thereto. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention, including any other suitable combination of each technical feature. These simple modifications and combinations should also be regarded as the content disclosed by the present invention and fall within the protection scope of the present invention.

Claims

1. A nickel-based amorphous alloy material, characterized in that, The nickel-based amorphous alloy material has a composition represented by Chemical Formula Ni a Nb b Ta c P d Fe e (I), where a, b, c, d, and e are the mass percentage contents of the atoms of the corresponding components respectively, 40 ≤ a ≤ 60, 10 ≤ b ≤ 30, 10 ≤ c ≤ 30, 1 ≤ d ≤ 15, 0 ≤ e ≤ 15, and a + b + c + d + e = 100 is satisfied.

2. The nickel-based amorphous alloy material according to claim 1, wherein, In formula I, 45 ≤ a ≤ 55, 10 ≤ b ≤ 20, 10 ≤ c ≤ 20, 1 ≤ d ≤ 10, 5 ≤ e ≤ 15; Preferably, in formula I, 49 ≤ a ≤ 51, 10 ≤ b ≤ 15, 10 ≤ c ≤ 15, 5 ≤ d ≤ 10, 10 ≤ e ≤ 15.

3. The nickel-based amorphous alloy material according to claim 1 or 2, wherein, In formula I, 2 ≤ a / c ≤ 4, preferably 3 ≤ a / c ≤ 4; and / or, in formula I, 0.5 ≤ b / c ≤ 1.5, preferably 0.7 ≤ b / c ≤ 1.

4. The nickel-based amorphous alloy material according to any one of claims 1-3, wherein, The nickel-based amorphous alloy material has a completely amorphous structure; and / or, the nickel-based amorphous alloy material is in the form of a block, thin strip, sheet, wedge shape, or stepped shape; and / or, the nickel-based amorphous alloy material has a length of 50-100 cm, a width of 2-3 mm, and a thickness of 20-50 μm.

5. The nickel-based amorphous alloy material according to any one of claims 1-4, wherein, The width ΔT of the supercooled liquid region of the nickel-based amorphous alloy material x is ≥50K, preferably 100 - 150K; and / or, the glass transition temperature T of the nickel-based amorphous alloy material g ≥800K, preferably 980 - 1000K; and / or, the crystallization temperature T of the nickel-based amorphous alloy material x ≥850K, preferably 1100 - 1150K; and / or, the reduced glass transition temperature of the nickel-based amorphous alloy material ≥ 0.5 K, preferably 0.6-1 K; and / or, in 80°C, 32 wt% concentrated hydrochloric acid, the annual corrosion rate of the nickel-based amorphous alloy material ≤ 0.2 μm / a, preferably ≤ 0.01, more preferably 0 μm / a.

6. A method for preparing a nickel-based amorphous alloy material, characterized in that, The preparation method includes: (1) In an inert atmosphere, melting alloy raw materials satisfying formula I to obtain an alloy ingot; (2) Sequentially performing impurity removal, cleaning, and liquid rapid quenching on the alloy ingot to obtain a nickel-based amorphous alloy material; Among them, the nickel-based amorphous alloy material has the chemical formula Ni a Nb b Ta c P d Fe e (I) shown in the composition, where a, b, c, d, and e are the mass percentage contents of the atoms of the corresponding components respectively, 40 ≤ a ≤ 60, 10 ≤ b ≤ 30, 10 ≤ c ≤ 30, 1 ≤ d ≤ 15, 0 ≤ e ≤ 15, and a + b + c + d + e = 100 is satisfied.

7. The preparation method according to claim 6, wherein, In step (1), By element, in the alloy raw materials, the mass ratio of nickel, niobium, tantalum, phosphorus, and iron satisfies (40-60):(10-30):(10-30):(1-15):(0-15), preferably (45-55):(10-20):(10-20):(1-10):(5-15), more preferably (49-51):(10-15):(10-15):(5-10):(10-15); and / or, the melting is carried out in a vacuum arc melting furnace or a levitation induction melting furnace; And / or, the smelting conditions include: the vacuum degree is (3 - 5)×10 -3 Pa; the arc current is 100 - 150 A; the number of times is 3 - 5 times.

8. The preparation method according to claim 6 or 7, wherein, In step (2), The liquid rapid quenching is carried out in a melt spinning quenching device, including: melting the alloy by induction heating, with an induction heating current of 5-10 A; using the copper mold casting method, directly pouring the molten metal into the copper mold to rapidly cool it to form a bulk metallic glass, with a spraying pressure of 0.02-0.05 MPa, the copper mold is selected from water-cooled and non-water-cooled methods, and the pouring method is selected from differential pressure casting, vacuum suction casting, and squeeze casting; or, Adjust the distance between the bottom of the quartz tube and the surface of the copper wheel to be 1 - 2 mm, and adjust the rotational speed of the copper wheel to 30 - 40 m / s; evacuate to make the vacuum degree in the cavity reach 1×10 -2 Pa, and fill with inert gas for protection; use induction heating to melt the alloy, and the induction heating current is 5 - 10 A; set the injection pressure to 0.02 - 0.05 MPa, and use the inert gas to inject the molten alloy from the small hole at the bottom of the quartz tube onto the high-speed rotating copper wheel.

9. A nickel-based amorphous alloy material prepared by the preparation method according to any one of claims 6-8.

10. The nickel-based amorphous alloy material according to any one of claims 1-5 and 9 is applied in the field of industrial scenarios with high temperature, chlorine and concentrated hydrochloric acid, preferably in the fields of petrochemical, chemical, pharmaceutical, and molten salt power generation.

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