Centimeter-level bulk amorphous alloy with strong oxidation resistance and preparation method of centimeter-level bulk amorphous alloy

Abstract

The invention belongs to the technical field of amorphous alloys, and particularly relates to a centimeter-level bulk amorphous alloy with strong oxidation resistance and a preparation method of the centimeter-level bulk amorphous alloy. The centimeter-level bulk amorphous alloy resistant to strong oxidation does not contain precious metal and toxic elements, and through compounding of other elements, the corrosion resistance of the centimeter-level bulk amorphous alloy is improved under the condition that the amorphous forming ability and the mechanical property of the centimeter-level bulk amorphous alloy are guaranteed; the rare earth elements are adopted for deoxidizing the amorphous alloy and improving the amorphous forming ability, and meanwhile oxygen affinity elements such as Co and Cr are adopted for deoxidizing; the corrosion resistance of the amorphous alloy is greatly improved by forming a plurality of compact oxidation films, such as niobium oxide, chromium oxide, cobalt oxide and the like, which are mutually embedded.

Description

Technical Field

[0001] This invention belongs to the field of amorphous alloy technology, specifically relating to a centimeter-scale bulk amorphous alloy with strong oxidation resistance and its preparation method. Background Technology

[0002] As a novel material, amorphous alloys possess excellent properties due to their unique long-range disorder and short-range order liquid-like structure, such as high strength, high hardness, corrosion resistance, and catalytic properties.

[0003] Zr-based amorphous alloys are relatively inexpensive and mass-produced bulk amorphous alloys among all amorphous alloy systems. With the increasing application and development of Zr-based amorphous alloys in various fields, such as 3C (computers, communications, and consumer electronics) and marine applications, the performance requirements for them in certain special applications are becoming increasingly stringent, particularly in terms of corrosion resistance. Substances containing Cl- ions and strong oxidizing agents, such as seawater, bleach, and disinfectants, can negatively impact their corrosion resistance. Therefore, improving the corrosion resistance of amorphous alloys plays a crucial role in promoting their application and development. Summary of the Invention

[0004] The purpose of this invention is to provide a centimeter-scale bulk amorphous alloy with strong oxidation resistance and its preparation method.

[0005] A first aspect of the present invention provides a centimeter-scale bulk amorphous alloy with strong oxidation resistance, the chemical formula of which is: Zr a Cu b Al c Ni d Nb e Ti f M h N j ;in

[0006] M is one or more of the rare earth elements Y, Sc, Dy, and Ho;

[0007] N is a Co and / or Cr element; and

[0008] a, b, c, d, e, f, h, and j represent the atomic percentages of each element, and their ranges are as follows:

[0009] 50<a<65, 10<b<30, 5<c<15, 5<d<15, 0≤e<6, 0<f≤5, 0≤h≤0.5, 0≤j≤2.

[0010] In one embodiment of this application, preferably, 50 < a < 60, 10 < b < 25, and 0 < e ≤ 5.

[0011] In one embodiment of this application, preferably, when N is an element Co, 0 ≤ j ≤ 1.

[0012] In one embodiment of this application, preferably, when N is an element Cr, 0 ≤ j < 0.2.

[0013] In one embodiment of this application, preferably, when N is two elements, Co and Cr, their atomic percentages are 0≤Co≤0.8 and 0≤Cr<0.2, respectively.

[0014] A second aspect of the present invention provides a method for preparing a centimeter-scale bulk amorphous alloy with strong oxidation resistance as described above, comprising:

[0015] Raw materials are configured according to the atomic percentage of each element;

[0016] Melting is carried out under an argon atmosphere;

[0017] The uniformly smelted alloy is weighed to the appropriate weight and then die-cast using a mold to produce different sizes according to requirements.

[0018] In one embodiment of this application, the melting is carried out by electric arc melting under an argon atmosphere, and the melting is repeated 3-4 times during the electric arc melting process.

[0019] In one embodiment of this application, the melting is carried out by induction melting under an argon atmosphere. During the induction melting process, the refractory metal Nb is pre-melted into a first-melting-point intermediate alloy or directly melted using a low-melting-point intermediate alloy.

[0020] The beneficial effects of this invention are that the centimeter-scale bulk amorphous alloy with strong oxidation resistance does not contain precious metals or toxic elements. By compounding other elements, its corrosion resistance is improved while ensuring its amorphous forming ability and mechanical properties. Not only are rare earth elements used to deoxidize the amorphous alloy and improve its amorphous forming ability, but also oxygen-loving elements such as Co and Cr are used for deoxidation. The corrosion resistance of the amorphous alloy is greatly improved by forming multiple dense oxide films, such as niobium oxide, chromium oxide, cobalt oxide, etc., which are interlocked.

[0021] Other features and advantages of the invention will be set forth in the following description, and will be apparent in part from the description, or may be learned by practicing the invention. The objects and other advantages of the invention are realized and obtained through the structures particularly pointed out in the description and the drawings.

[0022] To make the above-mentioned objects, features and advantages of the present invention more apparent and understandable, preferred embodiments are described below in detail with reference to the accompanying drawings. Attached Figure Description

[0023] To more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0024] Figure 1 This is the XRD pattern of the φ10mm bar from Example 1;

[0025] Figure 2 This is the XRD pattern of the φ10mm bar from Example 2;

[0026] Figure 3 This is an XRD image of the φ10mm bar from Example 3;

[0027] Figure 4 This is an XRD image of the φ10mm bar from Example 4;

[0028] Figure 5 This is an XRD image of the φ10mm bar from Example 5;

[0029] Figure 6 This is the XRD image of a φ10mm bar as shown in Comparative Example 1;

[0030] Figure 7 This is the XRD image of a φ10mm bar as shown in Comparative Example 2;

[0031] Figure 8 The image shown is the XRD image of the φ7mm bar in Comparative Example 2.

[0032] Figure 9 This is the XRD image of a φ5mm bar as shown in Comparative Example 3. Detailed Implementation

[0033] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0034] Because amorphous alloys are obtained through rapid solidification of molten metal, they possess the same structure as molten metal and lack the defects found in alloys, such as dislocations, vacancies, and intergranular gaps. Therefore, corrosion of amorphous alloys does not result in intergranular corrosion caused by these defects. However, smaller ions, such as chloride ions, which can easily pass through interatomic gaps, can cause corrosion in amorphous alloys.

[0035] To improve the resistance of amorphous alloys to chloride ion and strong oxidative corrosion, increasing the density of the oxide layer as a passivation layer is an important means to prevent chloride ion and strong oxidative corrosion. Specifically, for the components of an amorphous alloy, the more components there are, the better the alloy's amorphous forming ability. Trace amounts of Co can improve the alloy's amorphous forming ability and also enhance its corrosion resistance. The mixed enthalpy of Cr and Zr is positive, which reduces the alloy's amorphous forming ability, but at that point, their oxides will increase the corrosion resistance of the amorphous alloy.

[0036] In one embodiment of this application, a centimeter-scale bulk amorphous alloy with strong oxidation resistance is used, wherein the chemical formula of the amorphous alloy is: Zr a Cu b Al c Ni d Nb e Ti f M h N j Where M is one or more of the rare earth elements Y, Sc, Dy, and Ho; N is Co and / or Cr; and a, b, c, d, e, f, h, and j are the atomic percentages of each element, and their ranges are 50 < a < 65, 10 < b < 30, 5 < c < 15, 5 < d < 15, 0 ≤ e < 6, 0 < f ≤ 5, 0 ≤ h ≤ 0.5, and 0 ≤ j ≤ 2.

[0037] In this embodiment, preferably, 50 < a < 60, 10 < b < 25, and 0 < e ≤ 5.

[0038] In this embodiment, preferably, when N is an element Co, 0≤j≤1.

[0039] In this embodiment, preferably, when N is Cr, 0 ≤ j < 0.2.

[0040] In this embodiment, preferably, when N is composed of two elements, Co and Cr, their atomic percentages are 0 ≤ Co ≤ 0.8 and 0 ≤ Cr < 0.2, respectively.

[0041] In this embodiment, the centimeter-sized bulk amorphous alloy with strong oxidation resistance as described above can be prepared by the following method: raw materials are prepared according to the atomic percentage of each element; melting is carried out under an argon atmosphere; the uniformly melted alloy is weighed to an appropriate weight, and die-cast using a mold to form different sizes as required.

[0042] In this embodiment, optionally, the melting is carried out by electric arc melting under an argon atmosphere, and the melting is repeated 3-4 times during the electric arc melting process.

[0043] In this embodiment, optionally, the melting is carried out by induction melting under an argon atmosphere. During the induction melting process, the refractory metal Nb is pre-melted into a first-melting-point intermediate alloy or directly melted using a low-melting-point intermediate alloy.

[0044] Examples and Comparative Examples

[0045] The chemical formulas of each embodiment and comparative example are shown in Table 1. The preparation and testing processes are as follows:

[0046] 1) Clean the surface oxide layer and adhering substances according to the condition of the industrial material surface.

[0047] 2) Convert the atomic percentage of each element into a mass ratio and weigh each component.

[0048] 3) Select the pre-melting method based on whether the composition contains Nb and whether an Nb intermediate alloy is used. If no intermediate alloy is used, perform Ni-Nb arc pre-melting, melting 3-4 times to ensure uniform alloy melting.

[0049] 4) When using electric arc melting, place the easily oxidized components in the middle layer and place the rest in order of melting point from low to high. Repeat melting 3-4 times to ensure uniform alloy melting. When using induction melting, place the high melting point in the middle of the crucible and the low melting point in the top layer.

[0050] 5) Grind the uniformly smelted alloy to remove the surface oxides, and then dry it to further reduce the impact of oxides on subsequent die casting.

[0051] 6) Weigh the ground and dried materials to the appropriate weight and then die-cast φ5, φ7, and φ10mm rods. All die-casting molds used are copper molds.

[0052] 7) The bar stock was water-cooled and cut with a diamond saw blade. The cut products were subjected to XRD testing, and the φ5 sample was subjected to a compressive strength test. The test results are shown in Table 1.

[0053] Table 1

[0054] Example Alloy composition GFA / mm Compressive strength / MPa Example 1 Zr54.7Cu13.5Ni14Al9Ti3.2Nb4.3Co1Y0.3 φ10 2065 Example 2 Zr55.5Cu13.3Ni14.1Al9.2Ti3Nb4.3Cr0.1Y0.5 φ10 2017 Example 3 Zr55.6Cu13Ni14Al9Ti3.2Nb4.3Co0.3Cr0.1Y0.3 φ10 1975 Example 4 Zr55.5Cu13.2Ni14Al9Ti3Nb4.2Co0.5Cr0.1Y0.5 φ10 2005 Example 5 Zr52Cu17.9Ni14.3Al10Ti4Nb1Co0.5Sc0.3 φ10 1987 Comparative Example 1 Zr52Cu17.9Ni14.6Al10Ti5Y0.5 φ10 2074 Comparative Example 2 Zr55.4Cu13.1Ni14.2Al9.3Ti3.2Nb4.3Y0.5 φ10 2001 Comparative Example 3 Zr52.1Cu17.9Ni12.6Al10Ti5Co2Y0.4 φ7 2113 Comparative Example 4 Zr52.5Cu17.9Ni14.1Al10Ti4.5Cr0.5Y0.5 φ5 1873

[0055] See the XRD patterns of each embodiment and comparative example. Figures 1 to 9 As shown in the XRD patterns and the table above, the amorphous properties of the amorphous alloys in Examples 1-5 are all greater than φ10mm, and their compressive strengths show little difference. Comparative examples show that Comparative Examples 3 and 4 exhibit lower amorphous formation.

[0056] The corrosion resistance of each embodiment and comparative example was tested by immersion-based weight loss corrosion test: Five rods, each 5mm in diameter and 20mm thick, were used. It is important to note that the sample surface was polished with 1000-2000 grit sandpaper to avoid the influence of defects such as flow lines on the corrosion rate. The samples were immersed in a corrosion solution at room temperature for 72 hours. The corrosion solutions used in this test were mainly H2O2 solution, NaCl solution, and 6% NaClO concentration CLOS bleach concentrate. The test results are shown in Table 2.

[0057] Table 2

[0058]

[0059] Combining the examples in the table above and comparing the corrosion rates in different solutions, it can be seen that the corrosion rates in examples 1-5 are relatively low in strongly oxidizing bleach solutions. Adding Co and Cr, when Nb is present, is beneficial to further improve their resistance to strong oxidizing corrosion.

[0060] In summary, the centimeter-scale bulk amorphous alloy with strong oxidation resistance and its preparation method of the present invention have the following advantages:

[0061] 1. The Zr-based amorphous alloy of the present invention has centimeter-level amorphous forming capability even when using industrial-grade materials, and can be fully industrialized for production and application.

[0062] 2. This invention contains no toxic elements or precious metals, which is beneficial for the application and development of amorphous alloys in the fields of wearables and medicine.

[0063] 3. This invention adds Co and Cr, which are beneficial for improving corrosion resistance. These elements are conducive to combining with oxygen. Under the condition of adding rare earth elements to remove oxygen, adding these two elements is more conducive to removing oxygen and impurities during the alloy smelting process.

[0064] 4. This invention improves the corrosion resistance of amorphous alloys by adding corrosion-resistant elements to increase the content and types of dense oxide layers. For example, the oxide of Nb alone is not very effective against strong oxidative corrosion, and although the addition of Cr is not conducive to the formation ability of amorphous alloys, by adding a small amount, not only can multiple oxides be used to resist corrosion, but the distribution of multiple elements also avoids the reduction in corrosion resistance caused by the low local content of a single element.

[0065] Based on the above-described preferred embodiments of the present invention, and through the foregoing description, those skilled in the art can make various changes and modifications without departing from the inventive concept. The technical scope of this invention is not limited to the contents of the specification.

Claims

1. A centimeter-scale bulk amorphous alloy with strong oxidation resistance, characterized in that, The chemical formula of the amorphous alloy is: Zr a Cu b Al c Ni d Nb e Ti f M h N j ;in M is one or more of the rare earth elements Y, Sc, Dy, and Ho; N is a Co and / or Cr element; and a, b, c, d, e, f, h, and j represent the atomic percentages of each element, and their ranges are 50 < a < 65, 10 < b < 30, 5 < c < 15, 5 < d < 15, 0 ≤ e < 6, 0 < f ≤ 5, 0 ≤ h ≤ 0.5, and 0 ≤ j ≤ 2.

2. The centimeter-scale bulk amorphous alloy according to claim 1, characterized in that, 50<a<60, 10<b<25, 0<e≤5.

3. The centimeter-scale bulk amorphous alloy according to claim 1, characterized in that, When N is an element of Co, 0 ≤ j ≤ 1.

4. The centimeter-scale bulk amorphous alloy according to claim 1, characterized in that, When N is a single element Cr, 0 ≤ j < 0.

2.

5. The centimeter-scale bulk amorphous alloy according to claim 1, characterized in that, When N is either Co or Cr, their atomic percentages are 0 ≤ Co ≤ 0.8 and 0 ≤ Cr < 0.2, respectively.

6. A method for preparing a centimeter-scale bulk amorphous alloy with strong oxidation resistance as described in any one of claims 1-5, characterized in that, include: Raw materials are configured according to the atomic percentage of each element; Melting is carried out under an argon atmosphere; The uniformly smelted alloy is weighed to the appropriate weight and then die-cast using a mold to produce different sizes according to requirements.

7. The preparation method according to claim 6, characterized in that, The melting is carried out by electric arc melting under an argon atmosphere, and the melting is repeated 3-4 times during the electric arc melting process.

8. The preparation method according to claim 6, characterized in that, The melting is carried out by induction melting under an argon atmosphere. During the induction melting process, the refractory metal Nb is either pre-melted into a first-melting-point intermediate alloy or directly melted using a low-melting-point intermediate alloy.

Images