WO2017080212A1 - High-toughness amorphous composite material, preparation method therefor and application thereof - Google Patents

Abstract

A high-toughness amorphous composite material, a preparation method therefor and an application thereof, the high-toughness amorphous composite material being prepared to comprise a base alloy part and a toughness enhancement part; the element composition and respective atom molar percentage contents of the base alloy part being: Zr: 45-65%, Hf: 5-15%, Al: 10-20%, Ni: 10-20%, an M1 component: 5-10% and an M2 component: 2-8%; the M1 component being one or more of the elements Sn, Bi, Si and Cu; the M2 component being one or both of the elements Ag and Pd; the purity of each of the elements in the base alloy part being greater than 99.9%; the toughness enhancement part being one or more of WC, SiC, TiC, TiN and ZrC nanometer powder, the amount of which is 2-10% of the volume of the base alloy part. The amorphous composite material has good impact toughness, and is characterized by achieving, without any need for machining, excellent toughness and impact resistance.

Description

High toughness amorphous composite material and preparation method and application thereof Technical field

The invention relates to the technical field of amorphous composite materials, and more particularly to a high toughness amorphous composite material and a preparation method and application thereof.

Background technique

Amorphous alloy refers to an alloy material in which the atomic arrangement is short-range order and long-range disorder is densely packed. Therefore, the amorphous alloy does not have defects such as grain boundaries and dislocations of the crystalline material. This structural feature makes the amorphous alloy have many excellent mechanical properties, such as high hardness, high strength, and good corrosion resistance, but at the same time, the amorphous alloy also has poor plasticity and toughness, and is susceptible to brittle fracture as a structural member. The problem, these shortcomings have always restricted the use of amorphous alloy components.

The toughness of a metal is the ability of a material to absorb energy during plastic deformation and fracture. The better the toughness, the less likely it is that brittle fracture will occur. The better the toughness of the material, the greater its ability to withstand impact strength, and the better the properties that do not break under the impact load. In order to improve the toughness of amorphous alloys, many researchers have done a lot of research. A Zr-Cu-Ni-Nb-Al-based amorphous alloy is provided in the Chinese patent No. 201010609177.3 entitled "Amorphous Alloy Surface Treatment Method and Amorphous Alloy Parts Made by the Method", and then After the amorphous alloy member is polished, sandblasting is performed to form a plurality of micro-cracks on the surface of the amorphous alloy member as a shear band to improve the yield strength and plastic deformation resistance of the amorphous alloy member.

The above-described solution process is not only complicated, but also cannot be used on complex amorphous alloy members, and is completely unsuitable for those members that require appearance quality.

Summary of the invention

The technical problem to be solved by the present invention is that, in view of the above-mentioned drawbacks of the prior art, a first object of the present invention is to provide a high-hardness amorphous composite material, which is improved by the composition of a base alloy system and a toughness-enhancing system. Adding new component elements and adjusting the component content to obtain a high-toughness and impact-resistant amorphous composite material with good forming ability is suitable for making complex components.

A second object of the present invention is to provide a method for preparing a high toughness amorphous composite material which can be adapted to mass production.

A third object of the invention is to provide an application of a high toughness amorphous composite.

The first object of the present invention can be achieved by adopting the following technical solutions:

A high toughness amorphous composite material prepared from a base alloy portion and a toughness-enhancing portion;

The elemental composition and atomic mole percentage of the base alloy portion are Zr: 45-65%, Hf: 5-15%, Al: 10-20%, Ni: 10-20%, M1 component: 5-10 %, M2 component: 2-8%; the M1 component is one or more of Sn, Bi, Si, Cu elements; the M2 component is one or two of Ag, Pd elements; The purity of each element of the base alloy portion is greater than 99.9%;

The toughness-enhancing portion is one or more of WC, SiC, TiC, TiN, and ZrC nano-powders, and the amount thereof is 2-10% of the volume of the base alloy.

Zr-based bulk amorphous composites have high glass forming ability, corrosion resistance and forming ability. The addition of Hf atoms of the same group has a certain substitution effect on Zr atoms in the alloy, which makes the interaction between different metal atoms in the alloy. The force is enhanced, and the macroscopic performance is that the alloy structure is relatively dense and has good forming properties after cooling, and Al and Ni are commonly added elements in the Zr-based amorphous alloy.

The inventors of the present invention have found in practice that the addition of one or more of the elements of Sn, Bi, Si, and Cu can effectively increase the plasticity and toughness of the above-mentioned Zr-based amorphous alloy, and the reason thereof is, from the viewpoint of microstructure, The atomic size and surface energy of Sn, Bi, Si and Cu are similar to those of Zr and Hf, and are slightly different in the formation of amorphous In the dense structure of gold, Sn, Bi, Si and Cu atoms easily diffuse into Zr and Hf atoms to form various non-directional metal bonds. Adding Ag and Pd elements further enhances the entropy and chaos of the entire alloy system. Until these disordered metal bonds meet the reinforcing portions of WC, SiC, TiC, TiN, ZrC, forming plastic particles resembling crystalline states. The amorphous composite material thus formed is subjected to an impact force during the deformation process, and during the deformation process, the plastic particles similar to the crystalline state will isolate the shear band, thereby preventing the expansion of the shear band, thereby realizing Good impact resistance toughness on a macro level. The particle size of WC, SiC, TiC, TiN, and ZrC nano-powders is preferably controlled at 10-100 nm. The ultra-fine nano-powder is complicated and expensive due to the preparation process, and the excessively coarse particle size leads to uneven alloy system.

As a preferred embodiment of the present invention, the elemental composition and atomic mole percentage of the base alloy portion are Zr: 45-60%, Hf: 5-10%, Al: 10-15%, Ni: 15- 20%, M1 component: 5-8%, M2 component: 5-8%.

As a preferred embodiment of the present invention, the M1 component is preferably Sn or Cu.

As a preferred embodiment of the present invention, each nanofine powder in the toughness-enhancing portion has a particle diameter of 10 to 100 nm.

As a preferred embodiment of the present invention, the toughness-enhancing portion is preferably ZrC nanopowder. Because ZrC can not only enhance the overall toughness of the amorphous composite, but also introduces other impurity elements for the Zr-based amorphous alloy, and avoids the crystallization of the alloy which may be caused by the addition of too many elements.

As a preferred embodiment of the present invention, the toughness-enhancing portion is added in an amount of 8 to 10% by volume of the base alloy.

The second object of the present invention can be achieved by adopting the following technical solutions:

A method for preparing a high toughness amorphous composite material comprises the following steps:

(1) Weigh the raw materials of the base alloy portion and the raw materials of the toughness-enhancing portion according to the formulation ratio, and mix the raw materials of the base alloy portion with the raw materials of the toughness-enhancing portion to obtain a mixed raw material;

(2) The raw material obtained in the step (1) is smelted by arc melting in a vacuum condition or an argon atmosphere, and in the process of melting the raw material, all the raw materials are converted into a melt under the condition of a regular vibration melting furnace, and repeated Smelting 3-4 times; the vacuum degree of the smelting process is 10 ^-1 -10 ^-3 Pa, and the pressure of the argon atmosphere is 0.01-0.05 MPa, and after cooling, an amorphous composite ingot is obtained;

The inventors of the present invention have found in practice that since the WC, SiC, TiC, TiN, and ZrC nanopowders having the toughness-enhancing portion are added to the raw material of the amorphous composite material, it is essential to uniformly mix the alloy raw materials in the alloy smelting process. If it is not uniform, it will cause local defects of the amorphous composite material, resulting in defects of local mechanical properties. Therefore, in the process of preparing the amorphous alloy of the present invention, the raw material melting process needs to be carried out in a regular vibration melting furnace until all the raw materials are converted into a melt, and this function is appropriately improved by a melting furnace, such as a clampable melting furnace. The mechanical device of the regularly moving high temperature resistant metal can be realized, and will not be described here.

(3) The amorphous composite ingot is formed by a conventional metal material forming process to obtain a high toughness amorphous composite product.

Preferably, after the smelting in the step (2), the cooling rate is 10 - 10 ³ K/s.

Preferably, in the step (3), the conventional metal material forming process refers to a conventional die casting process or a conventional die casting process.

A third object of achieving the present invention can be achieved by adopting the following technical solutions:

The first object of the present invention is the use of the high-hardness amorphous composite material: it is used in consumer electronic products, medical device products, aerospace industrial products, machine instrument industrial products, and automobile industrial products. Such as punches, crimping blocks, etc. in stamping equipment.

The beneficial effects of implementing the invention are:

(1) By improving the composition of the base alloy system and the toughness enhancement system, adding new component elements, adjusting the component content, and obtaining an amorphous composite with high toughness and impact resistance and good forming ability. Material, suitable for making complex components.

(2) The amorphous composite material of the present invention has a size of up to 30 mm and is suitable for forming a complicated structural member.

(3) The preparation process of the amorphous composite material of the present invention is simple and easy, and can be produced without special conditions, and is suitable for industrial production.

detailed description

Hereinafter, the present invention will be further described in conjunction with specific embodiments:

Example 1-13:

The amorphous composite materials of Examples 1-13 were obtained by weighing the corresponding raw materials according to the ratios in Table 1, and then preparing according to the following steps. The basic alloy partial raw materials and the toughness-enhancing portion raw material formulations are shown in Table 1 below, and the values are corresponding. Atom mole percentage:

Table 1 Basic alloy part of raw materials and toughness enhanced part of the raw material formula

The purity of the alloy raw material selected in the examples is greater than 99.9%, and the reinforcing portion of the alloy is ZrC nano-powder. The average particle size of the micropowder is 100 nm, and the amount of the ZrC nanopowder is 8% of the partial volume of the base alloy. The materials used in the present invention are all commercially available.

Preparation method of high toughness amorphous alloy:

(1) The nano-powder of the base alloy portion raw material and the toughness-enhancing portion having a purity greater than 99.9% is compounded according to the above amorphous alloy composition, and stirred and uniformly mixed.

(2) The raw materials to be mixed are smelted by arc melting in an argon atmosphere. In the raw material melting process, the melting furnace regularly shake until all starting material is converted to melt, melting is repeated three times; the degree of vacuum melting process is 10 ^-3 Pa, argon pressure of 0.01MPa, cooled to give an amorphous alloy casting ingot. The cooling rate after smelting was 10 ² K/s.

(3) The above amorphous composite material product is obtained by a die casting method.

The toughness of the above amorphous composite product was evaluated, and the metal pendulum tester was used to test according to "GB/T229-2007 Metal Material Charpy Pendulum Impact Test Method", and the amorphous alloy was fabricated at room temperature of 25 ° C. Standard samples were tested. The standard impact sample is 55cm long, the cross section is 10×10cm square section, the V-shaped notch, the pendulum blade is 2mm, and the absorption power KV2 of the test sample. The higher the KV2 value, the better the impact toughness of the sample. Table 2.

Table 2 Impact toughness test results of the amorphous composite materials of Examples 1-13

Numbering	KV2
1	215
2	205
3	222
4	213
5	211
6	207
7	209
8	218
9	222
10	223
11	215

12	224
13	258

As can be seen from Table 2, the amorphous composite materials of Examples 1-13 all have a KV2 value of 205 or more and a high impact toughness.

Further, the amorphous composite material of Examples 1-13 can be formed in a size of 15 cm or more, preferably 30 cm.

Example 14-65

The amorphous composite materials of Examples 14-65 were different from the toughness-enhancing portions, and the test methods for the raw materials of the base alloy according to the ratios in Table 1 were the same as those of Examples 1-13; The toughness-enhancing part of the raw material is one of WC, SiC, TiC, TiN nano-powder, the average particle size of the fine powder is 100 nm, and the amount of the nano-powder is 8% of the partial volume of the base alloy. The test results are shown in Table 3-6:

Table 3 Impact toughness test results of the amorphous composite materials of Examples 14-26

Example	KV2 (WC micro powder)
14	216
15	206
16	220
17	208
18	214
19	204
20	207
twenty one	221
twenty two	214
twenty three	224
twenty four	245
25	224
26	252

Table 4 Impact Toughness Test Results of the Amorphous Composites of Examples 27-39

Example	KV2 (SiC micropowder)
27	205
28	199

29	204
30	209
31	211
32	189
33	195
34	215
35	206
36	214
37	222
38	218
39	237

Table 5 Impact Toughness Test Results of the Amorphous Composite Materials of Examples 40-52

Example	KV2 (TiC micro powder)
40	199
41	189
42	204
43	206
44	203
45	201
46	198
47	182
48	199
49	221
50	206
51	208
52	219

Table 6 Impact toughness test results of the amorphous composite materials of Examples 53-65

Example	KV2 (TiN micro powder)
53	201
54	202
55	212
56	204
57	210
58	199
59	199
60	209
61	210
61	220
63	231
64	225

65

235

Comparative Examples 1-5

The Zr-Hf-Al-Ni quaternary alloy system was used as a control test. The alloy preparation method and test method were the same as those in Examples 1-13 except that the elements, atomic mole percentage and test results of the alloy in the comparative examples were obtained. Table 7 below:

Table 7 compares the alloy raw material formulations of Examples 1-5

Comparative example	Zr	Hf	Al	Ni	KV2
1	55	5	20	20	85
2	56	8	18	18	89
3	58	10	17	15	92
4	62	6	15	17	99
5	63	6	15	16	102

It can be seen from Examples 1-66 and Comparative Examples 1-5 that the amorphous composite material of the present invention has good impact toughness and has high toughness and impact resistance without mechanical processing, wherein the impact resistance is as in Examples 1-13. The better, the toughness enhancement part is selected as ZrC nano-powder, because ZrC can not only enhance the overall toughness of the amorphous composite, but also does not introduce other impurity elements for the Zr-based amorphous alloy, avoiding the possibility of adding too many elements. The resulting alloy is crystallized, so its impact resistance is superior to other nanopowders. Moreover, the amorphous composite material of the present invention is formed to a size of up to 30 mm, and is suitable for forming a complicated member.

Various other changes and modifications may be made by those skilled in the art in light of the above-described technical solutions and concepts, and all such changes and modifications are intended to fall within the scope of the appended claims.

Claims (10)

1. A high toughness amorphous composite material characterized by being prepared from a base alloy portion and a toughness-enhancing portion;

   The elemental composition and atomic mole percentage of the base alloy portion are Zr: 45-65%, Hf: 5-15%, Al: 10-20%, Ni: 10-20%, M1 component: 5-10 %, M2 component: 2-8%; the M1 component is one or more of Sn, Bi, Si, Cu elements; the M2 component is one or two of Ag, Pd elements; The purity of each element of the base alloy portion is greater than 99.9%;

   The toughness-enhancing portion is one or more of WC, SiC, TiC, TiN, and ZrC nano-powders, and the amount thereof is 2-10% of the volume of the base alloy.
2. The high tenacity amorphous composite according to claim 1, wherein the elemental alloy portion has an elemental composition and an atomic mole percentage of Zr: 45-60%, Hf: 5-10%, and Al: 10-15%, Ni: 15-20%, M1 component: 5-8%, M2 component: 5-8%.
3. The high tenacity amorphous composite according to claim 1, wherein the M1 component is Sn or Cu.
4. The high-toughness amorphous composite according to claim 1, wherein each of the nano-powders in the toughness-enhancing portion has a particle diameter of 10 to 100 nm.
5. The high tenacity amorphous composite according to claim 1, wherein the toughness-enhancing portion is a ZrC nanopowder.
6. The high tenacity amorphous composite according to claim 1, wherein the toughness-enhancing portion is added in an amount of from 8 to 10% by volume of the base alloy.
7. A method for preparing a high-toughness amorphous composite material according to any one of claims 1 to 6, which The feature is that the following steps are specifically included:

   (1) Weigh the raw materials of the base alloy portion and the raw materials of the toughness-enhancing portion according to the formulation ratio, and mix the raw materials of the base alloy portion with the raw materials of the toughness-enhancing portion to obtain a mixed raw material;

   (2) The raw material obtained in the step (1) is smelted by arc melting in a vacuum condition or an argon atmosphere, and in the process of melting the raw material, all the raw materials are converted into a melt under the condition of a regular vibration melting furnace, and repeated Smelting 3-4 times; the vacuum degree of the smelting process is 10 ^-1 -10 ^-3 Pa, and the pressure of the argon atmosphere is 0.01-0.05 MPa, and after cooling, an amorphous composite ingot is obtained;

   (3) The amorphous composite ingot is formed by a conventional metal material forming process to obtain a high toughness amorphous composite product.
8. The method for preparing a high-toughness amorphous composite according to claim 7, characterized in that, after the smelting in the step (2), the cooling rate is 10 - 10 ³ K/s.
9. The method for preparing a high-toughness amorphous composite according to claim 7, wherein in the step (3), the conventional metal material forming process refers to a conventional die casting process or a conventional die casting process.
10. Use of a high toughness amorphous composite material according to any one of claims 1 to 6, characterized in that it is used for consumer electronic products, medical device products, aerospace industry products, machine instrument industrial products , automotive industry products.