WO2017067183A1 - High-strength amorphous alloy, preparation method therefor and application thereof - Google Patents

Abstract

A high-strength amorphous alloy, which is composed of Zr_aAl_bCu_cNi_dBe_eSn_fM1_gM2_h, wherein a, b, c, d, e, f, g and h are the corresponding atomic percentage contents in the amorphous alloy, and are respectively 40%≤a≤70%, 5%≤b≤30%, 5%≤c≤15%, 5%≤d≤15%, 0.05%≤e≤3%, 0.2%≤f≤4%, 0.5%≤g≤5%, 1%≤h≤5%; M1 is one or more of Hf, Ta and lanthanide elements, and M2 is one or more of Ti, Sc, Fe and Co elements.The amorphous alloy is high in strength, good in plasticity and suitable as die materials and mechanical structural materials.

Description

High-strength amorphous alloy and preparation method and application thereof Technical field

The invention relates to an amorphous alloy material, in particular to a high-strength, amorphous-forming zirconium-based amorphous alloy material, a preparation method and application thereof.

Background technique

Mechanical structural materials refer to a class of engineering materials whose mechanical or mechanical properties are the main application indicators, specifically, the yield strength, fracture strength, fracture toughness, plastic elongation, elastic modulus, deep drawability, Key indicators such as fatigue performance. Traditional mechanical structural materials include tool steel, stainless steel, heat-resistant steel, aluminum alloy, nickel alloy, titanium alloy, and various composite materials, such as ceramic reinforced metal matrix composite materials, which have advantages in application. They also have their own insurmountable shortcomings, such as corrosion of steel, low strength of aluminum alloy, and difficulty in controlling the interface of composite materials. In some special fields, structural materials encounter special requirements that are often unmatched by traditional materials. Compared with traditional crystalline alloy materials, bulk amorphous alloy materials have great advantages in many applications, with superior mechanical properties, processing properties, soft magnetic hard magnetic properties and unique expansion characteristics, and resistance to various media. Corrosion ability, good biocompatibility, etc., these excellent properties make amorphous alloys have broad application prospects in many fields. Up to now, amorphous alloy systems have developed many products with excellent properties for mechanical structural materials. For example, CoFeTaB bulk amorphous alloys can achieve a compressive strength of 5185 MPa, which creates the highest record of natural metal material strength; ZrTiCuNiBe bulk The crystal alloy has brittleness at room temperature but the elastic strain limit can reach 2%; the CuZrAl bulk amorphous alloy has room temperature plasticity and can be work hardened. Among many amorphous alloy systems, Zr-Al-Cu-Ni quaternary alloy system can prepare amorphous alloy materials with excellent amorphous forming ability and thermal stability, such as Zr ₆₅ Al _7.5 Ni ₁₀ Cu _17.5 . On the basis of the quaternary alloy system, a number of new amorphous alloy materials with other functions have been developed by changing the preparation process and alloy distribution ratio.

The patent application No. 201510222401.6 entitled "A series of Zr-Al-Ni-Cu bulk amorphous alloys with room temperature compression plasticity and high strength" discloses a series of amorphous Zr-Al-Ni-Cu systems. Alloy and its preparation process, Zr _51.5 Al _13.6 Ni _14.9 Cu ₂₀ , Zr ₅₂ Al _12.9 Ni _13.8 Cu _21.3 , Zr _52.5 Al _12.2 Ni _12.6 Cu _22.7 , Zr ₅₃ Al _11.6 Ni _11.7 Cu _23.7 , Zr _53.5 Al _10.9 Ni were prepared. _10.6 Cu ₂₅ , Zr ₅₄ Al _10.2 Ni _9.4 Cu _26.4 , Zr _54.5 Al _9.6 Ni _8.4 Cu _27.5 and Zr ₅₅ Al _8.9 Ni _7.3 Cu _28.8 . The yield strength of the alloy is 1737.5-2041.9 MPa, the compressive strength is 1892.6-2184.6 MPa, and the plastic strain is 0.4-19.1%.

A Ni-Co-Y-La-Al five-element alloy system is disclosed in Chinese Patent No. 201210435848.8 entitled "Preparation of an Aluminum-Based Composite Material with Ultra-High Strength and Controllable Plasticity". The aluminum-based amorphous alloy of the system has an aluminum-based conforming material having a breaking strength of 1500 MPa or more by an improved formulation and process, and the plasticity can reach 21%.

How to prepare an amorphous alloy with better mechanical properties, good amorphous forming ability and forming ability, and large-scale stable production capacity is still the direction of research efforts.

Summary of the invention

The invention provides a Zr-based amorphous alloy with high strength, good plasticity, excellent amorphous forming ability, compactness and good amorphous forming ability, and a preparation method thereof, and the Zr-based amorphous alloy particularly improves the breaking strength.

The technical problem to be solved by the present invention is achieved by the following technical solutions:

1, raw material formula

The amorphous alloy composition is Zr _a Al _b Cu _c Ni _d Be _e Sn _f M1 _g M2 _h , wherein a, b, c, d, e, f, g, h are the corresponding atomic percentages in the amorphous alloy The content is 40%≤a≤70%, 5%≤b≤30%, 5%≤c≤15%, 5%≤d≤15%, 0.05%≤e≤3%, 0.2%≤f≤4 %, 0.5% ≤ g ≤ 5%, 1% ≤ h ≤ 5%; M1 is one or more of Hf, Ta, lanthanides, and M2 is one of Ti, Sc, Fe, Co or A variety. Among them, Zr, Al, Cu, and Ni as the main elements can ensure the stability of the amorphous alloy as a whole and a certain amorphous forming ability.

Further preferably, 55%≤a≤65%, 10%≤b≤30%, 7%≤c≤12%, 7%≤d≤12%, 0.1%≤e≤2%, 1%≤f≤3% , 1% ≤ g ≤ 4%, 2% ≤ h ≤ 5%.

More preferably, M1 is one or both of Hf and Ta.

The inventors have found through extensive experiments that the addition of a very small amount of Be element makes the various types of atomic clusters in the amorphous alloy more dense. When the amorphous alloy is smelted, it can be clearly seen that the addition of a small amount of Be element can enhance the viscosity of the amorphous alloy melt as a whole, thereby improving the overall forming ability of the amorphous alloy and the compactness of the final product. Because the oxide of Be element has certain toxicity, and the addition of Be element also affects the formation ability of amorphous, the amount of Be added should not be too much, and the atomic percentage accounts for 0.05-3% of the whole alloy. It is 0.1% to 2%, and further preferably 1% to 2%, and the toxicity of the Be element in the added range is negligible.

Many high-strength amorphous alloys have poor moldability and plasticity, and although they have excellent mechanical properties, they have no practical application in industry. In the present invention, Sn element is added, Sn has a low melting point and is easily oxidized, and a small amount of addition helps to improve the plasticity of the amorphous alloy product, and can enhance the practical performance of the amorphous alloy material without affecting the strength.

The lanthanoid elements, Hf and Ta are adjacent elements of the same period, and their properties are similar. In the zirconium-based amorphous alloy, the main element Zr can be substituted to different degrees, which increases the force between different element atoms, and the macroscopic performance is cooling. The post alloy structure is relatively dense and has good forming properties. The addition of lanthanide, Hf and Ta elements can inhibit the crystallization tendency of the amorphous alloy and improve the stability of the melt, that is, the ability to form amorphous. The equivalent order is Hf>Ta> lanthanide in the same amount of additive. A good effect can be obtained by adding an atomic percentage of 0.5% to 5% of such an element, and it is preferably 1% to 4%, and still more preferably 1% to 3%.

Ti, Sc, Fe, and Co are the same periodic elements, and their properties are very stable. At the same time, Ti, Sc, Fe, and Co can form coupling atom pairs with Zr, Be, and Al, and form a dense structure with extremely high degree of chaos. Greatly improve the strength and degeneration ability of amorphous alloys. When Ti, Sc, Fe, and Co elements are separately added to the Zr-Al-Cu-Ni quaternary alloy, the amorphous forming ability is greatly reduced, and if too much is added, a bulk amorphous alloy having practical value may not be obtained. It is necessary to simultaneously add lanthanide, Hf, and Ta elements to offset the decrease in the amorphous forming ability of the Ti, Sc, Fe, and Co elements. The atomic percentage of Ti, Sc, Fe, and Co elements added is 1% to 5%, preferably 2% to 5%, and still more preferably 3% to 5%.

Further, an Mn element having an atomic percentage of 0.1% to 0.5% may be added to the above amorphous alloy. The Mn element is stable, and can replace Al and Cu in the amorphous alloy phase, increasing the force between different element atoms, improving the amorphous forming ability, and forming a coupling atom pair with Zr, Be, and Al. It can greatly improve the strength and deformability of amorphous alloys.

2, the preparation method

Step 1. The metal raw material is weighed according to the composition ratio of the amorphous alloy, and the purity of the metal raw material is greater than 99.5%. In general, in order to obtain an amorphous alloy with good amorphous forming ability, the purity of the amorphous raw material is very high, and it is often required to be greater than 99.9%, because once the impurities in the raw material are excessive, the oxygen in the raw material forms oxides. In the process of amorphous molding, the internal crystallization of the alloy is induced as a seed crystal, thereby affecting the formation of an amorphous metal. The lanthanide, Hf, Ta, and Sn elements added in the present invention can suppress the crystallization tendency, absorb oxygen in the alloy, inhibit the formation of crystal nuclei, and improve the formation ability of the amorphous metal in the alloy. By adding the lanthanide, Hf, Ta, and Sn elements in the ratio of the present invention, the purity requirement of the amorphous alloy raw material can be lowered, and the quality of the produced amorphous alloy product is not affected, and the production cost is lowered.

Step 2: After mixing the raw materials, the raw materials are smelted by arc melting or other conventional smelting methods under an argon atmosphere or vacuum, and cooled to obtain a mother alloy ingot; when the formulation of the present invention is smelted, a very low vacuum is not required. The smelting device is required to be high, and the time for vacuuming is increased to increase the cost. The degree of vacuum in the smelting process is 10 ^-1 ~ 10 ^-2 Pa, which can meet the requirements in a short time, suitable for industrial production; the argon atmosphere can be kept at 05 MPa (here, the argon atmosphere pressure can also be selected 0.1, 0.2, 0.3, 0.4 MPa; of course, it is also possible to select a vacuum with a vacuum of 10 ^-1 Pa, 10 ^-2 Pa or 10 ^-3 Pa, which is very easy to achieve because of the length of the description. After the smelting, the cooling rate is 10 ² -10 ³ K/s, and an amorphous alloy excellent in molding ability can be obtained.

Step 3: obtaining the above amorphous alloy product by a conventional amorphous alloy preparation method such as suction casting or die casting. The zirconium-based amorphous alloy of the present invention can be used in the preparation of consumer electronic products, medical device products, and also in the aerospace industry and the automotive industry. Due to its high strength and good plasticity, it is especially suitable for use as a mold material and a mechanical structural material.

The invention has the following beneficial effects:

(1) The zirconium-based amorphous alloy of the present invention has high strength and good plasticity, and is particularly suitable for use as a mold material or a mechanical structural material.

(2) The zirconium-based amorphous alloy in the present invention has a compact structure and a good molding ability.

(3) The zirconium-based amorphous alloy in the present invention has excellent forming ability and an amorphous forming ability of up to 35 mm.

(4) The zirconium-based amorphous alloy in the present invention has a simple preparation process and is not harsh in process conditions, and is suitable for industrial production.

(5) The required range of the zirconium-based amorphous alloy raw material in the present invention is loose, and the manufacturing cost can be reduced.

detailed description

Example 1

The amorphous raw material is composed of Zr _a Al _b Cu _c Ni _d Be _e Sn _f M1 _g M2 _h according to the alloy composition, wherein a, b, c, d, e, f, g, h are corresponding to the amorphous alloy The atomic percentage, M1 is one or more of Hf, Ta, and a lanthanoid element, and M2 is one or more of Ti, Sc, Fe, and Co elements. The smelting is carried out under vacuum or in an argon atmosphere, and the purity of the metal raw material is more than 99.5%, and the vacuum degree is in the range of 10 ^-1 to 10 ^-2 Pa. If an argon atmosphere is selected, the argon gas pressure is maintained. 0.5 MPa. The cooling rate is 10 ² to 10 ³ K/s, and there is no significant effect. After the smelting is cooled, a zirconium-based amorphous alloy ingot is obtained, and an amorphous alloy product is obtained by a conventional amorphous alloy preparation method such as suction casting or die casting.

The mechanical properties of the amorphous alloy in the present invention are characterized according to the results of the bending test and the compression test, and the bending test is carried out according to "YB/T 5349-2014 Test Method for Flexural Mechanical Properties of Metallic Materials", and the compression test is in accordance with "GB/T 7314-2005". Metallic material room temperature compression test method".

The alloy composition is Zr _a Al _b Cu _c Ni _d Be _e Sn _f M1 _g M2 _h , where ah is the atomic percentage of the element, and is smelted and shaped according to the following table:

Serial number	a	b	c	d	e	f	g	h
1	40.0	25.0	15.0	12.0	0.2	0.2	2.6	5.0
2	42.0	22.0	12.0	15.0	0.5	1.0	2.5	5.0
3	45.0	25.0	15.0	10.0	1.0	1.5	1.5	1.0
4	48.0	20.0	13.0	8.0	1.2	2.0	3.8	4.0
5	50.0	18.0	10.0	10.0	1.5	2.5	5.0	3.0
6	51.0	15.0	11.0	12.0	1.8	3.0	2.2	4.0
7	52.0	16.0	10.0	12.0	2.0	3.5	1.5	3.0
8	55.0	18.0	9.0	10.0	0.2	4.0	1.8	2.0
9	56.0	15.0	8.0	10.0	2.0	2.5	3.0	3.5
10	58.0	16.0	8.0	10.0	1.0	1.0	3.0	3.0
11	60.0	17.0	8.0	9.0	1.2	1.5	0.5	2.8
12	62.0	12.0	8.0	9.0	1.5	2.0	1.0	4.5
13	63.0	10.0	7.0	8.0	1.8	2.5	3.7	4.0
14	64.0	8.0	7.0	8.0	2.0	3.0	4.0	4.0

15	65.0	8.0	7.0	7.0	0.2	3.5	4.3	5.0
16	68.0	8.0	5.0	7.0	1.0	4.0	2.0	5.0
17	70.0	5.0	5.0	5.0	2.0	3.0	5.0	5.0

M1 and M2 are selected as follows (the value after the element symbol is the atomic percentage of the element):

Serial number	M1	M2
1	Hf2.6	Ti1.5, Sc1.5, Fe1, Co1
2	Ta2.5	Ti1.5, Sc1.5, Fe1, Co1
3	Hf1, Ta0.5	Ti0.4, Fe0.3, Co0.3
4	Hf3.0, La0.8	Ti2, Fe1, Co1
5	La5.0	Ti1, Sc1, Co1
6	Ce2.2	Ti2, Sc1, Co1
7	Ta1.0, Pr0.5	Ti1, Sc1, Fe1
8	Hf1.0, Nd0.8	Ti1, Sc0.5, Fe0.5
9	Hf2, Pm1	Sc1.5, Fe1, Co1
10	Hf2, Sm1	Sc1, Fe1, Co1
11	Hf0.4, Eu0.1	Ti2.0, Sc0.8
12	Ta0.5, Gd0.5	Fe2.5, Co2
13	Ta2.5, Tb1.2	Ti2, Co2
14	Dy2, Ho2	Sc2, Fe2
15	Er4.0, Lu0.3	Sc2.5, Co2.5
16	Hf1, Yb1	Ti5
17	Hf2.5, Ta2.5	Co5

The test results are as follows:

As can be seen from Example 1, the amorphous alloy product of the present invention has high strength, good plasticity, and good amorphous forming ability.

Example 2

The amorphous alloy product and the characterization method were the same as in Example 1. The composition of the alloy is Zr _a Al _b Cu _c Ni _d Be _e Sn _f M1 _g M2 _h Mn _x , wherein ah and x are atomic percentages of elements, and the ratio between the elements selected by M1 and M2 and the elements is the same as in the first embodiment. Melt and form according to the following table:

Serial number	a	b	c	d	e	f	g	h	X
1	39.9	25.0	15.0	12.0	0.2	0.2	2.6	5.0	0.1
2	41.8	22.0	12.0	15.0	0.5	1.0	2.5	5.0	0.2
3	44.7	25.0	15.0	10.0	1.0	1.5	1.5	1.0	0.3
4	47.6	20.0	13.0	8.0	1.2	2.0	3.8	4.0	0.4
5	49.5	18.0	10.0	10.0	1.5	2.5	5.0	3.0	0.5
6	50.9	15.0	11.0	12.0	1.8	3.0	2.2	4.0	0.1
7	51.8	16.0	10.0	12.0	2.0	3.5	1.5	3.0	0.2
8	54.7	18.0	9.0	10.0	0.2	4.0	1.8	2.0	0.3
9	55.6	15.0	8.0	10.0	2.0	2.5	3.0	3.5	0.4
10	57.5	16.0	8.0	10.0	1.0	1.0	3.0	3.0	0.5
11	59.9	17.0	8.0	9.0	1.2	1.5	0.5	2.8	0.1
12	61.8	12.0	8.0	9.0	1.5	2.0	1.0	4.5	0.2
13	62.7	10.0	7.0	8.0	1.8	2.5	3.7	4.0	0.3
14	63.6	8.0	7.0	8.0	2.0	3.0	4.0	4.0	0.4
15	64.5	8.0	7.0	7.0	0.2	3.5	4.3	5.0	0.5
16	67.5	8.0	5.0	7.0	1.0	4.0	2.0	5.0	0.5
17	69.5	5.0	5.0	5.0	2.0	3.0	5.0	5.0	0.5

The test results are as follows:

It can be seen from Example 2 that the addition of Mn element has different degrees of improvement in the strength, plasticity and formation size of the amorphous alloy.

Comparative example

The amorphous alloy product and the characterization method were the same as in Example 1. The composition of the alloy is Zr _a Al _b Cu _c Ni _d , where ad is the atomic percentage of the element and is smelted and shaped according to the following table:

Serial number	a	b	c	d
1	40.0	25.0	15.0	20.0
2	45.0	25.0	20.0	10.0
3	50.0	20.0	15.0	15.0
4	55.0	18.0	12.0	15.0
5	60.0	17.0	10.0	13.0
6	65.0	12.0	10.0	13.0
7	70.0	10.0	12.0	8.0

The test results are as follows:

As can be seen from the test results of the comparative examples, the amorphous alloy of the present invention has a very good effect on the strength and formation size of the Zr-Al-Cu-Ni quaternary alloy.

It should be noted that the above embodiments are only used to illustrate the technical solutions of the embodiments of the present invention, and are not limited thereto, although the embodiments of the present invention are described in detail with reference to the preferred embodiments. A person skilled in the art should understand that the technical solutions of the embodiments of the present invention may be modified or equivalently replaced, and the modified technical solutions may not deviate from the technical solutions of the embodiments of the present invention.

Claims (10)

1. A high-strength amorphous alloy characterized in that the amorphous alloy has a composition of Zr _a Al _b Cu _c Ni _d Be _e Sn _f M1 _g M2 _h , wherein a, b, c, d, e, f, g And h is the corresponding atomic percentage in the amorphous alloy, respectively 40% ≤ a ≤ 70%, 5% ≤ b ≤ 30%, 5% ≤ c ≤ 15%, 5% ≤ d ≤ 15%, 0.05% ≤ e ≤ 3%, 0.2% ≤ f ≤ 4%, 0.5% ≤ g ≤ 5%, 1% ≤ h ≤ 5%; M1 is one or more of Hf, Ta, lanthanides, M2 It is one or more of Ti, Sc, Fe, and Co elements.
2. The amorphous alloy according to claim 1, wherein M1 is one or both of Hf and Ta.
3. The amorphous alloy according to claim 1 or 2, wherein said 55% ≤ a ≤ 65%, 10% ≤ b ≤ 30%, 7% ≤ c ≤ 12%, 7% ≤ d ≤ 12 %, 0.1% ≤ e ≤ 2%, 1% ≤ f ≤ 3%, 1% ≤ g ≤ 4%, 2% ≤ h ≤ 5%.
4. The amorphous alloy according to any one of claims 1 to 3, wherein an Mn element having an atomic percentage of 0.1% to 0.5% is further added to the amorphous alloy.
5. A method of producing the amorphous alloy according to any one of claims 1 to 4, characterized in that:

   Step 1. The metal raw material is weighed according to the proportion of the amorphous alloy composition, and the purity of the metal raw material is greater than 99.5%.

   Step 2: mixing the raw materials, performing smelting, and cooling to obtain a mother alloy ingot;

   Step 3: preparing the obtained mother alloy ingot by a die casting or die casting process to obtain the amorphous alloy product.
6. The method for preparing an amorphous alloy according to claim 5, wherein the cooling rate after the smelting in the second step is from 10 ² to 10 ³ K/s.
7. A method of producing an amorphous alloy according to claim 5, wherein the smelting in the second step is carried out under vacuum conditions, wherein the degree of vacuum is from 10 ^-1 to 10 ^-2 Pa.
8. The method for producing an amorphous alloy according to claim 5, wherein the smelting in the second step is carried out in an argon atmosphere, wherein the argon atmosphere pressure is 0.1 to 0.5 MPa.
9. A method of producing an amorphous alloy according to claim 5, wherein the smelting in the second step is arc smelting.
10. The use of the amorphous alloy according to any one of claims 1 to 9, characterized in that the amorphous alloy is used as a mold material or a mechanical structural material in consumer electronics, medical device products, aerospace industry and In the automotive industry.