CN113930695B - Al-containing low-density block amorphous alloy and preparation method and application thereof - Google Patents

Al-containing low-density block amorphous alloy and preparation method and application thereof Download PDF

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CN113930695B
CN113930695B CN202111206025.3A CN202111206025A CN113930695B CN 113930695 B CN113930695 B CN 113930695B CN 202111206025 A CN202111206025 A CN 202111206025A CN 113930695 B CN113930695 B CN 113930695B
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刘思路
路新行
彭炜
张晓平
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Panxing New Alloy Material Changzhou Co ltd
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Abstract

The invention belongs to the technical field of amorphous alloy, and particularly relates to an Al-containing low-density block amorphous alloy and a preparation method thereofA method and an application; the atomic percentage expression of the Al-containing low-density bulk amorphous alloy is as follows: al (Al) a ETM b Ni c Cu d Si e Wherein ETM is one or more of groups IVB-VIIB; a is more than or equal to 18 and less than or equal to 20; b is more than or equal to 53 and less than or equal to 56; c is more than or equal to 11 and less than or equal to 14; d/a is more than or equal to 0.60 and less than or equal to 0.85; e is more than 0 and less than or equal to 2; and a + b + c + d + e =100; the Al-containing low-density bulk amorphous alloy does not contain a metal element Be, has low density, strong amorphous forming capability and excellent mechanical property.

Description

Al-containing low-density block amorphous alloy and preparation method and application thereof
Technical Field
The invention belongs to the technical field of amorphous alloys, and particularly relates to an Al-containing low-density bulk amorphous alloy, and a preparation method and application thereof.
Background
The alloy has the characteristics of light specific gravity, low cost and easy processing. Has been widely applied in the fields of 3C products, electronic and electric appliances and the like for a long time.
The 3C electronic products are abbreviated as computers (computers), communication (Communication) and consumer electronics (consumer electronics). At present, a plurality of IT industries enter the digital 3C field at a large scale, and digital 3C fusion technology products are taken as break-through openings for development and become new bright points of the IT industries.
Disclosure of Invention
The invention provides an Al-containing low-density bulk amorphous alloy and a preparation method and application thereof.
In order to solve the technical problem, the invention provides an Al-containing low-density bulk amorphous alloy, which comprises the following atomic percentage expressions: al (Al) a ETM b Ni c Cu d Si e Wherein ETM is one or more of groups IVB-VIIB; a is more than or equal to 18 and less than or equal to 20; b is more than or equal to 53 and less than or equal to 56; c is more than or equal to 11 and less than or equal to 14; d/a is more than or equal to 0.60 and less than or equal to 0.85; e is more than 0 and less than or equal to 2; and a + b + c + d + e =100.
In another aspect, the present invention further provides a method for preparing a low-density bulk amorphous alloy containing Al, comprising: sequentially adding the raw materials into a smelting furnace according to the sequence of high and low melting points, and smelting to prepare alloy liquid; and injecting the alloy liquid into a die, and die-casting to obtain the low-density block amorphous alloy containing aluminum and Al.
In a third aspect, the invention also provides a method for using the low-density bulk amorphous alloy containing Al in 3C electronic products.
The Al-containing low-density bulk amorphous alloy disclosed by the invention does not contain a metal element Be, but the content of the Al element in the composition is not low and is close to 20%, and the contents of Cu and Ni are relatively low, so that the density is low; on the other hand, because the series of amorphous alloys do not contain Be, the series of amorphous alloys can meet the production and use requirements of safety and environmental protection; through modification and enhancement of trace element Si, the stacking among large atoms and small atoms in the composition elements is more compact, the large atoms and the small atoms have strong amorphous forming capability, and a water-cooling copper die casting method is adopted to prepare the bulk amorphous alloy with the critical dimension not less than 5mm; the series of alloys have excellent mechanical properties by adopting trace element modification and enhancement; finally, the modification and enhancement effects of the trace elements greatly improve the conductivity of the series of amorphous alloys.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and drawings.
In order to make the aforementioned and other objects, features and advantages of the present invention comprehensible, preferred embodiments accompanied with figures are described in detail below.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is an XRD pattern of amorphous alloy rods made in some examples of the invention.
Detailed Description
To make the objects, 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, and it is apparent that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In recent years, the 3C industry has been rapidly developed, and among them, the housing of notebook computers, digital cameras, communication phones, etc. is required to be light and thin, so that a low-density alloy material is required.
The invention provides an Al-containing low-density block amorphous alloy, which has the atomic percentage expression as follows: al (Al) a ETM b Ni c Cu d Si e Wherein ETM is one or more of groups IVB-VIIB; a is more than or equal to 18 and less than or equal to 20; b is more than or equal to 53 and less than or equal to 56; c is more than or equal to 11 and less than or equal to 14; d/a is more than or equal to 0.60 and less than or equal to 0.85; e is more than 0 and less than or equal to 2; and a + b + c + d + e =100.
Wherein, cu atomic radius
Figure BDA0003303973530000031
Radius of Al atom
Figure BDA0003303973530000032
The difference in the radii of Cu atoms and Al atoms is about 12%. In addition, the enthalpy of mixing of Cu and Al is a negative value, and the content ratio d/a of Cu and Al is between 0.60 and 0.85, so that a stable short-range ordered structure is formed, and the content of Al is further improved, so that the overall density is reduced.
Specifically, the Al-containing low-density bulk amorphous alloy does not contain a metal element Be, but the Al element content in the composition is not low and is close to 20%, and the Cu and Ni contents are relatively low, so that the density is low; on the other hand, because the series of amorphous alloys do not contain Be, the series of amorphous alloys can meet the production and use requirements of safety and environmental protection; through modification and enhancement of trace element Si, stacking among large atoms and small atoms in the composition elements is more compact, the large atoms and the small atoms have strong amorphous forming capacity, and a water-cooling copper die casting method is adopted to prepare a block amorphous alloy with the critical dimension not less than 5mm; the series of alloys have excellent mechanical properties by adopting trace element modification and enhancement; finally, the modification and enhancement effects of the trace elements greatly improve the conductivity of the series of amorphous alloys.
Wherein, optionally, the ETM may be but is not limited to one or more of Ti, zr, hf, nb.
Optionally, the density of the Al-containing low-density bulk amorphous alloy can be, but is not limited to, 6.05-6.25 g/cm 3 。
Optionally, the critical dimension of the Al-containing low-density bulk amorphous alloy is not less than 5mm.
Optionally, the tensile yield strength of the Al-containing low-density bulk amorphous alloy is not lower than 1200MPa.
Optionally, the room temperature resistivity of the Al-containing low-density bulk amorphous alloy is not more than 245 mu omega cm.
Further, the invention also provides a preparation method of the low-density block amorphous alloy containing Al, which comprises the following steps: sequentially adding the raw materials into a smelting furnace according to the sequence of high and low melting points, and smelting to prepare alloy liquid; and injecting the alloy liquid into a die, and die-casting to obtain the low-density block amorphous alloy containing aluminum and Al.
Wherein, optionally, the smelting furnace can be but not limited to a vacuum arc furnace or a cold crucible suspension furnace or a vacuum induction furnace.
Alternatively, the mold may be, but is not limited to, a water-cooled copper mold.
Specifically, the mass of each element is converted according to the atomic percentage in the expression; after removing oxide skins on the surfaces of the raw materials, cleaning the raw materials by using industrial ethanol; the processed metal raw materials are sequentially stacked in a vacuum arc furnace or a cold crucible suspension furnace or a vacuum induction furnace according to the sequence of the melting point, and are smelted after the correctness is confirmed. After the master alloy is fully and uniformly smelted, obtaining an alloy ingot; and (3) using vacuum die casting equipment, and finally pressing the alloy cast ingot into water-cooled copper molds with different sizes to obtain the block amorphous alloy.
Further, the Al-containing low-density bulk amorphous alloy provided by the invention is used for 3C electronic products.
Example 1
The Al-containing low-density bulk amorphous alloy comprises the following components: al (Al) 19 Zr 55 Ni 11 Cu 14 Si 1 The preparation method comprises the following steps:
weighing the components according to a proportion, sequentially putting Al, cu, ni and Zr into a vacuum arc melting furnace, putting Si in the middle, vacuumizing to below 0.1Pa, and then introducing argon of 0.5Pa and striking an arc for melting; after the alloy is melted and solidified, turning over and continuing arc striking and smelting, and repeating for two to three times until the alloy is homogenized to form an alloy ingot; and taking out the alloy ingot, melting the alloy ingot in a die casting machine, and pressing the melted alloy ingot into a water-cooling copper mold with the diameter of 5mm to obtain a block amorphous alloy rod. After the amorphous bar is processed into a tensile sample, a tensile test is carried out, and the test result shows that the yield strength of the amorphous bar is 1627MPa; the amorphous sample had a resistivity of 212. Mu. Omega. Cm measured at room temperature.
Example 2
The Al-containing low-density bulk amorphous alloy comprises the following components: al (Al) 20 Hf 1 Zr 52 Ni 14 Cu 12 Si 1 The preparation method comprises the following steps:
weighing the components in proportion, sequentially putting Al, cu, hf, ni and Zr into a vacuum arc melting furnace, putting Si in the middle, vacuumizing to below 0.1Pa, and then introducing argon of 0.5Pa and striking an arc for melting; after the alloy is melted and solidified, turning over and continuing arc striking and smelting, and repeating for two to three times until the alloy is homogenized to form an alloy ingot; taking out the alloy ingot, melting the alloy ingot in a die casting machine, and pressing the melted alloy ingot into a water-cooling copper mold with the diameter of 5mm to obtain a block amorphous alloy rod; after the amorphous bar is processed into a tensile sample, a tensile test is carried out, and the test result shows that the yield strength is 1413MPa; the resistivity of the amorphous sample was measured to be 229 μ Ω cm at room temperature.
Example 3
Al-containing low-density block amorphous alloyThe composition of (A) is as follows: al (Al) 18 Hf 1 Zr 52 Ni 14 Cu 12 Si 3 The preparation method comprises the following steps:
weighing the components in proportion, sequentially putting Al, cu, hf, ni and Zr into a vacuum arc melting furnace, putting Si in the middle, vacuumizing to below 0.1Pa, and then introducing argon of 0.5Pa and striking an arc for melting; after the alloy is melted and solidified, turning over and continuing arc striking and smelting, and repeating for two to three times until the alloy is homogenized to form an alloy ingot; taking out the alloy ingot, melting the alloy ingot in a die casting machine, and pressing the alloy ingot into a water-cooling copper mold with the diameter of 7mm to obtain a block amorphous alloy rod; after the amorphous bar is processed into a tensile sample, a tensile test is carried out, and the test result shows that the yield strength of the amorphous bar is 1572MPa; the resistivity of the amorphous sample was measured to be 207. Mu. Omega. Cm at room temperature.
Example 4
The Al-containing low-density bulk amorphous alloy comprises the following components: al (Al) 18 Ti 9 Zr 45 Ni 12 Cu 15 Si 1 The preparation method comprises the following steps:
weighing the components in proportion, sequentially putting Al, cu, ni, ti and Zr into a vacuum arc melting furnace, putting Si in the middle, vacuumizing to below 0.1Pa, and then introducing argon of 0.5Pa and striking an arc for melting; after the alloy is melted and solidified, turning over and continuing arc striking and smelting, and repeating for two to three times until the alloy is homogenized to form an alloy ingot; taking out the alloy ingot, melting the alloy ingot in a die casting machine, and pressing the melted alloy ingot into a water-cooling copper mold with the diameter of 5mm to obtain a block amorphous alloy rod; after the amorphous bar is processed into a tensile sample, a tensile test is carried out, and the test result shows that the yield strength of the amorphous bar is 1257MPa; the resistivity of the amorphous sample was measured to be 245 μ Ω cm at room temperature.
Example 5
The Al-containing low-density bulk amorphous alloy comprises the following components: al (Al) 18 Ti 5 Zr 47 Ni 12 Cu 15 Si 3 The preparation method comprises the following steps:
weighing the components according to a proportion, sequentially putting Al, cu, ni, ti and Zr into a vacuum arc melting furnace, putting Si in the middle, vacuumizing to below 0.1Pa, and then introducing argon of 0.5Pa and striking an arc for melting; after the alloy is melted and solidified, turning over and continuing arc striking and smelting, and repeating for two to three times until the alloy is homogenized to form an alloy ingot; taking out the alloy ingot, melting the alloy ingot in a die casting machine, and pressing the melted alloy ingot into a water-cooling copper mold with the diameter of 5mm to obtain a block amorphous alloy rod; after the amorphous bar is processed into a tensile sample, a tensile test is carried out, and the test result shows that the yield strength of the amorphous bar is 1389MPa; the resistivity of the amorphous sample was measured to be 221 μ Ω cm at room temperature.
Comparative example 1
The alloy comprises the following components: al (Al) 19 Zr 55 Ni 12 Cu 11 Si 3 The preparation method comprises the following steps:
weighing the components in proportion, sequentially putting Al, cu, ni and Zr into a vacuum arc melting furnace, putting Si in the middle, vacuumizing to below 0.1Pa, and then introducing argon of 0.5Pa and striking an arc for melting; after the alloy is melted and solidified, turning over and continuing arc striking and smelting, and repeating for two to three times until the alloy is homogenized to form an alloy ingot; and taking out the alloy ingot, melting the alloy ingot in a die casting machine, and pressing the melted alloy ingot into a water-cooling copper mold with the diameter of 3mm to obtain a block amorphous alloy rod. The amorphous bar has a certain degree of crystallization phenomenon, and the density is 6.068g/cm 3 (ii) a After the amorphous bar is processed into a tensile sample, a tensile test is carried out, and the test result shows that the yield strength is 1141MPa, and the mechanical property is reduced due to the reduction of amorphous forming capability; the amorphous sample had a resistivity of 273. Mu. Omega. Cm measured at room temperature, and the resistance increased due to the decrease in amorphous formability.
Comparative example 2
The alloy comprises the following components: al (Al) 21 Hf 1 Zr 52 Ni 14 Cu 12 The preparation method comprises the following steps:
weighing the components in proportion, sequentially putting Al, cu, hf, ni and Zr into a vacuum arc melting furnace, vacuumizing to below 0.1Pa, and then introducing argon of 0.5Pa and striking an arc for melting; after the alloy is melted and solidified, turning over and continuing arc striking and smelting, and repeating for two to three times until the alloy is homogenized to form an alloy ingot; taking out the alloy ingot and pressingMelting in casting machine, pressing into water-cooled copper mold with diameter of 3mm to obtain block alloy rod, completely crystallizing, and fragmenting part of the rod, wherein the density is 6.248g/cm 3 (ii) a After the alloy bar is processed into a tensile sample, a tensile test is carried out, and the test result shows that the yield strength of the alloy bar is 305MPa; the resistivity of the alloy sample was measured to be 293. Mu. Omega. Cm at room temperature.
Comparative example 3
The alloy composition is as follows: al (aluminum) 17 Ti 9 Zr 45 Ni 13 Cu 16 The preparation method comprises the following steps:
weighing the components according to the proportion, sequentially putting Al, cu, ni, ti and Zr into a vacuum arc melting furnace, vacuumizing to below 0.1Pa, and then introducing argon of 0.5Pa and striking an arc for melting; after the alloy is melted and solidified, turning over and continuing arc striking and smelting, and repeating for two to three times until the alloy is homogenized to form an alloy ingot; and taking out the alloy ingot, melting the alloy ingot in a die casting machine, pressing the melted alloy ingot into a water-cooling copper mold, wherein the alloy ingot cannot be completely filled and amorphous alloy cannot be obtained.
The alloy materials obtained in the examples and comparative examples were subjected to performance tests, and the data are summarized in table 1.
TABLE 1 Performance data of the alloy materials prepared in the examples and comparative examples
Figure BDA0003303973530000071
Figure BDA0003303973530000081
As can Be seen from the data in fig. 1 and table 1, the Al-containing low-density bulk amorphous alloy containing no metal element Be, having a low density, a strong amorphous forming ability, and excellent mechanical properties was obtained in the examples of the present invention; the alloy in comparative example 1, which had a d/a value of 0.58, had restricted amorphous formability, and the reduction in amorphous formability led to a reduction in mechanical properties and an increase in resistance; the alloy material in the comparative example 2 has a d/a value of 0.57, no trace element Si is modified and enhanced, the mechanical property is seriously influenced, and the resistance is increased; the alloy material in comparative example 3 has a d/a value of 0.94, no trace element Si is modified and enhanced, the amorphous forming ability is restricted, an amorphous alloy cannot be obtained, and the alloy cannot be subjected to mechanical property and electrical property tests.
In conclusion, the Al-containing low-density bulk amorphous alloy provided by the invention does not contain the metal element Be, but the content of the Al element in the composition is not low and is close to 20%, and the contents of Cu and Ni are relatively low, so that the density is low; on the other hand, because the series of amorphous alloys do not contain Be, the series of amorphous alloys can meet the production and use requirements of being safer and more environment-friendly; through modification and enhancement of trace element Si, the stacking among large atoms and small atoms in the composition elements is more compact, the large atoms and the small atoms have strong amorphous forming capability, and a water-cooling copper die casting method is adopted to prepare the bulk amorphous alloy with the critical dimension not less than 5mm; the series of alloys have excellent mechanical properties by adopting trace element modification and reinforcement; finally, the modification and enhancement effects of the trace elements greatly improve the conductivity of the series of amorphous alloys.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.

Claims (4)

1. An Al-containing low-density bulk amorphous alloy is characterized in that the atomic percentage expression is as follows:
Al a ETM b Ni c Cu d Si e wherein
ETM is Zr;
18≤a≤20；
53≤b≤56；
11≤c≤14；
0.60≤d/a≤0.85；
e is more than 0 and less than or equal to 2; and
a+b+c+d+e＝100；
the density of the Al-containing low-density block amorphous alloy is 6.05-6.25 g/cm 3 ；
The room temperature resistivity of the Al-containing low-density bulk amorphous alloy is not more than 245 mu omega cm;
the critical dimension of the Al-containing low-density bulk amorphous alloy is not less than 5mm;
the tensile yield strength of the Al-containing low-density bulk amorphous alloy is not lower than 1200MPa.
2. A preparation method of low-density block amorphous alloy containing Al is characterized by comprising the following steps:
sequentially adding the raw materials of each component as defined in claim 1 into a smelting furnace according to the sequence of melting point to smelt to obtain alloy liquid;
and injecting the alloy liquid into a die, and die-casting to obtain the low-density block amorphous alloy containing aluminum and Al.
3. The method according to claim 2,
the smelting furnace is a vacuum arc furnace or a cold crucible suspension furnace or a vacuum induction furnace.
4. The method according to claim 2,
the mould is a water-cooling copper mould.
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