CN114606452B - High-plasticity Hf-based two-phase amorphous alloy and preparation method thereof - Google Patents
High-plasticity Hf-based two-phase amorphous alloy and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-plasticity Hf-based amorphous alloy with an atomic percentage composition formula of Hf a Cu b Ni c Al d Ag e Wherein a is more than or equal to 30 and less than or equal to 65, b is more than or equal to 25 and less than or equal to 35,5 and less than or equal to 25,4 and less than or equal to 15,0 and less than or equal to 5, and satisfies a + b + c + d + e =100, the amorphous alloy is a dual-phase amorphous structure, and the dual-phase amorphous structure is composed of an HfNiAlAg-rich amorphous alloy matrix and Cu-rich second-phase amorphous alloy particles. The alloy has high strength and high plasticity. The invention also discloses a preparation method of the high-plasticity Hf-based amorphous alloy, which comprises the following steps: preparing materials according to the atomic percentage composition formula of the high-plasticity Hf-based amorphous alloy, and uniformly smelting to prepare a master alloy; and preparing the molten master alloy into the high-plasticity Hf-based amorphous alloy by a copper mold suction casting method. The method is simple and efficient, and saves resources.
Description
Technical Field
The invention belongs to the design and preparation technology of amorphous alloy materials, and particularly relates to a high-plasticity Hf-based amorphous alloy and a preparation method thereof.
Background
The Amorphous alloy (Amorphous alloy) also called Metallic glass (Metallic glass) has long-range disordered and short-range ordered atomic structures and isotropic physical characteristics, has a unique glass transition temperature point, and has the characteristics of glass, metal, solid and liquid. Amorphous materials are disordered as a whole, but atoms are also bonded together by chemical bonds, so that a certain regularity, i.e., short-range order, is observed in the limited close proximity of the atoms.
In the 60 th century of the 20 th century amorphous alloys began to be studied by professor Duwez of the university of california, producing amorphous strips of several tens of microns thickness by means of copper wheel spinning, and were thus presented in our lives. In 1974, chen et al prepared amorphous alloy of Pd-Cu-Si ternary system by suction casting method, and successfully crossed the size of amorphous alloy from micron level to millimeter level. In 1982, turnbull et al added P element into Pd-Ni system, and successfully increased the size of amorphous alloy from previous millimeter level to centimeter level by using boron oxide fluxing method. With the lapse of time, in the 20 th century, the end of the 80 s to the early 90 s, inoue et Al, northeast Japan university, adopt a multi-alloying method, and a series of La-Al-Ni ternary system alloys which can replace precious metal systems and have high amorphous forming capability are discovered successively, so that a road is paved for industrial production, the application of amorphous alloys is promoted, and the research of bulk amorphous alloys is rapidly developed to dozens of individual systems from original systems.
Amorphous alloy refers to alloy, also called metallic glass, in which atoms are distributed in a topological disordered manner in a three-dimensional space in a solid state and relatively stable form is maintained in a certain temperature range, and when the critical dimension of the amorphous alloy reaches a millimeter level, the amorphous alloy can be called bulk amorphous alloy, and has excellent mechanical properties such as high strength, high hardness and high elastic limit, and low plasticity or severe brittleness becomes a key problem of applying the bulk amorphous alloy to structural materials.
The Hf-based amorphous alloy has excellent mechanical properties such as high strength, high wear resistance, high corrosion resistance and the like, but has poor plasticity at room temperature and is difficult to process; the wide application of the Hf-based amorphous alloy is limited. In order to improve the plasticity of the bulk amorphous alloy, nanocrystals are generated in a heat treatment mode, so that the plasticity of the bulk amorphous alloy is improved, and a large amount of manpower and material resources are wasted.
Therefore, it is highly desirable to design an Hf-based amorphous alloy with high strength, high wear resistance, and avoiding poor plasticity.
Disclosure of Invention
The invention provides a high-plasticity Hf-based amorphous alloy which has high strength and high plasticity.
A high-plasticity Hf-base amorphous alloy with atomic percentage composition formula of Hf a Cu b Ni c Al d Ag e Wherein a is more than or equal to 30 and less than or equal to 65, b is more than or equal to 25 and less than or equal to 35,5 and less than or equal to 25,4 and less than or equal to 15,0 and less than or equal to e and less than 5, and the amorphous alloy meets the condition that a + b + c + d + e =100, is a dual-phase amorphous structure, and the dual-phase amorphous structure is composed of an amorphous alloy matrix rich in HfNiAlAg and a second phase amorphous alloy rich in Cu.
By adding to Hf-Cu-Ni-Al a material which has a positive enthalpy of mixing with both Cu and NiAg element, phase separation usually occurs between elements with positive enthalpy of mixing. The Hf has larger negative mixed enthalpy (delta H) with Ni, al and Ag elements Hf-Al ＝-39kJ/mol，ΔH Hf-Ni ＝-42kJ/mol，ΔH Hf-Ag = 13 kJ/mol), and the Ag, cu and Ni three elements have positive mixed enthalpy (Delta H) Ag-Cu ＝+2kJ/mol，ΔH Ag-Ni ＝+15kJ/mol，ΔH Cu-Ni = 4 kJ/mol). Therefore, the four elements of HfNiAlAg are more easily combined to form two amorphous phases rich in HfNiAlAg and Cu. In work on free volume studies using Monte Carlo simulations, it was found that amorphous local structures can be divided into soft and hard domains. The hard regions are composed of enriched icosahedral clusters, while the soft regions contain more free volume. Structural inhomogeneities therefore make it easier to create more free volume than a homogeneous structure. The large amount of free volume in dispersed distribution is beneficial to the formation, branching and interaction of multiple shear bands, thereby improving the plasticity of the bulk amorphous alloy.
The atomic proportions of elements Hf, ni, al and Ag in the HfNiAlAg-rich amorphous alloy matrix are respectively that a is more than or equal to 30 and less than or equal to 55, c is more than or equal to 10 and less than or equal to 20, d is more than or equal to 4 and less than or equal to 15, and e is more than 0 and less than or equal to 3.
The atomic proportion of the element Cu in the Cu-rich second-phase amorphous alloy particles is 39-70%.
The diameter of the Cu-rich second-phase amorphous alloy particles is 4-10nm, and the Cu-rich second-phase amorphous alloy particles account for 5-55% of the volume of the amorphous alloy matrix.
The atomic percentage of Cu, ni and Ag is that b is more than or equal to 25 and less than or equal to 35,5 and less than or equal to c and less than or equal to 15,0 and less than or equal to e and less than or equal to 2.5, the diameter of the Cu-rich second-phase amorphous alloy particles is 5-9nm, and the Cu-rich second-phase amorphous alloy particles account for 15-55% of the volume of the amorphous alloy matrix.
The diameter of the high-plasticity Hf-based amorphous alloy is 1-10mm, the yield strength is 2325-2450MPa, and the plastic strain is 3.0-4.3%.
The invention also provides a preparation method of the high-plasticity Hf-based amorphous alloy, which comprises the following steps:
(1) Preparing materials according to the atomic percentage composition formula of the high-plasticity Hf-based amorphous alloy, and uniformly smelting to prepare a master alloy;
(2) And preparing the molten master alloy into the high-plasticity Hf-based amorphous alloy by a copper mold suction casting method.
When the copper mold suction casting method is adopted, the cooling rate of the molten alloy is 10 2 ～10 3 k/s。
The invention adopts a copper mold suction casting method, and adds Ag element which has positive mixing enthalpy with Cu and Ni in Hf-Cu-Ni-Al under a proper cooling rate, wherein the Hf element has larger negative mixing enthalpy (delta H) with Ni, al and Ag element Hf-Al ＝-39kJ/mol，ΔH Hf-Ni ＝-42kJ/mol，ΔH Hf-Ag = 13 kJ/mol), and the Ag, cu and Ni three elements have positive mixed enthalpy (Delta H) Ag-Cu ＝+2kJ/mol，ΔH Ag-Ni ＝+15kJ/mol，ΔH Cu-Ni = 4 kJ/mol). Therefore, the four elements of HfNiAlAg are more easily combined to form two amorphous phases rich in HfNiAlAg and Cu.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the invention, ag element which has positive mixing enthalpy with Cu and Ni is introduced into Hf-based amorphous alloy to form two mutually incompatible liquid phases, and a two-phase amorphous composite material is formed after glass transition and solidification.
(2) According to the invention, the Ag-added Hf-based amorphous alloy is made to generate a two-phase alloy by a copper mold suction casting method, so that the heat treatment process is saved, the toughness-increasing effect is achieved, and the prepared Hf-based amorphous alloy has high plasticity.
Drawings
FIG. 1 is an XRD diffraction pattern of example 1 and comparative examples 1-2;
FIG. 2 is a DSC chart of example 1 and comparative examples 1-2;
FIG. 3 is a graph of compressive stress-strain curves for example 1 and comparative examples 1-2;
FIG. 4 is a TEM image of example 1 and comparative examples 1-2, wherein FIG. 4a is a TEM image of example 1, FIG. 4b is a TEM image of comparative example 1, and FIG. 4c is a TEM image of comparative example 2;
fig. 5 is TEM images of example 1 and comparative examples 1 to 2, in which fig. 5a is a STEM image of example 1, fig. 5b is a STEM image of comparative example 1, and fig. 5c is a STEM image of comparative example 2.
Detailed Description
Because of the presence of some easily oxidizable elements in the alloy system of this experiment, the experimental raw materials used, high purity Ni, high purity Al, high purity Hf and high purity Ag, were all greater than 99.95wt.%, and high purity Cu was 99.99wt.%. The preparation process of the alloy is as follows:
(1) Raw materials are prepared. Removing oxide skin and impurities on the surface of the sample by using an ultrasonic cleaner and a grinding machine; weighing by using a high-precision electronic balance to prepare raw materials according with the chemical formula proportion, wherein the weighing precision is +/-0.05 mg in the weighing process of each raw material;
(2) And smelting a master alloy ingot. Putting the prepared raw materials into a high vacuum arc melting furnace until the vacuum degree reaches 4 multiplied by 10 -3 After Pa, repeatedly washing with argon gas for more than three times, then introducing argon gas to initiate an arc on Ti, melting the raw materials, starting electromagnetic stirring after complete melting, repeatedly turning each alloy ingot for four times, and smelting for five times;
(3) And (5) carrying out suction casting on the bulk amorphous. And (3) cutting the master alloy ingot smelted in the last step into small pieces, polishing to remove impurities such as oxide skin, grease and the like on the surface of the master alloy, then carrying out vacuum arc smelting again, and carrying out suction casting on molten metal by adopting a copper mold to form the bulk amorphous alloy. Since the copper mold has 10 2 ～10 3 The cooling rate of k/s can store the long-range disordered short-range ordered atomic arrangement of the solution to a solid state, thereby preparing the bulk amorphous alloy.
The performance test method comprises the following steps:
1. and (3) carrying out phase structure test on the prepared sample by XRD, wherein the test angle is 20-80 degrees, the test speed is 4 degrees/min, and 30-60 degrees is selected for convenience of curve statistics for description.
2. An amorphous alloy having a diameter of 2mm was subjected to DSC curve test at a heating rate of 20K/min. The glass transition temperature (Tg), crystallization temperature (Tx), melting temperature (Tm), and liquidus temperature (Tl) can be observed, further determining that the sample is an amorphous alloy.
3. A sample with a height of 4mm is cut out, a compression experiment is carried out at room temperature by adopting a 100kN universal tester, and the strain rate is 1 multiplied by 10 < -4 > s -1 The compressive stress-strain curves of examples 1 to 3 and comparative examples 1 to 2 were obtained.
Example 1
The amorphous alloy comprises Hf 48 Cu 29.25 Ni 9.75 Al 12 Ag 1 The preparation method comprises the steps of adopting high-purity Ni, high-purity Al, high-purity Hf and high-purity Ag with the purity of more than 99.95wt.% and high-purity Cu with the purity of 99.99wt.% as raw materials, preparing the raw materials according to the proportion of a chemical formula, putting the raw materials into a high-vacuum arc melting furnace for melting, and preparing a master alloy ingot. And cutting the master alloy ingot, smelting again, and preparing the bulk amorphous alloy by adopting a copper mold suction casting method. Wherein the prepared amorphous alloy is a bar with the diameter of 2mm or 5 mm.
As shown in fig. 1, the XRD result shows that example 1 is a pure amorphous structure and a bulk amorphous alloy having a diameter of 5mm can be prepared. As shown in fig. 2, the glass transition temperature Tg =780.9K, the supercooled liquid region Δ Tx =81.5K, and the initial melting temperature Tm =1238.7K of the amorphous alloy.
As shown in FIG. 3, the yield strength of example 1 was about 2325MPa, and the plastic strain was about 4.3%. As shown in fig. 4a, the high-resolution TEM image shows that the selected-area electron diffraction in the figure all presents a single diffuse scattering ring, which proves that the whole structure of the TEM image is in an amorphous state. Example 1 has two different phase contrasts, i.e. two amorphous phases, where the darker amorphous phase is homogeneous in morphology, i.e. a Cu-rich second phase amorphous alloy, with dimensions in the range of 5-9nm. As shown in FIG. 5a, the second phase amorphous alloy accounts for 15.9-51.5% of the amorphous alloy matrix by volume. The two-phase separation structure can promote local atom rearrangement of the amorphous alloy, prevent multiple nucleation and propagation of the shear band, and enhance the plasticity of the amorphous alloy at the size and density.
Example 2
The procedure of example 1 was different in that the amorphous alloy component was Hf 48 Cu 29.25 Ni 9.75 Al 12.5 Ag 0.5 Example 2 prepared a pure amorphous structure and was able to prepare a bulk amorphous alloy with a diameter of 10 mm. The glass transition temperature Tg =783.0K, the supercooled liquid region Δ Tx =78.8K, and the initial melting temperature Tm =1239.2K of the amorphous alloy.
The yield strength of the amorphous alloy prepared in example 2 is about 2400MPa, and the plastic strain is about 3.4%. The high-resolution TEM image shows that the selected region electron diffraction shows a single diffuse scattering ring, and the structure is proved to be an amorphous structure as a whole. The amorphous alloy prepared in example 2 has two different phase contrasts, namely two amorphous phases, wherein the darker amorphous phase has a uniform morphology with a size of 4-8nm, and the second phase amorphous alloy accounts for 5.7-22.8% of the volume of the amorphous alloy matrix. The two-phase separation structure can promote local atom rearrangement of the amorphous alloy, prevent multiple nucleation and propagation of the shear band, and enhance the plasticity of the amorphous alloy at the size and density.
Example 3
The amorphous alloy comprises Hf 48 Cu 29.25 Ni 9.75 Al 10 Ag 2 In example 3, high-purity Ni, high-purity Al, high-purity Hf, and high-purity Ag, each having a purity of more than 99.95 wt%, and high-purity Cu, each having a purity of 99.99 wt%, were used as raw materials, and the raw materials were mixed according to the formula, and placed in a high-vacuum arc melting furnace to be melted, thereby preparing a master alloy ingot. And cutting the master alloy ingot, smelting again, and preparing the bulk amorphous alloy by adopting a copper mold suction casting method. Wherein the prepared amorphous alloy is a bar with the diameter of 2mm or 5 mm.
Example 3 is a pure amorphous structure and a bulk amorphous alloy with a diameter of 5mm can be prepared. The glass transition temperature Tg =776.5K, the supercooled liquid region Δ Tx =76.5K, and the initial melting temperature Tm =1235.2K of the amorphous alloy.
Example 3 had a yield strength of about 2320MPa and a plastic strain of about 3.0%. The whole structure of the material is in an amorphous structure. Example 3 has two different phase contrasts, i.e. two amorphous phases, and example 2 has two different phase contrasts, i.e. two amorphous phases, wherein the darker amorphous phase has a uniform morphology with a size of 5-10nm, and the second phase amorphous alloy accounts for 10.5-41.9% of the volume of the amorphous alloy matrix.
Comparative example 1
The amorphous alloy comprises Hf 48 Cu 29.25 Ni 9.75 Al 13 The method comprises the steps of adopting high-purity Ni, high-purity Al, high-purity Hf and high-purity Ag with the purity of more than 99.95 wt% and high-purity Cu with the purity of 99.99 wt% as raw materials, preparing the raw materials according to a chemical formula proportion, putting the raw materials into a high-vacuum arc melting furnace for melting, and preparing a master alloy ingot. And cutting the master alloy ingot, smelting again, and preparing the bulk amorphous alloy by adopting a copper mold suction casting method. Wherein the prepared amorphous alloy is a bar with the diameter of 2mm or 5 mm.
As shown in fig. 1, the XRD result shows that the amorphous alloy prepared in comparative example 1 has a single pure amorphous structure. As shown in fig. 2, the glass transition temperature Tg =786K, the supercooled liquid region Δ Tx =76.7K, and the initial melting temperature Tm =1240.4K.
As shown in FIG. 3, comparative example 1 had a yield strength of about 2410MPa and a plastic strain of about 2.7%. As shown in fig. 4b, the high-resolution TEM image shows that the selected regions in the image all show a single diffuse scattering ring by electron diffraction, which proves that the whole structure of the high-resolution TEM image shows an amorphous structure. As shown in fig. 5b, the amorphous alloy of comparative example 2 is a uniform amorphous alloy short-range structure, has no contrast of apparent contrast between light and shade, i.e., has no two-phase separation structure, and has poorer plasticity compared with example 1.
Comparative example 2
The amorphous alloy comprises Hf 48 Cu 29.25 Ni 9.75 Al 8 Ag 5 In comparative example 2, high-purity Ni, high-purity Al, high-purity Hf, and high-purity Ag, each having a purity of greater than 99.95wt.%, and high-purity Cu, each having a purity of 99.99wt.%, were used as raw materials, and the raw materials were prepared according to the formula ratio, and placed in a high-vacuum arc melting furnace to be melted, thereby preparing a master alloy ingot. And cutting the master alloy ingot, smelting again, and preparing the bulk amorphous alloy by adopting a copper mold suction casting method.
As shown in fig. 1, the XRD result shows that comparative example 2 is a pure amorphous structure, and a bulk amorphous alloy having a diameter of 2mm can be prepared. As shown in fig. 2, the glass transition temperature Tg =767.1K, the supercooled liquid region Δ Tx =67.9K, and the initial melting temperature Tm =1222.8K.
As shown in FIG. 3, the yield strength of the amorphous alloy obtained in comparative example 2 was about 2203MPa, and the plastic strain was about 1.05%. As shown in fig. 4c, the high-resolution TEM image shows that the selected regions in the image all show a single diffuse scattering ring by electron diffraction, which proves that the whole structure of the high-resolution TEM image shows an amorphous structure. As shown in FIG. 5c, comparative example 2 has two different phase contrasts, i.e., two amorphous phases, and the second phase amorphous alloy accounts for 3.1 to 8.7% by volume of the amorphous alloy matrix, as compared to examples 1 to 3, and the plasticity is reduced.
Claims (6)
1. The high-plasticity Hf-based two-phase amorphous alloy is characterized in that the atomic percentage composition formula is Hf a Cu b Ni c Al d Ag e Wherein a is more than or equal to 30 and less than or equal to 65, b is more than or equal to 25 and less than or equal to 35,5 and less than or equal to 25,4 and less than or equal to 15,0 and less than or equal to 5, and satisfies a + b + c + d + e =100, the amorphous alloy is a dual-phase amorphous structure, and the dual-phase amorphous structure is composed of an HfNiAlAg-rich amorphous alloy matrix and Cu-rich second-phase amorphous alloy particles;
the atomic proportion of the element Cu in the Cu-rich second-phase amorphous alloy particles is 39-70%, the diameter of the Cu-rich second-phase amorphous alloy particles is 4-10nm, and the Cu-rich second-phase amorphous alloy particles account for 5-55% of the volume of the amorphous alloy matrix.
2. The high plasticity Hf-based dual phase amorphous alloy as recited in claim 1, wherein the atomic proportions of the elements Hf, ni, al and Ag in the HfNiAlAg-rich amorphous alloy matrix are 30. Ltoreq. A.ltoreq.55, 10. Ltoreq. C.ltoreq.20, 4. Ltoreq. D.ltoreq.15 and 0. Ltoreq. E.ltoreq.3, respectively.
3. The high-plasticity Hf-based dual-phase amorphous alloy as claimed in claim 1, wherein the atomic percentage content of Cu, ni and Ag is 25 ≤ b ≤ 35,5 ≤ c ≤ 15,0 < e ≤ 2.5, the diameter of the Cu-rich second-phase amorphous alloy particles is 5-9nm, and the volume percentage of the Cu-rich second-phase amorphous alloy particles in the amorphous alloy matrix is 15-55%.
4. The high plasticity Hf based dual phase amorphous alloy as claimed in claim 1, wherein the diameter of the high plasticity Hf based dual phase amorphous alloy is 1-10mm, the yield strength is 2325-2450MPa, and the plastic strain is 3.0-4.3%.
5. The method for preparing a high plasticity Hf-based dual phase amorphous alloy according to any one of claims 1 to 4, comprising:
(1) Preparing materials according to the atomic percentage composition formula of the high-plasticity Hf-based two-phase amorphous alloy, and uniformly smelting to prepare a master alloy;
(2) The molten master alloy is made into the high-plasticity Hf-based dual-phase amorphous alloy by a copper mold suction casting method.
6. The method for preparing high plasticity Hf-based dual phase amorphous alloy according to claim 5, wherein the cooling rate of the molten master alloy is 10 when the copper mold suction casting method is adopted 2 ~10 3 k/s。
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