CN108715979B - Amorphous composite material with oxygen modulation phase change and preparation method thereof - Google Patents

Amorphous composite material with oxygen modulation phase change and preparation method thereof Download PDF

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CN108715979B
CN108715979B CN201810530835.6A CN201810530835A CN108715979B CN 108715979 B CN108715979 B CN 108715979B CN 201810530835 A CN201810530835 A CN 201810530835A CN 108715979 B CN108715979 B CN 108715979B
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牟娟
赵子彦
王沿东
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Northeastern University China
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22C1/1047—Alloys containing non-metals starting from a melt by mixing and casting liquid metal matrix composites
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Abstract

The inventionBelongs to the technical field of metal materials, and discloses an oxygen-modulated phase-change amorphous composite material and a preparation method thereof. The main chemical composition of the composite material is TiaZrbNicCudBeeOfWherein a, b, c, d, e and f are atomic percentages of corresponding elements, a is more than or equal to 31 and less than or equal to 63, b is more than or equal to 26 and less than or equal to 40, c is more than or equal to 0.1 and less than or equal to 6, d is more than or equal to 1 and less than or equal to 10, e is more than or equal to 1 and less than or equal to 22, f is more than or equal to 0.1 and less than or equal to 6, and a + b + c + d + e; the material is an amorphous composite material with deformation-induced martensite phase transformation. The method mainly comprises the step of adding oxide of metal M into the alloy during smelting to realize the addition of O element, wherein M is one or more of Ti, Zr and Cu. The addition of the O element can effectively modulate the dynamic characteristics and distribution form of the deformation induced martensite phase transformation, so that the amorphous composite material has excellent comprehensive mechanical properties such as high strength, large plasticity, good work hardening capacity and the like. The invention has important guiding significance for industrial production and practical application of amorphous alloy and composite material thereof.

Description

Amorphous composite material with oxygen modulation phase change and preparation method thereof
Technical Field
The invention belongs to the technical field of metal materials, and particularly relates to an oxygen-modulated phase-change amorphous composite material and a preparation method thereof.
Background
The amorphous alloy has many excellent performances such as high strength, high hardness, high elastic limit, good corrosion resistance and the like due to the structural characteristics of long-range disorder and short-range order. But amorphous alloys rely on highly localized shear band deformation and their uniform structure causes the shear band to rapidly propagate once it has been initiated and brittle failure occurs throughout the entire sample. In order to improve the plasticity of the amorphous alloy, researchers use the concept that a second phase added in a crystalline material hinders dislocation motion for reference, and design an amorphous composite material by adding the crystalline second phase with an uneven structure into a uniform amorphous matrix. By optimizing the factors such as the size, distribution, orientation and the like of the crystalline phase, the interception effectiveness of the second relative shear band is improved, so that the amorphous composite material shows considerable tensile plasticity. However, the conventional amorphous composite material tends to show a processing softening phenomenon, which greatly limits the development and application of the amorphous composite material. In recent years, amorphous composite materials having strain-induced phase transition behavior have been the focus of research in the field of materials due to their good tensile plasticity and work hardening capability. Researchers attribute the improvement in plastic deformability and the appearance of work hardening capability to deformation-induced transformation behavior and the interaction of shear bands during deformation. The dynamic characteristics and distribution conditions of the deformation-induced phase transition behavior are important factors influencing the mechanical properties of the amorphous composite material.
The β dendritic phase with a body-centered cubic structure as an as-cast structure of the TiZrNiCuBe reinforced amorphous composite material is uniformly distributed on an amorphous phase matrix, the dendritic phase can generate martensite phase transformation from β phase to α' phase of an orthogonal structure in the deformation process, the phase transformation starts from an elastic deformation stage of the deformation and continues to a plastic deformation stage of the composite material, the generation of the phase transformation can cause the internal stress of the amorphous composite material to be transferred from the dendritic phase to the amorphous matrix phase, so that the nucleation of a shear band in the amorphous phase and the initiation of multiple shear bands are facilitated, namely, the generation and development of the phase transformation and the distribution state can obviously influence the deformation process of the amorphous composite material.
In the Ti alloy, O is taken as a strong and stable element of α phase, and the precipitation of β phase is inhibited by adding the O element, so that the TA system Ti alloy is obtained.
Disclosure of Invention
The invention provides an oxygen modulated phase-change amorphous composite material and a preparation method thereof, wherein O elements with different contents are added into a TiZr-based amorphous composite material, so that the β → α martensite phase-change process in the loading process is controllable, and the purpose of simultaneously improving the strength and the plastic deformation capacity of the amorphous composite material is achieved.
The technical scheme of the invention is as follows:
an oxygen-modulated phase-change amorphous composite material is prepared from TiaZrbNicCudBeeOfWherein a, b, c, d, e and f are atom percentages of corresponding elements, a is more than or equal to 31 and less than or equal to 63, b is more than or equal to 26 and less than or equal to 40, c is more than or equal to 0.1 and less than or equal to 6, d is more than or equal to 1 and less than or equal to 10, e is more than or equal to 1 and less than or equal to 22, f is more than or equal to 0.1 and less than or equal to 6, and a + b + c + d + e.
Furthermore, the cast structure of the composite material is β dendritic crystal phase with body center cubic, which is uniformly distributed on an amorphous phase matrix, and the volume fraction of β dendritic crystal phase is 5-95%, which changes with the change of chemical composition.
Further, the martensite phase generated by the deformation induction of the amorphous composite material is uniformly distributed fine laths. The composite material is obtained by adding a proper amount of oxygen element, so that the stress distribution in the composite material is more effectively adjusted, and the aim of improving the mechanical property is fulfilled.
The preparation method of the amorphous composite material with the oxygen modulation phase change comprises the following steps:
(1) smelting: under vacuum or argon protection, smelting an alloy and a corresponding metal oxide according to the atomic percentage of each element in the chemical composition of the composite material, wherein the O element is realized by adding an oxide of a metal M into the alloy during smelting; the M is one or more of Ti, Zr and Cu;
(2) casting: and (3) rapidly solidifying in vacuum or under the protection of argon, wherein the cooling speed is higher than 1K/s during solidification and molding, and the formation of an amorphous phase is ensured.
The invention has the following beneficial effects:
1. according to the TiZr-based amorphous composite material containing the O element, the addition of the O element inhibits the β → α 'phase change in the loading process, and changes the appearance and distribution of the precipitated α' phase, so that the control of the phase change process and the mechanical property is realized.
2. According to the TiZr-based amorphous composite material containing the O element, the O element with a proper proportion is added, so that β phase is inhibited to be converted into a coarse α 'phase, and a fine and uniformly distributed α' phase is precipitated, so that the multiple shear bands are effectively induced to germinate, the single shear band is inhibited to rapidly expand, and the composite material with excellent mechanical properties, such as high strength (about 2200MPa) and large compression plasticity (about 13%), is obtained.
3. According to the TiZr-based amorphous composite material containing the O element, the adjustment and control of the work hardening rate in a certain range are realized by adding the O elements with different contents.
Drawings
SEM photographs of (a) an amorphous composite sample containing 6 at.% O and (b) an amorphous composite sample containing 0O in fig. 1.
Fig. 2 is a compressive stress-strain curve of an amorphous composite sample containing O in an amount of 0, 1 at.%, 6 at.%.
Fig. 3 is an SEM photograph after deformation of (a) an amorphous composite sample containing 0O and (b) an amorphous composite sample containing 1 at.% O.
In fig. 4, TEM photographs and diffraction spots of samples after compression fracture of (a) an amorphous composite material containing 0 and (b) an amorphous composite material containing 6 at.% of O.
Detailed Description
The present invention will be described in detail with reference to the drawings and examples.
Table 1 example material formulations
Figure BDA0001677129350000041
Example 1:
preparing a TiZr-based amorphous composite material with the O content of 6 at.%:
the first step is as follows: weighing pure metal raw materials and CuO (the purity is more than 99.9%) according to the atomic percentage of the number 1 in the table 1, wherein O is added in a CuO form, Cu is added in a CuO and pure metal Cu form, and the rest elements are added in a pure metal form, and the weighing precision is 0.001 g;
the second step is that: smelting in a high-vacuum non-consumable electric arc furnace to obtain 80g of master alloy ingot;
the third step: 25g of master alloy is taken and cast by a copper mold to obtain a rod-shaped sample with the diameter of 8 mm.
Example 2:
this example differs from example 1 in that the amount of O contained therein is different, and the composite material obtained by the preparation has an O content of 1 at.%; ZrO of O2Form addition of Zr as ZrO2And pure metallic Zr form addition.
The first step is as follows: pure metal raw materials and ZrO were weighed in the atomic percentage of number 2 in Table 12(purity greater than 99.9%) with a weighing precision of 0.001 g;
the second step is that: same as example 1;
the third step: same as in example 1.
Example 3:
this example differs from example 1 in that the amount of O contained therein is different, and the composite material obtained by the preparation has an O content of 5 at.%; o is TiO2Added in the form of TiO, Ti2And pure metallic Ti form.
The first step is as follows: weighing pure metal raw material and TiO according to the atomic percentage of number 3 in Table 12(purity greater than 99.9%) with a weighing precision of 0.001 g;
the second step is that: same as example 1;
the third step: same as in example 1.
Example 4:
this example is different from example 1 in that it contains O in an amount of 0.1 atomic%.
The first step is as follows: weighing pure metal raw materials and CuO (the purity is more than 99.9%) according to the atomic percentage of the number 4 in the table 1, wherein the weighing precision is 0.001 g;
the second step is that: same as example 1;
the third step: same as in example 1.
Comparative example: selecting a TiZr amorphous composite material without O
And (3) structural and performance characterization:
the microstructures of the samples of example 1 and the control group were two-phase structures in which crystalline dendritic phases were distributed in an amorphous matrix phase, as shown in fig. 1(a) (b), respectively, the addition of O element reduced the size of the dendritic phase and accompanied by aging, as compared to the control group, and the crystalline phases were all single body-centered cubic β phases by XRD analysis.
Cutting the bar-shaped test specimens to 2 x 4mm3The sample was compressed. And (3) carrying out compression performance test on the cuboid sample by using a universal mechanical testing machine. FIG. 2 is a stress-strain curve under compressive load for the samples of example 1, example 2, and the control. It can be seen that the addition of O improves the strength and plasticity; the different contents of O element affect the plasticity, yield strength, breaking strength and work hardening rate of the amorphous composite material.
The sample has β → α' martensite phase transformation in the compression process, because of the function of inhibiting the martensite phase transformation by adding O element, the dynamic characteristic and the distribution form of the deformation induced martensite phase transformation are effectively modulated, namely, the proper amount of oxygen element is added, so that the deformation induced martensite phase is uniformly distributed fine laths, as shown in fig. 4(a) (b), the microstructure is very beneficial to the formation of multiple shear bands of the amorphous composite material in the deformation process, as shown in fig. 3(a) (b), thereby greatly improving the plasticity of the material.

Claims (3)

1. The preparation method of the amorphous composite material with the oxygen modulation phase change is characterized by comprising the following steps of:
(1) smelting: under the protection of vacuum or argon, alloy and corresponding metal oxide are smelted according to the atomic percentage of each element in the chemical composition of the composite material, and the main chemical composition of the composite material is TiaZrbNicCudBeeOfWherein a, b,c. d, e and f are atomic percent of corresponding elements, a is more than or equal to 31 and less than or equal to 63, b is more than or equal to 26 and less than or equal to 40, c is more than or equal to 0.1 and less than or equal to 6, d is more than or equal to 1 and less than or equal to 10, e is more than or equal to 1 and less than or equal to 22, f is more than or equal to 5 and less than or equal to 6, and a + b + c + d +; wherein, the O element is realized by adding oxide of metal M into the alloy during smelting; the M is one or more of Ti, Zr and Cu;
(2) casting: and (3) rapidly solidifying in vacuum or under the protection of argon, wherein the cooling speed is higher than 1K/s during solidification and molding, and the formation of an amorphous phase is ensured.
2. The method of claim 1, wherein the as-cast structure of the composite material is β dendrite phase with body-centered cubic structure uniformly distributed on the amorphous phase matrix, and the volume fraction of β dendrite phase is 5% -95%.
3. The method of claim 1 or 2, wherein the martensite phase generated by the amorphous composite material is uniformly distributed fine laths.
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JPS63273592A (en) * 1987-04-30 1988-11-10 Daido Steel Co Ltd Ti brazing material
JP2001316784A (en) * 2000-05-09 2001-11-16 Toshiba Corp Bulky amorphous alloy, method for producing bulky amorphous alloy and high strength member

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US5567251A (en) * 1994-08-01 1996-10-22 Amorphous Alloys Corp. Amorphous metal/reinforcement composite material
CN101886232B (en) * 2009-05-14 2011-12-14 比亚迪股份有限公司 Amorphous alloy-based composite material and preparation method thereof
CN102296253B (en) * 2010-06-23 2016-01-06 中国科学院金属研究所 Interior raw toughness strengthens Ti base amorphous composite and preparation method thereof mutually
CN103741080B (en) * 2014-01-15 2016-02-17 西北工业大学 (Ti-Zr-Nb-Cu-Be)-O system amorphous composite and preparation method thereof
CN105886965A (en) * 2016-05-06 2016-08-24 西北工业大学 Element N and O co-doped ti-based amorphous composite and preparation method thereof

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JPS63273592A (en) * 1987-04-30 1988-11-10 Daido Steel Co Ltd Ti brazing material
JP2001316784A (en) * 2000-05-09 2001-11-16 Toshiba Corp Bulky amorphous alloy, method for producing bulky amorphous alloy and high strength member

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