CN112267055B - ZrTi-based eutectic high-entropy alloy and preparation method thereof - Google Patents
ZrTi-based eutectic high-entropy alloy and preparation method thereof Download PDFInfo
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- CN112267055B CN112267055B CN202011062194.XA CN202011062194A CN112267055B CN 112267055 B CN112267055 B CN 112267055B CN 202011062194 A CN202011062194 A CN 202011062194A CN 112267055 B CN112267055 B CN 112267055B
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Abstract
The invention discloses a ZrTi-based eutectic high-entropy alloy and a preparation method thereof, wherein the chemical composition expression of the alloy is Zr3Ti3FeaCobNicWherein a, b and c are atomic percentages of Fe, Co and Ni elements, respectively, and satisfy the following conditions that a is 0 and b is 1; b is 0, a is 1; c is 0, a is 1, or a is 2/3. The alloy components with the components designed in advance are prepared by utilizing a vacuum arc melting technology. The alloy microstructure consists of a ZrTi-beta phase with BCC structure and Zr with FCC structure2Ti2(Fea,Cob,Nic) Two phases form a rod-shaped complete eutectic structure. By designing the eutectic components, the casting performance of the ZrTi alloy is improved, and the machining process is reduced, so that the eutectic high-entropy alloy has wide application prospects in the fields of aerospace, machinery and nuclear industry.
Description
Technical Field
The invention relates to the technical field of metal materials, in particular to a ZrTi-based eutectic high-entropy alloy and a preparation method thereof.
Background
The ZrTi alloy has excellent performance far higher than that of other aerospace metal structure materials such as aviation aluminum materials, aviation steel materials and the like, and has great potential as a structure material in the aerospace field. But the processing performance is poor, so that the mechanical processing procedures of the ZrTi alloy are reduced as much as possible in the preparation process of the part, and the net forming rate of the part is improved, which has great value in promoting the application of the ZrTi alloy. The alloy part prepared by the casting method has the advantages that a cast blank is nearly formed, the purpose of no machining or little machining is achieved, the cost is reduced, and the manufacturing time is reduced to a certain extent. However, the solid solution high-entropy alloy has poor fluidity, a certain temperature range of solidification temperature, poor casting performance, easy generation of serious micro/macro segregation and the like, and is not favorable for casting and molding of the high-entropy alloy. Eutectic alloys, however, have some special properties: (1) the mixing of the components forming the eutectic alloy enables the melting point of the alloy to be lower than that of each component, so that the alloy is more convenient to operate in the melting and casting processes, and meanwhile, the corresponding industrial production cost is saved; (2) compared with pure component metals, the eutectic alloy has better fluidity, reduces dendritic crystals generated by blocking liquid flow in the solidification process of the alloy, and improves the casting performance of the alloy; (3) because the eutectic reaction occurs at a specific certain temperature and is constant temperature transformation (without a solidification temperature range), the alloy casting defects such as common shrinkage cavity and segregation can be effectively reduced; (4) the structures obtained by eutectic solidification are various in forms, typical regular layer sheets and rods can become in-situ composite materials with excellent performance. Therefore, the eutectic component design is an effective way for solving the problem of poor processability of the refractory eutectic high-entropy alloy, improving the casting performance of the alloy and further obtaining a high-quality casting.
At present, a great number of eutectic high-entropy alloys are reported which are obtained by adding elements such as Zr, Ti, Hf, V, Nb, Ta and Mo and take CoCrFeNi base or CoCrNi as a matrix. Most of two phases in the eutectic structure consist of a tough fcc phase and a brittle and hard Laves/bcc phase, thereby achieving comprehensive strong plasticity mechanical properties. In 2014, Lu-Ying et al (Lu Y, et al. Rep,2014,4:6200.) of the university of the great theory of engineering proposed the concept of eutectic high-entropy alloy, and prepared AlCoCrFeNi with excellent comprehensive performance2.1The fully eutectic high-entropy alloy is composed of two phases of soft ordered fcc (L12) and hard ordered bcc (B2) and has lamellar morphology.
However, the research on the ZrTi-based eutectic high-entropy alloy is less at present. Zhu et al (Zhu M, et al. materials Letters,2020,272.) prepared a series of CrNbTiZrAlx refractory eutectic high-entropy alloys, which are eutectic structures consisting of bcc and Laves. However, the compressive mechanical properties of the alloy are poor, and the alloy has no yield stage and plastic deformation during compression and is obviously brittle fracture. When x is 0.75, the steel sheet has a eutectic complete structure, a breaking strength of 417MPa, and an elongation at break of 4.48%. Obviously, the strength and plasticity of the eutectic high-entropy alloy with the components are low enough not to meet engineering application, so that the development of a ZrTi-based eutectic high-entropy alloy system is necessary. The eutectic point exists between Zr and Ti and Fe, Co and Ni on the side close to ZrTi, and the Zr, the Ti, the Fe, the Co and the Ni are in infinite solid solution with each other, so that the potential of forming eutectic high-entropy alloy is realized.
Disclosure of Invention
In order to solve the problem of poor fluidity of the ZrTi high-entropy alloy, the invention aims to provide the ZrTi-based eutectic high-entropy alloy with excellent casting performance and the preparation method thereof, which are used in the fields of aerospace, machinery and nuclear industry.
The technical means adopted by the invention are as follows:
a ZrTi-based eutectic high-entropy alloy with the chemical composition expression of Zr3Ti3FeaCobNicWherein a, b and c are atomic mole ratios of Fe, Co and Ni elements, respectively, and satisfy a + b + c ═ 2, where a ═ 0 and b ═ c ═ 1; b is 0, a is 1; c is 0, a is 1, or a is 2/3.
Further, the alloy microstructure consists of a ZrTi-beta phase with BCC structure and Zr with FCC structure2Ti2(Fea,Cob,Nic) Two phases form a rod-shaped complete eutectic structure.
Further, when c is 0, a is 1, and the molecular formula of the alloy is Zr in each atomic molar ratio3Ti3FeCo, said alloy being made of BCC phase and Zr2Ti2The (Fe, Co) phase is compounded to form a rod-shaped eutectic structure.
Further, when b is 0, a is 1, and the molecular formula of the alloy is Zr in a molar ratio of each atom3Ti3FeNi, the alloy is composed of BCC phase and Zr2Ti2The (Fe, Ni) phase is compounded to form a rod-shaped eutectic structure.
Further, when a is 0, b is 1, and the molecular formula of the alloy is Zr in the molar ratio of each atom3Ti3CoNi, said alloy is composed of BCC phase and Zr2Ti2The (Co, Ni) phase is compounded to form a rod-shaped eutectic structure.
Further, when a ═ b ═ c ═ 2/3, the molecular formula of the alloy is Zr in the molar ratio of each atom3Ti3Fe2/ 3Co2/3Ni2/3Said alloy is composed of BCC phase and Zr2Ti2The (Fe, Co, Ni) phase is compounded to form a rod-shaped eutectic structure.
The invention also provides a preparation method of the ZrTi-based eutectic high-entropy alloy, which comprises the following steps:
(1) calculating the mass of metal simple substances Zr, Ti, Fe, Co and Ni according to the required molar ratio, and weighing, wherein the purity of the raw materials of the metal simple substances Zr, Ti, Fe, Co and Ni is more than or equal to 99.95%;
(2) placing the metal simple substances Zr, Ti, Fe, Co and Ni weighed in the step (1) into a copper crucible in an electric arc melting furnace according to the sequence that the melting point in the furnace is sequentially increased from bottom to top;
(3) vacuumizing the arc melting furnace to 5 x 10-3Filling high-purity inert gas as protective gas after Pa; then carrying out power-on smelting of pure titanium ingots for removing residual oxygen in the furnace;
(4) electrifying to smelt, turning over the cast ingot, repeatedly smelting until the cast ingot is uniform, and cooling to obtain the eutectic high-entropy alloy.
Further, in the step (4), the smelting times are 4-6 times, and each smelting time is 2-5 minutes.
Further, in the step (4), cooling is carried out in a water-cooling copper mold.
Compared with the prior art, the invention has the following beneficial effects:
1. by designing the alloy components, several eutectic-structure ZrTi-based high-entropy alloys are obtained, the defect of difficult processing of the ZrTi alloy is overcome, and the casting forming rate is improved.
2. The invention utilizes the vacuum arc melting technology to prepare the medium-entropy alloy with the pre-designed components to obtain the medium-high temperature resistant eutectic high-entropy alloy Zr3Ti3FeaCobNicThe product isThe alloy material has the structural and performance characteristics that: the microstructure is composed of BCC phase and Zr2Ti2The (Fe, Co, Ni) phase is compounded to form a rod-shaped complete eutectic structure.
3. The alloy has engineering application value and can be widely popularized in the fields of metal materials and preparation thereof.
Drawings
FIG. 1 shows Zr in example 13Ti3XRD pattern of FeCo cast ingot;
FIG. 2 shows Zr in example 13Ti3SEM photograph of FeCo ingot;
FIG. 3 shows Zr in example 23Ti3XRD pattern of FeNi cast ingot;
FIG. 4 shows Zr in example 23Ti3SEM photo of FeNi cast ingot;
FIG. 5 shows Zr in example 33Ti3XRD pattern of CoNi cast ingot;
FIG. 6 shows Zr in example 33Ti3SEM photograph of CoNi ingot;
FIG. 7 shows Zr in example 43Ti3Fe2/3Co2/3Ni2/3XRD pattern of the cast ingot;
FIG. 8 shows Zr in example 43Ti3Fe2/3Co2/3Ni2/3SEM photograph of ingot;
Detailed Description
The present invention will be described in further detail with reference to the following examples:
example one
A ZrTi-based eutectic high-entropy alloy with a chemical composition expression of Zr3Ti3FeCo, its preparation method includes the following steps:
step one, respectively weighing 30.86gZr, 16.19gTi, 6.29gFe and 6.64gCo according to the molar ratio of 3:3:1:1, wherein the purity of each metal simple substance Zr, Ti, Fe and Co raw material is more than or equal to 99.95%;
step two, placing the metal simple substances of the single metals Zr, Ti, Fe and Co prepared in the step one in an electric arc melting device in sequence according to the sequence of melting points from low to high, and placing the metal simple substances in a vacuum melting furnaceDegree of 5X 10-3Introducing argon as a protective gas when the pressure is Pa, and electrifying to smelt pure titanium ingots before electrifying to smelt the elemental metal for removing residual oxygen;
step three, electrifying to turn over and repeatedly smelt for 5 times after removing residual oxygen, wherein the smelting time is 3min each time till the smelting is uniform, and cooling in a water-cooling copper mold to obtain Zr3Ti3FeCo eutectic high entropy alloy.
Example two
An eutectic high-entropy alloy with chemical composition expressed as Zr3Ti3The preparation method of FeNi is the same as that of example 1, except that the individual metal elements weighed in the first step are 30.87gZr, 16.20gTi, 6.30gFe and 6.62 gNi.
EXAMPLE III
An eutectic high-entropy alloy with chemical composition expressed as Zr3Ti3CoNi, the preparation method is the same as that of example 1, except that the individual metal elements weighed in the first step are 30.69gZr, 16.11gTi, 6.61gCo and 6.58 gNi.
Example four
An eutectic high-entropy alloy with chemical composition expressed as Zr3Ti3Fe2/3Co2/3Ni2/3The preparation method is the same as that of the above example 1, except that the metal elements weighed in the first step are 30.81gZr, 16.17gTi, 4.19gFe, 4.42gCo and 4.40gNi respectively.
Results of the experiment
The samples of the embodiments 1 to 4 are analyzed by an X-ray diffractometer, the eutectic high-entropy alloy is embedded into a sample with the size of phi 5mm multiplied by 5mm by a metallographic sampler, the surface of the sample is ground by 400#, 800#, 1200# and 2000# metallographic abrasive paper in sequence, and then the sample is polished; the X-ray diffractometer is used for measuring the X-ray diffraction spectrum of the light rare earth high-entropy alloy, the scanning angle range is 20-100 ℃, the scanning speed is 4 DEG/min, and the results are shown in figure 1, figure 3, figure 5 and figure 7.
The results of observing the tissues of the samples prepared in examples 1 to 4 with a scanning electron microscope are shown in fig. 2, 4, 6 and 8.
FIGS. 1 and 2 are examples Zr of the present invention3Ti3FeCo alloy XRD and SEM show that the alloy is formed by BCC phase and Zr2Ti2The (Fe, Co) phase is compounded to form a rod-shaped eutectic structure.
FIGS. 3 and 4 are examples Zr of the present invention3Ti3XRD and SEM of FeNi alloy show that the alloy is formed by BCC phase and Zr2Ti2The (Fe, Ni) phase is compounded to form a rod-shaped eutectic structure.
FIGS. 5 and 6 are examples Zr of the present invention3Ti3XRD and SEM of CoNi alloy show that the alloy is formed by BCC phase and Zr2Ti2The (Co, Ni) phase is compounded to form a rod-shaped eutectic structure.
FIGS. 7 and 8 show Zr in example Zr of the present invention3Ti3Fe2/3Co2/3Ni2/3XRD and SEM of the alloy show that the alloy is composed of BCC phase and Zr2Ti2The (Fe, Co, Ni) phase is compounded to form a rod-shaped eutectic structure.
The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments, and any other embodiments obtained by changing, combining and simplifying the basic principle of the present invention belong to the protection scope of the present application.
Claims (9)
1. A ZrTi-based eutectic high-entropy alloy is characterized in that: the chemical composition expression of the alloy is Zr3Ti3FeaCobNicWherein a, b and c are atomic mole ratios of Fe, Co and Ni elements, respectively, and satisfy a + b + c ═ 2, where a ═ 0 and b ═ c ═ 1; b is 0, a is 1; c is 0, a is 1, or a is 2/3.
2. An alloy according to claim 1, wherein the alloy microstructure is comprised of BCC-structured ZrTi- β phase and FCC-structured Zr2Ti2(Fea,Cob,Nic) Two arePhase composition, forming a rod-shaped complete eutectic structure.
3. An alloy as claimed in claim 1, wherein when c is 0, a is 1, and said alloy has the formula Zr in each atomic molar ratio3Ti3FeCo, said alloy being made of BCC phase and Zr2Ti2The (Fe, Co) phase is compounded to form a rod-shaped eutectic structure.
4. An alloy according to claim 1, wherein when b is 0, a is 1, and the formula of said alloy is Zr in the molar ratio of the atoms3Ti3FeNi, the alloy is composed of BCC phase and Zr2Ti2The (Fe, Ni) phase is compounded to form a rod-shaped eutectic structure.
5. An alloy according to claim 1, wherein when a is 0, b is 1, and the formula of said alloy is Zr in the molar ratio of the atoms3Ti3CoNi, said alloy is composed of BCC phase and Zr2Ti2The (Co, Ni) phase is compounded to form a rod-shaped eutectic structure.
6. An alloy as claimed in claim 1, wherein when a, b, c, 2/3, the alloy has the formula Zr in the molar ratio of the atoms3Ti3Fe2/3Co2/3Ni2/3Said alloy is composed of BCC phase and Zr2Ti2The (Fe, Co, Ni) phase is compounded to form a rod-shaped eutectic structure.
7. A method for preparing an alloy according to any one of claims 1 to 6, comprising the steps of:
(1) calculating the mass of metal simple substances Zr, Ti, Fe, Co and Ni according to the required molar ratio, and weighing, wherein the purity of the raw materials of the metal simple substances Zr, Ti, Fe, Co and Ni is more than or equal to 99.95%;
(2) placing the metal simple substances Zr, Ti, Fe, Co and Ni weighed in the step (1) into a copper crucible in an electric arc melting furnace according to the sequence that the melting point in the furnace is sequentially increased from bottom to top;
(3) vacuumizing the arc melting furnace to 5 x 10-3Introducing high-purity inert gas after Pa, and then melting pure titanium ingots to remove residual oxygen;
(4) electrifying to smelt, turning over the cast ingot, repeatedly smelting until the cast ingot is uniform, and cooling to obtain the eutectic high-entropy alloy.
8. The preparation method according to claim 7, wherein in the step (4), the smelting times are 4-6 times, and each smelting time is 2-5 minutes.
9. The production method according to claim 7, wherein in the step (4), cooling is performed by a water-cooled copper mold.
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| CA1189982A (en) * | 1981-09-25 | 1985-07-02 | Moshe Eizenberg | Electrical multilayer contact for microelectronic structure |
| CN109706363A (en) * | 2019-01-11 | 2019-05-03 | 中南大学 | A kind of eutectic high-entropy alloy and its method of preparation |
| CN109750209A (en) * | 2019-03-27 | 2019-05-14 | 广东工业大学 | A kind of Ultra-fine Grained eutectic high-entropy alloy and preparation method thereof |
| CN110499445A (en) * | 2019-09-12 | 2019-11-26 | 北京理工大学 | A kind of eutectic high-entropy alloy and preparation method thereof |
| US20200109467A1 (en) * | 2018-10-04 | 2020-04-09 | City University Of Hong Kong | High entropy alloy structure and a method of preparing the same |
| US20200157663A1 (en) * | 2018-11-20 | 2020-05-21 | City University Of Hong Kong | High entropy alloy structure and a method of prepating the same |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CA1189982A (en) * | 1981-09-25 | 1985-07-02 | Moshe Eizenberg | Electrical multilayer contact for microelectronic structure |
| US20200109467A1 (en) * | 2018-10-04 | 2020-04-09 | City University Of Hong Kong | High entropy alloy structure and a method of preparing the same |
| US20200157663A1 (en) * | 2018-11-20 | 2020-05-21 | City University Of Hong Kong | High entropy alloy structure and a method of prepating the same |
| CN109706363A (en) * | 2019-01-11 | 2019-05-03 | 中南大学 | A kind of eutectic high-entropy alloy and its method of preparation |
| CN109750209A (en) * | 2019-03-27 | 2019-05-14 | 广东工业大学 | A kind of Ultra-fine Grained eutectic high-entropy alloy and preparation method thereof |
| CN110499445A (en) * | 2019-09-12 | 2019-11-26 | 北京理工大学 | A kind of eutectic high-entropy alloy and preparation method thereof |
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