CN111797502B - Method for designing high-entropy alloy components based on electronic alloy theory - Google Patents
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Abstract
Hair brushThe method comprises the steps of firstly calculating an average Md value and an average Bo value of a target high-entropy alloy, then obtaining a phase structure of the target high-entropy alloy according to the relation between the average Md value and the average Bo value, then obtaining the weight percentage of each component according to the phase structure and the expression of the target high-entropy alloy, and finally weighing each component according to the weight percentage to perform alloying smelting to obtain the target high-entropy alloy; the phase structure of the target high-entropy alloy is obtained according to the relation between the average Md value and the average Bo value
And
the phase structure of the target high-entropy alloy is judged according to the relationship (A). The method of the invention firstly provides the phase structure of the high-entropy alloy to be predicted based on the electronic alloy theory, the prediction is rapid and accurate, the cost and the time waste caused by the fact that the alloy can be known only by analyzing the alloy after actual smelting in the prior art are avoided, and the method has great application prospect.
Description
Technical Field
The invention belongs to the technical field of alloy component design, and relates to a method for designing high-entropy alloy components based on an electronic alloy theory.
Background
In 2004, professors of samber leaf and Cantor break through the design shackle of the traditional alloy which mainly adopts the enthalpy of mixing of thermodynamic parameters, a novel alloy design concept which mainly adopts the entropy of mixing is provided, the component system of the solid solution alloy is enriched, and the performance of the alloy is promoted in a jump manner. High-entropy alloys (HEA), which are alloys formed from five or more metals in equal or approximately equal amounts. The multi-principal element characteristics of the high-entropy alloy enable an alloy system to have a plurality of performances different from those of the traditional alloy (the strength, the fracture resistance, the tensile strength, the corrosion resistance and the oxidation resistance are better than those of the traditional alloy), so that the material science and the engineering are considerably emphasized.
High entropy alloys are known for their high "configuration entropy" at high temperatures, and typically have simple solid solution structures such as Body Centered Cubic (BCC), Face Centered Cubic (FCC), or Hexagonal Close Packed (HCP). To investigate the phase stability of the high-entropy alloy, the Valence Electron Concentration (VEC), the electronegativity (Δ χ), the atomic radius difference (Δ r), and the mixed entropy (Δ S)mix) Enthalpy of mixing (Δ H)mix) And the like are proposed to predict the formation rule of the phase. Guo et al summarized that VEC is an important factor affecting the phase structure of high-entropy alloys, and generally, when VEC is less than 6.87, a BCC phase structure tends to be formed; above 8.00, the FCC phase structure tends to form; between 6.87 and 8.00 FCC + BCC dual-phase structure is generally formed, but this is only an empirical rule, cannot distinguish whether solid solution is ordered or disordered, cannot predict the formation of sigma phase, and cannot accommodate all high entropy alloy systems. The research team also proposed, omega: (
Wherein T ismTheoretical melting point, unit: K) and a regular model of the phase structure of the high-entropy alloy is predicted by two factors of delta r, namely when omega is more than or equal to 1.1 and delta r is less than or equal to 6.6 percent, the high-entropy alloy is in a solid solution structure, otherwise, intermetallic compounds or other ordered structures are formed. Since the phase structure and phase composition of the alloy have a decisive influence on the properties thereof, it has been revealed that the phase stability of the high-entropy alloy is an important prerequisite and guarantee for the design and development of high-entropy alloys with excellent properties.
The molecular orbital theory introduces a parameter Md (an alloy element d orbital level) to research a high-entropy alloy taking nickel, cobalt and iron as a matrix, and the research finds that an FCC phase is formed when the Md is less than 1.09 and a TCP or GCP phase is formed when the Md is greater than 1.09, and the critical value is changed aiming at different high-entropy alloy systems, but the rule cannot select a fixed parameter and cannot guide the design of components of the high-entropy alloy. Although the prior art makes a plurality of related researches aiming at the mechanism and the like of the high-entropy alloy and can help the design and development of the high-entropy alloy to a certain extent, the prior art cannot effectively guide the component design of the high-entropy alloy.
Therefore, the development of a method for guiding the design of the high-entropy alloy components is of practical significance.
Disclosure of Invention
The invention aims to overcome the defect that the prior art cannot effectively guide the design of high-entropy alloy components, and provides a method for guiding the design of the high-entropy alloy components.
In order to achieve the purpose, the invention provides the following technical scheme:
a method for designing high-entropy alloy components based on an electronic alloy theory comprises the steps of firstly calculating an average Md value and an average Bo value of a target high-entropy alloy, then obtaining a phase structure of the target high-entropy alloy according to the relation between the average Md value and the average Bo value, then obtaining the weight percentage of each component according to the phase structure and an expression (equal atomic ratio or near equal atomic ratio) of the target high-entropy alloy, and finally weighing each component according to the weight percentage to perform alloying and smelting to obtain the target high-entropy alloy;
the phase structure of the target high-entropy alloy is obtained according to the relation between the average Md value and the average Bo value
The target high-entropy alloy generates an FCC single phase in an as-cast state;
the target high-entropy alloy generates an FCC + sigma phase in an as-cast state;
the target high entropy alloy generates an FCC single phase or an FCC + sigma phase in an as-cast state; wherein,
and
average Bo values of the target high-entropy alloysAnd average Md values.
The method for designing the high-entropy alloy components based on the electronic alloy theory firstly provides the corresponding relation between the average Md value, the average Bo value and the phase structure of the target high-entropy alloy, then can obtain (predict) the phase structure of the target high-entropy alloy according to the corresponding relation, the method can quickly, accurately and reliably obtain the phase structure of the target high-entropy alloy, avoids the great waste in cost and time that the alloy can be known only by analyzing the alloy after actual smelting in the prior art, originally provides a new idea for predicting the phase structure of the target high-entropy alloy based on the electronic alloy theory compared with the prior art, provides a new direction for the development of the technology, and has great application prospect.
The corresponding relation of the average Md value, the average Bo value and the phase structure of the target high-entropy alloy is obtained by researching Ni-series, Fe-series, Ti-series and Co-series high-entropy alloys, calculating the average Md value and the average Bo value, analyzing the phase structures of the high-entropy alloys of the systems, drawing an Md-Bo diagram shown in figure 1 on the basis, and analyzing the Md-Bo diagram, wherein as can be seen from figure 1, the larger the value of Bo/Md is, the more easily an FCC stable phase is formed in different alloy systems. Particularly, the higher average Bo value in the high-entropy alloy is beneficial to forming strong covalent bonds, so that the performance of the alloy is more excellent, and the lower average Md value is beneficial to forming an FCC stable phase, so that the formation of a sigma harmful phase is avoided.
As a preferred technical scheme:
according to the method for designing the components of the high-entropy alloy based on the electronic alloy theory, the average Md value and the average Bo value of the target high-entropy alloy are calculated by using a cluster method. The scope of the present invention is not limited thereto, and only this is taken as an example, and other suitable methods may be used to calculate the average Md value and the average Bo value, and the method of calculating the average Md value and the average Bo value should be consistent to avoid the error caused by the calculation method.
The cluster method is to perform molecular orbital calculation on a structural model consisting of an aggregation of a plurality of atoms in the high-entropy alloy, study the electronic state of the internal region of the crystal structure, and give the following definition formula to the calculation of the average Md and average Bo values in the complex alloy:
wherein, (Md)iAnd (Bo)iMd and Bo values, x, of the i components, respectivelyiIs the atomic percentage of the i component in the target high entropy alloy.
The method for designing the components of the high-entropy alloy based on the electronic alloy theory comprises the following specific steps of obtaining the weight percentage of each component according to the phase structure and the expression of the target high-entropy alloy: and obtaining the atomic percentage of each component according to the phase structure and the expression of the target high-entropy alloy, and converting the atomic percentage into the weight percentage.
The method for designing the components of the high-entropy alloy based on the electronic alloy theory specifically adopts a vacuum melting method to melt all components under the protection of inert gas. The alloying melting method of the present invention is not limited thereto, and only one possible technical solution is illustrated here, and those skilled in the art can select a suitable alloying melting method according to actual needs.
According to the method for designing the components of the high-entropy alloy based on the electronic alloy theory, the alloy ingot needs to be inverted and remelted for many times during alloying smelting so as to ensure the uniformity of the prepared high-entropy alloy ingot.
According to the method for designing the high-entropy alloy components based on the electronic alloy theory, the inversion remelting frequency is 3-5 times, and the inversion remelting frequency can be specifically set according to actual conditions.
Has the advantages that:
(1) according to the method for designing the components of the high-entropy alloy based on the electronic alloy theory, the phase structure of the high-entropy alloy is predicted by utilizing the interaction relation between the d electron orbital energy level Md and the covalent bond strength Bo value in the electronic alloy theory, so that the high-entropy alloy can be ensured to be a stable FCC phase, the generation of a sigma harmful phase is effectively avoided, and the excellent performance of the obtained high-entropy alloy is ensured;
(2) the method for designing the components of the high-entropy alloy based on the electronic alloy theory firstly provides the method for predicting the phase structure of the high-entropy alloy based on the electronic alloy theory, the prediction is quick and accurate, the great waste of cost and time for understanding the combined structure of the alloy only by analyzing the alloy after actual smelting in the prior art is avoided, and the method has great application prospect.
Drawings
FIG. 1 is Md-Bo diagram of Cr-series and V-series high-entropy alloys;
FIG. 2 shows CoFeNiMnV of example 10.25XRD diffraction spectrum diagram of the high-entropy alloy;
FIG. 3 shows CoFeNiMnV of example 20.5XRD diffraction spectrum diagram of the high-entropy alloy;
FIG. 4 shows CoFeNiMnV of example 30.75XRD diffraction spectrum diagram of the high-entropy alloy;
FIG. 5 is an XRD diffraction spectrum diagram of the CoFeNiMnV high-entropy alloy in example 4;
FIG. 6 shows CoCrFeNiMo in example 50.5XRD diffraction spectrum diagram of the high-entropy alloy;
FIG. 7 shows CoCrFeNiMo in example 60.85XRD diffraction spectrum chart of the high-entropy alloy.
Detailed Description
The following further describes the embodiments of the present invention with reference to the attached drawings.
Example 1
A method for designing high-entropy alloy components based on an electronic alloy theory comprises the following steps:
(1) the target high-entropy alloy is CoFeNiMnV0.25Obtaining the target high entropy alloy CoFeNiMnV by the cluster method0.25Average Md value of
And average Bo value
(2) Obtaining the phase structure of the target high-entropy alloy according to the relation between the average Md value and the average Bo value, which specifically comprises the following steps:
(3) obtaining the atomic percentage of each component (specifically: Co) according to the phase structure and expression of the target high-entropy alloy23.53％、Fe23.53％、Ni23.53％、Mn23.53％、V5.88％) Then converting the weight percentage of the mixture into the weight percentage;
(4) weighing the components according to the weight percentage, smelting the components under the protection of inert gas by adopting a vacuum smelting method to prepare 75g of target high-entropy alloy ingot, and carrying out 3-5 times of inverted remelting on the target high-entropy alloy ingot during alloying smelting.
After the target high-entropy alloy ingot is prepared, an X-ray diffractometer is used for detecting the target high-entropy alloy ingot, and an XRD diffraction spectrum diagram of the target high-entropy alloy ingot is shown in figure 2.
Example 2
A method for designing high-entropy alloy components based on an electronic alloy theory comprises the following steps:
(1) the target high-entropy alloy is CoFeNiMnV0.5The average Md value of the target high-entropy alloy CoFeNiMnV0.25 is calculated by a cluster method
And average Bo value
(2) Obtaining the phase structure of the target high-entropy alloy according to the relation between the average Md value and the average Bo value, which specifically comprises the following steps:
(3) obtaining the atomic percentage of each component (specifically: Co) according to the phase structure and expression of the target high-entropy alloy22.22％、Fe22.22％、Ni22.22％、Mn22.22％、V11.11％) Then converting the weight percentage of the mixture into the weight percentage;
(4) weighing the components according to the weight percentage, smelting the components under the protection of inert gas by adopting a vacuum smelting method to prepare 75g of target high-entropy alloy ingot, and carrying out 3-5 times of inverted remelting on the target high-entropy alloy ingot during alloying smelting.
After the target high-entropy alloy ingot is prepared, an X-ray diffractometer is used for detecting the target high-entropy alloy ingot, and an XRD diffraction spectrum diagram of the target high-entropy alloy ingot is shown in figure 3.
Example 3
A method for designing high-entropy alloy components based on an electronic alloy theory comprises the following steps:
(1) the target high-entropy alloy is CoFeNiMnV0.75, and the average Md value of the target high-entropy alloy CoFeNiMnV0.25 is calculated by a cluster method
And average Bo value
(2) Obtaining the phase structure of the target high-entropy alloy according to the relation between the average Md value and the average Bo value, which specifically comprises the following steps:
(3) obtaining the atomic percentage of each component (specifically: Co) according to the phase structure and expression of the target high-entropy alloy21.05％、Fe21.05％、Ni21.05％、Mn21.05％、V15.79％) Then converting the weight percentage of the mixture into the weight percentage;
(4) weighing the components according to the weight percentage, smelting the components under the protection of inert gas by adopting a vacuum smelting method to prepare 75g of target high-entropy alloy ingot, and carrying out 3-5 times of inverted remelting on the target high-entropy alloy ingot during alloying smelting.
After the target high-entropy alloy ingot is prepared, an X-ray diffractometer is used for detecting the target high-entropy alloy ingot, and an XRD diffraction spectrum diagram of the target high-entropy alloy ingot is shown in figure 4.
Example 4
A method for designing high-entropy alloy components based on an electronic alloy theory comprises the following steps:
(1) the target high-entropy alloy is CoFeNiMnV1Obtaining the target high entropy alloy CoFeNiMnV by the cluster method0.25Average Md value of
And average Bo value
(2) Obtaining the phase structure of the target high-entropy alloy according to the relation between the average Md value and the average Bo value, which specifically comprises the following steps:
(3) obtaining the atomic percentage of each component (specifically: Co) according to the phase structure and expression of the target high-entropy alloy20％、Fe20％、Ni20％、Mn20％、V20％) Then converting the weight percentage of the mixture into the weight percentage;
(4) weighing the components according to the weight percentage, smelting the components under the protection of inert gas by adopting a vacuum smelting method to prepare 75g of target high-entropy alloy ingot, and carrying out 3-5 times of inverted remelting on the target high-entropy alloy ingot during alloying smelting.
After the target high-entropy alloy ingot is prepared, an X-ray diffractometer is used for detecting the target high-entropy alloy ingot, and an XRD diffraction spectrum diagram of the target high-entropy alloy ingot is shown in figure 5.
Example 5
A method for designing high-entropy alloy components based on an electronic alloy theory comprises the following steps:
(1) the target high-entropy alloy is CoCrFeNiMo0.5Obtaining the target high entropy alloy CoCrFeNiMo by cluster method0.5Average Md value of
And average Bo value
(2) Obtaining the phase structure of the target high-entropy alloy according to the relation between the average Md value and the average Bo value, which specifically comprises the following steps:
(3) obtaining the atomic percentage of each component (specifically: Co) according to the phase structure and expression of the target high-entropy alloy22.22％、Cr22.22％、Fe22.22％、Ni22.22％、Mn22.22％、Mo11.11％) Then converting the weight percentage of the mixture into the weight percentage;
(4) weighing the components according to the weight percentage, smelting the components under the protection of inert gas by adopting a vacuum smelting method to prepare 75g of target high-entropy alloy ingot, and carrying out 3-5 times of inverted remelting on the target high-entropy alloy ingot during alloying smelting.
After the target high-entropy alloy ingot is prepared, an X-ray diffractometer is used for detecting the target high-entropy alloy ingot, and an XRD diffraction spectrum diagram of the target high-entropy alloy ingot is shown in figure 6.
Example 6
A method for designing high-entropy alloy components based on an electronic alloy theory comprises the following steps:
(1) the target high-entropy alloy is CoCrFeNiMo0.85Obtaining the target high entropy alloy CoCrFeNiMo by cluster method0.85Average Md value of
And average Bo value
(2) Obtaining the phase structure of the target high-entropy alloy according to the relation between the average Md value and the average Bo value, which specifically comprises the following steps:
(3) obtaining the atomic percentage of each component (specifically: Co) according to the phase structure and expression of the target high-entropy alloy20.62％、Cr20.62％、Fe20.62％、Ni20.62％、Mn20.62％、Mo17.53％) Then converting the weight percentage of the mixture into the weight percentage;
(4) weighing the components according to the weight percentage, smelting the components under the protection of inert gas by adopting a vacuum smelting method to prepare 75g of target high-entropy alloy ingot, and carrying out 3-5 times of inverted remelting on the target high-entropy alloy ingot during alloying smelting.
After the target high-entropy alloy ingot is prepared, an X-ray diffractometer is used for detecting the target high-entropy alloy ingot, and an XRD diffraction spectrum diagram of the target high-entropy alloy ingot is shown in figure 7.
According to the method for designing the components of the high-entropy alloy based on the electronic alloy theory, the phase structure of the high-entropy alloy is predicted by utilizing the interaction relation between the d electronic orbital energy level Md and the covalent bond strength Bo value in the electronic alloy theory, so that the high-entropy alloy can be ensured to be a stable FCC phase, the generation of a sigma harmful phase is effectively avoided, and the excellent performance of the obtained high-entropy alloy is ensured; the method for predicting the phase structure of the high-entropy alloy based on the electronic alloy theory is provided for the first time, the prediction is fast and accurate, the problem that the cost and the time of the combined structure of the alloy can be known only by analyzing the alloy after actual smelting in the prior art is solved, and the method has great application prospect.
Although specific embodiments of the present invention have been described above, it will be appreciated by those skilled in the art that these embodiments are merely illustrative and various changes or modifications may be made without departing from the principles and spirit of the invention.
Claims (6)
1. A method for designing high-entropy alloy components based on an electronic alloy theory is characterized by comprising the steps of firstly calculating an average Md value and an average Bo value of a target high-entropy alloy, then obtaining a phase structure of the target high-entropy alloy according to the relation between the average Md value and the average Bo value, then obtaining the weight percentage of each component according to the phase structure and the expression of the target high-entropy alloy, and finally weighing each component according to the weight percentage to perform alloying smelting to obtain the target high-entropy alloy;
the phase structure of the target high-entropy alloy is obtained according to the relation between the average Md value and the average Bo value
The target high-entropy alloy generates an FCC single phase in an as-cast state;
the target high-entropy alloy generates an FCC + sigma phase in an as-cast state;
the target high entropy alloy generates an FCC single phase or an FCC + sigma phase in an as-cast state; wherein,
and
the average Bo value and the average Md value of the target high-entropy alloy are respectively shown.
2. The method for designing the components of the high-entropy alloy based on the electronic alloy theory as claimed in claim 1, wherein the average Md value and the average Bo value of the target high-entropy alloy are calculated by a cluster method.
3. The method for designing the components of the high-entropy alloy based on the electronic alloy theory as claimed in claim 1, wherein the weight percentages of the components obtained according to the phase structure and the expression of the target high-entropy alloy are as follows: and obtaining the atomic percentage of each component according to the phase structure and the expression of the target high-entropy alloy, and converting the atomic percentage into the weight percentage.
4. The method for designing the components of the high-entropy alloy based on the electronic alloy theory as claimed in claim 1, wherein the alloying smelting is to smelt the components under the protection of inert gas by a vacuum smelting method.
5. The method for designing the components of the high-entropy alloy based on the electronic alloy theory as claimed in claim 4, wherein the alloy ingot is subjected to multiple times of inverted remelting during alloying smelting.
6. The method for designing the components of the high-entropy alloy based on the electronic alloy theory is characterized in that the number of times of inversion remelting is 3-5 times.
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| US4824637A (en) * | 1985-08-29 | 1989-04-25 | Natsuo Yukawa | Alloy phase stability index diagram |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4824637A (en) * | 1985-08-29 | 1989-04-25 | Natsuo Yukawa | Alloy phase stability index diagram |
| CN111118339A (en) * | 2020-01-06 | 2020-05-08 | 华南理工大学 | Si-containing high-strength low-modulus medical titanium alloy and additive manufacturing method and application thereof |
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| 热处理温度对AlxCoCrFeNi 系高熵合金组织和硬度的影响;曾鹏 等;《上海金属》;20200531;全文 * |
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