CN114959394A - Design method and application of BCC structure solid solution alloy - Google Patents
Design method and application of BCC structure solid solution alloy Download PDFInfo
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- 238000013461 design Methods 0.000 title claims abstract description 32
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- 229910052751 metal Inorganic materials 0.000 claims abstract description 50
- 238000005275 alloying Methods 0.000 claims abstract description 28
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 25
- 238000000926 separation method Methods 0.000 claims abstract description 10
- 238000000746 purification Methods 0.000 claims abstract description 8
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
- C22C27/02—Alloys based on vanadium, niobium, or tantalum
- C22C27/025—Alloys based on vanadium, niobium, or tantalum alloys based on vanadium
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/501—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion
- C01B3/503—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion characterised by the membrane
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/501—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion
- C01B3/503—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion characterised by the membrane
- C01B3/505—Membranes containing palladium
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Abstract
The invention discloses a design method of a BCC structure solid solution alloy and application thereof in hydrogen separation and purification. The BCC structure solid solution alloy takes VB group metal elements as main components and takes other metal elements M as alloying elements; the method comprises electronegativity regulation and/or lattice matching, wherein the electronegativity regulation is to select alloying elements with hydrogen-repelling property, and the lattice matching is to dope different alloying elements which can cause opposite lattice distortion of main components. The solid solution alloy film designed and prepared by the method has the characteristics of small lattice distortion, stable structure, hydrogen embrittlement resistance, excellent hydrogen permeation comprehensive performance and the like.
Description
Technical Field
The invention relates to the technical field of metal functional material design and high-purity gas separation, and mainly relates to a design method of a BCC structure solid solution alloy for hydrogen separation/purification.
Background
The metal membrane separation method has a series of advantages of good oxidation resistance, excellent thermal stability, high hydrogen selectivity and the like, and is an efficient hydrogen separation/purification method. Palladium and palladium alloys (such as Pd-Ag alloy) have better comprehensive performance of hydrogen permeation and hydrogen embrittlement resistance, and are the only alloy membrane material for realizing industrial application at present. But the scale application of the palladium source is limited due to the rare property and high cost of the palladium source. Group VB metals (V, Nb, Ta) having Body Centered Cubic (BCC) structures have excellent hydrogen diffusion properties with hydrogen diffusion rates greater than other metal crystals by more than 1 order of magnitude (including FCC Pd), with the V metal having the highest hydrogen diffusion coefficient (> 3.0X 10) -7 mol·m -1 ·s -1 ·Pa -0.5 T is more than or equal to 320 ℃. Therefore, research on the use of group VB metals for hydrogen separation/purification is particularly interesting. However, the VB group metal of the BCC structure has problems of hydrogen embrittlement and structural failure due to high hydrogen dissolution. The problem of hydrogen embrittlement of the BCC structure alloy film is solved by two ways, namely, the working temperature and the pressure of the BCC structure alloy film are regulated and controlled within a reasonable range; secondly, the BCC structure is modulated by alloying to reduce the hydrogen dissolving amount of the BCC structure and further improve the hydrogen embrittlement resistance mechanical property of the BCC structure. The latter approach is receiving more attention from the practical point of view of the alloy film.
Researches of Japanese scholars A.Suzuki and the like show that the metal vanadium is alloyed with iron or cobalt, so that the solubility of hydrogen can be obviously reduced, the hydrogen brittleness resistance of the metal vanadium is improved, and the hydrogen permeability of the metal vanadium is improved. The research of V, N, Alimov and the like shows that the alloying of V and Pd can effectively reduce the high hydrogen solubility of V metal, and V 94.8 Pd 5.2 Has better comprehensive hydrogen permeability. Research by Kwang Hee Kim and the like of Korean scholars shows that the effect of ternary alloying regulation and control metal V is better than that of single element doping, and the lattice shrinkage and lattice expansion elements of Fe and Al co-alloying effectively enable the lattice constant of pure V to generate smaller lattice distortion and maintain higher hydrogen permeability. However, the effective alloy types and proportions are screened from a large amount of alloying elements, the test period is long, and the workload is huge.Therefore, scientific, reasonable and efficient screening of doping elements and new alloy design schemes must be explored.
Disclosure of Invention
The invention aims to solve the technical problem of providing a design method and application of a BCC structure solid solution alloy, which are used for solving the problems of hydrogen embrittlement and structure failure caused by over-high hydrogen dissolution of VB group metal with a BCC structure and are difficult to be used for hydrogen separation and purification.
In order to solve the technical problems, the invention adopts the following technical scheme:
on one hand, the invention provides a design method of BCC structure solid solution alloy, which takes VB group metal elements as main components and takes other metal elements M as alloying elements; the method comprises electronegativity regulation and/or lattice matching, wherein the electronegativity regulation is to select alloying elements with hydrogen-repelling property, and the lattice matching is to dope different alloying elements which can cause opposite lattice distortion of main components.
In most embodiments, the group VB metal element is V, Nb or Ta; the alloying element M is at least two of Pd, Fe, Mo, W, Al, Ti and Ni, and the doping amount of the alloying element M is not more than 18 at.%.
In most embodiments, the electronegativity regulation shown is specifically: the affinity energy of main component VB group metal elements and hydrogen atoms is taken as a reference, alloying elements with the characteristic of hydrogen repellency are selected for solid solution doping, and the hydrogen solubility of the solid solution alloy is regulated and controlled by adjusting the species and the proportion of the doping elements, so that the comprehensive performance of hydrogen permeation is improved.
In most embodiments, the lattice match is specifically: in the solid solution range, obtaining a lattice parameter change diagram of the VB group metal single-doped different alloying elements M, calculating corresponding lattice distortion rate, and screening proper alloying elements and proportion based on the thought that lattice expansion and lattice contraction are mutually offset so as to realize that the lattice parameter of the prepared solid solution alloy approaches to the pure main component metal and the corresponding lattice distortion is reduced to the minimum.
In at least one embodiment, when electronegativity control and lattice matching are used simultaneously, the design requirements of electronegativity control are met, then lattice matching is performed, electronegativity control is used for roughing alloying element types, and lattice matching is used for fine-tuning an alloy structure.
On the other hand, the invention also provides application of the BCC structure solid solution alloy obtained by using the design method in hydrogen separation and purification.
In at least one embodiment, the BCC structure solid solution alloy is V 93.75 Pd 3.125 Al 3.125 (ii) a Or is V 100- 2x Pd 2x 、V 100-2x Fe 2x Or V 100-2x Pd x Fe x Wherein x is 1,2 or 4; or is Nb 100-2x W 2x 、Nb 100-2x Ti 2x Or Nb 100- 2x W x Ti x Wherein x is 1,2,4 or 5.
In at least one embodiment, the BCC structure solid solution alloy is V 96 Pd 2 Fe 2 The hydrogen permeability coefficient of which is that of a commercial membrane Pd 77 Ag 23 4.7 times of; after further fine modification, BCC structure solid solution alloy V is obtained 87.82 Fe 4.18 Pd 8 Hydrogen permeability coefficient and Pd 77 Ag 23 But has better hydrogen embrittlement resistance.
The design method of the invention is based on the 'electronegativity regulation' and 'lattice matching' strategies, and carries out component matching and structure modulation on the BCC structure solid solution alloy from the atomic (electronic) scale, thereby realizing reasonable tailoring of material performance. The two structure modulation strategies can be used independently or in combination. The solid solution alloy film obtained by design and preparation has the characteristics of small lattice distortion, stable structure, hydrogen embrittlement resistance, excellent hydrogen permeation comprehensive performance and the like, wherein V is 96 Pd 2 Fe 2 The hydrogen permeability coefficient of the alloy at the temperature of 673K is 11.931 multiplied by 10 -8 mol H 2 m -1 ·s -1 ·Pa -1/2 Is a commercial membrane Pd 77 Ag 23 (2.52×10 -8 mol H 2 m -1 ·s -1 ·Pa -1/2 ) 4.7 times of the total weight of the product. The design method providesThe novel concept of efficient and convenient doped element screening and alloy design is provided. The design method is also suitable for design and preparation of similar material systems.
Drawings
FIG. 1 shows that in example 1, V 93.75 Pd 6.25 Alloy and V 93.75 Pd 3.125 Al 3.125 Hydrogen solubility of the alloy.
FIG. 2 shows that in example 2, V 93.75 Pd 6.25 Alloy and V 93.75 Pd 3.125 Al 3.125 The room temperature hydrogen diffusion coefficient of the alloy.
FIG. 3 shows the electron localization function of Pd and Fe doped V-based solid solution in example 2.
FIG. 4 shows the hydrogen solubility at 673K for the V-Pd system and V-Pd-Fe system alloys in example 2.
FIG. 5 shows the XRD spectra of the metal V and V-Fe, V-Pd-Fe system alloy in example 2.
FIG. 6 is an XRD refined spectrum of the V-Fe system alloy in example 2.
FIG. 7 shows an XRD refinement of the V-Pd system alloy in example 2.
FIG. 8 is a XRD refinement of the V-Pd-Fe system alloy in example 2.
FIG. 9 is a graph showing the change in lattice constant of a V-based solid solution in example 2.
FIG. 10 is a graph showing the change in lattice constant of a Nb-based solid solution in example 3.
Detailed Description
The invention relates to a method for designing BCC structure solid solution alloy applied to hydrogen separation/purification. Namely, the 'lattice matching' and 'electronegativity regulation' strategies are adopted to carry out component matching and structure modulation on the BCC structure solid solution alloy from an atom (electron) scale, and further the tailoring design of the alloy material performance is realized.
Among them, the "lattice matching" strategy: by adopting a combination mode of ' positive bias (lattice expansion) + ' negative bias (lattice contraction) ' and adjusting the types and proportions of doping elements, the lattice distortion of main component metals is inhibited to the maximum extent, so that the lattice parameters of the doped solid solution alloy are close to those of pure metals, and the stability of the lattice structure and the performance of the doped solid solution alloy is kept. "electronegativity regulation" strategy: in order to reduce the hydrogen solubility of the alloy, alloying elements with the hydrogen-repellent characteristic are selected, and the affinity of the solid solution alloy and hydrogen and the hydrogen solubility are regulated and controlled through the optimized combination of the types and the proportions, so that the hydrogen permeability of the alloy is improved. The two strategies of lattice matching and electronegativity regulation can be used independently or in combination. From the performance analysis of designed alloy, the 'lattice matching' strategy is obviously superior to the 'electronegativity regulation' strategy, and the reasonable component design approach is as follows: lattice matching is the main, and electronegativity regulation is the auxiliary.
Wherein, the main component of the solid solution alloy is one of VB group metals (V, Nb and Ta) with BCC structure, the alloying elements are other metals M (Pd, Fe, Mo, W, Al, Ti, Ni and the like), and the doping amount is less than or equal to 18 at.%.
The preparation method of the designed alloy can refer to the following steps: 1) preparing raw materials: taking block-shaped high-purity raw materials, and shearing the raw materials to form particles, so that the raw materials are convenient to weigh, uniformly mix and smelt; 2) cleaning raw materials: cleaning the granular raw materials in absolute ethyl alcohol and acetone solution in sequence to remove tiny impurities on the surfaces of the raw materials; 3) calculating the raw material components: calculating the weighing mass of each component of the components of the ingot to be smelted according to the alloy atomic ratio designed by the experiment; 4) weighing and proportioning: weighing raw materials by using an electronic balance with the precision of one ten thousandth, and uniformly mixing; 5) arc melting: putting the uniformly mixed raw materials into a copper crucible, firstly smelting a pure titanium ingot to absorb residual oxygen, and then smelting an alloy sample; 6) preparing an alloy mother ingot by an arc melting method, and cutting out a sheet-shaped sample with the thickness of 0.8mm by a wire-cut electric discharge machine; and (3) grinding by using 800#, 1000#, 1500# and 2000# abrasive paper, polishing by using 0.5 mu m alumina particles to form a mirror surface, sputtering 150-200 nm palladium films on two surfaces of the sample by adopting a magnetron sputtering method, and testing the hydrogen permeation performance of the flaky sample at different temperatures.
The present invention is illustrated and explained below by means of several examples, it being understood that the following examples are not intended to limit the present invention.
Example 1 design and preparation of V-Pd-Al ternary solid solution alloy (electronegativity control)
Step 1), selecting Pd and Al as doping elements, wherein the electronegativity of H, V, Pd and Al is shown in Table 1, the electronegativity of Pd is 2.20, doping Pd element in metal V causes the electronegativity of V-based solid solution to be increased, hydrogen solubility of V-based alloy is reduced, but too low hydrogen solubility is not beneficial to hydrogen transmission, and in order to balance the electronegativity, Al element with electronegativity of 1.61 is selected for doping to form V-Pd-Al ternary solid solution alloy.
TABLE 1 atomic radii and relative electronegativity of the elements
Step 2), designing with the mass ratio of pure metals V and Pd of 93.75:6.25 respectively, and smelting with high-purity V and Pd as raw materials to obtain V 93.75 Pd 6.25 And (5) alloy ingot casting.
Step 3), replacing Pd with Al, designing with the mass ratio of pure metal V, Pd to Al of 93.75:3.125:3.125, respectively, and smelting with high-purity V, Pd and Al as raw materials to obtain V 93.75 Pd 3.125 Al 3.125 And (5) alloy ingot casting.
Step 4), to demonstrate the effect of Pd and Al doping on the electronegativity of the metal V, V was doped 93.75 Pd 6.25 Alloy ingot and V 93.75 Pd 3.125 Al 3.125 The alloy ingot was cut into small pieces and then placed in a high precision gas adsorption analyzer to characterize the hydrogen solubility (H/M) of the alloy powder samples at 523K, 573K, and 623K test temperatures, with the results shown in fig. 1.
Step 5), the reduction of hydrogen solubility of the V-based alloy caused by the doping of Pd, comparing with V 93.75 Pd 6.25 Alloy and V 93.75 Pd 3.125 Al 3.125 The hydrogen solubility of the alloy is known at different temperatures, and V is known at the same temperature 93.75 Pd 3.125 Al 3.125 The hydrogen absorption equilibrium pressure of the alloy is reduced and the hydrogen solubility is increased because Pd has high electronegativity and H atoms are dissolved into V 93.75 Pd 6.25 It becomes difficult to obtain an alloy having a solid solution in which a part of Al having a low electronegativity is substituted for Pd and H atoms are easily dissolved in V 93.75 Pd 3.125 Al 3.125 In the alloy solid solution, the hydrogen solubility is increased, which shows that the electronegativity of the V-based solid solution can be regulated and controlled by reasonably selecting the doping elements.
Step 6), to demonstrate the effect of Pd and Al doping on the hydrogen diffusion coefficient of V-based solid solutions, V was doped 93.75 Pd 6.25 Alloy ingot and V 93.75 Pd 3.125 Al 3.125 The alloy ingot is ground into powder particles, and the V is tested by adopting a constant potential step method 93.75 Pd 6.25 Alloy sample and V 93.75 Pd 3.125 Al 3.125 The room temperature hydrogen diffusion coefficient of the alloy sample is shown in fig. 2. V is obtained by calculation 93.75 Pd 6.25 And V 93.75 Pd 3.125 Al 3.125 The room temperature hydrogen diffusion coefficients of the alloy samples were 1.12X 10, respectively -10 cm 2 ·s -1 And 5.03X 10 -10 cm 2 ·s -1 . From this analyzable, V 93.75 Pd 6.25 Has a room temperature hydrogen diffusion coefficient lower than V 93.75 Pd 3.125 Al 3.125 Room temperature hydrogen diffusion coefficient, which is related to the electronegativity of the doping element, V when Al replaces a portion of Pd 93.75 Pd 3.125 Al 3.125 The electronegativity of the solid solution alloy is less than V 93.75 Pd 6.25 Electronegativity of solid solution alloys such that V 93.75 Pd 3.125 Al 3.125 The room temperature hydrogen diffusion coefficient of the alloy is improved, which shows that the introduction of Al improves the hydrogen permeability of the V-Pd binary solid solution, and this shows that the room temperature hydrogen diffusion coefficient of the V-based solid solution can be improved through reasonable electronegativity regulation.
Example 2 design and preparation of V-Pd-Fe ternary solid solution alloy (electronegativity control + lattice matching)
Step 1), selecting Pd and Fe as doping elements in metal V, H,V, Pd electronegativity of Fe As shown in Table 1, Pd has electronegativity of 2.20, doping metal V with Pd element causes V-based solid solution electronegativity to increase, and in order to balance electronegativity, Fe element with electronegativity of 1.83 is selected and doped to form V-Pd-Fe ternary solid solution alloy. While considering the lattice matching strategy, V has an atomic radius of
Atomic radius of Pd of
Atomic radius of Fe is
The purpose of lattice matching can be achieved by reasonably regulating and controlling the doping proportion of double-doped Pd and Fe in the metal V, and electronegativity regulation and lattice matching strategies can be simultaneously satisfied.
Step 2), in order to verify the influence of electronegativity on the hydrogen solubility of the V-based solid solution, calculating an electron local function of the Pd and Fe doped V-based solid solution through a first principle, as shown in FIG. 3; according to the electron localization function diagram, the H atoms deviate from the original tetrahedral positions in the V-Pd solid solution, and the H atoms are still in the original tetrahedral positions in the V-Fe solid solution, which also proves that the elements with relatively high electronegativity have strong hydrogen-repelling ability, and can reduce the hydrogen solubility of the V-based solid solution.
Step 3), further proving the influence of Pd and Fe doping on the electronegativity of the metal V through experiments, and enabling the metal V to have higher electronegativity 100-2x Pd 2x System and V 100-2x Pd x Fe x The hydrogen solubility (H/M) of the alloy powder sample was characterized by placing the (x ═ 1,2,4) system alloy small piece sample in a high-precision gas adsorption analyzer, and the test temperature of 673K was as shown in fig. 4. From PCT curve analysis, V 100-2x Pd 2x The system alloy has higher hydrogen equilibrium pressure and lower hydrogen solubility, and the comparison shows that V is formed after the Fe element is doped 100-2x Pd x Fe x The hydrogen equilibrium pressure of the system alloy was reduced and the hydrogen solubility was increased, and it was found that the element having high electronegativity could reduce the hydrogen dissolution of the V-based solid solutionAnd the electronegativity can be regulated by reasonably introducing a third component element for doping.
Step 4), design V 100-2x Pd 2x ，V 100-2x Fe 2x And V 100-2x Pd x Fe x The (x ═ 1,2,4) alloy solid solution alloy is prepared by smelting high purity V, Pd and Fe as raw material to prepare V 100-2x Pd 2x ，V 100-2x Fe 2x And V 100-2x Pd x Fe x And (5) casting an alloy ingot.
Step 5), XRD test is carried out on the V-based solid solution alloy, XRD diffraction patterns of different solid solution alloys are obtained, and the result is shown in figure 5. According to XRD diffraction pattern analysis, only a diffraction peak corresponding to a single-phase bcc-V structure is observed, and no second phase appears, which indicates that the prepared alloy is a V-based solid solution alloy. Meanwhile, the XRD diffraction pattern of the V-based solid solution alloy is compared with the XRD diffraction peak of the metal V, so that the peak position of the diffraction peak of the V-Fe system solid solution alloy is shifted to the right, the rightward offset is increased along with the increase of the doping amount, the peak position of the diffraction peak of the V-Pd system solid solution alloy is shifted to the left, the leftward offset is increased along with the increase of the doping amount, the peak position of the diffraction peak of the V-Pd-Fe system solid solution alloy is not obviously shifted, and the effect of lattice matching is achieved. When the diffraction peak position shifts to the right, lattice contraction occurs, and the diffraction peak position shifts to the left, lattice expansion occurs, as is known from the analysis using the bragg equation (2dsin θ ═ n λ). Thus, the doping of Fe causes the vanadium-based solid solution lattice to contract, and the doping of Pd causes the vanadium-based solid solution lattice to expand, which are related to the atomic radii of the two, and V has an atomic radius of
Greater than the atomic radius of Fe
And less than the atomic radius of Pd
Step 6) ofFurther obtaining lattice parameters of different solid solution alloys, and performing crystal structure refinement on each solid solution alloy to obtain corresponding lattice parameters, wherein the refinement results are shown in fig. 6-8, and the lattice parameter refinement results are shown in fig. 9. Through analysis, when Pd is doped, the metal V undergoes lattice expansion, the expansion distortion degree is continuously increased along with the increase of the doping amount, and the lattice constant is in a linear increasing trend; when Fe is doped, the metal V undergoes lattice shrinkage, the shrinkage distortion degree is in positive correlation with the doping amount, and the lattice constant is in a linear descending trend. In addition, it can be observed that under the same doping ratio, the contraction distortion rate generated by doping Fe is larger than the expansion distortion rate generated by doping Pd, and slight lattice contraction distortion also occurs when double doping Pd and Fe. This is primarily related to the atomic radii of the three metals, V being
Atomic radius of Pd of
Atomic radius of Fe is
The degree of lattice contraction (Fe doping) is greater than the degree of lattice expansion (Pd doping) for the same doping amount. In conclusion, Pd and Fe are codoped into the metal V to form the solid solution, and compared with the pure metal V, the V-Pd-Fe-based solid solution has the lattice constant basically equivalent to that of the pure V, so that the aim of lattice matching is fulfilled.
And 7) obtaining the expansion rate and the shrinkage rate of the V-Pd/V-Fe according to the refining result, and then selecting the doping amount of Pd and the doping amount of Fe according to the expansion rate and the shrinkage rate.
Step 8), calculating V according to the expansion rate and the shrinkage rate of V-Pd/V-Fe 87.82 Fe 4.18 Pd 8 Preparing ternary solid solution alloy, and then preparing V through processes of smelting, wire cutting, grinding and polishing and the like 87.82 Fe 4.18 Pd 8 The crystal lattice parameter is obtained by fine modification of the crystal structure of the ternary solid solution alloy sheet, and the result shows that V is 87.82 Fe 4.18 Pd 8 Ternary solid solutionLattice constant of alloy
Tends to be pure V
The V-based solid solution alloy with small lattice distortion and moderate electronegativity can be obtained by reasonable element selection and proportion design in the steps, and the feasibility of lattice matching and electronegativity regulation is demonstrated.
In order to prove the hydrogen permeation performance of the V-Pd-Fe ternary solid solution alloy, the V-based solid solution alloy sheet is polished into a mirror surface, then 150 nm-200 nm palladium membranes are subjected to magnetron sputtering on two surfaces, hydrogen permeation experiments are carried out on related membranes and the hydrogen permeation performance of the related membranes is compared with that of a pure palladium membrane, and the result shows that V is 96 Pd 2 Fe 2 At 673K, its hydrogen permeability coefficient is 11.931X 10 -8 mol H 2 m -1 ·s -1 ·Pa -1/2 Is Pd under the same conditions 77 Ag 23 (2.52×10 -8 mol H 2 m -1 ·s -1 ·Pa -1/2 ) About 4.7 times of that of V 87.82 Fe 4.18 Pd 8 The hydrogen permeability coefficient of the ternary solid solution alloy is equal to Pd 77 Ag 23 The performance of the catalyst is equivalent, and simultaneously, the catalyst has better hydrogen embrittlement resistance. Therefore, the alloy solid solution alloy material is designed through electronegativity regulation and lattice matching, and the hydrogen-infiltrated alloy material with excellent performance can be obtained.
Example 3 design and preparation of Nb-W-Ti ternary solid solution alloy (electronegativity control + lattice matching)
Step 1), based on the concept of V-based solid solution, the design method is applied to the Nb-based solid solution alloy. The electronegativity of the metal Nb is 1.60, pure Nb has higher hydrogen solubility, and hydrogen embrittlement is easy to occur when the metal Nb is used for a hydrogen permeation material, so that other elements need to be introduced to regulate the hydrogen solubility.
Step 2), we chose the doping metal W (electronegativity 2.36, atomic radius) according to Table 1
) Reduce the hydrogen solubility of Nb-based solid solutions, and on the other hand, the atomic radius of W is smaller than that of Nb
The Nb is doped with W to cause lattice contraction, so a third component is required to be introduced to regulate the lattice contraction and reduce the degree of lattice distortion.
Step 3), in order to reduce the degree of lattice distortion, while taking into account electronegativity control, the element Ti (electronegativity 1.54, atomic radius) is selected here
) As a third component.
Step 4), design Nb 100-2x W 2x ，Nb 100-2x Ti 2x And Nb 100-2x W x Ti x (x is 1,2,4,5) system solid solution alloy, and Nb is prepared through smelting, wire cutting, grinding and polishing 100-2x W 2x ，Nb 100-2x Ti 2x And Nb 100-2x W x Ti x A solid solution alloy flake;
step 5), XRD test is carried out on the Nb-based solid solution sheet to obtain XRD diffraction patterns of different solid solution alloys, crystal structures of all the solid solution alloys are refined to obtain corresponding lattice parameters, the refined result is shown in figure 10, W/Ti single doping can cause lattice shrinkage of the Nb-based solid solution, the lattice distortion degree is related to the atomic radius of the Nb-based solid solution, when a third component Ti is introduced into the Nb-W binary solid solution, the lattice constant of the Nb-based solid solution is increased, the lattice distortion degree is reduced, and the purpose of lattice matching is achieved;
and 6) polishing the Nb-based solid solution sheet into a mirror surface, carrying out magnetron sputtering on 150-200 nm palladium films on two surfaces of each sample, and carrying out a hydrogen permeation experiment on related membranes, wherein the Nb-based solid solution alloy meets the hydrogen permeation requirement at 573-673K, and the hydrogen permeation coefficient is equivalent to that of pure Pd.
Claims (9)
1. A design method of BCC structure solid solution alloy is characterized in that: the BCC structure solid solution alloy takes VB group metal elements as main components and takes other metal elements M as alloying elements; the method comprises electronegativity regulation and/or lattice matching, wherein the electronegativity regulation is to select alloying elements with hydrogen-repelling property, and the lattice matching is to dope different alloying elements which can cause opposite lattice distortion of main components.
2. The design method according to claim 1, wherein: the VB group metal element is V, Nb or Ta; the alloying element M is at least two of Pd, Fe, Mo, W, Al, Ti and Ni, and the doping amount of the alloying element M is not more than 18 at.%.
3. The design method according to claim 1, wherein the electronegativity control is specifically: the affinity energy of main component VB group metal elements and hydrogen atoms is taken as a reference, alloying elements with the characteristic of hydrogen repellency are selected for solid solution doping, and the hydrogen solubility of the solid solution alloy is regulated and controlled by adjusting the species and the proportion of the doping elements, so that the comprehensive performance of hydrogen permeation is improved.
4. The design method according to claim 1, wherein the lattice matching is in particular: in the solid solution range, obtaining a lattice parameter change diagram of the VB group metal single-doped different alloying elements M, calculating corresponding lattice distortion rate, and screening proper alloying elements and proportion based on the thought that lattice expansion and lattice contraction are mutually offset so as to realize that the lattice parameter of the prepared solid solution alloy approaches to the pure main component metal and the corresponding lattice distortion is reduced to the minimum.
5. The design method according to claim 1, wherein: when electronegativity regulation and lattice matching are used, the design requirement of electronegativity regulation is met, then lattice matching is carried out, the electronegativity regulation is used for roughing alloying element types, and the lattice matching is used for fine adjustment of an alloy structure.
6. Use of a BCC structure solid solution alloy obtained by the design method of any of claims 1-5 in hydrogen separation and purification.
7. Use according to claim 6, characterized in that: the BCC structure solid solution alloy is V 93.75 Pd 3.125 Al 3.125 (ii) a Or is V 100-2x Pd 2x 、V 100-2x Fe 2x Or V 100-2x Pd x Fe x Wherein x is 1,2 or 4; or is Nb 100-2x W 2x 、Nb 100-2x Ti 2x Or Nb 100-2x W x Ti x Wherein x is 1,2,4 or 5.
8. Use according to claim 6, characterized in that: the BCC structure solid solution alloy is V 96 Pd 2 Fe 2 。
9. Use according to claim 6, characterized in that: the BCC structure solid solution alloy is V 87.82 Fe 4.18 Pd 8 。
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| CN115565631A (en) * | 2022-10-27 | 2023-01-03 | 哈尔滨工业大学 | Method for improving oxidation resistance of copper by alloying based on first-nature principle |
| CN115652160A (en) * | 2022-11-05 | 2023-01-31 | 北京东方红升新能源应用技术研究院有限公司 | Vanadium alloy membrane material for separating and purifying ammonia decomposition hydrogen and preparation method thereof |
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| CN115565631A (en) * | 2022-10-27 | 2023-01-03 | 哈尔滨工业大学 | Method for improving oxidation resistance of copper by alloying based on first-nature principle |
| CN115652160A (en) * | 2022-11-05 | 2023-01-31 | 北京东方红升新能源应用技术研究院有限公司 | Vanadium alloy membrane material for separating and purifying ammonia decomposition hydrogen and preparation method thereof |
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