The present invention relates is a porous metal.
Conventionally, multiporous porous metals having three-dimensional structures have been developed in order to be used for catalysts, sensors, condensers, and the like, which require large specific surface areas. In particular, in order to make specific surface areas as large as possible, the development of porous metals with small pore and ligament sizes has been advanced by the inventors and others, and porous metals of Fe, FeCo, Ti, V, Nb, Ag, Au, and the like have been obtained (see, for example, Non-Patent Literature 1 to 4).
These porous metals have been produced by a so-called molten metal dealloying method developed by the present inventors (see, for example, Patent Literature 1). This method is a method to obtain a metal member having fine openings by placing a metallic material in a metal bath, the metallic material containing both a second constituent and a third constituent having positive and negative heats of mixing relative to a first constituent, respectively, and including a compound, an alloy, or a non-equilibrium alloy having a melting point that is higher than the solidifying point of the metal bath made of the first constituent, wherein said metal bath is controlled to a temperature lower than a minimum value of a liquidus temperature within a range of compositional variations in which the amount of the third constituent in the metallic material decreases down to a point where the metallic material becomes substantially the second constituent so that the third constituent is selectively dissolved into the metal bath.
Meanwhile, in recent years, a high entropy alloy (High Entropy Alloy; HEA) that is a multicomponent alloy of five or more components, is composed of 5 or more kinds of principal metal elements, and contains respective elements in equal or nearly equal atomic proportions has been proposed (see, for example, Non-Patent Literature 5 or 6). Though the high entropy alloy is a multicomponent alloy the high entropy alloy exists as a solid solution of a single phase or mixed phases thereof, and the configurational entropy is maximized, and, therefore, has high stability, In addition, the high entropy alloy has low Gibbs free energy at high temperatures and also has high thermodynamic stability. By utilizing such features, the application of the high entropy alloy as a material having thermal resistance, high corrosion resistance, high mechanical strength, or high ductility has been progressed (see, for example, Patent Literature 2 or 3).
Further, conventionally, it has been confirmed that when a twin crystal exists on the surface of a crystal, surface diffusion is trapped by the twin interfaces, which causes a delay in surface diffusion (see, for example, Non-Patent Literature 7).
The porous metal disclosed in Non-Patent Literature 1 to 4 has a ligament size of several micrometers or less, a large specific surface area, and excellent characteristics. However, in order to obtain a porous metal having further excellent characteristics, the development of a porous metal having a smaller ligament size and a large specific surface area has been required.
The present invention has been made in view of such a problem, and an object of the present invention is to provide a porous metal having a much smaller ligament size.
The present inventors have confirmed that, when the porous metal disclosed in Non-Patent Literature 1 to 4 is produced, surface diffusion proceeds during the progression of dealloying in order to decrease a surface energy, which makes the ligament size gradually larger. Then, in order to achieve the above-described object, the present inventors have focused on a high entropy alloy as a material of which surface diffusion hardly proceeds during production and which is capable of suppressing the growth of ligaments, and thus completed the present invention.
That is, the porous metal according to the present invention comprises a crystal of an alloy, the alloy containing n or more kinds of elements, n being an integer of 3 or more, the alloy having a composition of each element of from {(100/n)−(75/n)} at % to ((100/n) +(75/n)} at %, and the porous metal having a ligament size of 220 nm or less.
With regard to the porous metal according to the present invention, the alloy is composed of a so-called high. entropy alloy or a medium entropy alloys and the configurational entropy of each element is maximized, and, therefore, the diffusion rate of each element becomes slow, surface diffusion during the production is suppressed, and the growth of ligaments can be suppressed. Accordingly, the porous metal according to the present invention has a smaller ligament size compared with conventional low entropy alloys, not only when the porous metal according to the present invention is a high entropy alloy composed of 5 or more kinds of elements, but also when the porous metal according to the present invention is a medium entropy alloy composed of a smaller number of constituent elements than the high entropy alloy.
The thermodynamic mixing entropy ΔSmix can be provided by the formula (1), and the high entropy alloy can be defined by using the mixing entropy ΔSmix according to the formula (2).
Here, R is the gas constant (8.314 J/K/mol), xi is a molar fraction of the component i, and n is the number of constituent elements.
By using the thermodynamic mixing entropy ΔSmix, the medium entropy alloy (Medium Entropy Alloy; MEA) and the low entropy alloy (Low Entropy Alloy; LEA) can be defined according to the formula (3) and the formula (4), respectively.
1.0R≤ΔSmix≤1.5R (MEA) (3)
ΔSmix≤1.0R (LEA) (4)
With regard to an alloy with an equiatomic composition composed of 4 elements, ΔSmix is 1.398, R and with regard to an alloy with an equiatomic composition composed of 5 elements, ΔSmix is 1.61 R.
It is preferable that the porous metal according to the present invention has a ligament size of 5 nm or more and/or 100 nm or less. The ligament size refers to a diameter of a cross section perpendicular to the extension direction of the ligament.
It is preferable that the porous metal according to the present invention has a low-energy interface on the surface of the alloy. The low-energy interface is, for example, a coincidence site lattice grain boundary (Coincidence Site Lattice (CSL) boundary) having a low grain boundary energy represented by a twin interface. In this case, surface diffusion becomes slow due to the low-energy interface, and, therefore, the growth of ligaments is further suppressed, which can make the ligament size much smaller.
With regard to the porous metal according to the present invention, it is preferable that the alloy contains one or more refractory metal elements. In particular, it is preferable that the alloy contains (100/n) at % or more of the refractory metal element. In these cases, with regard to surface diffusion, an element having a higher melting point makes the activation energy larger, and, therefore, when the alloy contains more refractory metal elements with a high melting point, the ligament size can become smaller more efficiently.
With regard to the porous metal according to the present invention, it is preferable that the alloy contains a solid solution of respective elements. In this case, the alloy may be a solid solution of a single phase, multiple phases of a solid solution, or a composite phase of a solid solution as a main component and an intermetallic compound. In these cases also, the ligament size can be made much smaller. In addition, the alloy may have a body centered cubic lattice structure, a face centered cubic lattice structure, or a hexagonal close packed structure.
With regard to the porous metal according to the present invention, for example, when the alloy contains 5 kinds of elements, it is preferable that a composition of each element is from 5 at % to 35 at %. In this case, respective elements of the alloy may be composed of, for example, Ti, V, Nb, Mo, and Ta. In addition to the above, for example, the porous metal according to the present invention may be composed of an alloy such as NbTaTiZr, MoTiVZr, HfNbTaTiZr, MoNbTaW, MoNbTaVW, MoNbTaW, MoNbTaVW, CoCrMoNbTi, CrMoNbTaVW, CrMoNbReTaVW, CrMoNbTaTiVWZr, and CrMoNbTaTiVZr.
According to the present invention, it is possible to provide a porous metal having a much smaller ligament size.
An embodiment of the present invention is described hereinafter with reference to an Example and the like.
A porous metal of an embodiment of the present invention comprises a crystal of an alloy, the alloy containing n or more kinds of elements, n being an integer of 3 or more, and having a composition of each element of from {(100/n)−(75/n)} at % to {(100/n)+(75/n)} at %. In addition, a porous metal of an embodiment of the present invention has a ligament size of 220 nm or less.
When the porous metal of an embodiment of the present invention contains, for example, 3 kinds of elements, the composition of each element is from 8.3 at % to 58.3 at %. When the porous metal of an embodiment of the present invention contains 4 kinds of elements, the composition of each element is from 6.2 at % to 43.8 at %. When the porous metal of an embodiment of the present invention contains 5 kinds of elements, the composition of each element is from 5 at % to 35 at %. When the porous metal of an embodiment of the present invention contains 6 kinds of elements, the composition of each element is from 4,1 at % to 29.2 at %. When the porous metal of an embodiment of the present invention contains 7 kinds of elements, the composition of each element is 3.5 at % to 25 at %. Further, it is preferable that the porous metal of an embodiment of the present invention is an alloy composed of a solid solution of respective elements,
The porous metal of an embodiment of the present invention is composed of a so-called high entropy alloy or a medium entropy alloy, and the configurational entropy of each element is maximized, and, therefore, the diffusion rate of each element becomes slow, surface diffusion during the production is suppressed, and the growth of ligaments can be suppressed. Accordingly, the porous metal of an embodiment of the present invention has a smaller ligament size as compared with conventional low entropy alloys.
Hereinafter, as an Example, porous metals of an embodiment of the present invention were produced, and observation and measurement of ligament sizes and the like were performed.
Porous metals of an embodiment of the present invention were produced by using the molten metal dealloying method described in. Patent Literature 1. First, as a precursor alloy, a precursor alloy containing 20 at % in total of the 5 elements of Ti, V, Nb, Mo, and Ta along with 80 at % of Ni was prepared. The precursor alloy contained Ti, V, Nb, Mo, and Ta in approximately equal atomic proportions. The precursor alloy was melted by arc melting such that each component was mixed, and from the alloy after solidification, a sheet-like precursor with a thickness of 0.5 mm was cut out. In addition, a metal bath composed of Mg was prepared. In the Example, the precursor alloy had a fraction of Ni of 80 at %, but in order to produce porous metals, a fraction of Ni may generally be from 30 to 80 at %. When the fraction of Ni is 80 at %, the smallest ligaments can be obtained. When a fraction of Ni is 50 at %, a porous structure having a large specific surface area per area can be obtained. When a fraction of Ni is 30 at %, a porous material having the highest mechanical strength can be obtained.
Here, Mg is a first constituent in the molten metal dealloying method, 5 elements of Ti, V, Nb, Mo, and Ta are second constituents, and Ni is a third constituent. The five elements of Ti, V, Nb, Mo, and Ta have a positive heat of mixing relative to Mg and at the same time, they are immiscible with Mg. Ni has a negative heat of mixing relative to Mg. The melting point of Mg used in the metal bath was 650° C., so in order to make dealloying at 600° C. possible when the metal bath at 600° C. was used, an Mg alloy molten metal having a lower melting point that was lowered by adding 10 at % of Ca was used.
Next, a porous metal was produced according to a method shown in
Porous metals were produced by setting a temperature of the metal bath to a range of 600° C. to 900° C. and setting an immersion time into the metal bath to a range of 10 minutes to 120 minutes. The measurement result by an X-ray diffraction (XRD) method with regard to the precursor used for the production of the porous metals is shown in
As shown in
The observation result by a scanning electron microscope (SEM) of each porous metal produced from the FCC by being immersed in a metal bath at 600, 700, 800, or 900° C. for 10 minutes is shown in
The measurement results by an X-ray diffraction (XRD) method with regard to a porous metal produced by being immersed in a metal bath at 800° C. for 120 minutes and a porous metal produced by being immersed in a metal bath at 900° C. for 120 minutes are shown in
With regard to a BCC porous metal obtained by being immersed in a metal bath at 900° C. for 10 minutes, the blended amount of each element is shown in Table 2. As shown in Table 2, the porous metal contains the 5 elements of Ti, V, Nb, Mo, and Ta in approximately equal atomic proportions, and it is thought that they form a high entropy alloy (HEA). Accordingly, it was confirmed that even when a precursor having a complex combination of elements was utilized, only Ni was selectively dissolved. In addition, it is thought that the content of refractory metal elements affects the sizes of ligaments and pores.
The observation results by a transmission electron microscope (TEM) of a porous metal produced by being immersed in a metal bath at 600° C. for 10 minutes and a porous metal produced by being immersed in a metal bath at 800° C. for 10 minutes are shown in
As shown in
The observation results by a scanning electron microscope (SEM) of BCC porous metals obtained by being immersed in the metal bath at 800° C., 850° C., and 900° C. for 10 minutes, 30 minutes, and 60 minutes are shown in
As shown in
The mean ligament size of each of the porous metals (high entropy alloys; HEAs) obtained by being immersed in the metal bath at 600° C., 800° C., 850° C., and 900° C. for 10 minutes, as well as each of the porous metals obtained by being immersed in the metal bath at 700° C., 800° C., 850° C., and 900° C. for 60 minutes was plotted against the normalized value (Tmelting point/Tdealloying temperature) obtained by dividing the melting point of the porous metal by the temperature of the metal bath at the time of dealloying. The resulting plot graph is shown in.
As shown in
A crystal orientation map and a grain boundary map of a porous metal produced by being immersed in the metal bath at 900″C for 120 minutes are shown in
With regard to porous metals produced by being immersed in the metal bath at 600″C to 900° C. for 10 minutes to 120 minutes, the evaluation tests of the mechanical characteristics of ligaments were performed by a nanoindentation method in accordance with ISO 14577. From the obtained test results, the yield strength of each ligament was obtained, which is shown in
Number | Date | Country | Kind |
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2019-019274 | Feb 2019 | JP | national |