The present invention relates to a method for producing a nano-composite metal member and a method for joining phase-separated metal solids.
A conventional method for producing a nano-composite metal material using heat involves a step of mixing a plurality of materials to be used, and melting the materials by heating them to the melting point or higher of at least one of the materials (for example, see Patent Literature 1).
Conventionally, the present inventors have developed, namely, a molten metal refining method as a method for producing a porous metal member. This method involves immersing a metal material comprising a compound, an alloy, or a nonequilibrium alloy that simultaneously contains a second component and a third component having a positive heat of mixing and a negative heat of mixing, respectively, relative to a first component and having a melting point higher than the solidifying point of a metal bath comprising the first component in a molten metal bath that is controlled to have a temperature lower than the lowest liquidus temperature over the range of compositional variation, in which the third component is decreased so that the metal material is mainly composed of the second component, thereby selectively eluting the third component in the molten metal bath and thus obtaining a metal member having microgaps (for example, see Patent Literature 2). According to the molten metal refining method, a porous body made of the metal material having nanometer-sized microgaps can be readily produced.
Furthermore, it has been reported that when solid Ni and solid Mg are brought into contact with each other and heat treatment is performed to conduct an interfacial reaction between different solid metals, interdiffusion takes place between Ni and Mg, and then a compound comprising Mg2Ni is formed in the interface part(for example, see Non Patent Literature 1).
Non Patent Literature 1: M. Y. Tsai, M. H. Chou and C. R. Kao, “Interfacial reaction and the dominant diffusing species in Mg-Ni system”, Journal of Alloys and Compounds, 5 Mar. 2009, 471, p.90-92
The method for producing a nano-composite metal material according to Patent Literature 1 is problematic in that melting is performed by heating to the melting point or higher of at least one material, which results in an increased cost of heating to such a melting point or higher and an increased cost of equipment for handling molten metal. The method is also problematic in that handling of molten metal leads to increased labor and the like and complicated production processes.
The present invention has been achieved noting such problems and an objective of the present invention is to provide a method for producing a nano-composite metal member, by which a nano-composite metal member can be readily produced, and the production cost can be reduced, and a method for joining phase-separated metal solids using the same principle.
To achieve the above objective, the method for producing a nano-composite metal member according to the present invention comprises bringing a solid metal body comprising a first component into contact with a solid metal material comprising a compound, an alloy or a non-equilibrium alloy that simultaneously contains a second component and a third component having a positive heat of mixing and a negative heat of mixing, respectively, relative to the first component, and then performing heat treatment at a predetermined temperature for a predetermined length of time, so as to cause interdiffusion between the first component and the third component.
The method for producing a nano-composite metal member according to the present invention is based on a metallurgic technique focusing on the properties whereby when a solid metal body is brought into contact with a solid metal material comprising a compound, an alloy or a non-equilibrium alloy, and then heat treatment is performed, interdiffusion takes place so that a third component is diffused from the metal material into the metal body and a first component is diffused from the metal body into the metal material depending on the heat of mixing relative to the first component of the metal body. In the interdiffusion process, the second component has a positive heat of mixing relative to the first component, and thus is not diffused to the metal body side. Accordingly, a co-continuous-structured nano-composite metal member can be produced, in which portions comprising the first component and the third component and portions comprising the second component are intertwined with each other in nanometer order in the metal material.
The method for producing a nano-composite metal member according to the present invention does not require heating to the melting point or higher of a metal body or a metal material to be used herein because of the use of interdiffusion between solids, and does not generate any molten metal during the production processes. Accordingly, compared to cases in which melting is performed, the heating cost can be reduced and neither facility nor labor is required for handling molten metal. As described above, the method for producing a nano-composite metal member according to the present invention enables a nano-composite metal member to be easily produced and the production cost thereof to be reduced.
Interdiffusion between solids slowly proceeds, compared to elution to a metal bath as described in Patent Literature 2, so that a nano-composite metal member, in which portions comprising a first component and a third component and portions comprising a second component are intertwined with each other more finely, can be produced by the method for producing a nano-composite metal member according to the present invention.
The method for producing a nano-composite metal member according to the present invention varies the temperature and the length of time for heat treatment, so as to be able to change the size of each component of a composite member to be produced. Moreover, since the reaction proceeds from the surface of a metal material due to diffusion of the first component, and heat treatment is stopped in the middle thereof, only the surface of the metal material can be subjected to conjugation, and a nano-composite metal member can be produced only on the surface. Furthermore, a metal material is shaped into any form such as a thin film and a hollow shape, and thus a nano-composite metal member in an arbitrary shape wherein conjugation takes place on the surface or throughout the member can also be produced. A nano-composite metal member can also be produced by performing vapor deposition of a first component on the surface of a metal material, and then heat treatment.
According to the method for producing a nano-composite metal member according to the present invention, when the melting point of the first component on the basis of the absolute temperature is no less than a half of the melting point of the second component on the basis of the absolute temperature, the first component and the second component may be used in an opposite order. In this case, a co-continuous-structured nano-composite metal member can be produced, in which portions comprising the second component and the third component and portions comprising the first component are intertwined with each other in nanometer order in the metal material.
In the method for producing a nano-composite metal member according to the present invention, a first component, a second component, and a third component may be pure elements of a single type or elements of multiple types, respectively. Note that in the present invention, examples of metal components include metalloid elements such as carbon, silicon, boron, germanium, and antimony. Furthermore, the term “heat of mixing” refers to calories (negative heat of mixing) generated or calories (positive heat of mixing) absorbed when 2 or more types of substances are mixed at a constant temperature.
In the method for producing a nano-composite metal member according to the present invention, the heat treatment is preferably performed such that after the metal body is brought into contact with the metal material, the first component and the third component are interdiffused for binding with each other.
In the method for producing a nano-composite metal member according to the present invention, the temperature of the heat treatment is preferably maintained at a temperature that is no less than 50% of the melting point of the metal body on the basis of the absolute temperature. This case can ensure the easy production of a nano-composite metal member having a smaller size in each component.
In the method for producing a nano-composite metal member according to the present invention, for acceleration of interdiffusion, during heat treatment, the solid metal body and the solid metal material are preferably brought into close contact with each other via their polished faces. In particular, the contact face of the metal body, which is to be in contact with the metal material, and the contact face of the metal material, which is to be in contact with the metal body, are subjected in advance to mirror finishing, and then during the heat treatment, the polished contact face of the metal body and the polished contact face of the metal material are preferably brought into close contact with each other.
In the method for producing a nano-composite metal member according to the present invention, the first component preferably comprises Li, Mg, Ca, Cu, Zn, Ag, Pb, Bi, a rare earth metal element, or a mixture that is an alloy or a compound containing any one of them as a major component, the second component preferably comprises any one of Ti, Zr, Hf, Nb, Ta, Cr, V, Mo, W, Fe, Co, Ni, C, Si, Ge, and Sn, or a mixture that is an alloy or a compound containing a plurality of them, and the third component preferably comprises any one of Li, Mg, Ca, Mn, Fe, Co, Ni, Cu, Ti, Zr, Hf, Nb, Ta, Cr, Mo, and W, or a mixture containing a plurality of them. For example, the first component may comprise Mg, the third component may comprise Ni, and the metal material may comprise a Ni-containing alloy.
The method for joining phase-separated metal solids according to the present invention comprises: forming an alloy layer in which a third component having a negative heat of mixing relative to the first component is alloyed on the surface of at least one of a solid first metal body comprising a first component, and, a solid second metal body comprising a second component having a positive heat of mixing relative to the first component; bringing the first metal body into contact with the second metal body so that the alloy layer is sandwiched between the two; and performing heat treatment at a predetermined temperature for a predetermined length of time, so as to cause interdiffusion between the first component and/or the second component, and the third component.
The method for joining phase-separated metal solids according to the present invention can join phase-separated solid metals, which are generally joined with difficulty, through the use of interdiffusion between solids, based on the principle similar to that of the method for producing a nano-composite metal member according to the present invention. The method for joining phase-separated metal solids according to the present invention involves performing heat treatment upon the forming of an alloy layer on the surface of the first metal body, so as to diffuse the third component to the second metal body side, and diffuse the second component to the alloy side, so that finally a co-continuous-structured nanocomposite formation comprising portions that comprise the first component and the third component, and portions that comprise the second component and the third component in the interface of the first metal body and the second metal body is generated. Furthermore, when an alloy layer is formed on the surface of the second metal body, heat treatment is performed to diffuse the third component to the first metal body side and diffuse the first component to the alloy side, and thus finally a co-continuous-structured nanocomposite formation comprising portions that comprise the first component and the third component, and portions that comprise the second component and the third component is generated in the interface of the first metal body and the second metal body.
Moreover, when alloy layers are formed on surfaces of both the first metal body and the second metal body, heat treatment is performed to diffuse the first component and diffuse the second component within the alloy layers, and thus finally a co-continuous-structured nanocomposite formation comprising portions that comprise the first component and the third component and portions that comprise the second component and the third component is generated in the interface of the first metal body and the second metal body. In this manner, the method for joining phase-separated metal solids according to the present invention makes it possible to firmly join such phase separation-based first metal body and second metal body via the co-continuous-structured nanocomposite formation to be generated in the interface of the two.
The method for joining phase-separated metal solids according to the present invention is based on the principle similar to that of the method for producing a nano-composite metal member according to the present invention, and thus can be implemented by a method similar to the method for producing a nano-composite metal member according to the present invention. Furthermore, as a first component, a second component and a third component, the same components as the first component, the second component and the third component to be used in the method for producing a nano-composite metal member according to the present invention can be used.
According to the present invention, a method for producing a nano-composite metal member, by which a nano-composite metal member can be readily produced, and the production cost can be reduced, and a method for joining phase-separated metal solids using the same principle as that of the former method can be provided.
Hereafter, embodiments of the present invention are described below based on drawings with reference to examples.
According to the method for producing a nano-composite metal member of an embodiment of the present invention, firstly, as shown in
In a specific example shown in
Next, as shown in
In a specific example shown in
As shown in
A scanning electron micrograph when heat treatment was similarly performed at 460° C. for 12 hours is shown in
As shown in
Composition analysis was conducted by TEM to further specifically examine the composition of the nano-composite metal member in the reaction layer 13 in
The relationship between the time for heat treatment and the thickness of the reaction layer 13 was examined when heat treatment was performed at 440° C., 460° C., and 480° C., and then shown in
An Arrhenius plot obtained by plotting the rate constant “k” of each temperature of heat treatment found in
A 30-micron thick Ti50Cu50 (atom %) amorphous ribbon (metal material 12) was pressed at 20 MPa against a mirror-polished Mg plate (metal body 11), the resultant was heated to 480° C.; that is, the temperature corresponding to no less than 50% of the melting point of Mg, and then maintained. Therefore, a co-continuous-structured nanocomposite formation comprising portions containing Cu (third component) and Mg (first component) as major components and portions containing Ti (second component) as a major component was formed in the contact interface of the two.
Furthermore, a 1-micron thick Mn85C15 (atom %) alloy thin film (metal material 12) was deposited on a 30-micron thick Ag foil (metal body 11) by a magnetron sputtering technique. The thin film was subjected to heat treatment in an argon atmosphere at 800° C., Mn was diffused from the alloy thin film to the Ag foil side, so that a co-continuous-structured nanocomposite formation comprising portions containing Ag (first component) and Mn (third component) as major components and portions containing C (second component) as a major component was formed in the interface part.
Furthermore, a 1-micron thick Mn85C15 (atom %) alloy thin film (metal material 12) was deposited on the 30-micron thick Cu foil (metal body 11) by a magnetron sputtering technique. The thin film was subjected to heat treatment in an argon atmosphere at 800° C., Mn was diffused from the alloy thin film to the Cu foil side, and thus a co-continuous-structured nanocomposite formation comprising portions containing Cu (first component) and Mn (third component) as major components and portions containing C (second component) as a major component was formed in the interface part.
A (Fe0.8Cr 0.2)50Ni50 alloy (metal material 12) was pressed at 20 MPa to a 30-micron thick Mg86Ni9Ca5 (atom %) metal glass ribbon (metal body 11), and then the temperature was increased to 140° C. or more, which is the glass transition temperature of the metal glass ribbon. Therefore, the metal glass ribbon was transformed into a super cooled liquid, and then the viscous flow phenomenon caused the two into contact with no gaps regardless of their surface finishing state. Next, the resultant was heated to and maintained at 450° C. that is the temperature corresponding to no less than 50% of the melting point of the Mg86Ni9Ca5 alloy. In this manner, a co-continuous-structured nanocomposite formation comprising portions containing Mg (first component) and Ni (third component) as major components and portions containing Fe and Cr (second component) as major components was formed in the contact interface between the two.
As described above, the method for producing a nano-composite metal member of an embodiment of the present invention does not require heating to the melting point or higher of the metal body 11 or the metal material 12 to be used herein because of the use of interdiffusion between solids, and does not generate molten metal in the production processes. Therefore, compared to a case in which melting is performed, the heating cost can be reduced and neither facility nor labor for handling molten metal is required. Accordingly, the method for producing a nano-composite metal member of an embodiment of the present invention can readily produce a nano-composite metal member and can reduce the production cost.
In addition, according to the method for producing a nano-composite metal member of an embodiment of the present invention, a reaction proceeds from the surface of the metal material 12 due to diffusion of the first component, so that conjugation can be caused to take place only on the surface of the metal material 12 by stopping heat treatment in the middle thereof, and a nano-composite metal member can be produced only on the surface. Furthermore, the metal material 12 is formed into any shape such as thin film or hollow shape, and thus a metal member formed in an arbitrary shape, in which conjugation takes place on the surface or throughout the member, can also be produced.
Mg (metal body 11; first component) was deposited by vacuum deposition on the surface of a coil spring (metal material 12) made of HASTELLOY C-276 (Ni57Cr16Mo16W4Fe5 (wt %) alloy), and then heat treatment was performed for 12 hours in an Ar gas atmosphere at 460° C. at which all compounds in the coil spring and Mg can maintain the solid phase. Scanning electron (SEM) micrographs of the coil spring made of HASTELLOY C-276 before vacuum deposition, and the results of analyzing each element (Ni, Mo, Cr, Fe, W) by EDX (energy dispersive X-ray spectrometry) are shown in
As shown in
As described above, according to the method for producing a porous member of an embodiment of the present invention, the steam of the first component was sprayed over the surface of the metal material 12 for adhesion, followed by heat treatment, so that a nano-composite metal member can also be produced. In this case, even if the metal material 12 has a complicated shape, a nano-composite metal member can be relatively readily produced. Therefore, for example, a stent or the like in which conjugation takes place only on the surface can be produced.
The method for joining phase-separated metal solids of an embodiment of the present invention involves, firstly, as shown in
In addition, the alloy layer 23 can be formed by: pasting the third-component metal to the surface of the first metal body 21 and/or the second metal body 22 and then performing heat treatment; or immersing the surface portions of the first metal body 21 and/or the second metal body 22 in a metal bath comprising the third component.
Next, the first metal body 21 and the second metal body 22 are pressed against each other to bring them into contact with each other, so as to sandwich the alloy layer 23 between the metal bodies, and then heat treatment is performed at a predetermined temperature for a predetermined length of time. Heat treatment is performed by maintaining a temperature corresponding to no less than 50% of the melting point of the first metal body 21 based on the absolute temperature. Therefore, as shown in
In a specific example shown in
With the anchor effect of the thus generated co-continuous structured nanocomposite formation 24, the phase-separated first metal body 21 and second metal body 22 can be joined firmly. Therefore, according to the method for joining phase-separated metal solids of an embodiment of the present invention, phase-separated solid metals that are generally joined with difficulty can be joined using interdiffusion between solids based on the principle similar to that of the method for producing a nano-composite metal member of an embodiment of the present invention.
11 Metal body
12 Metal material
13 Reaction layer
21 First metal body
22 Second metal body
23 Alloy layer
24 Co-continuous structured nanocomposite formation
Number | Date | Country | Kind |
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2016-026732 | Feb 2016 | JP | national |
Filing Document | Filing Date | Country | Kind |
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PCT/JP2017/001155 | 1/16/2017 | WO | 00 |