METHOD FOR PRODUCING NANO-COMPOSITE METAL MEMBER AND METHOD FOR JOINING PHASE-SEPARATED METAL SOLIDS

Abstract

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 principle same as that of the former method are provided. A nano-composite metal member is obtained by 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.

Claims

1. A method for producing a nano-composite metal member, which 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 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.

2. The method for producing a nano-composite metal member according to claim 1, wherein the heat treatment is performed after the contact of the metal body with the metal material, so that the first component and the third component are interdiffused for binding with each other.

3. The method for producing a nano-composite metal member according to claim 1, wherein the heat treatment is performed by maintaining a temperature corresponding to no less than 50% of the melting point of the metal body on the basis of the absolute temperature.

4. The method for producing a nano-composite metal member according to claim 1, wherein the contact face of the metal body with the metal material and the contact face of the metal material with the metal body are mirror-finished in advance, and during the heat treatment, the contact face of the metal body and the contact face of the metal material are brought into close contact with each other.

5. The method for producing a nano-composite metal member according to claim 1, wherein the first component 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 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 thereof, and the third component 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 thereof.

6. The method for producing a nano-composite metal member according to claim 1, wherein the first component comprises Mg, the third component comprises Ni, and the metal material comprises a Ni-containing alloy.

7. A method for producing a nano-composite metal member, which comprises bringing a solid metal body comprising a second component into contact with a solid metal material comprising a compound, an alloy or a non-equilibrium alloy that simultaneously contains a first component and a third component, and performing heat treatment at a predetermined temperature for a predetermined length of time so as to cause interdiffusion between the second component and the third component, wherein the second component and the third component have a positive heat of mixing and a negative heat of mixing, respectively, relative to the first component, and the melting point of the first component on the basis of the absolute temperature corresponds to no less than a half of the melting point of the second component on the basis of the absolute temperature.

8. A method for joining phase-separated metal solids, comprising: forming an alloy layer in which a third component having a negative heat of mixing relative to a first component is alloyed on the surface of at least one of a solid first metal body comprising the 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 to sandwich the alloy layer between the metal bodies; and performing heat treatment at a predetermined temperature for a predetermined length of time; and thus causing interdiffusion between the first component and/or the second component, and the third component.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0024] FIG. 1 is a schematic perspective view showing the method for producing a nano-composite metal member of an embodiment of the present invention.

[0025] FIG. 2 shows a scanning electron micrograph of a metal body and a metal material after heat treatment, when the heat treatment of the method for producing a nano-composite metal member of an embodiment of the present invention was performed at 460 C. for 12 hours, and the results of analyzing each element (Ni, Fe, Cr, and Mg) in a rectangular region by EDX.

[0026] FIG. 3 shows (a) a scanning electron micrograph of a metal body and a metal material after heat treatment, (b) an enlarged micrograph of (a) at position A, (c) an enlarged micrograph of (a) at position B, and (d) an enlarged micrograph of (a) at position C, when the heat treatment of the method for producing a nano-composite metal member of an embodiment of the present invention was performed at 460 C. for 12 hours.

[0027] FIG. 4 shows a transmission electron micrograph when the heat treatment of the method for producing a nano-composite metal member of an embodiment of the present invention was performed at 460 C. for 12 hours.

[0028] FIG. 5 shows: (a) a scanning electron micrograph of a metal body and a metal material when the heat treatment of the method for producing a nano-composite metal member of an embodiment of the present invention was performed at 480 C. for each time length of heat treatment (6 hours, 12 hours, 24 hours, 48 hours, and 72 hours); and (b) a graph showing the relationship between the time for heat treatment and the thickness of the reaction layer, when the heat treatment of the same was performed at 440 C., 460 C., and 480 C.

[0029] FIG. 6 is an Arrhenius plot of the rate constant k of the temperature of each heat treatment found in FIG. 5(b).

[0030] FIG. 7 shows (a) a scanning electron micrograph of a coil spring made of HASTELLOY C-276, the metal material used in the method for producing a porous member of an embodiment of the present invention, (b) an enlarged micrograph of the surface of the coil spring, and (c) an enlarged micrograph of a portion of (b).

[0031] FIG. 8 shows (a) a scanning electron micrograph of the surface of the coil spring, the metal material shown in FIG. 7 and (b) the results of analyzing each element (Ni, Mo, Cr, Fe and W) in the (a) region by EDX.

[0032] FIG. 9 shows: (a) a scanning electron micrograph of a cross section of the coil spring, when Mg was deposited by vacuum deposition on the surface of the coil spring, the metal material shown in FIG. 7, and then heat treatment was performed at 460 C. for 12 hours according to the method for producing a porous member of an embodiment of the present invention; and (b) an enlarged micrograph of the reaction layer (composite layer) of (a).

[0033] FIG. 10 is a schematic perspective view showing the method for joining phase-separated metal solids in an embodiment of the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0034] Hereafter, embodiments of the present invention are described below based on drawings with reference to examples.

[0035] According to the method for producing a nano-composite metal member of an embodiment of the present invention, firstly, as shown in FIG. 1(a), a solid metal body 11 comprising a first component and a solid metal material 12 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 are used and brought into contact with each other.

[0036] In a specific example shown in FIG. 1, pure magnesium (pure Mg) is used as the metal body 11, and (Fe.sub.0.8Cr.sub.0.2).sub.50Ni.sub.50 alloy is used as the metal material 12. At this time, the first component is Mg, the second component is Fe.sub.0.8Cr.sub.0.2, and the third component is Ni. Moreover, the contact face of the metal body 11 and the contact face of the metal material 12 are each polished flat in advance for mirror finishing, and thus are brought into close contact via the contact faces. For mirror finishing, an ion peeling process or the like can be employed.

[0037] Next, as shown in FIG. 1(b), a load is applied (loading) to the interface between the metal body 11 and the metal material 12 so as to prevent separation thereof during treatment, and then annealing is performed as heat treatment. Heat treatment is performed by maintaining a temperature corresponding to no less than 50% of the melting point of the metal body 11 on the basis of the absolute temperature. Accordingly, depending on the heat of mixing relative to the first component that is the metal body 11, interdiffusion takes place so that the third component is diffused from the metal material 12 into the metal body 11, and the first component is diffused from the metal body 11 into the metal material 12. The second component of the metal material 12 has positive heat of mixing relative to the first component, so that the second component is not diffused to the metal body 11 side. Therefore, as shown in FIG. 1(c), in the metal material 12, a reaction region (reaction layer) 13, in which portions comprising the first component and the third component and portions comprising the second component are mixed with each other in nanometer order, is obtained, so that a nano-composite metal member can be produced.

[0038] In a specific example shown in FIG. 1, the melting point of the metal body 11, Mg, is 650 C. (923 K). Hence, when heat treatment is performed at about 420 C. to 510 C., interdiffusion takes place so that Ni is diffused from the metal material 12 into the metal body 11, and the metal body 11, Mg, is diffused into the metal material 12. The Fe.sub.0.8Cr.sub.0.2 of the metal material 12, is not diffused to the metal body 11 side. In this manner, the reaction layer 13, in which Mg.sub.2Ni comprising Mg and Ni, and portions comprising Fe.sub.0.8Cr.sub.0.2 are mixed with each other in nanometer order in the metal material 12, is obtained, and thus a nano-composite metal member can be produced.

[0039] FIG. 2 shows a scanning electron micrograph (SEM) when heat treatment was actually performed at 460 C. for 12 hours, and the results of analyzing each element (Ni, Fe, Cr, and Mg) by EDX (energy dispersive X-ray spectrometry). Furthermore, the results of performing composition analysis at positions A to D in FIG. 2 using a transmission electron microscope (TEM) are shown in Table 1. In addition, at the right end of Table 1, the chemical compositions of substances inferred on the basis of the composition analysis are indicated. In FIG. 2, positions A and B are located within a region of the metal body 11 before heat treatment, and positions C and D are located within a region of the metal material 12 before heat treatment.

[0040] As shown in FIG. 2 and Table 1, it was confirmed that only Mg was present at position A in the metal body 11 distant from the contact face with the metal material 12, and the composition was not changed by heat treatment. It was also confirmed that Mg.sub.2Ni was present at position B in the metal body 11 near the contact face with the metal material 12, and Ni was diffused from the metal material 12 into the metal body 11 by heat treatment, so as to bind with Mg. Furthermore, it was confirmed that Fe.sub.0.8Cr.sub.0.2 and Mg.sub.2Ni were present at position C in the metal material 12 near the contact face with the metal body 11, and Mg was diffused from the metal body 11 into the metal material 12 by heat treatment, so as to bind with Ni. It was also confirmed that Mg was not detected, but (Fe.sub.0.8Cr.sub.0.2).sub.50Ni.sub.50 was present at position D in the metal material 12 distant from the contact face with the metal body 11, and the composition was not changed by heat treatment. As described above, it was confirmed that heat treatment caused interdiffusion whereby Ni was diffused from the metal material 12 into the metal body 11, and Mg of the metal body 11 was diffused into the metal material 12, and thus Mg and Ni were bound in the diffusion regions to form Mg.sub.2Ni.

[0041] A scanning electron micrograph when heat treatment was similarly performed at 460 C. for 12 hours is shown in FIG. 3(a). In addition, enlarged micrographs at each position (A to C) in FIG. 3(a) are shown in FIG. 3(b) to (d). Positions A to C are located in the reaction layer 13 (the region between a pair of arrows on the left edge of FIG. 3(a)) in which the first component, Mg, was diffused, among the regions of the metal material 12 before heat treatment. Position B is located in the neighborhood of the center of the reaction layer 13. Position A is located near the contact face with the metal body 11, the location of which is closer to the contact face than that of Position B. Position C is located in the neighborhood of the dealloying front where Mg is diffused; that is, Position C is located in the neighborhood of the boundary between the reaction layer 13 and regions in which the metal material 12 remains unchanged.

[0042] As shown in FIG. 3(b) to (d), it was confirmed within the reaction layer 13 that Mg.sub.2Ni (bright portions in the Figure) and Fe.sub.0.8Cr.sub.0.2 (dark portions in the Figure) were mixed with each other in nanometer order of several hundred nanometers (nm) or less, thereby forming a nano-composite. In particular, it was confirmed in the neighborhood of the dealloying front where the first component, Mg, was diffused, that as shown in FIG. 3(d), Mg.sub.2Ni and Fe.sub.0.8Cr.sub.0.2 in filamentous forms were mixed with each other in nanometer order of 100 nm or less.

[0043] Composition analysis was conducted by TEM to further specifically examine the composition of the nano-composite metal member in the reaction layer 13 in FIG. 3(a). A transmission electron micrograph of the position subjected to composition analysis is shown in FIG. 4. As a result of the composition analysis, the dark portions in FIG. 4 were confirmed to be Fe.sub.0.819Cr.sub.0.172Ni.sub.0.009, and have a composition similar to Fe.sub.0.8Cr.sub.0.2 in which Ni remained to some extent. Moreover, the bright portions in FIG. 4 were confirmed to be a Mg.sub.2Ni intermetallic compound although Fe and Cr were slightly detected. As described above, the nano-composite metal member shown in FIG. 4 was confirmed to be an Fe.sub.0.819Cr.sub.0.172Ni.sub.0.009/Mg.sub.2Ni co-continuous nano-composite metal member.

[0044] 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 FIG. 5. As shown in FIG. 5(a), how the reaction layer 13 was increased as the time for heat treatment passed can be confirmed. Furthermore, as shown in FIG. 5(b), the presence of a relationship represented by x.sup.2=k.Math.(tt.sub.0) between the thickness x of the reaction layer 13 and the time t for heat treatment was confirmed. Here, k indicates the rate constant, and t.sub.0 indicates the latent time taken for the reaction to start. Moreover, it was confirmed that as the temperature of heat treatment increased, the enlarging rate of the reaction layer 13 increased.

[0045] An Arrhenius plot obtained by plotting the rate constant k of each temperature of heat treatment found in FIG. 5(b) is shown in FIG. 6. The activation energy E of interdiffusion due to heat treatment, which was found from FIG. 6, was 280 kJ/mol.

Other Examples

[0046] A 30-micron thick Ti.sub.50Cu.sub.50 (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.

[0047] Furthermore, a 1-micron thick Mn.sub.85C.sub.15 (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.

[0048] Furthermore, a 1-micron thick Mn.sub.85C.sub.15 (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.

[0049] A (Fe.sub.0.8Cr .sub.0.2).sub.50Ni.sub.50 alloy (metal material 12) was pressed at 20 MPa to a 30-micron thick Mg.sub.86Ni.sub.9Ca.sub.5 (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 Mg.sub.86Ni.sub.9Ca.sub.5 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.

[0050] 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.

[0051] 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.

[0052] 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 (Ni.sub.57Cr.sub.16Mo.sub.16W.sub.4Fe.sub.5 (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 FIG. 7 and FIG. 8, respectively. In addition, a scanning electron micrograph of the cross section of the coil spring after heat treatment is shown in FIG. 9.

[0053] As shown in FIG. 7 and FIG. 8, the coil spring made of HASTELLOY C-276 was confirmed to be a multiphasic alloy containing a p phase and a phase in which Mo (second component) was concentrated, and a phase in which Ni (third component) was concentrated. Further, as shown in FIG. 9, it was confirmed that reaction layer 13 was formed in the contact interface between a vapor-deposited Mg layer and the coil spring by heat treatment. Within the reaction layer 13, it was confirmed that the Ni component was selectively diffused (dealloying) from the phase into Mg, and a co-continuous-structured nanocomposite formation was formed, in which portions (dark portions in the figure) containing Ni (third component) and Mg (first component) as major components, and portions (bright portions in the figure) in which Mo (second component) was concentrated because of depletion of Ni from the phase were mixed in nanometer order.

[0054] 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.

[0055] The method for joining phase-separated metal solids of an embodiment of the present invention involves, firstly, as shown in FIG. 10(a), with the use of a solid first metal body 21 comprising a first component, and a solid second metal body 22 comprising a second component having a positive heat of mixing relative to the first component, forming an alloy layer 23 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 the first metal body 21 and the second metal body 22. In a specific example shown in FIG. 10, the alloy layer 23 is formed on the surface of the first metal body 21.

[0056] 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.

[0057] 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 FIG. 10(b), interdiffusion takes place between the first component and/or second component, and the third component, and thus finally a co-continuous structured nanocomposite formation 24 comprising portions that comprises the first component and the third component, and portions that comprises the second component and the third component is generated in the interface of the first metal body 21 and the second metal body 22.

[0058] In a specific example shown in FIG. 10, heat treatment is performed, so that the third component is diffused to the second metal body 22 side, and the second component is diffused to the alloy layer 23 side, and thus finally a co-continuous structured nanocomposite formation 24 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 21 and the second metal body 22.

[0059] 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.

REFERENCE SIGNS LIST

[0060] 11 Metal body

[0061] 12 Metal material

[0062] 13 Reaction layer

[0063] 21 First metal body

[0064] 22 Second metal body

[0065] 23 Alloy layer

[0066] 24 Co-continuous structured nanocomposite formation