JP5751659B2 - Metallic glass nanowire and manufacturing method thereof - Google Patents

Description

  The present invention relates to a method for producing a nanowire composed of a metallic glass material.

In recent years, with the development of various microscopy methods with atomic resolution, new nanostructures have been discovered, nanoscale electronic phenomena such as quantum effects are being elucidated, and material properties peculiar to these nanoregions have been actively promoted. Nanotechnology research to be put into practical use is being vigorously promoted. Although it is a nanotechnology research called “Nanotech” that has gained general recognition, the number of successful examples of practical application of nanotech to industry is very limited. This is because it is very difficult to handle because of its complicated production technology for creating nanostructures and its small nano size.
For example, carbon nanotubes that are considered promising as parts materials for electronic devices and nano electro mechanical systems (NEMS) in the future, and in fact, some carbon nanotubes that have already been put into practical use and are undergoing competitive research and development ( In carbon nanotube (CNT), although it is in the form of an array, a multi-layer CNT synthetic method of metric class [Non-patent Document 2] and single-walled CNT in millimeter units [Non-patent Document 3] has been gradually developed.

On the other hand, when looking at the mechanical properties of CNT, the tensile strength measured by Atomic Force Microscope (AFM) has been reported to be astonishing as 63 GPa, but the strength measurement is about 10 μm. This was carried out on CNTs having a short length [Non-patent Document 4]. Similar results have been confirmed by transmission electron microscope (TEM) observations, but the failure process without constriction is observed, and it is reported that defect sites are involved in the destruction. [Non-Patent Document 5].
In addition, single crystal silicon nanowires, which are expected to be used as ultimate transistor elements, are still difficult to lengthen, and this limitation is a problem common to crystalline nanowires and is a drag on full-scale practical application of nanowires. It has become.

An important point for overcoming this lengthening problem is that all conventional one-dimensional nanowires are composed of crystalline phases. In general, crystalline materials contain various defect sites such as dislocations, point defects, twins, and grain boundaries, even if they are nano-sized. The existence of these defect sites is important when lengthening high-strength nanowires. Serious effect.
On the other hand, the metallic glass nanowires [Non-patent Document 1, Patent Document 14] discovered by the present inventor are amorphous (FIG. 1) and are not affected by defect sites such as dislocations. Furthermore, there is an advantage that superplasticity in the supercooled liquid region peculiar to glass can be used, and it is possible to fabricate nanowires with a length of more than millimeters and high strength that has been difficult with nanowires based on crystalline materials. It is. Furthermore, since metallic glass materials have various excellent functionalities depending on their alloy configurations, the creation of these excellent functional nanowires can greatly contribute to technological development.

The Inoue group at Tohoku University has created an extremely large “bulk-shaped metallic glass” by stabilizing the supercooled liquid state of metallic glass that exhibits a clear glass transition that cannot be seen with ordinary amorphous metals. Has attracted worldwide attention as a new material from Japan. Metallic glass has high resistance to plastic deformation because it has no dislocations, and realizes excellent material properties such as ultra-high strength, high elastic elongation, low Young's modulus, and high corrosion resistance. In the latest report, Zr-based bulk metallic glass with a diameter of 30 mm has been successfully produced [Non-patent Document 6].
On the other hand, the mechanical properties of these metallic glasses sufficiently satisfy the mechanical strength requirements of precision micromachines and micromachine parts, and their practical application is rapidly progressing in recent years. Ultra-precision gears (diameter 0.3 mm) Has been put into practical use as a material for the world's smallest geared motor with built-in [Non-patent Document 7]. In the endurance load test of this motor, it has been reported that the life is about 100 times longer than steel (SK4) gear.

The present inventor has independently searched and studied the application of these metallic glass materials having excellent mechanical properties to the field of nanotechnology research [Non-patent Documents 1 and 8, Patent Document 14]. It has been known for over 30 years that bulk metallic glass materials undergo shear fracture when subjected to mechanical tests such as tension and compression, and a unique wavy pattern of micron size appears on the fracture surface [ Non-patent document 9]. In recent years, the temperature distribution in the final stage of shear fracture has been analyzed, and the details of the fracture mechanism in which the temperature rises rapidly in a short time of about 100 ns immediately before fracture has been clarified [Non-patent Document 10]. This temperature rise is the result of the strain energy accumulated by tension or compression being released as thermal energy, which forms a thin supercooled liquid layer along the shear band. The supercooled liquid peculiar to this glassy material is deformed by viscous flow. Therefore, the wavy pattern appearing after the fracture is nothing but a structure in which the supercooled liquid layer is rapidly cooled by separation and solidified in a wavy shape.
The present inventor has observed the fracture surface in detail, and found that a nano-sized wire is formed on the fracture surface in addition to the micron-sized wavy pattern [Non-patent Document 1, Patent Document 14].

Japanese Patent Laid-Open No. 3-10041 Japanese Unexamined Patent Publication No. 3-158446 Japanese Unexamined Patent Publication No. 7-252559 JP-A-9-279318 JP 2001-254157 A JP 2001-303218 A JP 2004-42017 Gazette JP 2007-92103 A JP 2007-247037 JP 2007-332413 A JP 2008-1939 JP 2008-24985 A US Pat. No. 5,429,725 Japanese Patent Application 2008-183080, Nano-sized metallic glass structure, Yukihito Nakayama, etc.

K. S. Nakayama, Y. Yokoyama, G. Xie, Q. S. Zhang, M. W. Chen, T. Sakurai, and A. Inoue, "Metallic glass nanowire," Nano. Lett. 8, 516-519 (2008) M. Zhang, S. Fang, A. A. Zakhidov, S. B. Lee, A. E. Aliev, C. D. Williams, K. R. Atkinson, and R. H. Baughman, "Strong, Transparent, multifunctional, carbon nanotube sheets," Science 309, 1215-1219 (2005) K. Hata, D. N. Futaba, K. Mizuno, T. Namai, M. Yumura, and S. Iijima, "Water-assisted highly efficient synthesis of impurity free single walled carbon nanotubes," Science 19, 1362-1364 (2004) M.-F. Yu, O. Lourie, M. J. Dyer, K. Moloni, T. F. Kelly, and R. S. Ruoff, "Strength and breaking mechanism of maltiwalled carbon nanotubes under tensile load," Science 287, 637-640 (2000) BG Demczyk, YM Wang, J. Cumings, M. Hetman, W. Han, A. Zettl, RO Ritchie, "Direct mechanical measurement of the tensile strength and elastic modulus of multiwalled carbon nanotubes," Materials Science and Engineering 334, 173- 178 (2002) Y. Yokoyama, E. Mund, A. Inoue, and L. Schultz, "Production of Zr55Cu30Ni5Al10 glassy alloy rod of 30 mm in diameter by a cap-cast technique," Mater. Trans. 48, 3190-3192 (2007) Hiroshi Ishida, Hideki Takeda, Nobuyuki Nishiyama, Kenji Amitani, Kazuhiko Kita, Yukiharu Shimizu, Eri Watanabe, Eri Fukushima, Yasunori Saotome, Akihisa Inoue, “The World's Smallest and High Torque Geared Motor Using Metallic Glass Ultra-precision Gear” Teria 44, 431-433 (2005) KS Nakayama, Y. Yokoyama, T. Sakurai, and A. Inoue, "Surface properties of Zr50Cu40Al10 bulk metallic glass," Appl. Phys. Lett. 90, 183105 (2007) .F. Spaepen, "On the fracture morphology of metallic glasses, "Acta. Mater. 23, 615-621 (1975) J. J. Lewandowski and A. L. Greer, "Temperature rise at shear bands in metallic glasses," Nature Mater. 5, 15-18 (2006) Y. Kawamura, T. Nakamura, and A. Inoue, Scripta Mater. 39, 301-306 (1998) A. Inoue, Stabilization of metallic supercooled liquid and bulk amorphous alloys, Acta Mater., 48, 279-306 (2000)

The present inventor observes in detail the above-mentioned fracture surface generated by a mechanical test such as tension or compression of a bulk metallic glass material, and a nano-sized wire is formed on the fracture surface in addition to a micron-sized wavy pattern. [Non-patent document 1, Patent document 14]. This discovery leads to the possibility of producing a novel nanowire that inherits the properties of a metallic glass material having excellent functionality as a base material.
There is a need to develop a method for producing metallic glass nanowires [Non-patent Document 1, Patent Document 14] discovered by the present inventors from metallic glass materials.
It is technically significant to construct a nanostructure that is indispensable for constructing a nanoscale device from a metallic glass material that has no crystal slip surface, excellent tissue structure uniformity, mechanical strength, and corrosion resistance. it makes sense. In addition, the properties of metallic glass materials with various functionalities can be expected to be inherited by nano-sized structures, and there is a high possibility that they will be unique new practical nanomaterials that are completely different from existing crystalline nanostructures. is there.

The present inventor conducted research to observe in detail the characteristics of the deformation behavior leading to the fracture of the bulk metallic glass, and as described above, it was inclined with respect to the stress direction of the metallic glass in the compression and tension mechanical tests. A nano-sized wire or tube structure composed of the same compositional components as the base metal glass is formed on the shear surface generated in a plane close to the direction along the maximum shear stress surface without work hardening or crystallization. I found that it was formed. The mechanism of the generation of these nano-sized structures is caused by the superplastic characteristics of the metallic glass due to the high temperature, and is caused by the viscous flow due to the heat generation just before the fracture.
In this way, in order to perform superplastic processing on metallic glass, it is rapidly heated to the supercooled liquid region, and after processing, rapid cooling to avoid crystallization keeps the amorphous state by producing metallic glass nanowires. Recognized that the law can be established.
Since the metallic glass material has a supercooled liquid region and can be superplastically processed in the supercooled liquid state [Non-Patent Document 11], by using the processing means in the present invention, all metallic glass materials can be used. Generation of nanowires is possible.

The present invention provides the following.
[1] A metallic glass nanowire comprising metallic glass, wherein at least one of the dimensions is nano-sized, and the total length is 75 micrometers (μm) or more.
[2] The metal glass nanowire according to [1], wherein the diameter is 1000 nm or less.
[3] The metallic glass nanowire according to [1], wherein the diameter is 100 nm or less.
[4] A production method for producing the metallic glass nanowire according to any one of [1] to [3],
Ribbon-shaped or rod-shaped metallic glass is fixed at the end up and down and the lower end can be pulled, and in an atmosphere where oxidation can be prevented, the lower end is pulled,
(a) bringing the movable heat-heating filament into contact with the ribbon-shaped or rod-shaped metallic glass sample vertically;
(b) Fix the electrodes on the upper and lower ends and cut off the energization just before energization and breakage, or
(c) laser heating the ribbon-shaped or rod-shaped metal glass sample,
The metal glass is rapidly heated to the supercooled liquid region, and the formed metal glass nanowire is rapidly cooled to maintain the metal glass state of the nanowire, and the above [1] to [3 ] The metal glass nanowire manufacturing method characterized by manufacturing the metal glass nanowire as described in any one of.
[5] The production method according to the above [4], wherein the atmosphere capable of preventing oxidation is a vacuum.
[6] A manufacturing apparatus for manufacturing the metallic glass nanowire according to any one of [1] to [3],
A casing that achieves an atmosphere that can prevent oxidation of the metal glass sample, at least two fixtures that are arranged in the casing and fix the ribbon-shaped or rod-shaped metal glass up and down at the end, and fixing the lower end Load applying device for towing the tool,
(a) a movable thermal heating filament that can be brought into perpendicular contact with the ribbon-shaped or rod-shaped metallic glass sample;
(b) an electrode fixed to the fixture at the upper and lower ends of the sample and capable of energization and de-energization, or
(c) provided with any one of lasers capable of heating the ribbon-shaped or rod-shaped metal glass sample, rapidly heating the metal glass to a supercooled liquid region, and rapidly cooling the formed metal glass nanowire, thereby The metal glass nanowire production apparatus characterized in that the metal glass nanowire according to any one of the above [1] to [3] can be produced by maintaining the state of the metal glass.
[7] The manufacturing apparatus as described in [6] above, wherein the atmosphere capable of preventing oxidation is a vacuum.

According to the present invention, nanowires can be generated for all metallic glass materials. In addition, since the present invention uses a ribbon-like or fine-wire metallic glass material as a base material, it does not require a bulky metallic glass and can be applied to all metallic glass materials from that viewpoint.
According to the present invention, a nanostructure essential for constructing a nanoscale device is composed of a metallic glass material that has no crystal slip surface, excellent tissue structure uniformity, mechanical strength, and corrosion resistance. It becomes possible. In addition, it can be expected that the properties of metallic glass materials having various functionalities will be inherited by nano-sized structures, and this will be a unique new practical nanomaterial that is completely different from existing crystalline nanostructures.
Other objects, features, excellence and aspects of the present invention will be apparent to those skilled in the art from the following description. However, it is understood that the description of the present specification, including the following description and the description of specific examples and the like, show preferred embodiments of the present invention and are presented only for explanation. I want. Various changes and / or modifications (or modifications) within the spirit and scope of the present invention disclosed herein will occur to those skilled in the art based on the following description and knowledge from other parts of the present specification. Will be readily apparent. All patent documents and references cited herein are cited for illustrative purposes and are not to be construed as a part of this specification. is there.

Scanning electron microscope image of Pd-based metallic glass nanowires. Nanowires of 1 cm or more are generated at the tip of the ribbon-like sample. (a) Schematic of experimental chamber. Thermally heated filament can be moved horizontally by a linear introduction machine and contact the ribbon sample. (b) The filament is in contact with the ribbon. A weight is fixed to the lower end of the ribbon, and a strain is applied in the vertical direction by the load. (c) Since the lower side is cut after processing, it can be instantaneously separated from the filament as a heat source, and a rapid cooling condition can be realized. (a) Schematic of current heating method. (b) Schematic diagram of laser heating method.

In the present invention, a molded product made of a metallic glass material, for example, a metallic glass ribbon or thin wire, is heated rapidly to a supercooled liquid state while applying distortion, and processed in that state. It is characterized in that the amorphous structure is held in the nanowire by the accompanying rapid cooling.
The generated nanowire is confirmed to be in an amorphous state by observing an atomic structure using a transmission electron microscope. In addition, the nanowire has been subjected to mechanical measurement, and it has been confirmed that it has a Young's modulus equivalent to that of bulk metallic glass.

In the present specification, metallic glass (also referred to as glassy alloy) is a kind of amorphous alloy, but the glass transition point appears clearly. It is different from conventional amorphous alloys in that it indicates a supercooled liquid region on the high temperature side with this glass transition point as a boundary. That is, when the thermal behavior of metallic glass is examined using a differential scanning calorimeter, the endothermic temperature region appears after the glass transition temperature (T _g ) as the temperature rises, and heat is generated near the crystallization temperature (T _x ). Shows a peak, and when heated further, an endothermic peak appears at the melting point (T _m ). Each temperature point varies depending on the composition component of the metal glass. The supercooled liquid temperature region (ΔT _x ) is defined by ΔT _x = T _x -T _g , and ΔT _x is very large as 50 to 130 ° C, so that the stability of the cooling liquid state is high and crystallization is avoided. Amorphous state can be maintained. In conventional amorphous alloys, such thermal behavior is not observed and T _g does not exist.

In order to produce bulk metallic glass, the stability of the supercooled liquid state is an element, and as a composition for realizing this,
(1) A multi-component system with three or more components,
(2) The atomic size ratios of the three main components differ from each other by 12% or more,
(3) The heat of mixing of the three main components has a negative value to each other,
Has been reported as a rule of thumb (A. Inoue, Stabilization of metallic supercooled liquid and bulk amorphous alloys, Acta Mater., 48, 279-306 (2000): Non-Patent Document 11).
Various examples of the composition of the metallic glass material are known. For example, Japanese Patent Application Laid-Open No. 3-10041 [Patent Document 1], Japanese Patent Application Laid-Open No. 3-158446 [Patent Document 2], and Japanese Patent Application Laid-Open No. 7-252559. [Patent Document 3], JP-A-9-279318 [Patent Document 4], JP-A-2001-254157 [Patent Document 5], JP-A-2001-303218 [Patent Document 6], JP-A-2004 No.-42017 [Patent Document 7],
JP 2007-92103 [Patent Document 8], JP 2007-247037 [Patent Document 9], JP 2007-332413 [Patent Document 10], JP 2008-1939 [Patent Document 11]. ], JP 2008-24985
References disclosed in Japanese Patent Publication [Patent Document 12], US Pat. No. 5,429,725 [Patent Document 13], and the like can be referred to.

As metal glasses, Ln-Al-TM, Mg-Ln-TM, Zr-Al-TM (where Ln is a rare earth element, TM is a transition metal), etc. have been found. Many compositions have been reported until recently. Glass alloys may include bulk glass alloys such as Mg group, rare earth metal group, Zr group, Ti group, Fe group, Ni group, Co group, Pd group, Pd-Cu group, Cu group, Al group, etc. .
X _a M _b Al _c (X: Zr, Hf, M: Ni, Cu, Fe, Co, Mn, 25 ≦ a ≦ 85, 5 as an amorphous alloy with a wide temperature range in the supercooled liquid region and excellent workability <= B <= 70, 0 <= c <= 35) is known, for example, Unexamined-Japanese-Patent No. 3-158446 etc. can be referred.

Zr-based metallic glass contains more Zr than other elements in the alloy, in addition to Zr, Group 4 elements (e.g., Ti, Hf, etc. other than Zr), Group 5 elements (e.g., V, Nb, Ta, etc.), Group 6 elements (e.g., Cr, Mo, W, etc.), Group 7 elements (e.g., Mn, etc.), Group 8 elements (e.g., Fe, etc.), Group 9 elements (e.g., Co), Group 10 elements (e.g., Ni, Pd, Pt, etc.), Group 11 elements (e.g., Cu, Ag, etc.), Group 13 elements (e.g., Al, etc.), Group 14 elements (e.g., Si or the like, and those containing one or more elements selected from the group consisting of Group 3 elements (for example, Y, lanthanoid elements, etc.) (the periodic table of elements is IUPAC Nomenclature of Based on Inorganic Chemistry, 1989, and so on). In a typical case, the content of Zr varies depending on the elements other than Zr, but is 40% by mass or more, preferably 45% by mass or more, more preferably 45% by mass or more based on the entire alloy. Specifically, Zr ₅₀ Cu ₄₀ Al ₁₀ (hereinafter, the subscript indicates atomic%), Zr ₅₅ Cu ₃₀ Al ₁₀ Ni ₅ , Zr ₆₀ Cu ₂₀ Al ₁₀ Ni ₁₀ , Zr ₆₅ Cu ₁₅ Al ₁₀ Ni ₁₀ , Zr ₆₆ Cu ₁₂ Al ₈ Ni ₁₄ , Zr ₆₅ Cu _17.5 Al _7.5 Ni ₁₀ , Zr ₄₈ Cu ₃₆ Al ₈ Ag ₈ , Zr ₄₂ Cu ₄₂ Al ₈ Ag ₈ , Zr ₄₁ Ti ₁₄ Cu ₁₃ Ni ₁₀ Be ₂₂ , Zr ₅₅ Al ₂₀ Ni ₂₅ , Zr ₆₀ Cu ₁₅ Al ₁₀ Ni ₁₀ Pd ₅ , Zr ₄₈ Cu ₃₂ Al ₈ Ag ₈ Pd ₄ , Zr _52.5 Ti ₅ Cu ₂₀ Al _12.5 Ni ₁₀ , Zr ₆₀ Cu ₁₈ Al ₁₀ Co ₃ Ni ₉ etc. Can be mentioned. Among these, Zr-based glass alloys such as Zr ₅₀ Cu ₄₀ Al ₁₀ , Zr ₆₅ Cu ₁₅ Al ₁₀ Ni ₁₀ , Zr ₄₈ Cu ₃₂ Al ₈ Ag ₈ Pd ₄ , Zr ₅₅ Cu ₃₀ Al ₁₀ Ni ₅ are particularly preferable. Can be mentioned.

As the metal glass, a metal glass containing Pd and Pt as essential elements has been reported. For example, JP-A-9-279318 can be referred to. Further, Ni ₇₂ -Co _(8-x) -Mo _x -Z ₂₀ (x = 0, 2, 4 or 6 atomic%, Z = metalloid element) is known as a metallic glass material. Reference can be made to Japanese Patent No. 5429725. In addition to Pd, metals such as Nb, V, Ti, Ta, and Zr are known to have hydrogen permeation performance, and a metal glass centered on such a metal can exhibit hydrogen selective permeability.

In addition, Nb-Ni-Zr, Nb-Ni-Zr-Al, Nb-Ni-Ti-Zr, Nb-Ni-Ti-Zr-Co, Nb-Ni-Ti-Zr- Co-Cu, Nb-Co-Zr, Ni-V- (Zr, Ti), Ni-Cr-PB, Co-V-Zr
System, Cu-Zr-Ti system, and the like. For example, JP 2004-42017 A can be referred to. Specifically, Nb-Ni-Ti-Zr glass alloys such as Ni ₆₀ Nb ₁₅ Ti ₁₅ Zr ₁₀ and Ni ₆₅ Cr ₁₅ P ₁₆ B ₄ and Ni-Cr-PB glass alloys are particularly preferable. It is done.
Furthermore, examples of the metal glass include a metal-metalloid (semi-metal) metal glass alloy, a metal-metal metal glass alloy, and a hard magnetic metal glass alloy.
As a metal-metalloid (metalloid) -based metallic glass alloy containing Fe as a metal element, for example, other metal elements other than Fe and a metalloid element (metalloid element) are contained. , In, Sn containing one or more of them, P,
Examples thereof include those containing one or more of C, B, Ge, and Si. Metal
Examples of metal-based metallic glass alloys are mainly composed of one or more elements of Fe, Co, Ni and one of Zr, Nb, Ta, Hf, Mo, Ti, V or The thing containing 2 or more types of elements and B is mentioned.

In the present invention, as a suitable metallic glass, the metallic glass is composed of a plurality of elements, and at least one atom of Fe, Co, Ni, Ti, Zr, Mg, Cu, Pd as a main component is 30 to The thing contained in 80 atomic% is mentioned. Furthermore, at least one kind from each group in the range of 10-40 atomic% of group 6 elements (Cr, Mo, W) and 1-10 atomic% of group 14 elements (C, Si, Ge, Sn) These metal atoms may be combined. In addition, depending on the purpose, iron group elements can be Ca, B,
Elements such as Al, Nb, N, Hf, Ta, and P may be added within a range of 10 atomic% or less. Under these conditions, it may have a high glass forming ability.

An element containing at least Fe as a component element of the metallic glass has drastically improved corrosion resistance and is suitable. The Fe content in the metal glass is preferably 30 to 80 atomic%. When Fe is less than 30 atomic%, sufficient corrosion resistance cannot be obtained, and when it is more than 80 atomic%, it is difficult to form metallic glass. The more preferable proportion of Fe atoms is 35 to 60 atomic%
It is. The above-mentioned metallic glass composition contributes to lowering of processing at the same time as forming a stable amorphous phase metallic glass layer, and can form a uniform glass structure and a layered structure of crystalline metallic structure. Preferred compositions include, for example, Fe ₄₃ Cr ₁₆ Mo ₁₆ C ₁₅ B ₁₀ , Fe ₇₅ Mo ₄ P ₁₂ C ₄ B ₄ Si ₁ , Fe ₅₂ Co ₂₀ B ₂₀ Si ₄ Nb ₄ , Fe ₇₂ Al ₅ Ga ₂ P ₁₁ C ₆ B ₄ etc. are mentioned.
Further, as a preferred metal glass used in the present invention, Fe _100-abc Cr _a TM _b (C _1-X B _X P _y ) _c (where TM = V, Nb, Mo, Ta, W , Co, Ni, at least one of Cu, a,
b, c, x, y are 5 atom% ≤ a ≤ 30 atom%, 5 atom% ≤ b ≤ 20 atom%, 10 atom% ≤ c ≤ 35 atom%, 25 atom% ≤ a + b ≤ 50 atom, respectively. %, 35 atomic% ≦ a + b + c ≦ 60 atomic%, 0.11 ≦ x ≦ 0.85, 0 ≦ y ≦ 0.57]. For the metal glass, for example, JP-A-2001-303218 can be referred to.

The metallic glass may be a soft magnetic Fe-based metallic glass alloy. For example, JP 2008-24985 A and all patent documents and references cited therein can be referred to. Examples of soft magnetic metallic glass alloys include Fe- (Al, Ga) -metalloid, (Fe, Co, Ni)-(Zr, Hf, Nb, Ta) -B, (Fe, Co) -Si- B-Nb system, (Fe, Co) -Ln-B system, Fe-Si-BP- (C) system and the like may be included. Hard magnetic metallic glass alloys are also known, and examples of such hard magnetic metallic glass alloys may include Fe-Nd-B, Fe-Pr-B, Fe-Pt-B, and the like. .
As Co-based metallic glass, for example, JP-A-2007-332413 and all patent documents and references cited therein can be referred to. As the Ni-based metallic glass, for example, JP-A-2007-247037 and all patent documents and references cited therein can be referred to. As the Mg-based metallic glass, for example, JP-A 3-10041, JP-A 2001-254157, JP-A 2007-92103 and all patent documents and references cited therein can be referred to. As the Ti-based metallic glass, for example, JP-A-7-252559, JP-A-2008-1939 and all patent documents cited therein can be referred to.
Preferable compositions include, for example, Ti ₅₀ Cu ₂₅ Ni ₁₅ Zr ₅ Sn ₅ , Mg ₅₀ Ni ₃₀ Y _{20 and the} like.

In the present invention, “nanoscale” may be understood to refer to a case where at least two of the dimensions x, y, z representing a three-dimensional space mean nanosize, `` Size '' refers to a size of 1000 nanometers (nm) or less, more preferably a size of 500 nm or less, in some cases 200 nm or less, typically 150 nm. Less than, typically more than 120 nm, more typically less than 100 nm, even less than 80 nm, in some cases less than 70 nm, In other cases, it may refer to a size of 60 nm or less, a size of 55 nm or less, or a size of 50 nm or less. In the present invention, the “nanosize” can be various sizes from 1000 nm or less depending on the type of metal glass, and further, 40 nm or less or 30 nm. The following sizes, 20 nm or less, or even smaller, 10 nm or less, or 5 nm or less are also included. Typically, in the metallic glass nanowire of the present invention, it may be understood that the diameter of the wire refers to the “nanosize” described above.
As is clear from the above, the metallic glass nanowire of the present invention includes one of the dimensions, for example, the length may be the nano-size or more, for example, the one having a size of 1 micrometer (μm) or more. Is done.

The metallic glass nanowires of the present invention may include various shapes, and various forms are allowed depending on the type of metallic glass. For example, nanoscale, fine wire, fiber (nanofiber) , Filament, rod (nanorod), cylinder (nanocylinder) and the like.
The metallic glass nanowire may be any of a linear shape, a branched shape, a twisted shape, a coil shape, a spiral shape, and the like, and examples thereof include a linear shape and a cylindrical shape. The shape of the metal glass nanowire can be in various forms depending on the type of metal glass, and is acceptable. For example, the shape of the cross section of the thin wire is circular, elliptical, pear-shaped, etc. Any shape can be used as appropriate, but it is preferably circular or elliptical.

In the metallic glass nanowire, the diameter of the thin wire is 1000 nm or less, typically 500 nm or less, or 200 nm or less, and in some cases 150 nm or less. Or less than 120 nm, specifically less than 100 nm or less than 90 nm, or less than 85 nm or less than 80 nm, in other cases, 75 nm Less than or below 70 nm, more specifically below 65 nm or below 60 nm, more typically below 55 nm or below 50 nm. Or less than 45 nm, 40 nm or less, 35 nm or less, 30 nm or less, 20 nm or less, or 15 nm or less Size, in other cases, a size of 10 nm or less, or 5 nm or less It is.
The diameter of the thin wire can be various sizes depending on the type of metal glass, and can be various sizes from a size of 1000 nm or less, for example, a size of 10 nm or less. Or a size of 5 nm or less. The wire length of the metal glass nanowire can be 1 μm or more, and includes 5 μm or more, 10 μm or more, 20 μm or more, 30 μm or more, 50 μm or more. For example, 0.1 mm or more, 0.25 mm or more, 0.5 mm or more, 1.0 cm or more can be obtained.

In the metallic glass nanowire, the aspect ratio (ratio of the size of the wire diameter to the length) can be arbitrarily set to any value, and various values can be set depending on the type of the metallic glass. Is also possible, for example in the range 1:75 to 1: 500,000, or in the range 1: 100 to 1: 450,000, in some cases in the range 1: 250 to 1: 400,000, in other cases 1 : 500〜1: 5,000
The range can be selected.
In a typical example, the aspect ratio of the metallic glass nanowire of the present invention is, for example, 1: 1,000.
In the range of ~ 1: 500,000, or in the range of 1: 2,000 to 1: 450,000, in some cases in the range of 1: 1,000 to 1: 400,000, in other cases in the range of 1: 2,000 to 1: 400,000 can do.
In another specific embodiment, the aspect ratio of the metallic glass nanowires of the present invention is, for example, in the range of 1: 1,000 to 1: 10,000, alternatively in the range of 1: 10,000 to 1: 450,000, in some cases 1: It can be selected in the range of 1,000 to 1: 2,000, in other cases in the range of 1: 1,000 to 1: 5,000.
In one specific example, the present metallic glass nanowire has a diameter of about 100 to 500 nm and a thin wire length of about 75 to 20,000 μm. In another embodiment, the metallic glass nanowire has a diameter of approximately 10-100 nm and a thin wire length of approximately 100-15,000 μm.

Furthermore, in another specific example, examples of the present metallic glass nanowire include those having a diameter of about 40 to 120 nm and a thin wire length of about 500 to 13,000 μm. In another specific example, the metallic glass nanowire has a diameter of about 40 to 100 nm and a thin wire length of about 250 to 13,000 μm. In one further specific example, the present metallic glass nanowire has a diameter of about 100 to 500 nm and a thin wire length of about 400 to 7,500 μm. In another specific example, the metallic glass nanowire has a diameter of about 35 to 50 nm and a thin wire length of about 500 to 14,000 μm. In another specific example, examples of the present metallic glass nanowire include those having a diameter of approximately 60 to 80 nm and a thin wire having a length of approximately 80 to 150 μm. In another specific example, the metallic glass nanowire has a diameter of about 80 to 110 nm and a thin wire length of about 150 to 450 μm.
The thicknesses of the wire rods such as the above-described metallic glass nanowires are not necessarily the same, and may include those having a certain size.

In the metallic glass nanowire, the diameter of the thin wire is 1000 nm or less, and typically has a thickness of 100 nm or less. The length of the fine line can be 1 cm or more, and more than that is included. The aspect ratio can be arbitrarily set as appropriate. Since these sizes depend on the viscosity of the metallic glass in the high-temperature supercooled liquid region, various values can be obtained depending on the type of metallic glass. For example, the tip diameter is 100 nm
When the original diameter is 1000 nm, the average diameter is 550 nm, but when the total length is 1 cm, the aspect ratio is 1: 18,182.

  In one specific embodiment, the metallic glass nanowire of the present invention is an atmosphere in which ribbon-shaped or rod-shaped metallic glass can be fixed vertically at its end and pulled at its lower end to prevent oxidation. The metal glass nanowires are formed by bringing the movable heat-heating filament into contact with the ribbon-shaped or rod-shaped metal glass sample vertically under the pulling of the lower end thereof, and rapidly heating the metal glass to the supercooled liquid region. Can be manufactured while maintaining the metallic glass state of the nanowire. In another specific embodiment, the metallic glass nanowire of the present invention is an atmosphere in which ribbon-shaped or rod-shaped metallic glass can be fixed up and down at its end and pulled at its lower end to prevent oxidation. Inside, pulling the lower end, fixing the electrodes to the upper and lower ends, shutting off the energization just before energization and breaking, rapidly heating the metal glass to the supercooled liquid region, and rapidly cooling the formed metal glass nanowire Thus, the metal glass state of the nanowire can be maintained and manufactured. Furthermore, in one specific embodiment, the metallic glass nanowire of the present invention can fix a ribbon-shaped or rod-shaped metallic glass up and down at its end and tow its lower end to prevent oxidation. In a possible atmosphere, under the pulling of its lower end, the ribbon-shaped or rod-shaped metallic glass sample is laser-heated, the metallic glass is rapidly heated to the supercooled liquid region, and the formed metallic glass nanowire is rapidly cooled. The nanowire can be manufactured while maintaining the metallic glass state.

In a more preferred embodiment, the metallic glass nanowire of the present invention can be produced using a metallic glass nanowire production apparatus described below.
The metal glass nanowire manufacturing apparatus includes a casing that achieves an atmosphere capable of preventing oxidation of a metal glass sample, and at least two ribbon glass or rod-shaped metal glasses that are disposed in the casing and fixed vertically at the ends thereof. One fixture, a load applying device that pulls the fixture at the lower end,
(a) a movable thermal heating filament that can be brought into perpendicular contact with the ribbon-shaped or rod-shaped metallic glass sample;
(b) an electrode fixed to the fixture at the upper and lower ends of the sample and capable of energization and de-energization, or
(c) provided with any one of lasers capable of heating the ribbon-shaped or rod-shaped metal glass sample, rapidly heating the metal glass to a supercooled liquid region, and rapidly cooling the formed metal glass nanowire, thereby The metallic glass nanowire can be manufactured by maintaining the metallic glass state.

  The housing provided in the metallic glass nanowire manufacturing apparatus has an exhaust port, and the atmosphere surrounding the metal glass material for processing placed therein is substantially vacuumed by the exhaust device through the exhaust port. It can be the environment. Therefore, the casing may be a casing such as a vacuum chamber or a decompression chamber that is generally known in the art. The exhaust device may include a decompression pump, a vacuum pump, and the like, and the exhaust port is connected to the exhaust device. The exhaust device is, for example, a mechanical vacuum pump, a momentum transport type vacuum pump, for example, a rotor which is a rotating body having a metal turbine blade, and rotates at high speed, and exhausts gas molecules by blowing off gas molecules. It may include a turbo molecular pump (Turbo Molecular Pump; TMP) which is a pump.

The housing is arranged in the housing and pulls at least two fixtures for fixing the ribbon-shaped or rod-shaped metallic glass up and down at the ends thereof, and the fixture at the lower end of the starting metallic glass material. A load applying device can be provided.
The metal glass nanowire manufacturing apparatus is also fixed to a movable heat heating filament that can be brought into perpendicular contact with the ribbon-shaped or rod-shaped metal glass sample disposed in the housing, and a fixture at the upper and lower ends of the sample. In addition, an electrode capable of energizing and interrupting energization and / or a laser capable of heating the ribbon-shaped or rod-shaped metal glass sample can be provided.
Examples of the heating filament include a tungsten filament coil, and the heating filament may be supplied with power by a heating current supply circuit.
The load applied to the lower end of the starting metallic glass material may be gravity-weighted using a weight, or may be mechanically-weighted towed, and further, movement of each device, temperature control, current Supply, power supply, and the like can be performed by a control device.

In the following, typical manufacturing process steps will be described with reference to a specific apparatus.
FIG. 2 (a) shows a substantially cylindrical chamber-type apparatus having a vacuum chamber having a space in which a sample can be arranged and fixed substantially at the center. The apparatus has an exhaust port, and the inside of the chamber can be substantially evacuated by a pump. Thus, the hot filament contact method under gravity load is shown in FIG. A weight was applied to the lower end of the ribbon-shaped or linear metal glass sample to apply a load, and the upper end was fixed to the ceiling of the chamber. Local rapid heating is realized by moving the filament preheated in vacuum horizontally until it contacts the ribbon [FIG. 2 (b)]. Heating is performed in a vacuum to suppress surface oxidation. When the temperature reaches the glass transition temperature or higher, the ribbon is cut by viscous flow deformation, but locally a liquid cross-linked state as shown in Fig. 2 (c) occurs, depending on the viscosity of the sample at high temperature and the load conditions. As a result, nanowires are generated. Since the lower side of the ribbon is instantaneously disconnected from the heat source, the rapid cooling condition is satisfied, and as a result, the amorphous phase can be maintained.

The electric heating method is shown in FIG. Electrodes are fixed to the upper and lower ends of the ribbon-shaped sample, and a load is applied as in FIG. In a preliminary experiment, an appropriate value may be selected by measuring a current value when the voltage is increased at a constant rate. For example, when the heating temperature rises with an increase in power, the ribbon shape is constricted. Further, when the electric power increases, the viscosity decreases due to high-temperature heating and breaks, but nanowires can be generated by cutting off the voltage (current) just before the break.

The laser heating method is shown in FIG. A laser capable of adjusting the pulse width from millisecond to nanosecond or less can realize rapid heating and cooling, and is therefore an ideal heat source from the viewpoint of avoiding crystallization, that is, maintaining an amorphous phase. Further, uniform heating can be performed in the irradiation region. Preliminary experiments have been carried out, and laser irradiation heating has been successfully performed on metallic glass ribbons and rod-shaped samples with a diameter of 1 mm in the atmosphere. As a result, 0.5 to 4.0 ms pulse width
It has been confirmed that the sample can be cut by applying a heat amount of ˜20 J. Therefore, nanowires can be produced by heating while applying a load in vacuum to prevent nanowire surface oxidation.

This metallic glass nanowire is a key material for nanomaterials (NMS), and is useful as an electrode material, a motor material, a nanoelectronics material, a nanomedical device, a nanosensor, an optical material, and the like. Metallic glass nanowires can be used in, for example, medical equipment, nanotechnology applied equipment, magnetic materials, and electronics equipment, including magnetic materials, semiconductor wiring, electrode materials, and the like. The metallic glass nanowire, metallic glass nanorod, and the like are useful as ultrahigh-strength materials and superelastic elongation materials in the nano-region because their mechanical strength is not affected by local defects and dislocations.

Metallic glasses, especially bulk metallic glasses, are viscous metals, exhibit high tensile strength, large elastic limit values, large fracture strength, high toughness, etc., high hardness, high elasticity, and very high strength. The material shows excellent corrosion resistance and wear resistance. Metallic glass is a material having a low Young's modulus, smoothness and transferability, a high specific surface area material, high permeability and scratch resistance, and is also promising as a magnetic material. Metallic glass makes good use of its excellent mechanical strength, corrosion resistance, surface smoothness, precision castability, superplasticity, etc., and uses it as a solenoid valve, actuator, spring member, position sensor, reception sensor, magnetic sensor, tension Applications such as sensors, strain sensors, torque sensors, and pressure sensors are also expected, medical equipment such as endoscopes, rotabrators, and thrombus aspiration catheters, precision engineering equipment, industrial equipment including industrial compact and high-performance devices, and inspections Applications to robots, industrial robots, micro factories, etc. are also being considered.
Metallic glass materials further include, for example, cutting tools, spring materials, high-frequency transformers, choke coils, high-speed mechanism members, precision machine parts, precision optical members, space materials, electrode materials, fuel cell members, transportation equipment members, aircraft members, Applications and applications to precision medical equipment, nuclear power plants, biomaterials, chemical plants, etc. can be expected. Accordingly, metallic glass nanowires and the like are expected to be used in a wide range of fields such as fields that make use of the characteristics of the above-mentioned metallic glass, micromachines, semiconductors and precision electronic components.

The nanowire is an important constituent material element when constructing a nanoelectromechanical system. Therefore, it is possible to utilize the excellent properties of metallic glass such as ultra-high strength, super-elastic elongation, and ultra-soft magnetism in the nano region using the metallic glass nanowire of the present invention, In addition to the substrate material of the system, nano-magnetic sensors and metallic glass nanowires up to several centimeters long can be used for advanced medical devices.For example, if the nanowire diameter is about 100 nm, it can be compared with human cells. It is small enough to allow invasion into the human body without causing pain, etc., so as a sensor, direct diagnosis from the affected area and stimulation of current only to the affected cells without affecting surrounding cells It becomes possible to activate or destroy malignant tumors.
The present invention will be described in detail with reference to the following examples, which are provided merely for the purpose of illustrating the present invention and for reference to specific embodiments thereof. These exemplifications are for explaining specific specific embodiments of the present invention, but are not intended to limit or limit the scope of the invention disclosed in the present application. In the present invention, it should be understood that various embodiments based on the idea of the present specification are possible.
All examples were performed or can be performed using standard techniques, except as otherwise described in detail, and are well known and routine to those skilled in the art. .

An attempt was made to produce metallic glass nanowires using the apparatus shown in FIG. The apparatus shown in FIG. 2 is a substantially cylindrical chamber-type apparatus having a vacuum chamber having a space in which a sample can be arranged and fixed substantially in the center. The apparatus has an exhaust port, and the inside of the chamber can be substantially evacuated by a pump. The apparatus can perform a hot filament contact method under a gravity load. Within the chamber, a weight was applied to the lower end of the ribbon-shaped or linear metallic glass sample and a load was applied, and the upper end was fixed to the ceiling of the chamber. Local rapid heating is realized by moving the filament preheated in vacuum horizontally until it contacts the ribbon (FIG. 2 (b)). Heating is performed in a vacuum to suppress surface oxidation. When the temperature reaches the glass transition temperature or higher, the ribbon is cut by viscous flow deformation, but locally a liquid cross-linked state as shown in Fig. 2 (c) occurs, depending on the viscosity of the sample at high temperature and the load conditions. As a result, nanowires are generated. Since the lower side of the ribbon is instantaneously disconnected from the heat source, the rapid cooling condition is satisfied, and as a result, the amorphous phase can be maintained.

The metallic glass ribbon sample used in this example was prepared by a melt spinning method.
In the apparatus of FIG. 2, the upper and lower ends of the metal glass ribbon were fixed in a vacuum chamber, and heated using a tungsten filament under the conditions shown in Table 1. The filament was moved in the horizontal direction so that heat was transferred to the metallic glass ribbon. The load applied to the ribbon sample was a weight of 1.70 g so that a vertical constant load of 16.7 mN was applied. The inside of the vacuum chamber was evacuated using a turbo molecular pump to create a vacuum atmosphere.
The temperature of the filament was measured using a radiation thermometer (emissivity 0.35) before contacting the sample, and adjusted so that the heating temperature became a predetermined temperature. The heated filament comes into contact with the sample, and processing by viscous flow is performed. At that time, the glass transition temperature is rapidly heated to a temperature higher than the glass transition temperature, but the glass transition temperature at which processing starts varies depending on the material alloy composition.
Several metallic glass nanowires were obtained at one time as shown in FIG. 2C. The metallic glass nanowire obtained under these conditions had a diameter of 100 nm and a length of 0.5 mm or more.

Zr ₄₈ Cu ₃₂ Ag ₈ Al ₈ Pd ₄ metallic glass nanowires were observed with a scanning electoron microscope (SEM) and, in one example, had a length of 500 micrometers or more and an approximate diameter of several. It was about 100 nm, showing uniform morphological characteristics, and no catalyst cluster appeared at the end of the nanowire. In addition, as a result of analysis with an energy dispersive X-ray spectroscopy apparatus, it is shown to contain Zr, Cu, Al, Ag, and Pd, which is the same as the composition of the starting sample. It was confirmed. SEM observation confirmed that metallic glass nanowires having a diameter of approximately 230 nm to approximately 290 nm and a length of 500 micrometers or more were obtained.

As in Example 1, production of Zr-based metallic glass nanowires was attempted using the apparatus shown in FIG. The metallic glass ribbon sample used in this example was prepared by a melt spinning method. The amount of power to the filament was reduced to 0.23W.
With the metallic glass composition of Zr ₆₅ Cu ₁₅ Ni ₁₀ Al ₁₀ , metallic glass nanowires with a diameter of 60 nm and a length of 0.5 mm were obtained at a heating temperature of 973 K.
When this metal glass nanowire was observed by SEM, it was the said size, and showed a uniform morphological feature, and any catalyst cluster did not appear in the terminal part of the nanowire. Further, as a result of analysis with an energy dispersive X-ray spectrometer, it was confirmed that the composition was the same as that of the starting sample.

So far, the following metallic glass materials have been successfully produced using the method of FIG. 2 in the present invention.
(1) Pd-based metallic glass
In the metallic glass alloy composition of Pd ₄₀ Cu ₃₀ Ni ₁₀ P ₂₀ , a nanowire having the following shape was obtained by processing under the following conditions (FIG. 1).
Metal glass ribbon shape: cross section 0.03 x 0.8 mm ² , length about 3 cm
Load: 152 mN
Atmosphere: 1.2 × 10 ⁻⁸ Torr or less Vacuum Filament power: 0.145 W
Filament temperature (measured with a radiation thermometer): 450-550 ° C
Metallic glass nanowire Diameter: Min. 40 nm
Length: up to 1.3 cm

(2) Fe-based metallic glass
In the metallic glass alloy composition of Fe ₇₆ (Si _0.3 B _0.5 P _0.2 ) ₂₄ , treatment was performed under the following conditions, and nanowires having the following shapes were obtained.
Metal glass ribbon shape: cross section 0.03 x 0.8 mm ² , length about 3 cm
Load: 131 mN
Atmosphere: 5.4 × 10 ^-8 Torr or less Vacuum Filament power: 0.364 W
Filament temperature (measured with a radiation thermometer): 725-775 ° C
Metallic glass nanowire diameter: 70 nm minimum
Length: up to 100 micrometers

(3) Au-based metallic glass
In the metallic glass alloy composition of Au ₄₉ Ag _5.5 Pd _2.3 Cu _26.9 Si1 _6.3 , it was processed under the following conditions, and nanowires having the following shapes were obtained.
Metal glass ribbon shape: cross section 0.03 x 0.8 mm ² , length about 3 cm
Load: 243 mN
Atmosphere: 5.2 × 10 ⁻⁸ Torr or less Vacuum Filament power: 0.066 W
Filament temperature (measured with a radiation thermometer): approx. 300 ° C
Metallic glass nanowire diameter: 100 nm minimum
Length: up to 250 micrometers

When these metal glass nanowires were observed by SEM, they were the above-mentioned size and showed uniform morphological characteristics, and no catalyst clusters appeared at the end portions of the nanowires. Further, as a result of analysis with an energy dispersive X-ray spectrometer, it was confirmed that the composition was the same as that of the starting sample.
In the examples, a ribbon-like sample having a width of 0.8 to 1 mm, a thickness of 20 to 50 μm, and a length of 3 cm was used, but this is a size for performing the experiment easily.
When Pd-based metallic glass was used, metallic glass nanowires having a length of 1 cm or more as shown in FIG. 1 were obtained.

The temperature of the filament was measured using a radiation thermometer (emissivity 0.35) before contacting the sample, and the heating temperature was adjusted to 500 to 700 ° C. The heated filament comes into contact with the sample, and processing by viscous flow is performed. At that time, the glass transition temperature is rapidly heated to a temperature higher than the glass transition temperature, but the glass transition temperature at which processing starts varies depending on the material alloy composition. For example, the typical glass transition temperature of Pd ₄₀ Cu ₃₀ Ni ₁₀ P ₂₀ in Pd-based metallic glass is 561 K (N. Nishiyama, A. Inoue, and JZ Jiang,
Appl. Phys. Lett. 78, 1985 (2001)] and Zr ₆₅ Al ₁₀ Ni ₁₀ Cu _{15 which} is a typical Zr-based metallic glass, 652 K (Y. Kawamura, T. Shibata, and A. Inoue, Appl. Phys. Lett. 71, 779
(1997)].

In order to prevent nanowire surface oxidation and maintain hot filament, the chamber atmosphere is preferably a vacuum of 10 ⁻⁸ Torr or less. Although stress in the range of 17 to 243 mN was applied to the lower end of the ribbon sample, the stress dependence in nanowire generation could not be confirmed. Therefore, the stress may be sufficient to give an arrangement that allows the ribbon-like sample to make vertical contact with the filament.

The technology of the present invention has the following applicability in the industry.
Bulk metallic glass exhibits high tensile strength, large elastic limit, large fracture strength, high toughness, low Young's modulus, and corrosion resistance, so nanostructures that have inherited these properties are MEMS and nanoelectromechanical systems (NEMS) It is a material that becomes the axis of For example, Zr-based metallic glass nanowires are pressure sensors, precision engineering equipment parts, and industrial small size. Applications to industrial equipment including high-performance devices, industrial robots, and micro / nano factories are also possible.

A technology that utilizes Mg or Pd amorphous alloy having hydrogen storage properties as a hydrogen sensitive member in a hydrogen sensor is disclosed (Japanese Patent Laid-Open No. 2005-256028). If Pd-based metallic glass nanowires are used as the sensor for the hydrogen sensor, high sensitivity, trace hydrogen concentration measurement, and miniaturization can be expected, contributing to the safe use of hydrogen energy. The application of a hydrogen generator utilizing hydrogen catalysis with high Pd is also conceivable.

An amorphous sputtered film composed of Fe, Ni, and Co has been reported as a highly sensitive magneto-impedance element (Japanese Patent Laid-Open No. 2000-292506). Fe-based metallic glass has soft magnetic properties as a similar magnetic sensor, and if nanowires are made of this material, it can be expected to be applied to ultra-high sensitivity and ultra-small magnetic sensors. Furthermore, since the Au-based metallic glass nanowire has an Au alloy ratio of about 50%, high conductivity can be expected, and application as a lead wire in wire bonding on a nano-sized semiconductor device can be expected.

  In addition to the above micromachines, semiconductors, precision electronic components, and sensor components, it is expected to be used in a wide range of fields such as biomaterials that utilize the characteristics of metallic glass. It is clear that the present invention can be carried out in addition to the alloy compositions specifically described in the examples, and the elastic deformation region is wide due to the fact that the nanowire retains the low Young's modulus characteristics, and flexible deformation is possible.

The metallic glass nanowires produced by the present invention make use of the excellent properties of metallic glass, for example, excellent mechanical strength, corrosion resistance, surface smoothness, precision castability, superplasticity, etc. Applicable for applications such as solenoid valves, magnetic sensors, pressure sensors, medical equipment such as endoscopes, rotabrators, thrombus suction catheters, precision engineering equipment, industrial equipment including industrial small and high performance devices, inspection robots Applications to industrial robots and micro factories are also expected. The metallic glass nanowires of the present invention include the fields that make use of the characteristics of the metallic glass, the fields of micromachines, semiconductors and precision electronic parts, and electrode materials, motor materials, nanoelectronic materials, nanomedical devices, nanosensors, optical It is useful as a material and is expected to be used in a wide range of fields such as medical devices, nanotechnology applied devices, magnetic materials, and electronic devices including magnetic materials, semiconductor wiring, and electrode materials.
It will be apparent that the invention may be practiced otherwise than as particularly described in the foregoing description and examples. Many modifications and variations of the present invention are possible in light of the above teachings, and thus are within the scope of the claims appended hereto.

Claims (7)

A metallic glass nanowire, characterized in that it is composed of metallic glass, is nano-sized with at least one dimension of 1000 nm or less , and has a total length of 0.5 mm or more.   The metal glass nanowire according to claim 1, wherein the diameter is 1000 nm or less.   The metal glass nanowire according to claim 1, wherein the diameter is 100 nm or less. A manufacturing method for manufacturing the metallic glass nanowire according to any one of claims 1 to 3,
Ribbon-shaped or rod-shaped metallic glass is fixed at the end up and down and the lower end can be pulled, and in an atmosphere where oxidation can be prevented, the lower end is pulled,
(a) bringing the movable heat-heating filament into contact with the ribbon-shaped or rod-shaped metallic glass sample vertically;
(b) the electrode is fixed turning off the power energized just before breaking the upper and lower ends, or
(c) laser heating the ribbon-shaped or rod-shaped metal glass sample,
The metal glass is rapidly heated to the supercooled liquid region and the formed metal glass nanowire is rapidly cooled to maintain the metal glass state of the nanowire. A method for producing a metallic glass nanowire according to claim 1, wherein the metallic glass nanowire is produced.   The manufacturing method according to claim 4, wherein the atmosphere capable of preventing oxidation is a vacuum. A manufacturing apparatus for manufacturing the metallic glass nanowire according to any one of claims 1 to 3,
A casing that achieves an atmosphere that can prevent oxidation of the metal glass sample, at least two fixtures that are arranged in the casing and fix the ribbon-shaped or rod-shaped metal glass up and down at the end, and fixing the lower end Load applying device for towing the tool,
(a) a movable thermal heating filament that can be brought into perpendicular contact with the ribbon-shaped or rod-shaped metallic glass sample;
(b) an electrode fixed to the fixture at the upper and lower ends of the sample and capable of energization and de-energization, or
(c) provided with any one of lasers capable of heating the ribbon-shaped or rod-shaped metal glass sample, rapidly heating the metal glass to a supercooled liquid region, and rapidly cooling the formed metal glass nanowire, thereby The metal glass nanowire production apparatus according to any one of claims 1 to 3, wherein the metal glass nanowire according to any one of claims 1 to 3 can be produced by maintaining the state of the metal glass.   The manufacturing apparatus according to claim 6, wherein the atmosphere capable of preventing oxidation is a vacuum.