WO2022204168A1 - Metallic glass materials and methods of making the same - Google Patents

Metallic glass materials and methods of making the same Download PDF

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Publication number
WO2022204168A1
WO2022204168A1 PCT/US2022/021372 US2022021372W WO2022204168A1 WO 2022204168 A1 WO2022204168 A1 WO 2022204168A1 US 2022021372 W US2022021372 W US 2022021372W WO 2022204168 A1 WO2022204168 A1 WO 2022204168A1
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WIPO (PCT)
Prior art keywords
substrate
homogeneous mixture
metals
heating
group
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PCT/US2022/021372
Other languages
French (fr)
Inventor
Liangbing Hu
Yonggang Yao
Qi DONG
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University Of Maryland, College Park
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Publication of WO2022204168A1 publication Critical patent/WO2022204168A1/en

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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C45/00Amorphous alloys
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05Metallic powder characterised by the size or surface area of the particles
    • B22F1/054Nanosized particles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00Making metallic powder or suspensions thereof
    • B22F9/16Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00Making metallic powder or suspensions thereof
    • B22F9/16Making metallic powder or suspensions thereof using chemical processes
    • B22F9/30Making metallic powder or suspensions thereof using chemical processes with decomposition of metal compounds, e.g. by pyrolysis
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/11Making amorphous alloys
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2999/00Aspects linked to processes or compositions used in powder metallurgy

Definitions

  • the present disclosure relates generally to multi-element materials, and more particularly, to metallic glass materials (e.g., nanoparticles or bulk materials) and methods for forming such metallic glass materials.
  • metallic glass materials e.g., nanoparticles or bulk materials
  • Amorphous materials have been used for window glass, solar cells, telecommunications, and structure materials among many other diverse applications. While conventional fabrication techniques have produced metallic glass materials, nanoscale amorphous materials are rare, due in part to the lack of effective methods for inducing glass formation at the nanoscale. In such conventional techniques, rapid quenching from a high temperature melt is used to avoid crystallization. Yet at the nanoscale, achieving rapid quenching is challenging. In prior attempts, electrodeposition methods (e.g., on the microsecond time scale) was used to induce glass formation; however, only amorphous oxides could be obtained. In other prior attempts, wet- chemical approaches were used to induce glass formation, but only amorphous phosphides could be obtained.
  • Embodiments of the disclosed subject matter system provide metallic glass materials, for example, metallic glass nanoparticles.
  • the metallic glass material can be formed of multiple metals (e.g., at least two) combined together in a homogeneous solid mixture exhibiting an amorphous or substantially amorphous (e.g., with limited or no medium-range order) structure.
  • the metallic glass materials can be formed by subjecting precursor materials to a thermal shock, for example, a short duration (e.g., ⁇ 10 s, such as ⁇ 1 s), high- temperature (e.g., > 1000 K, such as about 2000 K) heating pulse followed by rapid quenching.
  • a thermal shock for example, a short duration (e.g., ⁇ 10 s, such as ⁇ 1 s), high- temperature (e.g., > 1000 K, such as about 2000 K) heating pulse followed by rapid quenching.
  • the rapid quenching after the heating pulse is done at a sufficiently high cooling rate (e.g., an absolute value of the cooling rate is greater than or equal to 10 4 K/s, such as > 10 5 K/s, or even > 10 6 K/s) that the time for cooling (e.g., to a temperature less than a melting temperature of one, some, or all of the metals of the precursors) is at least an order of magnitude less (e.g., at least two orders of magnitude less) than a diffusion timescale for the metal atoms (or other components forming the ultimate material).
  • a sufficiently high cooling rate e.g., an absolute value of the cooling rate is greater than or equal to 10 4 K/s, such as > 10 5 K/s, or even > 10 6 K/s
  • the time for cooling e.g., to a temperature less than a melting temperature of one, some, or all of the metals of the precursors
  • the time for cooling e.g., to a temperature less than a melting temperature of one,
  • a method can comprise loading a plurality of precursors onto a substrate.
  • the plurality of precursors can comprise metal salts of at least two different metals.
  • the method can further comprise heating the loaded substrate at a heating rate to a first temperature and maintaining the loaded substrate at the first temperature for a first time.
  • the method can also comprise, after the first time, cooling the substrate from the first temperature at a cooling rate such that a metallic glass material is formed on the substrate.
  • the metallic glass material can comprise a homogeneous mixture of the at least two different metals and forming a single amorphous solid.
  • a structure can comprise a metallic glass material comprising a homogeneous mixture of at least two metals and forming a single amorphous solid.
  • FIG. 1 is an exemplary process flow diagram of a method for fabricating a metallic glass material, according to one or more embodiments of the disclosed subject matter.
  • FIG. 2 is a graph of an exemplary temperature profile for forming a metallic glass material, according to one or more embodiments of the disclosed subject matter.
  • FIG. 3 A is a simplified schematic diagram of an exemplary configuration for fabricating metallic glass materials via conduction heating, according to one or more embodiments of the disclosed subject matter.
  • FIG. 3B is a simplified schematic diagram of an exemplary configuration for fabricating metallic glass materials via radiative heating, according to one or more embodiments of the disclosed subject matter.
  • FIG. 3C is a simplified schematic diagram of an exemplary configuration for fabricating metallic glass materials employing active cooling via directed gas flow, according to one or more embodiments of the disclosed subject matter.
  • FIG. 3D is a simplified schematic diagram of an exemplary configuration for fabricating metallic glass materials employing active cooling via a working fluid flow, according to one or more embodiments of the disclosed subject matter.
  • FIG. 4 illustrates a computing environment in which the disclosed technologies may be implemented.
  • FIG. 5A is an image of a fabricated metallic glass nanoparticle.
  • FIG. 5B illustrates average two-dimensional power spectrum of multiple experimental images of fabricated metallic glass nanoparticles.
  • FIGS. 5C-5D are 4- ⁇ thick slices of a three-dimensional reconstruction in the x-y plane and y-z plane, respectively, of a fabricated metallic glass nanoparticle.
  • FIG. 6A illustrates a three-dimensional model of a fabricated metallic glass nanoparticle.
  • FIG. 6B is a graph of local bond orientational order (BOO) parameters of atoms in a fabricated metallic glass nanoparticle.
  • FIG. 6C is a graph of pair distribution function (PDF) of disordered atoms in a fabricated metallic glass nanoparticle.
  • PDF pair distribution function
  • FIG. 6D is a graph of partial PDFs between types 1, 2, and 3 atoms.
  • FIG. 7A is a graph illustrating the ten most abundant Voronoi polyhedra in a fabricated metallic glass nanoparticle.
  • FIG. 7B illustrates six representative Voronoi polyhedra.
  • FIG. 7C illustrates distribution of 3-, 4-, 5-, and 6-edged polyhedral faces of the Voronoi polyhedra in a fabricated metallic glass nanoparticle.
  • FIG. 7D illustrates distribution of coordination numbers for types 1, 2, and 3 atoms.
  • FIG. 8A illustrates representative pairs of solute-centered clusters connected with each other by sharing one, two, three, four, and five atoms.
  • FIG. 8B illustrates statistical distribution of the number of solute-centered cluster pairs in a fabricated metallic glass nanoparticle.
  • FIG. 8C is a histogram of four types of medium-range orders (MROs) as a function of size, with the inset illustrating the fraction of solute center atoms in the four types of MROs.
  • MROs medium-range orders
  • FIG. 8D shows the distribution of four types of MROs with eight solute center atoms or more.
  • FIGS. 9A-9B illustrate the distribution of the four types of MROs with respect to length and volume, respectively.
  • FIG. 9C illustrates partial PDFs of the fcc-like, hcp-like, bcc-like, and sc-like solute centers in a fabricated metallic glass nanoparticle.
  • FIG. 9D illustrates distribution of sharing one, two, three, four, and five atoms between neighboring solute-centered clusters for the four types of MROs.
  • FIG. 10A is a graph of average and maximum temperatures measured during fabrication of metallic glass nanoparticles.
  • FIG. 10B shows an energy-dispersive X-ray spectroscopy (EDS) spectrum for the elements of Ni, Co, Ru, Rh, Pd, Ag, Ir, and Pt in a fabricated metallic glass nanoparticle.
  • EDS energy-dispersive X-ray spectroscopy
  • Thermal shock Application of a sintering temperature for a time period having a duration less than about 10 seconds.
  • the duration of the time period of sintering temperature application is in a range of about 1 microsecond to about 10 seconds, inclusive, for example, about 55 milliseconds.
  • Sintering temperature A maximum temperature at a surface of a heating element when energized (e.g., by application of a current pulse) and/or at a surface of a material being sintered.
  • the sintering temperature is at least about 1000 K, for example, in a range of about 1000 K to about 3000 K.
  • a temperature at a material being sintered (e.g., precursors on a substrate) within the furnace can match or substantially match (e.g., within 10%) the temperature of the heating element.
  • Particle size A maximum cross-sectional dimension (e.g., diameter) of one or more particles.
  • an identified particle size represents an average particle size for all particles (e.g., an average of the maximum cross-sectional dimensions).
  • the particle size can be measured according to one or more known standards, such as, but not limited to, ASTM B214-16 entitled “Standard Test Method for Sieve Analysis of Metal Powders,” ASTM B330-20 entitled “Standard Test Methods for Estimating Average Particle Size of Metal Powders and Related Compounds Using Air Permeability,” ASTM B822- 20 entitled “Standard Test Method for Particle Size Distribution of Metal Powders and Related Compounds by Light Scattering,” and ASTM B922-20 entitled “Standard Test Method for Metal Powder Specific Surface Area by Physical Adsorption,” all of which are incorporated by reference herein.
  • Nanoparticle A particle composed of at least two different elements and having a particle size less than or equal to about 1 pm. In some embodiments, each nanoparticle has a size of about 100 nm or less, for example, about 25 nm or less.
  • Metal Includes those individual chemical elements classified as metals on the periodic table, including alkali metals, alkaline earth metals, transition metals, lanthanides, and actinides, as well as alloys formed from such metals.
  • Metallic glass A solid alloy formed by a mixture of at least two metals that having a disordered atomic-scale structure, e.g., amorphous or substantially amorphous (e.g., without long-range order) as opposed to crystalline.
  • the alloy is formed as a nanoparticle having only short-range order (e.g., order over no more than two atom spacings).
  • the alloy is formed as a nanoparticle having one or more portions with medium-range order (e.g., in a range of 0.5-5 nm, inclusive) but without exhibiting long-range order across the nanoparticle.
  • the terms metallic glass, amorphous metal, and glass forming multi-element have been used interchangeably herein.
  • Standard molar entropy The entropy content of one mole of pure substance at normal temperature and pressure (e.g., 298 K, 1 atm).
  • the metallic glass materials can be formed using a thermal shock fabrication, where very high temperatures (e.g., at least 1000 K, such as in a range of 1000-3000 K) are achieved over a short duration (e.g., ⁇ 10 s, such as ⁇ 1 s, for example, ⁇ 100 ms, such as ⁇ 55 ms) with rapid ramping to/from temperature (e.g., at least 10 3 K/s).
  • very high temperatures e.g., at least 1000 K, such as in a range of 1000-3000 K
  • ⁇ 10 s such as ⁇ 1 s
  • ⁇ 100 ms such as ⁇ 55 ms
  • rapid ramping to/from temperature e.g., at least 10 3 K/s.
  • rapid quenching after heating is performed at a sufficiently high cooling rate (e.g., an absolute value of the cooling rate is greater than or equal to 10 4 K/s, such as > 10 5 K/s, or even > 10 6 K/s) that the time for cooling (e.g., to a temperature less than a melting temperature of one, some, or all of the metals of the precursors) is at least an order of magnitude less (e.g., at least two orders of magnitude less) than a diffusion timescale for the metal atoms (or other components forming the ultimate material).
  • the rapid quenching can be fast enough to avoid crystallization (or at least minimize large scale crystallization) during solidification of the component elements.
  • the rapid quenching may be achieved by providing passive cooling features, active cooling features, or both.
  • the metallic glass material e.g., nanoparticle
  • the metallic glass material can be formed of a homogeneous mixture of multiple metals (e.g., at least 2, such as 3 or more, for example, 7-8 different elements) that form a single amorphous solid (e.g., exhibiting only short-range order, or alternatively areas having no more than medium-range order).
  • each of the component elements of the metallic glass have a standard molar entropy (e.g., as measured in J/mol-K) that differs from an average of standard molar entropies for all of the component elements by no more than 20%.
  • each of the component elements of the metallic glass have a standard molar entropy that is in a range of 25-45 J/mol-K, inclusive (e.g., in a range of 29-43 J/mol-K).
  • one, some, or all of the component elements of the metallic glass are transition metals, for example, selected from Groups 8-12 of the periodic table (e.g., an element in any of Groups 8-11).
  • the component elements of the metallic glass comprise Co, Ni, Ru, Rh, Pd, Ag, Ir, Pt, Zr, Cu, Fe,
  • the metallic glass may comprise 8 elements, for example, a CoNiRuRhPdAglrPt nanoparticle or a (PdPt)4o(CuZn)3o(FeCoNi)ioP2o nanoparticle.
  • Embodiments of the disclosed subject matter are not limited to the above noted compositions for the metallic glass. Rather, according to the teachings of the present disclosure, metallic glass materials can be induced for many combinations of metals (and/or other elements) that have a high glass-forming ability, as long as the rapid quenching rate is faster than a critical cooling rate required for glass formation (which critical rate may depend on the material composition but may in general be at least 10 5 K/s).
  • FIG. 1 illustrates an exemplary method 100 for fabricating a metallic glass material.
  • the method 100 can initiate at process block 102, where an appropriate substrate (e.g., capable of withstanding temperatures in excess of 1000 K) is provided.
  • a carbon-based substrate can be provided, such as a substrate formed by a network of carbon nano-fibers (CNFs).
  • CNFs carbon nano-fibers
  • substrates other than carbon-based structures can be used.
  • the substrate can be formed of a metal oxide, such as but not limited to silica, zeolite, titania, or ceria.
  • the substrate can be omitted altogether, for example, where precursor materials are flowed or passed through a heating zone without otherwise being supported by a structure.
  • the provision of process block 102 can include fabrication of the carbon-based substrate from a starting material.
  • a polymer nanofiber network e.g., polyacrylonitrile
  • the method 100 can proceed to process block 104, where the provided substrate can optionally be subjected to thermal activation, which may be effective to create surface defects in the substrate, e.g., for effective nanoparticle dispersion.
  • thermal activation can be at a temperature 750 °C for 2 hours in a carbon dioxide atmosphere.
  • the method 100 can proceed to process block 106, where the substrate is loaded with one or more precursors for the elements in the mixture of the desired metallic glass material.
  • the precursors can include metal salts in solution (e.g., chloride or hydrate forms in ethanol).
  • the loading can be provided by dip coating the substrate in the precursor solution, and then drying (e.g., at room temperature). Alternatively or additionally, the loading can be via any other application method, such as, but not limited to, brushing, spraying, printing, or rolling the solution onto the substrate.
  • the loading of precursors can mirror the desired composition for the mixture of the resulting of the metallic glass material, for example, such that a desired ratio of at least two metals is attained.
  • the method 100 can proceed to subject the substrate loaded with precursors to a thermal shock process 108.
  • the systems and methods for thermal shock process can be similar to those disclosed in U.S. Publication No. 2018/0369771, entitled “Nanoparticles and systems and methods for synthesizing nanoparticles through thermal shock,” U.S. Publication No. 2019/0161840, entitled “Thermal shock synthesis of multielement nanoparticles,” International Publication No. WO 2020/236767, entitled “High temperature sintering systems and methods,” and International Publication No. WO 2020/252435, entitled “Systems and methods for high temperature synthesis of single atom dispersions and multi-atom dispersions,” all of which are incorporated by reference herein.
  • the thermal shock process 108 can be achieved by a pulsed heating profile, with (i) a rapid heating per process block 110 to a sintering temperature, (ii) a short dwell period, where the temperature is maintained at or about the sintering temperature per process block 112 until a predetermined pulse duration, ti, is reached per decision block 114, and (iii) a rapid quenching per process block 116.
  • the method 100 can proceed to terminal block 118, where the metallic glass can be used or otherwise adapted for subsequent use (e.g., by removing from the substrate).
  • the thermal shock process 108 may be performed more than once (e.g., by subjected to multiple pulsed temperature profiles).
  • FIG. 2 illustrates an exemplary pulsed temperature profile 200 for the thermal shock process 108.
  • the temperature profile 200 can provide a sintering temperature TH (e.g., at least 1000 K, such as in a range of 1000-3000 K, inclusive, for example, ⁇ 2000 K or greater) for a relatively short time period ti (e.g., less than or equal to 10 s, such as in a range of about 1 ps to 10 s, inclusive, for example, ⁇ 55 ms).
  • the high temperature can be sufficient to melt all of the constituent elements and/or induce high temperature uniform mixing.
  • the temperature profile 200 can provide a rapid transition to and/or from the high temperature TH.
  • the temperature profile 200 can exhibit a heating ramp rate RH (e.g., to high temperature TH from a low temperature TL, such as room temperature (e.g. 20-25 °C) or an elevated ambient temperature (e.g., 100-200 °C)) of at least 10 3 K/s, such as 10 4 - 10 5 K/s, inclusive.
  • RH heating ramp rate
  • the heating of process blocks 110-112 can be provided by conductive Joule heating (e.g., via the substrate or an element in thermal communication with the substrate and/or the precursors), radiative Joule heating (e.g., by a heating element spaced from the substrate and/or the precursors), microwave heating, laser heating, electron beam heating, spark discharge heating, or any other heating mechanism capable of providing the requisite heating rate and temperatures.
  • conductive Joule heating e.g., via the substrate or an element in thermal communication with the substrate and/or the precursors
  • radiative Joule heating e.g., by a heating element spaced from the substrate and/or the precursors
  • microwave heating e.g., laser heating, electron beam heating, spark discharge heating, or any other heating mechanism capable of providing the requisite heating rate and temperatures.
  • the temperature profile 200 can exhibit a cooling ramp rate Rc (e.g., to a low temperature TL from high temperature TH and/or from the high temperature TH to a melting temperature of one or more of the constituent metals) of at least 10 4 K/s, such as > 10 5 K/s or even > 10 6 K/s.
  • the rapid cooling offered by ramp rate Rc can solidify the constituent metals without otherwise allowing crystallization thereof (or at least avoiding any long-range crystallization).
  • the cooling of process block 116 can be achieved by de activating, de-energizing, or otherwise terminating the heating of process blocks 110-112.
  • the cooling of process block 116 can be achieved using one or more passive cooling features (e.g., heat sinks thermally coupled to the heating element and/or substrate, etc.), one or more active cooling features (e.g., fluid flow directed at the substrate and/or the heater, fluid flow through the substrate or a heat sink thermally coupled thereto, etc.), or any combination thereof.
  • passive cooling features e.g., heat sinks thermally coupled to the heating element and/or substrate, etc.
  • active cooling features e.g., fluid flow directed at the substrate and/or the heater, fluid flow through the substrate or a heat sink thermally coupled thereto, etc.
  • a system can be provided for forming a metallic glass material according to the method 100 of FIG. 1.
  • the system can include one or more process stations corresponding to different process blocks 102-116.
  • the system can include a coating station to load the substrate with precursors, a thermal enclosure to contain the substrate during heating, and a current source with electrical connections to the substrate to effect the desired thermal shock process.
  • the system can include a controller or control module configured to control the various components of the system to perform the method 100.
  • the thermal shock profile for forming a metallic glass material can be provided by a Joule heating element in conductive thermal communication with the precursors.
  • FIG. 3A illustrates an exemplary fabrication configuration 300 where a substrate 302 (e.g., carbon-based substrate) is used as a Joule heating element.
  • Precursors 304 can be loaded onto the substrate 302 (e.g., on one or more surfaces thereof and/or within the substrate) and a current source 306 can be electrically connected to ends of the substrate 302.
  • the substrate 302 By passing a current from the source 306 through the substrate 302, the substrate 302 can be heated so as to subject the precursors 304 to the desired sintering temperature.
  • a controller 312 can be operatively coupled to the source 306 to control operation thereof, for example, to provide the heating pulse profile 200 of FIG. 2.
  • the substrate 302 may be supported over a gap or trench 310 by heat sink portions 308a, 308b, which may help accelerate cooling when the current is removed from the substrate 302 by the current source 306.
  • the substrate can be suspended over a trench and connected to copper electrodes by silver paste, which electrodes can provide electrical contact for heating while also acting as heat sinks for more effective cooling.
  • the thermal shock profile for forming a metallic glass material can be provided by a remote heating mechanism, such as a radiative Joule heating element, a microwave source, a laser, an electron beam system, a spark discharge system, etc.
  • a remote heating mechanism such as a radiative Joule heating element, a microwave source, a laser, an electron beam system, a spark discharge system, etc.
  • FIG. 3B illustrates an exemplary fabrication configuration 320 where a substrate 322 (e.g., carbon-based substrate or metal oxide substrate) supports precursors 304 thereon but is otherwise not used to provide heating.
  • remote heating mechanism 326 can be provided in a spaced arrangement from the precursors 304 and constructed to generate a heating zone 330 subjected to the desired sintering temperature.
  • a controller 312 can be operatively coupled to the remote heating mechanism 326 to control operation thereof, for example, to provide the heating pulse profile 200 of FIG. 2.
  • the substrate 322 may be supported on a heat sink 328, which may help accelerate cooling when the heating by mechanism 326 is discontinued.
  • FIGS. 3A-3B rely on passive techniques for cooling of the substrate
  • active cooling techniques can be used in addition to or in place of passive techniques in some embodiments.
  • the active cooling techniques can include a flow of fluid directed at the substrate, the heating zone, and/or the heating mechanism.
  • FIG. 3C illustrates an exemplary fabrication configuration 340 where gas flow nozzles 344 direct a cooling gas flow 346 toward the substrate 342 and materials 304 supported thereon.
  • the cooling gas flow 346 can comprise an inert gas (e.g., nitrogen, argon, helium, neon, krypton, xenon, radon, or oganesson) at a temperature much less than the sintering temperature, for example, less than 200 °C such as at or about room temperature (e.g., 20-25 °C). In some embodiments, the cooling gas flow 346 can be cooled below room temperature.
  • a controller 348 can be operatively coupled to the remote heating mechanism 326 to control operation thereof, for example, to provide the heating pulse profile 200 of FIG. 2.
  • the controller 348 can also be operatively coupled to the gas flow nozzles 344 to control operation thereof, for example, to control a timing of the gas flow (e.g., to initiate gas flow to coincide with an end of the sintering duration, ti), a flow rate of the gas, or any other variable.
  • the active cooling techniques can include a flow of fluid through the substrate (or a structure in thermal communication therewith) for heat transfer.
  • FIG. 3D illustrates an exemplary fabrication configuration 360 where a heat transfer fluid is passed through a heat sink 364 thermally coupled to substrate 362 having materials 304 thereon.
  • the heat transfer fluid can be pumped via hydraulic pump 368 to an inlet 372 of conduit 366, where it absorbs heat from the heat sink 364 and carries the heat away via outlet 374.
  • the heat transfer fluid can comprise a liquid, such as water or a refrigerant.
  • the heat transfer fluid can be introduced at a temperature, TL, that is much less than the sintering temperature, for example, less than 200 °C such as at or about room temperature (e.g., 20-25 °C). In some embodiments, the heat transfer fluid can be cooled below room temperature.
  • a controller 370 can be operatively coupled to the remote heating mechanism 326 to control operation thereof, for example, to provide the heating pulse profile 200 of FIG. 2.
  • the controller 370 can also be operatively coupled to the pump 368 to control operation thereof, for example, to control a timing of the fluid flow (e.g., to initiate heat transfer fluid flow into inlet 372 to coincide with an end of the sintering duration, ti), a flow rate of the heat transfer fluid, or any other variable.
  • the heat transfer fluid exiting the outlet 374 can be recirculated back to the inlet 372 via pump 368 after being cooled (e.g., via a cross-flow heat exchanger).
  • the heat transfer fluid exiting the outlet 374 can be discarded (e.g., via a drain) without recirculation.
  • FIGS. 3A-3D illustrate specific configurations for fabricating metallic glass materials
  • embodiments of the disclosed subject matter are not limited thereto. Rather, other passive cooling mechanisms beyond those specifically illustrated could be used to enhance natural conduction, convection, and/or radiation to cool the materials. Alternatively or additionally, other active cooling mechanisms could be used, such as but not limited to thermoelectric cooling. Additional configurations are also possible according to one or more contemplated embodiments.
  • FIG. 4 depicts a generalized example of a suitable computing environment 431 in which the described innovations may be implemented, such as aspects of method 100, controller 312, controller 348, and/or controller 370.
  • the computing environment 431 is not intended to suggest any limitation as to scope of use or functionality, as the innovations may be implemented in diverse general-purpose or special-purpose computing systems.
  • the computing environment 431 can be any of a variety of computing devices (e.g., desktop computer, laptop computer, server computer, tablet computer, etc.).
  • the computing environment 431 includes one or more processing units 435, 437 and memory 439, 441.
  • the processing units 435, 437 execute computer-executable instructions.
  • a processing unit can be a general-purpose central processing unit (CPU), processor in an application-specific integrated circuit (ASIC) or any other type of processor.
  • ASIC application-specific integrated circuit
  • FIG. 4 shows a central processing unit 435 as well as a graphics processing unit or co-processing unit 437.
  • the tangible memory 439, 441 may be volatile memory (e.g., registers, cache, RAM), non-volatile memory (e.g., ROM, EEPROM, flash memory, etc.), or some combination of the two, accessible by the processing unit(s).
  • volatile memory e.g., registers, cache, RAM
  • non-volatile memory e.g., ROM, EEPROM, flash memory, etc.
  • the memory 439, 441 stores software 433 implementing one or more innovations described herein, in the form of computer-executable instructions suitable for execution by the processing unit(s).
  • a computing system may have additional features.
  • the computing environment 431 includes storage 461, one or more input devices 471, one or more output devices 481, and one or more communication connections 491.
  • An interconnection mechanism such as a bus, controller, or network interconnects the components of the computing environment 431.
  • operating system software provides an operating environment for other software executing in the computing environment 431, and coordinates activities of the components of the computing environment 431.
  • the tangible storage 461 may be removable or non -removable, and includes magnetic disks, magnetic tapes or cassettes, CD-ROMs, DVDs, or any other medium which can be used to store information in a non-transitory way, and which can be accessed within the computing environment 431.
  • the storage 461 can store instructions for the software 433 implementing one or more innovations described herein.
  • the input device(s) 471 may be a touch input device such as a keyboard, mouse, pen, or trackball, a voice input device, a scanning device, or another device that provides input to the computing environment 431.
  • the output device(s) 471 may be a display, printer, speaker, CD- writer, or another device that provides output from computing environment 431.
  • the communication connection(s) 491 enable communication over a communication medium to another computing entity.
  • the communication medium conveys information such as computer-executable instructions, audio or video input or output, or other data in a modulated data signal.
  • a modulated data signal is a signal that has one or more of its characteristics set or changed in such a manner as to encode information in the signal.
  • communication media can use an electrical, optical, radio-frequency (RF), or another carrier.
  • Any of the disclosed methods can be implemented as computer-executable instructions stored on one or more computer-readable storage media (e.g., one or more optical media discs, volatile memory components (such as DRAM or SRAM), or non-volatile memory components (such as flash memory or hard drives)) and executed on a computer (e.g., any commercially available computer, including smart phones or other mobile devices that include computing hardware).
  • a computer e.g., any commercially available computer, including smart phones or other mobile devices that include computing hardware.
  • the term computer-readable storage media does not include communication connections, such as signals and carrier waves.
  • Any of the computer-executable instructions for implementing the disclosed techniques as well as any data created and used during implementation of the disclosed embodiments can be stored on one or more computer-readable storage media.
  • the computer-executable instructions can be part of, for example, a dedicated software application or a software application that is accessed or downloaded via a web browser or other software application (such as a remote computing application).
  • Such software can be executed, for example, on a single local computer (e.g., any suitable commercially available computer) or in a network environment (e.g., via the Internet, a wide-area network, a local-area network, a client-server network (such as a cloud computing network), or other such network) using one or more network computers.
  • any functionality described herein can be performed, at least in part, by one or more hardware logic components, instead of software.
  • illustrative types of hardware logic components include Field-programmable Gate Arrays (FPGAs), Program-specific Integrated Circuits (ASICs), Program-specific Standard Products (ASSPs), System-on-a-chip systems (SOCs), Complex Programmable Logic Devices (CPLDs), etc.
  • any of the software-based embodiments can be uploaded, downloaded, or remotely accessed through a suitable communication means.
  • suitable communication means include, for example, the Internet, the World Wide Web, an intranet, software applications, cable (including fiber optic cable), magnetic communications, electromagnetic communications (including RF, microwave, and infrared communications), electronic communications, or other such communication means.
  • provision of a request e.g., data request
  • indication e.g., data signal
  • instruction e.g., control signal
  • any other communication between systems, components, devices, etc. can be by generation and transmission of an appropriate electrical signal by wired or wireless connections.
  • Samples were synthesized by a carbothermal shock technique with a high cooling rate, which were used to create alloyed nanoparticles of multiple metal components.
  • the multi- component metallic nanoparticle samples were synthesized using a thermal shock procedure.
  • Individual metal salts e.g., chlorides or their hydrate forms
  • the individual salt precursor solutions with different cations were mixed and sonicated for 30 minutes.
  • the homogenously mixed precursor solution was then loaded onto carbon substrates (e.g., reduced graphene oxide).
  • Each sample (e.g., substrate with mixed precursors thereon) was suspended on a trench and connected with copper electrodes by silver paste for both heating and effective cooling as a giant heat sink.
  • Thermal shock synthesis was triggered by electric Joule heating in an inert gas environment (e.g., an argon-filled glovebox) using a voltage or current source (e.g., Keithley 2425 SourceMeter), where the high temperature and duration can be effectively controlled by tuning the input power and duration.
  • the temperature of this process was monitored by a high-speed camera with a pixel size of 25 pm.
  • the samples were heated to a temperature as high as 1763 K for 55 milliseconds, as shown in FIG. 10 A.
  • the cooling rate was estimated to be ⁇ 5.1-6.9x 10 4 K/s, which can make metallic glasses.
  • the resulting metallic glass nanoparticles on the substrate were dispersed in ethanol with sonication, and subsequently deposited onto 5-nm-thick silicon nitride membranes.
  • the membranes with nanoparticles thereon were then baked at 100 °C for 12 hours in vacuum to eliminate any hydrocarbon contamination.
  • Both energy-dispersive X-ray and electron energy loss spectroscopy data show that the nanoparticles were still in metallic form and were not oxidized during the experiment.
  • the energy- dispersive X-ray spectroscopy data shows that the nanoparticles are composed of eight elements: Co, Ni, Ru, Rh, Pd, Ag, Ir, and Pt.
  • tomographic tilt series were acquired from seven nanoparticles using a scanning transmission electron microscope with an annular dark-field detector.
  • a tilt series of 55 images was acquired from particles having a disordered structure, as shown in FIG. 5 A. Although some crystalline features were present in several images, the 2D power spectra calculated from the images show the amorphous halo, as shown in FIG. 5B.
  • the tilt series was reconstructed and the 3D atomic positions were traced and classified, as shown in FIG. 5C.
  • atomic electron tomograph AET is only sensitive enough to classify the eight elements into three different types: Co and Ni as type 1, Ru, Rh, Pd and Ag as type 2, and Ir and Pt as type 3.
  • AET atomic electron tomograph
  • the 3D atomic model of the nanoparticles was obtained, in particular, 8322, 6896, and 3138 atoms for types 1, 2, and 3, respectively.
  • atom tracing, and classification procedure 55 images from the experimental atomic model were calculated using multi-slice simulations. The reconstruction, atom tracing, and classification procedure were then applied to obtain a new 3D atomic model from the 55 multi-slice images.
  • FIG. 6A shows the experimental 3D atomic model of the nanoparticle with type 1, 2, and 3 atoms.
  • BOO local bond orientational order
  • fee face-centered cubic
  • hep hexagonal close-packed
  • bcc body-centered cubic
  • FIG. 6B shows the local BOO parameters of all the atoms in the nanoparticle, indicating the majority of atoms severely deviate from the fee, hep, and bcc crystal structures.
  • the normalized BOO parameter was used to identify the crystal nuclei.
  • the criterion of the normalized BOO parameter > 0.5 15.46% of the total atoms forming crystal nuclei in the nanoparticle were identified, which crystal nuclei contributed to the crystalline features observed in several images.
  • the characteristic width of the crystalline-amorphous interface was determined to be 3.69 A in the nanoparticle, indicating that the crystal nuclei have a minimal effect on the structural disorder beyond a few angstroms.
  • the analysis focuses on disordered atoms with a normalized BOO parameter ⁇ 0.5.
  • FIG. 6C shows the pair distribution function (PDF) of the amorphous structure of the 3D atomic model.
  • PDF pair distribution function
  • the ratios of the second, third, fourth and fifth to the first peak position are 1.74, 1.99, 2.64 and 3.51, respectively.
  • the partial PDFs between types 1, 2, and 3 atoms are shown in FIG. 6D.
  • the type 11, 12, 13, 22, 23 and 33 bond lengths were determined to be 2.59, 2.71, 2.78, 2.72, 2.75 and 2.9 A, respectively.
  • the partial PDF for the type 33 pairs exhibits a unique feature with the second peak higher than the first peak, indicating that the majority of type 3 atoms are distributed beyond the short-range order (SRO).
  • Voronoi tessellation was used to characterize the local atomic arrangement. This method identifies the nearest neighbor atoms around each central atom to form a Voronoi polyhedron, which is designated by a Voronoi index ⁇ m, m, m, m> with m denoting the number of /-edged faces.
  • FIG. 7A shows the ten most abundant Voronoi polyhedra in the nanoparticle with a fraction ranging from 5.02% to 1.72%, most of which are geometrically disordered and commonly observed in model metallic glasses, such as ⁇ 0,4,4,3>, ⁇ 0,3,6,3>, ⁇ 0,4,4,2> and ⁇ 0,3,6,2> (shown in FIG. 7B).
  • model metallic glasses such as ⁇ 0,4,4,3>, ⁇ 0,3,6,3>, ⁇ 0,4,4,2> and ⁇ 0,3,6,2> (shown in FIG. 7B).
  • FIG. 7C shows the local symmetry distribution of all the faces of the Voronoi polyhedra.
  • the 3-edged, 4- edged, 5- edged, and 6-edged faces account for 3.27%, 29.14%, 43.91% and 23.67%, respectively, with the 5-edged faces being most abundant in the SRO.
  • only 7.03% of all the Voronoi polyhedra are distorted icosahedra, including Voronoi indices ⁇ 0,0,12,0>, ⁇ 0,1,10,2>, ⁇ 0,2,8,2> and ⁇ 0,2,8, 1>. This indicates that most 5-edged faces do not form distorted icosahedra in the glass-forming nanoparticle.
  • the distribution of the coordination number (CN) was also calculated, as shown in FIG. 7D, where the average CNs of types 1, 2, and 3 atoms were found to be 11.97, 12.02, and 12.41, respectively.
  • the chemical SRO was quantified using the Warren- Cowl ey parameters, indicating that the type 11 and 23 bonds are favored while the type 12 and 33 bonds are unfavored, which results are consistent with observations of the shortening of the type 11 and 23 bonds and the lengthening of the type 12 and 33 bonds.
  • MRO medium-range order
  • metallic glasses has been broadly defined as the nanometer-scale structural organization beyond the SRO
  • MRO was investigated here in the framework of the efficient cluster packing model, which hypothesizes that solute atoms are surrounded by randomly-positioned solvent atoms to form solute-centered clusters.
  • the solute- centered clusters can be densely packed to constitute crystal-like MROs in metallic glasses.
  • the partial PDF of type 33 atom pairs of FIG. 6D was analyzed. It was observed that the highest peak is at 4.77 A and 1.49 times higher than the nearest neighbor peak.
  • type 3 atoms were found to be distributed in the second coordination shell, which is between the first (3.86 A) and the second minimum (6.08 A) of the PDF curve (FIG. 6C).
  • These type 3 atoms act as solute atoms and are surrounded mainly by type 1 and 2 solvent atoms to form solute-centered clusters.
  • the solute- centered clusters connect with each other by sharing one (a vertex), two (an edge), and/or three atoms (a face), as well as protrude into each other by sharing four and five atoms, as shown in FIG. 8 A.
  • FIG. 8B shows the statistical distribution of the number of the solute-centered cluster pairs, which share from one to five atoms.
  • a breadth-first search algorithm was implemented to look for the fee-, hep-, bcc-, simple cubic (sc-) and icosahedral-like structures of the solute centers. This algorithm globally searched for the MRO with a maximum number of solute centers.
  • Each MRO was defined to have five or more solute centers with each solute center falling within a 0.75 A radius to the fee, hep, bcc, sc lattice or icosahedral vertices.
  • FIG. 8C shows the histogram of the four types of MROs as a function of the size, where the inset illustrates the fraction of the solute center atoms in the four types of MROs.
  • FIG. 8D shows a 3D distribution of MROs with each having eight solute centers or more. To verify the analysis, MROs with a 1 A and 0.5 A radius cut-off were also searched, and the coexistence of the four types of MROs with different cut-off radii was observed.
  • FIGS. 9A-9B show the length and volume distribution of the MROs in the glass-forming nanoparticle.
  • the average length of the fee-, hep-, bcc- and sc-like MROs was measured to be 2.27 ⁇ 0.50, 2.40 ⁇ 0.42,
  • the partial PDFs of all the fee-, hep-, bcc- and sc-like solute centers in the glass-forming nanoparticle and their corresponding maximum peak positions are at 4.62, 4.77, 4.82 and 3.88 A, respectively, as shown in FIG. 9C. These peak positions represent the average nearest neighbor distances of the solute centers in the four crystal-like MROs, and the broadened peaks signify the severe deviation from the crystal lattices.
  • the partial PDF of the sc-like MROs has two peaks and the ratio of the second to the first peak position is about 2 (FIG.
  • 9D shows the distribution of sharing one, two, three, four and five atoms between neighboring solute-centered clusters for the four types of MROs, confirming that the solute-centered clusters in the sc-like MROs tend to share more atoms with their neighbors than those in other types of MROs.
  • the quantitative analysis of the SRO and MRO in a multi-component glass-forming nanoparticle provides direct experimental evidence to support the general framework of the efficient cluster packing model, that is, solute-centered clusters are densely packed in some parts of the sample to form crystal-like MROs.
  • the method and analyses described herein can be extended to other sample geometries, such as but not limited to thin films or extended objects (e.g., bulk materials having at least one dimension greater than or equal to 1 mm).
  • a method comprising: heating a plurality of precursors at a heating rate to a first temperature, the plurality of precursors comprising metal salts of at least two different metals; maintaining the plurality of precursors at the first temperature for a first time; and after the first time, cooling from the first temperature at a cooling rate such that a metallic glass material is formed, wherein the metallic glass material comprises a homogeneous mixture of the at least two different metals and forming a single amorphous solid.
  • a method comprising: loading a plurality of precursors onto a substrate, the plurality of precursors comprising metal salts of at least two different metals; heating the loaded substrate at a heating rate to a first temperature; maintaining the loaded substrate at the first temperature for a first time; and after the first time, cooling the substrate from the first temperature at a cooling rate such that a metallic glass material is formed on the substrate, wherein the metallic glass material comprises a homogeneous mixture of the at least two different metals and forming a single amorphous solid.
  • a duration of the cooling is at least ten times less than timescales of diffusion of atoms of the at least two different metals in the homogeneous mixture.
  • cooling at the cooling rate is from the first temperature to a second temperature that is less than melting temperatures of the at least two different metals.
  • cooling rate is at least 10 4 K/s.
  • cooling rate is at least 10 5 K/s.
  • cooling rate is at least 10 6 K/s.
  • each metal salt comprises a chloride or hydrate form of the respective metal.
  • the heating rate is at least 10 3 K/s; the first time is in a range of about 1 ps to about 10 s, inclusive; the first temperature is in a range of about 1000 K to about 3000 K, inclusive; or any combination of the above.
  • the heating rate is at least 10 4 K/s; the first time is about 55 ms; the first temperature is about 2000 K or greater; or any combination of the above.
  • Clause 11 The method of any clause or example herein, in particular, any one of Clauses 2-
  • the loading comprises coating the substrate in a solution of the precursor metal salts and subsequently drying the coated substrate.
  • the substrate comprises a carbon-based structure.
  • the substrate comprises a plurality of carbon nanofibers.
  • heating comprises providing an electric current to the substrate so as to cause Joule heating.
  • heating comprises Joule heating, radiative heating, microwave heating, laser heating, electron beam heating, spark discharge heating, or any combination of the foregoing.
  • the metallic glass material is formed as a metallic glass nanoparticle.
  • each of the at least two different metals has a standard molar entropy measured in J/mol-K that differs from an average of standard molar entropies for all of the least two different metals by no more than 20%.
  • each of the at least two different metals has a standard molar entropy that is in a range of 25-45 J/mol-K, inclusive.
  • each of the at least two different metals has a standard molar entropy that is in a range of 29-43 J/mol-K, inclusive.
  • the at least two different metals are selected from a group consisting of Group 8-11 transition metals.
  • the homogeneous mixture comprises Co, Ni, Ru, Rh, Pd, Ag, Ir, Pt, Zr, Cu, Fe, Al, Mg, Ti, Zn, P, or any combination of the foregoing.
  • the at least two different metals are selected from a group consisting of Co, Ni, Ru, Rh, Pd, Ag, Ir, and Pt.
  • the homogeneous mixture is composed of at least seven metals.
  • the homogeneous mixture is composed of Co, Ni, Ru, Rh, Pd, Ag, Ir, and Pt.
  • Clause 27 The method of any clause or example herein, in particular, any one of Clauses 1- 25, wherein the homogeneous mixture is composed of Pd, Pt, Cu, Zn, Fe, Co, Ni, and P.
  • Clause 28 The method of any clause or example herein, in particular, Clause 27, wherein the homogeneous mixture satisfies a chemical formula of (PdPt)4o(CuZn)3o(FeCoNi)ioP2o.
  • Clause 29 The method of any clause or example herein, in particular, any one of Clauses 1- 28, wherein the homogeneous mixture exhibits no more than short-range order.
  • Clause 30 A structure formed by the method of any clause or example herein, in particular, any one of Clauses 1-29.
  • a structure comprising: a metallic glass material comprising a homogeneous mixture of at least two metals and forming a single amorphous solid.
  • Clause 32 The structure of any clause or example herein, in particular, any one of Clauses 30-31, wherein the metallic glass material is formed as a metallic glass nanoparticle.
  • Clause 33 The structure of any clause or example herein, in particular, any one of Clauses 30-32, wherein each element in the homogeneous mixture has a standard molar entropy measured in J/mol-K that differs from an average of standard molar entropies for all elements in the homogeneous mixture by no more than 20%.
  • Clause 34 The structure of any clause or example herein, in particular, any one of Clauses 30-33, wherein each element in the homogeneous mixture has a standard molar entropy that is in a range of 25-45 J/mol-K, inclusive.
  • Clause 35 The structure of any clause or example herein, in particular, any one of Clauses 30-34, wherein each element in the homogeneous mixture has a standard molar entropy that is in a range of 29-43 J/mol-K, inclusive.
  • Clause 36 The structure of any clause or example herein, in particular, any one of Clauses 30-35, wherein the at least two metals are transition metals.
  • Clause 37 The structure of any clause or example herein, in particular, any one of Clauses 30-36, wherein the homogeneous mixture comprises a Group 8 transition metal, a Group 9 transition metal, a Group 10 transitional metal, a Group 11 transition metal, a Group 12 transition metal, or any combination of the foregoing.
  • Clause 38 The structure of any clause or example herein, in particular, any one of Clauses 30-37, wherein the at least two metals are selected from a group consisting of Group 8-11 transition metals.
  • Clause 39 The structure of any clause or example herein, in particular, any one of Clauses 30-38, wherein the homogeneous mixture comprises Co, Ni, Ru, Rh, Pd, Ag, Ir, Pt, Zr, Cu, Fe, Al, Mg, Ti, Zn, P, or any combination of the foregoing.
  • Clause 40 The structure of any clause or example herein, in particular, any one of Clauses 30-39, wherein the at least two metals are selected from a group consisting of Co, Ni, Ru, Rh,
  • Clause 41 The structure of any clause or example herein, in particular, any one of Clauses 30-40, wherein the homogeneous mixture is composed of at least seven metals.
  • Clause 42 The structure of any clause or example herein, in particular, any one of Clauses 30-41, wherein the homogeneous mixture is composed of Co, Ni, Ru, Rh, Pd, Ag, Ir, and Pt.
  • Clause 43 The structure of any clause or example herein, in particular, any one of Clauses 30-41, wherein the homogeneous mixture is composed of Pd, Pt, Cu, Zn, Fe, Co, Ni, and P.
  • Clause 44 The structure of any clause or example herein, in particular, Clause 43, wherein the homogeneous mixture satisfies a chemical formula of (PdPt)4o(CuZn)3o(FeCoNi)ioP2o.
  • Clause 45 The structure of any clause or example herein, in particular, any one of Clauses 30-44, wherein the homogeneous mixture exhibits no more than short-range order.
  • Clause 46 The structure of any clause or example herein, in particular, any one of Clauses 30-45, further comprising a substrate supporting the metallic glass material thereon.
  • Clause 47 The structure of any clause or example herein, in particular, any one of Clauses 30-46, wherein the substrate is a carbon-based substrate.
  • Clause 48 The structure of any clause or example herein, in particular, any one of Clauses 30-47, wherein the substrate comprises a plurality of carbon nanofibers.
  • Clause 49 The structure of any clause or example herein, in particular, any one of Clauses 30-48, wherein the substrate comprises a metal oxide.
  • Clause 50 The structure of any clause or example herein, in particular, any one of Clauses 30-49, wherein the substrate comprises silica, zeolite, titania, ceria, or any combination of the foregoing.
  • any of the features illustrated or described herein, for example, with respect to FIGS. 1- 10B and Clauses 1-50, can be combined with any other feature illustrated or described herein, for example, with respect to FIGS. 1-lOB and Clauses 1-50 to provide systems, devices, materials, structures, methods, and embodiments not otherwise illustrated or specifically described herein.
  • any or both of the active cooling features of FIGS. 3C-3D can be combined with any or both of the passive cooling features of FIGS. 3A-3B.
  • the remote heating mechanism of FIGS. 3B-3D can be combined with the conductive Joule heating mechanism of FIG. 3A, e.g., to provide simultaneous conductive and remote heating.
  • Other combinations and variations are also possible according to one or more contemplated embodiments. Indeed, all features described herein are independent of one another and, except where structurally impossible, can be used in combination with any other feature described herein.

Abstract

Precursor metal salts of at least two different metals can be loaded onto a substrate. The substrate can be heated at a heating rate to a first temperature, and then maintained at the first temperature for a first time. The first temperature can be in a range of 1000-3000 K, and the first time can be in a range of 1 µs – 10 s. After the first time, the substrate can be cooled from the first temperature at a cooling rate, such that a metallic glass material is formed on the substrate. The metallic glass material can comprise a homogeneous mixture of the at least two different metals and forming a single amorphous solid.

Description

METALLIC GLASS MATERIALS AND METHODS OF MAKING THE SAME
CROSS-REFERENCE TO RELATED APPLICATIONS
The present application claims the benefit of U.S. Provisional Application No. 63/164,425, filed March 22, 2021, entitled “Metallic Glass Nanoparticles and Methods of Making the Same,” which is incorporated by reference herein in its entirety.
FIELD
The present disclosure relates generally to multi-element materials, and more particularly, to metallic glass materials (e.g., nanoparticles or bulk materials) and methods for forming such metallic glass materials.
BACKGROUND
Amorphous materials have been used for window glass, solar cells, telecommunications, and structure materials among many other diverse applications. While conventional fabrication techniques have produced metallic glass materials, nanoscale amorphous materials are rare, due in part to the lack of effective methods for inducing glass formation at the nanoscale. In such conventional techniques, rapid quenching from a high temperature melt is used to avoid crystallization. Yet at the nanoscale, achieving rapid quenching is challenging. In prior attempts, electrodeposition methods (e.g., on the microsecond time scale) was used to induce glass formation; however, only amorphous oxides could be obtained. In other prior attempts, wet- chemical approaches were used to induce glass formation, but only amorphous phosphides could be obtained. Accordingly, prior fabrication methods have not been able to produce metallic glass materials, for example, materials on the nanoscale (e.g., nanoparticles). Nor has there been presented a technique that can be universally applied to achieve amorphous materials of different compositions. Embodiments of the disclosed subject matter may address one or more of the above-noted problems and disadvantages, among other things.
SUMMARY
Embodiments of the disclosed subject matter system provide metallic glass materials, for example, metallic glass nanoparticles. The metallic glass material can be formed of multiple metals (e.g., at least two) combined together in a homogeneous solid mixture exhibiting an amorphous or substantially amorphous (e.g., with limited or no medium-range order) structure.
In some embodiments, the metallic glass materials can be formed by subjecting precursor materials to a thermal shock, for example, a short duration (e.g., < 10 s, such as < 1 s), high- temperature (e.g., > 1000 K, such as about 2000 K) heating pulse followed by rapid quenching. In some embodiments, the rapid quenching after the heating pulse is done at a sufficiently high cooling rate (e.g., an absolute value of the cooling rate is greater than or equal to 104 K/s, such as > 105 K/s, or even > 106 K/s) that the time for cooling (e.g., to a temperature less than a melting temperature of one, some, or all of the metals of the precursors) is at least an order of magnitude less (e.g., at least two orders of magnitude less) than a diffusion timescale for the metal atoms (or other components forming the ultimate material).
In one or more embodiments, a method can comprise loading a plurality of precursors onto a substrate. The plurality of precursors can comprise metal salts of at least two different metals. The method can further comprise heating the loaded substrate at a heating rate to a first temperature and maintaining the loaded substrate at the first temperature for a first time. The method can also comprise, after the first time, cooling the substrate from the first temperature at a cooling rate such that a metallic glass material is formed on the substrate. The metallic glass material can comprise a homogeneous mixture of the at least two different metals and forming a single amorphous solid.
In one or more embodiments, a structure can comprise a metallic glass material comprising a homogeneous mixture of at least two metals and forming a single amorphous solid.
Any of the various innovations of this disclosure can be used in combination or separately. This summary is provided to introduce a selection of concepts in a simplified form that are further described below in the detailed description. This summary is not intended to identify key features or essential features of the claimed subject matter, nor is it intended to be used to limit the scope of the claimed subject matter. The foregoing and other objects, features, and advantages of the disclosed technology will become more apparent from the following detailed description, which proceeds with reference to the accompanying figures.
BRIEF DESCRIPTION OF THE DRAWINGS
Embodiments will hereinafter be described with reference to the accompanying drawings, which have not necessarily been drawn to scale. Where applicable, some elements may be simplified or otherwise not illustrated in order to assist in the illustration and description of underlying features. Throughout the figures, like reference numerals denote like elements.
FIG. 1 is an exemplary process flow diagram of a method for fabricating a metallic glass material, according to one or more embodiments of the disclosed subject matter.
FIG. 2 is a graph of an exemplary temperature profile for forming a metallic glass material, according to one or more embodiments of the disclosed subject matter. FIG. 3 A is a simplified schematic diagram of an exemplary configuration for fabricating metallic glass materials via conduction heating, according to one or more embodiments of the disclosed subject matter.
FIG. 3B is a simplified schematic diagram of an exemplary configuration for fabricating metallic glass materials via radiative heating, according to one or more embodiments of the disclosed subject matter.
FIG. 3C is a simplified schematic diagram of an exemplary configuration for fabricating metallic glass materials employing active cooling via directed gas flow, according to one or more embodiments of the disclosed subject matter.
FIG. 3D is a simplified schematic diagram of an exemplary configuration for fabricating metallic glass materials employing active cooling via a working fluid flow, according to one or more embodiments of the disclosed subject matter.
FIG. 4 illustrates a computing environment in which the disclosed technologies may be implemented.
FIG. 5A is an image of a fabricated metallic glass nanoparticle.
FIG. 5B illustrates average two-dimensional power spectrum of multiple experimental images of fabricated metallic glass nanoparticles.
FIGS. 5C-5D are 4-Ά thick slices of a three-dimensional reconstruction in the x-y plane and y-z plane, respectively, of a fabricated metallic glass nanoparticle.
FIG. 6A illustrates a three-dimensional model of a fabricated metallic glass nanoparticle.
FIG. 6B is a graph of local bond orientational order (BOO) parameters of atoms in a fabricated metallic glass nanoparticle.
FIG. 6C is a graph of pair distribution function (PDF) of disordered atoms in a fabricated metallic glass nanoparticle.
FIG. 6D is a graph of partial PDFs between types 1, 2, and 3 atoms.
FIG. 7A is a graph illustrating the ten most abundant Voronoi polyhedra in a fabricated metallic glass nanoparticle.
FIG. 7B illustrates six representative Voronoi polyhedra.
FIG. 7C illustrates distribution of 3-, 4-, 5-, and 6-edged polyhedral faces of the Voronoi polyhedra in a fabricated metallic glass nanoparticle.
FIG. 7D illustrates distribution of coordination numbers for types 1, 2, and 3 atoms.
FIG. 8A illustrates representative pairs of solute-centered clusters connected with each other by sharing one, two, three, four, and five atoms. FIG. 8B illustrates statistical distribution of the number of solute-centered cluster pairs in a fabricated metallic glass nanoparticle.
FIG. 8C is a histogram of four types of medium-range orders (MROs) as a function of size, with the inset illustrating the fraction of solute center atoms in the four types of MROs.
FIG. 8D shows the distribution of four types of MROs with eight solute center atoms or more.
FIGS. 9A-9B illustrate the distribution of the four types of MROs with respect to length and volume, respectively.
FIG. 9C illustrates partial PDFs of the fcc-like, hcp-like, bcc-like, and sc-like solute centers in a fabricated metallic glass nanoparticle.
FIG. 9D illustrates distribution of sharing one, two, three, four, and five atoms between neighboring solute-centered clusters for the four types of MROs.
FIG. 10A is a graph of average and maximum temperatures measured during fabrication of metallic glass nanoparticles.
FIG. 10B shows an energy-dispersive X-ray spectroscopy (EDS) spectrum for the elements of Ni, Co, Ru, Rh, Pd, Ag, Ir, and Pt in a fabricated metallic glass nanoparticle.
DETAILED DESCRIPTION
General Considerations
For purposes of this description, certain aspects, advantages, and novel features of the embodiments of this disclosure are described herein. The disclosed methods and systems should not be construed as being limiting in any way. Instead, the present disclosure is directed toward all novel and nonobvious features and aspects of the various disclosed embodiments, alone and in various combinations and sub-combinations with one another. The methods and systems are not limited to any specific aspect or feature or combination thereof, nor do the disclosed embodiments require that any one or more specific advantages be present, or problems be solved. The technologies from any embodiment or example can be combined with the technologies described in any one or more of the other embodiments or examples. In view of the many possible embodiments to which the principles of the disclosed technology may be applied, it should be recognized that the illustrated embodiments are exemplary only and should not be taken as limiting the scope of the disclosed technology.
Although the operations of some of the disclosed methods are described in a particular, sequential order for convenient presentation, it should be understood that this manner of description encompasses rearrangement, unless a particular ordering is required by specific language set forth below. For example, operations described sequentially may in some cases be rearranged or performed concurrently. Moreover, for the sake of simplicity, the attached figures may not show the various ways in which the disclosed methods can be used in conjunction with other methods. Additionally, the description sometimes uses terms like “provide” or “achieve” to describe the disclosed methods. These terms are high-level abstractions of the actual operations that are performed. The actual operations that correspond to these terms may vary depending on the particular implementation and are readily discernible by one skilled in the art.
The disclosure of numerical ranges should be understood as referring to each discrete point within the range, inclusive of endpoints, unless otherwise noted. Unless otherwise indicated, all numbers expressing quantities of components, molecular weights, percentages, temperatures, times, and so forth, as used in the specification or claims are to be understood as being modified by the term “about.” Accordingly, unless otherwise implicitly or explicitly indicated, or unless the context is properly understood by a person skilled in the art to have a more definitive construction, the numerical parameters set forth are approximations that may depend on the desired properties sought and/or limits of detection under standard test conditions/methods, as known to those skilled in the art. When directly and explicitly distinguishing embodiments from discussed prior art, the embodiment numbers are not approximates unless the word “about” is recited. Whenever “substantially,” “approximately,” “about,” or similar language is explicitly used in combination with a specific value, variations up to and including 10% of that value are intended, unless explicitly stated otherwise.
Directions and other relative references may be used to facilitate discussion of the drawings and principles herein, but are not intended to be limiting. For example, certain terms may be used such as “inner,” “outer,”, “upper,” “lower,” “top,” “bottom,” “interior,” “exterior,” “left,” right,” “front,” “back,” “rear,” and the like. Such terms are used, where applicable, to provide some clarity of description when dealing with relative relationships, particularly with respect to the illustrated embodiments. Such terms are not, however, intended to imply absolute relationships, positions, and/or orientations. For example, with respect to an object, an “upper” part can become a “lower” part simply by turning the object over. Nevertheless, it is still the same part, and the object remains the same.
As used herein, “comprising” means “including,” and the singular forms “a” or “an” or “the” include plural references unless the context clearly dictates otherwise. The term “or” refers to a single element of stated alternative elements or a combination of two or more elements unless the context clearly indicates otherwise.
Although there are alternatives for various components, parameters, operating conditions, etc. set forth herein, that does not mean that those alternatives are necessarily equivalent and/or perform equally well. Nor does it mean that the alternatives are listed in a preferred order, unless stated otherwise. Unless stated otherwise, any of the groups defined below can be substituted or unsubstituted.
Unless explained otherwise, all technical and scientific terms used herein have the same meaning as commonly understood to one skilled in the art to which this disclosure belongs. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present disclosure, suitable methods and materials are described below. The materials, methods, and examples are illustrative only and not intended to be limiting. Features of the presently disclosed subject matter will be apparent from the following detailed description and the appended claims.
Overview of Terms
The following explanations of specific terms and abbreviations are provided to facilitate the description of various aspects of the disclosed subject matter and to guide those skilled in the art in the practice of the disclosed subject matter.
Thermal shock. Application of a sintering temperature for a time period having a duration less than about 10 seconds. In some embodiments, the duration of the time period of sintering temperature application is in a range of about 1 microsecond to about 10 seconds, inclusive, for example, about 55 milliseconds.
Sintering temperature: A maximum temperature at a surface of a heating element when energized (e.g., by application of a current pulse) and/or at a surface of a material being sintered. In some embodiments, the sintering temperature is at least about 1000 K, for example, in a range of about 1000 K to about 3000 K. In some embodiments, a temperature at a material being sintered (e.g., precursors on a substrate) within the furnace can match or substantially match (e.g., within 10%) the temperature of the heating element.
Particle size: A maximum cross-sectional dimension (e.g., diameter) of one or more particles. In some embodiments, an identified particle size represents an average particle size for all particles (e.g., an average of the maximum cross-sectional dimensions). In some embodiments, the particle size can be measured according to one or more known standards, such as, but not limited to, ASTM B214-16 entitled “Standard Test Method for Sieve Analysis of Metal Powders,” ASTM B330-20 entitled “Standard Test Methods for Estimating Average Particle Size of Metal Powders and Related Compounds Using Air Permeability,” ASTM B822- 20 entitled “Standard Test Method for Particle Size Distribution of Metal Powders and Related Compounds by Light Scattering,” and ASTM B922-20 entitled “Standard Test Method for Metal Powder Specific Surface Area by Physical Adsorption,” all of which are incorporated by reference herein.
Nanoparticle. A particle composed of at least two different elements and having a particle size less than or equal to about 1 pm. In some embodiments, each nanoparticle has a size of about 100 nm or less, for example, about 25 nm or less.
Metal. Includes those individual chemical elements classified as metals on the periodic table, including alkali metals, alkaline earth metals, transition metals, lanthanides, and actinides, as well as alloys formed from such metals.
Metallic glass : A solid alloy formed by a mixture of at least two metals that having a disordered atomic-scale structure, e.g., amorphous or substantially amorphous (e.g., without long-range order) as opposed to crystalline. In some embodiments, the alloy is formed as a nanoparticle having only short-range order (e.g., order over no more than two atom spacings). Alternatively, in some embodiments, the alloy is formed as a nanoparticle having one or more portions with medium-range order (e.g., in a range of 0.5-5 nm, inclusive) but without exhibiting long-range order across the nanoparticle. The terms metallic glass, amorphous metal, and glass forming multi-element have been used interchangeably herein.
Standard molar entropy. The entropy content of one mole of pure substance at normal temperature and pressure (e.g., 298 K, 1 atm).
Introduction
Disclosed herein is a novel class of multi-element glass materials, in particular metallic glass materials (e.g., nanoparticles). In some embodiments, the metallic glass materials can be formed using a thermal shock fabrication, where very high temperatures (e.g., at least 1000 K, such as in a range of 1000-3000 K) are achieved over a short duration (e.g., < 10 s, such as < 1 s, for example, < 100 ms, such as ~ 55 ms) with rapid ramping to/from temperature (e.g., at least 103 K/s). In some embodiments, rapid quenching after heating is performed at a sufficiently high cooling rate (e.g., an absolute value of the cooling rate is greater than or equal to 104 K/s, such as > 105 K/s, or even > 106 K/s) that the time for cooling (e.g., to a temperature less than a melting temperature of one, some, or all of the metals of the precursors) is at least an order of magnitude less (e.g., at least two orders of magnitude less) than a diffusion timescale for the metal atoms (or other components forming the ultimate material). The rapid quenching can be fast enough to avoid crystallization (or at least minimize large scale crystallization) during solidification of the component elements. In some embodiments, the rapid quenching may be achieved by providing passive cooling features, active cooling features, or both. In some embodiments, the metallic glass material (e.g., nanoparticle) can be formed of a homogeneous mixture of multiple metals (e.g., at least 2, such as 3 or more, for example, 7-8 different elements) that form a single amorphous solid (e.g., exhibiting only short-range order, or alternatively areas having no more than medium-range order). In some embodiments, each of the component elements of the metallic glass have a standard molar entropy (e.g., as measured in J/mol-K) that differs from an average of standard molar entropies for all of the component elements by no more than 20%. In some embodiments, each of the component elements of the metallic glass have a standard molar entropy that is in a range of 25-45 J/mol-K, inclusive (e.g., in a range of 29-43 J/mol-K). In some embodiments, one, some, or all of the component elements of the metallic glass are transition metals, for example, selected from Groups 8-12 of the periodic table (e.g., an element in any of Groups 8-11). In some embodiments, the component elements of the metallic glass comprise Co, Ni, Ru, Rh, Pd, Ag, Ir, Pt, Zr, Cu, Fe,
Al, Mg, Ti, Zn, P, or any combination of the foregoing, as shown in Table 1 below. In some embodiments, the metallic glass may comprise 8 elements, for example, a CoNiRuRhPdAglrPt nanoparticle or a (PdPt)4o(CuZn)3o(FeCoNi)ioP2o nanoparticle.
Table 1: Exemplary elements for metallic glass material
Figure imgf000010_0001
Embodiments of the disclosed subject matter are not limited to the above noted compositions for the metallic glass. Rather, according to the teachings of the present disclosure, metallic glass materials can be induced for many combinations of metals (and/or other elements) that have a high glass-forming ability, as long as the rapid quenching rate is faster than a critical cooling rate required for glass formation (which critical rate may depend on the material composition but may in general be at least 105 K/s).
Exemplary Methods for Fabricating Metallic Glass
FIG. 1 illustrates an exemplary method 100 for fabricating a metallic glass material. The method 100 can initiate at process block 102, where an appropriate substrate (e.g., capable of withstanding temperatures in excess of 1000 K) is provided. For example, a carbon-based substrate can be provided, such as a substrate formed by a network of carbon nano-fibers (CNFs). In some embodiments, substrates other than carbon-based structures can be used. For example, where the substrate is not used to provide conductive heating (e.g., acting as a Joule heating element), the substrate can be formed of a metal oxide, such as but not limited to silica, zeolite, titania, or ceria. Alternatively, in some embodiments, the substrate can be omitted altogether, for example, where precursor materials are flowed or passed through a heating zone without otherwise being supported by a structure.
In some embodiments, the provision of process block 102 can include fabrication of the carbon-based substrate from a starting material. For example, a polymer nanofiber network (e.g., polyacrylonitrile) can be formed by electrospinning and then carbonized (e.g., by heating at 900 °C for 2 hours) to yield the network of CNFs for subsequent use as the substrate. The method 100 can proceed to process block 104, where the provided substrate can optionally be subjected to thermal activation, which may be effective to create surface defects in the substrate, e.g., for effective nanoparticle dispersion. For example, when using CNF films as the substrate, the thermal activation can be at a temperature 750 °C for 2 hours in a carbon dioxide atmosphere.
The method 100 can proceed to process block 106, where the substrate is loaded with one or more precursors for the elements in the mixture of the desired metallic glass material. In some embodiments, the precursors can include metal salts in solution (e.g., chloride or hydrate forms in ethanol). In some embodiments, the loading can be provided by dip coating the substrate in the precursor solution, and then drying (e.g., at room temperature). Alternatively or additionally, the loading can be via any other application method, such as, but not limited to, brushing, spraying, printing, or rolling the solution onto the substrate. The loading of precursors can mirror the desired composition for the mixture of the resulting of the metallic glass material, for example, such that a desired ratio of at least two metals is attained.
The method 100 can proceed to subject the substrate loaded with precursors to a thermal shock process 108. For example, the systems and methods for thermal shock process can be similar to those disclosed in U.S. Publication No. 2018/0369771, entitled “Nanoparticles and systems and methods for synthesizing nanoparticles through thermal shock,” U.S. Publication No. 2019/0161840, entitled “Thermal shock synthesis of multielement nanoparticles,” International Publication No. WO 2020/236767, entitled “High temperature sintering systems and methods,” and International Publication No. WO 2020/252435, entitled “Systems and methods for high temperature synthesis of single atom dispersions and multi-atom dispersions,” all of which are incorporated by reference herein.
The thermal shock process 108 can be achieved by a pulsed heating profile, with (i) a rapid heating per process block 110 to a sintering temperature, (ii) a short dwell period, where the temperature is maintained at or about the sintering temperature per process block 112 until a predetermined pulse duration, ti, is reached per decision block 114, and (iii) a rapid quenching per process block 116. After the thermal shock process 108, the method 100 can proceed to terminal block 118, where the metallic glass can be used or otherwise adapted for subsequent use (e.g., by removing from the substrate). Alternatively, in some embodiments, the thermal shock process 108 may be performed more than once (e.g., by subjected to multiple pulsed temperature profiles).
FIG. 2 illustrates an exemplary pulsed temperature profile 200 for the thermal shock process 108. The temperature profile 200 can provide a sintering temperature TH (e.g., at least 1000 K, such as in a range of 1000-3000 K, inclusive, for example, ~ 2000 K or greater) for a relatively short time period ti (e.g., less than or equal to 10 s, such as in a range of about 1 ps to 10 s, inclusive, for example, ~ 55 ms). In some embodiments, the high temperature can be sufficient to melt all of the constituent elements and/or induce high temperature uniform mixing. In some embodiments, the temperature profile 200 can provide a rapid transition to and/or from the high temperature TH. For example, the temperature profile 200 can exhibit a heating ramp rate RH (e.g., to high temperature TH from a low temperature TL, such as room temperature (e.g. 20-25 °C) or an elevated ambient temperature (e.g., 100-200 °C)) of at least 103 K/s, such as 104- 105 K/s, inclusive. In some embodiment, the heating of process blocks 110-112 can be provided by conductive Joule heating (e.g., via the substrate or an element in thermal communication with the substrate and/or the precursors), radiative Joule heating (e.g., by a heating element spaced from the substrate and/or the precursors), microwave heating, laser heating, electron beam heating, spark discharge heating, or any other heating mechanism capable of providing the requisite heating rate and temperatures.
The temperature profile 200 can exhibit a cooling ramp rate Rc (e.g., to a low temperature TL from high temperature TH and/or from the high temperature TH to a melting temperature of one or more of the constituent metals) of at least 104 K/s, such as > 105 K/s or even > 106 K/s. The rapid cooling offered by ramp rate Rc can solidify the constituent metals without otherwise allowing crystallization thereof (or at least avoiding any long-range crystallization). In some embodiments, the cooling of process block 116 can be achieved by de activating, de-energizing, or otherwise terminating the heating of process blocks 110-112. Alternatively or additionally, in some embodiments, the cooling of process block 116 can be achieved using one or more passive cooling features (e.g., heat sinks thermally coupled to the heating element and/or substrate, etc.), one or more active cooling features (e.g., fluid flow directed at the substrate and/or the heater, fluid flow through the substrate or a heat sink thermally coupled thereto, etc.), or any combination thereof.
In some embodiments, a system can be provided for forming a metallic glass material according to the method 100 of FIG. 1. In some embodiments, the system can include one or more process stations corresponding to different process blocks 102-116. For example, the system can include a coating station to load the substrate with precursors, a thermal enclosure to contain the substrate during heating, and a current source with electrical connections to the substrate to effect the desired thermal shock process. In some embodiments, the system can include a controller or control module configured to control the various components of the system to perform the method 100.
Exemplary System Configurations for Fabricating Metallic Glass
In some embodiments, the thermal shock profile for forming a metallic glass material can be provided by a Joule heating element in conductive thermal communication with the precursors. For example, FIG. 3A illustrates an exemplary fabrication configuration 300 where a substrate 302 (e.g., carbon-based substrate) is used as a Joule heating element. Precursors 304 can be loaded onto the substrate 302 (e.g., on one or more surfaces thereof and/or within the substrate) and a current source 306 can be electrically connected to ends of the substrate 302.
By passing a current from the source 306 through the substrate 302, the substrate 302 can be heated so as to subject the precursors 304 to the desired sintering temperature. A controller 312 can be operatively coupled to the source 306 to control operation thereof, for example, to provide the heating pulse profile 200 of FIG. 2. In the illustrated example, the substrate 302 may be supported over a gap or trench 310 by heat sink portions 308a, 308b, which may help accelerate cooling when the current is removed from the substrate 302 by the current source 306. For example, in some embodiments, the substrate can be suspended over a trench and connected to copper electrodes by silver paste, which electrodes can provide electrical contact for heating while also acting as heat sinks for more effective cooling. In some embodiments, the thermal shock profile for forming a metallic glass material can be provided by a remote heating mechanism, such as a radiative Joule heating element, a microwave source, a laser, an electron beam system, a spark discharge system, etc. For example, FIG. 3B illustrates an exemplary fabrication configuration 320 where a substrate 322 (e.g., carbon-based substrate or metal oxide substrate) supports precursors 304 thereon but is otherwise not used to provide heating. Instead, remote heating mechanism 326 can be provided in a spaced arrangement from the precursors 304 and constructed to generate a heating zone 330 subjected to the desired sintering temperature. A controller 312 can be operatively coupled to the remote heating mechanism 326 to control operation thereof, for example, to provide the heating pulse profile 200 of FIG. 2. In the illustrated example, the substrate 322 may be supported on a heat sink 328, which may help accelerate cooling when the heating by mechanism 326 is discontinued.
Although FIGS. 3A-3B rely on passive techniques for cooling of the substrate, active cooling techniques can be used in addition to or in place of passive techniques in some embodiments. In some embodiments, the active cooling techniques can include a flow of fluid directed at the substrate, the heating zone, and/or the heating mechanism. For example, FIG. 3C illustrates an exemplary fabrication configuration 340 where gas flow nozzles 344 direct a cooling gas flow 346 toward the substrate 342 and materials 304 supported thereon. The cooling gas flow 346 can comprise an inert gas (e.g., nitrogen, argon, helium, neon, krypton, xenon, radon, or oganesson) at a temperature much less than the sintering temperature, for example, less than 200 °C such as at or about room temperature (e.g., 20-25 °C). In some embodiments, the cooling gas flow 346 can be cooled below room temperature. A controller 348 can be operatively coupled to the remote heating mechanism 326 to control operation thereof, for example, to provide the heating pulse profile 200 of FIG. 2. The controller 348 can also be operatively coupled to the gas flow nozzles 344 to control operation thereof, for example, to control a timing of the gas flow (e.g., to initiate gas flow to coincide with an end of the sintering duration, ti), a flow rate of the gas, or any other variable.
Alternatively or additionally, in some embodiments, the active cooling techniques can include a flow of fluid through the substrate (or a structure in thermal communication therewith) for heat transfer. For example, FIG. 3D illustrates an exemplary fabrication configuration 360 where a heat transfer fluid is passed through a heat sink 364 thermally coupled to substrate 362 having materials 304 thereon. The heat transfer fluid can be pumped via hydraulic pump 368 to an inlet 372 of conduit 366, where it absorbs heat from the heat sink 364 and carries the heat away via outlet 374. In some embodiments, the heat transfer fluid can comprise a liquid, such as water or a refrigerant. In some embodiments, the heat transfer fluid can be introduced at a temperature, TL, that is much less than the sintering temperature, for example, less than 200 °C such as at or about room temperature (e.g., 20-25 °C). In some embodiments, the heat transfer fluid can be cooled below room temperature. A controller 370 can be operatively coupled to the remote heating mechanism 326 to control operation thereof, for example, to provide the heating pulse profile 200 of FIG. 2. The controller 370 can also be operatively coupled to the pump 368 to control operation thereof, for example, to control a timing of the fluid flow (e.g., to initiate heat transfer fluid flow into inlet 372 to coincide with an end of the sintering duration, ti), a flow rate of the heat transfer fluid, or any other variable. In some embodiments, the heat transfer fluid exiting the outlet 374 can be recirculated back to the inlet 372 via pump 368 after being cooled (e.g., via a cross-flow heat exchanger). Alternatively, in some embodiments, the heat transfer fluid exiting the outlet 374 can be discarded (e.g., via a drain) without recirculation.
Although FIGS. 3A-3D illustrate specific configurations for fabricating metallic glass materials, embodiments of the disclosed subject matter are not limited thereto. Rather, other passive cooling mechanisms beyond those specifically illustrated could be used to enhance natural conduction, convection, and/or radiation to cool the materials. Alternatively or additionally, other active cooling mechanisms could be used, such as but not limited to thermoelectric cooling. Additional configurations are also possible according to one or more contemplated embodiments.
Computer Implementation
FIG. 4 depicts a generalized example of a suitable computing environment 431 in which the described innovations may be implemented, such as aspects of method 100, controller 312, controller 348, and/or controller 370. The computing environment 431 is not intended to suggest any limitation as to scope of use or functionality, as the innovations may be implemented in diverse general-purpose or special-purpose computing systems. For example, the computing environment 431 can be any of a variety of computing devices (e.g., desktop computer, laptop computer, server computer, tablet computer, etc.).
With reference to FIG. 4, the computing environment 431 includes one or more processing units 435, 437 and memory 439, 441. In FIG. 4, this basic configuration 451 is included within a dashed line. The processing units 435, 437 execute computer-executable instructions. A processing unit can be a general-purpose central processing unit (CPU), processor in an application-specific integrated circuit (ASIC) or any other type of processor. In a multi-processing system, multiple processing units execute computer-executable instructions to increase processing power. For example, FIG. 4 shows a central processing unit 435 as well as a graphics processing unit or co-processing unit 437. The tangible memory 439, 441 may be volatile memory (e.g., registers, cache, RAM), non-volatile memory (e.g., ROM, EEPROM, flash memory, etc.), or some combination of the two, accessible by the processing unit(s). The memory 439, 441 stores software 433 implementing one or more innovations described herein, in the form of computer-executable instructions suitable for execution by the processing unit(s).
A computing system may have additional features. For example, the computing environment 431 includes storage 461, one or more input devices 471, one or more output devices 481, and one or more communication connections 491. An interconnection mechanism (not shown) such as a bus, controller, or network interconnects the components of the computing environment 431. Typically, operating system software (not shown) provides an operating environment for other software executing in the computing environment 431, and coordinates activities of the components of the computing environment 431.
The tangible storage 461 may be removable or non -removable, and includes magnetic disks, magnetic tapes or cassettes, CD-ROMs, DVDs, or any other medium which can be used to store information in a non-transitory way, and which can be accessed within the computing environment 431. The storage 461 can store instructions for the software 433 implementing one or more innovations described herein.
The input device(s) 471 may be a touch input device such as a keyboard, mouse, pen, or trackball, a voice input device, a scanning device, or another device that provides input to the computing environment 431. The output device(s) 471 may be a display, printer, speaker, CD- writer, or another device that provides output from computing environment 431.
The communication connection(s) 491 enable communication over a communication medium to another computing entity. The communication medium conveys information such as computer-executable instructions, audio or video input or output, or other data in a modulated data signal. A modulated data signal is a signal that has one or more of its characteristics set or changed in such a manner as to encode information in the signal. By way of example, and not limitation, communication media can use an electrical, optical, radio-frequency (RF), or another carrier.
Any of the disclosed methods can be implemented as computer-executable instructions stored on one or more computer-readable storage media (e.g., one or more optical media discs, volatile memory components (such as DRAM or SRAM), or non-volatile memory components (such as flash memory or hard drives)) and executed on a computer (e.g., any commercially available computer, including smart phones or other mobile devices that include computing hardware). The term computer-readable storage media does not include communication connections, such as signals and carrier waves. Any of the computer-executable instructions for implementing the disclosed techniques as well as any data created and used during implementation of the disclosed embodiments can be stored on one or more computer-readable storage media. The computer-executable instructions can be part of, for example, a dedicated software application or a software application that is accessed or downloaded via a web browser or other software application (such as a remote computing application). Such software can be executed, for example, on a single local computer (e.g., any suitable commercially available computer) or in a network environment (e.g., via the Internet, a wide-area network, a local-area network, a client-server network (such as a cloud computing network), or other such network) using one or more network computers.
For clarity, only certain selected aspects of the software-based implementations are described. Other details that are well known in the art are omitted. For example, it should be understood that the disclosed technology is not limited to any specific computer language or program. For instance, aspects of the disclosed technology can be implemented by software written in C++, Java, Perl, any other suitable programming language. Likewise, the disclosed technology is not limited to any particular computer or type of hardware. Certain details of suitable computers and hardware are well known and need not be set forth in detail in this disclosure.
It should also be well understood that any functionality described herein can be performed, at least in part, by one or more hardware logic components, instead of software. For example, and without limitation, illustrative types of hardware logic components that can be used include Field-programmable Gate Arrays (FPGAs), Program-specific Integrated Circuits (ASICs), Program-specific Standard Products (ASSPs), System-on-a-chip systems (SOCs), Complex Programmable Logic Devices (CPLDs), etc.
Furthermore, any of the software-based embodiments (comprising, for example, computer-executable instructions for causing a computer to perform any of the disclosed methods) can be uploaded, downloaded, or remotely accessed through a suitable communication means. Such suitable communication means include, for example, the Internet, the World Wide Web, an intranet, software applications, cable (including fiber optic cable), magnetic communications, electromagnetic communications (including RF, microwave, and infrared communications), electronic communications, or other such communication means. In any of the above-described examples and embodiments, provision of a request (e.g., data request), indication (e.g., data signal), instruction (e.g., control signal), or any other communication between systems, components, devices, etc. can be by generation and transmission of an appropriate electrical signal by wired or wireless connections.
Fabricated Examples and Experimental Results
Samples were synthesized by a carbothermal shock technique with a high cooling rate, which were used to create alloyed nanoparticles of multiple metal components. The multi- component metallic nanoparticle samples were synthesized using a thermal shock procedure. Individual metal salts (e.g., chlorides or their hydrate forms) were dissolved in ethanol at a concentration of 0.05 mol/L. After completely dissolving with hydrochloric acid, the individual salt precursor solutions with different cations were mixed and sonicated for 30 minutes. The homogenously mixed precursor solution was then loaded onto carbon substrates (e.g., reduced graphene oxide). Each sample (e.g., substrate with mixed precursors thereon) was suspended on a trench and connected with copper electrodes by silver paste for both heating and effective cooling as a giant heat sink. Thermal shock synthesis was triggered by electric Joule heating in an inert gas environment (e.g., an argon-filled glovebox) using a voltage or current source (e.g., Keithley 2425 SourceMeter), where the high temperature and duration can be effectively controlled by tuning the input power and duration. The temperature of this process was monitored by a high-speed camera with a pixel size of 25 pm. The samples were heated to a temperature as high as 1763 K for 55 milliseconds, as shown in FIG. 10 A. The cooling rate was estimated to be ~5.1-6.9x 104 K/s, which can make metallic glasses.
After thermal shock synthesis, the resulting metallic glass nanoparticles on the substrate were dispersed in ethanol with sonication, and subsequently deposited onto 5-nm-thick silicon nitride membranes. The membranes with nanoparticles thereon were then baked at 100 °C for 12 hours in vacuum to eliminate any hydrocarbon contamination. Both energy-dispersive X-ray and electron energy loss spectroscopy data show that the nanoparticles were still in metallic form and were not oxidized during the experiment. As shown in FIG. 10B, the energy- dispersive X-ray spectroscopy data shows that the nanoparticles are composed of eight elements: Co, Ni, Ru, Rh, Pd, Ag, Ir, and Pt. In addition, tomographic tilt series were acquired from seven nanoparticles using a scanning transmission electron microscope with an annular dark-field detector. A tilt series of 55 images was acquired from particles having a disordered structure, as shown in FIG. 5 A. Although some crystalline features were present in several images, the 2D power spectra calculated from the images show the amorphous halo, as shown in FIG. 5B. After pre-processing and image denoising, the tilt series was reconstructed and the 3D atomic positions were traced and classified, as shown in FIG. 5C. Since the image contrast in the 3D reconstruction depends on the atomic number, presently atomic electron tomograph (AET) is only sensitive enough to classify the eight elements into three different types: Co and Ni as type 1, Ru, Rh, Pd and Ag as type 2, and Ir and Pt as type 3. After atom classification, the 3D atomic model of the nanoparticles was obtained, in particular, 8322, 6896, and 3138 atoms for types 1, 2, and 3, respectively. To verify the reconstruction, atom tracing, and classification procedure, 55 images from the experimental atomic model were calculated using multi-slice simulations. The reconstruction, atom tracing, and classification procedure were then applied to obtain a new 3D atomic model from the 55 multi-slice images. By comparing the two models, it was estimated that 97.37% of atoms were correctly identified with a 3D precision of 21 pm. FIG. 6A shows the experimental 3D atomic model of the nanoparticle with type 1, 2, and 3 atoms. To quantitatively characterize the atomic structure, local bond orientational order (BOO) parameters were used to distinguish between the disordered, face-centered cubic (fee), hexagonal close-packed (hep), and body-centered cubic (bcc) structures. FIG. 6B shows the local BOO parameters of all the atoms in the nanoparticle, indicating the majority of atoms severely deviate from the fee, hep, and bcc crystal structures.
To separate crystal nuclei from the amorphous structure, the normalized BOO parameter was used to identify the crystal nuclei. By choosing the criterion of the normalized BOO parameter > 0.5, 15.46% of the total atoms forming crystal nuclei in the nanoparticle were identified, which crystal nuclei contributed to the crystalline features observed in several images. The characteristic width of the crystalline-amorphous interface was determined to be 3.69 A in the nanoparticle, indicating that the crystal nuclei have a minimal effect on the structural disorder beyond a few angstroms. In the following description, the analysis focuses on disordered atoms with a normalized BOO parameter < 0.5.
FIG. 6C shows the pair distribution function (PDF) of the amorphous structure of the 3D atomic model. The ratios of the second, third, fourth and fifth to the first peak position are 1.74, 1.99, 2.64 and 3.51, respectively. The partial PDFs between types 1, 2, and 3 atoms are shown in FIG. 6D. By fitting a Gaussian to the first peaks in the partial PDFs, the type 11, 12, 13, 22, 23 and 33 bond lengths were determined to be 2.59, 2.71, 2.78, 2.72, 2.75 and 2.9 A, respectively. In particular, the partial PDF for the type 33 pairs exhibits a unique feature with the second peak higher than the first peak, indicating that the majority of type 3 atoms are distributed beyond the short-range order (SRO).
To determine the SRO in the glass-forming nanoparticle, Voronoi tessellation was used to characterize the local atomic arrangement. This method identifies the nearest neighbor atoms around each central atom to form a Voronoi polyhedron, which is designated by a Voronoi index <m, m, m, m> with m denoting the number of /-edged faces. FIG. 7A shows the ten most abundant Voronoi polyhedra in the nanoparticle with a fraction ranging from 5.02% to 1.72%, most of which are geometrically disordered and commonly observed in model metallic glasses, such as <0,4,4,3>, <0,3,6,3>, <0,4,4,2> and <0,3,6,2> (shown in FIG. 7B). To examine the effect of the precision of AET on the Voronoi analysis, the experimental error was added to a CuesZns metallic glass model obtained from molecular dynamics simulations. By comparing the Voronoi polyhedra with and without the error, the precision of AET was found to have only a small effect on the Voronoi tessellation, suggesting that the small fractions of the Voronoi polyhedra in the glass-forming nanoparticle are mainly due to its poor glass forming ability.
FIG. 7C shows the local symmetry distribution of all the faces of the Voronoi polyhedra. The 3-edged, 4- edged, 5- edged, and 6-edged faces account for 3.27%, 29.14%, 43.91% and 23.67%, respectively, with the 5-edged faces being most abundant in the SRO. However, only 7.03% of all the Voronoi polyhedra are distorted icosahedra, including Voronoi indices <0,0,12,0>, <0,1,10,2>, <0,2,8,2> and <0,2,8, 1>. This indicates that most 5-edged faces do not form distorted icosahedra in the glass-forming nanoparticle. From the Voronoi tessellation, the distribution of the coordination number (CN) was also calculated, as shown in FIG. 7D, where the average CNs of types 1, 2, and 3 atoms were found to be 11.97, 12.02, and 12.41, respectively. Based on the partial CNs, the chemical SRO was quantified using the Warren- Cowl ey parameters, indicating that the type 11 and 23 bonds are favored while the type 12 and 33 bonds are unfavored, which results are consistent with observations of the shortening of the type 11 and 23 bonds and the lengthening of the type 12 and 33 bonds.
While the medium-range order (MRO) in metallic glasses has been broadly defined as the nanometer-scale structural organization beyond the SRO, the MRO was investigated here in the framework of the efficient cluster packing model, which hypothesizes that solute atoms are surrounded by randomly-positioned solvent atoms to form solute-centered clusters. The solute- centered clusters can be densely packed to constitute crystal-like MROs in metallic glasses. To quantitatively test this model with experimental data, the partial PDF of type 33 atom pairs of FIG. 6D was analyzed. It was observed that the highest peak is at 4.77 A and 1.49 times higher than the nearest neighbor peak. In addition, 85.47% of type 3 atoms were found to be distributed in the second coordination shell, which is between the first (3.86 A) and the second minimum (6.08 A) of the PDF curve (FIG. 6C). These type 3 atoms act as solute atoms and are surrounded mainly by type 1 and 2 solvent atoms to form solute-centered clusters. The solute- centered clusters connect with each other by sharing one (a vertex), two (an edge), and/or three atoms (a face), as well as protrude into each other by sharing four and five atoms, as shown in FIG. 8 A.
FIG. 8B shows the statistical distribution of the number of the solute-centered cluster pairs, which share from one to five atoms. To locate the MRO in the glass-forming nanoparticle, a breadth-first search algorithm was implemented to look for the fee-, hep-, bcc-, simple cubic (sc-) and icosahedral-like structures of the solute centers. This algorithm globally searched for the MRO with a maximum number of solute centers. Each MRO was defined to have five or more solute centers with each solute center falling within a 0.75 A radius to the fee, hep, bcc, sc lattice or icosahedral vertices. Four types of MROs (fee-, hep-, bcc- and sc-like) were found to coexist in the sample. Although icosahedral-like MROs were not observed in this sample, it is possible for such MROs to exist in other metallic glasses. FIG. 8C shows the histogram of the four types of MROs as a function of the size, where the inset illustrates the fraction of the solute center atoms in the four types of MROs. FIG. 8D shows a 3D distribution of MROs with each having eight solute centers or more. To verify the analysis, MROs with a 1 A and 0.5 A radius cut-off were also searched, and the coexistence of the four types of MROs with different cut-off radii was observed.
MROs with a 0.75 A radius cut-off were quantitatively characterized. FIGS. 9A-9B show the length and volume distribution of the MROs in the glass-forming nanoparticle. The average length of the fee-, hep-, bcc- and sc-like MROs was measured to be 2.27 ± 0.50, 2.40 ± 0.42,
2.07 ± 0.38, 2.11 ± 0.48 nm, respectively, with the corresponding average volume of 1.80 ±
0.64, 1.96 ± 0.53, 1.63 ± 0.46 and 1.96 ± 0.74 nm3. The partial PDFs of all the fee-, hep-, bcc- and sc-like solute centers in the glass-forming nanoparticle and their corresponding maximum peak positions are at 4.62, 4.77, 4.82 and 3.88 A, respectively, as shown in FIG. 9C. These peak positions represent the average nearest neighbor distances of the solute centers in the four crystal-like MROs, and the broadened peaks signify the severe deviation from the crystal lattices. Compared with the other three partial PDFs, the partial PDF of the sc-like MROs has two peaks and the ratio of the second to the first peak position is about 2 (FIG. 9C), which corresponds to the ratio of the diagonal to the side length of a square. The shorter nearest neighbor distance of the sc-like MROs compared to the other three crystal-like MROs indicates that the sc-like solute-centered clusters are more closely connected with their neighbors. FIG.
9D shows the distribution of sharing one, two, three, four and five atoms between neighboring solute-centered clusters for the four types of MROs, confirming that the solute-centered clusters in the sc-like MROs tend to share more atoms with their neighbors than those in other types of MROs. The quantitative analysis of the SRO and MRO in a multi-component glass-forming nanoparticle provides direct experimental evidence to support the general framework of the efficient cluster packing model, that is, solute-centered clusters are densely packed in some parts of the sample to form crystal-like MROs. The chemical SRO, the bond shortening and lengthening, and the coexistence of fee-, hep-, bcc- and sc-like MROs were observed in the glass-forming nanoparticle. By quantifying their length, volume and 3D structure, it was found that the MROs not only have a large variation in length and volume, but also severely deviate from the crystal lattices, as shown in FIG. 9C. As the size of the MROs is comparable to that of shear transformation zones in metallic glasses, AET could also be applied to determine the 3D atomic structures related to shear transformation zones and link the structure and properties of metallic glasses.
Although the focus herein has been on a multi-element glass-forming nanoparticles, the method and analyses described herein can be extended to other sample geometries, such as but not limited to thin films or extended objects (e.g., bulk materials having at least one dimension greater than or equal to 1 mm).
Additional Examples of the Disclosed Technology
In view of the above-described implementations of the disclosed subject matter, this application discloses the additional examples in the clauses enumerated below. It should be noted that one feature of a clause in isolation, or more than one feature of the clause taken in combination, and, optionally, in combination with one or more features of one or more further clauses are further examples also falling within the disclosure of this application.
Clause 1. A method comprising: heating a plurality of precursors at a heating rate to a first temperature, the plurality of precursors comprising metal salts of at least two different metals; maintaining the plurality of precursors at the first temperature for a first time; and after the first time, cooling from the first temperature at a cooling rate such that a metallic glass material is formed, wherein the metallic glass material comprises a homogeneous mixture of the at least two different metals and forming a single amorphous solid.
Clause 2. A method comprising: loading a plurality of precursors onto a substrate, the plurality of precursors comprising metal salts of at least two different metals; heating the loaded substrate at a heating rate to a first temperature; maintaining the loaded substrate at the first temperature for a first time; and after the first time, cooling the substrate from the first temperature at a cooling rate such that a metallic glass material is formed on the substrate, wherein the metallic glass material comprises a homogeneous mixture of the at least two different metals and forming a single amorphous solid.
Clause 3. The method of any clause or example herein, in particular, any one of Clauses 1-
2, wherein a duration of the cooling is at least ten times less than timescales of diffusion of atoms of the at least two different metals in the homogeneous mixture.
Clause 4. The method of any clause or example herein, in particular, any one of Clauses 1-
3, wherein the cooling at the cooling rate is from the first temperature to a second temperature that is less than melting temperatures of the at least two different metals.
Clause 5. The method of any clause or example herein, in particular, any one of Clauses 1-
4, wherein the cooling rate is at least 104 K/s.
Clause 6. The method of any clause or example herein, in particular, any one of Clauses 1-
5, wherein the cooling rate is at least 105 K/s.
Clause 7. The method of any clause or example herein, in particular, any one of Clauses 1-
6, wherein the cooling rate is at least 106 K/s.
Clause 8. The method of any clause or example herein, in particular, any one of Clauses 1-
7, wherein each metal salt comprises a chloride or hydrate form of the respective metal.
Clause 9. The method of any clause or example herein, in particular, any one of Clauses 1-
8, wherein: the heating rate is at least 103 K/s; the first time is in a range of about 1 ps to about 10 s, inclusive; the first temperature is in a range of about 1000 K to about 3000 K, inclusive; or any combination of the above.
Clause 10. The method of any clause or example herein, in particular, any one of Clauses 1-
9, wherein: the heating rate is at least 104 K/s; the first time is about 55 ms; the first temperature is about 2000 K or greater; or any combination of the above. Clause 11. The method of any clause or example herein, in particular, any one of Clauses 2-
10, wherein the loading comprises coating the substrate in a solution of the precursor metal salts and subsequently drying the coated substrate.
Clause 12. The method of any clause or example herein, in particular, any one of Clauses 2-
11, wherein the substrate comprises a carbon-based structure.
Clause 13. The method of any clause or example herein, in particular, any one of Clauses 2-
12, wherein the substrate comprises a plurality of carbon nanofibers.
Clause 14. The method of any clause or example herein, in particular, any one of Clauses 2-
13, wherein the heating comprises providing an electric current to the substrate so as to cause Joule heating.
Clause 15. The method of any clause or example herein, in particular, any one of Clauses 1-
14, wherein the heating comprises Joule heating, radiative heating, microwave heating, laser heating, electron beam heating, spark discharge heating, or any combination of the foregoing.
Clause 16. The method of any clause or example herein, in particular, any one of Clauses 1-
15, wherein the metallic glass material is formed as a metallic glass nanoparticle.
Clause 17. The method of any clause or example herein, in particular, any one of Clauses 1-
16, wherein each of the at least two different metals has a standard molar entropy measured in J/mol-K that differs from an average of standard molar entropies for all of the least two different metals by no more than 20%.
Clause 18. The method of any clause or example herein, in particular, any one of Clauses 1-
17, wherein each of the at least two different metals has a standard molar entropy that is in a range of 25-45 J/mol-K, inclusive.
Clause 19. The method of any clause or example herein, in particular, any one of Clauses 1-
18, wherein each of the at least two different metals has a standard molar entropy that is in a range of 29-43 J/mol-K, inclusive.
Clause 20. The method of any clause or example herein, in particular, any one of Clauses 1-
19, wherein the at least two different metals are transition metals.
Clause 21. The method of any clause or example herein, in particular, any one of Clauses 1-
20, wherein the at least two different metals comprise a Group 8 transition metal, a Group 9 transition metal, a Group 10 transitional metal, a Group 11 transition metal, a Group 12 transition metal, or any combination of the foregoing. Clause 22. The method of any clause or example herein, in particular, any one of Clauses 1-
21, wherein the at least two different metals are selected from a group consisting of Group 8-11 transition metals.
Clause 23. The method of any clause or example herein, in particular, any one of Clauses 1-
22, wherein the homogeneous mixture comprises Co, Ni, Ru, Rh, Pd, Ag, Ir, Pt, Zr, Cu, Fe, Al, Mg, Ti, Zn, P, or any combination of the foregoing.
Clause 24. The method of any clause or example herein, in particular, any one of Clauses 1-
23, wherein the at least two different metals are selected from a group consisting of Co, Ni, Ru, Rh, Pd, Ag, Ir, and Pt.
Clause 25. The method of any clause or example herein, in particular, any one of Clauses 1-
24, wherein the homogeneous mixture is composed of at least seven metals.
Clause 26. The method of any clause or example herein, in particular, any one of Clauses 1-
25, wherein the homogeneous mixture is composed of Co, Ni, Ru, Rh, Pd, Ag, Ir, and Pt.
Clause 27. The method of any clause or example herein, in particular, any one of Clauses 1- 25, wherein the homogeneous mixture is composed of Pd, Pt, Cu, Zn, Fe, Co, Ni, and P.
Clause 28. The method of any clause or example herein, in particular, Clause 27, wherein the homogeneous mixture satisfies a chemical formula of (PdPt)4o(CuZn)3o(FeCoNi)ioP2o.
Clause 29. The method of any clause or example herein, in particular, any one of Clauses 1- 28, wherein the homogeneous mixture exhibits no more than short-range order.
Clause 30. A structure formed by the method of any clause or example herein, in particular, any one of Clauses 1-29.
Clause 31. A structure comprising: a metallic glass material comprising a homogeneous mixture of at least two metals and forming a single amorphous solid.
Clause 32. The structure of any clause or example herein, in particular, any one of Clauses 30-31, wherein the metallic glass material is formed as a metallic glass nanoparticle.
Clause 33. The structure of any clause or example herein, in particular, any one of Clauses 30-32, wherein each element in the homogeneous mixture has a standard molar entropy measured in J/mol-K that differs from an average of standard molar entropies for all elements in the homogeneous mixture by no more than 20%. Clause 34. The structure of any clause or example herein, in particular, any one of Clauses 30-33, wherein each element in the homogeneous mixture has a standard molar entropy that is in a range of 25-45 J/mol-K, inclusive.
Clause 35. The structure of any clause or example herein, in particular, any one of Clauses 30-34, wherein each element in the homogeneous mixture has a standard molar entropy that is in a range of 29-43 J/mol-K, inclusive.
Clause 36. The structure of any clause or example herein, in particular, any one of Clauses 30-35, wherein the at least two metals are transition metals.
Clause 37. The structure of any clause or example herein, in particular, any one of Clauses 30-36, wherein the homogeneous mixture comprises a Group 8 transition metal, a Group 9 transition metal, a Group 10 transitional metal, a Group 11 transition metal, a Group 12 transition metal, or any combination of the foregoing.
Clause 38. The structure of any clause or example herein, in particular, any one of Clauses 30-37, wherein the at least two metals are selected from a group consisting of Group 8-11 transition metals.
Clause 39. The structure of any clause or example herein, in particular, any one of Clauses 30-38, wherein the homogeneous mixture comprises Co, Ni, Ru, Rh, Pd, Ag, Ir, Pt, Zr, Cu, Fe, Al, Mg, Ti, Zn, P, or any combination of the foregoing.
Clause 40. The structure of any clause or example herein, in particular, any one of Clauses 30-39, wherein the at least two metals are selected from a group consisting of Co, Ni, Ru, Rh,
Pd, Ag, Ir, and Pt.
Clause 41. The structure of any clause or example herein, in particular, any one of Clauses 30-40, wherein the homogeneous mixture is composed of at least seven metals.
Clause 42. The structure of any clause or example herein, in particular, any one of Clauses 30-41, wherein the homogeneous mixture is composed of Co, Ni, Ru, Rh, Pd, Ag, Ir, and Pt.
Clause 43. The structure of any clause or example herein, in particular, any one of Clauses 30-41, wherein the homogeneous mixture is composed of Pd, Pt, Cu, Zn, Fe, Co, Ni, and P.
Clause 44. The structure of any clause or example herein, in particular, Clause 43, wherein the homogeneous mixture satisfies a chemical formula of (PdPt)4o(CuZn)3o(FeCoNi)ioP2o.
Clause 45. The structure of any clause or example herein, in particular, any one of Clauses 30-44, wherein the homogeneous mixture exhibits no more than short-range order. Clause 46. The structure of any clause or example herein, in particular, any one of Clauses 30-45, further comprising a substrate supporting the metallic glass material thereon.
Clause 47. The structure of any clause or example herein, in particular, any one of Clauses 30-46, wherein the substrate is a carbon-based substrate.
Clause 48. The structure of any clause or example herein, in particular, any one of Clauses 30-47, wherein the substrate comprises a plurality of carbon nanofibers.
Clause 49. The structure of any clause or example herein, in particular, any one of Clauses 30-48, wherein the substrate comprises a metal oxide.
Clause 50. The structure of any clause or example herein, in particular, any one of Clauses 30-49, wherein the substrate comprises silica, zeolite, titania, ceria, or any combination of the foregoing.
Conclusion
Any of the features illustrated or described herein, for example, with respect to FIGS. 1- 10B and Clauses 1-50, can be combined with any other feature illustrated or described herein, for example, with respect to FIGS. 1-lOB and Clauses 1-50 to provide systems, devices, materials, structures, methods, and embodiments not otherwise illustrated or specifically described herein. For example, any or both of the active cooling features of FIGS. 3C-3D can be combined with any or both of the passive cooling features of FIGS. 3A-3B. In another example, the remote heating mechanism of FIGS. 3B-3D can be combined with the conductive Joule heating mechanism of FIG. 3A, e.g., to provide simultaneous conductive and remote heating. Other combinations and variations are also possible according to one or more contemplated embodiments. Indeed, all features described herein are independent of one another and, except where structurally impossible, can be used in combination with any other feature described herein.
In view of the many possible embodiments to which the principles of the disclosed technology may be applied, it should be recognized that the illustrated embodiments are only examples and should not be taken as limiting the scope of the disclosed technology. Rather, the scope is defined by the following claims. We therefore claim all that comes within the scope and spirit of these claims.

Claims

1. A method, comprising: loading a plurality of precursors onto a substrate, the plurality of precursors comprising metal salts of at least two different metals; heating the loaded substrate at a heating rate to a first temperature; maintaining the loaded substrate at the first temperature for a first time; and after the first time, cooling the substrate from the first temperature at a cooling rate such that a metallic glass material is formed on the substrate, wherein the metallic glass material comprises a homogeneous mixture of the at least two different metals and forming a single amorphous solid.
2. The method of claim 1, wherein a duration of the cooling is at least ten times less than timescales of diffusion of atoms of the at least two different metals in the homogeneous mixture.
3. The method of claim 1, wherein the cooling at the cooling rate is from the first temperature to a second temperature that is less than melting temperatures of the at least two different metals.
4. The method of claim 1, wherein the cooling rate is at least 104 K/s.
5. The method of claim 4, wherein the cooling rate is at least 105 K/s.
6. The method of claim 5, wherein the cooling rate is at least 106 K/s.
7. The method of claim 1, wherein each metal salt comprises a chloride or hydrate form of the respective metal.
8. The method of claim 1, wherein: the heating rate is at least 103 K/s; the first time is in a range of about 1 ps to about 10 s, inclusive; the first temperature is in a range of about 1000 K to about 3000 K, inclusive; or any combination of the above.
9. The method of claim 8, wherein: the heating rate is at least 104 K/s; the first time is about 55 ms; the first temperature is at least 2000 K; or any combination of the above.
10. The method of claim 1, wherein the loading comprises coating the substrate in a solution of the precursor metal salts and subsequently drying the coated substrate.
11. The method of claim 1, wherein the substrate comprises a carbon-based structure.
12. The method of claim 11, wherein the carbon-based structure comprises a plurality of carbon nanofibers.
13. The method of claim 11, wherein the heating comprises providing an electric current to the substrate so as to cause Joule heating.
14. The method of claim 1, wherein the heating comprises Joule heating, radiative heating, microwave heating, laser heating, electron beam heating, spark discharge heating, or any combination of the foregoing.
15. The method of claim 1, wherein the metallic glass material is formed as a metallic glass nanoparticle.
16. The method of claim 1, wherein each of the at least two different metals has a standard molar entropy measured in J/mol-K that differs from an average of standard molar entropies for all of the least two different metals by no more than 20%.
17. The method of claim 1, wherein each of the at least two different metals has a standard molar entropy that is in a range of 25-45 J/mol-K, inclusive.
18. The method of claim 1, wherein each of the at least two different metals has a standard molar entropy that is in a range of 29-43 J/mol-K, inclusive.
19. The method of claim 1, wherein the at least two different metals are transition metals.
20. The method of claim 1, wherein the at least two different metals comprise a Group 8 transition metal, a Group 9 transition metal, a Group 10 transitional metal, a Group 11 transition metal, a Group 12 transition metal, or any combination of the foregoing.
21. The method of claim 1, wherein the at least two different metals are selected from a group consisting of Group 8-11 transition metals.
22. The method of claim 1, wherein the homogeneous mixture comprises Co, Ni, Ru, Rh, Pd, Ag, Ir, Pt, Zr, Cu, Fe, Al, Mg, Ti, Zn, P, or any combination of the foregoing.
23. The method of claim 1, wherein the at least two different metals are selected from a group consisting of Co, Ni, Ru, Rh, Pd, Ag, Ir, and Pt.
24. The method of claim 1, wherein the homogeneous mixture is composed of at least seven metals.
25. The method of claim 1, wherein the homogeneous mixture is composed of Co,
Ni, Ru, Rh, Pd, Ag, Ir, and Pt.
26. The method of claim 1, wherein the homogeneous mixture is composed of Pd, Pt, Cu, Zn, Fe, Co, Ni, and P.
27. The method of claim 26, wherein the homogeneous mixture satisfies a chemical formula of (PdPt)4o(CuZn)3o(FeCoNi)ioP2o.
28. The method of claim 1, wherein the homogeneous mixture exhibits no more than short-range order.
29. A structure formed by the method of any one of claims 1-28.
30. A structure comprising: a metallic glass material comprising a homogeneous mixture of at least two metals and forming a single amorphous solid.
31. The structure of claim 30, wherein the metallic glass material is formed as a metallic glass nanoparticle.
32. The structure of claim 30, wherein each element in the homogeneous mixture has a standard molar entropy measured in J/mol-K that differs from an average of standard molar entropies for all elements in the homogeneous mixture by no more than 20%.
33. The structure of claim 30, wherein each element in the homogeneous mixture has a standard molar entropy that is in a range of 25-45 J/mol-K, inclusive.
34. The structure of claim 30, wherein each element in the homogeneous mixture has a standard molar entropy that is in a range of 29-43 J/mol-K, inclusive.
35. The structure of claim 30, wherein the at least two metals are transition metals.
36. The structure of claim 30, wherein the homogeneous mixture comprises a Group
8 transition metal, a Group 9 transition metal, a Group 10 transitional metal, a Group 11 transition metal, a Group 12 transition metal, or any combination of the foregoing.
37. The structure of claim 30, wherein the at least two metals are selected from a group consisting of Group 8-11 transition metals.
38. The structure of claim 30, wherein the homogeneous mixture comprises Co, Ni,
Ru, Rh, Pd, Ag, Ir, Pt, Zr, Cu, Fe, Al, Mg, Ti, Zn, P, or any combination of the foregoing.
39. The structure of claim 30, wherein the at least two metals are selected from a group consisting of Co, Ni, Ru, Rh, Pd, Ag, Ir, and Pt.
40. The structure of claim 30, wherein the homogeneous mixture is composed of at least seven metals.
41. The structure of claim 30, wherein the homogeneous mixture is composed of Co, Ni, Ru, Rh, Pd, Ag, Ir, and Pt.
42. The structure of claim 30, wherein the homogeneous mixture is composed of Pd, Pt, Cu, Zn, Fe, Co, Ni, and P.
43. The structure of claim 42, wherein the homogeneous mixture satisfies a chemical formula of (PdPt)4o(CuZn)3o(FeCoNi)ioP2o.
44. The structure of claim 30, wherein the homogeneous mixture exhibits no more than short-range order.
45. The structure of claim 30, further comprising a substrate supporting the metallic glass material thereon.
46. The structure of claim 45, wherein the substrate is a carbon-based substrate.
47. The structure of claim 46, wherein the carbon-based substrate comprises a plurality of carbon nanofibers.
48. The structure of claim 45, wherein the substrate comprises a metal oxide.
49. The structure of claim 45, wherein the substrate comprises silica, zeolite, titania, ceria, or any combination of the foregoing.
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US20080044488A1 (en) * 2004-05-29 2008-02-21 Jose Zimmer Nano Glass Powder and Use Thereof, in Particular Multicomponent Glass Powder with a Mean Particle Size of Less Than 1 µm
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