CA2287648C - Electrodes de metal amorphe/verre metallique pour processus electrochimiques - Google Patents

Electrodes de metal amorphe/verre metallique pour processus electrochimiques Download PDF

Info

Publication number
CA2287648C
CA2287648C CA002287648A CA2287648A CA2287648C CA 2287648 C CA2287648 C CA 2287648C CA 002287648 A CA002287648 A CA 002287648A CA 2287648 A CA2287648 A CA 2287648A CA 2287648 C CA2287648 C CA 2287648C
Authority
CA
Canada
Prior art keywords
metallic glass
electrode
ni
selected
consistant
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CA002287648A
Other languages
French (fr)
Other versions
CA2287648A1 (en
Inventor
Donald W. Kirk
Steven J. Thorpe
Original Assignee
Donald W. Kirk
Steven J. Thorpe
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Donald W. Kirk, Steven J. Thorpe filed Critical Donald W. Kirk
Priority to CA002287648A priority Critical patent/CA2287648C/en
Publication of CA2287648A1 publication Critical patent/CA2287648A1/en
Application granted granted Critical
Publication of CA2287648C publication Critical patent/CA2287648C/en
Application status is Expired - Fee Related legal-status Critical
Anticipated expiration legal-status Critical

Links

Classifications

    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/86Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8605Porous electrodes
    • H01M4/8621Porous electrodes containing only metallic or ceramic material, e.g. made by sintering or sputtering
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C33/00Making ferrous alloys
    • C22C33/003Making ferrous alloys making amorphous alloys
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C45/00Amorphous alloys
    • C22C45/04Amorphous alloys with nickel or cobalt as the major constituent
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/041Electrodes; Manufacture thereof not otherwise provided for characterised by the material characterised by the material of the substrate
    • C25B11/0426Electrodes; Manufacture thereof not otherwise provided for characterised by the material characterised by the material of the substrate consisting of plurality elements or compounds
    • C25B11/0431Metal alloys

Abstract

Metallic glass / amorphous metal electrodes produced by rapid solidification (i) having a structure that is either amorphous or nanocrystalline, (ii) containing the principal alloying element as Ni, (iii) containing alloying additions of Co and at least one member of group IVB, VB, VIB VIIB and/or VIIIB, preferably Cr and V, in the range of 0 to 20 at. %, and when combined with Ni, represent 0.75 to 0.85 of the atomic fraction of the alloy, and (iv) containing metalloid elements compris ed preferably of one or more of the elements C, B, Si and P either singly or in combination to represent 0.15 to 0.25 atomic faction of the alloy. The electrodes have excellent thermal stability, improved stability in an aqueous electrolyte and can provide improved current efficiency - anodic overpotential performance. They are used in the electrolysis of aqueous electrolyte solutions such as mixtures of caustic and water in th e production of oxygen and hydrogen.

Description

AMORPHOUS METAL/METALLIC GLASS AMORPHOUS METAL / METALLIC GLASS ELECTRODES FOR ELECTROCHEMICAL PROCESSES ELECTRODES FOR ELECTROCHEMICAL PROCESSES FIELD OF THE INVENTION FIELD OF THE INVENTION This invention relates to an improved electrode material for use in electrochemical processes and particularly an amorphous metal/metallic glass electrode material intended for constituting the active surface of an electrode for use in the electrolysis of aqueous solutions and more particularly in the electrochemical production of oxygen and hydrogen by said electrolysis. This invention porte sur year Improved electrode material for use in electrochemical processes and PARTICULARLY year amorphous metal / metallic glass electrode material Intended for Constituting the active surface of an electrode for use in the electrolysis of aqueous solutions and more PARTICULARLY in the electrochemical production of oxygen and Said hydrogen by electrolysis. BACKGROUND OF THE INVENTION BACKGROUND OF THE INVENTION In electrolytic cells for the production of hydrogen and oxygen, such as those of the bipolar and unipolar type, an aqueous caustic solution is electrolyzed to produce oxygen at the anode and hydrogen at the cathode with the overall reaction being the decomposition of water to yield hydrogen and oxygen. In electrolytic cells for the production of hydrogen and oxygen, Such As Those of the bipolar and unipolar type, an aqueous caustic solution is electrolyzed to Produce oxygen at the anode and hydrogen at the cathode with the overall reaction being white the decomposition of water to yield hydrogen and oxygen. The products of the electrolysis are maintained separate by use of a membrane/separator. The products of the electrolysis are maintained separate by use of a membrane / separator. Use of amorphous metalslmetallic glasses and nanocrystalline materials, as electrocatalysts for the hydrogen and oxygen evolution reaction are known. Use of amorphous and nanocrystalline materials metalslmetallic glasses, as electrocatalysts for the hydrogen and oxygen evolution reaction are known. The terms "amorphous metal" The terms "amorphous metal" or "metallic glass" are well understood in the art and define a material which contains no long range structural order but can contain short ratige structure and chemical ordering. or "metallic glass" are well Understood in the art and define a material qui contains no long range structural order goal can Contain shorts ratige chemical structure and ordering. Henceforth, in this specification and claims both terms will be used as being synonymous and are interchangeable. Henceforth, in this specification and claims Both terms will be used as being white Synonymous and are interchangeable. The term "nanocrystalline" refers to a material that possesses a crystallite grain size of the order of a few nanometers; The term "nanocrystalline" Refers to a material That Possesses a crystallite grain size of the order of A Few nanometers; ie ie the crystalline components have a grain size of less than about 10 nanometers. the crystalline components-have a grain size of less than about 10 nanometers. Further, the term "metallic glass" embraces such nanocrystalline materials in this specification and claims. Further, the term "metallic glass" embraces Such nanocrystalline materials in this specification and claims. In an electrolysis application, not all of the voltage that is passed through the cell during electrolysis is utilized in the production of hydrogen and oxygen. In an electrolysis application, not all of the That Is Passed through the cell voltage is Utilized During electrolysis in the production of hydrogen and oxygen. This loss this loss

-2- 1033 of efficiency of the cell is often referred to as the cell overpotential required to allow the reaction to proceed at the desired rate and is in excess of the reversible thermodynamic decomposition voltage. -2- 1033 of efficiency of the cell is Often Referred to as the cell overpotential required to allow the reaction to proceed at the Desired spleen and is in excess of the reversible thermodynamic decomposition voltage. This cell overpotential can arise from: (i) reactions occurring at either the cathode or the anode, (ii) a potential drop because of the solution ohmic drop between the two electrodes, or (ifi) a potential drop due to the presence of a membrane / separator material placed between the anode and cathode. This cell overpotential can Arise from: (i) Occurring reactions at Either the cathode or the anode, (ii) a potential drop Because of the solution ohmic drop entre les two electrodes, gold (IFIs) has potential drop due to the presence of a membrane / separator material Placed entre les anode and cathode. The latter two efficiencies are fixed by the nature of the cell design while (i) is directly a result of the activity of the electrode material employed in the cell including any activation or pre-treatment steps. The lathing two efficiencies are fixed by the nature of the cell design while (i) Directly is a result of the activity of the electrode material employed in the cell Including Any or activating pre-treatment steps. Performance of an electrode is then directly related to the overpotential observed at both the anode and cathode through measurement of the Tafel slope and the exchange current density (hereinafter explained). Performance of an electrode is Then Directly related to the overpotential Observed at Both the anode and cathode through measurement of the Tafel slope and the exchange current density (hereinafter Explained). Superior electrode performance for the electrolysis of water may be achieved by the use of addition of metal salts to the electrolyte as "homogeneous" Superior performance electrode for the electrolysis of water May be Achieved by the use of the addition of metal salts to the electrolyte as "homogeneous" catalysts that function only in the liquid phase. Catalysts That function only in the liquid phase. These "homogeneous" catalysts suffer from the difficulty of having to add these additions to an operating cell to be functional, along with the toxicity of the metal salts in powder form and the disposal of electrolyte containing these additions. These "homogeneous" Catalysts Suffer from the difficulty of HAVING to add thesis additions to an operating cell to be functional, along with the toxicity of the metal salts in powder form and the disposal of electrolyte Containing thesis additions. A desirable alternative would then be a base alloy comprised of Ni, and one or more of these metallic salt constituents which would still provide the same operating characteristics of a low voltage, high current cell behaviour corresponding to the evolution of hydrogen or oxygen while being electrochemically stable in the alkaline solution. A alternative desirable Would Then be a base alloy comprised of Ni, and one or more of These metallic salt constituents Which would still Provide la même operating characteristics of a low voltage, high current cell behavior Corresponding to the evolution of hydrogen or oxygen while being white electrochemically stable in the alkaline solution. United States Patent No. 5,429,725, issued July 04, 1995 to Thorpe, SJ and Kirk, DW describes the improved electrocatalytic behaviour of alloys made by combinations of the two elements Mo and Co in a Ni-base metallic glass. United States Patent No. 5,429,725, Issued July 04, 1995 to Thorpe SJ and Kirk, DW Describes Improved the electrocatalytic behavior of alloys made by combinations of the two elements Mo and Co in a Ni-based metallic glass. However, this is still a need for higher exchange current densities combined with lower Tafel slopes in the (Cr, V)- containing alloys compared with the Mo-containing alloys and, accordingly, a need for enhanced operating efficiency of electrocatalyst material for alkaline water electrolysis '. HOWEVER, this is still a need for Higher exchange current densified combined with lower Tafel slopes in the (Cr, V) - Containing alloys Compared with the Mo-containing alloys and, accordingly, a need for enhanced operating efficiency of electrocatalyst material for alkaline water electrolysis. ' '

-3- 1033 REF'ERENCE LIST -3- 1033 REF'ERENCE LIST The present specification refers to the following publications, PUBLICATIONS: The present specification Refers to The Following publications PUBLICATIONS: 1. Lian, K. Kirk, DW and Thorpe, SJ, "Electrocatalytic Behaviour of Ni-base Amorphous Alloys", Electrochim. 1. Lian, K. Kirk, DW and Thorpe, SJ, "Electrocatalytic Behavior of Ni-based Amorphous Alloys" Electrochim. Acta, 36, p. Acta, 36, p. 537-545, (1991) 2. Kreysa, G. and Hakansson, "Electrocatalysis by Amorphous Metals of Hydrogen and Oxygen Evolution in Alkaline Solution", J. Electroanal. 537-545, (1991) 2. Kreysa, G. and Hakansson, "Electrocatalysis by Amorphous Metals of Hydrogen and Oxygen Evolution in Alkaline Solution" J. Electroanal. Chem., 201, p. Chem., 201, p. 61-83, (1986). 61-83, (1986). 3. Podesta, JJ, Piatti, RCV, Arvia, AJ, Ekdunge, P., Juttner, K. and Kreysa, G., "The Behaviour of Ni-Co-P base Amorphous Alloys for Water Electrolysis in Strongly Alkaline Solutions Prepared through Electroless Deposition", Int. 3. Podesta, JJ, Piatti, RRS Arvia, AJ, Ekdunge, P., Juttner, K. and Kreysa, G., "The Behavior of Ni-Co-P base Amorphous Alloys for Water Electrolysis Alkaline Solutions Prepared in Strongly through electroless Deposition ", Int. J. J. Hydrogen Energy, 17, p. Hydrogen Energy, 17, p. 9- 22, (1992). 9- 22, (1992).

4. Alemu, H. and Juttner, K., "Characterization of the Electrocatalytic Properties of Amorphous Metals for Oxygen and Hydrogen Evolution by Impedance Measurements", Electrochim. 4. Alemu, H. and Juttner, K., "Characterization of the Electrocatalytic Properties of Amorphous Metals for Oxygen and Hydrogen Evolution by Impedance Measurements" Electrochim. Acta., 33, p. Acta., 33, p. 1101-1109, (1988). 1101-1109, (1988).

5. Huot, J.-Y., Trudeau, M., Brossard, L. and Schultz, R. "Electrochemical and Electrocatalytic Behaviour of an Iron Base Amorphous Alloy in Alkaline Solution at 70 C", J. Electrochem. 5. Huot, JY, Trudeau, Mr. Brossard, L. and Schultz, R. "Electrochemical and Electrocatalytic Behavior of Iron Base Amorphous Alloy year in Alkaline Solution at 70 C," J. Electrochem. Soc., 136, p. Soc., 136, p. 2224-2230, (1989). 2224-2230, (1989).

6. Vracar, Lj., and Conway, BE, "Temperature Dependence of Electrocatalytic Behaviour of Some Glassy Transition Metal Alloys for Cathodic Hydrogen Evolution in Water Electrolysis", Int. 6. Vracar, Lj., And Conway, BE, "Temperature Dependence of Electrocatalytic Behavior of Some Transition Metal Glassy Alloys for Cathodic Hydrogen Evolution in Water Electrolysis", Int. J. Hydrogen Energy, 15, p. J. Hydrogen Energy, 15, p. 701-713 (1990). 701-713 (1990).

7. Wilde, BE, Manohar, M., Chattoraj, I., Diegle, RB and Hays, AK, "The Effect of Amorphous Nickel Phosphorous Alloy Layers on the Absorption of Hydrogen into Steel", Proc. 7. Wilde, BE, Manohar, M., Chattoraj, I., Diegle, RB and Hays, AK, "The Effect of Nickel Phosphorous Amorphous Alloy Layers on the Absorption of Hydrogen into Steel", Proc. Symp. Symp. Corrosion, Electrochemistry and Catalysis of Metallic Glasses, 88-1, Ed. RB Diegle and K. Hashimoto, Electrochemical Society, Pennington, p. Corrosion, Electrochemistry and Catalysis of Metallic Glasses, 88-1, ed. RB Diegle and K. Hashimoto, Electrochemical Society, Pennington, p. 289-307 (1988). 289-307 (1988).

8. Divisek, J., Schmitz, H. and Balej, "Ni and Mo Coatings as Hydrogen Cathodes", J. Appl. 8. Divisek J. Schmitz, H. and Balej, "Ni and Mo have Coatings Hydrogen Cathodes", J. Appl. Electrochem., 19, p. Electrochem., 19, p. 519-530, (1989). 519-530, (1989).

9. Huot, J.-Y. and Brossard, L., "In-situ Activation of Nickel Cathodes by Sodium Molybdate during Alkaline Water Electrolysis at Constant Current", J. 9. Huot, JY and Brossard, L., "In-situ activation of Nickel cathodes by Sodium Molybdate During Alkaline Water Electrolysis at Constant Current" J. Appl. Appl. Electrochem., 20, p. Electrochem., 20, p. 281, (1990). 281, (1990).

10. Huot, J.-Y. and Brossard, "In-situ Activation of Nickel Cathodes during Alkaline Water Electrolysis by Dissolved Iron and Molybdenum Species", J. 10. Huot, JY and Brossard, "In-situ activation of Nickel Cathode During Alkaline Water Electrolysis by Dissolved Iron and Molybdenum Species" J. Appl. Appl. Electrochem., 21, p. Electrochem., 21, p. 508, (1991). 508, (1991).

11. Raj, IA and Vasu, KI, "Transition Metal-based Hydrogen Electrodes in Alkaline Solution- Electrocatalysis on Nickel-based Binary Alloy Coatings", Int. 11. Raj, IA and Vasu, KI, "Metal-based Transition Hydrogen Electrodes in Alkaline Solution-Electrocatalysis is Nickel-based Binary Alloy Coatings", Int. J. Hydrogen Energy, 20, p. J. Hydrogen Energy, 20, p. 32, (1990). 32, (1990).

12. Jaksic, MM, Johansen, B., and Ristic, M., "Electrocatalytic In-situ Activation of Noble Metals for Hydrogen Evolution" in Hydrogen En= ProgLress VII I, TN Veziroglu and PK Takahashi, Eds., Pergamon Press, NY, p. 12. Jaksic, Mr. Johansen, B., and Ristic, M., "Electrocatalytic In-situ activation of Noble Metals for Hydrogen Evolution" in Hydrogen In ProgLress VII = I, TN Veziroglu and PK Takahashi, Eds., Pergamon Press, NY, p. 461, (1990). 461, (1990). SITMMARY OF THE INVENTION SITMMARY OF THE INVENTION It is an object of this invention to provide an improved electrode having an electrochemically active surface that can be used for the electrolysis of water. It is an object of this invention to Provide Improved electrode year HAVING electrochemically active surface That year can be used for the electrolysis of water. It is a further object of this invention to provide an improved electrode that is chemically stable in an alkaline environment for both static and dynamic cycling operations of the cell. It is a further Top object of this invention to Provide Improved electrode year chemically stable That Is in an alkaline environment for Both static and dynamic cycling operations of the cell. It is a further object of the present invention to provide an improved electrode material that is sufficiently active so as to reduce either or both the anodic overpotential for oxygen evolution or the cathodic overpotential for hydrogen evolution. It is a further Top object of the present invention to Provide Improved year electrode material That Is Sufficiently active so as to Reduce Either or Both the anodic overpotential for oxygen evolution or the cathodic overpotential for hydrogen evolution. It is a further object to provide an electrode that contains relatively inexpensive elemental constituents compared to the platinum group metals. It is a further Top object to Provide That year electrode contains Relatively inexpensive elemental constituents Compared To the platinum group metals. It is a further object to provide an electrode whose total processing operations necessary to final electrode fabrication are minimized in comparison to conventional electrode materials. It is a further Top object to Provide electrode year total Whose Necessary processing operations to final electrode production are minimized in comparison to conventional electrode materials. It is a further object to provide an electrode which can be operated at elevated temperatures in an alkaline environment to provide enhanced performance since the overpotential required to produce either hydrogen or oxygen is reduced as the operational temperature of the cell is increased. It is a further Top object to Provide an electrode qui peut être operated at elevated temperature in an alkaline environment to Provide Enhanced Performance since the overpotential required to Produce Either hydrogen or oxygen is Reduced operational as the temperature of the cell is Increased. Accordingly, the invention provides in one aspect a metallic glass of use in electrochemical processes, said metallic glass consisting essentially of a material of the general nominal composition (Ni,Co)loo-x_t Ax Zt wherein: Accordingly, the invention Provides in one aspect a metallic glass of use in electrochemical processes, Said metallic glass Consisting Essentially of a material of the nominal general composition (Ni, Co) loo-x_t Ax Zt où: A is a member selected from the group consisting of IVb, Vb, VIb VIIb and VIII of the Periodic Table; A is a member selected from the group consistant en IVb, Vb, VIb and VIII VIIb of the Periodic Table; Z is a member selected from the group consisting of carbon and a metalloid element selected from group IIIa, IVa, Va and VIa of the Periodic Table; Z is a member selected from the group consistant en carbon and a metalloid element selected from Group IIIa, IVa, Va and VIa of the Periodic Table; and wherein x, t and (100-xt) are atomic percents. and où x, t and (100-xt) are atomic percents. Preferably, A is at least one metal selected from the group consisting of Ti, V, Cr, Mn, Fe, Zr, Nb, Mo, Tc, Hg, Ta, and W; Preferably, A is at least one metal selected from the group Consisting of Ti, V, Cr, Mn, Fe, Zr, Nb, Mo, Tc, Hg, Ta, and W; and wherein x is selected from about 1 to 20 atomic percent, more preferably x is selected from about 1-5 atomic percent. où and x is selected from about 1 to 20 atomic percent, more preferably X is selected from about 1-5 atomic percent. Preferably, Z is at least one member selected from the group consisting of silicon, phosphorus, carbon, and boron; Preferably, Z is au moins un member selected from the group consistant en silicon, phosphorus, carbon, and boron; and wherein t is selected from about 15 to 25 atomic percent, more preferably t is about 20 atomic percent. où and t is selected from about 15 to 25 atomic percent, more preferably t is about 20 atomic percent. The metallic glass is most preferably in an elemental and homogenous state but some degree of non-homogeneity in both anionic and cationic form can be tolerated. The metallic glass is MOST preferably in an elemental state and homogenous but some degree of non-homogeneity in Both anionic and cationic form can be tolerated. It will be understood that the general formula defined hereinabove represents a nominal composition and thus allows of some degree of variance from the exact atoniic ratios shown. It Will Be Understood que la general formula defined hereinabove Represents a nominal composition and THUS Allows of Some degree of variance from the exact atoniic ratios shown. Preferred materials according to the invention have the nominal compositions selected from NiSOCo25Cr5B2D,NiS0Co25V5B20 and Ni45Co25Cr5V5B20. Preferred materials selon the invention-have the nominal compositions selected from NiSOCo25Cr5B2D, NiS0Co25V5B20 and Ni45Co25Cr5V5B20. The alloys of the present invention are readily made into self-supporting structures. The alloys of the present invention are Readily made into self-supporting structures. In a further aspect, the invention provides an electrode of use in an electrochemical cell comprising a metallic glass consisting of a material as hereinabove deflned. In a further Top aspect, the invention of use Provides an electrode in an electrochemical cell comprenant metallic glass material was consistant en deflned as hereinabove. The electrode may act as an anode, cathode or both as a working electrode. The electrode May act as an anode or cathode Both have a working electrode. The materials of the invention may constitute a full electrode or a surface coating on a substrate such as a metal or other electrically conductive material. The materials of the invention May Constitute a full gold electrode surface coating was subbed Such As Metal has other gold Electrically Conductive material. In a yet further aspect, the invention provides an improved process for the electrochemical production of oxygen and hydrogen from an aqueous solution in an electrochemical cell, said process comprising electrolysing said aqueous solution with electrodes, said improvement comprising one or more of said electrodes comprising a metallic glass consisting essentially of a material as hereinabove defined. In a yet further Top aspect, the invention Provides an Improved process for the electrochemical production of oxygen and hydrogen from an aqueous solution in an electrochemical cell, Said process comprenant electrolysing Said aqueous solution with electrodes, Said improvement comprenant one or more of Said electrodes comprenant Essentially metallic glass consistant of a material as hereinabove defined. In the electrolytic production of oxygen and hydrogen, the aqueous solution is alkaline. In the electrolytic production of hydrogen and oxygen, the aqueous solution is alkaline. Surprisingly, the metallic glasses according to the invention do not suffer from the loss of element "A" during use and retain electrolytic activity under severe conditions of use. Surprisingly, the metallic glasses selon the invention do not Suffer from the loss of element "A" During use and retain electrolytic activity under severe conditions of use. Thus, we have found that the presence of element "A" in the alloys of the invention, while providing the unexpected advantages hereindescribed, surprisingly, does not result in dissolution of the element "A" under alkaline electrolysis conditions. THUS, we-have found the presence of element That "A" in the alloys of the invention, while providing good the unexpected advantages hereindescribed, surprisingly, does not result in dissolution of the element "A" under alkaline electrolysis conditions. Thus, the invention provides a metallic glass / amorphous metal electrode material for electrochemical processes produced by rapid solidification (i) having a structure that is either amorphous or nanocrystalline, (n) containing the principal alloying elements as Ni and Co, (iii) containing alloying additions such as Cr, V, Ti, Mn, Fe and the like in the range of 1 to 20 at. THUS, the invention Provides a metallic glass / amorphous metal electrode material for electrochemical processes produced by rapid solidification (i) Having a structure That Is Either amorphous nanocrystalline gold (n) Containing the main alloying elements as Ni and Co, (iii) Containing alloying additions Such as Cr, V, Ti, Mn, Fe and the like in the range of 1 to 20 at. %, and when combined with Ni and Co, represent 0.75 to 0.85 of the atomic fraction of the alloy, and (iv) containing metalloid elements comprised preferably of one or more of the elements C, B, Si and P %, And when to combined with Ni and Co, Represent 0.75 to 0.85 of the atomic fraction of the alloy, and (iv) Containing metalloid elements preferably comprised of one or more of the elements C, B, Si and P either singly or in combination to represent 0.15 to 0.25 atomic fraction of the alloy. Either singly or in combination to Represent 0.15 to 0.25 atomic fraction of the alloy. The electrodes have excellent thermal stability, improved stability in an aqueous electrolyte and can provide improved current efficiency - anodic or cathodic overpotential performance. The electrodes-have excellent thermal stability, Improved stability in an aqueous electrolyte and can Provide Improved current efficiency - anodic or cathodic overpotential performance. They are of use in the electrolysis of aqueous electrolyte solutions such as mixtures of caustic (KOH, NaOH) and water in the production of oxygen and hydrogen. They are of use in the electrolysis of aqueous electrolyte solutions Such As mixtures of caustic (KOH, NaOH) and water in the production of oxygen and hydrogen. The electrodes are comprised of low cost transition metals in combination with metalloid elements in specific ratios to permit the alloy composition to be solidified into an amorphous state. The electrodes are comprised of low cost transition metals in combination with metalloid elements in specific ratios to permit the alloy composition to be solidified into an amorphous state. They offer improved current efficiencies via anodic or cathodic overpotential performance and offer improved stability in both static and cyclic exposures. They offer current Improved efficiencies through anodic or cathodic overpotential offer performance and stability Improved in Both static and cyclic exposures. They can be used in concentrated alkaline solutions and at elevated temperatures for improved electrode performance. They can be used in Concentrated alkaline solutions and at elevated temperature for Improved electrode performance. The electrodes are of use in the electrolysis of alkaline solutions resulting in the production of hydrogen and oxygen via the decomposition of water, and also additional uses in electrodes for fuel cells, electro-organic synthesis or environmental waste treatment. The electrodes are of use in the electrolysis of alkaline solutions resulting and in the production of hydrogen and oxygen through the decomposition of water, and aussi additional uses in electrodes for fuel cells, electro-organic synthesis or environmental waste treatment. Processing methodology of rapid solidification offers many cost advantages compared to the preparation of conventional Raney Ni type electrodes. Processing methodology of rapid solidification Many offers cost advantages Compared to the preparation of conventional Raney Ni type electrodes. The process is a single step process from liquid metal to finished catalyst, which can be fabricated in the form of ribbons or wires for weaving into a mesh grid. The process is a single step process from liquid metal to finished catalyst, qui peut être fabricated in the form of ribbons or wires for weaving into a grid mesh. The process can also be used to produce sheets, powders, flakes, etc. The process can be used to Produce aussi sheets, powders, flakes, etc. which can further be consolidated into a desired shape or patterned. qui further Top can be consolidated into a Desired shape patterned gold. By comparison, conventional electrode fabrication involves the production of a billet or rod, wire drawing and annealing operations, weaving to form a wire mesh grid, surface treatment, powder deposition, powder consolidation and an activation step. By comparison, conventional electrode manufacturing Involves the production of a ticket or rod, wire drawing and annealing operations, weaving to form a wire mesh grid, surface treatment, powder deposition, powder consolidation and an activation step. Table 1 summarizes the results of prior art investigations involving transition metal-metalloid glasses. Table 1 summarizes the results of prior art investigations Involving transition metal-metalloid glasses. The performance of an electrocatalyst in Table 1 has been summarized in terms of two principle parameters: (i) the Tafel slope, P., and (ii) the logarithm of the exchange current density, log io. The performance of an electrocatalyst in Table 1 has-been Summarized in terms of principle two parameters: (i) the Tafel slope, P., and (ii) the logarithm of the exchange current density, log io. The exchange current density is equivalent to the reversible rate of a reaction at equilibrium at the standard half-cell or redox potential. The exchange current density is equivalent to the rate of a reversible reaction at equilibrium at the standard half-cell redox potential gold. The Tafel slope refers to the slope of the line representing the relation between overpotential and the rate of a reaction reflected as current density where there exists linearity on a semilogarithmic plot of overpotential and current density. The Tafel slope Refers to the slope of the line Representing the relationship entre overpotential and the rate of reaction was reflected as current density Where There exists linearity was semilogarithmic plot of overpotential and current density. Table 1.0: Polarization Data of Ni-Co base Amorphous Metals for HER in Alkaline Solutions Amorphous Solution Temperature -log io Qr Referenc Electrode (A/cmz (mV/decade e ) ) NisoCozs.SiisBio 1M KOH 30 5.7 110,178 1 30 6.5 90 2 50 10.6 93 2 70 7.6 127 2 90 7.9 113 2 Surface-treated 1M KOH 30 5.4 91,145 1 NisoCossSiiaBio 1M KOH 30 5.8 101,144 1 Surface-treated 1M KOH 30 5.4 111,166 1 CosoNissPisBio 1M KOH 30 5.4 124,174 1 Surface-treated 1M KOH 30 5.1 110,173 1 Thermally-treated and 1M KOH 30 4.0 100 3 anodically oxidized 50 3.2 120 3 Ni5.5Co9oP45 70 2.8 120 3 90 2.2 100 3 Nis8Co2oSi1oB12 1M KOH 30 5.0 140 2 50 4.7 146 2 70 4.7 155 2 90 4.3 145 2 Co2sNi1oFe5SinBi6 1M KOH 30 4.6 174 2 50 5.5 119 2 70 5.4 120 2 90 5.3 128 2 NiMMo2oSi5Bs 1M KOH 30 4.1 165 2 70 3.8 106 2 Amorphous Solution Temperature -log io Referenc Electrode (A/cm2 (mV/decade e ) ) 90 3.6 276 2 Fe39Ni39Mo2Sii2B8 1M KOH 30 5.0 123 2 50 4.8 150 2 70 4.9 173 2 90 4.9 167 2 Ni7sSi8B14 1M KOH 25 6.0 140 4 30 6.1 102 2 50 4.3 Table 1.0: Data Polarization of Ni-Co-based Amorphous Metals for HER in Alkaline Solutions Amorphous Solution Temperature -log io Qr Referenc electrode (A / cm (mV / decade e)) NisoCozs.SiisBio 1M KOH 30 5.7 110.178 1 30 6.5 90 2 50 10.6 93 2 70 7.6 127 2 90 7.9 113 2 Surface-treated 1M KOH 30 5.4 91.145 1 NisoCossSiiaBio 1M KOH 30 5.8 101.144 1 Surface-treated 1M KOH 30 5.4 111.166 1 CosoNissPisBio 1M KOH 30 5.4 124.174 1 Surface-treated 1M KOH 30 110.173 5.1 1 Thermally-treated and 1M KOH 30 4.0 100 3 50 3.2 anodically oxidized Ni5.5Co9oP45 120 3 70 2.8 120 3 90 2.2 100 3 Nis8Co2oSi1oB12 1M KOH 30 5.0 140 2 50 4.7 146 2 70 4.7 155 2 90 4.3 145 2 Co2sNi1oFe5SinBi6 1M KOH 30 4.6 174 2 50 5.5 119 2 70 5.4 120 2 90 5.3 128 2 NiMMo2oSi5Bs 1M KOH 30 4.1 165 2 70 3.8 106 2 Amorphous Solution Temperature -log io Referenc electrode (A / cm2 (mV / decade e)) 90 3.6 276 Fe39Ni39Mo2Sii2B8 2 1M KOH 30 5.0 123 2 50 4.8 150 2 70 4.9 173 2 90 4.9 167 2 Ni7sSi8B14 1M KOH 25 6.0 140 4 30 6.1 102 2 50 4.3 150 4 50 4.4 144 2 70 4.9 130 2 75 3.8 125 4 90 4.4 148 2 Anodically oxidized 30% KOH 70 2.9 130 5 FeaoNi4oBzo 1M KOH 30 3.9 174 2 50 3.8 184 2 70 4.3 230 2 90 3.0 188 2 Ni66.5Mo23.5Bio 0.5M 25 5.6 120 6 NaOH 150 4 50 4.4 144 2 70 4.9 130 2 75 3.8 125 4 90 4.4 148 2 Anodically oxidized 30% KOH 2.9 130 70 5 FeaoNi4oBzo 1M KOH 30 3.9 174 2 50 3.8 184 2 70 4.3 230 2 90 3.0 188 2 Ni66.5Mo23. 5Bio 0.5M NaOH 25 5.6 120 6 Ni5e.5Mo23sFe1oB1o 0.5M 25 5.3 100 6 NaOH Ni5e.5Mo23sFe1oB1o 0.5M NaOH 25 5.3 100 6 Ni5e.5Mo215CnoBio 0.5M 25 5.0 135 6 NaOH Ni5e.5Mo215CnoBio 0.5M NaOH 25 5.0 135 6 NinP2oCio coating 1N NaOH 25 6.2-8.4 65-95 7 Ni75Cr5P2o 1M HC1* 30 3.5 - 8 Ni73CnP2o 1M HCI* 30 3.8 - 8 Ni7oCnoP2o 1M HC1* 30 4.0 - 8 * not for electrolysis in an alkaline media Table 2: Polarization Data of Ni-Co base Amorphous Metals for HER in Alkaline Solution with Homogeneous Catalyst additions Substrate and Addition Solution Tem rature -log i Q Referenc of Catalyst (ppm x 103) ~ 0 c (A/cm2 (mV/decade e ) ) Substrate Co 7.6M KOH 70 3.9 79 9 Fe 3.9 80 Ni 3=7 95 Pt 4.2 75 Fe addition = 0.014 Substrate Co 7.6M KOH 70 3.4 151 10 Fe 3.1 154 Ni 2.8 182 Pt 3.1 163 Mo addition = 0.024 Fe addition = 0.024 Substrate mild steel 6.OM KOH 80 - 112 11 NiSO4 addition = 80 Na2MoO4 addition = 20 Substrate mild steel 6.OM KOH 80 - 112 11 NiSO4 addition = 80 Na2MoO4 addition = 20 Substrate mild steel 6.OM KOH 80 - 25 11 NiSO4 addition = 80 Na2WO4 addition = 20 Substrate mild steel 6.OM KOH 80 - 50 11 NiSOa addition = 80 ZnSO4 addition = 40 Substrate mild steel 6.OM KOH 80 - 25 11 NiSO4 addition = 80 NinP2oCio coating 1N NaOH 6.2-8.4 65-95 25 7 Ni75Cr5P2o 1M HC1 30 * 3.5 - 8 Ni73CnP2o 1M HCl 30 * 3.8 - 8 Ni7oCnoP2o 1M HC1 4.0 * 30 - 8 * not for electrolysis in an alkaline media Table 2: Data of Polarization Ni-Co base Amorphous Metals for HER in Alkaline Solution with Homogeneous Catalyst Addition and additions Substrate Solution Tem erasure -log i Q Referenc of Catalyst (ppm x 103) ~ 0 c (A / cm2 (mV / decade e)) Substrate Co 7.6 M KOH 70 3.9 3.9 79 9 Fe 80 Ni 3 Pt = 7 95 4.2 75 Fe = 0.014 Substrate Co addition 7.6M KOH 70 3.4 151 Fe 10 Ni 3.1 154 2.8 182 3.1 163 Mo addition Pt = 0.024 Fe = 0.024 Substrate addition mild steel 6.OM KOH 80-112 11 NiSO4 addition = 80 Na2MoO4 addition = 20 Substrate mild steel 6.OM KOH 80-112 11 NiSO4 addition = 80 Na2MoO4 addition = 20 Substrate mild steel 6.OM KOH 80-25 11 NiSO4 addition = 80 Na2WO4 addition = 20 Substrate mild steel 6.OM KOH 80-50 11 NiSOa addition = 80 ZnSO4 addition = 40 Substrate mild steel 6.OM KOH 80-25 11 NiSO4 addition = 80 FeSO4 addition = 20 Substrate mild steel 6.OM KOH 80 - 112 11 NiSO4 addition = 80 CoSO4 addition = 20 Substrate mild steel 6.OM KOH 80 - 150 11 NiSO4 addition = 80 CrO3 addition = 20 Substrate Pt 5.OM KOH 25 - 80 12 Molybdate addition The electrodes described in Table 1 contain various combinations of the transition metals in combinat,ion with (Ni,Co) but: none of them incorporate element "A" in addition as described above. FeSO4 addition = 20 Substrate mild steel 6.OM KOH 80-112 11 NiSO4 addition = 80 CoSO4 addition = 20 Substrate mild steel 6.OM KOH 80-150 11 NiSO4 addition = 80 CrO3 addition = 20 Substrate Pt 5.OM KOH 25 - 80 12 The electrodes Molybdate addition Described in Table 1 Contain various combinations of the transition metals in Kombinat ion with (Ni, Co) purpose: none of them Incorporate element "A" in addition as described Above. The electrodes described in Table 2 derive activity from the presence of the dissolved salts of element "A" as described above when added to the solution phase of the electrolytic cell, but not when incorporated directly into the substrate material. The electrodes Described in Table 2 activity derived from the presence of the Dissolved salts of element "A" as described Above When added to the phase of the electrolytic cell solution, but not Directly When incorporated into the substrate material. BRIEF DESCRIPTION OF THE DRAWINGS BRIEF DESCRIPTION OF THE DRAWINGS In order that the invention may be better understood, preferred embodiments will now be described by way of example only, with reference to the accompanying drawings, wherein: In order que la invention May be better Understood, preferred embodiments will now be Described by way of example only, with reference to the Accompanying drawings, où: Fig. Fig. 1 is a schematic diagram of an apparatus for making a metallic glass according to the invention; 1 is a schematic diagram of an apparatus for making a metallic glass selon the invention; Fig. Fig. 2 is a schematic diagam detailing the interior of the vacuum chamber of the apparatus shown in Fig. 2 is a schematic Diagam detailing the interior of the vacuum chamber of the apparatus shown in Fig. 1; 1; Fig. Fig. 3 is a perspective representation of a boron nitride ceraniic crucible of use in the apparatus of Fig. 3 is a perspective representation of a boron nitride crucible ceraniic of use in the apparatus of Fig. 1; 1; Fig. Fig. 4 is a schematic diagram of a three component cell used in the evaluation of the electrochemical activity and stability of the materials according to the invention; 4 is a schematic diagram of a three component cell used in the evaluation of the electrochemical activity and stability of the materials selon the invention; Fig. Fig. 5 is a diagrammatic representation of the apparatus of use in obtaining electrochemical measurements, and wherein the sanie numeral denotes like parts. 5 is a diagrammatic representation of the apparatus of use in Obtaining electrochemical measurements, and où le sanies numeral Denotes like shares. DETAILED DESCRIPTTON OF 'THE PREFERRED DETAILED DESCRIPTTON OF 'THE PREFERRED EMBODIlVIENTS OF THE INVENTION EMBODIlVIENTS OF THE INVENTION The general methods for the preparation and testing of the materials according to the invention followed those described in aforesaid United States Patent No. 5,429,725. The general methods for the preparation and testing of the materials selon the invention Followed Those Described in Aforesaid United States Patent No. 5,429,725. EXPERIMENTAL EXPERIMENTAL Electrode metallic glass materials were prepared as follows having the nominal composition: Electrode metallic glass materials Were Prepared as follows HAVING the nominal composition: This Example illustrates the preparation electrodes having a nominal composition: This Example illustrates the preparation electrodes Having a nominal composition: Ni50Co25 Cr5 B20 A series of processing trials were performed to fabricate amorphous alloy ribbons by the melt-spinning technique. Cr 5 Ni50Co25 B20 A series of processing trials Were Performed to fabricate amorphous alloy ribbons by the melt-spinning technique. The process was divided into two steps. The process Was divided into two steps. The first step was termed "pre-melting" where a powder mixture of pure materials, ie, nickel, cobalt, chromium, and boron, was charged onto a water cooled copper hearth, and melted via the use of vacuum arc melting. The first step Was termed "pre-melting" where a powder mixture of pure materials, ie, nickel, cobalt, chromium, boron and, Was charged onto a water cooled copper hearth, and melted through the use of vacuum arc melting. The second step employed a boron nitride ceramic crucible, which enabled the pre-melted and crushed button to be remelted and superheated to a temperature higher than 1100 C in the vacuum chamber. The second step was employed boron nitride ceramic crucible, qui enabled the pre-melted and crushed button to be remelted and superheated to a temperature Higher Than 1100 C in the vacuum chamber. A stream of molten metal was then blown through a thin slit of the ceramic crucible on to the peripheral surface of a massive copper wheel rotating at a high speed. A stream of molten metal Was Then blown through a thin slit of the ceramic crucible is to the peripheral surface of a massive copper wheel rotating at a high speed. Rapid quenching took place on the cold surface of the wheel, and the solidified deposit was produced in the form of thin ribbons. Rapid quenching eu lieu on the cold surface of the wheel, and the solidified deposit Was Produced in the form of thin ribbons. A concise description of amorphous metal production is given in the following subsections. A concise description of amorphous metal production is Given In The Following subsections. Apparatus: Apparatus: Melt-Spinner D-7400 Tubingen, Edmund BiihlerkGermany 3.3 x 10"2 Pascal High Vacuum Chamber Induction Heater : TOCCOTRON 2EG103~The Ohio Crankshaft Co., USA Melt Spinner-D-7400 Tubingen, Edmund BiihlerkGermany 3.3 x 10 "2 Pascal High Vacuum Chamber Induction Heater: TOCCOTRON 2EG103 ~ The Ohio Crankshaft Co., USA Maximum output 10 kW, 450 kHz Pyrometer : Model ROS-SU, Capintec Institute Inc., USA Maximum output 10 kW 450 kHz Pyrometer: Model ROS-SU, Capintec Institute Inc., USA Fig. Fig. I illustrates the experimental apparatus consisting of a melt-spinner shown generally as 10 and an induction heating unit shown generally as 12. The melt-spinner assembly 10 comprised a high vacuum chamber 14, a ribbon collector tube 16, and a controller 18. The vacuum chamber 14 was connected to an argon cylinder 20 that supplied argon gas for purging the chamber 14 and pressurizing a ceramic crucible 22 (Fig. 2) in order to eject a molten mass of liquid material (not shown). I illustrates the experimental apparatus consistant of a melt-spinner Generally shown as 10 and an induction heating unit as shown Generally 12. The melt-spinner assembly 10 comprised a high vacuum chamber 14, a ribbon collector tube 16, and a controller 18. The was vacuum chamber 14 connected to an argon cylinder 20 That Supplied argon gas for purging the chamber 14 and pressurizing a ceramic crucible 22 (FIG. 2) in order to eject a molten mass of liquid material (not shown). The temperature of the molten mass of liquid in ceramic crucible 22 is measured by means of an optical pyrometer 24 attached to a quartz window 26 located above vacuum * Trade-mark chamber 14. The temperature of the molten mass of liquid in ceramic crucible 22 is Measured by moyen de year optical pyrometer 24 attached to a quartz window 26 Located Above vacuum * Trade-mark chamber 14. Induction heater unit 12 was comprised of an induction heater coil 28 (Fig. 2) in vacuum chamber 14, a 3-stage step-up transformer and a closed-loop water recirculator (not shown) which supplied cooling water through the induction coil during heating. Induction heater unit 12 Was comprised of an induction heater coil 28 (Fig. 2) in vacuum chamber 14, a 3-stage step-up transformation and a closed-loop water recirculator (not shown) qui Supplied cooling water through the induction coil During heating. Fig. Fig. 2 shows the arrangement of a copper ivheel 30 (20 cm in diameter, 3.8 cm in width), ceramic crucible 22 induction coil 28 in high vacuum chamber 14 and ribbon guide 32. 2 shows the arrangement of a copper ivheel 30 (20 cm in diameter, 3.8 cm in width), ceramic crucible 22 induction coil 28 in the high vacuum chamber 14 and ribbon guide 32. A: Premelting The targeted chemical compositions exemplified are collectively expressed as Ni50Co2Cr5%. A: The Targeted Premelting chemical compositions are Exemplified Collectively Expressed as Ni50Co2Cr5%. Because the compositional range of the alloy is relatively small, careful sample preparation was required to ensure an effective comparison in subsequent electrochemical measurements. Because the compositional range of the alloy is Relatively Small, careful sample preparation Was required to Ensure effective year comparison in subsequent electrochemical measurements. In order to achieve the targeted compositions with high accuracy, pure material powders were utilized to fabricate pre-melted buttons first by vacuum arc melting followed by mechanical crushing and remelting using vacuum induction melting. In order to accomplish achieve the Targeted compositions with high accuracy, pure material powders Were Utilized to fabricate pre-melted buttons first by vacuum arc melting Followed by mechanical crushing and remelting using vacuum induction melting. In the exemplified powders each mixture contained 50 atomic % In the Exemplified powders Each mixture contained 50 atomic% nickel, 25 atomic % Co and 20 atomic % of boron. nickel, 25 atomic% Co and 20 atomic% of boron. The remaining 5 atomic % was made up with element A, in this example chromium. The remaining 5% atomic Was Made up with element A, in this example chromium. In an alternate embodiment of this invention, the boron was added in the form of an intermetallic compound like nickel boride which acted as a melting point depressant and enabled the whole powder mixture to start melting at a relatively low temperature, ca.1035 C. In an alternate Embodiment of this invention, the boron Was added in the form of an intermetallic compound like nickel boride qui ACTED as a melting point depressant and enabled the whole powder mixture to start melting at a Relatively Low Temperature, ca.1035 C. A batch of 20 - 50 g of the powder mixture was charged into a quartz crucible (ID = 19.05 mm, OD = 22.2 mm, height = 130 mm, with round bottom). A batch of 20 - 50 g of the powder mixture Was charged into a quartz crucible (ID = 19.05 mm, OD = 22.2 mm, height = 130 mm, with round bottom). The quartz crucible was mounted in the vacuum chamber of the melt-spinner and centered in the induction coil. The quartz crucible Was mounted in the vacuum chamber of the melt-spinner and centered in the induction coil. The vacuum chamber was then purged three times with argon and evacuated to ca. The vacuum chamber Was Then purged three times with argon and Evacuated to ca. 5 x 104 torr (7 x 10-' Pa) before heating. 5 x 104 Torr (7 x 10- 'Pa) before heating. The material powder mixture was melted at greater than 1100 C in the quartz crucible. The material powder mixture Was melted at Greater Than 1100 C in the quartz crucible. The weight loss ratio of materials through pre-melting was found to be < 1 weight % for all constituents. The weight loss ratio of materials through pre-melting Was found to be <1% weight for all constituents.

-13- 1033 B: Melt Spinning The melt spinner used in this work was an experimental sized model manufactured by Edmund Buhlerv'GMBH capable of processing in batch mode 5 -gram samples of alloy mixtures. -13- 1033 B: Melt Spinning The melt spinner used in this work Was an experimental sized model Manufactured by Edmund Buhlerv'GMBH capable of processing in batch mode 5 -gram samples of alloy mixtures. The melt-spinner assembly comprised a high vacuum chamber, a ribbon collector tube, and a motor speed controller. The melt-spinner assembly comprised a high vacuum chamber, a ribbon collector tube and a motor speed controller. The induction heater unit was comprised of an induction heater coil in the vacuum chamber, a 3-stage step-up transformer, and a closed-loop water recirculator, which supplied cooling water through the induction coil during heating. The induction heater unit was comprised of an induction heater coil in the vacuum chamber, a 3-stage step-up transforming, and a closed-loop water recirculator, qui Supplied cooling water through the induction coil During heating. The vacuum chamber was connected to an argon cylinder that supplied gas for purging the chamber and pressurizing the ceramic crucible in order to eject a molten mass of liquid. The vacuum chamber Was connected to an argon cylinder That Supplied gas for purging the chamber and pressurizing the ceramic crucible in order to eject a molten mass of liquid. The temperature of the molten mass of liquid in the ceramic crucible was measured by means of an optical pyrometer that was attached to a quartz window located above the vacuum chamber One or two pre-melted buttons were charged into the BN ceramic crucible. The temperature of the molten mass of liquid in the ceramic crucible Was Measured by optical pyrometer year moyen de That Was attached to a quartz window Located above-the vacuum chamber One or two pre-melted buttons Were charged into the BN ceramic crucible. Boron nitride has the advantages of high hardness at elevated temperatures and good oxidation resistance that enabled the molten liquid to be superheated to over 14000C without any chemical reaction with the crucible. Boron nitride Has the advantages of high hardness at elevated temperatures and good oxidation resistance That enabled the molten liquid to be superheated to over 14000C Without Any chemical reaction with the crucible. The crucible was mounted above the Cu wheel in the vacuum chamber. The crucible Was mounted above-the Cu wheel in the vacuum chamber. The chamber was purged and evacuated in the same manner as that described during premelting. The chamber purged Was Evacuated and in the Sami Manner As That Described During premelting. The pre-melted button(s) was superheated in the crucible by the induction coil until the liquid temperature reached a stable maximum temperature, which was dependent on the alloy composition. The pre-melted button (s) Was superheated in the crucible by the induction coil up to the liquid temperature atteint a maximum stable temperature, qui Was dependent on the alloy composition. The molten mass of liquid was ejected by argon pressure on to the wheel through a fine slit nozzle (0.5 x 15 mm). The molten mass of liquid Was ejected by argon pressure it to the wheel through a thin slit nozzle (0.5 x 15 mm). Planar amorphous ribbons were formed on the surface of the wheel rotating counterclockwise and driven along the ribbon guides to the collector tube. Planar amorphous ribbons Were FORMED on the surface of the wheel rotating counterclockwise and driven along the ribbon guide to the collector tube. This particular form of melt spinning is referred to as the planar flow casting technique. This Particular form of melt spinning is Referred to as the planar flow casting technique. From the wheel rotation speed, a quenching rate was estimated to be ca. From the wheel rotation speed, quenching spleen Was Estimated to be ca. l 06 C/sec. the 06 C / sec. One side of the ribbon was free from contact with the wheel and had a shiny appearance (shiny side) compared with the dull appearance for the other side in contact with the wheel (wheel side). One side of the ribbon Was free from contact with the wheel and Had a shiny appearance (shiny side) Compared with the dull appearance for the other side in contact with the wheel (wheel side). To minimize surface imperfections on the dull side due to contact with the wheel, the peripheral surface of the wheel was thoroughly polished with diamond paste and degreased with * Trade-mark To minimize surface imperfections on the dull side due to contact with the wheel, the peripheral surface of the wheel Was Thoroughly polished with diamond paste and degreased with * Trade-mark

-14- 1033 acetone before each run. -14- 1033 acetone before Each run. Standard experimental parameters of the melt-spinning operation are summarized in Table 3. Standard experimental parameters of the melt-spinning operation are Summarized in Table 3. Table 3: S of Operational Parameters of Melt-S innin Clearance between the bottom most edge of the 0.5 mm crucible and the wheel surface Point of impingement 12 degrees counterclockwise from the top of the wheel Pre-melt button weight 20-50 g Vacuum chamber pressure 7 x 10 Pa or lower Molten ejection pressure 40 kPa Wheel rotation speed 1800-2900 rpm LSuperheat temperature higher than 1100 C Table 3: S of Operational Parameters of Melt-S innin Clearance entre les MOST bottom edge of the crucible 0.5 mm and the wheel surface point of impingement 12 degrees counterclockwise from the top of the wheel button Pre-melt weight 20-50 g Vacuum chamber pressure 7 x 10 Pa or lower Molten ejection pressure 40 kPa Wheel rotation speed from 1800 to 2900 rpm LSuperheat temperature Higher than 1100 C The alloys of the invention so produced by planar flow casting were submitted to the following further types of evaluation. The alloys of the invention so produced by planar flow casting Were Submitted To The Following further Top types of evaluation. The first evaluation relates to the actual composition of the alloys produced as poor recoveries during melting can produce substantial deviations between the nonzinal and actual composition of a given alloy. The first evaluation concerne un the actual composition of the alloys have poor Produced Recoveries During melting can Produce substantial businesses deviations entre les nonzinal and actual composition of a Given alloy. The second evaluation relates to the structure of the alloys produced as the processing method produces a metastable structure that is amorphous or nanocrystalline in nature. The second evaluation concerne un the structure of the alloys Produced as the processing method Produces a metastable amorphous structure That Is gold nanocrystalline in nature. The third evaluation relates to the electrode perfomiance in relation to the overvoltage necessary for hydrogen production for as-melt spun ribbons under conditions related to the electrolysis of an alkaline solution. The Third Assessment porte sur perfomiance the electrode in relation to the Necessary overvoltage for hydrogen production for as melt spun ribbons under conditions related to the electrolysis of an alkaline solution. The fourth evaluation refers to the examination of the surface of the ,electrode materials used under both constant potential and conditions of potential cycling as described above. The fourth assessment Refers to the examination of the surface of the, electrode materials used under constant Both potential and conditions of potential cycling as described Above. The first test was performed in order to obtain reliable information on the elemental composition of the amorphous alloys using inductively coupled plasma The first test Was Performed in order to obtenir reliable information on the elemental composition of the amorphous alloys using inductively coupled plasma

- 15 - 1033 spectroscopy (ICP). - 15-1033 spectroscopy (ICP). Although only a very small weight loss, less than 1 weight %, was found during the premelting operation, if the loss was due to a single component, inaccuracies in the targeted compositions would result. ALTHOUGH only a very small weight loss, less than 1 weight%, Was found DURING THE premelting operation, if the loss Was due to a single component, inaccuracies in the Targeted compositions Would result. Additionally, there was concern about any compositional fluctuation in the longitudinal direction of the amorphous ribbon. Additionally, There Was Any concern about compositional fluctuation in the longitudinal direction of the amorphous ribbon. For this reason, two positions designated as center and tail were taken from each ribbon and analyzed. For this reason, two positions designated as center and tail Were taken from Each ribbon and Analyzed. ICP is a technique that provides a quantitative analysis of almost all elements with a high level of detectability. ICP is a technical That Provides a quantitative analysis of Almost all elements with a high level of detectability. The technique requires that the sainple to be analyzed be dissolved in an aqueous solution because the sample is introduced to the inductively coupled plasma in the form of an aerosol. The technique requires que la sainple to be Analyzed be Dissolved in an aqueous solution Because The sample is Introduced to the inductively coupled plasma in the form of an aerosol. Each amorphous ribbon was dissolved into concentrated nitric acid and diluted with water and hydrochloric acid to complete the designated matrix solution which contained 4 weight % HNO3 and 4 weight % HCI. Each amorphous ribbon Was Dissolved into Concentrated nitric acid and diluted with water and hydrochloric acid to complete the designated matrix solution qui contained 4 weight% HNO 3 and 4 weight% HCl. For experimental error analysis, some standard solutions were prepared with pure material powders: The major elements analyzed were Ni, Co, Cr, V, and B. Expected concentrations of Ni, Co, Cr, V, and B in the standard and sample solutions are summarized in Table 4. For experimental error analysis, standard solutions Some Were Prepared with pure material powders: The Staff Were Analyzed elements Ni, Co, Cr, V, and B. Expected concentrations of Ni, Co, Cr, V, and B in the standard and sample solutions are Summarized in Table 4.

- 16 - 1033 Table 4: Summary of Expected Concentrations of ICP Samples (ppm) Serial Solute Ni Co Cr or VB - from 16 to 1033 Table 4: Summary of Samples Expected Concentrations of ICP (ppm) Solute Serial Ni Co Cr or VB No. No. #1 Blank (1) 0 0 0 0 #2 Standard (2) - metals 10.00 10.00 10.00 0 #3 Standard (3) - metals 100.00 100.00 100.00 #4 NiS4CoZCr1B20center 53.7 24.7 0.9 20.6 #5 Ni Co Cr B tail 54.0 24.8 1.0 20.1 #6 Standard 1~ 54.0 25.0 1.0 20.0 #7 Ni50Co25Cr5B20 center 50.6 24.6 5.0 19.9 #8 Ni Co Cr B~ tail 49.9 24.6 5.7 19.7 ~ Standard 5 50.0 25.0 5.0 20.0 #10 N'i3SCo2,Cr~% center 35.6 25.1 20.2 19.1 #11 Ni35Co2CrMB20tail 35.7 25.1 20.2 18.9 #12 Standard 35.0 25.0 20.0 20.0 #13 Ni50Co25VSB20 center 50.8 25.3 4.6 19.3 #14 Ni Co VB tail 50.9 25.3 4.7 19.1 #15 Standard S~ 50.0 25.0 5.0 20.0 #16 Standard B 1 0 0 0 10 #17 Standard B2 0 0 0 25 #18 Standard B3 0 0 0 50 #19 Standard B4 0 0 0 100 The second test was performed using the technique of X-ray diffraction in order to confirm the degree of crystallinity of the manufactured ribbons. # 1 Blank (1) 0 0 0 0 # 2 Standard (2) - metals 10.00 10.00 10.00 0 # 3 Standard (3) - metals 100.00 100.00 100.00 # 4 NiS4CoZCr1B20center 53.7 24.7 0.9 20.6 No. 5 Ni Co Cr B tail 54.0 24.8 1.0 20.1 Standard # 1 ~ 6 54.0 25.0 1.0 20.0 # 7 Ni50Co25Cr5B20 center 50.6 24.6 5.0 19.9 # 8 Ni Co Cr B ~ tail 49.9 24.6 5.7 19.7 ~ Standard 5 50.0 25.0 5.0 20.0 # 10 Do i3SCo2, Cr ~% 35.6 25.1 20.2 center 19.1 # 11 Ni35Co2CrMB20tail 35.7 25.1 20.2 18.9 # 12 Standard 35.0 25.0 20.0 20.0 # 13 Ni50Co25VSB20 center 50.8 25.3 4.6 19.3 # 14 Ni Co VB tail 50.9 25.3 4.7 19.1 # 15 Standard S ~ 50.0 25.0 5.0 20.0 # 16 Standard B 1 0 0 0 10 # 17 Standard B2 0 0 0 25 # 18 Standard B3 0 0 0 50 # 19 Standard B4 0 0 0 100 The second test Was Performed using technique the of X-ray diffraction in order to confirm the degree of crystallinity of the Manufactured ribbons . For comparison, measurements were also carried out on crystallized fragments of the amorphous alloys as well as pure elemental nickel, cobalt, chromium, boron and the intermetallic nickel boride. For comparison, the carried out measurements Were aussi is crystallized fragments of the amorphous alloys as well as pure elemental nickel, cobalt, chromium, boron and the intermetallic nickel boride. The amorphous samples were prepared by cutting ribbons into 4 mm x 10 mm rectangular pieces. The amorphous samples Were Prepared by cutting into ribbons 4 mm x 10 mm rectangular pieces. The samples were then degreased with acetone, methanol and deionized water in sequence. The samples Were Then degreased with acetone, methanol and deionized water in sequence. The crystallized fragments had the same bulk composition as the corresponding amorphous alloy and were primarily in the form of brittle plate-like powder. The crystallized fragments Sami Had the bulk composition as the amorphous alloy and Corresponding Were Primarily in the form of brittle plate-like powder. To avoid preferential diffraction due to the plate-like surface of the fragments, the crystallized amorphous alloy was ground to form a fine , ...~ -..w...~ To Avoid preferential diffraction due to the plate-like surface of the fragments, the crystallized amorphous alloy Was ground to form a thin, ... ~ - ~ .. w ...

- 17 - 1033 powder in an agate mortar and dispersed on a slide glass before measurement. - 17 - 1033 powder in an agate mortar and was dispersed glass slide before measurement. Diffraction patterns were measured on a Siemens'tD5000 X-ray diffractometer using 50 kV Cu-Ko radiation with a Ni filter in the range of 20 to 70 degree-20 at a scan rate of 2 degree-20 per minute. Diffraction patterns Were Measured we Siemens'tD5000 X-ray diffractometer using Cu-50 kV Ko radiation with a Ni filter in the range of 20 to 70 degree-20 at a scan rate of 2 degree-20 per minute. The data was processed by Diffrac AT software. The data processed by Diffrac Was AT software. The third test involved determining the electrochemical overpotential for hydrogen evolution by determination of the Tafel slope and exchange current density for the alloys produced above. The third test Involved Determining the electrochemical overpotential for hydrogen evolution by determination of the Tafel slope and exchange current density for the alloys Produced Above. Working electrodes were prepared from the Ni-Co-Cr-B amorphous alloy ribbons of ca. Working electrodes Were Prepared from the Ni-Co-Cr-B amorphous alloy ribbons of ca. 20-50 m thickness and 4 to 15 mm in width. 20-50 m thickness and 4 to 15 mm in width. The shiny side of the ribbon was ground, polished, and degreased. The shiny side of the ribbon Was ground, polished, and degreased. The as-polished ribbon was cut into approximately 10 mm x 10 mm pieces, and each piece was joined to an insulated copper lead. The as-polished ribbon cut into Was Approximately 10 mm x 10 mm pieces, and Each Piece Was joined to an insulated copper lead. The joined area, unpolished wheel side, and periphery of the polished side were thoroughly coated three times at 24 hr intervals by Amercoat 90 epoxy resin. The joined area, unpolished side wheel, and Periphery of the polished side Were Thoroughly coated three times at 24 hr intervals by Amercoat 90 epoxy resin. This masking coat resists either alkaline or acidic environments. This masking coat resists Either alkaline or acidic environments. The exposed geometrical surface area of the fabricated electrodes was typically 0.03 0.01 cm. The exposed geometrical surface area of ​​the electrodes fabricated Typically Was 0.03 0.01 cm. The electrolytic cell shown in Fig. The electrolytic cell shown in Fig. 4 generally as 40 had a three-compartment structure consisting of a 300 ml capacity main body formed of Teflon containing a worldng electrode 42 of the ribbon of alloy of the invention, a 1/2" Teflori tube 44 housing a counter electrode 46, and a 1/4" Teflon PTFE tube filled with mercury-mercuric oxide paste (Hg/HgO) 48. The compartments were separated by electrolyte-permeable membranes 50 in the form of a diaphragm or frit. 4 Generally you 40 Had a three-compartment structure consistant en 300 ml capacity hand FORMED body of Teflon Containing has worldng electrode 42 of the ribbon of alloy of the invention, a 1/2 "tube Teflori housing 44 has counter electrode 46, and a 1/4 "PTFE Teflon tube filled with mercury-mercuric oxide paste (Hg / HgO) 48. The compartments Were separated by electrolyte-permeable membrane 50 in the form of a diaphragm fried gold. The counter electrode 46 was a 25 mm x 12.5 mm platinum gauze with a surface area of ca.. The counter electrode 46 Was a 25 mm x 12.5 mm platinum gauze with a surface area of ​​ca .. 4.4 cm2. 4.4 cm2. The Hg/HgO paste in aqueous IM KOH solution was used as a reference electrode 52. The tip 54 of a Luggin caapillary of the reference electrode compartment was placed a distance of ca. The Hg / HgO paste in IM aqueous KOH solution Was used as reference electrode 52. The tip 54 of a Luggin caapillary of the reference electrode compartment Was Placed distance of ca. 2 mm to the working electrode surface of the alloys of the invention. 2 mm to the working electrode surface of the alloys of the invention. All potentials quoted herein are referred to the Hg/HgO electrode in IM All potentials are quoted HEREIN Referred to the Hg / HgO electrode in IM KOH solution at 30 C. The electrolyte was aqueous 8 M potassium hydroxide solution prepared with KOH and Type I water that had undergone pre-electrolysis for a minimum of 24 hours to remove any impurities in the KOH. KOH solution at 30 C. The electrolyte Was aqueous potassium hydroxide solution 8M Prepared with KOH and water Type I HAD That Undergone pre-electrolysis for a minimum of 24 hours to remove Any impurities in the KOH. The electrolyte was replaced with fresh electrolyte and was deaerated by argon at a rate of 30 ml/min prior * Trade-mark The electrolyte Was REPLACED with fresh electrolyte and Was deaerated by argon at a rate of 30 ml / min prior * Trade-mark

- 18 - 1033 to each experiment. - 18 - 1033 To Each experiment. Argon bubbling was continued during the experiment. Argon bubbling Was continued During the experiment. The solution temperature was controlled at 700C in an 18 L water bath 56 (Fig. 5) with an immersion heater (Polystat Immersion Circulator, Cole-Palmer). The temperature Was controlled solution at 700C in year 18 L water bath 56 (FIG. 5) with an immersion heater (Polystat Immersion Circulator, Cole-Palmer). The apparatus used for electrochemical measurements comprises water bath 56 in electrical contact with a potentiostat/galvanostat Hokuto Denko HA-with a 200 MHz Pentium II personal computer 60, through a GPIB interface 62 and arbitrary function generator (Hokuto Denko HA-105B) 66. The apparatus used for electrochemical included measurements water bath 56 in electrical contact with a potentiostat / galvanostat Hokuto Denko HA-with a 200 MHz Pentium II personal computer 60 through a GPIB interface 62 and arbitrary function generator (Hokuto Denko HA-105B) 66. The electrocatalytic activity of the amorphous alloys for the hydrogen evolution reaction (I ER) was studied by a quasi-steady-state polarization technique. The electrocatalytic activity of the amorphous alloys for the hydrogen evolution reaction (I RE) Was Studied by a quasi-steady-state polarization technique. In practice, polarization curves of the amorphous electrodes were measured under quasi-potentiostatic conditions at a very low sweep rate of 2 mV/min. In practice, polarization curves of the amorphous electrodes Were Measured under quasi-potentiostatic conditions at a very low sweep rate of 2 mV / min. This potential sweep rate was found to be the maximum sweep rate that provided reproducible steady-state measurements. This potential sweep rate Was found to be the maximum rate sweep That Provided reproducible steady-state measurements. The as-polished working electrode was rinsed ultrasonically with acetone, methanol, and Type I water in sequence prior to testing. The as-polished working electrode Was ultrasonically rinsed with acetone, methanol, and Type I water in sequence prior to testing. The electrode was then placed in the cell with deaerated 1M KOH solution and held at a potential of -1.3 V vs. The electrode Was Then Placed in the cell with deaerated 1M KOH solution and Held at a potential of -1.3 V vs. I4g/HgO for 3 hours to clean the electrode surface electrochemically. I4g / HgO for 3 hours to clean the electrode surface electrochemically. The potential was swept over the range of -0.9 to -1.5 V The potential Was swept over the range of -0.9 to -1.5 V vs. vs. Hg/HgO for multiple cycles in order to assess the Tafel behaviour of the electrode response. Hg / HgO for multiple cycles in order for Assessment to the Tafel behavior of the electrode response. Polarization curves were replicated at least three times for each electrode and analyzed for their reproducibility. Polarization curves Were replicated at least three times and For Each electrode Analyzed for Their reproducibility. The fourth test was performed on amorphous alloy and crystalline surfaces to compare the degree of surface roughening and hence electrode degradation by using optical and scanning electron microscopy prior to and post use as an electrocatalyst in the cell. The fourth test Was Performed amorphous alloy is crystalline surfaces and to compare the degree of surface roughening and hence electrode degradation by using optical and scanning electron microscopy prior to and post use as an electrocatalyst in the cell. Optical investigation was achieved using a light stereoscope and light metallograph. Optical investigation Was Achieved using a stereoscope light and light metallograph. Electron imaging was accomplished using a HitachrS-570 SEM equipped with a Link Analytical 10/85s x-ray analyzer. Electron imaging Was Accomplished using a HitachrS-570 SEM equipped with a Link Analytical 10 / 85s x-ray analyzer. Nominal imaging conditions were: accelerating voltage - 20kV, beam current - 100 A, sample tilt - 150. Were nominal imaging conditions: accelerating voltage - 20kV, beam current - 100 A, sample tilt - 150. In the first test a quantitative composition analysis by Inductively Coupled Plasma (ICP) Spectroscopy was performed. In the first test quantitative composition analysis by Inductively Coupled Plasma (ICP) Spectroscopy Was performed. The average experimental composition of each amorphous ribbon as determined by the ICP analysis is listed in * Trade-mark The average experimental composition of Each amorphous ribbon as Determined by the ICP analysis is listed in * Trade-mark

-19- 1033 Table 5. All of the measured compositions of the amorphous ribbons were in good agreement with the targeted compositions. 1033 -19- Table 5. All of the Measured compositions of the amorphous ribbons Were in good agreement with the Targeted compositions. An average magnitude of the deviation of the actual from the nominal composition was < 1 atomic %. An average magnitude of the deviation of the actual from the nominal composition Was <1 atomic%. Variations of principal element concentrations were also measured at two different longitudinal positions over the ribbon such as center and tail. Variations of main element concentrations Were aussi Measured at two different longitudinal positions over the ribbon Such As center and tail. There was no significant difference in the compositions at different positions. There Was no significant difference in the compositions at different positions. From these data, the amorphous ribbons can be regarded as homogeneous in the longitudinal direct"ron. From thesis data, the amorphous ribbons Can Be Regarded as homogeneous in the longitudinal direct "ron. Table 5: Com osition of the Amo hous Ribbons atomic ercen e Targeted Composition Measured Composition Ni54CouCr1B20 Ni53.7Co24.8Cri.oB20.i Ni50Co25Cr5B20 N149.9Co24.6Cr5.7B 19.7 Ni45Co25Cr1aB20 Ni45.iCo24.9Crio.oB20.0 Ni4OCouCr1SB20 Ni4O 3Co25Cr15.oB19.7 Ni3SCouCr2~B20 Ni35.7Co25.iCr2o.2Bi8.9 Ni50Co25V5B20 NiS0.9Cou 3V4..tB19.1 In the second test, the structure of the ribbon was assessed using x-ray diffraction, as it is an integral part of the electrode performance independent of the exact composition of the electrode material. Table 5: Com osition of the Amo hous e Ribbons atomic ercen Targeted Composition Composition Measured Ni54CouCr1B20 Ni53.7Co24.8Cri.oB20.i Ni50Co25Cr5B20 N149.9Co24.6Cr5.7B 19.7 Ni45Co25Cr1aB20 Ni45.iCo24.9Crio.oB20.0 Ni4OCouCr1SB20 Ni4O 3Co25Cr15. oB19.7 Ni3SCouCr2 ~ B20 Ni35.7Co25.iCr2o.2Bi8.9 Ni50Co25V5B20 NiS0.9Cou 3V4..tB19.1 In the second test, the structure of the ribbon Was Assessed using x-ray diffraction, as it is an integral part of the electrode performance independent of the exact composition of the electrode material. It is known that a typical X-ray diffraction (XRD) pattern of an amorphous material is a broad spectrum with no prominent sharp peaks relating to crystalline structure. It is Known That a typical X-ray diffraction (XRD) pattern of an amorphous material is a broad spectrum with no sharp prominent peaks Relating to crystalline structure. Thus, qualitative confirmation of the amorphous nature of an alloy is demonstrated by a broad band peak in its XRD profile. THUS, qualitative confirmation of the amorphous nature of an alloy is Demonstrated by a broad band peak in icts XRD profile. As additional information, an index, viz. As additional information, an index, viz. effective crystallite dimension was calculated to evaluate the largest potential size of crystal embryos in the melt-spun ribbons. effective crystallite size Was Calculated to evaluate-the Largest potential size of crystal embryos in the melt-spun ribbons. The effective crystallite dimension is expressed by the equation: The effective crystallite size is Expressed by the equation: D = 0.91~ D = 0.91 ~ f3cos6 where D is the effective crystallite dimension in nm and k is wavelength of the Cu-Ko f3cos6 Where D is the effective crystallite dimension in nm and k is the wavelength of Cu-K

- 20 - 1033 radiation, ie 0.1542 nm. - 20-1033 radiation, ie 0.1542 nm. 13 denotes the full width of a given diffraction peak in radians at half the maximum intensity. 13 Denotes the full width of a diffraction peak in radians Given at half the maximum intensity. 0 is the Bragg angle of the peak maximum. 0 is the Bragg angle of the maximum peak. The effective crystallite dimension was measured for all the melt-spun ribbons. The effective crystallite size Was Measured for all the melt-spun ribbons. Results of the calculations are summarized in Table 6. The melt-spun Ni-Co-Cr-B alloys displayed very small values of the effective crystallite dimension determined from their broad band peak width in X-ray diffraction confirming the amorphous nature of the melt spun ribbons. Results of the calculations are Summarized in Table 6. The melt-spun Ni-Co-Cr-B alloys displayed very small values ​​of the effective crystallite size Determined from Their broad band width peak in X-ray diffraction Confirming the amorphous nature of the melt spun ribbons. Table 6: Effective C stallite Dimension Amorphous Peak Apparent Full Width Effective Alloy Maximum Mean of Half the Crystallite Composition Position d-Spacing Maximum Dimension 20(0) d(A) Intensity D (nm) 13 (rad) Ni3SCo25Cr2OB20 45.1 1.993 0.138 1.1 Ni50Co25Cr5B20 45.7 2.015 0.126 1.2 Ni51.4Co25 3.6 2 Cr B0 46.3 2.015 0.136 1.1 In the third test, the electroca.talytic perfonmance of the various amorphous electrodes was measured and compared to the behaviour of the crystalline elemental constituents. Table 6: Effective C stallite Dimension Amorphous Peak Apparent Full Width Effective Alloy Maximum Mean of Half the Crystallite Composition d-Spacing Position Maximum Dimension 20 (0) d (A) Intensity D (nm) 13 (rad) Ni3SCo25Cr2OB20 45.1 1.993 0.138 1.1 Ni50Co25Cr5B20 2.015 0.126 45.7 1.2 3.6 Ni51.4Co25 2 Cr B0 46.3 2.015 0.136 1.1 In the third test, the electroca.talytic perfonmance of the various amorphous electrodes Was Measured and Compared to the behavior of the crystalline elemental constituents. In the potential range of -0.9 to -1. In the potential range of -0.9 to -1. 5 V vs. 5 V vs. Hg/HgO, the current responses (polarization curves) of crystalline Ni, C;o, Cr, and the amorphous Ni-Co-(Cr,V)-B alloys varied from ca. Hg / HgO, the current responses (polarization curves) of crystalline Ni, C o, Cr, and the amorphous Ni-Co (Cr, V) -B alloys varied from ca. 0.001 to 1000 mA/cm2. 0001 to 1000 mA / cm2. A linear correlation was found in the potential vs. A linear correlation Was found in the potential vs. logarithmic current plot (Tafel plot) which were analyzed to obtain Tafel parameters, ~ , and i , by a statistical regression method. logarithmic current pad (Tafel plot) qui Were Analyzed to obtenir Tafel parameters, ~, and i, by a statistical regression method. The Tafel slopes and exchange current densities are summarized in Table 7. The Tafel slopes and Exchange current densified are Summarized in Table 7.

-21- 1033 Table 7: Tafel Parameters of Electrodes for the HER in 1M KOH at 30 C 1033 -21- Table 7: Tafel Parameters of electrodes for the HER in 1M KOH at 30 C MATERIAL TAFEL PARAMETERS TAFEL MATERIAL PARAMETERS ... ... -E= -togio ~ c C stalline Ni 1.25-1.56 3.2i-0.3 239f14 Co 1.25-1.44 4.0 0.1 178 4 Mo 1.20-1.40 6.6 0.2 90 4 Amorphous Ni50Co25Cr5B20 1.01-1.50 3.15 161 Ni35Co25Cr2OB20 1.01-1.50 3.58 114 Ni5oCo25VSB20 1.00-1.50 3.96 100 Ni.nMo8B20 0.94-1.55 4.0 0.04 180 2 NVo2Mo6B20 1.00-1.50 5.1 0.07 142 3 Ni50Co4Mo4B20 1.00-1.50 5.1 0.03 148 2 * Potential range (V vs. Hg/HgO), * * Exchange current density (A/cm2), *** Tafel slope (mV/decade), high field Appreciable differences in the current density values were clearly observed as a function of the compositions of the amorphous alloys as shown in Table 7. -E = c ~ C -togio stalline Neither 1.25-1.56 3.2i-0.3 239f14 Co 1.25-1.44 4.0 0.1 178 4 MB 1.20-1.40 6.6 0.2 90 4 Amorphous Ni50Co25Cr5B20 1.01-1.50 3.15 1.01-1.50 3.58 114 161 Ni35Co25Cr2OB20 Ni5oCo25VSB20 1.00- 1.50 3.96 100 4.0 0.04 180 Ni.nMo8B20 0.94-1.55 1.00-1.50 NVo2Mo6B20 2 5.1 0.07 142 3 5.1 0.03 148 1.00-1.50 Ni50Co4Mo4B20 2 * Potential range (V vs. Hg / HgO), * Exchange current density (A / cm2 ) *** Tafel slope (mV / decade), high field Appreciable differences in the current density gains Clearly Were Observed as a function of the compositions of the amorphous alloys as shown in Table 7. The following ranking of the electrocatalytic activity was found: The Following ranking of the electrocatalytic activity Was found: N150CO25V5B20 > Ni35Co25Cr2o$20 I Ni50Co25Cr5B20 This ranking order does not simply follow the order of magnitude of the Cr/V N150CO25V5B20> Ni35Co25Cr2o $ 20 I Ni50Co25Cr5B20 This ranking order does not simply follow the order of magnitude of the Cr / V content in the amorphous alloys, but is particular to the elemental form. content in the amorphous alloys, the goal is to Particular elemental form. The highest electrocatalytic activity of Ni50Co25V5B20 amongst the amorphous alloys could possibly be attributed to the synergetic effect of Ni-Co-V that may influence the nature of the oxide film formed on this amorphous alloy. The Highest electrocatalytic activity of the amorphous alloys Ni50Co25V5B20 Amongst Could Possibly Attributed To be the synergetic effect of Ni-Co-V That May influence the nature of the oxide film on this amorphous alloy FORMED. The improvement of this invention compared with United States Patent No. 5,429,725 is also evident from 'Table 7 by comparison of the performance of the amorphous alloys. The improvement of this invention Compared with United States Patent No. 5,429,725 est evident from 'Table 7 by comparison of the performance of the amorphous alloys. The invention shows higher exchange The invention shows Higher Exchange

- 22 - 1033 current densities combined with lower Tafel slopes in the (Cr,V)-containing alloys compared with the Mo-containing alloys; - 22 - 1033 combined with lower current densified Tafel slopes in the (Cr, V) -containing alloys Compared with the Mo-containing alloys; both features contribute to enhanced operating efficiency of the material as an electrocatalyst for alkaline water electrolysis. Both features contribuer to enhanced operating efficiency of the material as an electrocatalyst for alkaline water electrolysis. In the fourth test, in order to obtain additional information on the condition of the electrode surface after multiple cycles of operation, specimens were examined using optical and scanning electron microscopy (SEM). In the fourth test, in order to obtenir additional information on the condition of the electrode surface after multiple cycles of operation, specimens Were Examined using optical and scanning electron microscopy (SEM). It was found that the potential cycled crystalline Ni, Co and Mo electrodes had thick corrosion product layers. It was found que le potential cycled crystalline Ni, Co and Mo electrodes HAD thick corrosion product layers. Crystalline Ni electrodes after 200 and 600 cycles showed a growth in the corrosion layer with potential cycling. Crystalline Ni electrodes after 200 and 600 cycles Showed growth in the corrosion layer with potential cycling. The crystalline Co electrode showed a sign of crystallization / dissolution reactions by polygon-plate-like uniform deposits on the electrode surface. The crystalline Co electrode Showed a sign of crystallization / dissolution reactions by polygon-plate-like uniform deposits on the electrode surface. The crystalline Mo electrode showed a severely corroded surface and a remaining skeleton structure that indicated the active dissolution of Mo. All ciystalline electrodes showed much higher roughness than their as-polished state. The crystalline Mo electrode Showed has Severely corroded surface and a remaining skeleton structure Indicated That the dissolution of active electrodes MB All ciystalline much Showed Higher than roughness Their as-polished state. In contrast, potential cycled amorphous electrodes showed very smooth surfaces and no indication of corrosion. In contrast, potential cycled amorphous electrodes Showed very smooth surfaces and no indication of corrosion. Only a slight surface layer (probably Ni oxides) could be seen characterized by a dull transparent film that covered the very smooth surface of the amorphous alloys. Only a slight surface layer (probably Ni oxides) Could Be caractérisé seen by a dull transparent film covered That the very smooth surface of the amorphous alloys. No significant difference was found between the amorphous electrodes pre and post cycling. No significant difference Was found entre les amorphous electrodes pre and post cycling. Hence, after exposure to severe potential cycling conditions, the amorphous alloy electrodes were more stable than the crystalline electrodes of the elements Ni, Co or Mo. Hence, after exposure to severe potential cycling conditions, the amorphous alloy electrodes Were more stable than the crystalline electrodes of the elements Ni, Co or Mo. Although this disclosure had described and illustrated certain preferred embodiments of the invention, it is to be understood that the invention is not restricted to these particular embodiments. ALTHOUGH this disclosure HAD Described and illustrated certain preferred embodiments of the invention, it is to be Understood que la invention is not restricted to thesis Particular embodiments. Rather, the invention includes all embodiments that are functional or mechanical equivalents of the specific embodiment and features that have been described and illustrated. Rather, the invention includes all embodiments That are functional or mechanical equivalents of the specific features and Embodiment-have beens That Described and illustrated.

Claims (14)

We claim: We claim:
1. A metallic glass of use in electrochemical processes, said metallic glass consisting of a homogeneous material of the general nominal composition (Ni,Co)100-xt A x Z t wherein: 1. A metallic glass of use in electrochemical processes, Said metallic glass consistant of a homogeneous material of the nominal general composition (Ni, Co) 100-xt A x Z t où: Ni and Co are always present; Ni and Co are always present; A is at least one member selected from the group consisting of lVb, Vb, VIb VIIb and VIII of the Periodic Table; At least one member is selected at from the group consistant en IVb, Vb, VIb and VIII VIIb of the Periodic Table; provided that at least one of Cr and V is present and that A cannot be Fe or Mo; Provided That at least one of Cr and V is present and That A can not be Fe or Mo; Z is at least one of a member selected from the group consisting of carbon and a metalloid element selected from group IIIa, IVa, Va and VIa of the Periodic Table; Z is at least one of a member selected from the group consistant en carbon and a metalloid element selected from Group IIIa, IVa, Va and VIa of the Periodic Table; wherein x is selected from 1 to 20 atomic percent; où x is selected from 1 to 20 atomic percent; t is selected from 15 to 25 atomic percent; t is selected from 15 to 25 atomic percent; and 100-xt is selected from 55-84 atomic percent. and 100-xt is selected from 55-84 atomic percent.
2. A metallic glass as claimed in claim 1 wherein A is at least one metal selected from the group consisting of Ti, V, Cr, Mn, Zr, Nb, Tc, Ta, and W. 2. A metallic glass as Claimed in claim 1 A où est au moins un metal selected from the group consistant en Ti, V, Cr, Mn, Zr, Nb, Tc, Ta, and W.
3. A metallic glass as claimed in claim 2 wherein x is selected from I to 5 atomic percent. 3. A metallic glass as Claimed in claim 2 où X is selected from I to 5 atomic percent.
4. A metallic glass as claimed in claim 1 wherein Z is at least one member selected from the group consisting of silicon, phosphorus, carbon, and boron. 4. A metallic glass as Claimed in claim 1 Z où est au moins un member selected from the group consistant en silicon, phosphorus, carbon, and boron.
5. A metallic glass as claimed in claim 4 wherein t is 20 atomic percent. 5. A metallic glass as Claimed in claim 4 t où est 20 atomic percent.
6. A metallic glass as claimed in claim 1 wherein said Ni, Co, A and Z are in an elemental state. 6. A metallic glass as Claimed in claim 1 où Said Ni, Co, A and Z are in an elemental state.
7. A metallic glass as claimed in claim 1 consisting of a material having the nominal composition of Ni50Co25Cr5B20. 7. A metallic glass as Claimed in claim 1 of a consistant material HAVING the nominal composition of Ni50Co25Cr5B20.
8. A metallic glass as claimed in claim 1 consisting of a material having the nominal composition of Ni50Co25V5B20. 8. A metallic glass as Claimed in claim 1 of a consistant material HAVING the nominal composition of Ni50Co25V5B20.
9. A metallic glass as claimed in claim 1 consisting of a material having the preferred nominal composition of Ni45Co25V5Cr5B20. 9. A metallic glass as Claimed in claim 1 of a consistant material HAVING the preferred nominal composition of Ni45Co25V5Cr5B20.
10. An electrode for use in an electrochemical cell comprising a metallic glass consisting of a material as claimed in any one of claims I to 9. 10. An electrode for use in an electrochemical cell comprenant metallic glass material have a consistant en Any Claimed in one of claims I to 9.
11. An electrode as claimed in claim 10 comprising a support and on at least a portion of said support a coating comprising said metallic glass. 11. An electrode as Claimed in claim 10 comprenant support and is at least a portion of a coating Said support comprenant Said metallic glass.
12. An electrode as claimed in claim 10 or claim 11 in the form of a self-supporting structure. 12. An electrode as Claimed in claim 10 or claim 11 in the form of a self-supporting structure.
13. An electrode as claimed in any one of claims 10 to 12 wherein said electrochemical cell is for the electrochemical production of oxygen and hydrogen from an aqueous solution. 13. An electrode as Claimed in Any one of claims 10 to 12 où est Said electrochemical cell for the electrochemical production of oxygen and hydrogen from an aqueous solution.
14. An improved process for the electrochemical production of oxygen and hydrogen from an aqueous alkaline solution in an electrochemical cell, said process comprising electrolysing said aqueous solution with electrodes, said improvement comprising one or more of said electrodes comprising a metallic glass consisting of a material as claimed any one of claims 1 to 9. 14. An Improved Process for the electrochemical production of oxygen and hydrogen from an aqueous alkaline solution in an electrochemical cell, Said Said process comprenant electrolysing aqueous solution with electrodes, Said improvement comprenant one or more of electrodes Said comprenant metallic glass material was consistant en Any Claimed as one of claims 1 to 9.
CA002287648A 1999-10-26 1999-10-26 Electrodes de metal amorphe/verre metallique pour processus electrochimiques Expired - Fee Related CA2287648C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CA002287648A CA2287648C (en) 1999-10-26 1999-10-26 Electrodes de metal amorphe/verre metallique pour processus electrochimiques

Applications Claiming Priority (10)

Application Number Priority Date Filing Date Title
CA002287648A CA2287648C (en) 1999-10-26 1999-10-26 Electrodes de metal amorphe/verre metallique pour processus electrochimiques
EP00971182A EP1230412A2 (en) 1999-10-26 2000-10-23 Amorphous metal/metallic glass electrodes for electrochemical processes
AU10135/01A AU1013501A (en) 1999-10-26 2000-10-23 Amorphous metal/metallic glass electrodes for electrochemical processes
BR0014994-2A BR0014994A (en) 1999-10-26 2000-10-23 Metallic glass for use in electrochemical processes, the electrode for use in an electrochemical cell and process for the electrochemical production of oxygen and hydrogen from an aqueous solution in an electrochemical cell
CN00814770A CN1382229A (en) 1999-10-26 2000-10-23 Amorphous metal/metallic glass electrodes for electrochemical processes
PCT/CA2000/001251 WO2001031085A2 (en) 1999-10-26 2000-10-23 Amorphous metal/metallic glass electrodes for electrochemical processes
MXPA02002673A MXPA02002673A (en) 1999-10-26 2000-10-23 Amorphous metal metallic glass electrodes for electrochemical processes.
JP2001533216A JP2003513170A (en) 1999-10-26 2000-10-23 Amorphous metal / metal glass electrode for an electrochemical method
NO20020957A NO20020957A (en) 1999-10-26 2002-02-27 Amorphous metal / metal flap electrodes for electrochemical processes
ZA200201857A ZA200201857B (en) 1999-10-26 2002-03-06 Amorphous metal/metallic glass electrodes for electrochemical process.

Publications (2)

Publication Number Publication Date
CA2287648A1 CA2287648A1 (en) 2001-04-26
CA2287648C true CA2287648C (en) 2007-06-19

Family

ID=4164494

Family Applications (1)

Application Number Title Priority Date Filing Date
CA002287648A Expired - Fee Related CA2287648C (en) 1999-10-26 1999-10-26 Electrodes de metal amorphe/verre metallique pour processus electrochimiques

Country Status (10)

Country Link
EP (1) EP1230412A2 (en)
JP (1) JP2003513170A (en)
CN (1) CN1382229A (en)
AU (1) AU1013501A (en)
BR (1) BR0014994A (en)
CA (1) CA2287648C (en)
MX (1) MXPA02002673A (en)
NO (1) NO20020957A (en)
WO (1) WO2001031085A2 (en)
ZA (1) ZA200201857B (en)

Families Citing this family (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100647672B1 (en) 2004-12-24 2006-11-23 삼성에스디아이 주식회사 A transparent electrode with thermal stability, a fabrication method of the same and a dye-sensitized solar cell comprising the same
JP4992085B2 (en) * 2007-02-23 2012-08-08 国立大学法人東京工業大学 Electroless plating film-form catalyst composition
WO2009063031A2 (en) 2007-11-16 2009-05-22 Akzo Nobel N.V. Electrode
US9984787B2 (en) 2009-11-11 2018-05-29 Samsung Electronics Co., Ltd. Conductive paste and solar cell
US9947809B2 (en) 2009-11-11 2018-04-17 Samsung Electronics Co., Ltd. Conductive paste and electronic device and solar cell including an electrode formed using the conductive paste
WO2012010940A2 (en) * 2010-07-21 2012-01-26 Institut Polytechnique De Grenoble Amorphous metal alloy
JP6346441B2 (en) 2010-07-21 2018-06-20 ロレックス・ソシエテ・アノニムRolex Sa Watch parts, including the amorphous metal alloy
KR101741683B1 (en) 2010-08-05 2017-05-31 삼성전자주식회사 Conductive paste and electronic device and solar cell including an electrode formed using the conductive paste
US8668847B2 (en) 2010-08-13 2014-03-11 Samsung Electronics Co., Ltd. Conductive paste and electronic device and solar cell including an electrode formed using the conductive paste
US8987586B2 (en) 2010-08-13 2015-03-24 Samsung Electronics Co., Ltd. Conductive paste and electronic device and solar cell including an electrode formed using the conductive paste
US8974703B2 (en) 2010-10-27 2015-03-10 Samsung Electronics Co., Ltd. Conductive paste and electronic device and solar cell including an electrode formed using the same
US9105370B2 (en) 2011-01-12 2015-08-11 Samsung Electronics Co., Ltd. Conductive paste, and electronic device and solar cell including an electrode formed using the same
US8940195B2 (en) 2011-01-13 2015-01-27 Samsung Electronics Co., Ltd. Conductive paste, and electronic device and solar cell including an electrode formed using the same
KR101814014B1 (en) 2011-03-25 2018-01-03 삼성전자주식회사 Conductive paste and electronic device and solar cell including an electrode formed using the conductive paste
KR101796658B1 (en) 2011-03-28 2017-11-13 삼성전자주식회사 Conductive paste and electronic device and solar cell including an electrode formed using the conductive paste
CA2847210A1 (en) 2011-09-01 2013-03-07 Simon TRUDEL Electrocatalytic materials, and methods for manufacturing same
KR20130065444A (en) 2011-12-09 2013-06-19 삼성전자주식회사 Conductive paste and electronic device and solar cell including an electrode formed using the conductive paste
JP5822235B2 (en) * 2012-06-08 2015-11-24 住友金属鉱山エンジニアリング株式会社 The method of removing the oxide nitrogen
US20160168675A1 (en) * 2013-07-12 2016-06-16 Hewlett-Packard Development Company, L.P. Amorphous thin metal film
JP5949792B2 (en) * 2014-01-15 2016-07-13 株式会社豊田中央研究所 Crystalline electrode material and insoluble electrode
US10177310B2 (en) 2014-07-30 2019-01-08 Hewlett Packard Enterprise Development Lp Amorphous metal alloy electrodes in non-volatile device applications

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4150981A (en) * 1977-08-15 1979-04-24 Allied Chemical Corporation Glassy alloys containing cobalt, nickel and iron having near-zero magnetostriction and high saturation induction
DE3063716D1 (en) * 1979-03-30 1983-07-21 Allied Corp Homogeneous ductile brazing foils
DE3515742C2 (en) * 1985-05-02 1988-02-25 Dechema Deutsche Gesellschaft Fuer Chemisches Apparatewesen E.V., 6000 Frankfurt, De
US4609442A (en) * 1985-06-24 1986-09-02 The Standard Oil Company Electrolysis of halide-containing solutions with amorphous metal alloys
DE3689059D1 (en) * 1985-08-02 1993-10-28 Daiki Engineering Co Surface-activated amorphous alloys and supersaturated alloys for electrodes used for electrolysis of solutions and processes for activation of the surfaces.
DE3853190T2 (en) * 1987-05-07 1995-08-24 Mitsubishi Materials Corp A high corrosion resistant amorphous alloy.
JPH0261036A (en) * 1988-08-24 1990-03-01 Riken Corp Temperature sensitive amorphous alloy
JPH04362162A (en) * 1991-06-06 1992-12-15 Nippon Steel Corp Amorphous alloy thin strip having crystallized layer at inside of sheet thickness and excellent in magnetic property
JPH0570903A (en) * 1991-09-13 1993-03-23 Akihisa Inoue High strength nickel-based alloy
JP2820613B2 (en) * 1994-03-29 1998-11-05 新日本製鐵株式会社 Bondable refractory material for liquid phase diffusion bonding alloy foil in an oxidizing atmosphere
CA2126136C (en) * 1994-06-17 2007-06-05 Steven J. Thorpe Amorphous metal/metallic glass electrodes for electrochemical processes

Also Published As

Publication number Publication date
BR0014994A (en) 2002-06-18
NO20020957A (en) 2002-04-24
MXPA02002673A (en) 2003-10-14
CA2287648A1 (en) 2001-04-26
CN1382229A (en) 2002-11-27
EP1230412A2 (en) 2002-08-14
JP2003513170A (en) 2003-04-08
WO2001031085A2 (en) 2001-05-03
ZA200201857B (en) 2002-12-24
WO2001031085A3 (en) 2001-09-20
AU1013501A (en) 2001-05-08
NO20020957D0 (en) 2002-02-27

Similar Documents

Publication Publication Date Title
US5876867A (en) Platinum skeleton alloy-supported electrocatalyst, electrode using the electrocatalyst, and process for producing the electrocatalyst
Lu et al. A selective and efficient electrocatalyst for carbon dioxide reduction
Kibsgaard et al. Building an appropriate active-site motif into a hydrogen-evolution catalyst with thiomolybdate [Mo 3 S 13] 2− clusters
Archer et al. The electrochemical properties of metallic glasses
Mitchell et al. Electrodeposition of Cobalt and Cobalt‐Aluminum Alloys from a Room Temperature Chloroaluminate Molten Salt
CA1207706A (en) Electrode of particles including boron valve metal, or iron group and active particles
Ishihara et al. Tantalum (oxy) nitrides prepared using reactive sputtering for new nonplatinum cathodes of polymer electrolyte fuel cell
Subbaraman et al. Trends in activity for the water electrolyser reactions on 3d M (Ni, Co, Fe, Mn) hydr (oxy) oxide catalysts
Deivaraj et al. Preparation of PtNi nanoparticles for the electrocatalytic oxidation of methanol
DE3118320C2 (en)
Skjerpe Intermetallic phases formed during DC-casting of an Al− 0.25 wt Pct Fe− 0.13 wt Pct Si alloy
Yoo et al. Platinum‐coated, nanoporous gold nanorod arrays: synthesis and characterization
US6797667B2 (en) Process for preparing an anode catalyst for fuel cells and the anode catalyst prepared therewith
KR910001492B1 (en) Corrosion-resistant amorphous surface alloy and the method
Cao et al. Catalytic behavior of Co3O4 in electroreduction of H2O2
Nkeng et al. Enhancement of surface areas of Co3O4 and NiCo2O4 electrocatalysts prepared by spray pyrolysis
Hakamada et al. Preparation of nanoporous Ni and Ni–Cu by dealloying of rolled Ni–Mn and Ni–Cu–Mn alloys
Tanaka et al. Preparation and evaluation of a multi-component catalyst by using a co-sputtering system for anodic oxidation of ethanol
US4169025A (en) Process for making catalytically active Raney nickel electrodes
CA1162423A (en) Corrosion resistant amorphous noble metal-base alloys
Natter et al. Tailor-made nanomaterials designed by electrochemical methods
CN86105605A (en) Electrolysis of halide-containing solutions with amorphous metal alloys
EP0203982B1 (en) Method for preparing an electrode and use thereof in electrochemical processes
Jeong et al. Electrolytic production of metallic uranium from U3O8 in a 20-kg batch scale reactor
US8691716B2 (en) Electrocatalysts based on mono/plurimetallic carbon nitrides for fuel cells fueled with hydrogen

Legal Events

Date Code Title Description
EEER Examination request
MKLC Lapsed (correction)
MKLA Lapsed