WO2012141761A1 - Methods of making and using palladium alloys - Google Patents

Methods of making and using palladium alloys Download PDF

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Publication number
WO2012141761A1
WO2012141761A1 PCT/US2012/000088 US2012000088W WO2012141761A1 WO 2012141761 A1 WO2012141761 A1 WO 2012141761A1 US 2012000088 W US2012000088 W US 2012000088W WO 2012141761 A1 WO2012141761 A1 WO 2012141761A1
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atomic percent
gas
alloy
metal
concentration
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PCT/US2012/000088
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French (fr)
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Han Nee
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Han Nee
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/022—Metals
    • B01D71/0223—Group 8, 9 or 10 metals
    • B01D71/02231—Palladium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/022—Metals
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/501—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion
    • C01B3/503—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion characterised by the membrane
    • C01B3/505—Membranes containing palladium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0405—Purification by membrane separation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Definitions

  • the invention relates to energy generation using various palladium alloys and methods of making the palladium alloys.
  • the alloys can also be used as hydrogen gas purification membrane and electrodes for electrochemical processes.
  • a palladium alloy In a hydrogen gas purification membrane, a palladium alloy is used due to its high diffusivity and solubility of hydrogen. With impure hydrogen at the high pressure (P-high) side, hydrogen gas will diffuse through the palladium alloy membrane with area A to the low pressure (P-low) side.
  • P-high high pressure
  • P-low low pressure
  • Permeation rate DxS[(P-high) l/2 -(P-low) l/2 ]/t equation A where t is the thickness of the membrane, and D and S are, respectively, the diffusion coefficient and the solubility of hydrogen atoms in the palladium alloy. Hydrogen gas dissolves in the metal as atoms according to the following equation:
  • the typical operation temperature of the Pd membrane is between 350 to 550 degrees C to get high permeability of hydrogen or its isotopes. Other gases either dissolve very little or diffuse slowly in the membrane. They thus will be separated from the hydrogen by the membrane.
  • the workhorse of the membrane material has been palladium with 23-25% silver by weight. This material exists as a single phase from room temperature to the highest operation temperature.
  • US patents 6,764,561 and 7,381,368 disclose a two-phase palladium-boron alloy for this purpose. This material will undergo phase changes if operated between room temperature and 450 degrees C. Because different Pd-B phases have different lattice spacing, cycling between room temperature and high temperature will cause lattice misfit to grow and stress between the phases which will eventually leads to cracks of the membrane. This material can operate at lower temperature, say below 400 to 410 degrees C to avoid phase transformation, but this will lower its permeation rate, because the diffusion rate of hydrogen nucleus lowers with temperature, which lowers the membrane's efficiency. Furthermore, because of the concentration gradient of the hydrogen in the membrane from the high pressure side to the low pressure side, the relative amount of the two phases will vary across the thickness of the membrane. This causes additional stresses at the interphase of the two phases which may leads to cracks. Therefore, its usefulness as a hydrogen membrane material is limited.
  • US patent 5,518,556 discloses a single phase boron-containing palladium or platinum alloy, but it was made by a chemical vapor deposition process and used as a hard coating for wear resistance purpose. It is not useful as a hydrogen permeation membrane.
  • Patterson discloses an energy producing device using nickel coated on palladium on a plastic ball as a cathode in an electrolytic cell.
  • the cell operates between room temperature and near 100 degrees C.
  • Patterson claimed a nuclear reaction driven by a chemical process. It had at least two substantial deficiencies, namely:
  • Hagelstein et al discloses an apparatus using deuterium and/or hydrogen deuterium in material such as palladium to generate energy from nuclear reaction. No palladium alloy composition is disclosed.
  • the palladium alloys used in this invention are palladium added with boron, carbon, or oxygen, singly or in combination.
  • concentration of oxygen as an alloying element in palladium ranges from about 0.01 atomic percent to about 1.0 atomic percent, and with a more preferred range from about 0.1 atomic percent to about 0.6 atomic percent.
  • concentration of carbon as an alloying element in palladium ranges from 0.01 atomic percent to about 10.0 atomic percent, and with a more preferred range from about 0.1 atomic percent to about 5.0 atomic percent.
  • the concentration of boron as an alloying element in palladium ranges from 0.01 atomic percent to about 20 atomic percent, and with a more preferred range from about 0.1 atomic percent to about 18 atomic percent.
  • the preferred operating pressure is from about 0.1 atmospheres to about 1000 atmospheres, with a more preferred range of about 1 atmospheres to about 100 atmospheres at the operating condition.
  • the preferred operating temperature for Pd- B, Pd-C and Pd-0 alloys are from about 400 to about 1065 degrees C, with a more preferred temperature range from about 450 to about 750 degrees C. These alloys all exist as single phase alloys at these operating temperatures and pressures.
  • These alloys can be prepared as a coating on a suitable substrate by typical physical vapor deposition processes such as sputtering, ion plating, thermal evaporation techniques, and so on. It is preferred that the substrate have an orientation of the ⁇ 100 ⁇ plane being parallel to the substrate surface, so that the coating will also have the same preferred orientation.
  • a wrought form of the alloys can be made by power metallurgy technique by first mixing powders of the various elements and going through a pressing, isostatic pressing and sintering process or a hot isostatic pressing process. This is followed by various metal-shaping processes such as hot forging or hot rolling. The alloys are then preferably annealed in a vacuum and quenched to room temperature.
  • a suitable rolling schedule can be developed to produce foils with a preferred orientation of the ⁇ 100 ⁇ plane being parallel to the surface and the (100) direction being parallel to the rolling direction.
  • the above mentioned palladium materials can be further alloyed with various oxides such as alumina, silicate, sodium oxide, calcium oxide, and so on. They are mechanically alloyed in powder form, then pressed and lightly sintered in a vacuum, or in hydrogen or deuterium gas, to achieve a porous structure of less than full density.
  • the above mentioned palladium alloys in coating, foil or porous form can be used as the core material to generate energy or heat in a pressurized chamber filled with deuterium (D2) gas, hydrogen (H2) gas or their isotope (HD), singly or in combination, at the above mentioned pressure and temperature. Excess energy or heat can be generated and triggered by the application of electric field, magnetic field, ultrasonic excitation etc. to the core material.
  • D2 deuterium
  • H2 hydrogen
  • HD isotope
  • These palladium alloys in various forms can also be used as hydrogen permeation membranes, hydrogen isotope separation membrane, or electrodes in various forms.
  • Excess heat or energy can also be generated by using the palladium alloys in various forms as a cathode with a counter electrode as an anode.
  • the electrodes are placed in an electrolyte of deuterium water or heavy water (D20), or semi-heavy water (HDO).
  • the electrolyte includes an ionic solution with substantial electrical conductivity.
  • a voltage is applied across the electrodes to electrolyze the solution and generate deuterium or HD gases. These gasses dissolve into the palladium electrode and cause the electrode to generate excess heat or excess energy.
  • a palladium and/or palladium alloys of this invention can be coated by electroplating, or by an electroless plating process, onto a wire core.
  • the core may be of copper, a copper alloy such as CDA 725, or an austenitic stainless steel such as 304S, 309S or 316S.
  • the wire core Before coating, the wire core is hard drawn to more than 90% reduction in diameter and then annealed to promote (100) fiber texture. After electroplating or electroless plating, the material is annealed in a vacuum at a suitable temperature to
  • the palladium or palladium alloy should have a thickness of 1 or 2 microns, with (100) fibrous texture.
  • FIG. 1 is a hydrogen permeation device.
  • FIG. 2 is a deuterium gas charging and energy generation device.
  • the palladium alloys used in this invention are palladium added with boron, carbon, or oxygen, singly or in combination.
  • concentration of oxygen as an alloying element in palladium ranges from about 0.01 atomic percent to about 1.0 atomic percent, with a more preferred range from about 0.1 atomic percent to about 0.6 atomic percent.
  • concentration of carbon as an alloying element in palladium ranges from 0.001 atomic percent to about 5.0 atomic percent, with a more preferred range from about 0.001 atomic percent to about 1.5 atomic percent.
  • concentration of boron as an alloying element in palladium ranges from 0.01 atomic percent to about 20 atomic percent and with a more preferred range from about 0.1 atomic percent to about 18 atomic percent.
  • the preferred operating pressure is from about 0.1 atmospheres to about 1000 atmospheres, with a more preferred range of about 1 atmospheres to about 100 atmospheres.
  • the preferred operating temperature for Pd-B, Pd-C and Pd-O alloys are from about 400 to about 1065 degrees C, with a more preferred temperature range from about 450 to about 750 degrees C.
  • the alloys all exist as a single phase at these operating temperatures and pressures.
  • These alloys can be prepared as a coating on a suitable substrate by typical physical vapor deposition processes such as sputtering, ion plating, thermal evaporation techniques, and so on. It is preferred that the substrate have an orientation of the ⁇ 100 ⁇ plane being parallel to the substrate surface so that the coating will also have the same preferred orientation.
  • a wrought form of the alloys can be made by power metallurgy technique by first mixing powders of the various elements and going through a pressing, isostatic pressing and sintering process or a hot isostatic pressing process. This is followed by various metal-shaping process such as hot forging or hot rolling. The alloys are then preferably annealed in a vacuum and quenched to room temperature.
  • a suitable rolling schedule can be developed to produce foils with a preferred orientation of the ⁇ 100 ⁇ plane being parallel to the surface and the (100) direction being parallel to the rolling direction.
  • the above mentioned palladium materials can be further alloyed with various oxides such as alumina, silicate, sodium oxide, calcium oxide, and so on. They are mechanically alloyed in powder form, then pressed and lightly sintered in a vacuum, or in hydrogen or deuterium gas, to achieve a porous structure of less than full density.
  • oxides such as alumina, silicate, sodium oxide, calcium oxide, and so on. They are mechanically alloyed in powder form, then pressed and lightly sintered in a vacuum, or in hydrogen or deuterium gas, to achieve a porous structure of less than full density.
  • the above mentioned palladium alloys in coating, foil or porous form can be used as the core material to generate energy or heat in a pressurized chamber filled with deuterium (D2) gas, hydrogen (H2) gas or their isotope (HD), singly or in combination at the above mentioned pressure and temperature. Excess energy or heat can be generated and triggered by the application of electric field, magnetic field, ultrasonic excitation etc. to the core material.
  • D2 gas deuterium
  • H2 gas or their isotope (HD) singly or in combination at the above mentioned pressure and temperature. Excess energy or heat can be generated and triggered by the application of electric field, magnetic field, ultrasonic excitation etc. to the core material.
  • These palladium alloys in various forms can also be used as hydrogen permeation membranes, hydrogen isotope separation membranes, or electrodes in
  • Excess heat or energy can also be generated by using the palladium alloys in various forms as a cathode with a counter electrode as an anode.
  • the electrodes are placed in an electrolyte of deuterium water or heavy water (D20), or semi-heavy water (HDO).
  • the electrolyte includes an ionic solution with substantial electrical conductivity.
  • a voltage is applied across the electrodes to electrolyze the solution and generate deuterium or HD gases. These gasses dissolve into the palladium electrode and cause the electrode to generate excess heat or excess energy.
  • the palladium and/or palladium alloys of this invention can be coated by electroplating, or by an electroless plating process, onto a wire core.
  • the core may be of copper, a copper alloy such as CDA 725, 99.99% purity nickel, nickel 200, or an austenitic stainless steel such as 304S, 309S or 316S.
  • the wire core is hard drawn to more than 90% reduction in diameter and then annealed to promote (100) fiber texture. After electroplating or electroless plating, the material is annealed in a vacuum at a suitable temperature to
  • the palladium or palladium alloy should have a thickness of 1 or 2 microns, with (100) fibrous texture.
  • the wrought form of the palladium alloy of the current invention one can use a powder metallurgy technique such as pressing and sintering.
  • a more preferred method is hot isostatic pressing using powders of the alloying elements of 99.99% purity.
  • Oxygen can be added as oxide, such as the oxides of boron, silicon, aluminum, sodium, calcium, and so on.
  • the powders are first thoroughly mixed in a vacuum at 100 to 200 degrees C. They are then put in a can and sealed.
  • the can is made from 1010 plain carbon steel, extra low carbon killed steel, or 304 stainless steel.
  • Hot Isostatic Pressing (HIP) is done by argon at a pressure of 10,000 to 30,000 psi and a temperature of 1100 to 1200 degrees C for one hour, or until full density and homogeneous microstructure is achieved.
  • the typical shape is either a billet form for rolling into foil, a rod form for drawing into wires, or a pancake form for a sputtering target.
  • the HIPed ingot goes through a series of hot rolling and cold rolling process, with more than 90% thickness reduction in the cold rolling process preferred, followed by final anneal at 900 to 1000 degrees C for an hour in a vacuum.
  • the ingot is then quenched to room temperature, with the resulting foil having a (100) preferred orientation and a single phase.
  • the resulting foil has high mechanical strength because of the alloying content. This offers the opportunity to produce a foil of reduced thickness for use as a hydrogen purification membrane.
  • the hydrogen permeation rate is higher, according to equation A before.
  • impure hydrogen gas is the feed material. It has a pressure in the 3 to 7 bar range and an operating temperature of 300 to 600 degrees C.
  • the standard membrane material is palladium with 23 to 25 % by weight of silver.
  • the membrane has a thickness of about 25 microns. Too thick a membrane will reduce the permeation rate at any given temperature. Too thin a layer will be too fragile to withstand the pressure differential and is liable to facture.
  • Palladium with boron, oxygen and carbon at low concentration is the preferred way to strengthen the membrane, because solid solution strengthening by interstitial atoms is much more effective than a substitutional solid solution hardening alloy (such as Pd-23 to25 % Ag). Further, a single phase alloy operating at 410 degrees C or above is preferred. This avoids phase changes at the operating temperature and the resulting stress generated due to different lattice spacing for different phases.
  • cold argon or nitrogen is used to flush the hydrogen out of the gas tubes and to quench the Pd membrane to room temperature.
  • Suitable substrates include oxygen free high conductivity copper, 99.99% purity nickel, nickel 200, cupronickel 70/30, tin bronzes (CDA902 through 917), aluminum bronze (CDA952 through 958), stainless steel 304S, 309S and 316S, and so on, provided that the substrates are made with a (100) preferred orientation.
  • the substrate is in a strip form with one or 2 cm in width. It is
  • the sputtering process can be further improved by a reactive sputtering process.
  • deuterium gas and/or deuterium hydrogen gas is fed into the sputtering chamber at a partial pressure of 0.1 to 5x10 "3 torr.
  • Argon is present with a partial pressure at 1 to 3xl0 "3 torr.
  • the residual gas pressure is 5xl0 "5 torr.
  • the preferred thickness of the coating is from 0.5 to about 3 microns, with a more preferred range of 1 to 2 microns.
  • the preferred deposition rate is 0.5 nm/sec or less, with a deposition rate of 0.3 microns/sec or less more preferred.
  • the palladium alloy coating will take on the preferred orientation (100) of the substrate.
  • the same substrate mentioned above can also be used as a substrate for thermal evaporation of palladium and boron simultaneously in a vacuum chamber.
  • the chamber is equipped with a high temperature effusion cell to evaporate palladium onto the substrate. It also is equipped with an electron gun to evaporate the boron onto the substrate.
  • a flux monitor can be used to feedback control the effusion cell and the electron gun energy for the proper ratio of boron and palladium on the substrate.
  • the substrate can be further heated by a boron nitride heater to a temperature of 800 to 900 degrees C.
  • the temperature of the substrate can be monitored by an optical pyrometer.
  • the typical vacuum pressure is between 10 "7 to 10 "9 torr.
  • the preferred deposition rate is 0.1 nm/sec.
  • the preferred thickness is from about 0.1 to about 5 microns, with a more preferred thickness of 1 to 3 microns.
  • Deuterium and or deuterium hydrogen gases can be fed into the chamber during deposition.
  • the gas can be in molecular form or in atomic form.
  • Atomic form is produced by first feeding molecular gas through a hot tungsten filament to dissociate the deuterium molecule. The deuterium atoms are then directed at the substrate.
  • partial pressure of the atomic deuterium can be between 10 " to 10 " torr.
  • the substrate can be rotating at between 1 to 60 rpm , with 20 to 30 rpm preferred.
  • the substrate is quenched with nitrogen or argon to cool the coated part to room temperature rapidly.
  • a staring material of 99.99% purity copper is melted in a vacuum furnace and cast into a water-chilled graphite mold to make a copper bar of 9 mm in diameter.
  • This bar is machined to 8 mm diameter and sent through a multi-pass drawing process to reduce its diameter to 0.4 mm or 400 microns, followed by an anneal at 450 degrees C for half an hour in a vacuum.
  • X-ray diffraction done on the 0.4 mm diameter copper wire shows a major fiber texture of (200) with a minor texture of (1 11) near the middle of the wire.
  • This wire is further degreased, cleaned and pickled in dilute hydrochloric acid, and then rinsed in DI water and dried by filtered hot air. It then is immersed in electroplating bath of the following composition: 3.7 gm/1 of PdCl 2 , 100 gm/1 of Na 2 HP0 4 12H 2 0, 20 gm/1 of (NH 4 ) 2 HP0 4 and 2.5 gm 1 of benzoic acid with balance D 2 0 or heavy water. After dissolving the salts, the bath is heated up to the boiling point to form the palladium complex. The pH of the bath is adjusted with
  • ammonium hydroxide to between 6 - 7.
  • the copper wire is made into a cathode, with a DC power supply and a current density of 10 mA per cm 2 , to plate 5 microns thickness of palladium at 40 to 50 degrees C.
  • X-ray diffraction of the Pd coated Cu wire shows (200) as the dominant peak of Pd. This indicates that the electroplated Pd has a major texture in (200).
  • the wire is further draw down through successive smaller diameter dies to a final gauge of 25 microns in diameter, followed by cleaning, degreasing and acid pickling. It is then annealed at 450 degrees C for half an hour, then at 850 degrees C for one hour, in a vacuum.
  • This Pd coated wire is put into a pressure chamber.
  • the chamber is filled with deuterium gas at 50 bars. Electric voltage is applied at two ends of the wire to pass sufficient current to heat up the wire to 450 degrees C. Heat is generated at a rate substantially higher than the resistance heating by the current passed through the wire.
  • copper wire is made to a final gage of 50 microns, then cleaned and annealed in a vacuum at 450 degrees C for half an hour. It is then electroless palladium plated in a bath of the following composition: PdCl 2 4.0gm/liter, NH 4 OH 0.6M, Trimethyamine borate 2.5gm/liter,
  • Mercaptobenzothiazole 3.5 mg/liter, with the balance of deuterium oxide or heavy water with pH at 1 1 and temperature 45 degrees C.
  • the bath has a plating rate of 1.6 to 1.8 microns per hour. Plating time is approximately one hour.
  • the Pd coated wire is then put into a chamber pressurized to 50 bar with a 50:50 mixture of deuterium gas(D 2 ) and HD.
  • An electric current is then passed through the wire to heat up the wire, at a heating rate not more than 15 degrees C per minute, to 900 degrees C.
  • the wire stays at 900 degrees C for one hour.
  • the electric current is then reduced to cool the wire to 500 degrees C.
  • the current is feed-back controlled by a temperature sensing device to keep the temperature of the wire between 500 and 650 degrees C. Heat is generated at a rate substantially higher than the resistant heating by the electrical current passed through the wire.
  • This example is similar to Examples 1 and 2, but the starting wire material is 316SVM.
  • This is an austenitic grade stainless steel. It has a typical composition in weight % as follows: Carbon 0.03% max, Manganese 2.0%, Chromium 16 to 18%, Nickel 10 to 14%, Molybdenum 2 to 3%.
  • a clean grade is preferred, preferably using VIM (vacuum induction melting) or ESR (electroslag remelt) to minimize sulfur and phosphorus content.
  • the ingot is in bar form. It goes through successive wire drawing process with cold reduction of 90% or higher to a final gauge of 50 microns.
  • An intermediate anneal before the last cold drawing is acceptable. Both the intermediate anneal and the final anneal are done at 1 150 degrees C for an hour in a vacuum, followed by a quench to room temperature to preserve the austenitic micro structure and the face centered cubic lattice with dominant (100) fibrous texture.
  • the same process of Examples 1 and 2 can be followed to electroplate palladium to 2 microns thickness, with (100) preferred orientation.
  • 0.5 micron of electroless deposition may be accomplished with a borated bath with a palladium- boron alloy, having a boron content of about 10 atomic %.
  • Example 1 and 2 The same procedure as in Example 1 and 2 is then used.
  • the Pa coated stainless steel wire is pressurized in deuterium or deuterium hydrogen (HD) gas at 500 to 650 degrees C while a DC electric field of about 100 volts is applied across the 10 cm long wire with about 4 amperes of current flowing through the wire. Heat is generated at a substantially higher rate than the resistant heating by the applied voltage and the resultant current.
  • HD deuterium or deuterium hydrogen

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  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
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Abstract

A gas, comprising deuterium gas (D2), hydrogen gas (H2), or a gas of their isotope (HD), singly or in combination, is dissolved into a metal comprising an alloy of palladium with boron, carbon, oxygen, or any combination thereof. The temperature is about 400°C to about 1065°C, and the gas pressure is about 0.1 atmospheres to about 1000 atmospheres. The metal consists of a single phase. An electric field, magnetic field, or ultrasonic excitation is applied to the metal.

Description

METHODS OF MAKING AND USING PALLADIUM ALLOYS
BACKGROUND OF THE INVENTION
The invention relates to energy generation using various palladium alloys and methods of making the palladium alloys. The alloys can also be used as hydrogen gas purification membrane and electrodes for electrochemical processes.
In a hydrogen gas purification membrane, a palladium alloy is used due to its high diffusivity and solubility of hydrogen. With impure hydrogen at the high pressure (P-high) side, hydrogen gas will diffuse through the palladium alloy membrane with area A to the low pressure (P-low) side. The following equation describes the permeation phenomenon:
Permeation rate = DxS[(P-high)l/2-(P-low)l/2]/t equation A where t is the thickness of the membrane, and D and S are, respectively, the diffusion coefficient and the solubility of hydrogen atoms in the palladium alloy. Hydrogen gas dissolves in the metal as atoms according to the following equation:
H2 --> 2H+ + 2e~ equation B where a hydrogen molecule dissociates in metal into two hydrogen nuclei (each a proton with a nuclear spin of quantum number 1) and two electrons, which join the valance electrons of the host lattice. The same equations also apply to other hydrogen isotopes such as deuterium and tritium.
The typical operation temperature of the Pd membrane is between 350 to 550 degrees C to get high permeability of hydrogen or its isotopes. Other gases either dissolve very little or diffuse slowly in the membrane. They thus will be separated from the hydrogen by the membrane. The workhorse of the membrane material has been palladium with 23-25% silver by weight. This material exists as a single phase from room temperature to the highest operation temperature.
US patents 6,764,561 and 7,381,368 disclose a two-phase palladium-boron alloy for this purpose. This material will undergo phase changes if operated between room temperature and 450 degrees C. Because different Pd-B phases have different lattice spacing, cycling between room temperature and high temperature will cause lattice misfit to grow and stress between the phases which will eventually leads to cracks of the membrane. This material can operate at lower temperature, say below 400 to 410 degrees C to avoid phase transformation, but this will lower its permeation rate, because the diffusion rate of hydrogen nucleus lowers with temperature, which lowers the membrane's efficiency. Furthermore, because of the concentration gradient of the hydrogen in the membrane from the high pressure side to the low pressure side, the relative amount of the two phases will vary across the thickness of the membrane. This causes additional stresses at the interphase of the two phases which may leads to cracks. Therefore, its usefulness as a hydrogen membrane material is limited.
US patent 5,518,556 discloses a single phase boron-containing palladium or platinum alloy, but it was made by a chemical vapor deposition process and used as a hard coating for wear resistance purpose. It is not useful as a hydrogen permeation membrane.
In WO 98/03699, Patterson discloses an energy producing device using nickel coated on palladium on a plastic ball as a cathode in an electrolytic cell. The cell operates between room temperature and near 100 degrees C. Patterson claimed a nuclear reaction driven by a chemical process. It had at least two substantial deficiencies, namely:
1) The coefficient of thermal expansion between the plastic and the metal coatings are at least an order of magnitude different. This causes stresses between the coating layers and the core of plastic ball. Repeated temperature changes of the metal coated ball will cause the coating to flake off and will stop the energy generation process.
2) The electrolytic process was done in aqueous solutions. This limits its temperature to about the boiling point of the solution, or about 100 degrees C. A chemical process normally is a function of temperature: the higher the temperature, the higher the reaction rate. Limiting the operating temperature to about 100 degrees C means a low reaction rate and low efficiency system.
In US 2003/0230481 Al, Miley discloses an improved version of the above mentioned WO 98/03699 by Patterson, but the essential deficiencies of WO
98/03699 were still there.
In US 2009/0086877 Al, Hagelstein et al discloses an apparatus using deuterium and/or hydrogen deuterium in material such as palladium to generate energy from nuclear reaction. No palladium alloy composition is disclosed.
SUMMARY OF THE INVENTION
The palladium alloys used in this invention are palladium added with boron, carbon, or oxygen, singly or in combination. The concentration of oxygen as an alloying element in palladium ranges from about 0.01 atomic percent to about 1.0 atomic percent, and with a more preferred range from about 0.1 atomic percent to about 0.6 atomic percent. The concentration of carbon as an alloying element in palladium ranges from 0.01 atomic percent to about 10.0 atomic percent, and with a more preferred range from about 0.1 atomic percent to about 5.0 atomic percent. The concentration of boron as an alloying element in palladium ranges from 0.01 atomic percent to about 20 atomic percent, and with a more preferred range from about 0.1 atomic percent to about 18 atomic percent. The preferred operating pressure is from about 0.1 atmospheres to about 1000 atmospheres, with a more preferred range of about 1 atmospheres to about 100 atmospheres at the operating condition. The preferred operating temperature for Pd- B, Pd-C and Pd-0 alloys are from about 400 to about 1065 degrees C, with a more preferred temperature range from about 450 to about 750 degrees C. These alloys all exist as single phase alloys at these operating temperatures and pressures.
By applying an electric potential across the palladium alloy in various forms in the presence of deuterium gas, deuterium hydrogen or other deuterium isotope gases at the above mentioned temperature and pressure, substantial heat is generated in addition to the energy generated by resistance heating caused by an electric current passing through the alloy.
These alloys can be prepared as a coating on a suitable substrate by typical physical vapor deposition processes such as sputtering, ion plating, thermal evaporation techniques, and so on. It is preferred that the substrate have an orientation of the { 100} plane being parallel to the substrate surface, so that the coating will also have the same preferred orientation.
A wrought form of the alloys can be made by power metallurgy technique by first mixing powders of the various elements and going through a pressing, isostatic pressing and sintering process or a hot isostatic pressing process. This is followed by various metal-shaping processes such as hot forging or hot rolling. The alloys are then preferably annealed in a vacuum and quenched to room temperature.
For palladium alloys of a foil form, a suitable rolling schedule can be developed to produce foils with a preferred orientation of the { 100} plane being parallel to the surface and the (100) direction being parallel to the rolling direction. The above mentioned palladium materials can be further alloyed with various oxides such as alumina, silicate, sodium oxide, calcium oxide, and so on. They are mechanically alloyed in powder form, then pressed and lightly sintered in a vacuum, or in hydrogen or deuterium gas, to achieve a porous structure of less than full density.
The above mentioned palladium alloys in coating, foil or porous form can be used as the core material to generate energy or heat in a pressurized chamber filled with deuterium (D2) gas, hydrogen (H2) gas or their isotope (HD), singly or in combination, at the above mentioned pressure and temperature. Excess energy or heat can be generated and triggered by the application of electric field, magnetic field, ultrasonic excitation etc. to the core material.
These palladium alloys in various forms can also be used as hydrogen permeation membranes, hydrogen isotope separation membrane, or electrodes in
electrochemical cells.
Excess heat or energy can also be generated by using the palladium alloys in various forms as a cathode with a counter electrode as an anode. The electrodes are placed in an electrolyte of deuterium water or heavy water (D20), or semi-heavy water (HDO). The electrolyte includes an ionic solution with substantial electrical conductivity. A voltage is applied across the electrodes to electrolyze the solution and generate deuterium or HD gases. These gasses dissolve into the palladium electrode and cause the electrode to generate excess heat or excess energy.
Furthermore, a palladium and/or palladium alloys of this invention can be coated by electroplating, or by an electroless plating process, onto a wire core. The core may be of copper, a copper alloy such as CDA 725, or an austenitic stainless steel such as 304S, 309S or 316S.
Before coating, the wire core is hard drawn to more than 90% reduction in diameter and then annealed to promote (100) fiber texture. After electroplating or electroless plating, the material is annealed in a vacuum at a suitable temperature to
recrystallize the grain. It is then further hard drawn to gauge with more than 90% reduction. A final wire diameter of 25 to about 50 microns is preferred. The palladium or palladium alloy should have a thickness of 1 or 2 microns, with (100) fibrous texture.
BRIEF DESCRIPION OF THE DRAWINGS FIG. 1 is a hydrogen permeation device.
FIG. 2 is a deuterium gas charging and energy generation device.
DETAILED DESCRIPTION
The palladium alloys used in this invention are palladium added with boron, carbon, or oxygen, singly or in combination. The concentration of oxygen as an alloying element in palladium ranges from about 0.01 atomic percent to about 1.0 atomic percent, with a more preferred range from about 0.1 atomic percent to about 0.6 atomic percent. The concentration of carbon as an alloying element in palladium ranges from 0.001 atomic percent to about 5.0 atomic percent, with a more preferred range from about 0.001 atomic percent to about 1.5 atomic percent. The
concentration of boron as an alloying element in palladium ranges from 0.01 atomic percent to about 20 atomic percent and with a more preferred range from about 0.1 atomic percent to about 18 atomic percent.
The preferred operating pressure is from about 0.1 atmospheres to about 1000 atmospheres, with a more preferred range of about 1 atmospheres to about 100 atmospheres. The preferred operating temperature for Pd-B, Pd-C and Pd-O alloys are from about 400 to about 1065 degrees C, with a more preferred temperature range from about 450 to about 750 degrees C. The alloys all exist as a single phase at these operating temperatures and pressures. By applying an electric potential across the palladium alloy in various forms in the presence of deuterium gas, deuterium hydrogen or other deuterium isotope gases at the above mentioned temperature and pressure, substantial heat is generated in addition to the energy generated by resistance heating.
These alloys can be prepared as a coating on a suitable substrate by typical physical vapor deposition processes such as sputtering, ion plating, thermal evaporation techniques, and so on. It is preferred that the substrate have an orientation of the { 100} plane being parallel to the substrate surface so that the coating will also have the same preferred orientation.
A wrought form of the alloys can be made by power metallurgy technique by first mixing powders of the various elements and going through a pressing, isostatic pressing and sintering process or a hot isostatic pressing process. This is followed by various metal-shaping process such as hot forging or hot rolling. The alloys are then preferably annealed in a vacuum and quenched to room temperature.
For palladium alloys of a foil form, a suitable rolling schedule can be developed to produce foils with a preferred orientation of the { 100} plane being parallel to the surface and the (100) direction being parallel to the rolling direction.
The above mentioned palladium materials can be further alloyed with various oxides such as alumina, silicate, sodium oxide, calcium oxide, and so on. They are mechanically alloyed in powder form, then pressed and lightly sintered in a vacuum, or in hydrogen or deuterium gas, to achieve a porous structure of less than full density.
The above mentioned palladium alloys in coating, foil or porous form can be used as the core material to generate energy or heat in a pressurized chamber filled with deuterium (D2) gas, hydrogen (H2) gas or their isotope (HD), singly or in combination at the above mentioned pressure and temperature. Excess energy or heat can be generated and triggered by the application of electric field, magnetic field, ultrasonic excitation etc. to the core material. These palladium alloys in various forms can also be used as hydrogen permeation membranes, hydrogen isotope separation membranes, or electrodes in
electrochemical cells.
Excess heat or energy can also be generated by using the palladium alloys in various forms as a cathode with a counter electrode as an anode. The electrodes are placed in an electrolyte of deuterium water or heavy water (D20), or semi-heavy water (HDO). The electrolyte includes an ionic solution with substantial electrical conductivity. A voltage is applied across the electrodes to electrolyze the solution and generate deuterium or HD gases. These gasses dissolve into the palladium electrode and cause the electrode to generate excess heat or excess energy.
Furthermore, the palladium and/or palladium alloys of this invention can be coated by electroplating, or by an electroless plating process, onto a wire core. The core may be of copper, a copper alloy such as CDA 725, 99.99% purity nickel, nickel 200, or an austenitic stainless steel such as 304S, 309S or 316S. Before coating, the wire core is hard drawn to more than 90% reduction in diameter and then annealed to promote (100) fiber texture. After electroplating or electroless plating, the material is annealed in a vacuum at a suitable temperature to
recrystallize the grain. It is then further hard drawn to gauge with more than 90% reduction. The final wire diameter of 25 to about 50 microns is preferred. The palladium or palladium alloy should have a thickness of 1 or 2 microns, with (100) fibrous texture.
To make the wrought form of the palladium alloy of the current invention, one can use a powder metallurgy technique such as pressing and sintering. A more preferred method is hot isostatic pressing using powders of the alloying elements of 99.99% purity. Oxygen can be added as oxide, such as the oxides of boron, silicon, aluminum, sodium, calcium, and so on.
The powders are first thoroughly mixed in a vacuum at 100 to 200 degrees C. They are then put in a can and sealed. The can is made from 1010 plain carbon steel, extra low carbon killed steel, or 304 stainless steel. Hot Isostatic Pressing (HIP) is done by argon at a pressure of 10,000 to 30,000 psi and a temperature of 1100 to 1200 degrees C for one hour, or until full density and homogeneous microstructure is achieved. The typical shape is either a billet form for rolling into foil, a rod form for drawing into wires, or a pancake form for a sputtering target.
For foils, the HIPed ingot goes through a series of hot rolling and cold rolling process, with more than 90% thickness reduction in the cold rolling process preferred, followed by final anneal at 900 to 1000 degrees C for an hour in a vacuum. The ingot is then quenched to room temperature, with the resulting foil having a (100) preferred orientation and a single phase. The resulting foil has high mechanical strength because of the alloying content. This offers the opportunity to produce a foil of reduced thickness for use as a hydrogen purification membrane. The hydrogen permeation rate is higher, according to equation A before.
In a typical hydrogen purification membrane as depicted in FIG. 1 , impure hydrogen gas is the feed material. It has a pressure in the 3 to 7 bar range and an operating temperature of 300 to 600 degrees C. The standard membrane material is palladium with 23 to 25 % by weight of silver. The membrane has a thickness of about 25 microns. Too thick a membrane will reduce the permeation rate at any given temperature. Too thin a layer will be too fragile to withstand the pressure differential and is liable to facture.
Palladium with boron, oxygen and carbon at low concentration is the preferred way to strengthen the membrane, because solid solution strengthening by interstitial atoms is much more effective than a substitutional solid solution hardening alloy (such as Pd-23 to25 % Ag). Further, a single phase alloy operating at 410 degrees C or above is preferred. This avoids phase changes at the operating temperature and the resulting stress generated due to different lattice spacing for different phases. During shut down of the hydrogen purification device, cold argon or nitrogen is used to flush the hydrogen out of the gas tubes and to quench the Pd membrane to room temperature.
The same HIP process described in the previous paragraph can also be used to make sputtering targets and to coat the palladium alloy onto suitable substrates. Suitable substrates include oxygen free high conductivity copper, 99.99% purity nickel, nickel 200, cupronickel 70/30, tin bronzes (CDA902 through 917), aluminum bronze (CDA952 through 958), stainless steel 304S, 309S and 316S, and so on, provided that the substrates are made with a (100) preferred orientation. Preferably, the substrate is in a strip form with one or 2 cm in width. It is
continuously fed into a sputtering machine through a series of load locks, and palladium alloys are continuously sputtered onto the substrate.
The sputtering process can be further improved by a reactive sputtering process. In this reactive sputtering process, deuterium gas and/or deuterium hydrogen gas is fed into the sputtering chamber at a partial pressure of 0.1 to 5x10"3 torr. Argon is present with a partial pressure at 1 to 3xl0"3 torr. The residual gas pressure is 5xl0"5 torr.
The preferred thickness of the coating is from 0.5 to about 3 microns, with a more preferred range of 1 to 2 microns. The preferred deposition rate is 0.5 nm/sec or less, with a deposition rate of 0.3 microns/sec or less more preferred. The palladium alloy coating will take on the preferred orientation (100) of the substrate.
The same substrate mentioned above can also be used as a substrate for thermal evaporation of palladium and boron simultaneously in a vacuum chamber. The chamber is equipped with a high temperature effusion cell to evaporate palladium onto the substrate. It also is equipped with an electron gun to evaporate the boron onto the substrate. A flux monitor can be used to feedback control the effusion cell and the electron gun energy for the proper ratio of boron and palladium on the substrate. The substrate can be further heated by a boron nitride heater to a temperature of 800 to 900 degrees C. The temperature of the substrate can be monitored by an optical pyrometer. The typical vacuum pressure is between 10"7 to 10"9 torr. The preferred deposition rate is 0.1 nm/sec. The preferred thickness is from about 0.1 to about 5 microns, with a more preferred thickness of 1 to 3 microns.
Deuterium and or deuterium hydrogen gases can be fed into the chamber during deposition. The gas can be in molecular form or in atomic form. Atomic form is produced by first feeding molecular gas through a hot tungsten filament to dissociate the deuterium molecule. The deuterium atoms are then directed at the substrate. The
8 3
partial pressure of the atomic deuterium can be between 10" to 10" torr.
The substrate can be rotating at between 1 to 60 rpm , with 20 to 30 rpm preferred.
After deposition, the substrate is quenched with nitrogen or argon to cool the coated part to room temperature rapidly.
It is understood that whenever the word " hydrogen" or "deuterium", it means hydrogen nucleus, atom, or molecules or deuterium nucleus, atom or molecules or their isotopes as the case may be.
EXAMPLES
Example 1
A process to make palladium coated copper wire will be described here first.
A staring material of 99.99% purity copper is melted in a vacuum furnace and cast into a water-chilled graphite mold to make a copper bar of 9 mm in diameter. This bar is machined to 8 mm diameter and sent through a multi-pass drawing process to reduce its diameter to 0.4 mm or 400 microns, followed by an anneal at 450 degrees C for half an hour in a vacuum. X-ray diffraction done on the 0.4 mm diameter copper wire shows a major fiber texture of (200) with a minor texture of (1 11) near the middle of the wire.
This wire is further degreased, cleaned and pickled in dilute hydrochloric acid, and then rinsed in DI water and dried by filtered hot air. It then is immersed in electroplating bath of the following composition: 3.7 gm/1 of PdCl2, 100 gm/1 of Na2HP04 12H20, 20 gm/1 of (NH4)2HP04 and 2.5 gm 1 of benzoic acid with balance D20 or heavy water. After dissolving the salts, the bath is heated up to the boiling point to form the palladium complex. The pH of the bath is adjusted with
ammonium hydroxide to between 6 - 7.
The copper wire is made into a cathode, with a DC power supply and a current density of 10 mA per cm2, to plate 5 microns thickness of palladium at 40 to 50 degrees C. X-ray diffraction of the Pd coated Cu wire shows (200) as the dominant peak of Pd. This indicates that the electroplated Pd has a major texture in (200). The wire is further draw down through successive smaller diameter dies to a final gauge of 25 microns in diameter, followed by cleaning, degreasing and acid pickling. It is then annealed at 450 degrees C for half an hour, then at 850 degrees C for one hour, in a vacuum.
This Pd coated wire is put into a pressure chamber. The chamber is filled with deuterium gas at 50 bars. Electric voltage is applied at two ends of the wire to pass sufficient current to heat up the wire to 450 degrees C. Heat is generated at a rate substantially higher than the resistance heating by the current passed through the wire.
Example 2
In the same process as in Example 1, copper wire is made to a final gage of 50 microns, then cleaned and annealed in a vacuum at 450 degrees C for half an hour. It is then electroless palladium plated in a bath of the following composition: PdCl2 4.0gm/liter, NH4OH 0.6M, Trimethyamine borate 2.5gm/liter,
Mercaptobenzothiazole 3.5 mg/liter, with the balance of deuterium oxide or heavy water with pH at 1 1 and temperature 45 degrees C. The bath has a plating rate of 1.6 to 1.8 microns per hour. Plating time is approximately one hour.
The Pd coated wire is then put into a chamber pressurized to 50 bar with a 50:50 mixture of deuterium gas(D2) and HD. An electric current is then passed through the wire to heat up the wire, at a heating rate not more than 15 degrees C per minute, to 900 degrees C. The wire stays at 900 degrees C for one hour. The electric current is then reduced to cool the wire to 500 degrees C. The current is feed-back controlled by a temperature sensing device to keep the temperature of the wire between 500 and 650 degrees C. Heat is generated at a rate substantially higher than the resistant heating by the electrical current passed through the wire.
Example 3
This example is similar to Examples 1 and 2, but the starting wire material is 316SVM. This is an austenitic grade stainless steel. It has a typical composition in weight % as follows: Carbon 0.03% max, Manganese 2.0%, Chromium 16 to 18%, Nickel 10 to 14%, Molybdenum 2 to 3%. A clean grade is preferred, preferably using VIM (vacuum induction melting) or ESR (electroslag remelt) to minimize sulfur and phosphorus content.
The ingot is in bar form. It goes through successive wire drawing process with cold reduction of 90% or higher to a final gauge of 50 microns. An intermediate anneal before the last cold drawing is acceptable. Both the intermediate anneal and the final anneal are done at 1 150 degrees C for an hour in a vacuum, followed by a quench to room temperature to preserve the austenitic micro structure and the face centered cubic lattice with dominant (100) fibrous texture. Subsequently, the same process of Examples 1 and 2 can be followed to electroplate palladium to 2 microns thickness, with (100) preferred orientation. 0.5 micron of electroless deposition may be accomplished with a borated bath with a palladium- boron alloy, having a boron content of about 10 atomic %. An amorphous structure is produced. This is followed by an anneal at 950 degrees C for one hour in a vacuum to homogenize and recrystallize into a single phase, followed by a quench to room temperature. This produces a single phase Pd-B alloy.
The same procedure as in Example 1 and 2 is then used. The Pa coated stainless steel wire is pressurized in deuterium or deuterium hydrogen (HD) gas at 500 to 650 degrees C while a DC electric field of about 100 volts is applied across the 10 cm long wire with about 4 amperes of current flowing through the wire. Heat is generated at a substantially higher rate than the resistant heating by the applied voltage and the resultant current.
REFERENCES CITED
U.S. PATENT DOCUMENTS
5,518, 556 5/1996 Weber et al.
2003/0159922 A 1 8/2003 Miley 2003/0230481 Al 12/2003 Miley .
6,764,561 7/2004 Miles et al
7,381 ,368 6/2008 Miles et al.
2009/0086877 Al 4/2009 Hagelstein et al. FOREIGN PATENT DOCUMENTS
WO 99/19881 4/1999 Patterson et al.
OTHER PUBLICATIONS G. Alefeld and J. Volkl (editors), Hydrogen in Metals, Part I: Basic Properties, Springer- Verlag, 1978
G. Alefeld and J. Volkl (editors), Hydrogen in Metals, part II: Application-Oriented Properties, Springer- Verlag, 1978
G. Alefeld and J. Volkl (editors), Hydrogen in Metals, Part III: Properties and Applications, Springer- Verlag, 1997
Y. Fukai, The Metal-Hydrogen System: Basic Bulk Properties, 2nd Edition, Springer,
2010
Edmund Storms, The Science of Low Energy Nuclear Reaction: a Comprehensive Compilation of Evidence and Explanation About Cold Fusion, World Scientific,
2007
Jan Marwan and Steven Krivit (editors), Low-Energy Nuclear Reactions
Sourcebook, American Chemical Society Symposium Series 998, 2008, Oxford University Press
Jan Marwan and Steven Krivit (editors), Low-Energy Nuclear Reactions and New Energy Technologies Sourcebook Vol. 2, American Chemical Society Series 1029, 2009, Oxford University Press

Claims

CLAIMS I claim: 1 ) A method of dissolving a gas into a metal, wherein: a) the gas comprises deuterium gas (D2), hydrogen gas (H2), or a gas of their isotope (HD), singly or in combination; and wherein b) the method comprises: i) providing a metal comprising an alloy of palladium with boron, carbon, oxygen, or any combination thereof, wherein the alloy is characterized by consisting of a single phase at: (1) a temperature from about 400°C to about 1065°C; and (2) a gas pressure of about 0.1 atmospheres to about 1000 atmospheres; ii) exposing the metal to the gas, wherein: (1) the gas or the metal has a temperature of about 400°C to about 1065°C; and (2) the gas has a pressure of about 0.1 atmospheres to about 1000 atmospheres; and iii) applying an electric field, magnetic field, or ultrasonic excitation to the metal. 2) The method of Claim 1 , wherein boron is present in the alloy in a concentration of about 0.01 atomic percent to about 20 atomic percent. 3) The method of Claim 1, wherein carbon is present in the alloy a concentration of about 0.01 atomic percent to about 10 atomic percent. 4) The method of Claim 1 , wherein oxygen is present in the alloy in a concentration of about 0.01 atomic percent to about 1.0 atomic percent. 5) The method of Claim 1, wherein boron is present in the alloy in a concentration of about 0.1 atomic percent to about 18 atomic percent; 6) The method of Claim 1 , wherein carbon is present in the alloy a concentration of about 0.1 atomic percent to about 5.0 atomic percent. 7) The method of Claim 1 , wherein oxygen is present in the alloy in a concentration of about 0.1 atomic percent to about 0.6 atomic percent. 8) A method of dissolving a gas into a metal, wherein: a) the gas comprises deuterium gas (D2), hydrogen gas (H2), or a gas of their isotope (HD), singly or in combination; and wherein b) the method comprises: i) providing a metal comprising an alloy of palladium with boron, carbon, oxygen, or any combination thereof, wherein the alloy is characterized by consisting of a single phase at: (a) a temperature from about 450°C to about 750°C; and (b) a gas pressure of about 1 atmosphere to about 100 atmospheres; ii) exposing the metal to the gas, wherein:
(1) the gas or the metal has a temperature of about 450°C to about
750°C; and
(2) the gas has a pressure of about 0.1 atmospheres to about 1000
atmospheres; and
iii) applying an electric field, magnetic field, or ultrasonic excitation to the metal. 9) The method of Claim 8, wherein boron is present in the alloy in a concentration of about 0.01 atomic percent to about 20 atomic percent.
10) The method of Claim 8, wherein carbon is present in the alloy a concentration of about 0.01 atomic percent to about 10 atomic percent.
1 1) The method of Claim 8, wherein oxygen is present in the alloy in a concentration of about 0.01 atomic percent to about 1.0 atomic percent.
12) The method of Claim 8, wherein boron is present in the alloy in a concentration of about 0.1 atomic percent to about 18 atomic percent;
13) The method of Claim 8, wherein carbon is present in the alloy a concentration of about 0.1 atomic percent to about 5.0 atomic percent. 14) The method of Claim 8, wherein oxygen is present in the alloy in a concentration of about 0.1 atomic percent to about 0.6 atomic percent. 15) The method of any of Claims 1 to 14, wherein the metal comprises:
a) a foil; or
b) a porous structure of less than full density.
16) The method of any of Claims 1 to 14, wherein the metal comprises a coating on a substrate.
17) The method of Claim 16, wherein:
a) the substrate comprises a wire having a diameter of about 25 microns to about 50 microns;
b) the coating has a thickness of about 1 micron to about 2 microns
c) the coating has (100) fibrous texture. 18) A method of electrolyzing an electrolyte, wherein:
a) the electrolyte comprises:
i) heavy water (D20), water (H20), or semi-heavy water (HDO), singly or in combination; and
ii) an ionic solution with substantial electrical conductivity; and wherein b) the method comprises:
i) placing the metal of any of Claims 1 to 4, as a cathode, in the electrolyte; ii) providing a counter electrode as an anode; and
iii) applying a voltage across the electrodes.
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