EP0474724A1 - Verbesserungen an materialien - Google Patents

Verbesserungen an materialien

Info

Publication number
EP0474724A1
EP0474724A1 EP90908600A EP90908600A EP0474724A1 EP 0474724 A1 EP0474724 A1 EP 0474724A1 EP 90908600 A EP90908600 A EP 90908600A EP 90908600 A EP90908600 A EP 90908600A EP 0474724 A1 EP0474724 A1 EP 0474724A1
Authority
EP
European Patent Office
Prior art keywords
palladium
composition according
deuterium
lithium
modified
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.)
Withdrawn
Application number
EP90908600A
Other languages
English (en)
French (fr)
Inventor
Duncan Roy Coupland
Mark Lawrence Doyle
Robert John Potter
Ian Ray Mcgill
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Johnson Matthey PLC
Original Assignee
Johnson Matthey PLC
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
Priority claimed from GB898912639A external-priority patent/GB8912639D0/en
Priority claimed from GB898912638A external-priority patent/GB8912638D0/en
Priority claimed from GB898912640A external-priority patent/GB8912640D0/en
Priority claimed from GB898912774A external-priority patent/GB8912774D0/en
Priority claimed from GB898912637A external-priority patent/GB8912637D0/en
Priority claimed from GB898926442A external-priority patent/GB8926442D0/en
Application filed by Johnson Matthey PLC filed Critical Johnson Matthey PLC
Publication of EP0474724A1 publication Critical patent/EP0474724A1/de
Withdrawn legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21B—FUSION REACTORS
    • G21B3/00—Low temperature nuclear fusion reactors, e.g. alleged cold fusion reactors
    • 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
    • Y02E30/00—Energy generation of nuclear origin
    • Y02E30/10—Nuclear fusion reactors

Definitions

  • This invention concerns improvements in materials. More especially, it concerns improved materials for the heat-generating process now known as "cold fusion” or “solid state fusion”.
  • cathode materials which exhibit enhanced heat generating effects, for scientific study and for development of the process into a reliable and commercially utilisable power source. It should be understood that although this specification concentrates on the heat generating effect, the invention may find utility with respect to the other products of fusion, and hence may be used for the formation of tritium and/or the generation of neutrons.
  • composition of matter in which cold fusion takes place when the composition is loaded with deuterium comprising palladium modified to change the local environment for deuterium under cold fusion conditions.
  • the invention may also be considered to arise from a palladium having a high and substantially stable dislocation density, or point defect concentration.
  • the invention may be considered to arise from the incorporation into the palladium material of centres for stress during the cold fusion process, whether at point defects or at boundary regions at which stress is created.
  • a further embodiment incorporates a material having a high muon capture cross-section.
  • a yet further embodiment utilises a coating on the palladium material.
  • Another embodiment utilises palladium modified by the incorporation of lithium, especially enriched with Li .
  • this desired object may be attained, which will be more fully described hereinafter.
  • a first group of methods for forming the modified palladium include mechanical methods, for example to cold work the metal, or to rapidly cool molten metal, for example by melt spinning, suitably by cooling at rates of the order of 10 to 10 C sec , or by rapidly cycling the metal through ⁇ and ⁇ phases, according to methods generally known in the art.
  • the invention includes materials processed in such a way, generally known in the metallurgical art, to retain the ⁇ phase in the metal at high deuterium to metal ratios. The introduction of point defects by these methods is, however, sometimes not adequate since the defects may anneal out at temperatures as low as room temperature.
  • controlled grain size- may be achieved by controlled recrystallisation according to generally known principles in the metallurgical art, whereby the grain surface areas and number of triple points may be adjusted. It is one theory that point defects and possibly activity in the "cold fusion" process may be concentrated at the grain boundaries.
  • a particular embodiment of the invention utilises processing conditions to yield material having a fine grain structure in which the grains have an aspect ratio, considered as the ratio of length to diameter, of less than 10, and preferably approximately unity.
  • microstrueture in which substantially uniform grain size in the range from 10 to 40 microns is preferred, offers improved performance in at least the heat generating process.
  • These microstructures may be achieved by the competent metallurgist by methods generally known in the art, which will vary according to the prior metallurgical history of the palladium material, especially the extent of work hardening, and its current microstructure. For example, annealing a material with a grain size of less than 10 microns, and in which the aspect ratio of the grains is in excess of 10, to produce the desired grain sizes, is a method which is indicated to yield "active" palladium samples which exhibit the excess heat effect.
  • Suitable annealing conditions for a drawn material, are heating for approximately one hour at a temperature of approximately 650 C, desirably under vacuum or possibly under an inert gas. These temperature and time conditions may be varied, since there are a number of time-temperature curves depending upon the degree of work hardening, and providing that the desired microstructure is achieved.
  • additive is to be given a wide meaning as including materials, whether elements or compounds, which under normal usage would be considered to be impurities; in such a case, and providing the impurity has a beneficial overall effect, or at least no overall adverse effect, the impurity may be retained in the palladium, rather than being refined out. It may be desirable to reduce, rather than eliminate the amount of any such impurity.
  • additives as herein understood of elements such as gold, calcium, copper, iron and platinum, as well as boron, carbon, sulphur, silicon and lithium, and rare earth metals including particularly cerium, is therefore to be considered, especially as we expect the additive elements to concentrate at the grain boundaries, and thus have a considerable influence on the chemical and/or nuclear reactions taking place.
  • a further additive to be considered is uranium, especially U235.
  • a particular embodiment of the use of an additive is the formation of amorphous palladium materials, which may be achieved by the incorporation of an additive such as silicon.
  • PdSi and PdSiCr alloys can be produced quite readily in amorphous form, and although these devitrify at about 400 C, they are thought to be adequately stable up to these temperatures. It is considered that improved hydrogen/deuterium diffusion/solubility may be improved by utilising controlled devitrification to produce extremely short range order crystallinity.
  • Elements which are worthy of consideration for forming eutectics or near eutectics with palladium for the formation of amorphous materials include silicon, boron, carbon, lithium, potassium, sodium and iron.
  • a further embodiment of the use of an additive is the formation of dispersed oxide particles, for example zirconia, dispersed intermetallic compounds, for example LaNi c or FeTi, or dispersed hydride forming metals, within a palladium matrix.
  • dispersed oxide particles for example zirconia, dispersed intermetallic compounds, for example LaNi c or FeTi, or dispersed hydride forming metals, within a palladium matrix.
  • it may be suitable to microencapsulate the additive, for example by depositing Pd on the additive by standard electroless or electro plating techniques, followed by pressure sinter consolidation and cold deformation, or a sintering process may be used.
  • Other materials indicated for trial in the cold fusion process are powder metallurgy compacts, eg encased within a palladium skin, and Pd/AloO-, for example where the amount of Al relieve0- is approximately 2 to 5% by wt, or Pd/Ti where titanium particles are dispersed in a Pd/Ti solid solution or are in a palladium matrix but are surrounded by a Pd/Ti solid solution.
  • Such materials are believed to exhibit significant internal stress caused by differential expansion caused by volume changes on the formation of deuterides and related compounds, or solutions of deuterium, upon "charging" of the palladium material with deuterium during or prior to the cold fusion process.
  • the quantity of any additive is preferably less than about 20 at%, more preferably less than about 10 at%, and most preferably less than about 5 at%.
  • concentration of point defects may be monitored by the resistivity of the material, as well as by crystallography and surface spectroscopic techniques.
  • An embodiment of the present invention utilises the high stress and high point defect concentration arising from deposited coatings.
  • the coating may be solely palladium, or a palladium/additive mixture, and may be deposited upon a matrix by electroplating, electroless plating, sputtering, chemical vapour deposition, thick film techniques, electroforming (for example, varying the electroforming temperature can be utilised to tailor the stress and coating properties) or other method yielding the desired result.
  • the palladium may incorporate lithium.
  • the amount of lithium is less than about 20 at %, more preferably less than about 10 at %, most preferably less than about 5 at %, in any macroscopic region of material.
  • the lithium used is enriched with the isotope Li .
  • the normal proportion of Li in lithium is 7.4% by wt, and it is envisaged that Li contributes to the possible lithium-deuterium reaction.
  • a suitable enrichment would give a Li content of above 10% by weight of the lithium present, and this may usefully exceed 20% by weight.
  • Lithium may be incorporated into palladium by a number of different processes, including alloying, although the vast difference in melting point between lithium (mp ⁇ 180°C) and palladium (mp ⁇ 1700°C) means that at the melting point of palladium the lithium has a very significant vapour pressure and is easily lost by evaporation.
  • the lithium may be introduced into the palladium electrochemically, by using a palladium cathode in a lithium salt solution, or using a non-aqueous system, including, for example a molten salt system.
  • a palladium cathode in a lithium salt solution
  • a non-aqueous system including, for example a molten salt system.
  • thermal diffusion of lithium atoms from a deposited surface layer of lithium, the layer having been deposited by plating or any alternative deposition method. Diffusion methods are known to the skilled man in relation to other metals.
  • a powder route starting with LiH and Pd sponge, eg under a H/D atmosphere, may also be used.
  • a concentration gradient may be desirable in that there will be localised stress and palladium lattice point defects in the surface region, and this may influence the hydrogen/deuterium solubility and mobility, and in turn affect the heat generating effect.
  • the palladium/lithium materials of the invention may additionally comprise other metals or materials which do not adversely affect the overall performance or properties for the intended use, or which improve the performance or general properties of the material.
  • Another embodiment of the invention provides a palladium materia comprising palladium and an additive having a high captur cross-section for muons. In general, the muon captur cross-section increases with increasing atomic number.
  • the additive is an element selected from the rare earths, yttriu and scandium, and gadolinium or cerium are particularly indicated.
  • the Actinides are also to be considered, as well as some heavie elements such as uranium.
  • the additive may be a single additive or a combination of two o more of such additives, and may be present in admixture with othe substances which do not have an adverse effect on the hea generating process.
  • Suitable amounts of the additive are less than 15 at %, preferabl less than 8 at %, especially about 1 at %, based on the palladium. We believe that a balance should be attained between the amount o additive present, which affects the material's ability to capture muon, and the adverse effect the additive has upon deuteriu solubility in the palladium.
  • the invention also extends to an improved cold fusion proces comprising carrying out or initiating the process at a temperatur below ambient, preferably below 10°C, more preferably below 0°C and most preferably below -10°C, for example at a temperature o the order of -40 C to -70 C. Accordingly, it is preferred t operate the process with efficient heat removal, for example b excess heat removal by a flow of liquid through the anode material and optionally with external cooling. It will be appreciated that, particularly if an aqueous electrolyte is being used, the freezing point of the electrolyte must be below the operating temperature, and this may be achieved by the addition of a salt or an organic "anti-freeze" substance, for example methanol or ethylene glycol.
  • a salt or an organic "anti-freeze" substance for example methanol or ethylene glycol.
  • the invention also includes increasing the deuterium concentration by utilising a material not previously proposed, and which has the desired combination of hydrogen/deuterium solubility and diffusion characteristics.
  • the material may be selected from the rare earths, for example especially cerium, yttrium, scandium, the Actinides, uranium, tantalum, niobium, vanadium, intermetallics and mischmetals having the desired properties, and palladium/silver alloys.
  • the materials may incorporate dispersed hydrogen storage elements or compounds, of which Pd/Ag and LaNi,- may particularly be mentioned.
  • radioactivity by producing high energy emissions, may assist to initiate any fusion reaction, and therefore the invention contemplates the use of materials enriched with radioactive isotopes. Care has, of course, to be taken according to recognised procedures for handling radioactive substances.
  • the new materials are not ideally suited for use as electrodes in aqueous systems, for example because of the formation of passivating surface layers or competing reactions and gas formation or loss of physical properties in the presence hydrogen/deuteruim; and the invention includes surface coating t material with palladium or a palladium/silver alloy.
  • Such surfa coating may be effected in a number of ways, including electrole and electro plating, thin film depositions such as sputtering chemical vapour deposition, etc.
  • the invention further includes the new materials dispersed conventional metallurgical techniques in a stable matrix, of whi palladium and palladium/silver alloys are favoured.
  • the present invention provides titanium dispers in, or surface coated with, palladium or palladium/silver, which believed to offer particular advantages for use in aqueo electrolyte systems.
  • the inventions provides a palladium having modified surface.
  • the modified surface serves one or more of t following purposes: to increase hydrogen/deuterium adsorption; to control hydrogen/deuterium desorption; to control undesired surface reactions; to control surface area; to control surface qualitly, including controlling surface impuri levels; and to provide desired dimensional stability. It will be appreciated that if the hydrogen adsorption is increased while at the same time the hydrogen desorption is decreased, the overall effect is to increase the amount of hydrogen (and its isotopes) containable within the material, and to increase the opportunity for fusion or other heat generating processes.
  • the invention provides a material comprising a surface coating or modified surface region.
  • the material matrix may be palladium or a palladium alloy or solid solution.
  • the invention includes the incoporation of desired elements or compounds in a surface region, thereby to create a concentration gradient of element or compound, in the electrode material. This may be achieved by diffusion int the matrix from a coating, generally using thermally induce diffusion, and methods for creating a modified surface region ar known to the skilled man in relation to other materials.
  • Suitable coatings according to the invention include in particular palladium and palladium/silver alloys. It may be desirable to surface coat a palladium matrix with palladium, for example to coat with palladium black. Other surface coatings or surface regions may contain amorphous materials. A surface coating will also generally have a high stress and high concentration of point defects, and these may be advantageous in the "cold fusion" or heat generating process as discussed above, although we do not wish to be bound by any theory expressed herein.
  • the invention encompasses the use of the modified palladium materials as described above in a "cold fusion" type process.
  • the invention further provides a heat generating electrochemical process of the "cold fusion” type, comprising concentrating deuterium in a material according to the invention, for example by electrolysing D-0 utilising a cathode which is a modified palladium material as described above.
  • the invention additionally provides an electrolysis cell for use in a heat generating electrochemical process of the "cold fusion” type, comprising an anode, and a cathode which is a modified palladium material as described above.
  • palladium containing small amounts of additives was prepared, was melted and cast, Before being drawn twice to form an electrode rod of 8mm diameter.
  • One sample of the electrode was annealed under vacuum for one hour at 650 C.
  • Studies of the microstructure of the annealed rod compared to the unannealed rod showed that the unannealed rod had grain size of less than 10 microns maximum dimension, with a aspect ratio for the grains of greater than 10, whereas th annealed rod had recrystallised to a grain size of from 10 to 40 microns and with an aspect ratio of less than 10.
  • the rods were then used in a "cold fusion" electrolysis cell under conditions as reported in the literature.
  • the unannealed rod did not show any heat-generating activity despite a considerable period of charging, whereas the annealed rod exhibited the excess heat effect, with bursts of heat.
  • the palladium contained 0.002 % boron, 0.001 % copper, 0.001 % iron, 0.001 % platinum, 0.003 % gold and 0.003 % calcium, in addition to low amounts of aluminium, magnesium, nickel, silicon and silver.

Landscapes

  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Plasma & Fusion (AREA)
  • General Engineering & Computer Science (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Powder Metallurgy (AREA)
EP90908600A 1989-06-02 1990-05-30 Verbesserungen an materialien Withdrawn EP0474724A1 (de)

Applications Claiming Priority (12)

Application Number Priority Date Filing Date Title
GB898912639A GB8912639D0 (en) 1989-06-02 1989-06-02 Improvements in materials
GB8912640 1989-06-02
GB8912637 1989-06-02
GB8912638 1989-06-02
GB898912638A GB8912638D0 (en) 1989-06-02 1989-06-02 Improvements in materials
GB8912639 1989-06-02
GB8912774 1989-06-02
GB898912640A GB8912640D0 (en) 1989-06-02 1989-06-02 Improvements in materials
GB898912774A GB8912774D0 (en) 1989-06-02 1989-06-02 Improvements in materials
GB898912637A GB8912637D0 (en) 1989-06-02 1989-06-02 Improvements in materials
GB898926442A GB8926442D0 (en) 1989-11-22 1989-11-22 Improvements in materials
GB8926442 1989-11-22

Publications (1)

Publication Number Publication Date
EP0474724A1 true EP0474724A1 (de) 1992-03-18

Family

ID=27547050

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90908600A Withdrawn EP0474724A1 (de) 1989-06-02 1990-05-30 Verbesserungen an materialien

Country Status (3)

Country Link
EP (1) EP0474724A1 (de)
JP (1) JPH04505505A (de)
WO (1) WO1990015415A1 (de)

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05508713A (ja) * 1990-05-25 1993-12-02 ドレクスラー，ジェロウム 分布された重水素―リチウムエネルギー装置
EP0461690A3 (en) * 1990-06-13 1992-03-11 The Boeing Company Cold nuclear fusion thermal generator
AU2144392A (en) * 1991-06-11 1993-01-12 Electric Power Research Institute, Inc. Methods for cleaning cathodes
WO1992022909A1 (en) * 1991-06-13 1992-12-23 Purdue Research Foundation Solid state surface micro-plasma fusion device
WO1993000684A1 (en) * 1991-06-27 1993-01-07 Electric Power Research Institute, Inc. Apparatus for producing heat from deuterated palladium alloys
US5949835A (en) * 1991-07-01 1999-09-07 The United States Of America As Represented By The Secretary Of The Navy Steady-state, high dose neutron generation and concentration apparatus and method for deuterium atoms
US5942206A (en) * 1991-08-23 1999-08-24 The United States Of America As Represented By The Secretary Of The Navy Concentration of isotopic hydrogen by temperature gradient effect in soluble metal
WO1994016446A1 (en) * 1993-01-07 1994-07-21 Jerome Drexler Self-catalyzed nuclear fusion of lithium-6 and deuterium using alpha particles
US5411654A (en) * 1993-07-02 1995-05-02 Massachusetts Institute Of Technology Method of maximizing anharmonic oscillations in deuterated alloys
WO1996003751A1 (en) * 1994-07-21 1996-02-08 Gregory Lowell Millspaugh Method of and system for controlling energy, including in fusion reactors
AU2465595A (en) * 1995-05-01 1996-11-21 Massachusetts Institute Of Technology Method of maximizing anharmonic oscillations in deuterated alloys
US5672259A (en) * 1996-05-24 1997-09-30 Patterson; James A. System with electrolytic cell and method for producing heat and reducing radioactivity of a radioactive material by electrolysis
FR2777687B1 (fr) * 1998-04-17 2000-07-07 Conservatoire Nat Arts Procede et dispositif pour la production d'energie a partir d'un hydrure a caractere metallique
WO2007114845A2 (en) * 2005-12-05 2007-10-11 Energetics Technologies, L.L.C. Electrodes for low energy nuclear reaction power generators
IT1391275B1 (it) * 2008-08-08 2011-12-01 Nrl Naval Res Lab Materiale da utilizzare per la produzione di eccesso di potenza, con elevato caricamento di isotopi dell'idrogeno, e relativo procedimento di produzione
PL2515774T3 (pl) 2009-12-23 2014-08-29 Alcon Res Ltd Okulistyczna kaniula trokara z zaworem
US8343106B2 (en) 2009-12-23 2013-01-01 Alcon Research, Ltd. Ophthalmic valved trocar vent

Non-Patent Citations (1)

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Also Published As

Publication number Publication date
JPH04505505A (ja) 1992-09-24
WO1990015415A1 (en) 1990-12-13

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