WO1995015563A1 - Methods and apparatus for producing neutrons from proton conductive solids - Google Patents

Abstract

Apparatus and methods for producing neutrons at relatively low temperatures from a heterostructure based upon solid electrolytes. The methods involve selecting a solid hydrogen ion conducting electrolyte material which under predetermined conditions exhibits a phenomenon of nonlinear transport and distribution of diffused hydrogen isotopes. Generally, one of the conditions involves raising the material in the form of a solid electrolyte mass (190) to a predetermined temperature where nuclear reactions take place under predictable situations. The methods and apparatus also involve applying a voltage across the solid electrolyte mass (190) by means of an anode (180) and a cathode (170) disposed across opposite faces (290, 292) of the solid electrolyte mass (190) to construct a reactor element (150). At least the anode (180) and facing (290, 396) of mass (190) associated with anode (180) are made to be permeable to flow of isotopic hydrogen. The reactor element (150) is disposed in a vacuum chamber (110) which is serviced by a vacuum pump (222) and source of hydrogen isotope (256). A thermo-heater (140) is used to control operating temperature of mass (190) and a power suppy (160) is connected across anode (180) and cathode (170) to provide desired voltage and current.

Description

METHODS AND APPARATUS FOR PRODUCING NEUTRONS FROM PROTON CONDUCTIVE SOLIDS Technical Field

This invention is related to methods and apparatus for nuclear particle production in solid materials and more particularly to methods and apparatus which create high local densities of hydrogen isotopes inside solid materials having high proton conductivity and which thereby release products generally associated with a nuclear reaction. Background Art

In March 1989, Professors Pons and Fleischmann introduced a method which, they claimed, produced excess heat in a special electrolytic cell. The claimed energy was described as exceeding amounts that would be possible to generate by any known chemical reaction and was attributed by Pons and Fleischmann to be a nuclear fusion reaction such as between two deuterium atoms inside palladium lattice material at near normal room temperatures. For this reason the process of excess heat production was called "cold fusion" .

Since the Pons and Fleischmann announcement, experimental results which are the product of a large number of observations of heat, tritium, and neutron measurements have been published. A summary of such results and observations is found in an article by E.Storms, Review of Experimental Observations about Cold Fusion Effect, Fusion Tech., vol.20, (1991) . p.p.433-477. In particular, neutron production processes claimed to be involved in cold fusion are widely reported and are described to comprise a variety of devices, materials and methods. Among devices using different materials are those involving metals [M.Fleischmann and S.Pons. Electron. Chem. , (1989) , 261, 301-304.] , dielectrics [A.G.Lipson, D.M.Sakov, V.B.Kalinin et al . , Letters to Mag.of Tech.Physics, 1992, v.18, 16, p.p.52-56] , and bronze oxides [K.Kaliev, A.Baraboshkin, A.Sa gin et al . Phys. Lett. A, 1993, 172, 199-202] . One common feature among the many features of materials used in such devices is a high hydrogen absorption ability and high mobility of hydrogen atoms in some materials and in proton conductive solid electrolytes in particular.

Generally, electric conductivity in solids is the result of migration of charge carriers through macroscopic distances under influence of applied electrical fields. As is well known to one who is skilled in the art, those charge carriers which are available in nature have been divided into two types, electrons and ions. As a rule, at any given time, only one type of conductivity (either electronic or ionic) prevails in solids. Determination of the kind of conductivity in a particular solid can significantly depend upon exterior conditions, including the environment's composition and temperature.

In this light, conduction^' of electricity in ionic conductors, contrary to electronic conductors, is associated with transport of matter, in particular with transport of ions (i.e. cations and anions) . Ions disposed within an ion conducting lattice or sublattice are generally considered to be located in the appropriate centers of the lattice or sublattice frame and ionic movement is possible only with participation of lattice or sublattice defects. For such ions, there is a group of solid substances in which ions disposed in the lattices or sublattices move relatively fast (i.e. where ion mobility is comparable with ion mobility in aquatic solutions) referred to as "solid electrolytes", "solid ionic conductors", or "superionic conductors". Thus, one of the common feature of solid conductors is as high a prevailing ionic conductivity as found in regular aquatic solutions of electrolytes or in molten salts.

The number of substances which can be categorized as solid electrolytes is limited. A review of such substances is found in Solid Electrolytes, Ed.S.Geller,et al . Springer, 1977, 229pp, and made part of this disclosure by reference. Solid electrolytes mainly comprise ionic crystals and may be halogenids, partly metal oxides with prevailing ionic bonds and also a number of composites and glasses. Synthesized and investigated compounds having high ionic conductivity may number several hundred substances. For examples, different materials may have ionic current carriers for halogen and oxygen anions and cations of silver, copper, sodium, potassium and calcium, as well as cations of other metals.

Many proton conductors are also known. Information on such conductors is available from articles by J.Bruinik. J.Appl. Electrochem. , 1972, vol .2, #2, p.p.239- 249; by Ed J. Jensen et al . , Solid State Protonic Conductors for Fuel Cells and Sensors (I) , Odense Univ. Press, 1982, 337p.; by J. B. Goodenough et al. , Solid State Protonic Conductors for Fuel Cells and Sensors (III) , Univ.Press, 1985, 284p.; by E.W.Poulsen, High Conductivity Solid Ionic Conductors, Recent Trends and Applications; by Ed.T.Takahashi et al., World Sci.,1989, p.p.166-200] . In addition, there are a number of substances that exhibit mixed conductivity to several types of ions.

Currently known solid electrolytes are generally categorized into a few classes according to peculiarities of structure and to nature of ionic conductivity. These solid electrolytes are also categorized by types of predominant irregularities. For example solid electrolytes may be categorized by having (a) intrinsic structural irregularities and (b) admixture introduced irregularities.

Those solid electrolytes having intrinsic structural irregularities comprise silver halogenoid alpha-Agl and a number of substances with the common formula Ag₄MI₅, where "M" may be Rb, K, NH₄ or Cs₀₅K₀₅. Compounds of this group generally exhibit high conductivity due to silver ions as well as due to a number of fluorides of two- and three- state valency metals (the high conductivity being provided by highly mobile anions of fluorine) . A specific and important feature of many superionic substances with intrinsic structural irregularities is an inherent and definite critical temperature at which ionic conductivity changes in a spasmodic way.

Another specific and important feature of superionic substances is a high anisotropy of ionic conductivity. Such spasmodic modifications in superionic substances may be considered to be a result of phase transformation. Materials having high protonic conductivity, such as KH₂P0₄, from which neutron generation has previously been reported may be attributed to this class. See earlier referenced article by A.G. Lipson et al . Admixture introduced irregularities are found in compounds of a second type of solid electrolytes. Admixture irregularities can be interjected into ionic crystals by introducing ions having valence states different than the valence state of the host material into the compound. A typical example of a solid electrolyte with admixture irregularities is zirconium dioxide (Zr0₂) interjected with an addition of calcium oxide (CaO) or yttrium oxide Y₂0₃. Widely investigated and often used electrolytes with admixture discontinuities are solid electrolytes or solutions having fluoride structures and M0₂-M'0 and M0₂-M''₂0₃, where "M" may be Zr, Hf, Ce and Th; "M' " may be Ca, Sr and Ba; "M' ' " may be Sc, Y and lanthanoids . For a reference see an article by Ed. A. H. Hener and L. W. Hobbs titled Science and Technology of Zirconia, Advances in Ceramics, American Ceramics Society, 1981, vol.3,p.479.

Contrary to the electrolytes with intrinsic structural discontinuity, compounds with admixture discontinuity do not exhibit a temperature related spasmodic or abrupt change in ionic conductivity although conductivity of these electrolytes exponentially increases with increasing temperature. Typically, for this class of electrolytes, rapid protonic transport takes place at high temperatures (e.g. in the range of 1000 °C) . A third type of solid electrolytes embraces substances with amorphous (non-crystalline) structure. These substances comprise ion exchanging resins and glass-like materials. An important peculiarity of amorphous structure electrolytes is an absence of long- range order in atom locations while preserving short- range order of their locations.

A special type of solids with high ionic mobility is represented by bronze oxides of transient metals. Transient metals, such as vanadium, tungsten and molybdenum combine with oxygen to generate compounds that have an octahedral lattice structure. As the valence of metals in such compounds varies, the regular octahedral structure can be deformed with the result that oxides of the transient metals form space structural frames of composite configuration having channels available through which alkaline metals and alkaline rare earths as well as transition of protons may be transported. Specifically, the term bronze oxide is used with reference to a transient metal oxide that comprises an alkali or alkali rare earth metal, an example of which is Na_xW0₃._y, where x is a number less than one. Bronze oxides typically exhibit both high ionic mobility and moderate to high electronic conductivity. Neutron generation has been observed in bronze oxides as was reported in the earlier referenced 1993 Physics Letters A article by K. Kaliev, A. Baraboshkin, A. Samgin, et al .

Defects in ionic crystals play a critical and important role in proton mobility (conductivity) . Defects, typically referred to as point defects, define the physico-chemical features of solids. These defects are widely believed to form interstitial ion (atom) and in-lattice vacancies. An ideal crystal in which all the atoms are motionless and occupy fixed positions in an ideal lattice can only exist at the absolute zero degrees Kelvin. At any other temperature crystals are neither ideal nor perfect. Given the consideration that atoms contained within a lattice are understood to oscillate about a predetermined middle position, the resultant oscillations would also be understood to disturb the order of interstitial space. Distribution of defects in crystals is to some extent dependent upon the fact that increasing defect concentration decreases free energy of the crystal . The crystal defects may be divided into stoichiometric and non-stoichiometric (the latter being due to a change in crystal chemical composition) types. In addition to point defects, other imperfections may occur. Such imperfections may be pores, dislocations and interjected impurities.

Proton transport in solid electrolytes is commonly considered to occur (a) by proton jumping when the lattice ions serve as proton acceptors; (b) by channeling through a lattice having intrinsic channel structure; (c) in combination with a specific carrier mechanism using atom- ion- or molecule-carriers; and (d) in conjunction with surface or liquid phase mechanics.

In oxide materials, hydrogen defects can be formed from reactions with a hydrogen containing atmosphere. Hydrogen defects in oxide materials may participate in electron transport, which may be unipolar. In such oxide materials, hydrogen can be transported as both positive ion (H⁺, H₃0⁺) and negative ion (OH^") particles. At present several methods of loading solids with deuterium are known and summarized in an article entitled Review of Experimental Observations about the Cold Fusion Effect by Dr. E.Storms, published in Fusion Tech., vol.20, 1991. They are as follows: (a) a conventional wet electrolysis process in liquid electrolytes or electrolysis of molten salts; (b) direct loading of metals with deuterium under pressure;

(c) using electric current in gas-containing cells; (d) ion bombardment and implantation.

In direct gas loading technique, titanium or palladium is placed in D₂ gas at pressures ranging from less than 1 bar to greater than one megabar, but more commonly between 40 and 60 bar. Under such conditions, neutron emissions have been reported as having been detected, especially when titanium is used.

In the wet electrolysis approach, typically, a palladium or titanium cathode and a nickel or platinum anode are placed in an electrolyte consisting of a mixture of D₂0 and compounds derived from a group of compounds comprising LiOD, NaOD, and Li₂S0₄ mixed individually with the D₂0 or combined with other salts. Direct current of various magnitudes is passed between the electrodes. Because of the applied voltage, there appears to be a very high effective pressure generated within the metal and ions are given a modest energy. The chemically active deuterium is considered to react with the palladium or titanium cathode to form a hydride having a high but variable stoichiometry that depends on a complex set of circumstances. The stoichiometry that is achieved in localized regions is believed by experimenters to play a role of making the cold fusion effect occur. Neutron emission in combination with production of excess heat, protons, and tritium have been reported as having been detected using this method. A sudden change in charging current has been reported to trigger the emission and production of neutrons, heat, protons and tritium. However, spontaneous initiation also has been reported as being observed without an abrupt change.

In devices using electric current in gas-containing cells, a voltage sufficient to produce a gas discharge is applied to electrodes in low-pressure deuterium gas. The process theoretically gives the deuterium ions more energy than can be achieved in an electrolytic cell. Both palladium and titanium (as well as some other metals) have been used as the cathode. Large amounts of neutrons (and tritium, gamma rays, and X-rays and excess heat) have been reported in gas discharge experiments.

One study has reported neutron (and tritium) production by passing pulsed current through alternating layers of palladium and silicon disks in high-pressure D₂ gas.

In ion implantation experiments, ions (such as deuterons) are accelerated and impacted onto target materials. This technique not only implants deuterium into the metal lattice to give a very high deuterium-to- metal ratio, but also produces ion energies that approach hot fusion energy levels. Easily measured neutrons (and tritons, and protons) production have been reported from these experiments . Typically, all of the techniques listed above imply a required non-equilibrium state in a solid in order to initiate what is commonly referred to as a cold fusion process. Theoretically, an important and necessary special condition which must exist for initiation of any nuclear low temperature reaction is the presence of high, local concentrations of deuterium inside solid lattice.

An early report by A.L.Samgin et al . (a group comprising at least one of the inventors of this instant invention) entitled, "On the Possible Formation of Regions with High Hydrogen Isotope Concentration at Non-

Linear Diffusion in Transition Metals", from the Proc. All-Union Workshop "Chemistry and Technology of Hydrogen" ( "Hydrogen-91") , Zarechny, USSR, 1991, reported and described that nonlinear diffusion of hydrogen isotopes under strongly non-equilibrium boundary regimes can result in the formation of inhomogeneous space structures localized near the surface that can elevate concentration of hydrogen isotopes near the surface of solids. Hydrogen isotope nonlinear diffusion under essentially non-equilibrium boundary regimes, on one hand, reveals the role of non-equilibrium in formation of strongly inhomogeneous (with high concentration gradient) isotope distribution. On the other hand, cold fusion reactions may, one way or another, be connected with diffusive redistribution of isotopes and especially where isotope concentration is dramatically increased. Thus nonlinear diffusion and transport processes may be important in creating the conditions for relatively low temperature or cold fusion reactions to take place. Important to the concept which resulted in this instant invention is recognition of evidence that the such nonlinear diffusion or non-linear transport can take place not only in the hydrides of transient metals but also in other compounds, e.g. ones with mixed (ionic and electronic) conductivity such as compounds in the category of oxide bronzes.

It has been hypothesized that there is a connection between the formation of metastable local regions with elevated hydrogen isotope concentration and the emission of fusion related products, including neutrons, at lower temperatures. Some investigators reported successful experiments using solid electrolytes in various devices to trigger cold fusion reactions.

Currently, there are more than 700 known patents and invention certificates issued in many European countries, the United States of America and Japan. These patents and certificates disclose chemical electric cells, recharging batteries and fuel elements based on solid electrolytes and related methods and devices .

A French patent number 2,663,775, entitled "Electrolytic Reactor for Nuclear Fusion with Solid

Electrolyte" discloses a method of energy production in the kilowatt range. The disclosed reactor is made in a concentric structure which comprises a central axial electrode made of boron carbide and equipped with an automatic preheating system, a torus made of solid electrolyte and an outer electrode made of nickel. Extraction of energy from the reactor is by thermal or light radiation which is converted by thermo-electric, thermionic or magnetohydrodynamic converters to useful energy. Photovoltaic cells designed for cold conversion of radiation are also mentioned. The preferred form of fuel is deuterium. The ionic electrolyte is a tube made of lacunar lanthanum aluminate ceramic of chemical formula AlLa_{0 98}0₃. Operating temperature of the ceramic is around 1200° C. Electrolysis voltage is approximately 100V. Disclosure of Invention

A distinctive feature of experiments which have been carried out by a group from Institute of High-Temperature Electrochemistry and Ural Polytechnical Institute (Ekaterinburg, Russia) and comprising at least one inventor of the instant invention is the utilization of oxidized sodium-tungsten bronze Na_xW0₃. The results of the experiments are reported in an article by K. Kaliev et al . entitled "In Frontiers of Cold Fusion", 1993, Universal Academy Press, Inc., p.241-244; and by K.A.Kaliev, A.N.Baraboshkin, A.L.Samgin et al . in Physics Letters A172 (1993) , p.199-202.

Various degrees of tungsten valence states in bronze, rigidity of tungsten-oxygen octahedral frame and high mobility of the alkaline metal ions allow production of specific structures with extensive channels and ionic conductivity. In one series of experiments, bronze monocrystals of 8 to 12 mm size were placed in a vacuum chamber (10^~5 to 10^"6 torr) and subjected to heating in the presence of electric field. The monocrystals were cooled down to the room temperature and the chamber was filled with deuterium. Consistently, neutron- and gamma- radiation was recorded in excess of background quantities, amounting to a few hundred neutrons per minute. Such experiments demonstrated qualitative reproducibility of neutron signals.

Such experiments demonstrated the possibility of achieving nuclear reactions involving deuterium in solids, in particular in solid electrolytes with cation- electronic conductivity. Monocrystals of oxide tungsten bronze were used in such electrolytes to produce structures that determine the directions of deuterium ions movement.

The instant invention is based upon the above described phenomenon of nonlinear distribution of diffused hydrogen isotopes which occurs under strongly non-equilibrium boundary regimes in solid electrolytes with protonic or mixed conductivity. Such nonlinear distribution results in the formation of inhomogeneous space structures having elevated concentration of hydrogen isotopes near the surface of the solid electrolytes. It is assumed, though not necessarily, that nuclear reactions are, one way or another, connected with diffusive redistribution of hydrogen isotopes where their concentration is of greater than a predetermined critical density. This inventive device and method creatively takes advantage of diffusion nonlinearity process in creating a condition for cold fusion reactions to take place. In particular, the device and method control the diffusion and rate of migration of cations within a solid electrolyte to form spaces within the solid electrolyte having high densities of the cations. The device and associated apparatus comprise an active solid proton conductive electrolyte element disposed between and contiguous with an anode and a cathode. At least the anode is sufficiently permeable to deuterium to permit deuteron passage through the anode into the solid electrolyte. Even though an active solid electrolyte is permeable to deuterium, a relatively dense united heterostructure is formed by the electrodes and solid electrolyte. The apparatus also comprises a temperature control system having a sensor for sensing temperature of the solid electrolyte and a heater and a cooler for controllably changing the temperature in the solid electrolyte and maintaining the body of the solid electrolyte at a predetermined critical temperature. The apparatus also comprises a system for controlling the fluid environment in which the solid electrolyte is bathed. The system comprises a vacuum chamber which is releasibly sealable, a vacuum pump, a power supply and a source of deuterium.

The method associated with the apparatus comprises the steps of : a. selecting for the solid electrolyte a material which comprises non-linear proton conduction characteristics; b. determining a critical temperature at which the solid electrolyte exhibits protonic conductivity which results in a widely ranging deuterium distribution gradient; c. disposing the solid electrolyte between a cathode and an anode, the anode being made of proton (deuteron) permeable material which permits passage of deuterium from a surrounding fluid to the solid electrolyte; d. applying an electrically isolated temperature control system to the solid electrolyte to thereby maintain the solid electrolyte at a predetermined temperature; e. placing the solid electrolyte, electrodes and temperature control system in a vacuum chamber; f . sequentially removing fluid from the chamber, filling the chamber to a predetermined pressure with D₂, heating and maintaining the solid electrode at a predetermined temperature and applying a predetermined voltage across the electrodes (under some conditions it may be necessary to cyclicly vary the temperature of the solid electrode; when doing so, temperature lowering should be made at a controlled predetermined rate) ; and g. measuring emission of nuclear process formed products, such as neutrons, gamma rays, ions, excess energy, etc. The determining step comprising determining a critical temperature corresponding to a jump in protonic conductivity which is characteristic of the selected solid electrolyte. The measuring step providing a method for measuring neutrons generated in both a pulsed and continuous emission.

Accordingly, it is a primary object to provide a method for producing a nuclear reaction in a solid electrolyte at relatively low temperatures, i.e. at temperatures in the general range of 1000 °C.

It is another primary object to that the nuclear reaction method yield neutrons at a detectable and differentiable level of emission above background.

It is a fundamental object that the method comprise steps which use either or both of gas loading and electrolysis techniques for deuterium implantation into a solid state active material. It is yet another primary object to provide apparatus for generating neutrons at measured levels detectably and differentiably above background from a nuclear reaction at such relatively low temperatures within a solid electrolyte. It is another object to dispose the solid electrolyte as a part of said apparatus between a cathode and an anode.

It is an important object to select a perforated or otherwise formed anode which is permeable to deuterium and to create an operative united heterostructure of a metal electrode-solid electrolyte type. It is another important object that the relatively low temperature be selected to be a critical temperature at which there is a non-linear jump in protonic conductivity within the solid electrolyte and that in the region of the selected temperature and higher protonic conductivity there is a phase transformation of the solid electrolyte ..

It is a fundamental object that the heterostructure comprising the solid electrolyte have non-linear properties and therefore optimal electrolysis regime spaces comprising localized zones with relatively highly dense concentrations of protons or deuterons and other space comprising relatively inconsequential concentrations of protons or deuterons, all of which occur as a result of action of predetermined strong non- equilibrium conditions.

These and other objects and features of the present invention will be apparent from the detailed description taken with reference to accompanying drawings. It should be apparent to one who is skilled in the art that the current invention differs from the well known disclosure by Fleischmann and Pons . Electrolysis of a solid electrolyte with a solid (not liquid) composition is neither taught nor disclosed in any manner by Fleischmann and Pons. Different from a liquid cell, solid electrolytes possess appreciable protonic conduction in a hydrogen (or for deuteronic conduction in a deuterium) containing atmosphere at high temperature above 350° C. At 350° C which is unattainable in a liquid cell at reasonable pressures, the automatic transport of naked nuclei occurs since only hydrogen (or deuterium) ions exist. Under some conditions, other ionic conductivity of protonic species such as hydroxyl or oxonium ions also is possible, considering oxygen ion and other ions conductivity, but in selected materials protons transport may be close to unity and the role of other ions nearly absent. For this reason, in the current invention, it is possible to control the movement of naked nuclei in solids with special structure and composition. It is also possible to create localized zones near the surface with increased concentration of deuterium nuclei as a consequence of combined action of non-equilibrium electrolysis regimes and nonlinear properties of the solids (like nonlinear dependence of deuterium diffusivity from it's concentration) . It is postulated that the deuterium nuclei concentration in such localized zones is enough to decrease the nucleus- to-nucleus distances to the level necessary for nucleic interaction, resulting in neutron generation. If such is so, it the state of the sample is heterogeneous. An important basis for understanding the instant invention is found in examples which provides indirect confirmation of correctness of current theoretical postulates described above. The examples comprise facts previously published on neutron generation as a result of mechanical distortion of solids comprising D₂0 - ice, KH₂P0₄ in the paraelectric phase and bronze H_xW0₃. Each of these solids are protonic conductors. Protonic conductivity also exists in Cu₂0, CuO, NiO, Si0₂, zirconias and some perovskite type oxides (see, for example, the work of H. Iwahara et al . , Sol St. Ionics, 1981) . For this invention, material having a high temperature system based on SrCe0₃ may be used in which mobile species suggested is H⁺ (D⁺) . Some investigators have reported neutron emission observations in high-temperature superconductors comprising YBa₂Cu₃0₇__x. At a high temperature these substances may also become superionic conductors depending of external conditions, in which a transformation to a super conductivity state attends high ionic conductivity. All of these experimental observations are confirmed by the current invention. However, it should be emphasized that in all related examples of prior art, the basic difference between the prior art and the instant invention is that electrolysis was not previously disclosed or used as a method of external energy transfer. In the prior art comprised the use of physical distortion, thermo-cycling, high-pressure gas admission, etc. In the current invention, the generation method includes electrolysis, but does not obviate other external influence, such as thermo-cycling and saturation from the gas phase. Brief Description of the Drawings Figure 1 is a system schematic comprising a perspective of the core of the invention with portions removed for clarity of presentation.

Figure 2 is an exploded view of anode, a cylindrical solid electrolyte and a cathode elements of the invention seen in Figure 1.

Figure 3 is an embodiment of a sample holder which serves as both holder and electrodes for the sample.

Figure 4 is a perspective showing an outline of the exterior of a cylindrical solid electrolyte sample with two forms of interior virtual channels formed by various types of links of vacancies in the host lattice of the sample and spatial channels in the sample's lattice in direct meaning which may be three-, two- and one- dimensional . Figure 5 is a schematic section of a temperature cycling system comprising neutron detection apparatus with schematic representation of associated detection equipment . Modes for Carrying Out the Invention In this description, the term proximal is used to indicate the segment of the device normally closest to the object of the sentence describing its position. The term distal refers to the other end. Reference is now made to the embodiments illustrated in Figures 1-4 wherein like numerals are used to designate like parts throughout . One embodiment of this invention uses doped strontium ceroid as a high temperature protonic solid electrolyte the characteristics of which were previously investigated and reported by H.Iwahara, T.Esaka, H.Uchida and N.Maeda in Solid State Ionics, volume 3 of 4, page

359 (1981) and by H.Iwahara in High Temperature Protonic Conductors Based on Perovskite-type Oxides published in ISSI Letters 3 (1992) , volume 3, p.p. 11-13, and by Gorelov V.P. (one of the inventors of this instant invention) in "Ionic and Electronic Transmission in Solid Phase Systems" published in Scientific Works of Ural Branch of Academy of Science of the USSR, Sverdlovsk, 1992, p. 26-42.

DEFINE STRONTIUM CEROID (CERATE) MATERIAL The doped strontium ceroid material can be easily baked at 1450-1500°C producing a dense solid ceramic which have appreciable protonic conduction when vapor or hydrogen is introduced to the atmosphere at high temperatures. As was determined by the method of isotope exchange with reference to BaGe^Y^..., where "x" is a number less than one and "a" is a number less than 3, diffusivity of hydrogen and oxygen are different. Hence, protons, in this compound, are transmitted as individual free particles. In dry air, strontium ceroid is a p-type electron conductor. With increased humidity, proton conductivity increases while electronic conductivity decreases. In a dry hydrogen atmosphere (P_H20 ⁵ Torr, Temperature = 900° C) , the conductivity becomes unstable and strontium ceroid is altered to n-type electron conductivity as reported by H.Iwahara, T.Esaka, H.Uchida et al . in an article entitled "High Temperature Protonic Conductor Based on SrCe0₃ and its Absorption of Hydrogen Gas" published in Solid State Ionics, 18&.19 (1986) , p.p.1003- 1007] . The formula of material used in the invention may be generally designated as mCe₁._xR_y0₃._d, where d is less than or equal to x/2; y is less than x, x = 0.05-0.15; R may comprise La, Nd, Sm Cd, Dy, Er, Yb; M may be Sr or Ba. Generally there is a requirement for a hydrogen isotope in the surrounding atmosphere. Also note that undoped strontium cerate do not possess appreciable protonic conductivity.

It is important to note that the amount of deuterons in the sample at the beginning of the experiment is a function of preparation conditions; of the composition of initial sample and stoichiometry; of other experimental parameters such as temperature, pressure; of electrolysis regimes; and upon concentration of dopant. For neutron generation, absorbed deuteron concentration must exceed a critical value requiring care in manufacture, composition and preparation of the sample. Particularly, the degree of purity of the sample (conductivity channels state) and deflection of set stoichiometry may have a marked influence on the results. Ceramics with a deficiency of cerium (those having free strontium oxide in samples based on strontium cerate) quickly degrade in damp air such that experiment can not be repeated several times with the same sample. Importantly, dopants can considerably increase electric conductivity. Substitution by R⁺ ionscan considerably increase electrical conductivity. A small abundance or lack of cerium (<1%) can change the level of electric conductivity by a factor of ten. For ceramics based upon SrCe0₃ with additional R protonic conductivity decreases as humidity increases. Therefore, conductivity is generally sensible to atmospheric variables so results may be directly influenced by early preparation in a vacuum chamber. Besides protonic conductivity, at least one other condition must be satisfied for neutron generation within the sample. Such a condition may comprise energy passed to deuterons during the phase transformations in the sample. In the sample, nuclei mobility depends upon deuteron concentration and the sample structure. This mobility must be correlated with the speed of phase transformations occurring in the sample and hence with thermo-cycling speed. On the other hand, changing the phase transformation speed may result in displacement of the corresponding phase transformation temperature. Samples may undergo phase transformations at temperatures at which appreciable protonic conductivity is observed. During this process uneven change of conductivity mechanisms with simultaneously change of other physico- chemical properties and electric conductivity may take place. Another condition which is considered to promote nuclear processes which result in neutron generation is favorable changing of Coulombic potential of nuclei interacting in the sample. The anisotropy of electrical properties which is high in protonic conductors may also have an influence on the movement of electrons.

The near-surface layers of protonic conductive ceramics comprise zones of increased concentration which are situated in the region of the interphase boundary, especially when ceramics are covered with porous electrodes (from such metals as Pd, Pt, etc.) . As one who is skilled in ceramic coating art would understand, the technology of coating conductive covers exert a strong influence on experimental neutron generation results. The character of coating of the sample is likely the reason neutron generation may be localized in the transition layer of a metal-protonic conductor.

The interphase boundary is a distributed structure comprising three phases - metal, protonic conductive solid electrolyte and gas. A noted peculiarity is that two phases absorb portions of the third phase, isotopic hydrogen (which comprises deuterium) . During isotopic hydrogen absorption, a change in electrical and structural properties of the involved materials take place. A additional factor is current which flows from the interphase boundary during electrolysis. Increased temperature of electrolysis, which is necessary in this invention, accelerates a process of chemical diffusion at the interphase boundary which affects the sample construction. For these reasons, it is considered likely that electrical phenomena taking place on an interphase boundary of a solid electrolyte electrode as the result of an imposed electrical field may essentially influence the process of neutron generation.

Depth of an anticipated transition layer in the sample is formed by sample history, by structural peculiarities in the sample and the volume of deuterium dissolved by the sample. As known, the properties of transition layers may strongly influence physico-chemical processes. In the case of the contact metal-dielectric, for example, electronic density in a layer adjoined to metal is higher, than in an inner neighboring layer. Capillary phenomena play a especially large role in the transition layer.

In the transition layer, electronic subsystem interaction of one phase with nuclei subsystem of another phase may take place. In material possessing mixed (electronic-ionic) conductivity, the changing of properties of the electronic subsystem may strongly influence conduction of non-stationary processes within the transition layers.

Since the mobility of deuterons in protonic conductors is high and deuterons generally move as a group (rather than as a single particle) , the potential between deuterons in the group may essentially differ from the potential between deuterons in the deuterium molecule or in palladium deuteride. When an electrical field is applied the deuteron is transferred not individually but as a group so two phases of heterostructures exists, i.e. SrCeR_x0₃ and SrCER_xD_y0₃. As a result, a combination of the processes may bring the acceleration of particles into favorable conditions for neutron generation.

In the presently preferred embodiment, a high loading ratio and, therefore, a dense active saturation of deuterium within the ceramic is accomplished through the use of a combination of two loading techniques. Both electrolysis and direct gas loading are employed. This unification of two techniques accomplished by placing the active solid piece in D₂ gas atmosphere while additional implantation of deuterium into the solid is provided by electrolytic process. The electrolytic process comprises disposing a solid electrolyte between an anode and a cathode. As is described in detail hereafter, a pathway is provided for deuterium (or deuterons) flow into the solid electrolyte through the anode.

While the actual mechanism for producing neutrons within the instant invention is not precisely known, it is helpful in the design of apparatus to postulate a hypothetical source and cause of neutron and other nuclear product generation. As described above, a basis for fusion of adsorbed deuterons in a solid electrolyte may be absorbed deuterium cations having high mobility and accumulating into areas of high concentration. The high mobility and high concentration combining to provide high conductivity within the solid electrolyte and high concentration gradients providing spaces within the solid electrolyte structure having a sufficiently high deuterium-to-lattice host nuclei ratio to yield a measurable nuclear reaction.

To provide for occurrence of such accumulations and gradients in a material lattice, it is further hypothesized that undisturbed ion conductive channels be available where deuterons (other hydrogen ions) are able to move. These channels should provide opportunity for high density gradients of deuterons to exist relative to a pre-determined direction in the lattice frame. Such channels, depending upon the kind of solid electrolyte selected and pre-treatment applied to the selected electrolyte, may be modeled as either linear channels or specifically located vacancies in the crystal substructure of the electrolyte which are linked somehow with each other in a consecutive way.

Depending upon the chemical composition of ion conductors, the grade of their non-stoichiometry, availability of diversified structures or layers with different types of conductivity, their electrical features and the state of electron sub-systems may vary to a large scale and such is hypothesized to influence the rate of any resulting nuclear reaction.

Based upon the above considerations, an embodiment of the invention is seen as a system 100 in Figure 1. System 100 comprises a sealable vacuum chamber 110, a vacuum pumping system 120, a hydrogen gas source apparatus 130, a temperature control system 140, a reactor subsystem 150 and a power supply 160. Reactor subsystem 150, which is a key part of the invention, comprises a cathode plate 170, an anode plate 180 and a solid electrolyte mass 190. Reactor subsystem 150 further comprises a positioning subsystem, generally designated 200, for holding cathode plate 170, anode plate 180 and mass 190 in corresponding contact and in place within a hollow cylinder 210. Reactor subsystem 150 also comprises an electrical heating coil 220 which surrounds cylinder 210 as seen in Figure 1. In this version of the invention, it is possible to place electrical heating coil 220 on the outside of vacuum chamber 110.

Vacuum pumping system 120 comprises a vacuum pump 222, a fluid communicating tube 224, a valve 226, another fluid communicating tube 228 and a pressure meter 230. Vacuum chamber 110 comprises a hollow cylindrical body 232, a top cover 234 and a bottom cover 236. Although position is not critical, top cover 234 comprises a centrally disposed hollow stud 238 extending upward therefrom. Stud 238 is attached to cover 234 by a weldment 240 or other appropriate stud 238 to cover 234 sealing material. Stud 238 is further attached to or is a part of tube 228 to provide fluid communication between chamber 110 and vacuum pumping system 120. A pressure communicating stem 242 provides a pathway for delivery of pressure in tube 228 and therefore chamber 110 to meter 230. Tube 228 is connected to valve 226 which either dead ends tube 228 or permits fluid communication through tube 224 to vacuum pump 222. Vacuum pump 222 should be capable of pumping chamber 110 down to 10^"5 torr. Similarly meter 230 should be able to accurately read pressures in the 10^"6 torr range. Such meters, valves and pumps are known and are currently commercially available.

Bottom cover 236 comprises a hole in which a centrally disposed hollow stud 244 is permanently affixed to provide fluid communication to hydrogen gas source apparatus 130. Apparatus 130 comprises a fluid communicating tube 246, a fluid valve 248, a second fluid communicating tube 250, a pressure meter 252, a pressure communicating stem 254 and a hydrogen gas source 256. As seen in Figure 1, stud 244 is sealably connected to or an integral part of tube 250. Stem 254 delivers a measurable pressure to meter 252 from tube 250. On an end 258 proximal to valve 248, tube 250 connects to valve 248 which provides on-off control of fluid from hydrogen source 256. Fluid communication between valve 248 and source 256 is provided by tube 246. Valve 248 should be able to permit flow from source 256 to pressurize chamber 110 to pressures which range between 1 torr and 5 bar. Meter 252 should be capable of measuring and displaying pressures in the same range. Such hydrogen sources, valves and meters are currently commercially available.

Meters 230 and 252 may be the same meter if such a single meter can measure accurately through the ranges specified.

In the embodiment seen in Figure 1, cover 234 comprises a pair of apertures 260 and 262. Aperture 260 provides a sealed pathway, through sealing grommet 263 for each of two sensor wires 264 and 266, which are part of temperature control system 140. In addition, temperature control system 140 comprises a thermo-heater controller and power supply 268, power connecting wires 270 and 272 and wire to electrical heating coil 220 connections 274 and 276. Bottom cover 236 comprises one aperture 278 and associated pathway sealing grommet 280 to provide a pathway for wires 270 and 272 into chamber 110. Electrical heating coil 220 is preferably made of iridium wire wound for structural support around the exterior surface 282 of hollow cylinder 210. Hollow chamber 210 is may be made of any material having low outgassing properties and having sufficient structural strength to support heating coil 220, positioning system 200, cathode plate 170, mass 190, anode plate 180 and other associated parts requiring support, but is preferably made from quartz .

To sense the temperature of solid electrolyte mass 190, which is key to the maintenance of a predetermined temperature of mass 190 and the operation of the invention, a sensor 284 is imbedded into and in direct contact with a section of mass 190 and wires 264 and 266 extend therefrom to controller and power supply 268. Sensor 284 is selected and calibrated to sense heat of mass 190 for temperature control within a range of temperatures less than 1000 °C. Of course, each specific critical temperature is set and controlled by temperature control system 140. A more detailed discussion on selection of the specific critical temperature is provided hereafter. Design and fabrication of such temperature control systems is well known in the art and will therefore not be further treated herein. Briefly referencing Figure 2, the active portion of the reactor subsystem 150 comprises cathode plate 170, anode plate 180 and solid electrolyte mass 190. While solid electrolyte mass 190 is seen to have a cylindrical shape comprising a flat top surface 290 and a flat bottom surface 292, other shapes can be used with in the scope of the invention. Top surface 290 and bottom surface 292 may comprise an electrically conductive and, at least for top surface 290, a hydrogen isotope permeable coating for purposes which are described in detail hereafter.

Cathode plate 170 is brought into functional electrical contact with bottom surface 292 and anode plate 180 is similarly brought into contact with top surface 290. Specifically, solid electrolyte mass 190 is the active element of reactor 150. Mass 190 is preferably cylindrical in shape and is made of solid polycrystalline or monocrystalline electrolyte with deuteronic conductivity, e.g. strontium ceroid or barium ceroid. Mass 190 is located and held between the two electrodes 170 and 180. As seen in Figures 1 and 2, anode plate 180 may be made in the form of a porous disk which allows through penetration of hydrogen isotope (deuterium) gas to surface 290 which is an absorbing surface of the mass 190. Plates 170 and 180 and mass 190 may be a single heterostructure made by adheringly attaching electrical conducting material, as an example by spray coating, on surfaces 290 and 292.

Alternatively anode 180 may be made in the form of a helical spring 180' as seen in Figure 3. In any event it ^* is critical that a pathway be provided for isotopic hydrogen gas from the surrounding atmosphere through the space common to anode 180 and surface 290. Similarly it is important that the hydrogen gas, either in molecular or ionic form be passed by surface 290 into mass 190. In this manner one pole of an electrical circuit formed by anode 180 is established for introduction of isotopic hydrogen gas into mass 190. Anode 180 may be made of any electrically conductive material, such as tungsten or any other material which is relatively inert to chemical activity with top surface 290 and which can reliably withstand temperatures to 1000 °C. Cathode 170 may be made in the same form as and of the same materials as Anode 180. However, there may be no need for passage of either hydrogen isotope molecules or ions outward through surface 292. For this reason, cathode 170 may not be porous. Electrodes of reactor 150 are powered by wires 300 and 302, connected to cathode 170 and anode 180, respectively. As seen in Figure 1, wires 300 and 302 are sealable passed through orifice 262 in top cover 234 through a grommet 304 which is similar in form and function to grommet 263. Wires 300 and 302 deliver current and voltage from power supply 160 to cathode 170 and anode 180, respectively.

Power supply 160 is preferably a low voltage power supply which provides electric currents high as from few microamperes/cm² to hundreds of milliamperes/cm² flow through the active element. Such power supplies are known and available in the art.

As seen in Figure 1, reactor 150 is centrally disposed inside hollow chamber 210. Although other supporting apparatus may be used within the scope of the invention, supporting structure as shown in Figure 1 comprises a plurality of cross members 310, 312, 314 and 316, two plate supports 318 and 320, and coil springs 322 and 324. Note that the elastic properties of springs 322 and 324 must retain adequate mechanical constants at all operating temperatures. At the top of reactor 150, cross members 310 and 312 are solidly affixed to a top surface 330 of cylindrical chamber 210. Plate support 318 is affixed below cross members 310 and 312 and spring 324 is interposed between plate support 318 and anode 180.

Similarly, at the bottom of reactor 150, cross members 314 and 316 are solidly affixed to a bottom surface 332 of cylindrical chamber 210. Plate support 320 is affixed above cross members 314 and 316 and spring 322 is interposed between plate support 320 and cathode 170, thereby sandwiching and holding reactor 150 in place. As is well known in the art of vacuum chamber construction, top cover 234 is firmly affixed to hollow cylindrical body 232 by screws 340 or the like. Between top cover 234 and body 232, a gasket 350 is used to provide a seal. Gasket 350 should be chemically inert and sufficiently deformable to guarantee non-leakage. Preferably, gasket 350 is made of a deformable metal, such as copper. Gasket 352 is similar to gasket 350 and is disposed between bottom plate 236 and body 232 to form a seal thereat. Bottom cover 236 is attached to body 232 in a fashion similar to the attachment of top cover 234, but screws 340 are not shown. Finally, reactor 350 is centrally positioned in chamber 110 by securely affixing a brace, such as right angle brace 344 to body 232 and cylindrical chamber 210, as seen in Figure 1. Chamber 110 may be fabricated from stainless steel, quartz or any other material. Bottom cover 236 may be integral with chamber 110 or releasibly attached. Releasible attachment of top cover 234 to chamber 110 may be made by screws 340 or other vacuum chamber attachment apparatus well known in the art.

Though theory of operation is not vital to understanding how to make and use the invention, the following description of considerations basic to selection and fabrication of materials for solid electrolyte mass 190 is provided for clarity of understanding the invention. Referring to Figure 4, mass 190 is seen as a cylindrical disk, having a flat top surface 290 and a bottom surface 292. For this discussion, top surface 290 is associated with anode 180 and it is through this surface that the hydrogen isotope enters mass 190. For these reasons, surface 290 must be both conductive and permeable to hydrogen isotopes . To accomplish this a thin layer 396 of conductive material such as Pt may be deposited upon surface 290. Surface 292 must also be conductive but must not necessarily be permeable to hydrogen isotopes. Conductivity of surface 292 is enhanced by adding a thin layer 398 of conductive material preferably by vacuum deposition.

Two types of ionic pathways are shown schematically in mass 190. Manufactured pathways, represented by dashed lines 400 and 402 and 404 and 406, illustrate two hollow cylindrical columns 408 and 410, respectively. On one hand, such columns 408 and 410 may be produced by sample growth with predetermined properties and by electrochemical treatment of material, by chemically extracting a particular substance or impurity from the lattice of the material, such as extracting sodium or potassium.

On the other hand, virtual channels may already exist in virgin material. These channels are represented by dashed lines 420, 422, 424 and 426 in Figure 4. Dashed lines 420 and 422 trace a virtual channel 428; while dashed lines 424 and 426 trace a virtual channel 430. In all cases, ion pathways and/or channels are considered to describe paths of transport of ions within mass 190. Such movement is considered to be somewhat sporadic with accumulation of ions at specific places along the pathway or channel where density of ions is dramatically increased. Industrial Applicability

This invention is considered to be a forerunner of devices and methods which produce nuclear reactions in solid electrolytes. Past experimentation with the invention has concentrated on the generation of neutrons as a first proof of such nuclear reactions. Some of the solid electrolyte masses, generally 190, used and experiments which stem from such use are described hereafter as they apply to examples of methods and devices for which experimentation has been performed. Generally, each solid electrolyte mass is formed as a solid cylinder having a diameter of approximately 15 millimeters, a height of 2 millimeters and having a mass density on the order of 5.8 g/cm³. In one mass 190 embodiment, the active element consisted of SrCe₀₉₂Dy_{0 08}O₃__y (where "y" is a positive number less than 3) with platinum porous electrodes. The active element was installed into chamber 110 which was thereafter vacuumed down to a pressure of 10^"2 torr. Deuterium was then introduced into the chamber to a pressure of 1 bar and a DC potential of 1.5 V was applied across anode 180 and cathode 170. Immediately after application of the DC potential, temperature control system 140 was turned on and set to begin mass 190 heating. Initial electrolysis was carried out for 25 min. The initial current of electrolysis was around 30 microamperes when the mass 190 temperature was equal to 280°C. The current tended to gradually increase as temperature increased. Later, further a cycle of heating and followed by cooling of mass 190 to room temperature was established; total time for the heating/cooling cycle was three hours. When the temperature of the active element (mass 190) approached 680°C to 770°C, four single bursts of neutrons were observed over a period of approximately 20 minutes.

In another mass 190 embodiment, the active element consisted of a sample of BaCe₀₈₈Nd₀₁₂O₃__y with palladium electrodes installed into chamber 110. Chamber 110 was pumped down to a pressure of 10^~3 torr. Deuterium was introduced into the chamber to a pressure of 0.1 bar.

Heat was then applied to bring mass 190 to a temperature of 800 °C followed by cyclic cooling and heating through a 5 hour period. Electrolysis was started after the sample temperature reached 700°C. Electrolysis current was maintained in the range of 30 to 50 milliamperes. At the end of the period, the sample was kept at room temperature in the deuterium atmosphere for twenty hours, after which, the sample was heated again through a four hour period. At the end of the four hour period, chamber 110 was depressurized and then again pumped down to a pressure of 10^~3 torr. Next, chamber 110 was pressurized with deuterium to a pressure of 0.1 bar and heat was again applied to mass 190. During each thermo cycle, an additional supply of deuterium was allowed to flow into chamber 110 while the sample was kept hot. Heat was applied to bring mass 190 to temperature, after which contents of chamber 110 were allowed to cool in the presence of the deuterium atmosphere for three days to end preliminary treatment of the active element.

After the preliminary treatment, the active element was heated to 700°C and the electrolysis was applied. After four hours of electrolysis one neutron burst of eight counts per minute at an average background of two counts per minute was observed.

Exemplary experiments were made using cell designs consistent with the instant invention. However, as different neutron detector types were employed, different experimental geometries, including chamber 110 construction modifications and different background protection structure was employed as is well understood by one skilled in the neutron measurement art to be consistent with each neutron detector. Also, data was acquired by different methods, such as obtaining results from the detection apparatus by visual techniques, with the help of a strip chart recorder, on a monitor screen and reducing information on a computer.

In one experiment, a sample, as previously designated as mass 190, of SrCe_{0 92}Dy_{0 08}O₃._y was fabricated into a disk with a 15 mm diameter, 1.7 mm in width and ceramic density 5.8 g/cm³. The surface of mass 190 disk was spray-coated to add porous Pt electrodes. So made, the disk was installed into the chamber 110 which was pumped out to 10^"2 Torr. Chamber 110 was then filled with deuterium to a pressure of 1.2 Bar. The sample was heated to the working temperature (i.e. 720-780° C) at a predetermined rate .

In an embodiment seen in Figure 5, chamber 110 was positioned into an experimental system 500. Experimental system 500 comprised a heat protector 502, a plurality of neutron detectors 504 and associated amplifier systems 506, at least one high voltage power supply 508, a strip- chart recorder 510 and a protective enclosure 512. Each amplifier system 506 further comprised a preamplifier circuit 514, a spectroscopy amplifier 516, a discriminator 517 and a counter 518' . As is well understood by one skilled in the art of neutron measurement, system 500 also comprised a neutron moderator 518 which surrounded each neutron detector 504. Enclosure 512 was constructed as a hollow box and comprised enclosing side walls 520 and 522, a bottom wall 524, a back wall 526 and a top cover 528. A front wall, nearest a viewer of Figure 5, is not seen for convenience of presentation. At least one wall or cover is releasibly affixed to the other parts of enclosure 512 to permit access to other parts of system 500 contained therein. All walls and cover comprise neutron absorbing material, such as paraffin. Each neutron detector 504 is electrically connected to an amplifier system 506 which delivers a resulting amplified signal through a through-wall path, such as paths 530 and 532 in walls 520 and 522, respectively, to a spectroscopy amplifier 516. The signal out of each spectroscopy amplifier 516 is delivered to a counter 518' and also to strip-chart recorder 510.

Medially disposed between neutron moderators 518, is heat protector 502 which contained a chamber 110. Other electrical and fluid connections to chamber 110 are not provided in Figure 5 for clarity of presentation.

Method of operation comprised the following steps: 1. Initiating electrolysis with 7 volt potential and current from 52 to 32 mA through a period of 11.5 hours to the temperature of 750° C.

2. Turning electrolysis and sample heating off for a period of three hours.

3. Reinitiating heating to a temperature of 770° C and causing concurrent electrolysis with 20 mA current through a 14.5 hour period.

4. Again turning electrolysis and sample heating off for a period of 7.5 hours.

5. Reinitiating heating to a temperature of 750° C and causing concurrent electrolysis with a 6 mA current through a period of one hour.

6. Yet again turning electrolysis and sample heating off for a period of one hour.

7. Reinitiating heating to a temperature of 750° C . and causing concurrent electrolysis with 8 mA current through a 0.5 hour period.

8. Turning electrolysis and sample heating off for a period of 2.5 hours.

9. Reinitiating heating to a temperature of 750° C and causing electrolysis with 8 mA current to occur through a 0.5 hour period.

10. Turning heating and electrolysis off and removing chamber 110 from enclosure 512 and permitting contents of chamber 110 to cool to room temperature through a period of 0.5 hour. During neutron output measuring in steps 9 and 10, neutron output was observed to equal to 278 counts per hour. The observed count exceeded background by 56

(background during measuring in one week time interval was 202 counts per hour with root-mean-square dispersion σ=15) . Hereinafter, further cyclic heating with concurrent electrolysis did not produce observable neutron output which exceeded background.

A barium sample comprising BaCe₀₈₈Dy₀₁₂0₃ with Pd electrodes affixed thereto was placed into chamber 110. Chamber 110 was pumped to a reduced pressure of 5 * 10^"2 Torr. Background measurements were conducted during a few hours to establish a base-line count. After pumping, the chamber 110 was filled with D₂ to a pressure of 1 Bar.

An experiment involving the barium sample comprised the steps of: a. thermo-heating was turned on and electrolysis between the sample's electrodes was begun. Preliminary electrolysis current was 1.4 mA at a voltage of 6 V; b. conducting electrolysis was through a 20 hour period at a temperature of 750° C. Electrolysis current was 20 mA; c. heating the sample to 810° C at a controlled, predetermined rate; d. cycling the electrolysis current off and then, after 2 minutes, on again; e. turning the thermo-heater off (until a thermocouple placed near the sample and showed a temperature of 400° C) ; f. turning the thermo-heater on and heating the sample to 810° C. g. repeating steps e and f

One of the observed results (phenomena) occurred during passage of the sample through the 400 to 800° C- temperature interval which contained the temperature of phase transformation. The phenomena observed was a series of a few neutron impulses which exceeded background within a 1-second time interval. The excess neutron emission occurred only during cooling of the sample.

Of particular note was a neutron emission event which occurred in the first series in which the neutron count excess was ten times higher than background while displacement of the temperature only a few degrees from the temperature of emission, only a background level of neutron measurement (i.e. not exceeding a one σ level) .

Later in the cycling experiment, during two cycles a decrease of neutron emission was observed. In following thermo-cycles, no neutron measurements were found to be above background. Such measurements were considered to be a result of sample structure degradation.

Results were obtained with the help of an IBM PC AT computer, permitting impulse appearance time to be affixed with a precision of approximately 20 milliseconds. Temperature and pressure of deuterium were measured concurrent with measurement of impulse appearance time.

Production of neutrons has been recorded without electrolysis being implemented. In such cases, after a sample had been heated to the critical temperature in a deuterium atmosphere, the heater was turned off and the contents of chamber 110 cooled to room temperature. The procedure was cycled repeatedly. Neutron production appeared during these cycles both in pulsed and continuous manner.

The invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.

What is claimed and desired to be secured by Letters Patent is :

Claims

Claims

1. A method for generating neutrons within a solid electrolyte (190) comprising the steps of:

(a) selecting electrolyte material for the solid electrolyte (190) ;

(b) determining a critical temperature at which the electrolyte material exhibits protonic conductivity which results in a widely ranging hydrogen ion distribution gradient; (c) forming the material into the solid electrolyte (190) form consistent with application of a voltage potential across two opposing faces (290,292) of the solid electrolyte (190) , each said face (290,292) comprising a conductive covering (396,398) and at least one (396) of said conductive coverings being permeable to isotopic hydrogen;

(d) interposing the solid electrolyte (190) between an anode (180) and a cathode (170) to form a reactor element (150) ; (e) disposing the reactor element (150) into a vacuum chamber (110) ;

(f) removing fluid from said vacuum chamber (110) ;

(g) filling said chamber (110) with isotopic hydrogen to a predetermined pressure;

(h) applying a predetermined voltage across the anode (180) and cathode (170) ;

(i) raising the temperature of the solid electrolyte (190) to the critical temperature; and ^' (j) cycling the temperature from said critical temperature to a lower temperature at a predetermined rate.

2. A method for generating neutrons within a solid electrolyte (190) according to Claim 1 wherein the applying step precedes the filling step.

3. A method for generating neutrons within a solid electrolyte (190) according to Claim 1 wherein the raising step precedes the applying step.

4. A method for generating neutrons within a solid electrolyte (190) according to Claim 1 wherein the isotopic hydrogen of steps (c) and (g) is D₂.

5. A method for generating neutrons within a solid electrolyte (190) according to Claim 1 comprising the following additional steps : (k) returning the temperature of the solid electrolyte (190) to ambient temperature; and (1) removing the voltage.

6. A method for generating neutrons within a solid electrolyte (190) according to Claim 5 wherein steps (i) through (1) are repeated to generate successive bursts of neutrons emitted from the solid electrolyte (190) .

7. A method for generating neutrons within a solid electrolyte (190) according to Claim 1 wherein the electrolyte material selecting step comprises selecting material from a group comprising doped strontium ceroid, barium ceroid.

8. A method for generating neutrons within a solid electrolyte (190) according to Claim 1 wherein the material selecting step comprises selecting a material having the general chemical formula SrCe₀₉₂Dy₀₀₈O₃__y.

9. A method for generating neutrons within a solid electrolyte (190) according to Claim 1 wherein the material selecting step comprises selecting material having the general chemical formula BaCe₀₈₈Nd₀₁₂0₃._y

10. Apparatus for generating neutrons within a solid electrolyte (190) comprising: the solid electrolyte (190) which at a predetermined temperature exhibits protonic conductivity which results in a widely ranging hydrogen ion distribution gradient, said predetermined temperature being designated as a critical temperature; means (140) for raising, maintaining and decreasing temperature of the electrolyte (190) to the critical temperature at a predetermined rate; said solid electrolyte (190) comprising opposing faces (292,290) , each said face (290,292) comprising a conductive covering (396,398) and at least one (396) of said conductive coverings being permeable to isotopic hydrogen; an anode (180) and a cathode (170) between which the solid electrolyte (190) is interposed to form a reactor element (150) , at least said anode (180) being permeable to passage of isotopic hydrogen; a vacuum chamber (110) into which the reactor element (150) is disposed during neutron generation; means (120) for pumping fluid from said vacuum chamber (110) to a first predetermined pressure level; means (130) for filling said chamber (110) with isotopic hydrogen to a second predetermined pressure level; and means (160) for applying a predetermined voltage across the anode (180) and cathode (170) and thereby across the solid electrolyte (190) .

11. Apparatus for generating neutrons within a solid electrolyte (190) according to Claim 10 wherein said predetermined temperature is approximately 1000 °C .

12. Apparatus for generating neutrons within a solid electrolyte (190) according to Claim 10 wherein said temperature raising, maintaining and decreasing means (140) comprises a temperature sensor (284) imbedded into said solid electrolyte (190) .

13. Apparatus for generating neutrons within a solid electrolyte (190) according to Claim 10 wherein said pumping means (120) comprise means (222) for reducing the pressure in the vacuum chamber (110) to 10^~6 torr.

14. Apparatus for generating neutrons within a solid electrolyte (190) according to Claim 10 wherein said filling means (130) comprise means for (248,252) limiting and restricting pressure of gas introduced into the chamber (110) in a range of 1 torr to 5 bar.

15. Apparatus for generating neutrons within a solid electrolyte (190) according to Claim 10 wherein said voltage applying means (160,300,302) comprise means (160) for applying a voltage in the range of 1.5 to 3.0 volts with a controllable current ranging from one microampere to five hundred milliamperes .

16. A method of fabricating a reactor element (150) which, when immersed in an environment of a predetermined temperature, pressure of isotopic hydrogen and electric potential and current, emits particles normally associated with a nuclear reaction comprising the steps of:

(a) selecting electrolyte material for the solid electrolyte (190) which at said temperature exhibits hydrogen ion conduction which results in a widely ranging proton distribution gradient within said material;

(b) determining the temperature at which the electrolyte material exhibits the protonic conductivity; (c) forming the material into the solid electrolyte (190) form consistent with application of a voltage potential across two opposing faces (290,292) of the solid electrolyte (190) , each said face (290,292) comprising a conductive covering (396,398) and at least one (396) of said conductive coverings being permeable to isotopic hydrogen;

(d) interposing the solid electrolyte (190) between an anode (180) and a cathode (170) to form the reactor element (150) .