US20170038095A1

US20170038095A1 - Method for producing energy and apparatus therefor

Info

Publication number: US20170038095A1
Application number: US15/234,379
Authority: US
Inventors: Francesco Piantelli
Original assignee: MEIARINI Alessandro
Current assignee: MEIARINI ALESSANDRO
Priority date: 2008-11-24
Filing date: 2016-08-11
Publication date: 2017-02-09

Abstract

A method for producing energy by exothermal reactions between hydrogen and a transition metal comprises a step 110 of depositing an amount of crystals of the transition metal in the form of micro/nanometric clusters having a predetermined crystalline structure on a surface of a substrate, wherein each clusters has a number of atoms of the transition metal lower than a predetermined number of atoms, and in such a way that the substrate contains on its surface a number of clusters that is larger than a minimum number. The method provide also performing at least once a start-up sequence is performed at least once a start-up sequence comprising the step 114 of quantitatively removing any gas adsorbed in the substrate and in the transition metal by applying a predetermined vacuum degree, a step 120 of bringing hydrogen into contact with the crystals, a step 130 of heating the crystals up to an adsorption temperature higher than a predetermined critical temperature, thus causing hydrogen adsorption to the crystals forming a reaction core, and a step of impulsively acting on the reaction core in order to trigger the exothermal reactions between the hydrogen and the transition metal in the clusters. Once the reaction started, a step 140 is provided of removing heat from the reaction core in order to obtain a determined power and to maintain the temperature of the reaction core above the critical temperature.

Description

FIELD OF THE INVENTION

The present invention relates to a process for producing energy by exothermal reactions between a transition metal and hydrogen that is adsorbed on the crystalline structure of the transition metal.

DESCRIPTION OF THE PRIOR ART

A method for producing heat by exothermal reactions caused by hydrogen that is adsorbed on a Nickel reaction core has been described in WO95/20316, in the name of Piantelli et. al.. Improvements of the process are described in Focardi, Gabbani, Montalbano, Piantelli, Veronesi, “Large excess heat production in Ni—H systems”, in Il Nuovo Cimento, vol. IIIA, N.11, November 1998, and bibliography therein.
A problem that was observed during the experiments was the preparation of the cores on which hydrogen had to be adsorbed and the reactions had to be carried out. Such cores were made of Nickel and had the shape of small bars.
One of the various critical aspects of the process was the choice of a suitable method for adsorbing hydrogen and the quality of the hydrogen matter, as well as the repeatability of the triggering conditions of the process.
Other critical aspects were how to clean the small bar before the adsorption of the hydrogen, as well as how to optimize the optimal bar surface conditions and the method for triggering and shutting down the reactions.
Due to such problems, the set up of the process and its industrial exploitation turned out to be somewhat difficult.
A further critical aspect is the core sizing and design to attain a desired power.

SUMMARY OF THE INVENTION

It is therefore a feature of the present invention to provide a method for producing energy by exothermal reactions of hydrogen and a transition metal having a crystalline structure, which ensures repeatability of the triggering conditions of the reactions.
These and other features are accomplished by A method for producing energy by exothermal reactions between hydrogen and a transition metal, the method providing the steps of:

- depositing an amount of crystals of the transition metal in the form of micro/nanometric clusters having a predetermined crystalline structure on a surface of a substrate consisting of a solid body that has a predetermined volume and shape, wherein each of the clusters has a number of atoms of the transition metal lower than a predetermined number of atoms,
- and in such a way that the substrate contains on its surface a number of clusters that is larger than a minimum number, in particular the minimum number is at least 10⁹clusters per square centimetre;
- wherein a start-up sequence is performed at least once, the start-up sequence comprising the steps of:
  - bringing and maintaining for a predetermined cleaning time the substrate and the crystals to/at a predetermined vacuum degree, in order to quantitatively remove gas adsorbed in the substrate and in the transition metal;
  - bringing hydrogen into contact with the crystals;
  - heating the crystals up to an adsorption temperature higher than a predetermined critical temperature, thus causing an adsorption of hydrogen to the crystals, the substrate, the crystals and the hydrogen adsorbed thereto forming a reaction core;
  - impulsively acting on the reaction core in order to trigger the exothermal reactions between the hydrogen and the transition metal in the crystals;
- removing heat from the reaction core in order to obtain a determined power and to maintain the temperature of the reaction core above the critical temperature.

Advantageously, the step of depositing the amount of crystals is carried out in such a way that the determined quantity of crystals of the transition metal in the form of micro/nanometric clusters is proportional to the power.
The number of atoms that form each cluster is the variable through which the predetermined power can be obtained from a reaction core that comprises a predetermined amount of metal. In fact, each cluster is a site where a reaction takes place, therefore the power that can be obtained is substantially independent from the clusters size, i.e. from the number of atoms that form the cluster.
In particular, the number of atoms of the clusters is selected from a group of numbers that are known for giving rise to structures that are more stable than other aggregates that comprise a different number of atoms. Such stability is a condition to attain a high reactivity of the clusters with respect to hydrogen. For instance, a stability function has been identified for Nickel, which depends upon the number of atoms that form the clusters, obtaining specific stability peaks that correspond to that particular numbers.
Preferably, the hydrogen in use is molecular hydrogen H₂. As an alternative, the hydrogen can be at least in part preliminarily ionized to H⁻.
The transition metal can be selected from the group comprised of: Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Zn, Y, Zr, Nb, Pd, Mo, Tc, Ru, Rh, Ag, Cd, Lu, Hf, Ta, W, Re, Os, Ir, Pt, Au, lanthanoids, actinoids. Such metals belong to one of the four transition groups, i.e.:

- metals that have a partially filled 3d-shell, e.g. Nickel;
- metals that have a partially filled 4d-shell, e.g. Rhodium;
- metals that have a partially filled 5d-shell, i.e. the “rare earths” or lanthanoids, e.g. Cerium;
- metals that have a partially filled 5d-shell, i.e. the actinonoids, e.g. Thorium.

The metal can also be an alloy of two or more than two of the above listed metals.
Among the listed transition metals, or their alloys, those which crystallize in a crystalline structure selected from the group comprised of:

- face-centred cubic crystalline structure;
- body-centred cubic crystalline structure;
- compact hexagonal structure are preferred. Advantageously, metals are used that have a crystalline open face structure.

Preferably, the transition metal is Nickel. In particular, the Nickel is selected from the group comprised of:

- natural Nickel, i.e. a mixture of isotopes like Nickel 58, Nickel 60, Nickel 61, Nickel 62, Nickel 64;
- a Nickel that contains only one isotope, the isotope selected from the group comprised of:
  - Nickel 58;
  - Nickel 60;
  - Nickel 61;
  - Nickel 62;
  - Nickel 64;
- a formulation comprising at least two of such isotopes at a desired proportion.

Once hydrogen adsorption to the crystals has occurred, hydrogen can interact with the atoms of the clusters, provided that an activation energy threshold is exceeded.
A proton generation during the reactions has been experimentally detected in the cloud chamber, and the generated protons can be usefully used to trigger other reactions.
Advantageously, the predetermined number of the transition metal atoms of the clusters is such that a portion of material of the transition metal in the form of clusters or without clusters shows a transition of a physical property of the metal, the property selected from the group comprised of:

- thermal conductivity;
- electric conductivity;
- refraction index.

The micro/nanometric clusters structure is a requirement for the method to operate successfully. For each transition metal, a critical number of atoms can be identified below which a level discrete structure (electronic density, functional of the electronic density and Kohn-Sham effective potential) and Pauli antisymmetry, tend to prevail over a band structure according to Thomas-Fermi approach. The discrete levels structure is at the origin of the main properties of the clusters, some of which have been cited above. Such features can be advantageously used for analysing the nature of the surface, i.e. for establishing whether clusters are present or not.
In particular, the minimum number of clusters is at least 10¹⁰clusters per square centimetre, in particular at least 10¹¹clusters per square centimetre, more in particular at least 10¹²clusters per square centimetre.
Preferably, the clusters form on the substrate a thin layer of the metal, whose thickness is lower than 1 micron. In particular, such thickness is of the same magnitude of the lattice of the crystalline structure of the transition metal. In fact, the core activation by adsorption of hydrogen into the clusters concerns only a few surface crystal layers.
In particular, the step of depositing the transition metal is carried out by a process of physical deposition of vapours of the transition metal.
The process of depositing can be a process of sputtering, in which the substrate receives under vacuum a determined amount of the metal in the form of atoms that are emitted by a body that is bombarded by a beam of particles.
Alternatively, the process of depositing can comprise an evaporation step or a thermal sublimation step and a subsequent condensation step in which the metal condensates onto the substrate.
Alternatively, the process of depositing can be performed by means of an epitaxial deposition, in which the deposit attains a crystalline structure that is similar to the structure of the substrate, thus allowing the control of such parameters.
The transition metal can be deposited also by a process of spraying.
Alternatively, the step of depositing the transition metal can provide a step of heating the metal up to a temperature that is close to the melting point of the metal, followed by a step of slow cooling. Preferably, the slow cooling proceeds up to an average core temperature of about 600° C.
The step of depositing the metal is followed by a step of quickly cooling the substrate and the transition metal as deposited, in order to cause a “freezing” of the metal in the form of clusters that have a predetermined crystalline structure.
In particular, the quickly cooling occurs by causing a stream of hydrogen to flow proximate to the transition metal as deposited on the substrate, the current having a predetermined temperature that is lower than the temperature of the substrate.
In particular, the start-up sequence is iterated until the step of impulsively acting on the reaction core causes a permanent generation of heat, i.e. until a successful triggering of the reaction core takes place.
Advantageously, the vacuum degree applied during the step of bringing Hydrogen into contact with the crystals of the transition metal is at least 10⁻⁹bar. Preferably, this step of bringing and maintaining the substrate and the crystals to/at a predetermined vacuum occurs at a temperature set between 350° C. and 500° C.
Advantageously, the step of bringing and maintaining the substrate and the crystals to/at a predetermined vacuum degree is performed according to at least ten vacuum cycles, each vacuum cycle comprising creating the vacuum and subsequently restoring a substantially atmospheric pressure of hydrogen. This way, it is possible to quantitatively remove the gas adsorbed within the metal, in particular the gas which is adsorbed in the metal of the reaction core. In fact, it has been shown that such gas drastically limits or prevents the adsorption of the hydrogen in the clusters, even if an initial adsorption has occurred on the metal surface.
If the substrate and the deposited metal are exposed to a temperature above a given temperature, normally, and in particular for Nickel, well above 500° C., the cluster structure can be irremediably damaged.
Advantageously, during the step of bringing hydrogen into contact with the crystals, the hydrogen has a partial pressure set between 0,001 millibar and 10 bar absolute, in particular set between 1 millibar and 1 bar absolute, in order to ensure an optimal number of hits between the surface of the clusters and the hydrogen molecules: in fact, an excessive pressure increases the frequency of the hits, such that it can cause surface desorption, as well as other detrimental phenomena.
Advantageously, during the step of bringing hydrogen into contact with the clusters, the hydrogen flows with a speed less than 3 m/s. The hydrogen flows preferably according to a direction that is substantially parallel to the surface of the clusters deposited on the substrate. In these condition, the hits between the hydrogen molecules and the metal substrate occur according with small impact angles, which assist the adsorption on the surface of the clusters and prevents re-emission phenomena.
Advantageously, the step of creating a reaction core by hydrogen adsorption into the clusters is carried out at a temperature that is close to a temperature at which a sliding of the reticular planes of the transition metal, the temperature at which a sliding occurs is set between the respective temperatures that correspond to the absorption peaks α and β.
Advantageously, after the step of heating a step is provided of cooling the reaction core down to the room temperature, and the step of impulsively acting on the reaction core comprises a quick rise of the temperature of the reaction core from room temperature to the adsorption temperature. In particular, this quick temperature increase takes place in a time that is shorter than five minutes.
The critical temperature is normally set between 100 and 450° C., more often between 200 and 450° C. More in detail, the critical temperature is higher than the Debye temperature of the metal.
In particular, the step of impulsively acting on the reaction core provides an impulsive action selected from the group comprised of:

- a thermal shock, in particular caused by a flow of a gas, in particular of hydrogen, which has a predetermined temperature that is lower than the reaction core temperature;
- a mechanical impulse, in particular a mechanical impulse whose duration is less than 1/10 of second;
- a pressure impulse, In which the pressure of hydrogen in contact with the crystals is suddenly increased or decreased by additionally supplying/withdrawing an amount of hydrogen;
- an ultrasonic impulse, in particular an ultrasonic impulse whose frequency is set between 20 and 40 kHz;
- a laser ray that is impulsively cast onto the reaction core;
- an impulsive application of a package of electromagnetic fields, in particular the fields selected from the group comprised of: a radiofrequency pulse whose frequency is larger than 1 kHz; X rays; y rays;
- an electrostriction impulse that is generated by an impulsive electric current that flows through an electrostrictive portion of the reaction core;
- an impulsive application of a beam of elementary particles. In particular, such elementary particles selected from the group comprised of electrons, protons and neutrons;
- an impulsive application of a beam of ions of elements, in particular of ions of one or more transition metals, the elements selected from a group that excludes O; Ar; Ne; Kr; Rn; N; Xe.
- an electric voltage impulse that is applied between two points of a piezoelectric portion of the reaction core;
- an impulsive magnetostriction that is generated by a magnetic field pulse along the reaction core which has a magnetostrictive portion.

Preferably, before the step of impulsively acting on the reaction core a step is carried out of creating a temperature gradient, i.e. a temperature difference, between two points of the reaction core, the gradient in particular set between 10000 and 300° C.
Advantageously, a step is provided of modulating the energy that is delivered by the exothermal reactions.
In particular, the step of modulating comprises removing and/or adding reaction cores or reaction core portions from/to a generation chamber which contains one or more reaction cores during the step of removing the heat.
The step of modulating comprises a step of approaching/spacing apart sheets of the transition metal which form the reaction core in the presence of a hydrogen flow.
The step of modulating can furthermore be actuated by absorption protons and alpha particles in lamina-shaped absorbers that are arranged between sheets of the transition metal which form the reaction core. The density of such emissions is an essential feature for adjusting the power.
Advantageously, a step is provided of shutting down the exothermal reactions in the reaction core, that comprises an action selected from the group comprised of:

- a further mechanical impulse;
- cooling the reaction core below a predetermined temperature, in particular below the predetermined critical temperature;
- a gas flow, in particular an Argon flow, on the reaction core.

In particular, the step of shutting down the exothermal reactions can comprise lowering the heat exchange fluid inlet temperature below the critical temperature.
Advantageously, the exothermal reactions is carried out in the presence of a condition selected from the group comprised of:

- a magnetic induction field whose intensity is set between 1 Gauss and 70000 Gauss;
- an electric field whose intensity is set between 1 V/m and 300000 V/m.

The objects of the invention are also achieved by an energy generator that is obtained from a succession of exothermal reactions between hydrogen and a metal, wherein the metal is a transition metal, the generator comprising:

- a reaction core that comprises a predetermined amount of the transition metal;
- a generation chamber that in use contains the reaction core;
- a means for heating the reaction core within the generation chamber up to a temperature that is higher than a predetermined critical temperature;
- a means for impulsively acting on the reaction core, in order to texothermal reaction between the transition metal and the hydrogen;
- a means for removing from the generation chamber the heat that is developed during the reaction in the reaction core according to a determined power;
  the main feature of the generator is that:
- the reaction core comprises a determined quantity of crystals of the transition metal, the crystals being micro/nanometric clusters that have a predetermined crystalline structure according to the transition metal, each of the clusters having a number of atoms of the transition metal that is less than a predetermined number of atoms.

Advantageously, the determined quantity of crystals of the transition metal in the form of micro/nanometric clusters is proportional to the power. Preferably, the means for heating the reaction core comprises an electric resistance in which, in use, an electric current flows.
In particular, the reaction core comprises a substrate, i.e. a solid body that has a predetermined volume and a predetermined shape, on whose surface the determined quantity of micro/nanometric clusters of the transition metal is deposited, for at least 10⁹clusters per square centimetre, preferably at least 10¹⁹clusters per square centimetre, in particular at least 10¹¹clusters per square centimetre, more in particular at least 10¹²clusters per square centimetre.
Advantageously, the reaction core has an extended surface, i.e. a surface whose area is larger than the area of a convex envelope of the reaction core, in particular an area A and a volume V occupied by the reaction core with respect to a condition selected from the group comprised of:

- NV>12/L, in particular NV>100/L;
- NV>500 m²/m³,
  where L is a size of encumbrance of the reaction core, the extended surface in particular obtained using as substrate a body that is permeable to the hydrogen, the body preferably selected from the group comprised of:
- a package of sheets of the transition metal, each sheet having at least one face available for adsorbing the hydrogen, in particular a face that comprises an extended surface;

Preferably, the reaction core is arranged in use at a distance shorter than 2 mm from an inner wall of the generation chamber.
Advantageously, the generator comprises a means for modulating the energy that is released by the exothermal reactions.
The means for modulating can comprise a means for removing/adding reaction cores or reaction core portions from/into the generation chamber.
In particular, the reaction core comprises a set of thin sheets, preferably the thin sheets having a thickness that is less than one micron, that are arranged facing one another and the means for modulating comprises a structure that is adapted to approach and/or to space apart the sheets while a hydrogen flow is modulated that flows in a vicinity of the core.
Still in the case of a reaction core that comprises sheets that are arranged adjacent to one another, the means for modulating can comprise lamina-shaped absorbers that are arranged between the sheets of the transition metal which form the reaction core, the absorbers adapted to absorb protons and alpha particles that are emitted by the reaction core during the reactions.
Advantageously, the generator comprises furthermore a means for shutting down the reaction in the reaction core.
In particular, the means for shutting down are selected from the group comprised of:

- a means for creating a further mechanical impulse;
- a means for cooling the core below a predetermined temperature value, in particular below the predetermined critical temperature;
- a means for conveying a gas, in particular Argon, on the reaction core.

In particular, the reaction core comprises a set of thin sheets, preferably the sheets having a thickness that is less than one micron, the sheets arranged facing one another and the means for modulating provided by the structure and by the absorbers.
Advantageously, the generator comprises a section for producing a determined quantity of clusters on a solid substrate, the section comprising:

- a clusters preparation chamber;
- a means for loading the substrate in the clusters preparation chamber;
- a means for creating and maintaining vacuum conditions about the substrate within the clusters preparation chamber, in particular a means for creating and maintaining a residual pressure equal or less than 10⁻⁹bar;
- a means for heating and keeping the substrate at a high temperature in the clusters preparation chamber, in particular a means for bringing and keeping the substrate at a temperature set between 350° C. and 500° C. when the residual pressure is equal or less than 10⁻⁹bar;
- a means for depositing the transition metal on the substrate, preferably by a technique selected from the group comprised of:
  - a sputtering technique;
  - a spraying technique;
  - a technique comprising evaporation and then condensation of the predetermined amount of the metal on the substrate;
  - an epitaxial deposition technique;
  - a technique comprising heating the metal up to a temperature that is close to the melting point of the metal, the heating followed by a slow cooling;
- a means for quickly cooling the substrate and the transition metal, such that the transition metal is frozen as clusters that have the crystalline structure.

Advantageously, the section for producing a determined quantity of clusters comprises a means for detecting a transition of a physical property during the step of depositing, in particular of a physical property selected from the group comprised of:

- thermal conductivity;
- electric conductivity;
- refraction index.
  the transition occurring when the predetermined number of atoms of the transition metal in a growing cluster is exceeded.

Advantageously, the section for producing a determined quantity of clusters comprises a means for detecting a clusters surface density, i.e. a mean number of clusters in one square centimetre of the surface during the step of depositing.
Preferably, the section for producing a determined quantity of clusters comprises a thickness control means for controlling the thickness of a layer of the clusters, in order to ensure that the thickness is set between 1 nanometre and 1 micron.
Advantageously, the generator comprises a section for producing a reaction core, the section for producing a reaction core comprising:

- a hydrogen treatment chamber that is distinct from the generation chamber;
- a means for loading the determined quantity of clusters in the treatment chamber;
- a means for heating the determined quantity of clusters in the hydrogen treatment chamber up to a temperature that is higher than a predetermined critical temperature;
- a means for causing the hydrogen to flow within the hydrogen treatment chamber, the hydrogen having a predetermined partial pressure, in particular a partial pressure set between 0,001 millibar and 10 bar absolute, more in particular between 1 millibar and 1 bar absolute;
- a means for transferring the reaction core from the hydrogen treatment chamber into the generation chamber.

Advantageously, the section for producing a reaction core comprises a means for cooling down to room temperature the prepared reaction core, and the means for heating the reaction core within the generation chamber are adapted to heat the reaction core up to the predetermined temperature which is set between 100 and 450° C. in a time less than five minutes.
In particular, the quickly cooling in the clusters preparation chamber and/or the cooling down to room temperature in the hydrogen treatment chamber is/are obtained by means of the hydrogen flow on the reaction core, the flow having a predetermined temperature that is lower than the temperature of the reaction core.
The objects of the invention are also achieved by an apparatus for producing energy that comprises:

- a means for generating a substance in the vapour or gas state at a first predetermined pressure, the means for generating associated with a heat source;
- a means for expanding the substance from the first pressure to a second predetermined pressure producing useful work;
- a means for cooling the substance down to a predetermined temperature, in particular the predetermined temperature is less than the evaporation temperature of the substance in the vapour state;
- a means for compressing the cooled substance back to the first pressure;
  wherein the means are crossed in turn by a substantially fixed amount of the substance, the means for compressing feeding the means for generating; the main feature of this apparatus is that the heat source comprises an energy generator according to the invention as defined means above.

In particular, the above apparatus uses a closed Rankine cycle; advantageously, the thermodynamic fluid is an organic fluid that has a critical temperature and a critical pressure that are at least high as in the case of toluene, or of an ORC fluid, in particular of a fluid that is based on 1,1,1,3,3 pentafluoropropane, also known as HFC 245fa or simply as 245fa.

BRIEF DESCRIPTION OF THE DRAWINGS

The invention will be made clearer with the following description of an exemplary embodiment thereof, exemplifying but not !imitative, with reference to the attached drawings in which:

FIGS. 1 and 19 are block diagrams of embodiments of the method according to the invention;

FIG. 2 is a diagrammatical view of a crystal layer that is formed by clusters deposited on the surface of a substrate;

FIG. 3 indicates the transition metals that are most adapted to be used in the method according to the invention;

FIG. 4 is a diagrammatical representations of a face-centred cubic crystalline structure;

FIG. 5 diagrammatically represents a body-centred cubic crystalline structure;

FIG. 6 diagrammatically represents a crystalline compact hexagonal structure;

FIG. 7 is a block diagram of the parts of the step of prearranging clusters of FIG. 1, to obtain a clusters surface structure;

FIG. 8 shows a typical temperature profile of what is shown in FIG. 7;

FIG. 9 shows a typical thermal profile of a the method;

FIG. 10 shows a reactor that is adapted to produce energy, according to the present invention, by an impulsively triggered exothermal reaction of hydrogen adsorbed on a transition metal;

FIG. 11 diagrammatically shows a device for preparing a reaction core according to the invention;

FIG. 12 diagrammatically shows a generator that comprises the reactor of FIG. 10 and the device of FIG. 11;

FIGS. 13 and 14 show an alternate exemplary embodiments of the reaction core according to the invention;

FIG. 15 shows a temperature gradient through a reaction core;

FIGS. 16 a/b, 17 a/b and 18 a/b are diagrams showing the conditions of three start up events in three distinct cells prepared according to the method of the invention.

DESCRIPTION OF PREFERRED EXEMPLARY EMBODIMENTS

With reference to FIGS. 1 and 2, a method 100 according to the invention is described, for producing energy by a succession of exothermal reactions between hydrogen 31 and a transition metal 19.
In FIG. 3 the chemical elements which turned out to be suitable to react with hydrogen according to the method are indicated in the periodic table of elements. They are in detail, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Zn, Y, Zr, Nb, Pd, Mo, Tc, Ru, Rh, Ag, Cd, Lu, Hf, Ta, W, Re, Os, Ir, Pt, Au, lanthanoids, actinoids, an alloy of two or more than two of the above listed metals. They belong to one of the four transition metals groups, i.e.:

According to method 100, a step 110 is provided of depositing an amount of crystals of the transition metal in the form of micro/nanometric clusters 21, for example a layer of clusters 20 on a substrate 22, this layer 20 defined by a surface 23. A crystal layer 20 of thickness d, preferably set between 1 nanometre and 1 micron is diagrammatically shown in FIG. 2. The metal is deposited with a process adapted to ensure that the crystals as deposited have normally a number of atoms of the transition metal lower than a predetermined critical number, beyond which the crystal matter looses the character of clusters.
In the case of prearranging the clusters on a substrate, the process of depositing is adapted to ensure that 1 square centimetre of surface 23 defines on average at least 10⁹ clusters 21.
During the step 110 of prearranging a metal transition crystals in the form of clusters 21, the predetermined number of atoms of the transition metal of the clusters is controlled by observing a physical property of the transition metal, chosen for example among thermal conductivity, electric conductivity, refraction index. These physical quantities have a net transition, when the number of atoms of a crystal aggregate exceeds a critical number above which the aggregate looses the properties of a cluster. For each transition metal, in fact is a number of atoms detectable below which a discrete level structure according to Kohn-Sham tends to prevail over a band structure according to Thomas-Fermi, which is responsible of the main features that define the many features of the clusters, some of which properties are used for determining the nature of surface 23 during the step 110 of prearranging the clusters.
Clusters 21 (FIG. 2) have a crystalline structure 19 that is typical of the chosen transition metals or alloy of transition metals. In FIGS. 4 to 6 crystal reticules with open faces are shown, which assist the process of adsorption of hydrogen, into a cluster 21, characterised by such structural arrangement. They comprise:

- face-centred cubic crystalline structure, fcc (110) (FIGS. 4);
- body-centred cubic crystalline structure, bcc (111) (FIG. 5);
- compact hexagonal structure, hcp (1010) (FIG. 6).

For example, Nickel can crystallize according to the face-centred cubic structure shown in the perspective view of FIG. 4, where six atoms 2 are shown arranged according to a diagonal plane.
More detail of the step 110 of depositing crystals of the transition metal in the form of clusters 110 on the substrate, is given in the block diagram of FIG. 7 and in the temperature profile of FIG. 8. In particular, true step 113 of depositing, preferably by means of sputtering, or spraying, or epitaxial deposition, can be preceded by a step 111 of loading a substrate into a preparation chamber. The deposited metal is then heated further up to a temperature close to the melting temperature T_f(FIG. 8), in order to bring it to an incipient fusion, and then a slow cooling follows, step 118, in particular down to an average core temperature of about 600° C., after which a quick cooling 119 is carried out down to room temperature. This has the object of “freezing” the cluster structure that had been obtained at high temperature, which would otherwise evolve towards equilibrium structures, without stopping at a given cluster size, if the slow cooling 118 would be continued.
As depicted still in FIG. 1, the method comprises a subsequent start-up sequence, basically comprising subsequent step 114 of cleaning the substrate and the adsorbed metal, step 120 of bringing hydrogen into contact with the crystals of the transition metal in order to obtain a reaction core ready for performing the exothermal reaction, step 130 of heating the crystal up to above a critical temperature, and a step 140 of impulsively acting on the reaction core in order to trigger the exothermal reaction.
This sequence of steps 114, 120, 130, 140, which are described in detail below, is performed at least once. In another embodiment, the start-up sequence 114-140 is repeated until a successful triggering of the reaction core occurs caused by the step 140 of impulsively acting on the reaction core, as shown in FIG. 19.
Step 114 of cleaning the substrate, is preferably carried out by applying a vacuum degree to the substrate, preferably by repeatedly creating and removing a vacuum of at least 10⁻⁹bar at a temperature of at least 350° C. This step has the object of quantitatively removing any gas that is adsorbed on or adsorbed in the substrate, which would reduce drastically the adsorption of hydrogen 31 into clusters 21 even if a physical surface adsorption has been achieved.
The method provides then a treatment step 120 of the clusters with hydrogen 31, in which hydrogen 31 is brought into contact with surface 23 of the clusters 21, in order to obtain a population of molecules of hydrogen that is adsorbed on surface 23. A contribution to this process is given by a heating step 130 of surface 23 of the clusters up to a temperature T₁higher than a predetermined critical temperature T_D, as shown in FIG. 9.
Clusters 21 with the adsorbed hydrogen form a reaction core that is available for exothermal reactions, which can be triggered by a step 140 of impulsively acting on the reaction core. More in detail, step 140 consists of supplying an impulse of energy 26 enabling Hydrogen to be adsorbed on/into the surface of clusters 23.
In order to achieve a result that is industrially acceptable, it is necessary to reach a temperature higher than the Debye temperature T_D, for example the temperature T₁as shown in FIG. 9, which shows a typical temperature trend from step 130 of heating to step 170 of removing heat, during which a balance value is obtained of the temperature T_eqat the reaction core 1. The triggering step is assisted by the presence of a thermal gradient ΔT along the metal surface of the reaction core 1 as shown, for example, in FIG. 15.
Step 120 of feeding hydrogen is carried out in order to provide a relative pressure between 0,001 millibar and 10 bar, preferably between 1 millibar and 2 bar, to ensure an optimal number of hits of hydrogen molecules against surface 23, avoiding in particular surface desorption and other undesired phenomena caused by an excessive pressure. Moreover, the speed of the hydrogen molecules is lower than 3 m/s, and has a direction substantially parallel to surface 23, in order to obtain small angles of impact 39 that assist the adsorption and avoid back emission phenomena.
In FIG. 9, furthermore, the temperature is shown beyond which the reticular planes begins to slide with respect to one another, which is set between the temperatures corresponding to the absorption peaks α and β, above which the adsorption of hydrogen in clusters 21 is most likely.
FIG. 9 refers also relates the case in which, after the step of adsorption of hydrogen, that is effected at a temperature that is higher than critical temperature T_D, a cooling step 119 of the reaction core is carried out down to room temperature. Step 140 of impulsively acting on the reaction core follows then heating step 130 starting from room temperature up to predetermined temperature T₁, which is larger than Debye temperature T_Dof the transition metal, in a time t* that is as short as possible, preferably shorter than 5 minutes, in order not to affect the structure of the clusters and/or not to cause desorbing phenomena before step 140 of impulsively acting on the reaction core in order to start the exothermal reaction.
Critical temperature T_Dis normally set between 100 and 450° C., in particular between 200 and 450° C. hereafter the Debye temperature is indicated for some of the metals above indicated: Al 426K; Cd 186K; Cr 610K; Cu 344.5K;
Au 165K; a-Fe 464K; Pb 96K; a-Mn 476K; Pt 240K; Si 640K; Ag 225K; Ta 240K; Sn 195K; Ti 420K; W 405K; Zn 300K.
The start-up of the reaction is assisted by a gradient of temperature between two points of the reaction core, in particular set between 100° C. and 300° C., which has a trend like the example shown in FIG. 15.
In FIG. 10 an energy generator 50 is shown to carry out the invention, comprising a reaction core 1 housed in a generation chamber 53. The reaction core can be heated by an electric winding 56 that can be connected to a source of electromotive force, not shown. A cylindrical wall 55 separates generation chamber 53 from an annular chamber 54, which is defined by a cylindrical external wall 51 and have an inlet 64 and an outlet 65 for a heat exchange fluid, which is used for removing the heat that is developed during the exothermal reactions. The ends of central portion 51 are closed in a releasable way respectively by a portion 52 and a portion 59, which are adapted also for supporting the ends in an operative position.
Generator 50 also comprises a means 61, 62, 67 for impulsively acting on the reaction core, in order to trigger the exothermal reaction between Hydrogen and the transition metal, consisting of:

- a means for producing an impulsive electric current through an electrostrictive portion of the reaction core;
- a means for casting a laser impulse on the reaction core.

In FIGS. from 14 and 15 a different embodiment is shown of a reaction core having an extended surface, consisting of a tube bundle 86 where tubes 87 act as substrate for a layer 88 of transition metal that is deposited in the form of clusters at least on a surface portion of each tube 87.
The device of FIG. 11 has an elongated casing 10, which is associated with a means for making and maintaining vacuum conditions inside, not shown. In particular, the residual pressure during the step of cleaning the substrate is kept identical or less than 10⁻⁹absolute bar, for removing impurities, in particular gas that is not hydrogen. Furthermore, a means is provided, not shown in the figures, for moving substrate 3 within casing 10, in turn on at least three stations 11, 12 and 13. Station 11 is a chamber for preparation of the clusters where the surface of the substrate 3 is coated with a layer of a transition metal in the form of clusters by a process of sputtering. In chamber 11 a means is provided, not depicted, for bringing and maintaining the substrate at a temperature identical or higher than 350° C. In station 12 a cooling step 119 is carried out (FIGS. 9 and 10) of the deposited metal on the substrate, by feeding cold hydrogen and at a pressure preferably set between 1 millibar and 2 relative bar, so that they can be adsorbed on the metal. In station 13, instead, a controlling step is carried out of the crystalline structure, for example by computing a physical property, such as thermal conductivity, electric conductivity, or refraction index, in order to establish the nature of clusters of the crystals deposited on the substrate 3. Preferably, furthermore, a thickness control is carried out of the crystal layer and of the cluster surface density.
FIG. 12 represents diagrammatically a device 80 that comprises a single closed casing 90, in which a section for preparing a reaction core 1 of the type shown in FIG. 11 and a reactor 50 are enclosed, thus preserving the core from contamination, in particular from gas that is distinct from hydrogen during the time between the step of depositing the clusters and the step of triggering the reactions.

EXAMPLE

A plurality of cells containing reaction cores comprising micro/nanometric crystals in the form of cluster of Nickel, a transition metal, and Hydrogen absorbed therein was prepared according to the invention, i.e. according to steps 110-130 described above.
FIGS. 16 a/b, 17 a/b and 18 a/b relates to three start-up events of three distinct reaction cores, caused by a step 140 of impulsively acting ion the reaction cores. As it can be seen from FIGS. 16a, 17a, 18a , the impulsive action was a pressure impulse made by suddenly adding or removing Hydrogen from the cell. In these figures, a sudden pressure change marks the event giving rise to cell (core) activation. In coincidence with this event, a strong temperature increase occurs, in spite of the contemporaneous decrease of power (W) supplied to the cell from outside. This means that a heat generating process starts after the activation event, i.e. that an excess enthalpy is involved by the process. After an initial rise, a stationary temperature value is reached, due to the temperature regulation system.
The foregoing description of a specific embodiment will so fully reveal the invention according to the conceptual point of view, so that others, by applying current knowledge, will be able to modify and/or adapt for various applications such an embodiment without further research and without parting from the invention, and it is therefore to be understood that such adaptations and modifications will have to be considered as equivalent to the specific embodiment. The means and the materials to realise the different functions described herein could have a different nature without, for this reason, departing from the field of the invention. It is to be understood that the phraseology or terminology employed herein is for the purpose of description and not of limitation.

Claims

1. A method for producing energy by exothermal reactions between hydrogen and a transition metal, said method providing the steps of:

depositing an amount of crystals of said transition metal in the form of micro/nanometric clusters having a predetermined crystalline structure on a surface of a substrate consisting of a solid body that has a predetermined volume and shape, wherein each of said clusters has a number of atoms of said transition metal lower than a predetermined number of atoms,

and in such a way that said substrate contains on its surface a number of clusters that is larger than a minimum number, in particular said minimum number is at least 10⁹clusters per square centimetre, wherein a start-up sequence is performed at least once, said start-up sequence comprising the steps of:

bringing and maintaining for a predetermined cleaning time said substrate and said crystals to/at a predetermined vacuum degree, in order to quantitatively remove gas adsorbed in said substrate and in said transition metal;

bringing hydrogen into contact with said crystals;

heating said crystals up to an adsorption temperature higher than a predetermined critical temperature, thus causing an adsorption of hydrogen to said crystals, said substrate, said crystals and said hydrogen adsorbed thereto forming a reaction core;

impulsively acting on said reaction core in order to trigger said exothermal reactions between said hydrogen and said transition metal in said clusters;

removing heat from said reaction core in order to obtain a determined power and to maintain the temperature of said reaction core above said critical temperature.

2. A method according to claim 1, wherein said step of depositing said amount of crystals is carried out in such a way that said determined quantity of crystals of said transition metal in the form of micro/nanometric clusters is proportional to said power.

3. A method according to claim 1, wherein said minimum number is at least 10¹⁰clusters per square centimetre, in particular at least 10¹¹clusters per square centimetre, more in particular at least 10¹²clusters per square centimetre;

4. A method according to claim 1, wherein said step of depositing said amount of crystals is effected by a process of physical deposition on said substrate of a metal vapour that is made of said transition metal.

5. A method according to claim 1, wherein said step of depositing said amount of crystals is carried out by a process selected from the group comprised of:

sputtering;

a process comprising an evaporation or a sublimation of said transition metal, and thereafter a condensation of said transition metal on said substrate;

epitaxial deposition;

spraying;

heating said transition metal up to approaching the melting point and thereafter slow cooling said transition metal, in particular down to an average temperature of said reaction core of about 600° C.

6. A method according to claim 1, wherein after said step of depositing said amount of crystals a step is provided of quickly cooling said substrate and said deposited transition metal, in order to cause a “freezing” of said transition metal in the form of clusters having said crystalline structure, said step of quickly cooling selected from the group comprised of: tempering; causing a current of hydrogen to flow over said transition metal as deposited on said substrate, said hydrogen having a predetermined temperature that is lower than the temperature of said substrate.

7. A method according to claim 1, wherein said start-up sequence is iterated until said step of impulsively acting on said reaction core causes a permanent generation of heat, i.e. until a successful triggering of the reaction core occurs.

8. A method according to claim 1, wherein said vacuum degree is at least 10⁻⁹bar.

9. A method according to claim 1, wherein said substrate and said crystals are maintained at a temperature set between 350° C. and 500° C. during said cleaning time.

10. A method according to claim 1, wherein said step of bringing and maintaining said substrate and said crystals to/at a predetermined vacuum degree is performed according to at least ten vacuum cycles, each vacuum cycle comprising creating said vacuum and subsequently restoring a substantially atmospheric pressure of hydrogen.

11. A method according to claim 1, wherein during said step of bringing hydrogen into contact with said crystals said hydrogen has a partial pressure set between 0,001 millibar and 10 bar absolute, in particular between 1 millibar and 1 bar absolute.

12. A method according to claim 1, wherein during said step of bringing hydrogen into contact with said crystals said hydrogen flows at a speed lower than 3 m/s.

13. A method according to claim 12, wherein said hydrogen flows in a direction that is substantially parallel to a surface of said crystals deposited on said substrate.

14. A method according to claim 1, wherein after said heating step of said determined quantity of crystals a step is provided of cooling said reaction core down to room temperature, and said step of impulsively acting on said reaction core comprises a step of quickly rising the temperature of said reaction core from room temperature to said adsorption temperature, in particular said quick rise is carried out in a time shorter than five minutes.

15. A method according to claim 1, wherein said step of impulsively acting on said reaction core provides an impulsive action selected from the group comprised of:

a thermal shock, in particular caused by a flow of a gas, in particular of hydrogen, which has a predetermined temperature that is lower than the reaction core temperature;

a mechanical impulse, in particular a mechanical impulse whose duration is less than 1/10 of second;

a pressure impulse, in which the pressure of hydrogen in contact with the crystals is suddenly increased or decreased by additionally supplying/withdrawing an amount of hydrogen;

an ultrasonic impulse, in particular an ultrasonic impulse whose frequency is set between 20 and 40 kHz;

a laser ray that is impulsively cast onto said reaction core;

an impulsive application of a package of electromagnetic fields, in particular said fields selected from the group comprised of: a radiofrequency pulse whose frequency is larger than 1 kHz; X rays; y rays;

an electrostriction impulse that is generated by an impulsive electric current that flows through an electrostrictive portion of said reaction core;

an impulsive application of a beam of elementary particles; in particular, such elementary particles selected from the group comprised of electrons, protons and neutrons;

an impulsive application of a beam of ions of elements, in particular of ions of one or more transition metals, said elements selected from a group that excludes O; Ar; Ne; Kr; Rn; N; Xe.

an electric voltage impulse that is applied between two points of a piezoelectric portion of said reaction core;

an impulsive magnetostriction that is generated by a magnetic field pulse along said reaction core which has a magnetostrictive portion.

16. A method according to claim 1, wherein before said step of impulsively acting on said reaction core a step is carried out of creating a temperature gradient, i.e. a temperature difference, between two points of said reaction core, said gradient in particular set between 100° C. and 300° C.

17. A method according to claim 1, wherein said clusters have a face-centred cubic crystalline structure, fcc (110).

18. A method according to claim 1, comprising step of maintaining a condition selected from the group comprised of:

a magnetic induction field of intensity set between 1 Gauss and 70000 Gauss;

an electric field of intensity set between 1 V/m and 300000 V/m during said step of removing heat from said reaction core.