Metal hydride and metal hydroxide production in sealed environments

Abstract

Provided herein is an apparatus and method for performing heavy isotope reactions with metal hydroxides or hydrides comprising: a source of heavy water in communication with a liquid transfer pump; a flow meter that maintains a chamber pressure at or about ambient pressure and in communication with the liquid transfer pump opposite the source of heavy water for measuring the flow of the heavy water; a reaction chamber in communication with the flow meter, a heating unit in contact with the reaction chamber, a metal (M) within the reaction chamber, an output, in a condenser having an input and an output; a water / recycle container to receive condensed heavy water from the condenser; and one or more processors that control the liquid transfer pump, the flow meter, and the heating unit to control the formation of deuterated or tritiated metal hydroxides or hydrides.

Description

METAL HYDRIDE AND METAL HYDROXIDE PRODUCTION IN SEALED ENVIRONMENTS CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to U.S. Provisional Application Serial No. 63 / 551,878, filed February 9, 2024, the entire contents of which are incorporated herein by reference. TECHNICAL FIELD OF THE INVENTION

[0002] The present invention relates in general to the field of producing metal hydrides, and more particularly, to a novel method for metal hydride production in sealed environments, and an automated sequential deuteriation system for preparing deuterated metal hydroxides. STATEMENT OF FEDERALLY FUNDED RESEARCH

[0003] None. INCORPORATION-BY-REFERENCE OF MATERIALS FILED ON COMPACT DISC

[0004] None. BACKGROUND OF THE INVENTION

[0005] Without limiting the scope of the invention, its background is described in connection with the production of metal hydrides and deuterated metal hydroxide materials.

[0006] Rare earth metals such as erbium, and transition metals such as titanium, hold interest for hydrogen storage applications. Other light metallic elements, such as lithium, also react readily with hydrogen isotopes and hydroxide ions to form LiH, LiOH, where H here indicates any of the hydrogen isotopes (protium, deuterium (D), or tritium (T)). Recently, erbium deuteride and titanium deuteride have drawn more attention as a team at NASA revealed a method for triggering nuclear fusion in the deuterium atoms of solid ErD2, ErD3, and TiD2. Their peer-reviewed publications include: B. Steinetz, et al., Physical Review C, Volume 101 (April, 2020): “Nuclear fusion reactions in deuterated metals” and “Novel nuclear reactions observed in bremsstrahlung- irradiated deuterated metals.”1,2The ground-breaking work on the erbium-hydrogen system by Lundin (Reference Lundin 1968) documents three possible phases (α,β,γ) for this metal hydride.3,4The α phase can be understood as having the same hexagonal symmetry as that of the host metal, but with the addition of hydrogen in the host lattice as a solid solution. The β phase has a fluorite- type structure and usually occurs as a dihydride; hence, it is also referred to as the dihydride phase. Lundin (Lundin, 1968) also documented a tri-hydride phase (γ) which was explored by Tewelland King (Tewell and King, 2006)5. Other lanthanide elements are being considered as candidates for fusion applications due to their similar cross-sections when subjected to thermal neutron irradiation.

[0007] The textbook method of preparing LiD is similar to that of protium isotope in lithium hydride (LiH). This method consists of a direct combination of elements at 500-600oC in a stainless steel crucible, or "flush pot", that was originally designed at Los Alamos National Lab (LANL)6. The flush pot method typically uses a stainless-steel reaction vessel that is connected to an ordinary steel chamber through a gravity trap. A typical reaction pressure of D2 is about 50- 150 psi. Since lithium readily attacks other metals during the reaction, a uranium crucible method was also developed by LANL groups.6

[0008] Conventionally, deuterated alkali hydroxides are synthesized by reacting deuterium oxide (D2O) with the corresponding alkali metal M (M= Li, Na, K, Rb, and Cs) in a reaction vessel under controlled conditions, as shown in the following equation: 2M + 2D2O = 2MOD +D2

[0009] However, all these methods rely on expensive, complicated equipment or require materials that are not commercially available. Deuterium gas is also considerably expensive, costing $376 US dollars for 25 L (STP) gas (Sigma Aldrich website). Therefore, a more economically effective method needs to be developed for large-scale synthesis. SUMMARY OF THE INVENTION

[0010] As embodied and broadly described herein, an aspect of the present disclosure relates to a sealed system where metal hydrides may be formed in an optimal and scalable manner by adjusting the temperature, pressure, and flow rate of hydrogen gasses into the reaction chamber. Furthermore, the present disclosure also relates to the formation of deuterated and tritiated metal hydroxides through the subsequent exchange of hydrogen isotopes with protium in metal hydroxides in a sealed environment that permits the unused deuterium and tritium gasses to be recovered effectively, thereby increasing the safety and economic feasibility of the processes.

[0011] As embodied and broadly described herein, an aspect of the present disclosure relates to an apparatus for preparing heavy isotope reactions with metal hydroxides in a sealed environment comprising: a source of heavy water in fluid communication with a reaction chamber and comprises a heating unit that is in contact with at least part of the reaction chamber, wherein a metal (M) is placed within the reaction chamber, and an output in fluid communication with a condenser having an input and an output; a water / recycle container in fluid communication withthe output of the condenser to receive condensed heavy water from the condenser; and one or more processors that control the liquid transfer pump, the flow meter, and the heating unit to control the formation of deuterated or tritiated metal hydroxides. In one aspect, the metal M is selected from Li, Na, K, Rb, and Cs. In another aspect, the source of heavy water includes a liquid transfer pump and a flow meter in communication with the liquid transfer pump opposite the source of heavy water for measuring the flow of the heavy water that maintains the chamber pressure at or about ambient pressure, and wherein the reaction chamber comprises an anti-corrosive liner. In another aspect, a thermocouple in contact with the reaction chamber is connected to the processor to measure and control a temperature of the reaction chamber. In another aspect, a reaction catalyzed in the reaction chamber is selected from: 2M + 2D2O = 2MOD +D2; M2O+D2O= 2MOD; 2M2O2+2D2O = 4MOD+ O2; or M2CO3+CaO+D2O= CaCO3+ 2MOD.

[0012] In another aspect, the deuterated metal hydroxides are formed in the reaction chamber via hydrogen isotope exchange method with metal hydroxides (MOH, M= Li, Na, K, Rb, and Cs) in the reaction chamber, and following the formation of the deuterated metal hydroxides heating and evaporating the heavy water to produce a solid powder. In another aspect, a purity of a final product is determined by a molar ratio of the heavy water to metal hydroxides and cycle(s), approximated as 1-1 / (2R+1)N, where R is the molar ratio of heavy water to metal hydroxides and N is the number of cycle(s). In another aspect, a stirring device is positioned within the reaction chamber to stir the heavy water and the metal during a reaction. In another aspect, the apparatus further comprises one or more additional reaction chambers in series or in parallel to the reaction chamber to provide for a series of reactions under the control of the one or more processors. In another aspect, the heavy water is deuterated water (D2O) or tritiated water (T2O). In another aspect, a chamber pressure in the reaction chamber is at or about ambient pressure.

[0013] As embodied and broadly described herein, an aspect of the present disclosure relates to a method of making deuterated metal hydroxides via a hydrogen isotope exchange in a sealed environment comprising: providing a source of heavy deuterated water (D2O), tritiated water (T2O), or both, in fluid communication with a reaction chamber and that comprises a heating unit that is in contact with at least part of the reaction chamber, wherein a metal (M) is placed within the reaction chamber, and an output in fluid communication with a condenser having an input and an output; connecting a water / recycle container in fluid communication with the output of thecondenser to receive condensed heavy water from the condenser; and connecting one or more processors that control the liquid transfer pump, the flow meter, and the heating unit to control the formation of deuterated or tritiated metal hydroxides. In one aspect, the method further comprises the step of recycling the condensed heavy water to the source of heavy water. In another aspect, the metal M is selected from Li, Na, K, Rb, and Cs. In another aspect, the source of heavy water includes a liquid transfer pump and a flow meter in communication with the liquid transfer pump opposite the source of heavy water for measuring the flow of the heavy water that maintains the chamber pressure at or about ambient pressure, and wherein the reaction chamber comprises an anti-corrosive liner. In another aspect, a thermocouple in contact with the reaction chamber is connected to the processor to measure and control a temperature of the reaction chamber. In another aspect, a reaction catalyzed in the reaction chamber is selected from: 2M + 2D2O = 2MOD +D2; M2O+D2O= 2MOD; 2M2O2+2D2O = 4MOD+ O2; or M2CO3+CaO+D2O= CaCO3+ 2MOD.

[0014] In another aspect, the deuterated metal hydroxides are formed in the reaction chamber via hydrogen isotope exchange method with metal hydroxides (MOH, M= Li, Na, K, Rb, and Cs) in the reaction chamber, and following the formation of the deuterated metal hydroxides heating and evaporating the heavy water to produce a solid powder. In another aspect, a purity of a final product is determined by a molar ratio of the heavy water to metal hydroxides and cycle(s), approximated as 1-1 / (2R+1)N, where R is the molar ratio of heavy water to metal hydroxides and N is the number of cycle(s). In another aspect, the method further comprises stirring the heavy water and metal in the reaction chamber during a reaction. In another aspect, the method further comprises connecting one or more additional reaction chambers in series or in parallel to the reaction chamber to provide for a series of reactions under the control of the one or more processors. In another aspect, the heavy water is deuterated water (D2O) or tritiated water (T2O). In another aspect, a chamber pressure in the reaction chamber is at or about ambient pressure.

[0015] As embodied and broadly described herein, an aspect of the present disclosure relates to an apparatus for preparing heavy isotope reactions with metal hydrides in a sealed environment comprising: a sealed reaction chamber within a hermetically-sealed, temperature-controlled furnace comprising of a container or a region for containing a metal to be reacted with the hydrogen isotopes(s); and a manifold in sealed communication with the sealed reaction chamber, wherein one or more sensors measure a pressure of the hydrogen gasses in the reaction chamberand one or more valves control a flow of the hydrogen gasses in the sealed reaction chamber. In one aspect, the one or more valves are controlled by one or more microprocessors to optimize a rate of metal hydride growth. In another aspect, the metal hydrides are further processed by cutting with a water jet using ultra-pure water or laser cutting in an inert environment, and optionally, cutting does not use any heavy metal, e.g., tungsten, during processing, e.g., mining, refinement, cutting, and / or custom synthesis. In another aspect, a purity of the metal hydrides is determined by at least one of X-ray Fluorescence (XRF) or X-ray Diffraction (XRD) before using in nuclear power or nuclear reactor applications. In another aspect, the hydrogen isotopes(s) are selected from deuterium, tritium, or both.

[0016] As embodied and broadly described herein, an aspect of the present disclosure relates to a method for preparing heavy isotope reactions with metal hydrides in a sealed environment comprising: providing an apparatus comprising: a sealed reaction chamber within a hermetically- sealed, temperature-controlled furnace comprising of a container or a region for a metal to be reacted with the hydrogen isotopes(s); and a manifold in sealed communication with the sealed reaction chamber; measuring with one or more sensors a pressure of the hydrogen gasses in the reaction chamber; and controlling the temperature of the furnace and the pressure of hydrogen gasses within the furnace chamber with one or more valves while monitoring the flow of hydrogen gasses into the chamber, or alternatively to control the flow of the hydrogen gasses into the sealed reaction chamber while monitoring the pressure of the hydrogen gasses within the chamber. In one aspect, the one or more valves and the temperature-controlled furnace are controlled by one or more microprocessors to optimize a rate of metal hydride growth. In another aspect, the metal is selected from Li, Na, K, Rb, and Cs. In another aspect, the reaction chamber comprises an anti- corrosive liner. In another aspect, the one or more microprocessors control an equilibrium pressure between the metal and hydrogen gasses during the reactions to actively modulate the atomic ratios of the metal hydride. In another aspect, the metal hydrides are selected from rare earth metal deuterides or transition metal deuterides. In another aspect, the hydrogen gasses are selected from hydrogen, deuterium, tritium, or combinations thereof. In another aspect, the metal hydrides are further processed by cutting with a water jet using ultra-pure water or laser cutting in an inert environment, and optionally, cutting does not use any heavy metal, e.g., tungsten, during processing, e.g., mining, refinement, cutting, and / or custom synthesis. In another aspect, a purity of the metal hydrides is determined by at least one of X-ray Fluorescence (XRF) or X-ray Diffraction (XRD) before using in nuclear power or nuclear reactor applications. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] For a more complete understanding of the features and advantages of the present invention, reference is now made to the detailed description of the invention along with the accompanying figures and in which:

[0018] FIG.1 is a diagram of the present invention, depicting the connection of the liquid transfer pump and condenser to the evaporation synthesis apparatus.

[0019] FIG.2 is a diagram for the automated sequential deuteriation system to improve the purity.

[0020] FIG.3 shows FTIR spectrum of LiOH, LiOH.H2O, and LiOD.xD2O (0≤x≤1, the present product).

[0021] FIG.4 is a schematic diagram of the present invention in which the pressure controller and flow meter is connected to the synthesis apparatus.

[0022] FIG.5 is a more detailed schematic cross-sectional view of an apparatus for synthesizing the metal deuterides and tritides.

[0023] FIG.6 includes a schematic of the location within the device (top), and a graph (bottom) that shows temperatures and pressure plots over time, of the pressure control and temperature control curve for synthesizing ErD3.

[0024] FIG. 7 is a graph that shows the pressure and temperature of the pressure control and temperature control curve for synthesizing LiD.

[0025] FIG. 8 is a graph that shows the pressure control and temperature control curve for synthesizing TiD2. DETAILED DESCRIPTION OF THE INVENTION

[0026] While the making and using of various embodiments of the present invention are discussed in detail below, it should be appreciated that the present invention provides many applicable inventive concepts that can be embodied in a wide variety of specific contexts. The specific embodiments discussed herein are merely illustrative of specific ways to make and use the invention and do not delimit the scope of the invention.

[0027] To facilitate the understanding of this invention, a number of terms are defined below. Terms defined herein have meanings as commonly understood by a person of ordinary skill in the areas relevant to the present invention. Terms such as “a”, “an” and “the” are not intended to refer to only a singular entity, but include the general class of which a specific example may be used for illustration. The terminology herein is used to describe specific embodiments of the invention, but their usage does not delimit the invention, except as outlined in the claims.

[0028] The present invention uses automated pressure controllers operating near or only slightly above ambient pressure, and hence not requiring high-pressure hydrogen gas technology, and the use of flow controllers to measure and control the rate of hydrogen-isotope (most significantly, deuterium) gas introduction to the metallic reaction chamber.

[0029] The present invention utilizes a pressure controller and flow meter to synthesize metal hydride / deuteride materials in a controlled environment. By controlling the equilibrium pressure between the metal and deuterium gas, the inventors were able to actively tailor the atomic ratios of the final products. Additionally, this method uses a sealed environment, which involves less waste than flow-over techniques used in previous designs. This method is quite universal, not only can it be applied to lithium, erbium, and titanium, but also to other metals. This is a more environmentally friendly technique that may be applied to metal tritide synthesis, where capture of the expensive and radioactive hydrogen isotope tritium is essential. The flow meter also serves as an in-situ monitor of the atomic ratio, which indicates the yield of the reaction.

[0030] In the present approach, a pressure controller and flow meter are used to control the reaction process (i.e., the ‘experiment’) in a sealed environment. This approach turns out to be very universal to be applied to other metals including all the lanthanides, transition metals, and light element metals such as lithium, beryllium, sodium, magnesium, aluminum, potassium, calcium, etc.

[0031] Due to the lack of availability of raw materials, the inventors were unable to produce certain deuterated or tritiated metal hydroxides using the known conventional methods. For example, at present, Sigma-Aldrich sells a 100 g 7.5wt% LiOD solution for $358, equating to approximately $48 per gram. The cost for a kilogram would be $48,000. As such, there is a requirement for new apparatus and techniques for generating deuterated alkali hydroxides at a lower cost. To tackle this issue, the inventors developed a novel, automated sequential deuteriation system for deuterated alkali hydroxides.

[0032] The present invention employs a PC-controlled automated system to produce deuterated alkali hydroxides via hydrogen isotope exchange method with alkali hydroxides (MOH, M= Li, Na, K, Rb, and Cs) as precursors. This is followed by heating and evaporation to produce solid powders. Additionally, a condenser is utilized to recycle expensive heavy water for further use, which is an environmentally friendly and economically sound process. By using this system and approach, it was possible to achieve a 99% purity level at an order of magnitude lower cost.

[0033] Producing ultra-pure metals for nuclear experiments requires meticulous attention to minimizing contaminates at every stage including mining, refinement, cutting, to customsyntheses. Even after refining a metal to greater than 99.9% purity, it is still a level unacceptable for nuclear experiments, including contamination introduced during traditional cutting methods, when using a tungsten blade. During irradiation experiments, tungsten inclusions generate undesirable, long-lived isotopes of hafnium from interactions with fast neutrons. Tungsten inclusions interfere with accurate spectral analysis because they exhibit overlapping signals with actinides. Therefore, in some cases, it is imperative to prepare the precursor metals using an alternative cutting method when applying the synthesized materials to nuclear experimentation. Alternative methods include water jet cutting using ultra-pure water or laser cutting in an inert environment.

[0034] Avoiding tungsten while crushing / cutting / processing the metal hydrides is important to avoid heavy metal (e.g., tungsten) inclusion / contamination to reducing contaminants in any step of the process from mining, refinement, cutting, to custom synthesis. For example, tungsten from the surface of a hammer introduces trace levels of impurities in samples. Heavy metals like tungsten create a cascade of long-lifetime radioisotopes when irradiated, as such, strict purity standards must always be followed to prevent contamination with heavy metals. However, the same applies to all heavy elements, including those in the heavier lower half of the transition elements, and especially the actinide and lanthanide elements, which are particularly problematic. All impurities must be eliminated to the sub 0.001% level, and even lower when the impurities are heavy metals, lanthanides, and actinides. While certain elements are less problematic than others, for example, titanium does not activate much, even titanium should be reduced to sub- 0.001% impurity levels if it is not the target for irradiation.

[0035] Further, trace heavy metal and actinide metal diagnostics must be run before these materials are used in nuclear processes or experimentation. Diagnostics include, e.g., X-ray Fluorescence (XRF) and X-ray Diffraction (XRD). Trace activation analysis should be conducted before using ultra-pure materials for nuclear power or other nuclear reactor applications.

[0036] Example 1. Automated Sequential Deuteriation System for Preparing Deuterated Alkali Hydroxides.

[0037] Deuterated alkali hydroxides have a wide range of applications in different fields such as NMR solvents1, isotope labeling in chemistry and biology2, nuclear applications3, and others. Deuterated alkali hydroxides can also be used in deuterium exchange reactions in deuterated pharmaceuticals4. FDA granted marketing approval for the first deuterated drug molecule, deutetrabenazine (1; a racemic mixture), which is useful in treating chorea (an involuntary movement disorder) associated with Huntington’s disease and tardive dyskinesia.5,6,7It has been reported that the global deuterium-substituted drugs market is projected to grow from USD 241.2million in 2022 to USD 326.9 million by 2030, exhibiting a compound annual growth rate (CAGR) of 5.20% during the forecast period.8

[0038] The synthesis of deuterated alkali hydroxides has received considerable attention due to their use as raw materials in a wide range of applications. Conventionally, deuterated alkali hydroxides are synthesized by reacting deuterium oxide (D2O) with the corresponding alkali metal M (M= Li, Na, K, Rb, and Cs ) in a reaction vessel under controlled conditions, as shown in the following equation: 2M + 2D2O = 2MOD +D2

[0039] However, alternative routes for the synthesis of deuterated alkali hydroxides exist, including: M2O+D2O= 2MOD 2M2O2+2D2O = 4MOD+ O2M2CO3+CaO+D2O= CaCO3+ 2MOD

[0040] Each of these methods has limitations, such as safety concerns or complicated processing due to impurities. An alternative approach for producing deuterated compounds involves hydrogen isotope exchange, whereby one hydrogen isotope is replaced by another isotope in a molecule. This exchange can occur through various chemical or physical processes, such as reaction with a deuterated solvent, exposure to heavy water, or catalysis by enzymes that involve hydrogen transfer.9

[0041] The present invention employs a PC-controlled automated system, as depicted in FIG.1, to produce deuterated alkali hydroxides via hydrogen isotope exchange method with alkali hydroxides (MOH, M= Li, Na, K, Rb, and Cs) as precursors. This is followed by heating and evaporation to produce solid powders. Additionally, a condenser is utilized to recycle expensive heavy water for further use, which is an environmentally friendly and economically sound process.

[0042] As shown in FIG. 2, the purity of the final products is determined by the molar ratio of heavy water to alkali hydroxides and cycles, which can be expressed as 1-1 / (2R+1)N, where R is the molar ratio of heavy water to alkali hydroxides and N is the consecutive cycle number. Furthermore, this approach is economically advantageous compared to other sources. For instance, 500 g LiOH costs around $188 from Fishersci14, and heavy water costs approximately $1 / g in a bulk order from Sigma Aldrich15. By using the system and method of the present invention, and recycling heavy water, it was possible to produce LiOD with 96% purity at about $3-4 / g. Theprimary cost of this process is the deuterium isotope, and the minimal but inevitable losses that occur during the heavy water recycling process.

[0043] The inventors constructed a device and conducted FTIR measurements on the product. FIG.4 illustrates the FTIR spectrum of LiOH, LiOH.H2O, and LiOD.xD2O (0≤x≤1, our product). The IR band for O-H stretch is typically observed at 3400-3200 cm-1, which agrees with the Spectral Database for Organic Compounds (SDBS)16. In contrast, the O-D equivalent is shifted to 2600 cm-1. Following the deuteriation process utilizing the inventor’s device and approach, the OH stretching nearly disappears, and the O-D stretching becomes dominant in the spectrum, indicating a highly effective isotope exchange process of D for H using the inventor’s device and approach. Furthermore, this invention can be readily scaled-up to meet large-scale production demands.

[0044] FIG.1 is a diagram of the present invention, depicting the connection of the liquid transfer pump and condenser to the evaporation synthesis apparatus. The current design involves the use of a liquid transfer pump to transfer heavy water to the synthesis apparatus, with a flow meter monitoring the flow, and a condenser to recycle the heavy water. This design can be conveniently scaled up for large-scale production. Furthermore, all components are connected to a PC for process control automation and data acquisition. In FIG.1, a D2O bottle 1 is connected to a liquid transfer pump 2, which is connected to a flow meter 3. A Controller PC 4 is connected to the liquid transfer pump 2, the flow meter 3, the evaporation synthesis unit 5, and the thermocouple 6. A container 7, receives the output from the flow meter 3 with the D2O. The container 7 may include an anti-corrosion liner. A condenser 8, receives the output from the reaction in container 7, and the output 9, from the condenser 8, is stored as D2O waste, or distilled and recycled into the heavy water supply of the system.

[0045] FIG. 2 is a more detailed diagram for the automated sequential deuteriation system to improve the purity. The purity of the final products is determined by the molar ratio of heavy water to alkali hydroxides and cycles, which can be expressed as 1-1 / (2R+1)N, where R is the molar ratio of heavy water to alkali hydroxides and N is the consecutive cycle number.

[0046] FIG.3 shows FTIR spectrum of LiOH, LiOH.H2O, and LiOD.xD2O (0≤x≤1, the present product). Following the deuteriation process utilizing the inventor’s approach, the OH stretching nearly disappears, and the O-D stretching becomes dominant in the spectrum, indicating a highly effective isotope exchange process using the approach of the present invention.

[0047] Example 2. Metal Hydride Production in Sealed Environment.

[0048] Lithium hydride, including the deuteride (LiD), is a stable isotopic compound that is commonly used in deuterium storage and energy storage applications, because of its high melting point, low density, high deuterium concentration, and exceptional thermal stability in both vacuum and inert gases. It can also be used as a raw material for the synthesis of organic deuterides, deuterated solvents, and deuterated polymers. It may be used in future solid-state fusion reactor applications to stabilize a compact and controlled thermonuclear fusion reaction.

[0049] The present inventors recognized that, by controlling the gas pressure of D2 gas in a sealed environment via a pressure controller, it is possible to control the direction of the reaction, and thereby drive the reaction towards LiD. This same approach can be also applied to other metal deuterides, including rare earth metal deuterides and transition metal deuterides, such as titanium deuteride and erbium deuteride.

[0050] This example utilizes a pressure controller and flow meter to synthesize metal hydride / deuteride materials in a controlled environment. By controlling the equilibrium pressure between the metal and deuterium gas during the reactions, the inventors were able to actively tailor the atomic ratios of the final products. Additionally, this method uses a sealed environment, which involves less waste than flow-over techniques used in previous designs17. This is a more environmentally friendly technique that may be applied to metal tritide synthesis, where capture of the expensive and radioactive tritium is essential. The flow meter also serves as an in-situ monitor of the atomic ratio, with the integrated flow measurements indicating the yield of the reaction.

[0051] FIG.4 is a schematic diagram of the present invention in which the pressure controller and flow meter is connected to the synthesis apparatus. In one design, a flow controller is used to control the pressure during synthesis, and the flow meter is used to monitor the flow with the integration of the flow to measure the total gas introduced to the reactor, which can be used to calculate the ratio between metal and H / D / T. The design in FIG.1 may be easily expanded to a large platform to meet scale-up demands.

[0052] FIG.5 is a more detailed schematic cross-sectional view of an apparatus for synthesizing the metal deuterides and tritides. FIG.5 shows a tube furnace 10, a container 11 positioned within tube furnace 10, which container can be a stainless-steel tubing container. The container 11 is connected to valve 12. Within the container 11 are shown metal pellets or powders 13, which are positioned in a sample boat 14. Finally, a flow meter 15 is in communication with the valve 12, which is on the other side of the valve from container 11, to control the flow rate into the reactor.

[0053] FIG.6 includes a schematic of the location within the device (top), and a graph (bottom) that shows temperatures and pressure plots over time, of the pressure control and temperature control curve for synthesizing ErD3.

[0054] FIG. 7 is a graph that shows the pressure and temperature of the pressure control and temperature control curve for synthesizing LiD.

[0055] FIG. 8 is a graph that shows the pressure control and temperature control curve for synthesizing TiD2.

[0056] In certain aspects, the user will typically control the pressure of the hydrogen gasses (p, D, or T, or potentially some custom combination as necessary to achieve the material for the intended application), but it is possible that in some applications a user would simply control the flow and monitor the pressure instead, e.g., with set ‘never exceed’ pressure limits. This might be used to speed up the manufacturing process once the control of the metal hydrides growth was established.

[0057] It is contemplated that any embodiment discussed in this specification can be implemented with respect to any method, kit, reagent, or composition of the invention, and vice versa. Furthermore, compositions of the invention can be used to achieve methods of the invention.

[0058] It will be understood that particular embodiments described herein are shown by way of illustration and not as limitations of the invention. The principal features of this invention can be employed in various embodiments without departing from the scope of the invention. Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, numerous equivalents to the specific procedures described herein. Such equivalents are considered to be within the scope of this invention and are covered by the claims.

[0059] All publications and patent applications mentioned in the specification are indicative of the level of skill of those skilled in the art to which this invention pertains. All publications and patent applications are herein incorporated by reference to the same extent as if each individual publication or patent application was specifically and individually indicated to be incorporated by reference.

[0060] The use of the word “a” or “an” when used in conjunction with the term “comprising” in the claims and / or the specification may mean “one,” but it is also consistent with the meaning of “one or more,” “at least one,” and “one or more than one.” The use of the term “or” in the claims is used to mean “and / or” unless explicitly indicated to refer to alternatives only or the alternatives are mutually exclusive, although the disclosure supports a definition that refers to only alternatives and “and / or.” Throughout this application, the term “about” is used to indicate that a valueincludes the inherent variation of error for the device, the method being employed to determine the value, or the variation that exists among the study subjects.

[0061] As used in this specification and claim(s), the words “comprising” (and any form of comprising, such as “comprise” and “comprises”), “having” (and any form of having, such as “have” and “has”), “including” (and any form of including, such as “includes” and “include”) or “containing” (and any form of containing, such as “contains” and “contain”) are inclusive or open- ended and do not exclude additional, unrecited elements or method steps. In embodiments of any of the compositions and methods provided herein, “comprising” may be replaced with “consisting essentially of” or “consisting of”. As used herein, the phrase “consisting essentially of” requires the specified integer(s) or steps as well as those that do not materially affect the character or function of the claimed invention. As used herein, the term “consisting” is used to indicate the presence of the recited integer (e.g., a feature, an element, a characteristic, a property, a method / process step or a limitation) or group of integers (e.g., feature(s), element(s), characteristic(s), propertie(s), method / process steps or limitation(s)) only.

[0062] The term “or combinations thereof” as used herein refers to all permutations and combinations of the listed items preceding the term. For example, “A, B, C, or combinations thereof” is intended to include at least one of: A, B, C, AB, AC, BC, or ABC, and if order is important in a particular context, also BA, CA, CB, CBA, BCA, ACB, BAC, or CAB. Continuing with this example, expressly included are combinations that contain repeats of one or more item or term, such as BB, AAA, AB, BBC, AAABCCCC, CBBAAA, CABABB, and so forth. The skilled artisan will understand that typically there is no limit on the number of items or terms in any combination, unless otherwise apparent from the context.

[0063] As used herein, words of approximation such as, without limitation, “about”, "substantial" or "substantially" refers to a condition that when so modified is understood to not necessarily be absolute or perfect but would be considered close enough to those of ordinary skill in the art to warrant designating the condition as being present. The extent to which the description may vary will depend on how great a change can be instituted and still have one of ordinary skilled in the art recognize the modified feature as still having the required characteristics and capabilities of the unmodified feature. In general, but subject to the preceding discussion, a numerical value herein that is modified by a word of approximation such as “about” may vary from the stated value by at least ±1, 2, 3, 4, 5, 6, 7, 10, 12 or 15%.

[0064] Additionally, the section headings herein are provided for consistency with the suggestions under 37 CFR 1.77 or otherwise to provide organizational cues. These headings shall not limit or characterize the invention(s) set out in any claims that may issue from this disclosure. Specifically,and by way of example, although the headings refer to a “Field of Invention,” such claims should not be limited by the language under this heading to describe the so-called technical field. Further, a description of technology in the “Background of the Invention” section is not to be construed as an admission that technology is prior art to any invention(s) in this disclosure. Neither is the “Summary” to be considered a characterization of the invention(s) set forth in issued claims. Furthermore, any reference in this disclosure to “invention” in the singular should not be used to argue that there is only a single point of novelty in this disclosure. Multiple inventions may be set forth according to the limitations of the multiple claims issuing from this disclosure, and such claims accordingly define the invention(s), and their equivalents, that are protected thereby. In all instances, the scope of such claims shall be considered on their own merits in light of this disclosure, but should not be constrained by the headings set forth herein.

[0065] For each of the claims, each dependent claim can depend both from the independent claim and from each of the prior dependent claims for each and every claim so long as the prior claim provides a proper antecedent basis for a claim term or element.

[0066] To aid the Patent Office, and any readers of any patent issued on this application in interpreting the claims appended hereto, applicants wish to note that they do not intend any of the appended claims to invoke paragraph 6 of 35 U.S.C. § 112, U.S.C. § 112 paragraph (f), or equivalent, as it exists on the date of filing hereof unless the words “means for” or “step for” are explicitly used in the particular claim.

[0067] All of the compositions and / or methods disclosed and claimed herein can be made and executed without undue experimentation in light of the present disclosure. While the compositions and methods of this invention have been described in terms of preferred embodiments, it will be apparent to those of skill in the art that variations may be applied to the compositions and / or methods and in the steps or in the sequence of steps of the method described herein without departing from the concept, spirit, and scope of the invention. All such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope, and concept of the invention as defined by the appended claims. REFERENCES

[0068] 1. Jolanda E Reusser et al., Quantitative measures of myo-IP6 in soil using solution 31P NMR spectroscopy and spectral deconvolution fitting including a broad signal. Environmental science. Processes & impacts, 22(4), 1084-1094 (2020-03-20).

[0069] 2. Dayie TK, Olenginski LT, Taiwo KM. Isotope Labels Combined with Solution NMR Spectroscopy Make Visible the Invisible Conformations of Small-to-Large RNAs. Chem Rev.2022 May 25;122(10):9357-9394. doi: 10.1021 / acs.chemrev.1c00845. Epub 2022 Apr 20. PMID: 35442658; PMCID: PMC9136934.

[0070] 3. arxiv.org / abs / 1503.01280.

[0071] 4. E. Levernier, K. Tatoueix, S. Garcia-Argote, V. Pfeifer, R. Kiesling, E. Gravel, et al. JACS Au 2022 Vol. 2 Issue 4 Pages 801-808, DOI: 10.1021 / jacsau.1c00503, doi.org / 10.1021 / jacsau.1c00503.

[0072] 5. Schmidt, C. (2017) First deuterated drug approved Nat. Biotechnol. 35 (6) 493– 494 DOI: 10.1038 / nbt0617-493

[0073] 6. Claassen, D. O., Carroll, B., De Boer, L. M., Wu, E., Ayyagari, R., Gandhi, S., and Stamler, D. (2017) Indirect tolerability comparison of deutetrabenazine and tetrabenazine for Huntington disease Journal of Clinical Movement Disorders 4, 11 DOI: 10.1186 / s40734-017- 0051-5.

[0074] 7. www.ncbi.nlm.nih.gov / pmc / articles / PMC4579527.

[0075] 8.www.yahoo.com / lifestyle / global-deuterium-substituted-drugs-market-153000819.html.

[0076] 9. Grocholska, P.; Bąchor, R. Trends in the Hydrogen−Deuterium Exchange at the Carbon Centers. Preparation of Internal Standards for Quantitative Analysis by LC-MS. Molecules 2021, 26, 2989. https: / / doi.org / 10.3390 / molecules26102989.

[0077] 10. US Pat.5,830,763A.

[0078] 11. www.sigmaaldrich.com / US / en / product / aldrich / 347450.

[0079] 12. www.sigmaaldrich.com / US / en / product / aldrich / 372072.

[0080] 13. www.sigmaaldrich.com / US / en / product / aldrich / 176761.

[0081] 14.www.fishersci.com / shop / products / lithium-hydroxide-anhydrous-tci-america- 3 / L0225500G.

[0082] 15. www.sigmaaldrich.com / US / en / product / aldrich / 151882.

[0083] 16. sdbs.db.aist.go.jp / sdbs / cgi-bin / cre_index.cgi.

[0084] 17. GE Challenger, Contract W-7405-Eng.36, 1954, Los Alamos National Lab

Claims

What is claimed is:

1. An apparatus for preparing heavy isotope reactions with metal hydroxides in a sealed environment comprising: a source of heavy water in fluid communication with a reaction chamber; a heating unit that is in contact with at least part of the reaction chamber, wherein a metal (M) is placed within the reaction chamber, and an output in fluid communication with a condenser having an input and an output; a water / recycle container in fluid communication with the output of the condenser to receive condensed heavy water from the condenser; and one or more processors that control the pressure and temperature in the reaction that controls the formation of deuterated or tritiated metal hydroxides.

2. The apparatus of claim 1, wherein the metal M is selected from Li, Na, K, Rb, and Cs.

3. The apparatus of claim 1, wherein the source of heavy water includes a liquid transfer pump and a flow meter in communication with the liquid transfer pump opposite the source of heavy water that measures a flow of the heavy water into the reaction chamber and wherein the reaction chamber comprises an anti-corrosive liner.

4. The apparatus of claim 1, wherein a thermocouple in contact with the reaction chamber is connected to the processor to measure and control a temperature of the reaction chamber.

5. The apparatus of claim 1, wherein a reaction catalyzed in the reaction chamber is selected from: 2M + 2D2O = 2MOD +D2; M2O+D2O= 2MOD; 2M2O2+2D2O = 4MOD+ O2; or M2CO3+CaO+D2O= CaCO3+ 2MOD.

6. The apparatus of claim 1, wherein the deuterated metal hydroxides are formed in the reaction chamber via hydrogen isotope exchange method with metal hydroxides (MOH, M= Li, Na, K, Rb, and Cs) in the reaction chamber, and following the formation of the deuterated metal hydroxides heating and evaporating the heavy water to produce a solid powder.

7. The apparatus of claim 6, wherein a purity of a final product is determined by a molar ratio of the heavy water to metal hydroxides and cycle(s), approximated as 1-1 / (2R+1)N, where R is the molar ratio of heavy water to metal hydroxides and N is the number of cycle(s).

8. The apparatus of claim 1, wherein a stirring device is positioned within the reaction chamber to stir the heavy water and the metal during a reaction.

9. The apparatus of claim 1, further comprising one or more additional reaction chambers in series or in parallel to the reaction chamber to provide for a series of reactions under the control of the one or more processors.

10. The apparatus of claim 1, wherein the heavy water is deuterated water (D2O) or tritiated water (T2O).

11. The apparatus of claim 1, wherein the reaction chamber operates at a pressure at or about ambient pressure.

12. A method of making deuterated metal hydroxides via a hydrogen isotope exchange in a sealed environment comprising: providing a source of heavy deuterated water (D2O), tritiated water (T2O), or both, in fluid communication with a reaction chamber having an input in fluid communication with the source of D2O, T2O, or both and that comprises a heating unit that is in contact with at least part of the reaction chamber, wherein a metal (M) is placed within the reaction chamber, and an output in fluid communication with a condenser having an input and an output; connecting a water / recycle container in fluid communication with the output of the condenser to receive condensed heavy water from the condenser; and connecting one or more processors that control the liquid transfer pump, the flow meter, and the heating unit to control the formation of deuterated or tritiated metal hydroxides.

13. The method of claim 12, further comprising the step of recycling the condensed heavy water to the source of heavy water.

14. The method of claim 12, wherein the metal M is selected from Li, Na, K, Rb, and Cs.

15. The method of claim 12, wherein at least one of: the source further comprises a liquid transfer pump connecting the source of heavy water to a flow meter in communication with the liquid transfer pump opposite the source of heavy water for measuring the flow of the heavy water into the reaction chamber; the reaction chamber comprises an anti-corrosive liner; or a thermocouple in contact with the reaction chamber is connected to the processor to measure and control a temperature of the reaction chamber.

16. The method of claim 12, wherein a reaction catalyzed in the reaction chamber is selected from: 2M + 2D2O = 2MOD +D2; M2O+D2O= 2MOD; 2M2O2+2D2O = 4MOD+ O2; or M2CO3+CaO+D2O= CaCO3+ 2MOD.

17. The method of claim 12, wherein the deuterated metal hydroxides are formed in the reaction chamber via hydrogen isotope exchange method with metal hydroxides (MOH, M= Li, Na, K, Rb, and Cs) in the reaction chamber, and following the formation of the deuterated metal hydroxides heating and evaporating the heavy water to produce a solid powder.

18. The method of claim 17, wherein a purity of a final product is determined by a molar ratio of the heavy water to metal hydroxides and cycle(s), approximated as 1-1 / (2R+1)N, where R is the molar ratio of heavy water to metal hydroxides and N is the number of cycle(s).

19. The method of claim 12, further comprising stirring the heavy water and metal in the reaction chamber during a reaction.

20. The method of claim 12, further comprising connecting one or more additional reaction chambers in series or in parallel to the reaction chamber to provide for a series of reactions under the control of the one or more processors.

21. The method of claim 12, wherein the heavy water is deuterated water (D2O) or tritiated water (T2O).

22. The method of claim 12, wherein the reaction chamber operates at a pressure at or about ambient pressure.

23. An apparatus for preparing heavy isotope reactions with metal hydrides in a sealed environment comprising: a sealed reaction chamber within a hermetically-sealed, temperature-controlled furnace comprising of a container or a region for containing a metal to be reacted with the hydrogen isotopes(s); and a manifold in sealed communication with the sealed reaction chamber, wherein one or more sensors measure a pressure of the hydrogen gasses in the reaction chamber and one or more valves control a flow of the hydrogen gasses in the sealed reaction chamber.

24. The apparatus of claim 23, wherein the one or more valves are controlled by one or more microprocessors to optimize a rate of metal hydride growth.

25. The apparatus of claim 23, wherein the metal hydrides are further processed by cutting with a water jet using ultra-pure water or laser cutting in an inert environment, and optionally, cutting does not use a tungsten cutter.

26. The apparatus of claim 23, wherein a purity of the metal hydrides is determined by at least one of X-ray Fluorescence (XRF) or X-ray Diffraction (XRD) before using in nuclear power or nuclear reactor.

27. The apparatus of claim 23, wherein the hydrogen isotopes(s) are selected from deuterium, tritium, or both.

28. A method for preparing heavy isotope reactions with metal hydrides in a sealed environment comprising: providing an apparatus comprising: a sealed reaction chamber within a hermetically-sealed, temperature-controlled furnace comprising of a container or a region for a metal to be reacted with the hydrogen isotopes(s); and a manifold in sealed communication with the sealed reaction chamber; measuring with one or more sensors a pressure of the hydrogen gasses in the reaction chamber; and controlling the temperature of the furnace and the pressure of hydrogen gasses within the furnace chamber with one or more valves while monitoring the flow of hydrogen gasses into the chamber, or alternatively to control the flow of the hydrogen gasses into the sealed reaction chamber while monitoring the pressure of the hydrogen gasses within the chamber.

29. The method of claim 28, wherein the one or more valves and the temperature-controlled furnace are controlled by one or more microprocessors to optimize a rate of metal hydride growth.

30. The method of claim 28, wherein the metal is selected from Li, Na, K, Rb, and Cs.

31. The method of claim 28, wherein the reaction chamber comprises an anti-corrosive liner.

32. The method of claim 28, wherein the one or more microprocessors control an equilibrium pressure between the metal and hydrogen gasses during the reactions to actively modulate the atomic ratios of the metal hydride.

33. The method of claim 28, wherein the metal hydrides are selected from rare earth metal deuterides or transition metal deuterides.

34. The method of claim 28, wherein the hydrogen gasses are selected from hydrogen, deuterium, tritium, or combinations thereof.

35. The method of claim 28, wherein the metal hydrides are further processed by cutting with a water jet using ultra-pure water or laser cutting in an inert environment, and optionally, processing or cutting does not use any heavy metal.

36. The method of claim 28, wherein a purity of the metal hydrides is determined by at least one of X-ray Fluorescence (XRF) or X-ray Diffraction (XRD) before using in nuclear power or nuclear reactor.

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