Activated aluminum compositions

Abstract

Described herein are water-reactive aluminum compositions.

Description

[0001] ACTIVATED ALUMINUM COMPOSITIONS

[0002] CROSS-REFERENCE TO RELATED APPLICATION

[0003]

[0001] This application claims the benefit of and priority to U.S. Provisional Patent Application No. 63 / 672,944, filed on July 18, 2024, the disclosure of which is hereby incorporated by reference in its entirety for all purposes.

[0004] BACKGROUND

[0005]

[0002] Aluminum is a promising candidate for energy storage due to its high energy density, abundance, low cost, non- toxicity, non-volatility, and non-reactivity in storage. One method of extracting the energy from aluminum is to react the aluminum with water to form hydrogen and heat as described in Reaction 1 or Reaction 2.

[0006] • Al + 2 H2O — > 1.5 H2 + AIO(OH) + Qieaction (Reaction 1)

[0007] • Al + 3 H2O — 1.5 H2 + Al(0H)3 + Qreaction (Reaction 2)

[0008]

[0003] Untreated aluminum will typically not react with water due to the highly passivating oxide layer that forms on its surface. However, the oxide layer may be disrupted by an appropriate catalyst, thereby activating the aluminum to make it water-reactive.

[0009]

[0004] There exists a need to provide flexibility in the catalysts that may be used to produce the activated aluminum.

[0010] SUMMARY

[0011]

[0005] In one aspect, disclosed herein is a water-reactive aluminum composition comprising: aluminum or an alloy thereof having a surface oxide layer, an interior volume, and a microstructure; and an activating metal alloy consisting essentially of gallium and indium, wherein the activating metal alloy is disposed along the microstructure of the aluminum or alloy thereof and wherein the activating metal alloy is greater than about 20% indium by mass, and wherein when water is introduced to the composition, the aluminum or alloy thereof disintegrates to expose the interior volume to the water, and a rapid hydrolysis reaction occurs.

[0006] In some embodiments, the activating metal alloy is greater than or equal to about 30% indium by mass. In some embodiments, the activating metal alloy is greater than or equal to about 50% indium by mass. In some embodiments, the activating metal alloy is greater than or equal to about 25% indium by mass. In some embodiments, the activating metal alloy is about 75% gallium by mass and about 25% indium by mass. In some embodiments, the activating metal allow is about 67% gallium by mass and about 33% indium by mass. In some embodiments, the activating metal allow is about 50% gallium by mass and about 50% indium by mass. In some embodiments, the activating metal alloy is non-eutectic. In some embodiments, the aluminum or alloy thereof comprises scrap aluminum. In some embodiments, the aluminum or alloy thereof is derived, filtered from, sorted from, or otherwise separated from dross or other aluminum containing waste streams. In some embodiments, the aluminum or alloy thereof comprises at least one of shredded aluminum cans, aluminum foils, aluminum pellets, aluminum sheet panels, and aluminum dross. In some embodiments, the aluminum or alloy thereof comprises more than one of one of shredded aluminum cans, aluminum foils, aluminum pellets, aluminum sheet panels, and aluminum dross. In some embodiments, the aluminum or alloy thereof comprises aluminum foils and / or aluminum dross. In some embodiments, the aluminum or alloy thereof is in the form of a pellet formed by compressing one or more of shredded aluminum cans, aluminum foils, aluminum pellets, aluminum sheet panels, and aluminum dross into a pellet. In some embodiments, the pellet comprises compressed aluminum foils. In some embodiments, the aluminum or alloy thereof is recrystallized.

[0012]

[0007] In another aspect, disclosed herein is a water-reactive aluminum composition comprising: aluminum or an alloy thereof having a surface oxide layer, an interior volume, and a microstructure; and an activating metal alloy comprising gallium and indium, wherein the activating metal alloy is disposed along the microstructure of the aluminum or alloy thereof and wherein the activating metal alloy is greater than about 20% indium by mass and wherein the gallium is disposed at the grain boundaries of the microstructure, and wherein when water is introduced to the composition, the aluminum or alloy thereof disintegrates to expose the interior volume to the water, and a rapid hydrolysis reaction occurs.

[0013]

[0008] In some embodiments, the activating metal alloy is greater than or equal to about 30% indium by mass. In some embodiments, the activating metal alloy is greater than or equal to about 50% indium by mass. In some embodiments, the activating metal alloy is greater than or equal to about 25% indium by mass. In some embodiments, the activating metal alloy is about 75% gallium by mass and about 25% indium by mass. In some embodiments, the activating metal allow is about 67% gallium by mass and about 33% indium by mass. In some embodiments, the activating metal allow is about 50% gallium by mass and about 50% indium by mass. In some embodiments, the activating metal alloy further comprises tin and / or bismuth. In some embodiments, the activating metal alloy further comprises tin. In some embodiments, the activating metal alloy is non-eutectic. In some embodiments, the aluminum or alloy thereof comprises scrap aluminum. In some embodiments, the aluminum or alloy thereof is derived, filtered from, sorted from, or otherwise separated from dross or other aluminum containing waste streams. In some embodiments, the aluminum or alloy thereof comprises at least one of shredded aluminum cans, aluminum foils, aluminum pellets, aluminum sheet panels, and aluminum dross. In some embodiments, the aluminum or alloy thereof comprises more than one of one of shredded aluminum cans, aluminum foils, aluminum pellets, aluminum sheet panels, and aluminum dross. In some embodiments, the aluminum or alloy thereof comprises aluminum foils and / or aluminum dross. In some embodiments, the aluminum or alloy thereof is in the form of a pellet formed by compressing one or more of shredded aluminum cans, aluminum foils, aluminum pellets, aluminum sheet panels, and aluminum dross into a pellet. In some embodiments, the pellet comprises compressed aluminum foils. In some embodiments, the aluminum or alloy thereof is recrystallized.

[0014]

[0009] In another aspect, disclosed herein is a water-reactive aluminum composition comprising: aluminum or an alloy thereof having a surface oxide layer, an interior volume, and a microstructure; and an activating metal alloy comprising gallium and indium, wherein the activating metal alloy is disposed along the microstructure of the aluminum or the alloy thereof and wherein the activating metal alloy is equal to or greater than about 50% indium by mass, and wherein when water is introduced to the composition, the aluminum or alloy thereof disintegrates to expose the interior volume to the water, and a rapid hydrolysis reaction occurs.

[0010] In some embodiments, the activating metal alloy is less than or equal to about 50% gallium by mass. In some embodiments, the activating metal alloy further comprises tin and / or bismuth. In some embodiments, the activating metal alloy further comprises tin. In some embodiments, the activating metal alloy is equal to or greater than about 60% indium by mass.

[0015] In some embodiments, the activating metal alloy is equal to or greater than about 80% indium by mass. In some embodiments, the activating metal alloy is less than or equal to about 40% gallium by mass. In some embodiments, the activating metal alloy is less than or equal to about 30% gallium by mass. In some embodiments, the activating metal alloy is non-eutectic. In some embodiments, the aluminum or alloy thereof comprises scrap aluminum. In some embodiments, the aluminum or alloy thereof is derived, filtered from, sorted from, or otherwise separated from dross or other aluminum containing waste streams. In some embodiments, the aluminum or alloy thereof comprises at least one of shredded aluminum cans, aluminum foils, aluminum pellets, aluminum sheet panels, and aluminum dross. In some embodiments, the aluminum or alloy thereof comprises more than one of one of shredded aluminum cans, aluminum foils, aluminum pellets, aluminum sheet panels, and aluminum dross. In some embodiments, the aluminum or alloy thereof comprises aluminum foils and / or aluminum dross. In some embodiments, the aluminum or alloy thereof is in the form of a pellet formed by compressing one or more of shredded aluminum cans, aluminum foils, aluminum pellets, aluminum sheet panels, and aluminum dross into a pellet. In some embodiments, the pellet comprises compressed aluminum foils. In some embodiments, the aluminum or alloy thereof is recrystallized.

[0016] [Oil] In another aspect, disclosed herein is a water-reactive aluminum composition comprising: aluminum or an alloy thereof having a surface oxide layer, an interior volume, and a microstructure; and an activating metal alloy comprising gallium and indium, wherein the activating metal alloy is disposed along the microstructure of the aluminum or the alloy thereof and wherein the activating metal alloy is less than or equal to about 50% gallium by mass, and wherein when water is introduced to the composition, the aluminum or alloy thereof disintegrates to expose the interior volume to the water, and a rapid hydrolysis reaction occurs.

[0012] In some embodiments, the activating metal alloy is equal to or greater than about 50% indium by mass. In some embodiments, the activating metal alloy further comprises tin and / or bismuth. In some embodiments, the activating metal alloy further comprises tin. In some embodiments, the activating metal alloy is equal to or greater than about 60% indium by mass. In some embodiments, the activating metal alloy is equal to or greater than about 80% indium by mass. In some embodiments, the activating metal alloy is less than or equal to about 40% gallium by mass. In some embodiments, the activating metal alloy is less than or equal to about 30% gallium by mass. In some embodiments, the activating metal alloy is non-eutectic. In some embodiments, the aluminum or alloy thereof comprises scrap aluminum. In some embodiments, the aluminum or alloy thereof is derived, filtered from, sorted from, or otherwise separated from dross or other aluminum containing waste streams. In some embodiments, the aluminum or alloy thereof comprises at least one of shredded aluminum cans, aluminum foils, aluminum pellets, aluminum sheet panels, and aluminum dross. In some embodiments, the aluminum or alloy thereof comprises more than one of one of shredded aluminum cans, aluminum foils, aluminum pellets, aluminum sheet panels, and aluminum dross. In some embodiments, the aluminum or alloy thereof comprises aluminum foils and / or aluminum dross. In some embodiments, the aluminum or alloy thereof is in the form of a pellet formed by compressing one or more of shredded aluminum cans, aluminum foils, aluminum pellets, aluminum sheet panels, and aluminum dross into a pellet. In some embodiments, the pellet comprises compressed aluminum foils. In some embodiments, the aluminum or alloy thereof is recrystallized.

[0017] BRIEF DESCRIPTION OF THE DRAWINGS

[0018]

[0013] FIG. 1 is a graph showing the hydrogen flow (g / hr) and feedstock usage over time (%wt) resulting from the reaction of aluminum activated with catalyst Sample H (comprising about 67% gallium and about 33% indium by mass).

[0014] FIG. 2 is a graph showing power (kW) as a function of energy resulting from the reaction of aluminum activated with catalyst Sample H (comprising about 67% gallium and about 33% indium by mass).

[0019]

[0015] FIG. 3 is a graph showing the hydrogen flow (g / hr) and feedstock usage over time (%wt) resulting from the reaction of aluminum activated with catalyst Sample I (comprising about 50% gallium and about 50% indium by mass).

[0020]

[0016] FIG. 4 is a graph showing power (kW) as a function of energy resulting from the reaction of aluminum activated with catalyst Sample I (comprising about 50% gallium and about 50% indium by mass).

[0021] DETAILED DESCRIPTION

[0022]

[0017] Previous processes have typically used a catalyst composition of about 80% gallium and about 20% indium by mass, sometimes with the addition of a small amount of tin. It would be desirable to be tolerant to varying catalyst compositions to provide resilience against supply shortages or volatility in market prices for these materials.

[0023]

[0018] The present disclosure provides water-reactive aluminum compositions. The contemplated compositions are reactive with water or steam as described in Reaction 1 or Reaction 2.

[0024]

[0019] The contemplated water-reactive aluminum compositions may comprise primary aluminum, secondary aluminum, or any feedstock containing metallic aluminum. Some examples of various applicable feedstock include but are not limited to: pure aluminum, aluminum alloys, dross from aluminum smelting processes, dross from aluminum recycling processes, aluminum components that don’t meet product specifications or pass quality control, aluminum foils, and household waste food containers. Exact process conditions may be tuned depending on the chemistry, microstructure and physical morphology of the feedstock.

[0025]

[0020] The term “non-eutectic”, as used herein, refers to an alloy where the melting point of the alloy is higher than the melting point of at least one of the constituent metals.

[0026]

[0021] The term “microstructure” of aluminum, as used herein, refers to an arrangement of crystalline aluminum grains, intermetallic phases, and crystalline defects forming a larger aluminum particle or object, with grain boundaries at the interfaces between the individual aluminum grains.

[0027]

[0022] The terms “catalyst” and “activating metal alloy”, are used interchangeably herein and refer to a metallic alloy capable of diffusing in metallic aluminum and disrupting the superficial and interstitial aluminum oxide of metallic aluminum.

[0023] As used herein, a catalyst or activating metal alloy that consists “essentially of” one or more components is to be understood as consisting of said components and no more than trace amounts of any additional components (e.g., less than 0.5% by mass of each additional component).

[0028]

[0024] The term “feedstock”, as used herein, refers to any starting material which contains metallic aluminum including but not limited to pure aluminum, aluminum alloys, primary or secondary aluminum, and waste product which contains a significant amount (e.g., at least 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, or 80% by weight) of metallic aluminum. Feedstock may contain additional components including but not limited to plastic, other metals, ceramics, and organic compounds.

[0029]

[0025] The term “activated fuel”, as used herein, refers to an activated aluminum composition formed by treating aluminum or an alloy thereof with an activating metal alloy. When water is introduced to the activated fuel, the aluminum disintegrates to expose the interior volume to the water, and a rapid hydrolysis reaction occurs.

[0030]

[0026] The term “room temperature” as used herein refers to 20 °C.

[0031]

[0027] The term “elevated temperature” as used herein refers to any temperature above 20 °C.

[0028] The term “virgin alloy” as used herein refers to an activating metal alloy that has not previously been recovered or recycled from a previous reaction mixture, e.g., a reaction mixture resulting from Reaction 1 or Reaction 2.

[0032]

[0029] The term “aluminum foil” as used herein refers to aluminum in the form of a sheet having a thickness of less than or equal 0.2 mm.

[0033]

[0030] The term “peak reactivity” as used herein refers to the reactivity of a water-reactive aluminum composition that cannot be increased through additional curing time. Curing refers to the process by which an activating metal alloy applied to the surface of an aluminum-containing composition is allowed to diffuse through the bulk of the aluminum-containing composition over time to render the aluminum-containing composition reactive with water. Water-reactive aluminum compositions described herein having peak reactivity may have an average power output of greater than 1 .0 kW upon reaction with water and / or specific energies of greater than or equal to 6.5 kWh / kg.

[0034]

[0031] The term “about,” as used herein, means approximately, in the region of, roughly, or around. Unless otherwise stated for a numerical value noted, when the term “about” is used in conjunction with a numerical range, it modifies that range by extending the boundaries above and below the numerical values set forth. Unless otherwise stated for a numerical value noted, the term “about” is used herein to modify a numerical value above and below the stated value by a variance of 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 15%, 20%, 25%, or 50%. For nonlimiting example, a range of “about 2 to about 20” can mean 1.98 to 22, or 1 to 30, or other ranges therebetween. Unless otherwise stated for a percentage range noted, when the term “about” is used in conjunction with a percentage range, it modifies that range by extending the boundaries above and below the percentages set forth. Unless otherwise stated for the percentage noted, the term “about” is used herein to modify a percentage above and below the stated percentage by 1 %, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 15%, 20%, 25%, or 50% (as an absolute, which may be limited to 0% as a minimum), or by a percentage of the stated percentage i.e. 1% 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 15%, 20%, 25%, or 50% of the percentage. For nonlimiting example, a range of “about 2% to about 20%” can mean 1% to 21%, or 0% to 70%, or other ranges therebetween, or 1.98% to 22%, or 1% to 30% (as a percentage of the percentage range). For nonlimiting example, a percentage value of “about 30%” can mean 29% to 31%, or 0% to 80%, or other ranges therebetween, or 27% to 33%, or 15% to 45% (as a percentage of the percentage value), or other ranges therebetween. Unless otherwise stated for a numerical range noted, numerical ranges recited herein by endpoints include all numbers and fractions subsumed within that range (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.90, 4, and 5). It is also to be understood that all numbers and fractions thereof are presumed to be modified by the term “about.”

[0035]

[0032] As used herein an average particle diameter may be described in terms of the mean particle size characterized by any one of a sphere of ideal volume (dv), a sphere of identical weight (dw), a sphere of identical minimum length (dmin), a sphere passing same sieve aperture (dsieve), a sphere of identical maximum length, a sphere of identical surface area (ds), a sphere that diffuses at the same rate as the particle in a fluid (dh), or a sphere of identical sedimentation rate (dsed). The type of characterization of particle size may be determined by a skilled person in the art depending on how the particles are formed and their size. In a non-limiting example, pellet shaped particles having a diameter of 20 mm may be characterized by a sphere passing same sieve aperture (dsieve).

[0036]

[0033] As used herein an “average” size of a population of particles may be described in terms of the percentile of particles smaller than a given diameter. For example, a D10 value, or the 10th percentile, signifies the particle size below which 10% of the population's particles are found. In another example, the D50 value is the 50thpercentile, also known as the median particle size, is the size at which 50% of the population’s particles consists of particles smaller than this size. In a further example, the D90 value, or the 90th percentile, indicates the particle size below which 90% of the population's particles are located. In some embodiments, one percentile is used to define the average particle size. In some embodiments, all three percentiles are used to describe the size distribution of particles within a population.

[0034] Many different techniques known to those skilled in the art may be used to characterize the average diameter of a population and the distribution of particle sizes within a population. For example, a population of particles may be passed through one or more sieves, each sieve progressively smaller mesh sizes (dsieve).

[0037] Activated Aluminum Compositions

[0038]

[0035] In one aspect, provided herein is a water-reactive aluminum composition comprising: aluminum or an alloy thereof having a surface oxide layer, an interior volume, and a microstructure; and an activating metal alloy consisting essentially of gallium and indium, wherein the activating metal alloy is disposed along the microstructure of the aluminum or alloy thereof and wherein the activating metal alloy is greater than about 20% indium by mass, and wherein when water is introduced to the composition, the aluminum or alloy thereof disintegrates to expose the interior volume to the water, and a rapid hydrolysis reaction occurs.

[0036] In another aspect, provided herein is a water-reactive aluminum composition comprising: aluminum or an alloy thereof having a surface oxide layer, an interior volume, and a microstructure; and an activating metal alloy comprising gallium and indium, wherein the activating metal alloy is disposed along the microstructure of the aluminum or alloy thereof and wherein the activating metal alloy is greater than about 20% indium by mass and wherein the gallium is disposed at the grain boundaries of the microstructure, and wherein when water is introduced to the composition, the aluminum or alloy thereof disintegrates to expose the interior volume to the water, and a rapid hydrolysis reaction occurs.

[0037] In another aspect, provided herein is a water-reactive aluminum composition comprising: aluminum or an alloy thereof having a surface oxide layer, an interior volume, and a microstructure; and an activating metal alloy comprising gallium and indium, wherein the activating metal alloy is disposed along the microstructure of the aluminum or alloy thereof and wherein the activating metal alloy is greater than about 20% indium by mass, and wherein when water is introduced to the composition, the aluminum or alloy thereof disintegrates to expose the interior volume to the water, and a rapid hydrolysis reaction occurs, wherein the water-reactive aluminum composition is formed using a process comprising contacting the aluminum or alloy thereof with the activating metal alloy below the melting temperature of the aluminum or alloy thereof and allowing the activating metal alloy to diffuse through the microstructure of the aluminum or alloy thereof, thereby forming the water-reactive aluminum composition.

[0039]

[0038] In another aspect, provided herein is a water-reactive aluminum composition comprising: aluminum or an alloy thereof having a surface oxide layer, an interior volume, and a microstructure; and an activating metal alloy consisting of gallium and indium, wherein the activating metal alloy is disposed along the microstructure of the aluminum or alloy thereof and wherein the activating metal alloy is greater than about 20% indium by mass, and wherein when water is introduced to the composition, the aluminum or alloy thereof disintegrates to expose the interior volume to the water, and a rapid hydrolysis reaction occurs.

[0039] In some embodiments, the activating metal alloy is greater than or equal to about 21% indium by mass. In some embodiments, the activating metal alloy is greater than or equal to about 22% indium by mass. In some embodiments, the activating metal alloy is greater than or equal to about 23% indium by mass. In some embodiments, the activating metal alloy is greater than or equal to about 24% indium by mass. In some embodiments, the activating metal alloy is greater than or equal to about 25% indium by mass.

[0040]

[0040] In some embodiments, the activating metal alloy is greater than or equal to about 26% indium by mass. In some embodiments, the activating metal alloy is greater than or equal to about 27% indium by mass. In some embodiments, the activating metal alloy is greater than or equal to about 28% indium by mass. In some embodiments, the activating metal alloy is greater than or equal to about 29% indium by mass. In some embodiments, the activating metal alloy is greater than or equal to about 30% indium by mass.

[0041]

[0041] In some embodiments, the activating metal alloy is greater than or equal to about 31% indium by mass. In some embodiments, the activating metal alloy is greater than or equal to about 32% indium by mass. In some embodiments, the activating metal alloy is greater than or equal to about 33% indium by mass. In some embodiments, the activating metal alloy is greater than or equal to about 34% indium by mass. In some embodiments, the activating metal alloy is greater than or equal to about 35% indium by mass.

[0042]

[0042] In some embodiments, the activating metal alloy is greater than or equal to about 36% indium by mass. In some embodiments, the activating metal alloy is greater than or equal to about 37% indium by mass. In some embodiments, the activating metal alloy is greater than or equal to about 38% indium by mass. In some embodiments, the activating metal alloy is greater than or equal to about 39% indium by mass. In some embodiments, the activating metal alloy is greater than or equal to about 40% indium by mass.

[0043]

[0043] In some embodiments, the activating metal alloy is greater than or equal to about 45% indium by mass. In some embodiments, the activating metal alloy is greater than or equal to about 55% indium by mass. In some embodiments, the activating metal alloy is greater than or equal to about 55% indium by mass. In some embodiments, the activating metal alloy is greater than or equal to about 60% indium by mass. In some embodiments, the activating metal alloy is greater than or equal to about 65% indium by mass. In some embodiments, the activating metal alloy is greater than or equal to about 70% indium by mass. In some embodiments, the activating metal alloy is greater than or equal to about 75% indium by mass. In some embodiments, the activating metal alloy is greater than or equal to about 80% indium by mass. In some embodiments, the activating metal alloy is greater than or equal to about 85% indium by mass. In some embodiments, the activating metal alloy is greater than or equal to about 90% indium by mass. In some embodiments, the activating metal alloy is greater than or equal to about 95% indium by mass.

[0044]

[0044] In some embodiments, the activating metal alloy is about 75% gallium by mass and about 25% indium by mass. In some embodiments, the activating metal alloy is about 70% gallium by mass and about 30% indium by mass. In some embodiments, the activating metal alloy is about 65% gallium by mass and about 35% indium by mass. In some embodiments, the activating metal alloy is about 60% gallium by mass and about 40% indium by mass. In some embodiments, the activating metal alloy is about 55% gallium by mass and about 45% indium by mass. In some embodiments, the activating metal alloy is about 50% gallium by mass and about 50% indium by mass. In some embodiments, the activating metal alloy is about 45% gallium by mass and about 55% indium by mass. In some embodiments, the activating metal alloy is about 40% gallium by mass and about 60% indium by mass. In some embodiments, the activating metal alloy is about 35% gallium by mass and about 65% indium by mass. In some embodiments, the activating metal alloy is about 30% gallium by mass and about 70% indium by mass. In some embodiments, the activating metal alloy is about 25% gallium by mass and about 75% indium by mass. In some embodiments, the activating metal alloy is about 20% gallium by mass and about 80% indium by mass. In some embodiments, the activating metal alloy is about 15% gallium by mass and about 85% indium by mass. In some embodiments, the activating metal alloy is about 10% gallium by mass and about 90% indium by mass. In some embodiments, the activating metal alloy is about 5% gallium by mass and about 95% indium by mass.

[0045]

[0045] In some embodiments, the activating metal alloy is about 67% gallium by mass and about 33% indium by mass.

[0046]

[0046] In some embodiments, the activating metal alloy is non-eutectic.

[0047]

[0047] In another aspect, provided herein is a water-reactive aluminum composition comprising: aluminum or an alloy thereof having a surface oxide layer, an interior volume, and a microstructure; and an activating metal alloy comprising gallium and indium, wherein the activating metal alloy is disposed along the microstructure of the aluminum or the alloy thereof and wherein the activating metal alloy is equal to or greater than about 50% indium by mass, and wherein when water is introduced to the composition, the aluminum or alloy thereof disintegrates to expose the interior volume to the water, and a rapid hydrolysis reaction occurs.

[0048]

[0048] In some embodiments, the activating metal alloy is less than or equal to about 50% gallium by mass.

[0049]

[0049] In another aspect, provided herein is a water-reactive aluminum composition comprising: aluminum or an alloy thereof having a surface oxide layer, an interior volume, and a microstructure; and an activating metal alloy comprising gallium and indium, wherein the activating metal alloy is disposed along the microstructure of the aluminum or the alloy thereof and wherein the activating metal alloy is less than or equal to about 50% gallium by mass, and wherein when water is introduced to the composition, the aluminum or alloy thereof disintegrates to expose the interior volume to the water, and a rapid hydrolysis reaction occurs.

[0050] In some embodiments, the activating metal alloy is equal to or greater than about 50% indium by mass.

[0050]

[0051] In some embodiments, the activating metal alloy is equal to or greater than about 55% indium by mass. In some embodiments, the activating metal alloy is equal to or greater than about 60% indium by mass. In some embodiments, the activating metal alloy is equal to or greater than about 65% indium by mass. In some embodiments, the activating metal alloy is equal to or greater than about 70% indium by mass. In some embodiments, the activating metal alloy is equal to or greater than about 75% indium by mass. In some embodiments, the activating metal alloy is equal to or greater than about 80% indium by mass. In some embodiments, the activating metal alloy is equal to or greater than about 85% indium by mass. In some embodiments, the activating metal alloy is equal to or greater than about 90% indium by mass. In some embodiments, the activating metal alloy is equal to or greater than about 95% indium by mass.

[0051]

[0052] In some embodiments, the activating metal alloy is less than or equal to about 45% gallium by mass. In some embodiments, the activating metal alloy is less than or equal to about 40% gallium by mass. In some embodiments, the activating metal alloy is less than or equal to about 35% gallium by mass. In some embodiments, the activating metal alloy is less than or equal to about 30% gallium by mass. In some embodiments, the activating metal alloy is less than or equal to about 25% gallium by mass. In some embodiments, the activating metal alloy is less than or equal to about 20% gallium by mass. In some embodiments, the activating metal alloy is less than or equal to about 15% gallium by mass. In some embodiments, the activating metal alloy is less than or equal to about 10% gallium by mass. In some embodiments, the activating metal alloy is less than or equal to about 5% gallium by mass.

[0052]

[0053] In some embodiments, the activating aluminum composition further comprises tin and / or bismuth. In some embodiments, the activating metal alloy further comprises tin. In some embodiments, the activating metal alloy comprises gallium, indium, and tin and does not comprise bismuth.

[0053]

[0054] In some embodiments, the activating metal alloy is non-eutectic.

[0054]

[0055] In some embodiments of the methods described herein, the aluminum or alloy thereof is not in powder form. In some embodiments of the methods described herein, the aluminum or alloy thereof is in the form of pellets. In some embodiments, the pellets have an average diameter of about 5 mm, about 6 mm, about 7 mm, about 8 mm, about 9 mm, about 10 mm, about 15 mm, about 20 mm, about 30 mm, about 40 mm, about 50 mm, about 60 mm, about 70 mm, about 80 mm, about 90 mm, or about 100 mm. In some embodiments, the pellets have an average diameter of about 5 mm to about 20 mm. In some embodiments, the pellets have an average diameter of about 70 mm. As used herein the “pellets” are particles and may be characterized in terms of diameter and distribution of diameters using techniques commonly known to those skilled in the art.

[0055]

[0056]

[0056]

[0057] In some embodiments, the aluminum or alloy thereof comprises scrap aluminum. In some embodiments, the aluminum or alloy thereof is derived, filtered from, sorted from, or otherwise separated from dross or other aluminum containing waste streams. In some embodiments, the aluminum or alloy thereof comprises at least one of shredded aluminum cans, aluminum foils, aluminum pellets, aluminum sheet panels, and aluminum dross. In some embodiments, the aluminum or alloy thereof comprises more than one of one of shredded aluminum cans, aluminum foils, aluminum pellets, aluminum sheet panels, and aluminum dross. In some embodiments, the aluminum or alloy thereof comprises aluminum foils and / or aluminum dross.

[0057]

[0058] In some embodiments, the aluminum or alloy thereof is in the form of a pellet formed by compressing one or more of shredded aluminum cans, aluminum foils, aluminum pellets, aluminum sheet panels, and aluminum dross into the pellet. In certain embodiments, the pellet comprises compressed aluminum foils.

[0058]

[0059] In some embodiments, the aluminum or alloy thereof is recrystallized.

[0059]

[0060] In some embodiments of the water-reactive aluminum compositions disclosed herein, the activating metal alloy is about 2% to about 20%, about 2% to about 18%, about 2% to about 16%, about 2% to about 14%, about 2% to about 12%, about 2% to about 10%, about 2% to about 8%, or about 2% to about 4% of the total mass of the water-reactive aluminum composition. In some embodiments, the activating metal alloy is about 1%, about 2%, about 3%, about 4%, about 5%, about 6%, about 7%, about 8%, about 9%, about 10%, about 11%, about 12%, about 13%, about 14%, about 15%, about 16%, about 17%, about 18%, about 19%, about 20%, about 30%, about 40%, or about 50% of the total mass of the water-reactive aluminum composition.

[0060] EXAMPLES

[0061] EXAMPLE 1: Preparation of activated pure aluminum with the use of gallium-indium alloys

[0062]

[0001] In the experiments described below, power output, energy output, and yield were calculated by measuring the flow of hydrogen released during the reaction. Energy released as hydrogen from the reaction of aluminum with water was extrapolated from the hydrogen flow using the known higher heating value (HHV) combustion energy of hydrogen. Energy released as heat / steam from the reaction of aluminum with water was extrapolated from the hydrogen flow using the fixed ratio of hydrogen (51.2%) and heat (48.8%) released during the reaction of aluminum with water (see Reaction 1 and Reaction 2).

[0063]

[0061] Non-eutectic gallium-indium catalyst compositions indicated in Table 1 were preheated at 200 °C for 30 minutes in a sealed glass jar purged with argon gas. In parallel, 1000 g of pure aluminum feedstock in the form of 6 mm diameter spherical pellets were heated at 130 °C for 30 minutes in a steel can. The steel can was sized such that at least half of the interior volume was empty (e.g., a steel can having an interior volume of one quart). The steel can containing the aluminum was purged with argon and sealed before heating.

[0064] Table 1: Non-eutectic catalyst compositions used in preparation of exemplary activated aluminum samples

[0065]

[0062] After both the feedstock and the gallium-indium catalyst were preheated, gallium-indium catalyst was dispensed into the steel can containing the feedstock in a weight ratio of about 4-6.5 parts gallium-indium alloy per 100 parts feedstock. Both the catalyst glass jar and steel can containing the combined feedstock and catalyst were purged with argon and re-sealed.

[0066]

[0063] The steel can was agitated for 60 minutes at 50 °C such that the aluminum-catalyst mixture was thoroughly mixed.

[0067]

[0064] After this 60 minute period of activation, the mixed material was weighed to determine the final weight percent of catalyst, as some catalyst may be lost to the walls of the steel can. The final gallium-indium weight percent was 3-6 wt% of the total weight of the mixed material. The aluminum in this mixed material was reactive and would react readily with an oxidant (e.g., water). This activated mixture was considered “fuel’" and was stored in a sealed container filled with inert gas (e.g., argon). At this stage, the fuel had not reached peak reactivity and required additional “curing” to allow further diffusion of the catalyst through the microstructure of the feedstock. This was accomplished by allowing the fuel to sit at room temperature for 48 hours.

[0068]

[0065] This procedure may also be used to prepare activated aluminum using catalyst compositions having other gallium-indium weight ratios.

[0069]

[0066] The activated aluminum samples were reacted with water, and their reactivity was observed. FIGs. 1 and 3 show the hydrogen flow and feedstock usage over time of the reaction of Samples H and I with water, respectively. FIGs. 2 and 4 show the power output as a function of energy resulting from the reaction of Samples H and I with water, respectively. Samples H and I each demonstrated a reaction yield of greater than 80%.

[0070] EQUIVALENTS AND SCOPE

[0071]

[0067] In the claims articles such as "a," "an," and "the" may mean one or more than one unless indicated to the contrary or otherwise evident from the context. Claims or descriptions that include "or" between one or more members of a group are considered satisfied if one, more than one, or all of the group members are present in, employed in, or otherwise relevant to a given product or process unless indicated to the contrary or otherwise evident from the context. Provide herein are embodiments in which exactly one member of the group is present in, employed in, or otherwise relevant to a given product or process. Provided herein are embodiments in which more than one, or all of the group members are present in, employed in, or otherwise relevant to a given product or process.

[0072]

[0068] Furthermore, the inventions provided herein encompass all variations, combinations, and permutations in which one or more limitations, elements, clauses, and descriptive terms from one or more of the listed claims is introduced into another claim. For example, any claim that is dependent on another claim can be modified to include one or more limitations found in any other claim that is dependent on the same base claim. Where elements are presented as lists, e.g., in Markush group format, each subgroup of the elements is also disclosed, and any element(s) can be removed from the group. It should be understood that, in general, where the inventions provided and described herein, or aspects of the inventions described and provided herein, is / are referred to as comprising particular elements and / or features, certain embodiments of the inventions or aspects of the inventions consist, or consist essentially of, such elements and / or features. For purposes of simplicity, those embodiments have not been specifically set forth in haec verba herein. It is also noted that the terms "comprising" and "containing" are intended to be open and permits the inclusion of additional elements or steps. Where ranges are given, endpoints are included. Furthermore, unless otherwise indicated or otherwise evident from the context and understanding of one of ordinary skill in the art, values that are expressed as ranges can assume any specific value or sub-range within the stated ranges in different embodiments of the inventions described and provided herein, to the tenth of the unit of the lower limit of the range, unless the context clearly dictates otherwise.

[0073]

[0069] This application refers to various issued patents, published patent applications, journal articles, and other publications, all of which are incorporated herein by reference. If there is a conflict between any of the incorporated references and the instant specification, the specification shall control. In addition, any particular embodiment that falls within the prior art may be explicitly excluded from any one or more of the claims. Because such embodiments are deemed to be known to one of ordinary skill in the art, they may be excluded even if the exclusion is not set forth explicitly herein. Any particular embodiment can be excluded from any claim, for any reason, whether or not related to the existence of prior art.

[0074]

[0070] Each numerical value presented herein is contemplated to represent a minimum value or a maximum value in a range for a corresponding parameter. Accordingly, when added to the claims, the numerical value provides express support for claiming the range, which may lie above or below the numerical value, in accordance with the teachings herein. Every value between the minimum value and the maximum value within each numerical range presented herein (including any minimum, nominal, and maximum values shown in any tables), is contemplated and expressly supported herein, subject to the number of significant digits expressed in each particular range. The application expressly contemplates the ranges between the minimum and nominal values, nominal and maximum values, and minimum and maximum values.

[0075]

[0071] Those skilled in the art will recognize or be able to ascertain using no more than routine experimentation many equivalents to the specific embodiments described herein. The scope of the present embodiments described herein is not intended to be limited to the above Description, but rather is as set forth in the appended claims. Those of ordinary skill in the art will appreciate that various changes and modifications to this description may be made without departing from the spirit or scope of the present inventions, as defined in the following claims.

Claims

CLAIMSWHAT IS CLAIMED:

1. A water-reactive aluminum composition comprising: aluminum or an alloy thereof having a surface oxide layer, an interior volume, and a microstructure; and an activating metal alloy consisting essentially of gallium and indium, wherein the activating metal alloy is disposed along the microstructure of the aluminum or alloy thereof and wherein the activating metal alloy is greater than about 20% indium by mass, and wherein when water is introduced to the composition, the aluminum or alloy thereof disintegrates to expose the interior volume to the water, and a rapid hydrolysis reaction occurs.

2. A water-reactive aluminum composition comprising: aluminum or an alloy thereof having a surface oxide layer, an interior volume, and a microstructure; and an activating metal alloy comprising gallium and indium, wherein the activating metal alloy is disposed along the microstructure of the aluminum or alloy thereof and wherein the activating metal alloy is greater than about 20% indium by mass and wherein the gallium is disposed at the grain boundaries of the microstructure, and wherein when water is introduced to the composition, the aluminum or alloy thereof disintegrates to expose the interior volume to the water, and a rapid hydrolysis reaction occurs.

3. The water-reactive aluminum composition of claim 1 or 2, wherein the activating metal alloy is greater than or equal to about 30% indium by mass.

4. The water-reactive aluminum composition of claim 1 or 2, wherein the activating metal alloy is greater than or equal to about 50% indium by mass.

5. The water-reactive aluminum composition of claim 1 or 2, wherein the activating metal alloy is greater than or equal to about 25% indium by mass.

6. The water-reactive aluminum composition of claim 1 or 2, wherein the activating metal alloy is about 75% gallium by mass and about 25% indium by mass.

7. The water-reactive aluminum composition of claim 1 or 2, wherein the activating metal alloy is about 67% gallium by mass and about 33% indium by mass.

8. The water-reactive aluminum composition of claim 1 or 2, wherein the activating metal alloy is about 50% gallium by mass and about 50% indium by mass.

9. A water-reactive aluminum composition comprising: aluminum or an alloy thereof having a surface oxide layer, an interior volume, and a microstructure; and an activating metal alloy comprising gallium and indium, wherein the activating metal alloy is disposed along the microstructure of the aluminum or the alloy thereof and wherein the activating metal alloy is equal to or greater than about 50% indium by mass, and wherein when water is introduced to the composition, the aluminum or alloy thereof disintegrates to expose the interior volume to the water, and a rapid hydrolysis reaction occurs.

10. The water-reactive aluminum composition of claim 9, wherein the activating metal alloy is less than or equal to about 50% gallium by mass.

11. A water-reactive aluminum composition comprising: aluminum or an alloy thereof having a surface oxide layer, an interior volume, and a microstructure; and an activating metal alloy comprising gallium and indium, wherein the activating metal alloy is disposed along the microstructure of the aluminum or the alloy thereof and wherein the activating metal alloy is less than or equal to about 50% gallium by mass, and wherein when water is introduced to the composition, the aluminum or alloy thereof disintegrates to expose the interior volume to the water, and a rapid hydrolysis reaction occurs.

12. The water-reactive aluminum composition of claim 11 , wherein the activating metal alloy is equal to or greater than about 50% indium by mass.

13. The water-reactive aluminum composition of any one of claims 2-12, wherein the activating metal alloy further comprises tin and / or bismuth.

14. The water-reactive aluminum composition of any one of claims 2-12, wherein the activating metal alloy further comprises tin.

15. The water-reactive aluminum composition of any one of claims 9-14, wherein the activating metal alloy is equal to or greater than about 60% indium by mass.

16. The water-reactive aluminum composition of any one of claims 9-14, wherein the activating metal alloy is equal to or greater than about 80% indium by mass.

17. The water-reactive aluminum composition of any one of claims 9-14, wherein the activating metal alloy is less than or equal to about 40% gallium by mass.

18. The water-reactive aluminum composition of any one of claims 9-14, wherein the activating metal alloy is less than or equal to about 30% gallium by mass.

19. The water-reactive aluminum composition of any one of claims 1-18, wherein the activating metal alloy is non-eutectic.

20. The water-reactive aluminum composition of any one of claims 1-19 wherein the aluminum or alloy thereof comprises scrap aluminum.

21. The water-reactive aluminum composition of any one of claims 1-20, wherein the aluminum or alloy thereof is derived, filtered from, sorted from, or otherwise separated from dross or other aluminum containing waste streams.

22. The water-reactive aluminum composition of any one of claims 1-21, wherein the aluminum or alloy thereof comprises at least one of shredded aluminum cans, aluminum foils, aluminum pellets, aluminum sheet panels, and aluminum dross.

23. The water-reactive aluminum composition of any one of claims 1 -21 , wherein the aluminum or alloy thereof comprises more than one of one of shredded aluminum cans, aluminum foils, aluminum pellets, aluminum sheet panels, and aluminum dross.

24. The water-reactive aluminum composition of any one of claims 1-21, wherein the aluminum or alloy thereof comprises aluminum foils and / or aluminum dross.

25. The water-reactive aluminum composition of any one of claims 1-21, wherein the aluminum or alloy thereof is in the form of a pellet formed by compressing one or more of shredded aluminum cans, aluminum foils, aluminum pellets, aluminum sheet panels, and aluminum dross into a pellet.

26. The water-reactive aluminum composition of claim 25, wherein the pellet comprises compressed aluminum foils.

27. The water-reactive aluminum composition of any one of claims 1-26, wherein the aluminum or alloy thereof is recrystallized.

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