WO2023019357A1

WO2023019357A1 - Systems and methods for synthesis and production of energetic particles

Info

Publication number: WO2023019357A1
Application number: PCT/CA2022/051251
Authority: WO
Inventors: Haroon B. OQAB; George B. DIETRICH; John Wen; Jean-Pierre HICKEY; Anqi WANG; Yiqi Zhang
Original assignee: Oqab Dietrich Induction Inc.
Priority date: 2021-08-17
Filing date: 2022-08-17
Publication date: 2023-02-23
Also published as: CA3229185A1

Abstract

A method of synthesis of energetic particles, and associated systems, the method including providing a metal powder, dispersing the metal powder in a first fluid to form a first suspension, contacting the first suspension with an oxide precursor, aqueous ammonium hydroxide and a second fluid, to produce a first product, collecting product solids and inductively heating product solids to produce energetic core-shell particles.

Description

SYSTEMS AND METHODS FOR SYNTHESIS AND PRODUCTION OF ENERGETIC PARTICLES

Technical Field

[0001] The embodiments disclosed herein relate to energetic particles, and, in particular, to methods and systems for the synthesis and production spherical energetic core-shell particles, such as AI/CuO particles with a core shell structure.

Introduction

[0002] Energetic particles such as metallic materials and/or fuels can be used for heating and combustion as an alternative energy source to meet energy demands on Earth, and in Space. Metals have high energy densities, and as such, can be used in many applications, including batteries, energetic materials, and/or within propellants. Oxidation of metal powders can be used as an efficient energetic carrier method and energy source for a variety of applications. The exothermic reaction between the metal and an oxidizer releases heat and generates products such as metal oxides. In an application, by using this energy release to accelerate a fluid within a rocket nozzle and/or create heat for a heat engine, thrust may be generated. In another application, by using this energy release to heat a fluid within an electrical generation system, electricity may be generated.

[0003] Thermite material, which comprises a fuel (e.g. Al, Mg, Si, etc.) and oxidizer (metal oxide, fluoropolymer, iodine oxides, etc.), has been widely applied in military and civil fields. Along with the development of nanotechnology, sub-micron or nano- thermite materials have also been developed and investigated. Compared to traditional thermite material, sub-micron and nano-thermite materials showed significantly enhanced energetic performance such as shorter reaction delay, lowered activation energy, faster reaction rate, and higher pressure generated due to its significantly enlarged surface contact and shortened diffusion length. However, there are a few problems hindering the wider application of thermite materials to optimize its performance, including high sensitivity to external stimulus, reactive sintering of Al nanoparticles, and phase separation between fuel and oxidizer. [0004] Researchers have developed various thermite products with different structures, synthesis pathways, and additives to overcome the problems. Surfactants or self-assembly method were used to increase the avoid the occurrence of phase separation and reactive sintering. Graphene has been used to reduce the sensitivity to electrostatic discharge. Nanolaminates, nanosheets, and core-shell structures were developed to tune the reactivities of thermite products. Among these different structures and synthesis methodologies, energetic core-shell structures exhibit unique benefits. Due to maximized surface contact and short diffusion length between fuel and oxidizer, phase separation and reactive sintering of metals were eliminated, leading to enhanced energetic performance.

[0005] Such energetic core-shell structure particles are difficult and or complicated to manufacture with currently known methods.

[0006] Accordingly, there is a need for improved methods of, and systems for manufacturing metallic materials and/or fuels, such as energetic core-shell particles.

Summary

[0007] Provided herein is a system for the synthesis of energetic core-shell particles. The system includes a chamber for conducting particle synthesis reactions, an oxide source coupled to the chamber, for supplying the chamber with an oxide precursor, a metal source coupled to the chamber, for supplying the chamber with a metal, a nozzle, coupled to the chamber, for outputting synthesized energetic core-shell particles from the chamber and an inductive heating source, coupled to the chamber, for inductively heating chamber contents to synthesize energetic core-shell particles.

[0008] The system may further include an auxiliary material source, coupled to the chamber, for supplying the chamber with auxiliary materials.

[0009] The auxiliary materials for supply to the chamber may further include a gas, liquid, or another fluid.

[0010] The system may further include a capture storage system coupled to the nozzle, and configured to receive energetic core-shell particles from the nozzle, the capture storage system further configured to package energetic core-shell particles into a storage container.

[0011] The capture storage system may further include an inductive heating element, for heating stored energetic core-shell particles.

[0012] The system may further include an electromagnetic suspension subsystem, the electromagnetic suspension subsystem configured to suspend energetic core-shell particles outputted by the nozzle.

[0013] The system may further include a gel packaging subsystem coupled to the nozzle, the gel packaging subsystem configured to receive core shell particles from the nozzle, and encapsulate core shell particles into a gel capsule.

[0014] The nozzle may further include multiple sub-nozzles.

[0015] The system may further include an electromagnetic transmitter, for exposing contents of the chamber to electromagnetic radiation.

[0016] The system may further include an electromagnetic transmitter, for exposing energetic core-shell particles to electromagnetic radiation.

[0017] The system may further include an electromagnetic receiver, for receiving electromagnetic radiation emitted by the electromagnetic transmitter, to recover energy.

[0018] The system may further include a control system configured to adjust operation parameters of the system.

[0019] The control system may be configured to apply a trained machine learning model to adjust operation parameters of the system.

[0020] Provided herein is a method of synthesis of energetic particle. The method includes providing a metal powder, dispersing the metal powder in a first fluid to form a first suspension, contacting the first suspension with an oxide precursor, aqueous ammonium hydroxide and a second alcohol, to produce a first product, collecting product solids and inductively heating product solids to produce energetic core-shell particles.

[0021] The method may further include stirring the first product for a first period of time. [0022] The method may further include griding product solids before inductively heating product solids.

[0023] The method may further include processing product solids through a mesh sieve before inductively heating product solids.

[0024] The metal powder may be an aluminum powder.

[0025] The oxide precursor may be cupric nitrate.

[0026] The first fluid may be an alcohol.

[0027] The second fluid may be an alcohol.

[0028] The method may further include inductively heating the product solids to 250C.

[0029] The metal powder may have a mean particle size of 1 micron.

[0030] The metal powder may have a mean particle size of 40 nanometers.

[0031] Product solids may be collected through filtration.

[0032] The metal powder may be iron powder.

[0033] The ratio of metal power to oxide precursor may be configured such that the method produces energetic core-shell particles with a specific equivalence ratio, such that when the energetic core-shell particles are combusted, the combustion comprises a predetermined ignition delay.

[0034] Other aspects and features will become apparent, to those ordinarily skilled in the art, upon review of the following description of some exemplary embodiments.

Brief Description of the Drawings

[0035] The drawings included herewith are for illustrating various examples of articles, methods, and apparatuses of the present specification. In the drawings:

[0036] Figure 1 is a flow chart depicting a method of synthesizing energetic coreshell particles, according to one embodiment; [0037] Figure 2 is a flow chart depicting an alternate method of synthesizing metal oxide cores hell particles, according to another embodiment

[0038] Figure 3 is a diagram illustrating the synthesis methods of Figures 1-2, according to an embodiment;

[0039] Figure 4 is a block diagram illustrating a system for the synthesis of energetic core-shell particles, according to an embodiment;

[0040] Figure 5 is a block diagram illustrating a system for the synthesis of energetic core-shell particles, according to another embodiment;

[0041] Figure 6 is a block diagram illustrating a system for the synthesis of energetic core-shell particles, according to another embodiment;

[0042] Figure 7 is a block diagram illustrating a system for the synthesis of thermite mixtures, according to an embodiment;

[0043] Figure 8 is a block diagram illustrating a system for the synthesis of energetic core-shell particles, according to another embodiment;

[0044] Figure 9 is a block diagram illustrating a system for the synthesis of energetic core-shell particles, according to another embodiment;

[0045] Figure 10 is a block diagram illustrating a system for measurement of combustion parameters of energetic particles, according to an embodiment;

[0046] Figure 11 is a graph depicting captured ignition delay data for the combustion of energetic core-shell particles, according to an embodiment;

[0047] Figure 12 is a graph depicting measured ignition delay data for the combustion of energetic core-shell particles of various equivalence ratios and particle sizes, according to an embodiment;

[0048] Figure 13 is a block diagram illustrating a laser focused assisted ignitor system, according to an embodiment;

[0049] Figure 14 is a block diagram illustrating a detachable tethered plate system, according to an embodiment; [0050] Figure 15 is a block diagram illustrating a laser assist release system, according to an embodiment; and

[0051] Figure 16 is an additional block diagram illustrating the laser assist release system of Figure 15, according to an embodiment.

[0052] Figure 17 is a block diagram illustrating a system for multi-satellite operations, according to an embodiment; and

[0053] Figure 18 is an additional block diagram illustrating the system for multisatellite operations of Figure 17, according to an embodiment.

Detailed Description

[0054] Various apparatuses or processes will be described below to provide an example of each claimed embodiment. No embodiment described below limits any claimed embodiment and any claimed embodiment may cover processes or apparatuses that differ from those described below. The claimed embodiments are not limited to apparatuses or processes having all of the features of any one apparatus or process described below or to features common to multiple or all of the apparatuses described below.

[0055] Described herein are methods and systems for synthesizing energetic coreshell , such as metal-metal oxide core-shell particles, AI-CuO particles, which can be used to produce either micron- or nano- core-shell particles. AI-CuO energetic core-shell products generated by the method described herein exhibit a uniform core-shell structure with small CuO grains on the surface of Al particles. The method described herein may be extended to other metal and metal oxides, such that Al particles with an oxide core shell of a metal or non-metal other than copper may be generated, or metal particles other than aluminum particles, with an oxide core shell of any material known in the art may be generated.

[0056] Referring to Figure. 1 , illustrated therein is a flowchart depicting a method 100 of synthesizing energetic core-shell particles. Method 100 comprises steps 102, 104, 106, 108 and 110. While steps are listed in order, in some embodiments, method steps may be performed in any order. [0057] At step 102, a metal powder is provided. In some examples, the metal powder may be aluminum metal powder. In some examples, the metal powder may comprise spherical particles. In some examples, the metal powder may comprise a mean particle diameter of 1 micron. In some examples, the metal powder may comprise a mean particle diameter of 40 nanometers. In some examples, the metal powder may comprise a mean particle diameter of up to 100 microns. In some examples, the metal powder may comprise a mean particle diameter up to 100 nanometers. In other examples, various sizes of metal powders may be used to match user defined criteria.

[0058] In other examples, metal powders of other metals may be used. These metal powders may include iron, titanium, zirconium, magnesium, zinc, lithium, silicon, boron, tin, tungsten, molybdenum or any other metal known in the art.

[0059] In some examples, metal powders may be sourced from Earth. In other examples, sources may include recycling space debris, satellites in orbit, or other materials transported from Earth to space. In other examples, metal powders may be sourced from space. Sources may also include in-situ resources utilization such as materials from the Moon (lunar regolith), Mars (martian regolith), and/or asteroid sources.

[0060] In some examples, metal powders may be sourced from waste outputs of industrial processes, or products of other combustion processes or waste disposal from human or robotic activity.

[0061] At step 104, the metal powder is dispersed in a first alcohol to form a first suspension. In some examples, this first alcohol may comprise ethanol. In other examples, the alcohol may be selected from the group comprising: methanol, ethanol, propanol, butanol, pentanol or combinations thereof.

[0062] In other examples, a liquid other than an alcohol may be used at step 104 to form the dispersion. For example, the metal powder may be dispersed in water instead of an alcohol, or any other liquid or fluid known in the art.

[0063] In some examples, the dispersion of step 104 may comprise stirring a mixture of the metal powder and the first alcohol or subjecting such a mixture to sonication. In some examples, the first suspension produced at step 104 may comprise 0.5 grams of aluminum, and 100mL of alcohol.

[0064] At step 106, the first suspension is contacted with an oxide precursor, aqueous ammonium hydroxide and a second alcohol, to produce a first product. In some examples, the first suspension may comprise 0.5 grams of aluminum, and 100mL of alcohol, and at step 106, 1g of Cu(NO3)2 2.5H2O (oxide precursor) may be added, 2mL aqueous ammonium hydroxide (NH4OH, 15%) may be added, and 10mL of a second alcohol may be added.

[0065] In some examples, other ratios of metal (e.g. aluminum) to oxide precursor (e.g. Cu(NO3)2 2.5H2O) may be applied at step 106, resulting in final energetic coreshell particles with varying equivalence ratios.

[0066] In some examples, the second alcohol may comprise ethanol. In other examples, the second alcohol may be selected from the group comprising: methanol, ethanol, propanol, butanol, pentanol or combinations thereof.

[0067] At step 106 of method 100, Cu(NO3)2-2.5H2O was used as the oxide precursor, in order to form Al-Cu metal-oxide core shell particles, comprising a copper oxide shell. In other examples, other oxide precursors may be added to form other Al-Cu metal-oxide core shell particles, or metal-oxide core shell particles of other metals and/or oxides. For example, oxide precursors may be selected to produce the following oxides for application to the synthesis of energetic core-shell particles: CuO, NiO, TiO2, WO3, MoOs, Fe2Os, KMnC , or any other oxide known in the art.

[0068] In some examples, metal oxides, or oxide precursors may be sourced from Earth. Such sources may include recycling space debris, satellites in orbit, or other materials transported from Earth to space. In other examples, metal oxides, or oxide precursors may be sourced from space. Such sources may include the Moon (lunar regolith), Mars (martian regolith), and or asteroid sources.

[0069] In some examples, metal oxides, or oxide precursors may be sourced from waste outputs of industrial processes, or products of other combustion processes or waste disposal from human or robotic activity. [0070] In examples comprising the production of Al-Cu metal-oxide, after the contacting process of step 106 of method 100, a shell comprising [Cu(NH4)]2+ and OH’ is formed on the exterior of the aluminum particles, through electrostatic force. These shell covered particles may be present in the solution as solid particles (product solids).

[0071] At step 108, the first product is filtered to collect product solids. The first product may comprise aluminum particles comprising a shell comprising [Cu(NH4)]2+ and OH’.

[0072] The filtration of step 108 may be performed with vacuum assisted filtration. In some examples, this vacuum assisted filtration may be conducted with Whattman™, grade 42 filter paper.

[0073] In other examples, methods other than filtration may be utilized at step 108 to separate product solids from solution. Such methods may include centrifugation, evaporation, or any other method known in the art for separating solids from liquids.

[0074] At step 110, product solids are inductively heated to produce energetic coreshell particles. Product solids may comprise aluminum particles with a shell comprising [Cu(NH4)]2+ and OH’ is formed on the exterior. During the inductive heating process of step 110, the shell comprising [Cu(NH4)]2+ and OH’ is oxidized and converted to CuO.

[0075] In some examples, the inductive heating process of step 110 may be performed in air. In such examples, gaseous oxygen within the air may comprise the oxygen source for the oxidation of the [Cu(NH4)]2+ and OH shell. In other examples, heating may be performed in any other oxygen containing atmosphere, or any other atmosphere.

[0076] The heating process of step 110 may be performed at or near 250°C, for a period of time of two hours.

[0077] The inductive heating process at step 110 advantageously allows for precise temperature control, which may produce core shell particles of a higher quality, versus non-inductive heating methods. In some examples, inductive heating may directly heat ferromagnetic particles (e.g. iron), which may result in a reduction of waste heat during the operation of method 100, as the heat may be more precisely directed. [0078] Referring to Figure 2, illustrated therein is a flowchart depicting a method 200 of synthesizing energetic core-shell particles. Method 200 may comprise any or all steps of method 100, and additionally comprises steps 202, 204, and 206. While steps are listed in order, in some embodiments, method steps may be performed in any order.

[0079] At step 202, the first product is stirred for a first period of time. In some examples, this first period of time may comprise 4 hours. The first product may be stirred in a flask, with a magnetic stir bar. In other examples, any other method known in the art may be used to stir the first product at step 202, for example, an integrated agitator or stirring attachment within a chemical reaction vessel or tank. Step 202 may be performed between steps 106 and 108.

[0080] At step 204, product solids are processed through a mesh sieve. In some examples, the mesh sieve comprises a 140-mesh sieve. Product solids may be pushed or forced through a single mesh sieve, or a series of mesh sieves, of specifically configured mesh sizes and parameters. In some examples, product solids may be placed onto a mesh sieve, and vibrated or shaken to urge the product solids which may pass through the sieve (e.g. with particle sizes smaller than mesh hole sizes) to pass.

[0081] Step 204 may be performed after the completion of step 108, wherein product solids are collected.

[0082] After the completion of methods 100 and/or 200, metal-oxide core shell particles are produced. The metal-oxide core shell particles comprise a core of metal, surrounded by a thin layer of oxidizing material, such as a metal oxide. In some examples, the metal-oxide core shell particles may comprise a core of metallic aluminum, and a thin layer of CuO (copper oxide). Such particles may be used for thermite reactions, including any applications of such reactions described herein.

[0083] Referring now to Figure 3, shown therein is a schematic 300 of the synthesis methods 100/200 of AI/CuO energetic core-shell particles. Al particles 302 are subjected to hydrolysis at step 1 , to form the [Cu(NH4)]2+ and OH shell 304, and subsequently, heat treated to oxidize the [Cu(NH4)]2+ and OH shell to CuO 306, as shown in Figure 3. [0084] Particles produced using the methods (e.g. methods 100 and 200) and/ or system described herein, were analyzed to measure ignition delays under laser induced ignition.

[0085] Particles comprising various equivalence ratios were investigated, using laser ignition. The samples used for laser ignition were prepared according to methods such as methods 100 and 200 described herein. The sample mass was approximately 3.5 mg and 1 .75 mg for microparticles and nanoparticles respectively. Samples were held in a loose condition. There were 3 samples for each equivalent ratio to reduce possible experimental error. All the results described herein are average values calculated from these three samples.

[0086] The experimental setup used for laser ignition and high-speed imaging analysis is shown in system 1000 of Figure 10. A diode laser 1002 (3.5W) with 100 ms pulse duration is utilized to ignite the sample 1004, together with a focusing lens 1006 to increase the power density of the laser from 225 W/cm2 to 40 kW/ cm2. The sample 1004 was be heated up from above. A photodiode 1008 with 1 ns response time was configured to send the signal to trigger a Phantom high-speed camera 1010 to record at 200,000 fps and 500 ns exposure time with extreme dynamic range (EDR). To capture high time resolution signals, two oscilloscopes are used to capture signals.

[0087] The ignition delay is measured from the difference of the photodiode signals of illumination and that of ignition. The first “jump” in the photodiode signal implies the starting of the laser illumination and the second one indicates the starting of the thermite reaction, which are shown in graph 1100 of Figure 11 . There is a linear portion between the point of laser illumination and that of thermite reaction initiation on the curve, which indicates the ignition delay. The time gap between the moment that laser hits the sample and the moment that the sample become brighter in associated high speed camera videos also corresponds to the ignition delay. These two measurement methods were compared to one another to confirm results. All results returned values that were comparable between these two methods.

[0088] The ignition delays for different samples were calculated and shown in Table 1 below:

[0089] Since the results are quite different for microparticles and nanoparticles, they are considered separately. As shown in the table above, as well as graph 1200 of Figure 12, the ignition delay increases with the increase in equivalent ratio for microparticles, while the ignition delay is shortest for the nanoparticle sample with equivalent ratio of 2. The ignition delays for microparticles with equivalence ratio of 1 , 3, 5 are 5.832ms, 7. 209ms and 9.065ms and that for nanoparticles with equivalence ratio of 1 , 2, 3 are 0.542ms, 0.325ms, and 1 .847ms. The ignition delays for nano-samples are about one magnitude lower than that for micro-samples, which indicates the smaller diffusion distance plays an important role during initiation stage.

[0090] In some examples of the systems and methods described herein, the equivalence ratio of synthesized energetic core-shell particles may be specifically configured to produce particles with specific ignition delays. Particles with differing ignition delays may be beneficial depending on the final application of the particles.

[0091] Referring now to Figure 4, shown therein is a system diagram of a system 400 for the synthesis of energetic core-shell particles, according to an embodiment. System 400 may be operated to conduct methods such as methods 100 or 200 described herein, or other methods for the synthesis of energetic core-shell particles. The system 400 comprises chamber 402, metal source 404, oxide precursor source 406, nozzle 408, inductive heating source 410. In some examples, system 400 may optionally further comprise any or all of: electromagnetic transmitter 418, electromagnetic receiver 424, auxiliary material source 412, capture storage system 414, control system 422, valves 420 and magnetic suspension system 426, as pictured in Figure 4.

[0092] Chamber 402 comprises a mechanical structure configured to receive synthesis reactants. Chamber 402 may comprise a tubular structure, constructed from stainless steel. In other examples, chamber 402 may comprise any other shape known in the art, and may be constructed from any material compatible with the synthesis process system 400 is applying.

[0093] Chamber 402 may further comprise features for stirring or agitating contents within chamber 402, such as magnetic stirring systems, sonication systems, and/or integrated agitators or combinations of thereof.

[0094] Metal source 404 comprises a supply of metal particles, for the production of energetic core-shell particles by system 400. Metal source 404 may provide any metal required for the desired core shell synthesis process into chamber 402. Metals provided by metal source 404 may vary in morphology, particle size, and other parameters, depending on process parameters. Metal source 404 may be configured to continuously, or discretely supply metals into chamber 402.

[0095] Oxide precursor source 406 comprises a supply of oxide precursor materials, for the production of energetic core-shell particles by system 400. Oxide precursor source may provide any oxide precursor materials required for the desired core shell synthesis process into chamber 402. Oxide precursor materials eventually form or contribute to the oxide shell layer. Oxide precursor materials may comprise oxides, such as copper oxides, or materials which may eventually convert to oxides, such as cupric nitrate, as applied by method 100 described herein. Oxide precursor source 406 may be configured to continuously, or discretely supply oxide precursors into chamber 402.

[0096] Nozzle 408 comprises a mechanical structure coupled to chamber 402, for the output of materials from chamber 402. Nozzle 408 may comprise a tapered profile, such that materials may be output from chamber 402 to a precise output location. Nozzle 408 may be constructed from any material which may be compatible with the materials that are to be conveyed by nozzle 408. In some examples, nozzle 408 may be constructed from stainless steel.

[0097] Inductive heating source 410 comprises a device which may inductively heat ferromagnetic materials. Inductive heating source 410 may be coupled to chamber 402, nozzle 408, or other structures of system 400, to heat synthesis reactants when required. Inductive heating source 410 may be precisely controlled, such that materials heated by inductive heating source 410 may be heated to precise and consistent temperatures. Such precise temperature control may be particularly advantageous in space environments, as it is difficult to remove excess heat (e.g. excess heat must be radiated away). The high precision of inductive heat may reduce the amount of excess heat produced.

[0098] Auxiliary material source 412, comprises a component analogous to the metal source 404 and oxide precursor source 406 components, wherein auxiliary material source 412 may provide additional materials into chamber 402 to facilitate mechanical, physical and chemical processes required to produce energetic core-shell particles. Auxiliary materials may include alcohols such as ethanol, other reactants such as ammonium hydroxide, carrier fluids, including air, inert gasses, water, and other fluids, or any other substance known in the art which may be introduced into chamber 402 to improve or facilitate energetic core-shell synthesis.

[0099] In some examples, photosensitive polymers or monomers may be introduced into chamber 402 by auxiliary material source 412, such that photopolymerization reactions may be initiated by the application of visible light or other radiation.

[0100] Capture storage system 414 comprises a system which may receive energetic core-shell particles produced by system 400, and package these particles for storage or further use. Particles may be stored in an inert gas, liquid, gels and wax or the like.

[0101] Capture storage system 414 may further comprise inductive heating elements 416, for the application of heat during storage processes and operations.

[0102] Electromagnetic transmitter 418 comprises a device which may emit electromagnetic radiation. Electromagnetic radiation emitted by transmitter 418 may comprise ultraviolet radiation, visible light radiation, x-ray radiation, infrared radiation, or any other wavelength of radiation required for the process applied by system 400.

[0103] Contents, products or reactants provided to system 400 may be sensitive to certain forms of electromagnetic radiation. The presence of electromagnetic transmitter 418 allows system 400 to expose these contents, products or reactants of system 400 to desirable electromagnetic radiation.

[0104] Electromagnetic receiver 424, comprises a device which may absorb electromagnetic radiation, and convert this electromagnetic radiation into electrical energy. Electromagnetic receiver 424 may be configured to be compatible with the form and wavelength of electromagnetic radiation emitted by electromagnetic transmitter 418. Electromagnetic receiver 424 may reduce energy wasted by system 400 by capturing stray electromagnetic radiation produced by electromagnetic transmitter 418, and recycling this captured radiation back into electricity.

[0105] While in system 400 electromagnetic receiver 424 and electromagnetic transmitter 418 are pictured outside of chamber 402, in other embodiments, electromagnetic receiver 424 and electromagnetic transmitter 418 may be positioned such that contents within chamber 402 may be exposed to electromagnetic radiation by electromagnetic transmitter 418 before exiting chamber 402.

[0106] Valves 420 are present between components of system 400, including between metal source 404 and chamber 402, oxide precursor source 406 and chamber 402, auxiliary material source 412 and chamber 402, and any other portions of system 400 wherein flows of materials may be preferably controlled. In some examples, an additional valve may be integrated into nozzle 408. Valves 420 may be any form of valve known in the art which may be compatible with the materials processed by system 400. Valves 420 may preferably be electronically, and/or computer controlled.

[0107] Electromagnetic suspension system 426 comprises a system configured to receive energetic core-shell particles output by system 400 through nozzle 408. Magnetic suspension system 426 may apply and alter a magnetic field using electromagnets to the electrically conductive and/or magnetic particles to magnetically levitate the particles in place, and move the particles to desired positions, and maintain particle dispersal through the application of electromagnetic suspensions and/or magnetohydrodynamics.

[0108] Magnetic suspension system 426 may be of particular utility in space applications of system 400, as alternative methods of conveying energetic core-shell particles may be rendered ineffective in microgravity environments. [0109] Control system 422 comprises a set of components, coupled to other components of system 400, such that process parameters may be adjusted, to improve yield, reduce waste, reduce energy usage, or change energetic core-shell particle parameters and/or properties. Control system 422 may be coupled to metal source 404, oxide precursor source 406, valves 420, nozzle 408, or any other components of system 400.

[0110] In some examples, control system 422, may apply artificial intelligence (Al) and/or machine learning (ML) methods in the control of system 400. Control system 422 may apply trained AI/ML models and algorithms (including but not limited to neural networks, deep learning or the like). Such models may correlate or receive a plurality of user driven inputs, including: oxide precursor type, metal type, auxiliary material types, flow rates, temperatures, frequency, gravity, mixing, viscosity, time, equivalence ratio, morphology, domain (e.g. land, air, water space, etc.), or other input parameters. Such models may correlate or generate the following outputs: particle shape, core content, shell content, distribution and energy characteristics or other outputs based on the user driven inputs.

[0111] In other examples, control system 422 may apply other optimization schemes and methods to optimize the operation of system 400.

[0112] In operation, metals, and oxide precursor materials may be introduced into chamber 402, from metal source 404 and oxide precursor source 406 respectively. Other materials may be introduced into chamber 402 by auxiliary material source 412. Contents within chamber 402 may react, forming intermediate products, or final core shell particles. In some examples, contents of chamber 402 may be heated within chamber 402, or as they exit nozzle 408, using inductive heating source 410. Particles may exit nozzle 410. After exiting nozzle 410, particles may be further exposed to electromagnetic radiation by electromagnetic transmitter 418, suspended magnetically by magnetic suspension system 428, and/or packaged or stored by capture storage system 414, for further use.

[0113] Referring now to Figure 5, pictured therein is a system 500 for the production of energetic core-shell particles, according to another embodiment. System 500 is analogous to system 400, with analogous component reference characters incremented by 100.

[0114] Nozzle 510 differs from nozzle 410, in that nozzle 510 comprises multiple outlets. The multiple outlets of nozzle 510 allow for the output of energetic core-shell particles from chamber 502 to multiple positions. This may allow for packaging of energetic core-shell particles into multiple separate packages, storage containers, or subsequent systems, machines or processes.

[0115] Referring now to Figure 6, pictured therein is a system 600 for the production of energetic core-shell particles, according to another embodiment. System 600 comprises a subsystem, including components of system 400, as well as gel packaging subsystem 602. Subsystem 602 comprises body 604, die rolls 606, gel ribbon 608, and waste gelatin 612.

[0116] Particles produced by system 400 as described above may be provided to body 604 of subsystem 602. Particles may be placed on gel ribbon 608 (comprised of gelatin), and passed through die rolls 606, to form gels 610. Gels 610 comprise energetic core-shell particles encapsulated into gel. System 600 may also produce waste gelatin 612 as a by product of operation.

[0117] In other examples, substances other than gelatin may be used within gel ribbon 608, such as, without limitation, wax, or gelatin infused with other energetic particles, such as other energetic core-shell particles.

[0118] The production of gels 610 may advantageously store particles in a non- reactive form, and may in some configurations improve combustion characteristics of the energetic core-shell particles, by increasing spacing between particles within the gel 610.

[0119] Referring now to Figure 7, pictured therein is a system 700 for the production of thermite mixtures (nano- and/or micro-thermite), according to an embodiment. System 700 comprises metal source 704, metal oxide source 706, mixing chamber 702, heating chamber 708 and desiccator 710.

[0120] System 700 may be applied to mechanical mixing methods of thermite mixture production. Reactants are provided from metal oxide source 706 and metal source 704, into mixing chamber 702. Metal oxides and metals may be mixed (e.g. through sonication) in chamber 702. In some examples, a solvent such as ethanol may be introduced into chamber 702 to promote mixing. In some examples, magnetic stirring systems, sonication systems, and/or integrated agitators or combinations of thereof may be integrated into system 700.

[0121] Once mixed, contents of chamber 702 may be provided to heating chamber 708. Heating chamber 708 may apply inductive heating to heat either chamber 708 walls, or chamber 708 contents directly (e.g. if contents are ferromagnetic). Heating of chamber 708 may urge the evaporation of solvents provided into chamber 702. Inductive heating may result in greater temperature precision and control, and/or decreased energy use, versus other heating methods.

[0122] Contents may be transferred from heating chamber 708 to desiccator 710, to desiccate contents. Contents may be desiccated under vacuum, with the assistance of induction heating. Inductive heating may result in greater temperature precision and control, and/or decreased energy use, versus other heating methods.

[0123] Referring now to Figure 8, pictured therein is a system 800 for the production of energetic core-shell particles, according to an embodiment. System 800 comprises metal source 804, metal oxide source 806, mixing chamber 802, inductive heating chamber 808 and desiccator 810.

[0124] System 800 may apply a precipitation method of energetic core-shell particle synthesis. The precipitation method forms a copper complex on top of Al particles. The copper complex is further converted to CuO by annealing. Since the copper complex might also precipitate in the solution, the final AI/CuO thermite will be a mixture of CuO and AI/CuO core/shell particles.

[0125] Metal and metal oxide, Al, and CuO, are sourced from metal source 804, and metal oxide source 806 respectively, and provided to mixing chamber 802. Al, and CuO, are mixed and dispersed in ethanol and sonicated within chamber 802. Then, ammonium hydroxide solution, and copper nitrate hemi(pentahydrate) ethanol solution are added into the suspension of chamber 802. After stirring the contents within chamber 802, a copper complex is formed on the surface of the aluminum particles. This suspension is filtered and then dried in desiccator 810. Finally, the dried particles are annealed using inductive hearing chamber 808, converting the copper complex layer into copper oxide, forming aluminum, copper oxide core shell particles.

[0126] The application of inductive heating by chamber 808 may result in greater temperature precision and control, and/or decreased energy use, versus other heating methods.

[0127] Referring now to Figure 9, pictured therein is a system 900 for the production of energetic core-shell particles, according to an embodiment. System 900 comprises metal source 904, metal oxide source 906, mixing chamber 902, inductive heating chamber 908 and solution source 910.

[0128] System 900 may apply a displacement method of energetic core-shell particle synthesis. The displacement method galvanically displaces copper by aluminum, forming aluminum/copper core shell particles. Then, copper is further annealed to form copper oxide, forming energetic core-shell particles.

[0129] In operation of system 900, a CuSO4-based stock solution is prepared by dissolving CuSO4, Ethylenediaminetetraacetic acid and Triethanolamine in de-ionized water. This solution is provided from metal oxide source 906, into chamber 902. Then, NH4OH aqueous solution is added from solution source 910 into the CuSO4 solution within chamber 902, in a dropwise fashion. Next, aluminum particles are added from metal source 904 into the solution of chamber 902 and sonicated within chamber 902 to form a well-dispersed suspension. The solution is filtered and washed using alcohol, and then dried in a vacuum desiccator. Then the particles are annealed in inductive heating chamber 908 under ventilation to form energetic core-shell particles.

[0130] The application of inductive heating by chamber 908 may result in greater temperature precision and control, and/or decreased energy use, versus other heating methods.

[0131] Referring now to Figure 13, pictured therein is a laser focused assisted ignitor system 1300, according to an embodiment. System 1300 may be applied to clean up space debris 1302 and space junk in orbit. A plurality of satellites 1304 comprising system 1300 can be launched to low earth orbit to help clean up space debris. System 1300 may apply a laser assisted ignition system and energetic particles, such as the metal oxide core shell particles synthesized by the methods described herein. Ignition may be initiated by a laser and/or induction ignition system.

[0132] Referring now to Figure 14, pictured therein is a detachable tethered plate system 1400, according to an embodiment. System 1400 may be applied to tether objects 1402 in space to a spacecraft 1404. System 1400 may further comprise elements for mechanical functions such as mechanical connections, tracks, and joints, or the like.

[0133] System 1400 may be used for operations, logistics, maintenance, transportation from point to point, and/or orbit raising. In other implementations, the deployable plate is detachable, on board the tethered satellite subsystem, which can be released to be attached to a free flying object in space. The satellite system, acting as part of a network of satellites, with situation awareness may best position itself relative to a target object, and may use AI/ML algorithms and/or autonomous systems for docking. The tethered satellite subsystem may be outfitted with its own propulsion system for thrust. The deployable plates can be attached to the tethered satellite subsystem, which can attach itself to a plurality of surfaces on the target object, for example, to capture space debris. Using a laser-assisted ignition system, the deployable plates, via welding and/or sintering of filler, and/or energetic particles, can attach to a surface. Using the tethered system, the satellite system can reel back into place with the tethered satellite subsystem and provide the target object with propulsion for orbit raising, continued in space services, and/or de-orbiting applications. A plurality of space debris may be linked using the deployable plates to link objects in space to be collected and gathered for recycling and/or reuse.

[0134] In other implementations, the deployable plates and/or tethered satellite system, and/or satellite system may can be attached to satellites in orbit and transport for orbit raising or de-orbiting, maintenance by astronauts and/or robotic systems. In other implementations, detachable plates used for catch and release maneuvers, can have a plurality of mechanical connections such as hooks and rods, which can be linearly actuated, to attach and detach from the target object. [0135] Referring now to Figure 15, pictured therein is a laser assist release system 1500, according to an embodiment. System 1500 may be present be on a satellite to rendezvous and dock in an object in space. In some embodiments, system 1500 may be onboard a refueling satellite system, which captures, refuels the satellite and releases it for continuous operation. System 1500 can be attached to satellites in orbit and transport for orbit raising or de-orbiting, or maintenance by astronauts and/or robotic systems.

[0136] Referring now to Figure 16, pictured therein are additional components of laser assist release system 1500 of Figure 15, according to an embodiment. As seen in Figure 16, detachable disposable weld plates 1502 are present for catch and release maneuvers. Additionally, a rod 1504 may be linearly actuated and release hooks to detach from target, as pictured in Figure 16.

[0137] Referring now to Figure 17, pictured therein is a multi-satellite operations system 1600, according to an embodiment. System 1600 may comprise satellites 1602, which may be coupled to other satellites, or to one another. In some examples, a mothership with multiple small engines may connect to other satellites for logistics and maintenance operations.

[0138] Referring now to Figure 18, pictured therein are additional components of multi-satellite operations system 1600 of Figure 17, according to an embodiment. Additional satellites 1602 are present in Figure 18. Satellites 1602 may ignite energetic particles on ground, air, water or in space using laser sources.

[0139] In some examples, the systems and methods described herein may be modified to produce energetic core-shell particles with different properties, such as different core shell structures. Such core shell structures may include core-shell, multicore shell, multi-core hollow structure, yolk shell, multi-core hollow, core mesopores, sandwiched core shell, and embedded structures. In other examples, core shell structures or arrangements may include core-shell, double shell, multi-shell, concentration gradient, and full concentration gradient.

[0140] Thermite mixtures, including micro thermites, nano thermites, nano energetic core-shell particles, and micro energetic core-shell particles, such as those described, and synthesized by the methods and systems herein, may be applied to a number of uses requiring high density stored energy, high intensity energy, low carbon emission energy or combustion sources, remote operations (including earth orbit and outer space), and other requirements.

[0141] In some examples, a metal may be combined with an oxidizer, for example, air and/or water. The oxidizer may be used as the carrier, and as the source of oxidation of the metal. In other examples the fuel and oxidizer, in the form of a thermite, may both be located in the same metallic particle (for example a metal oxide coat on the outside of a metal particle). In some examples, these particles may be referred to as metallic fuels (such as metal, metallic, and/or energetic particles, thermites and/or micro, and/or nanothermites, or the like).

[0142] Metallic materials may contain energetic particles which are made up of a fuel and an oxidizer-typically a metal and a metal oxide, respectively. Nano thermites are composed of both the oxidizer and fuel within each particle, and are on the scale of 100 nanometers or below. The energy release per mass of particle is very large. In an example, using metallic fuel propellant including nano thermites or micro thermites, or a combination thereof, may be combined with an inert carrier gas and or liquid or fluid to disperse the propellant within a chamber for effective heating and/or combustion, leading to well-controlled heating, construction, power and thrust generation.

[0143] Metallic materials and or fuels (e.g., thermites, micro thermites, nano thermites) have high energy density, and when mixed with an inert gas, liquid and/or carrier fluid, are generally safer to handle and transport than conventional fuels. They may be synthesized and manufactured, and transported to be used and/or stored for future use. Propellants may be produced, stored and transported for dispatchable power. Stored energy may be in the form of materials. Fuels may be used to generate heat, for construction, power and propulsion applications.

[0144] In some examples, energetic core-shell particles may be used as sources for catalytic conversion of carbon dioxide (e.g. atmospheric carbon dioxide), such as thermocatalysis, photocatalysis and electrocatalysis processes for conversion of carbon dioxide to produce products such as CO, H2, Ch3OH, C2, and or CH, or other desired products derived from CO2 conversion processes. In some examples, energetic core- shell particles may be used as sources for catalytic conversion of methane. In other examples, energetic core-shell particles may be used as sources for catalytic conversion of other greenhouse gases.

[0145] In some examples, nano thermites may be used for propulsion, power generation, energy storage, and energy distribution. In some examples, nano thermites may be used for construction, including welding, additive manufacturing, and 3D printing, such as the inclusion core shells into materials for 3D printing to create 3D printable materials with user defined properties. In some examples, nano thermites may be used as battery cathodes. In some examples, nano thermites may be used as filters, such as mesh filters, comprising specific geometry which may specifically target certain particles, such that these certain particles may not pass through the filter, or vice versa.

[0146] In some examples, nano thermites may be applied to ignitor systems, wherein nano thermites are heated with a laser or induction heating system to initiate the ignition of another substance. Such an ignitor may be more portable and appropriately disposable than other ignitor systems.

[0147] In some examples, a spacecraft may synthesize energetic particles which may be applied to ignitor systems, wherein energetic particles are heated with a laser or induction heating system to initiate the ignition of another substance. The spacecraft may rendezvous and attach to an uncontrolled object in space such as a space junk, space debris, satellites at the end of their life-cycle, satellites that have ran out of fuel, second stages, asteroids or other space objects to provide motility and/or additional propulsion capabilities.

[0148] In some examples, a spacecraft may transport a plurality of other spacecrafts for operations, logistics, maintenance, transportation from point to and or orbit raising.

[0149] In some examples, a plurality of satellites can be launched and deployed in low earth orbit to help clean up space debris and space traffic management using a laser assisted ignition system and energetic particles. Assistance in ignition can be provided with a laser and/or induction heating system. A subsystem satellite with a deployable plate comprising a first layer of weld filler and/or energetic particles, and/or a second layer with energetic particles, may be used to serve as a catalyst which may be ignited using a laser and/or induction heating assisted ignition. The deployable plate can be ignited at a distance using a plurality of other satellites at different orbits. In other implementations, the ignition may occur from a plurality of fixed and mobile sources on the ground, in the air (e.g. from drones and/or airships), on water, and/or in space.

[0150] In an implementation, to capture and release an uncontrollable space object, including but not limited to space debris, satellites with no propulsion system, may capture second stages or other space objects larger than 10 cm, or asteroids, enabling the uncontrollable space object to be equipped with a new propulsion system and/or be refueled or undergo in-orbit servicing.

[0151] In other implementations, energetic particles may be used in conjunction with a plurality of shaping methods including but not limited to microemulsion, wetspinning, roll-to-roll casting, spin-coating, and or molding. In some implementations, shapes such microspheres, fibers, sheets, coatings, complex shapes, layered shapes, and/or monoliths can be created.

[0152] In other implementations, energetic core-shells may be used in addition to molecular precursor, nanoparticles, nanofibers, nanotubes, nanosheets or the like. In some examples, microstructures may be added, such as particle chains, fibrous structures and/or stacked flake structures.

[0153] In other implementation, the satellite system may carry a plurality of other satellites for in-space applications and services. In some implementations, the satellite subsystem may be onboard a refueling satellite system, which may capture, and refuel other satellites in space for servicing, and release these satellites for continuous operation or services beyond Low Earth Orbit.

[0154] In some examples, energetic core-shell particles may embedded into the structure of systems, under a reaction, and/or sintering and hardening process.

[0155] In some examples, energetic core-shell particles may be reacted in gas, for the application of propulsion, by heating and expanding this gas, generating thrust. [0156] In some examples, energetic core-shell particles may be applied to space based applications, such as space manufacturing, for products such as synthesizing compounds and mixtures that benefit from the microgravity environment and result in an improved conditions such as production of materials related to pharmaceutical drugs and/or other medical applications.

[0157] In some examples, energetic core-shell particles may be applied to drive reactions on Earth and or in Space.

[0158] In some examples, energetic core-shell particles may be applied to refueling of satellites in space. In some examples, magnetic fuels can be added to materials to make them more magnetic and enable mobile particles in varied gravity, particles can be moved within a system using magnetohydrodynamics. Magnetic properties of the fuel may be used to replenish systems in space.

[0159] While the above description provides examples of one or more apparatus, methods, or systems, it will be appreciated that other apparatus, methods, or systems may be within the scope of the claims as interpreted by one of skill in the art.

Claims

- 26 - Claims:

1. A system for the synthesis of energetic core-shell particles, the system comprising: a chamber for conducting particle synthesis reactions; an oxide source coupled to the chamber, for supplying the chamber with an oxide precursor; a metal source coupled to the chamber, for supplying the chamber with a metal; a nozzle, coupled to the chamber, for outputting synthesized energetic core-shell particles from the chamber; and an inductive heating source, coupled to the chamber, for inductively heating chamber contents to synthesize energetic core-shell particles.

2. The system of claim 1 , the system further comprising an auxiliary material source, coupled to the chamber, for supplying the chamber with auxiliary materials.

3. The system of claim 2, wherein auxiliary materials for supply to the chamber comprise a fluid.

4. The system of any one of claims 1 to 3, the system further comprising a capture storage system coupled to the nozzle, and configured to receive energetic coreshell particles from the nozzle, the capture storage system further configured to package energetic core-shell particles into a storage container.

5. The system of claim 4, wherein the capture storage system comprises an inductive heating element, for heating stored energetic core-shell particles.

6. The system of any one of claims 1 to 5, the system further comprising an electromagnetic suspension subsystem, the electromagnetic suspension subsystem configured to suspend energetic core-shell particles outputted by the nozzle. The system of any one of claims 1 to 6, the system further comprising a gel packaging subsystem coupled to the nozzle, the gel packaging subsystem configured to receive core shell particles from the nozzle, and encapsulate core shell particles into a gel capsule. The system of any one of claims 1 to 7, wherein the nozzle comprises multiple sub-nozzles. The system of any one of claims 1 to 8, the system further comprising an electromagnetic transmitter, for exposing contents of the chamber to electromagnetic radiation. The system of any one of claims 1 to 8, the system further comprising an electromagnetic transmitter, for exposing energetic core-shell particles to electromagnetic radiation. The system of claim 9 or 10, the system further comprising an electromagnetic receiver, for receiving electromagnetic radiation emitted by the electromagnetic transmitter, to recover energy. The system of any one of claims 1 to 11 , the system further comprising a control system configured to adjust operation parameters of the system. The system of claim 12, wherein the control system is configured to apply a trained machine learning model to adjust operation parameters of the system. A method of synthesis of energetic particles, the method comprising: providing a metal powder; dispersing the metal powder in a first fluid to form a first suspension; contacting the first suspension with an oxide precursor, aqueous ammonium hydroxide and a second alcohol, to produce a first product; collecting product solids; and inductively heating product solids to produce energetic core-shell particles. The method of claim 14, further comprising stirring the first productfor a first period of time. The method of claim 14 or 15, further comprising griding product solids before inductively heating product solids. The method of any one of claims 14 to 16, further comprising processing product solids through a mesh sieve before inductively heating product solids. The method of any one of claims 14 to 17, wherein the metal powder is aluminum powder. The method of any one of claims 14 to 18, wherein the oxide precursor is cupric nitrate. The method of any one of claims 14 to 19, wherein the first fluid is an alcohol. The method of any one of claims 14 to 20, wherein the second fluid is an alcohol. The method of any one of claims 14 to 21 , wherein the product solids are inductively heated to 250C. The method of any one of claims 14 to 22, wherein the metal powder comprises a mean particle size of 1 micron. - 29 - The method of any one of claims 14 to 22, wherein the metal powder comprises a mean particle size of 40 nanometers. The method of any one of claims 14 to 24, wherein product solids are collected through filtration. The method of any one of claims 14 to 25, wherein the metal powder is iron powder. The method of any one of claims 14 to 26, wherein the ratio of metal power to oxide precursor is configured such that the method produces energetic core-shell particles with a specific equivalence ratio, such that when the energetic core-shell particles are combusted, the combustion comprises a predetermined ignition delay. The method of any one of claims 14 to 27, wherein inductively heating product solids to produce energetic core-shell particles comprises improving energetic core-shell particles.