Patent ID: 12252452

DETAILED DESCRIPTION OF THE INVENTION

In one aspect of the disclosure, a coated fuel particle is provided, which may comprise a metal or metal alloy. Such a metal or metal alloy fuel may comprise a lithium aluminum (Li—Al) alloy, a lithium-silicon (Li—Si) alloy, or one or more of the myriad types of metal fuels and energetic materials. A Li—Al or Li—Si alloy is coated with one or more of a metal, metalloid or non-metal in the form of a zero-valent element, and/or in the form of an oxide, a nitride, a carbide, a halide, or a phosphate is provided; each coating may be a composite comprising one, two or more cations and/or one, two or more anions. Non-limiting examples of such include composite coatings that comprise silicon oxide and aluminum oxide, aluminum oxide and silicon nitride, silicon oxide and aluminum nitride, silicon oxide and aluminum phosphate. Such a coating may be applied using a solid state, liquid state or vapor state process. Examples of solid state processes include mixing and cladding. Examples of liquid state processes include chemical bath deposition, sol-gel, electrodeposition and similar. Examples of vapor deposition techniques can include molecular layering (ML), chemical vapor deposition (CVD), physical vapor deposition (PVD), atomic layer deposition (ALD), molecular layer deposition (MLD), vapor phase epitaxy (VPE), atomic layer chemical vapor deposition (ALCVD), ion implantation or similar techniques. In each of these, coatings are formed by exposing the powder to reactive precursors, which react either in the vapor phase (in the case of CVD, for example) or at the surface of the powder particles (as in ALD and MLD).

It has been discovered that additional processing steps are required to adequately apply vapor-phase coatings onto energetic materials comprising Alkali and Alkaline Earth metals (Groups I and II of the periodic table) due to unexpected interactions between the substrate surfaces and the precursor molecules. In the CVD or ALD process, suitable precursors to deposit an aluminum cation may include one or more of aluminum sec-butoxide, aluminum tribromide, aluminum trichloride, diethylaluminum ethoxide, dimethylaluminum isopropoxide, tris(ethylmethylamido)aluminum, tris(dimethylamido)aluminum, triethylaluminum, triisobutylaluminum, trimethylaluminum, tris(diethylamido)aluminum, or tris(ethylmethyl-amido)aluminum. These can be coupled simultaneously or sequentially with other anion-forming precursors to produce compounds described above, or a reducing precursor to produce a coating at least partially comprising a zero-valent form of an element. For example, trimethylaluminum and water, hydrogen peroxide, ozone or oxygen plasma may be used to deposit aluminum oxide, Al2O3; tris(diethylamido)aluminum and anhydrous ammonia may be used to deposit AlN coatings; an aluminum-comprising precursor may be paired simultaneously or sequentially with phosphine, tert-butylphosphine, tris(trimethylsilyl)phosphine, phosphorous oxychloride, triethylphosphate, trimethylphosphate to form an aluminum phosphate coating. Alternatively or in addition to, a cation-containing precursor may be paired with a multi-functional organic precursor such as ethylene glycol, ethanolamine, ethylene diamine, glycerol, glycidol or similar, to form an aluminum cation and an anion comprising carbon. However, the inventors have discovered that challenges arise when applying ALD coatings to Group I and II elements (and compounds comprising said elements), due to their ease of mobility, diffusivity, reactivity or other attribute that creates a diffusion layer interface between the substrate and coating, which is not predicted by classical ALD theory.FIG.2shows such an example in a transmission electron microscope image of a coated metal fuel particle having a distinct coating on the outside of the particle.

One or more of aluminum, silicon, boron, hafnium, tin, iron, magnesium, titanium, zirconium or beryllium are sometimes preferred coating cations over other cation materials. In some embodiments, aluminum and/or silicon are preferred, and within these, aluminum may be more beneficial when interfaced directly with the particle surface. In most embodiments, a metal fuel material is at least partially coated with a protective coating, wherein the metal fuel material is in the form of a powder comprised of a plurality of particles. A coating may comprise one or more elements in a zero-valent state, and/or one or more cations paired with one or more anions in various preferential compositions and ratios. As depicted inFIG.3, a coated metal fuel particle comprises at least a metal fuel particle, a coating, and optionally a diffusion layer, where the composition and thickness of the diffusion layer and coating layers are controllable based upon the selected process conditions. As further depicted inFIG.3, a coated metal fuel particle comprises at least a metal fuel particle10, a coating50, which is applied to the original interface position30of the coating layer prior to any diffusion. During or after the coating process, interface position30may disappear, forming an optional diffusion layer may optionally further comprise a first interdiffusion layer20, and/or a second interdiffusion layer40. First interdiffusion layer20represents inward diffusion of the coating material penetrating into the substrate particle dimension; second interdiffusion layer40represents outward diffusion of the substrate composition into the coating material thickness dimension. In the simplest case, a coating50does not have an interaction with the metal fuel particle10, such that interface30is ˜0.1 to 1.0 nanometers in thickness, and interdiffusion layers20and40are not present, and typically the thickness of 30 is independent of the thickness of coating50. Though this case is challenging to achieve with metal fuel particles that comprise lithium, silicon and/or aluminum, precise coating processes such as ALD can effectively achieve such a coated metal fuel particle if desirable. As described herein, a metal fuel particle10, a coating50and at least one interdiffusion layer may provide benefits including mechanical stability and environmental robustness during post processing steps. When at least one interdiffusion layer is present, it may be challenging to identify and/or isolate an interface30between 10 and 50. Preferential processes will apply a coating50of 1 nanometer to 500 nanometers in thickness, and form a diffusion layer having a total thickness (20+40) of 0.1 to 33% of the coating thickness. Preferential diffusion layers will have a thickness of 20 greater than a thickness of 40, where the thickness of the first interdiffusion layer20is at least 10%, preferably 25%, oftentimes 50%, and sometimes 100% greater than the thickness of the second interdiffusion layer40.

In some embodiments, coating50is in an amorphous or glassy phase. Such coatings may provide superior stability against reactivity with moisture, air or other environmental constituent. Coating50may increase the shelf-life of a metal fuel particle by 10, 20, 50 or 100%, and/or prevent the premature ignition of the metal fuel in a solid-rocket propellant. Silicate and aluminate materials are preferred for enhancing moisture stability of metal fuel particles. In some embodiments, coating50comprises at least 80% silicate and has a thickness of 2 to 20 nanometers. In other embodiments, coating50comprises at least 80% aluminate and has a thickness of 2 to 20 nanometers. Coating50may comprise an oxide, nitride, halide or phosphate of a metal, metalloid or non-metal, and optionally form a first interdiffusion layer20that comprises 60-90% lithium or aluminum, a second interdiffusion layer40that comprises 10-40% lithium or aluminum, or both.

In some embodiments, a coated metal fuel particle comprises a Li—Al or Li—Si alloy having an average particle size of 10 to 100 microns, a first coating of an aluminum oxide layer of 0.1 to 5.0 nanometers in thickness using an ALD process, and a second coating of a silicon oxide layer of 0.1 to 5.0 nanometers in thickness using an ALD process. Under certain conditions, a first interdiffusion layer and a second interdiffusion layer may each comprise LiaAlbSicOd. Preferred ranges for a first interdiffusion layer include: 0.1<a<0.2, 0.6<b<0.9, 0<c<0.1, and 0.01<d<0.2; Preferred ranges for a second interdiffusion layer include: 0<a<0.05, 0.2<b<0.8, 0.01<c<0.3, and 0.2<d<0.6.

In preferred embodiments, a coated metal fuel particle comprises a Li—Al or Li—Si alloy having an average particle size of 10 to 100 microns, and at least one coating comprising a metal, metalloid or non-metal cation X, and an anion Y selected from O, N, C, F, Cl, Br, I and P or combinations thereof, and wherein X is selected from the group Ac, Ag, Al, Am, As, At, Au, B, Ba, Be, Bh, Bi, Bk, Ca, Cd, Ce, Cf, Cm, Cn, Co, Cr, Cs, Cu, Db, Ds, Dy, Er, Es, Eu, Fe, Fm, Fr, Ga, Gd, Ge, Hf, Hg, Ho, Hs, In, K, La, Li, Lr, Lu, Lv, Mc, Md, Mg, Mn, Mo, Mt, Na, Nb, Nd, Nh, Ni, No, Np Og, Os, P, Pa, Pb, Pd, Pm, Po, Pr, Pt, Pu, Ra, Rb, Re, Rf, Rg, Rh, Ru, S, Sb, Sc, Se, Sg, Si, Sm, Sn, Sr, Ta, Tb, Tc, Te, Th, Ti, TI, Tm, Ts, U, V, W, Y, Yb, Zn, Zr, or combinations thereof, and XY is applied using an Atomic Layer Deposition process. The resulting composition is an Li—Al alloy particle having the form LiaAlbXcYdwhere a+b+c+d=1, 0.12<a<0.3, 0.7<b<0.88, c=0 and d=0; an interdiffusion layer having the form LiaAlbXcYdwhere a+b+c+d=1, 0.02<a<0.2, 0.1<b<0.6, 0.1<c<0.4, and 0.1<d<0.6; and a coating layer LiaAlbXcYd. where a+b+c+d=1, a=0, b=0, 0.2<c<1, and 0<d<0.86.

Yet in other embodiments, the thin film of reliability-improving material does not significantly affect the sintering of said particles. As used herein, the term “sintering” refers to atomistic diffusion between nanoparticle and the thin film or atomistic diffusion between particles. Also as used herein, the term “does not significantly affect the sintering of said particles” means the amount of sintering or the sintering temperature in the presence of the thin film coating is substantially similar to the amount of sintering or the sintering temperature of the same particles in the absence of a thin film coating. Generally, the amount of particle sintering in the presence of the thin film coating is no more than 15%, typically no more than 10%, and often no more than 5% different compared to the amount of particle sintering in the absence of the thin film coating. Alternatively, the sintering temperature in the presence of the thin film coating is within 50° C., typically within 30° C., and often within 20° C. of the particle sintering temperature in the absence of the thin film coating.

Still in other embodiments, the thin film of reliability-improving material comprises a thin film of wide bandgap material. As used herein, the term “wide bandgap material” refers to materials with electronic band gaps significantly larger than 1.5 electron volt (eV), typically larger than 3.0 eV, and often larger than 5.0 eV. In some instances, the wide bandgap material comprises a material selected from the group consisting of aluminum oxide, hafnium oxide, zirconium oxide, tantalum oxide, niobium oxide, lithium oxide, silicon oxide, calcium oxide, magnesium oxide, boron oxide, aluminum phosphate, titanium phosphate, lithium phosphate, calcium phosphate, aluminum nitride, gallium nitride, boron nitride, boron carbide, and a combination thereof. Still in other instances, the thickness of the thin film coating of wide bandgap material is 8 nm or less, typically 5.5 nm or less, and often 3.5 nm or less.

In other embodiments, the thin film of reliability-improving material comprises a thin film of semiconducting or conducting material. Exemplary semiconducting materials that are suitable for the present invention include, but are not limited to, zinc oxide, titanium oxide, cerium oxide, vanadium oxide, barium oxide, bismuth oxide, ruthenium oxide, indium oxide, tin oxide, lanthanum oxide, titanium nitride, tantalum nitride, silicon carbide, and ternary or quaternary combinations that include these and other analogous materials. Exemplary conducting materials that are useful in the present invention include, but are not limited to, metals (such as platinum, silver, gold, titanium, copper, zinc, chromium, nickel, iron, molybdenum, tungsten, ruthenium, palladium, indium, and tin), alloys or intermetallics (such as PtNi, FeCrAlY, AgPd, nichrome, and other conductive steels) and other electric conducting materials such as those containing carbons (such as graphite, graphene, diamond and diamond like carbon, and PEDOT and other conductive polymers). Such a thin film of controlled conductivity can provide a critical range in which a triggering event may be designed to occur, improving the metrics around the energy release. It was unexpected at the time of discovery that adjacent layers of functionally-graded materials designed around successive triggered release metrics could be used as a delayed-release mechanism, providing enhanced operational use time.

In one particular embodiment, the resistivity of said thin film of reliability-improving material is 50,000 μΩ-cm or less, typically 5,000 μΩ-cm or less, and often 500 μΩ-cm or less.

Yet in other embodiments, the thin film of reliability-improving material comprises a dopant material. Exemplary dopant materials that are useful in the invention include, but are not limited to, +5 valence materials into +4 valence materials (such as tantalum oxide doped into titanium oxide), +3 valence materials into +2 valence materials (such as aluminum oxide doped into zinc oxide), and commonly known doped transparent conductive oxides (such as fluorine-doped tin oxide). Typically, the dopant material increases the conductivity of the thin film of reliability-improving material by at least 20%, often by at least 50% and most often by at least 100%.

Still in other embodiments, a thermal oxidation onset temperature of the particles with the thin film coating is at least 10° C., typically at least 25° C., and often at least 100° C. higher than the same nanoparticles in the absence of said thin film of oxidation-resistant material.

Yet still in other embodiments, the average particle size of said particles is 1,000 nm or less, typically 800 nm or less, and often 500 nm or less. In many embodiments, larger particles are mixed with smaller particles as a means of increasing the overall tap density of the energetic materials, forming a bi-modal or multi-modal particle size distribution. In such embodiments, the thickness of the coating solution may be inversely proportional to the average diameter of the particles. In other embodiments, coated materials may be blended with uncoated materials. In certain embodiments, the output of the initiation event at the surface of uncoated materials (or materials having a different particle size) serves as the initiation event at the surface of another group of particles in the same device or system.

In many embodiments, the coating material compound comprises one or more of a: (i) metal oxide; (ii) metal halide; (iii) metal oxyflouride; (iv) metal phosphate; (v) metal sulfate; (vi) non-metal oxide, (vii) olivines, (viii) NaSICON structures, (ix) perovskite structures, (x) spinel structures, (xi) polymetallic ionic structures, (xii) metal organic structures or complexes, (xiii) polymetallic organic structures or complexes, (xiv) structures with periodic properties, (xv) functional groups that are randomly distributed, (xvi) functional groups that are periodically distributed, (xvii) functional groups that are checkered microstructure, (xviii) 2D periodic arrangements, and (ixx) 3D periodic arrangements;

Another aspect of the invention provides a device or component comprising a plurality of highly-energetic particles that are coated with a thin film of a reliability-improving material. Exemplary materials that are useful in the present invention include nanoparticles coated by materials including, but are not limited to, barium titanate, strontium titanate, barium strontium titanate, barium niobate, strontium niobate, barium strontium niobate, sodium niobate, potassium niobate, sodium potassium niobate, titania, zirconia, lead zirconate, lead zirconate titanate, calcium copper titanate, bismuth scandium oxide, bismuth zinc oxide, bismuth titanate, bismuth zinc titanate, zinc oxide, and zinc titanate. In some embodiments, the reliability-improving material comprises SiO2, ZrO2, B2O3, Bi2O3, Li2O, or a mixture thereof.

Still in other embodiment, the thin film coating reduces the densification onset temperature of said particles, or is a promoter of a particular interdiffusion layer composition and/or thickness that is preferentially constructed between the substrate and the coating as a result of a controlled interaction process. As used herein, the term “densification” means atomistic diffusion between or within the thin films, and/or interactions with additional densification aids (such as binders, glass or glass-forming powders) present in the system, as relevant. Also as used herein, the “densification onset temperature” means the temperature at which nanoparticles coated with thin films begin to densify and reduce the void space present between a plurality of said nanoparticles. The densification temperature of nanoparticles in the absence of a thin film coating is the same as the sintering temperature of the nanoparticles. For an energetic material, this densification may occur prior to constructing the device, or may be triggered to occur as a feature of the device itself. Alternatively, the thin film coating may serve as a solid precursor to liquid phase sintering of the nanoparticles, at temperatures substantially lower than the traditional sintering temperature of said nanoparticles. In general, the densification temperature of the nanoparticles is at least 25° C. lower, typically by at least 50° C. lower, and often by at least 100° C. lower than the sintering temperature of the same nanoparticles in the absence of the thin film coating.

In one particular embodiment, said particles comprise a lithium-containing metal or metal alloy fuel and said reliability-improving material comprises an oxide of a metal comprising bismuth, zinc, titanium, scandium, or a mixture thereof. In some instances within this embodiment, said reliability-improving material comprises zinc titanium oxide, bismuth zinc titanium oxide or bismuth scandium oxide.

In another embodiment, said particles comprise hydrogen and/or lithium, and said reliability-improving material comprises an oxide, nitride or phosphate of a metal selected from the group consisting of tantalum, sodium, potassium, or a mixture thereof. In some instances within this embodiment, said reliability-improving material comprises an alkali tantalate.

Yet in another particular embodiment, said reliability-improving material increases the mean time to initiation by at least 10% relative to the same device or component in the absence of said thin film of reliability-improving material.

Still in another particular embodiment, said thin film of reliability-improving material reduces the average grain size of sintered or aggregated particles by at least 20 nm, typically by at least 50 nm, and often by at least 100 nm when combined into dense parts.

A thin film coating present on the particles of the invention may reduce or prevent agglomeration or sintering at high temperature, e.g., during forming gas reduction process. In some cases, the thin film coating, e.g., SiO2coating, may reduce or prevent agglomeration or sintering but is thin enough to be permeable to reducing gas such as hydrogen while preventing sintering of nanoparticles. In some instances, compositions of the invention include MLD-coated particles where the thin film coatings become porous ceramic oxides to allow gas flow. In such instances, a second coating of thin film can be applied, e.g., after heat treatment. In other instances, the second coating of thin film provides an impermeable dielectric layer.

The thin film of coating can be applied to highly-energetic particles using a batch process, a semi-continuous process (e.g. as described in the aforementioned patent application entitled “Semi-Continuous Vapor Deposition Process For The Manufacture of Coated Particles”), one or more types of continuous processes (U.S. Patent Application Publication No. 20120009343 or U.S. patent application Ser. No. 15/426,789), as well as variations thereof including plasma-enhanced processes, or a combination thereof. The thin film coating in preferred embodiments is produced at least in part using an atomic layer deposition or molecular layer deposition process.

A batch process for coating powdered substrates requires the intermittent delivery of known amounts of vaporized precursors, potentially in large quantities. This limits many traditional delivery methods, like thermal mass flow controllers, which are geared to more consistent, continuous flows of chemicals and require a consistent and minimum threshold pressure differential across the device. For large scale powder coatings, where tens of grams of precursor must be delivered in a single pulse, this can be accomplished using a loss-in-weight monitoring process. The precursor container rests on a scale and is connected to the deposition system via flexible tubing that allows for the deflection of the precursor container in proportion to its mass. SeeFIG.4. As the liquid precursor vaporizes and enters the process stream, the mass in the container decreases. This change is detected in real-time by the scale, allowing for the delivered amount to be monitored. A calibration factor for the measured mass change can be used to compensate for any potential offsetting force on the container of the flexible line connecting the container to the deposition system. The loss-in-weight monitoring of the precursor container can be used both for feedback control of the precursor dosing, and as continuous process monitoring of the amount of precursor remaining on the system. This can be important when safety regulations limit the total amount of a hazardous precursors allowed on a coating system, and it necessary to know when to switch to a new container to prevent process interruptions.

Vaporization and delivery of the precursor can be a rate-limiting step for the batch ALD coating of powders. To speed this step up, precursor can be charged to a container of known volume and temperature prior to the dosing step (FIG.1). The precursor in the cell is maintained as a vapor at a higher pressure than the process gas stream and reaction vessel. When dosing of the precursor is required, an isolation valve is opened, and the pressure differential results in viscous flow of the precursor to the process gas stream and reactor vessel. The amount of precursor dosed can be monitored by measuring the pressure change in the charge cell (and temperature if needed). When a target amount has been dosed, the dosing isolation valve can be closed. As the powder in the reactor proceeds through the other steps in the process, such as soaks and purges, the charge cell can be refilled with precursor and allowed to equilibrate to the target temperature and pressure. The precursor can be added either as a vapor or as a liquid that vaporizes when heated to the temperature and pressure conditions of the cell.

In cases where ALD precursors react with the substrate (for example, TMA and water reacting with the AlLi substrate), the initial ALD cycles include some level of subsurface diffusion and/or non-self-limiting reaction. Lower deposition temperatures help limit this interaction. However, the deposition temperature must be sufficiently high to maintain the vapor pressure of the precursors (without condensation) at the flux required for the material throughput desired for production. Once a surface coating is nucleated, the growing film starts to act as a barrier for diffusion/reaction of the ALD precursor and allows for more efficient (exterior) coating growth. Higher flux and greater exposure of the precursors to the surface initially helps to nucleate a surface coating faster; however, higher flux and higher exposure also leads to more adverse reaction, material degradation (see TEM images inFIG.12) and adverse processing characteristics such as powder sticking and aggregation. In the extreme, the entire powder bed can seize. Powder aggregation is a significant barrier to high throughput processing. Some of this can be managed with during or post process milling or sieving, but processes that provide a barrier coating without aggregation are advantageous.

Generically, an ALD is simple, is monitored by in-situ tools or defined by a series of saturation experiments, and can be broken into these steps:1) Dose first precursor to saturation2) Purge out precursor and biproducts3) Does second precursor to saturation4) Purge out second precursor and biproducts
If this technique is applied to certain reactive powders (especially aluminium alloys such as AlLi alloy), either the barrier performance is poor because there is insufficient external barrier, or more likely the powder aggregates, or both.

We have found that the ALD process can be improved by breaking into different phases:

Phase 1: initial deposition onto untreated surface. Water is purposely underdosed and TMA initially dosed high (more than needed to saturate) and can be decreased on successive cycles but still higher than expected needed to saturate the surface. This is done to quickly saturate the subsurface with limited aggregation of the powder (suspected to be mostly caused by water). This phase preferably lasts 2-5 ALD cycles.
Phase 2: increasing the amount of water and the amount of TMA exposed to nucleate a barrier layer on the surface. Excess water aids in nucleating an Al2O3rich interface.
Phase 3: grow an increasingly self-limiting surface layer.
Phase 4: once a complete ALD layer is established a more typical ALD process can be established and the exposures reduced to what would saturate the surface.

To avoid over-exposing any portion of the powder bed the precursors are each delivered in sub-saturating doses. So that a recipe proceeds:1) Mini DOSE Precursor1a. Mini-Dose Prec1 (mini-dose=dose amount of precursor less than required to fully saturate all the surfaces*b. Hold prec1 in the chamberc. purge to clear manifold*d. Hold Prec1 in the chambere. Evacuate and purge chamberf. Blowback exhaust lineg. REPEAT back to “a” as many times a required2) PURGE Precursor 1a. Evacuate the chamberb. Purge the chamberc. Evacuate the chamberd. Repeat back to “a” as many times as required3) Mini Dose Precursor 2a. Mini-Dose Prec2 (mini-dose=dose amount of precursor less than required to fully saturate all the surfaces*b. Hold prec1 in the chamberc. purge to clear manifold*d. Hold Prec1 in the chambere. Evacuate and purge chamberf. Blowback exhaust lineg. REPEAT back to “a” as many times as required4) Purge Precursor 2a. Evacuate the chamberb. Purge the chamberc. Evacuate the chamberd. Repeat back to “a” as many times as required5) 1 full ALD cycle complete. Repeat back to 1 as many ALD cycles as required.Note: the speed of delivery (the amount of precursor required per dose) for high throughput runs requires that the precursors be delivered with a sweep gas flowing to bring the manifold/system into the viscous flow regime. Dosing the precursors alone does not achieve this.

Materials that are air and/or moisture sensitive, such as AlLi alloy particles need a barrier coating to prevent degradation, especially where it is desired to be able to store the materials for several years without degradation. The global location of storage (i.e. ambient conditions) and the method of storage of the powders are typically unknown. We have developed two accelerated tests to assess the quality of the coatings. We found that method 2 (temperature hold) is better for differentiation of the different kind of coatings and is probably more representative of real-world conditions. In both methods, an inert gas is bubbled through water and the humidified gas is passed onto the powder while mass of the solid is measured by thermal gravimetric analysis (TGA).

The water bubbler was held at a fixed temperature with a water bath. Argon was bubbled through the water at a constant rate and then into the TGA.

Method 1: Temperature Ramp with Humidity. Ramp 5° C./min to 350° C. Flow gas is Argon humidified by running the argon through water filled bubbler at 13° C. and 10 psig. Results are shown inFIG.5. Method 2: Temperature Constant with Humidity. Hold the temperature consistently at 45° C. for 18 hours. Flow gas is Argon humidified by running the argon through water filled bubbler at 13° C. and 10 psig. Results are shown inFIG.6.

Additional objects, advantages, and novel features of this invention will become apparent to those skilled in the art upon examination of the following examples thereof, which are not intended to be limiting.

EXAMPLES

Comparative Example 1: Baseline TMA/H2O Study on Group I (Hydrogen) containing energetic material powder. Al2O3ALD was applied to an energetic material in a fluidized bed ALD reactor under standard deposition conditions taught by the prior art.

Comparative Example 2a: Baseline TMA/H2O Study on Group I (Lithium) containing energetic material powder. Al2O3ALD was applied to a lithium-silicon energetic material in a fluidized bed ALD reactor under standard deposition conditions taught by the prior art. For this lithium-containing compound in the form of a lithium alloy, the ALD precursors underwent an adverse surface reaction with the substrate materials, and did not exhibit self-limiting growth at normal operating temperatures, pressures and exposure times.

Comparative Example 2b: Baseline TMA/H2O Study on Group I (Lithium) containing energetic material powder. Al2O3ALD was applied to a lithium-aluminum energetic material in a fluidized bed ALD reactor under standard deposition conditions taught by the prior art. For this lithium-containing compound in the form of a lithium alloy, the ALD precursors underwent an adverse surface reaction with the substrate materials, and did not exhibit self-limiting growth at normal operating temperatures, pressures and exposure times.

Comparative Example 3: Baseline TMA/H2O Study on Group I (Sodium) containing energetic material powder. Al2O3ALD was applied to a sodium-aluminum energetic material in a fluidized bed ALD reactor under standard deposition conditions taught by the prior art. For this sodium-containing compound in the form of a sodium alloy, the ALD precursors underwent an adverse surface reaction with the substrate materials, and did not exhibit self-limiting growth at normal operating temperatures, pressures and exposure times.

Comparative Example 4: Baseline TMA/H2O Study on Group II (Magnesium) containing energetic material powder. Al2O3ALD was applied to a lithium-silicon energetic material in a fluidized bed ALD reactor under standard deposition conditions taught by the prior art. For this lithium-containing compound in the form of a lithium alloy, the ALD precursors underwent an adverse surface reaction with the substrate materials, and did not exhibit self-limiting growth at normal operating temperatures, pressures and exposure times, albeit not as extreme as what was observed for Group I alloy materials.

Examples Overview: In an effort to understand the limitations of performing alumina ALD with TMA/H2O and identify the causes of uncontrolled surface growth and some bulk sintering of the materials in Comparative Examples 2a, 2b, 3 and 4, the powder of each respective Comparative Example was processed in a miniature reactor on a fluidized bed ALD apparatus. Methods include low-temperature chemistry, ranging from room temperature to temperatures up to about 100° C., deposition of seed and/or interlayers to provide a buffer between substrate and coating materials, tuning the number of sub-cycles within each cycle varying by deposited cation or anion as a means to tailor final coating compositions, and altering methods specific to each Group I or Group II metal containing alloy material suitable for use as an energetic material. During room temperature tests, fluidization was visually monitored through a glass Conflat nipple to characterize physical aggregation phenomena. Pressures monitored during the runs to watch for indications of plugging or solidification of the powder.

Example 1: TMA/H2O Study on Spheroidized Group I and II Alloy Powders In an effort to understand the limitations of performing alumina ALD with TMA/H2O and identify the causes of bulk sintering of the various powders seen during processing of the Comparative Examples in fluidized bed ALD reactors, 20 g batches of spheroidized powder were processed in a miniature reactor on a fluidized bed ALD apparatus. Chemistry was performed at room temperature, 60° C. and 100° C. During room temperature tests, fluidization was visually monitored through a glass Conflat nipple. Pressures monitored during the runs to watch for indications of plugging or solidification of the powder. By monitoring the mass spec products, a target exposure time corresponding to full surface ‘saturation’ was programmed for the TMA and water, and triangulated with surface area-inspired calculations. By keeping timing near saturation, 50 cycles of Al2O3ALD was performed at both room and elevated temperatures such that the powder substrate appeared to maintain its form and flowability after ALD. When the dose times for TMA and H2O were increased at 100° C., it was discovered after unloading that each powder had at least partially solidified into a solid mass at some time during the experiment.

All experiments were performed at a batch size of about 20 g in a miniature fluidized bed reactor (2.5 cm diameter) on a fluidized bed ALD apparatus. Bellows valves were installed at the inlet and outlet of the reactor so that pristine sphericized LiAl powder could be loaded and transferred to the fluidized bed ALD apparatus under inert atmosphere. The system was purged of air before exposing the powder to nitrogen flow for fluidization. Reaction byproducts were monitored using a mass spectrometer at the reactor outlet. TMA and H2O were both set to a temperature of 40° C., and the needle valves were set to 5 and 10, respectively. For the first experiment, a miniature reactor was set up with a short glass nipple at the bottom so that fluidization could be monitored during the run. Fluidization was observed at 10 sccm of nitrogen flow. To avoid overdosing during the first dose, short doses of about thirty seconds of TMA were performed six times (six sub-cycle exposures). Each time, mass 16 was observed on the mass spec, which is typical of CH4generation during TMA and water reactions. No TMA breakthrough was seen on mass 57 (or 72), and three total minutes of TMA exposure were calculated to be sufficient for saturation based on the total surface area of the batch.

On the first water dose, four thirty second doses (four sub-cycle exposures) were performed. During these water doses, no peak was observed on the mass spec for mass 16. Also, no water breakthrough was observed. Because of this irregularity, the mass spec was switched to histogram mode for the second cycle so other potential products could be monitored.

On the second cycle, TMA was dosed for a total of seven minutes (using sub-cycle exposure methods) without any signs of breakthrough. Again, methane was seen being produced. During the second water dose, methane generation was observed through mass 16. After an initial large spike of methane, the concentration dropped to a shoulder for two minutes at the same time hydrogen (mass 2) was observed. After, methane generation dropped to nearly zero and the water signal broke through and hydrogen continued to be generated at high concentrations. The hydrogen generation was hypothesized to be from water reacting with lithium in the bulk powder, producing hydrogen and lithium hydroxide, which was unexpected based upon the teachings of George. This reaction did not take place until the surface TMA was fully reacted and water was able to diffuse/migrate into the powder grain to react with subsurface lithium.

On the third cycle through the 50th cycle, dose times of 180 seconds were used for TMA and 110 seconds were used for water. A typical dose profile is shown in the figures. In each cycle, the methane generation during each subsequent water dose dropped and then leveled off, as seen in the figures. During the 49th cycle, the manifold pressure rose to about 40 Torr, indicating some sort of plug in a filter or other restriction of flow. Since the powder was observed to be free flowing upon unloading, it's possible that the filters became increasingly clogged with entrained powder over the course of the days-long run, and the powder receiving the same precursor treatments from excess reactant exposure was able to uptake excess coating materials and potentially allowed deposition to occur.

Example 2: Since TMA and H2O Al2O3ALD was successfully performed using sub-cycle exposure techniques and at room temperature, with small precursor flow rates and short, ‘just saturated’ dose times, the same test was performed at an elevated reactor temperature of 100° C. to mimic conditions that lead to problems during previous trials as described in the Comparative Examples. The miniature fluidization reactor was loaded without the glass Conflat nipple viewing section so that the reactor could be heat taped and insulated with the isolation valves. Again, a large amount of hydrogen was generated during the first water dose. Over time, hydrogen generation per cycle dropped during subsequent cycles. Unlike FN0271.12-1, which had the same dose timing at room temperature, this elevated temperature run did not see water breakthrough during any of the cycles. Also, after about 8 cycles, hydrogen began to be generated during the second half of the TMA cycle. This was not observed in the room temperature test.

Again, the powder was unloaded after 50 cycles and maintained its flowability and powder characteristics. No appreciable pressure rise was seen in this experiment, which may mean that the filters did not clog in the same way as the previous experiment which was performed over a longer overall time period.

To try and purposefully sinter the powder into a solid mass like what was seen during Comparative Example operations, an experiment was performed at 60° C. and 100° C. with longer dose times. Also, the sample was exposed to water before TMA/water cycling took place. Most notably, these water cycles were long enough to see breakthrough in the early cycles, which was not the case for Example 1. While no obvious signs of plugging were observed in the pressures during the run, the powder was found to be a solid clump upon unloading. This may indicate that prolonged periods of overdosing lead to sintering of Group I and Group II metal alloy energetic material powders into solid masses. This again runs counter to the teachings of the prior art.

It was shown that successful TMA/H2O chemistry can be performed on Group I and Group II metal alloy powders from room temperature to elevated temperatures of up to 100° C. if care is taken not to overdose the sample. It was necessary for the inventors to develop new methods of applying ALD coatings onto energetic materials in order to promote triggerable release phenomena described above. Prolonged dosing times on Group I metal alloy powders at 100° C. and higher, and Group II metal alloy powders at 120° C. led to sintering of the powder into increasingly densified solid clumps. Hydrogen generation was observed during water doses, which was an indicator of completion of the TMA/water reaction on the surface, as subsequent signals correspond to water migration into the bulk that reacts with Group I and Group II metal alloy powders, or Group I and Group II metal interdiffusion away from the bulk and to the surface that reacts with water.

In some embodiments, developed ALD methods include performing uniform deposition processes comprising sub-cycle exposures at temperatures ranging from room temperature to 100° C., with prolonged dosing times to determine the threshold sintering temperature of the particles begins. Also, leveraging mass spectrometry data (or analogous in-situ technique) to monitor signal generation of reactants, products and unexpected intermediate byproducts during the array of temperature tests, as a means of refining dosing techniques for highly-energetic materials. Examples of unexpected intermediate byproducts include hydrogen generated at higher concentrations during later doses while hydrogen generation during the water dose decreases over time.

Sample #FN0271.12-1: Al2O3ALD Test to see if fluidization changes after ‘just saturated’ TMA/H2O doses. Reaction run at 25° C.; TMA 40° C., orifice 5 μm; 180 sec dose, 360 sec purge; H2O 40° C., orifice@10 μm; 110 sec dose, 600 sec purge. Mass spectroscopy showed no methane generation during the water does on the first cycle at room temperature.

Sample #FN0271.12-2: Al2O3ALD at 100° C. reactor temperature TMA/H2O doses. Reaction run at 100° C.; TMA 40° C., orifice 5 μm; 180 sec dose, 360 sec purge H2O 40° C., orifice@10 μm; 110 sec dose, 600 sec purge.

Sample #FN0271.12-3: Al2O3ALD 100° C. reactor long doses. TMA/H2O doses. Reaction run at 100° C. TMA 40° C., orifice 5 μm; 180 sec dose, 360 sec purge; H2O 40° C., orifice@10 μm; 110 sec dose, 600 sec purge.

Sample #FN0260.19-1: Rapid SiO23 cycles of rapid SiO2on Li/Al alloy spherical powder.

Pre-Deposition

Heated reaction chamber to 100° C., w/25 sccm N2flow for 20 min.Heated Vaporizer (SB) to 150° C. w/25 sccm N2flowing through, to bypass; for 20 min.Reduced Vaporizer temp. to 125° C., stopped N2flow through vaporizer.Increased reaction chamber temperature to 125° C.
Process Conditionsreactor setpoint 100° C.Vaporizer with TPS set to 125° C.TMA set to 45° C., and manifold line (TIC-111) set to 80° C.H2O left at Room Temp. (˜29° C.).N2flow set to 25 sccm during TMA dose, purge, and H2O dose.N2flow set to 50 sccm during Tris(tert-pentoxy)silanol (TPS) dose.Deposition/Process Notes: First TMA dose took 25 min.; following four TMA doses were set to 15 min. each. Vaporizer internal temperature was ˜128° C. during TPS dosing.

The foregoing discussion of the invention has been presented for purposes of illustration and description and is not intended to limit the invention to the form or forms disclosed herein. All references cited herein are incorporated by reference in their entirety.