Arrested Reactive Milling Synthesis and Characterization of Sodium‐Nitrate Based Reactive Composites

Arrested reactive milling was used to synthesize three composite powders using sodium nitrate as an oxidizer, and magnesium, aluminum, and mechanically alloyed aluminum‐magnesium (Al_0.5Mg_0.5) as respective fuels. Both magnesium and aluminum powders formed flakes with varying thickness from hundreds of nm to several μm sandwiched between sodium nitrate particles. Three‐dimensional composite and nanocomposite particles were formed with Al Mg mechanically alloyed powder. No change in the crystallinity of any components was observed from X‐ray diffraction patterns of the composite materials. Materials were characterized using differential thermal analysis (DTA) and simultaneous thermogravimetry (TG), carried out in argon. In composite materials, the decomposition of sodium nitrate starts at lower temperatures than for pure sodium nitrate. Weight loss is observed to start at relatively low temperatures. The most significant exothermic events occur at substantially higher temperatures, and therefore in a material that may have been significantly altered from its initial state. The results of thermal analysis indicate that the composite with mechanically alloyed Al Mg powder is most stable at low temperatures. Ignition of the prepared composites was studied using a thin layer of powder coated on an electrically heated filament. These experiments showed that the composite with mechanically alloyed Al Mg powder ignites at lowest temperatures and thus is expected to have the shortest ignition delays in practical applications. The emission spectra of the prepared composites burning in air are presented.     

Demolition Mechanism and Behavior of Shaped Charge with Reactive Liner

The application of reactive materials on shaped charge liners has received much attention. Herein, the demolition mechanism and behavior of reactive materials based shaped charge liner are investigated by experiment, numerical simulation, and theoretical analysis. Three reactive shaped charge liners, composed of a mixture of Al/PTFE (26.5/73.5 wt‐%) powders, are fabricated by pressing and sintering. The damage effects of the multi‐layered target against reactive materials based shaped charge are investigated. The results show that the reactive liners create excellent collateral damage due to the release of chemical energy contained in reactive materials. An Eulerian computational model is developed to investigate penetration behavior of the reactive jet formed by shaped charge liner. In addition, a theoretical model based on cavity expansion is derived to predict the initiated location of reactive materials. Comprehensive analysis indicates that the TNT equivalence factor for these powder mixtures used in this work is 3.41–7.77 and that the self‐delay time is about 0.8 ms. This work will provide guidance and reference for the design of reactive shaped charge liner.     

Aluminum Burn Rate Modifiers Based on Reactive Nanocomposite Powders

Aluminum powders have long been used as additives in propellants, pyrotechnics, and explosives. Aluminum has a high enthalpy of combustion but relatively low burn rate. Addition of reactive nanocomposite powders can increase the burn rate of aluminum and thus the overall reaction rate of the energetic formulation. Replacing only a small fraction of the fuel by a nanocomposite material can enhance the reaction rate with little change to the thermodynamic performance of the formulation. This research showed the feasibility of the above concept using nanocomposite powders prepared by arrested reactive milling (ARM), a scalable “top‐down” technique for manufacturing reactive nanomaterials. The nanocomposite materials used in this study were 2B+Ti, and Al‐rich thermites: 8Al+3CuO, and 8Al+MoO₃. The reactive nanocomposite powders were added to micrometer‐sized aluminum powder and the mixture was aerosolized and burned in a constant volume chamber. The combustion atmosphere was varied using oxygen, nitrogen, and methane. The resulting pressure traces were recorded and processed to compare different types and amounts of modifiers. Additives of nanocomposite powders of 8Al+MoO₃ and 2B+Ti to micrometer‐sized aluminum were found to be effective in increasing both the rate of pressure rise and maximum pressure in the respective constant volume explosion experiments. It was observed that 20 wt.‐% of additive resulted in the best combination of the achieved burn rate and pressure.     

Combustion of Mechanically Alloyed Aluminum‐Magnesium Powders in Steam

Mechanically alloyed Al ⋅ Mg powders with the mole fraction of Al varied from 0.47 to 0.9 were burned at atmospheric pressure in water vapor. The powders were carried by nitrogen through the center of a hydrogen‐oxygen diffusion flame. The particles ignited in the steam at approximately 2500 K, generated as the hydrogen‐oxygen flame product. Filtered photomultiplier tubes were used to capture the optical emission traces of individual particles as they burned. It was assumed that the measured durations of individual emission pulses are representative of individual particle burn times. Distributions of the burn times were obtained for each powder and correlated with respective particle size distributions to relate particle burn times with their sizes. Color temperatures corresponding to the particle emission signals were also obtained. It was observed that the burn times measured for alloys were more close to those of pure Al than Mg; for particles smaller than 2–3 μm, burn times for the alloys were shorter than for pure metal particles. The effect was strongest for the alloy with 50 wt‐% of Mg (Al_0.47Mg_0.54). Approximately, burn times, τ, as a function of particle size, d, could be estimated using a τ∼dⁿ law, where n increased from 0.72 to 1.05 as the mole fraction of Mg increased from 0.1 to 0.53. The particle flame temperatures varied between 2500 and 3100 K for all alloys except for Al_0.7Mg_0.3, for which the temperatures were somewhat lower. The measured flame temperatures were reasonably close to the adiabatic flame temperatures calculated for combustion of mixed elemental Al and Mg in steam.     

Reactive‐Injecting Follow‐Through Shaped Charges from Sequent‐Material Conical Liners

Shaped charges using reactive‐metal liners have the potential for beyond‐penetration effects, e.g. thermodynamic events that increase pressure in a volume adjacent to the penetration. Shaped charge liners made from a copper penetrating‐ and an aluminum reactive‐component in a sequent‐material configuration were compared in tests to baseline homogeneous copper liners. Copper lined shaped charges had greater mild steel penetration performance, but lacked beyond‐penetration pressurization effects exhibited by the sequent‐material lined units. Jet capture experiments, beyond‐penetration constant‐volume tests, and thermochemical equilibrium calculations provide evidence supporting the aluminum slug comminution into unoxidized reactive fuel, augmenting beyond‐penetration effects.     

Dynamic Fragmentation and Blast from a Reactive Material Solid

Structural reactive material (SRM) is consolidated from a fine granular mixture of reactive materials towards the mixture theoretical maximum density with little porosity, thus bearing both high energy density and mechanical strength. A reactive hot spot concept was investigated for fine fragmentation of a SRM solid under explosive loading to augment air blast through rapid reaction of fine SRM fragments. In this concept, micro‐sized reactive materials were distributed in a fuel‐rich SRM solid, such as MoO₃ particles consolidated in a particulate aluminum base in 10Al+MoO₃. Intermetallic reactions of micro‐sized MoO₃ and nearby Al under explosive loading created heat and gas products to form microscale hot spots that initiated local fractures leading to fine fragments of the rest of Al. The SRM solid was made of a thick‐walled cylindrical casing, containing a high explosive in a detonation pressure range of 25–34 GPa with a casing‐to‐explosive mass ratio of 1.78. Experiments in a cylindrical chamber demonstrated the presence of a large amount of fine SRM fragments, whose reaction promptly after detonation significantly enhanced the primary and near field blast wave, as compared to the results from a baseline pure Al‐cased charge, thus indicating the feasibility of the concept.     

Mechanical properties of a cryogenically mechanically alloyed polycarbonate–poly(aryl ether ether ketone) system

The processing–property relationship of a model cryogenically mechanically alloyed polymer–polymer system [polycarbonate (PC) and poly(aryl ether ether ketone) (PEEK)] was investigated. PC and PEEK powders were cryogenically mechanically alloyed for 10 h, and the resulting two‐phase powder particles were processed into testable coupons with a miniature ram‐injection molder. The bulk mechanical properties of the coupons made from the mechanically alloyed powders and nonmechanically alloyed powders were investigated as a function of mechanical alloying and injection‐molding parameters. The injection‐molded coupons were mechanically tested in the three‐point‐bending mode. The results demonstrated that no measurable improvement was achieved in the energy to break, strain at failure, or failure strength in the coupons made from the mechanically alloyed materials in comparison with those of the coupons made from the nonmechanically alloyed powders. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1196–1202, 2003     

Formation and Penetration of Jets by Shaped Charges with Reactive Material Liners

Reactive material lining is an efficient damage enhancement technology that incorporates the defeat mechanisms of kinetic energy and chemical energy. The liners are fabricated by cold isostatically pressing at a pressure of 250 MPa. In this paper, the formation behaviors of jet with the polymer‐based reactive material liner are investigated by numerical simulation and X‐ray photographs. The corresponding simulations of jet formation are presented, and the results agree well with experimental ones. They show that the reactive material liner can shape almost continuous and straight jet. Compared with the conventional copper liner, the reactive material liner can shape jet in a shorter time, but the jet break easily and lose stability due to its poor ductility. Although the penetration depth is sacrificed slightly when penetrating steel target, the reactive material liner produce a significantly enlarged hole‐diameter.     

Nanocomposite Thermites with Calcium Iodate Oxidizer

Iodine bearing reactive materials and fuel additives are being developed to inactivate harmful aerosolized spores and bacteria by combined thermal and chemical effects. Nanocomposite thermites with aluminum and boron serving as fuels and calcium iodate as an oxidizer were prepared by arrested reactive milling. Both materials contained 80 wt % of calcium iodate. Morphology and particle sizes of the prepared materials were characterized using scanning electron microscopy (SEM). Both powders comprised particles finer than ca. 10 μm with fuel and oxidizer mixed on the submicrometer scale. Powders were exposed to room air to assess their stability. They were ignited as a thin coating on an electrically heated filament. Powders were injected in an air‐acetylene flame to observe combustion of individual particles. Pressed pellets for both prepared materials were prepared and ignited using a CO₂ beam. Al ⋅ Ca(IO₃)₂ oxidizes rapidly in room air, whereas no aging was detected for B ⋅ Ca(IO₃)₂. Ignition of Al ⋅ Ca(IO₃)₂ occurs around 1150 K, after both aluminum and calcium iodate melt. Ignition is accompanied by ejection of sintered particles undergoing microexplosions while they are combusting. Ignition of B ⋅ Ca(IO₃)₂ occurs between 600 and 700 K, before either of the components melt. Combustion is accompanied by the formation of a luminous halo above the material, suggesting a vapor‐phase reaction involving boron suboxides. Longer ignition delays are observed for the pellets of Al ⋅ Ca(IO₃)₂ heated by the CO₂ laser beam compared to similar pellets of B ⋅ Ca(IO₃)₂. Burn rates of B ⋅ Ca(IO₃)₂ pellets are nearly twice as fast as those of Al ⋅ Ca(IO₃)₂, primarily due to the lower ignition temperature for the boron‐based thermite. The flame temperatures obtained from the time‐integrated optical spectra are close to 2140 and 2060 K for Al ⋅ Ca(IO₃)₂ and B ⋅ Ca(IO₃)₂, respectively. Individual particles of B ⋅ Ca(IO₃)₂ injected into an air‐acetylene flame burn slower than similar Al ⋅ Ca(IO₃)₂ particles. Based on their better stability, lower ignition temperatures, shorter ignition delays, and longer burn times leading to a more gradual release of iodine, B ⋅ Ca(IO₃)₂ composites are suggested to be better suited as components of energetic formulations aimed to defeat stockpiles of biological weapons.     

Analysis of the aluminum reaction efficiency in a hydro-reactive fuel propellant used for a water ramjet

A high-pressure combustor and a metal/steam reactor are used to simulate the two-stage combustion of hydro-reactive propellants used for a water ramjet. Raw metal powders added to the propellants are the aluminum power, magnesium powder, 50/50 aluminum-magnesium alloy (AM), and ball-milled 50/50 aluminum-magnesium alloy (b-AM), which are characterized by using scanning electron microscopy (SEM), x-ray diffraction (XRD), and simultaneous thermogravimetric analysis (TGA). The efficiencies of the Al reaction in the raw metal in heated steam and in the propellants during the two-stage combustion are calculated. The results indicate that both Mg and Al in the alloys, whether b-AM or AM, can react completely in air when heated up to 950°C. The XRD patterns for the combustion products of the AM and b-AM alloys in heated steam contain magnesium oxide MgO, spinel Al₂MgO₄, and Al diffraction peaks. The Al reaction efficiencies of the AM and b-AM alloy powders in heated steam are much higher than that of the Al powders. The hydroxyl-terminated polybutadiene (HTPB)-ammonium perchlorate (AP)-(b-AM)-Mg and HTPB-AP-AM-Mg propellant systems exhibit good performance in terms of the Al reaction efficiency, which are better than that of the HTPB-AP-Al-Mg and HTPB-AP-Al systems.     

The Effect of Additives on the Burning Rate of Silicon‐Calcium Sulfate Pyrotechnic Delay Compositions

The effect of fuel particle size as well as the influence of inert and reactive additives on the burning rate of the Si‐CaSO₄ composition was evaluated. The burning rate decreased with increase in fuel particle size, while the enthalpy remained constant. Addition of fuels to the base composition increased the burning rate, with an increase from 12.5 mm ⋅ s⁻¹ to 43 mm ⋅ s⁻¹ being recorded upon 10 wt‐% Al addition. Ternary mixtures of silicon, calcium sulfate, and an additional oxidizer generally decreased the burning rate, with the exception of bismuth trioxide, where it increased. The Si‐CaSO₄ formulation was found to be sensitive to the presence of inert material, addition of as little as 1 wt‐% fumed silica stifled combustion in the aluminum tubes.     

Consolidation and mechanical properties of reactive nanocomposite powders

Reactive nanocomposite powders with bulk compositions of 8Al·MoO₃, 12Al·MoO₃, and 8Al·3CuO were prepared by arrested reactive milling (ARM) and consolidated into cylindrical and rectangular pellets using a uniaxial die. Pellets were pressed at room temperature without any binder. Reference pellets were prepared from conventional Al powder and from Al-metal oxide powder blends with bulk compositions identical to those of the nanocomposite powders. Materials could be consolidated to densities greater than 90% of the theoretical maximum density while maintaining their high reactivity. Tensile strength and flexural strength of the consolidated materials were measured using diametrical compression and three-point flexural strength tests, respectively. Higher strengths were observed for higher relative densities, and the strength of the composite materials was comparable to that of consolidated aluminum powders. Yield strength of the reactive nanocomposite powders was determined from compaction load vs. die displacement curves using the Heckel equation. It was greater for the nanocomposite powders as compared to the powder blends or pure aluminum. Organic, or low melting point metal binders were added to selected samples to improve strength. Respective pellets were pressed at temperatures above the melting point of the metal binder. The highest density (~ 2.9 g/cm³) and tensile strength (~ 17.5 MPa) was observed with indium as binder. All consolidated samples were found to be highly reactive, and the effect of partial reaction during consolidation remained below the limit quantifiable by differential scanning calorimetry.     

Microstructure and properties of NiAl/TiC composite synthesized by spark plasma sintering of mechanically activated elemental powders

In this study, NiAl/TiC_0.95 composite was synthesized by reactive spark plasma sintering of mechanically activated elemental powders. The microstructure and properties of activated powders and sintered samples were evaluated. The elemental powders were milled after different milling times and as-mixed and 10 h milled powder mixtures were sintered by the reactive spark plasma sintering method. The phase and the microstructure changes were evaluated by x-ray diffraction and scanning electron microscopy/energy dispersive spectroscopy, respectively. The XRD pattern of 0 h milled powder after sintering showed that Ni₃Al, Ni₂Al₃ beside NiAl and TiC_0.75 formed. While after the sintering of 10 h mechanically activated powder, the Ni₃Al and Ni₂Al₃ were eliminated and NiAl remained with TiC_0.95. The nanoindentation result of the SPSed sample showed a hardness of 12.2 ± 0.1 GPa with an elastic modulus of 25.0 ± 0.5 GPa.     

Structural evolution of mechanically alloyed nanocrystalline Fe–28Al powders

Mechanical alloying (MA) has been utilized to synthesize many equilibrium and/or nonequilibrium phases. The structural evolution of iron aluminides mechanically alloyed from a powder mixture of iron and aluminum has been studied using X-ray diffraction (XRD), differential scanning calorimetry (DSC) and transmission electron microscopy (TEM). It is found that, during mechanical milling under argon atmosphere, aluminum dissolves gradually into the bcc lattice of α-Fe, resulting in the formation of bcc-Fe₃Al solid solutions, locally with B2-ordered structure in some region. TEM investigation indicates that NNAPBs are formed during MA. Nanocrystalline microstructure is achieved in powders after 25-h milling, with the grain size about 78 nm.     

Transition from Impact‐induced Thermal Runaway to Prompt Mechanochemical Explosion in Nanoscaled Ni/Al Reactive Systems

The effect of microstructure on ignition sensitivity and reaction behavior is investigated for nanoscaled Ni/Al gasless reactive systems. Nanometric homogeneity of the reactive media was achieved through (a) conventional mixing of nanometric powders; (b) short‐term high‐energy ball milling (HEBM) of micrometer‐sized powders. Sensitivity to thermal inputs is investigated by differential thermal analysis and mechanical sensitivity is studied by high‐rate shear impacts. The composite Ni/Al particles prepared by HEBM were extremely thermally sensitive, with reaction initiating at 220 °C, compared to 559 °C for nanometric powder samples and 640 °C for un‐milled, micrometer‐sized Ni+Al powder mixture. In contrast, nanometric powder mixtures were more susceptible to ignition through mechanical means, exhibiting a high‐speed reaction mode that is not observed in HEBM samples. The high‐speed mode preferentially appears in high‐shear regions and is interpreted as a mechanically‐induced thermal explosion. Its progression is tied to the passage of a stress wave in the heterogeneous media that heats and mixes the materials, rather than being propagated due to chemical energy release. The microstructures unique to each material are considered responsible for their individually ignition sensitivities. Specifically, the finely interspersed porosity in nanometric powder mixtures allows direct heating of the reactive interface between Ni and Al particles during compression through pore collapse and plastic deformation, which leads to exceptionally high mechanical sensitivity. The HEBM materials have high specific reactant interface area in the bulk of each composite particle that enhances thermal sensitivity, but the relatively low specific interface area between particles is unfavorable to mechanical ignition.     

由高炉渣酸解废液制备镁铝尖晶石粉体

以含Mg2+和Al3+等有价元素的高炉渣酸解提硅废液为原料、尿素为沉淀剂,采用均匀沉淀法制备镁铝尖晶石粉体,研究了其产率及性能. 结果表明,最佳工艺条件为：反应温度100℃,尿素用量为理论用量的10倍,煅烧温度1100℃,保温时间2 h. 加入5%(w) Na2S2O4后,样品中Fe2O3含量从1.70%(w)降到0.49%(w),除铁率达71.2%,白度增加11度. 产品为富铝型镁铝尖晶石,且杂质含量远低于国家标准.     

Study on the Compatibility of Tetraethylammonium Decahydrodecaborate (BHN) with some Energetic Components and Inert Materials

The compatibility of tetraethylammonium decahydrodecaborate (BHN) with some energetic components and inert materials of solid propellants was studied by DSC method, where glycidyl azide polymer (GAP), cyclotrimethylenetrinitramine (RDX), cyclotetramethylenetetranitroamine (HMX), lead 3‐nitro‐1,2,4‐triazol‐5‐onate (NTO‐Pb), hexanitrohexaazaisowurtzitane (CL‐20), 3,4‐dinitrofurzanfuroxan (DNTF), N‐guanylurea‐dinitramide (GUDN), aluminum powder (Al, particle size=12.18 μm) and magnesium powder (Mg, particle size: 44–74 μm) were used as energetic components and polyoxytetramethylene‐co‐oxyethylene (PET), polyethylene glycol (PEG), addition product of hexamethylene diisocyanate and water (N‐100), hydroxyl terminated polybutadiene (HTPB), cupric adipate (AD‐Cu), cupric 2,4‐dihydroxy‐benzoate (β‐Cu), lead phthalate (ϕ‐Pb), carbon black (C. B.), aluminum oxide (Al₂O₃), 1,3‐dimethyl‐1,3‐diphenyl urea (C₂), di‐2‐ethylhexyl sebacate (DOS) and potassium perchlorate (KP), were used as inert materials. It was concluded that the binary systems of BHN with NTO‐Pb, CL‐20, aluminum powder, magnesium powder, PET, PEG, N‐100, AD‐Cu, β‐Cu, ϕ‐Pb, C. B., Al₂O₃, C₂, DOS, and KP are compatible, and systems of BHN with GAP and HMX are slightly sensitive, and with RDX, DNTF, and GUDN are incompatible. The impact and friction sensitivity data of BHN and BHN in combination with the energetic materials under present study were obtained, and there was no consequential affiliation between sensitivity and compatibility.     

氟化物包覆对镁铝合金与水催化反应效率的影响

为了提高镁铝合金与水的反应效率,采用氟化物对镁铝合金粉进行表面包覆,利用扫描电镜、X射线衍射仪和粒度分析仪对合金粉与高温水反应产物进行表征,对比研究了高温下不同比例的氟化物对镁铝合金与水催化反应效率的影响。结果表明,包覆氟化物的镁铝合金与高温水反应产物的粒径减小,分散性明显改善;固相燃烧产物中主要包含Al_2MgO_4、MgO和Al,表明Al未完全反应;合金粉包覆氟化物后铝的反应效率明显提高,其中,包覆质量分数2%氟橡胶和2%有机氟化物的合金粉反应效率高达89.7%,与未包覆样品相比提高了14.6%。     

Rate enhancement of hydrogen generation through the reaction of magnesium hydride with water by MgO addition and ball milling

The variations of the amount of hydrogen generated with the kind of powders and the condition of the magnesium and magnesium hydride powders were investigated. By the reaction of Al, TiH₂ and unmilled and milled Mg powders with water, the H₂ generation rates were very low and the quantities of H₂ generated were extremely small. The quantity of H₂ generated by the reaction of unmilled MgH₂ powder with water was greater than those generated by the reactions of Al, TiH₂, and unmilled and milled Mg powders with water. The MgH₂ powder milled for 2 h, with finer particles, generated much more H₂ by its reaction with water than unmilled MgH₂ powder. The MgH₂ + 5%MgO powder milled for 2 h generated much more H₂ by its reaction with water than the Al, TiH₂, unmilled Mg, milled Mg, unmilled MgH₂, and milled MgH₂ powders.     

Synthesis and Characterization of Amorphous Nano‐Alumina Powders with High Surface Area for Biodiesel Production

Nano‐alumina powders containing yttrium oxide were synthesized via the sol‐gel method using aluminum chloride hexahydrate as catalyst precursor. Fourier transform infrared analysis showed the presence of Al‐O and Al‐O‐Al bands in the powder structure and X‐ray diffraction spectra proved that the alumina was in the amorphous phase. The amorphous nano‐alumina powders were shown to be mesoporous with a high surface area, and both spherical and slit‐shaped particles were found in the calcined powder. A high percentage of conversion of oil to biodiesel was obtained in the transesterification reaction and the synthesized nano‐alumina powders could be easily regenerated for further use. The amorphous nano‐alumina powder can thus be recommended for use as active catalyst in the transesterification reaction for biodiesel production on the industrial scale.