Thermal Shock Synthesis of Metal Nanoclusters within On-the-Fly Graphene Particles.

Metal nanoclusters (1-10 nm) have drawn great attention because of their potential applications including energy storage, catalysis, nanomedicine, and electronic devices. However, manufacturing ultrasmall metal nanoparticles at high concentrations in an unaggregated state is not a solved problem. Here, we report an aerosol-based thermal shock technique for in situ synthesis of well-dispersed metal nanoclusters in on-the-fly graphene aerosols. A rapid thermal shock to the graphene aerosol has been used to nucleate and grow the metal nanoclusters with subsequent quenching to freeze the newly formed nanoclusters in the graphene aerosol matrix. A characteristic time analysis comparison with the experiment shows that the nanocluster formation is governed by nucleation and subsequent surface growth and that the graphene retards coagulation, enabling unaggregated metal nanoclusters. The method is generic, and we show the formation of sub-10 nm Ni, Co, and Sn nanoclusters. This continuous aerosol-based thermal shock technique offers considerable potential for the scalable synthesis of well-dispersed and uniform metal nanoclusters stabilized within a host matrix. As an example of potential application, we demonstrate very favorable catalytic properties.

In Situ Microscopic Studies on the Interaction of Multi-Principal Element Nanoparticles and Bacteria.

Multi-principal element nanoparticles are an emerging class of materials with potential applications in medicine and biology. However, it is not known how such nanoparticles interact with bacteria at nanoscale. In the present work, we evaluated the interaction of multi-principal elemental alloy (FeNiCu) nanoparticles with Escherichia coli (E. coli) bacteria using the in situ graphene liquid cell (GLC) scanning transmission electron microscopy (STEM) approach. The imaging revealed the details of bacteria wall damage in the vicinity of nanoparticles. The chemical mappings of S, P, O, N, C, and Cl elements confirmed the cytoplasmic leakage of the bacteria. Our results show that there is selective release of metal ions from the nanoparticles. The release of copper ions was much higher than that for nickel while the iron release was the lowest. In addition, the binding affinity of bacterial cell membrane protein functional groups with Cu, Ni, and Fe cations is found to be the driving force behind the selective metal cations' release from the multi-principal element nanoparticles. The protein functional groups driven dissolution of multielement nanoparticles was evaluated using the density functional theory (DFT) computational method, which confirmed that the energy required to remove Cu atoms from the nanoparticle surface was the least in comparison with those for Ni and Fe atoms. The DFT results support the experimental data, indicating that the energy to dissolve metal atoms exposed to oxidation and/or the to presence of oxygen atoms at the surface of the nanoparticle catalyzes metal removal from the multielement nanoparticle. The study shows the potential of compositional design of multi-principal element nanoparticles for the controlled release of metal ions to develop antibacterial strategies. In addition, GLC-STEM is a promising approach for understanding the nanoscale interaction of metallic nanoparticles with biological structures.

Enhancing the Combustion of Magnesium Nanoparticles via Low-Temperature Plasma-Induced Hydrogenation.

The hydrogenation of metal nanoparticles provides a pathway toward tuning their combustion characteristics. Metal hydrides have been employed as solid-fuel additives for rocket propellants, pyrotechnics, and explosives. Gas generation during combustion is beneficial to prevent aggregation and sintering of particles, enabling a more complete fuel utilization. Here, we discuss a novel approach for the synthesis of magnesium hydride nanoparticles based on a two-step aerosol process. Mg particles are first nucleated and grown via thermal evaporation, followed immediately by in-flight exposure to a hydrogen-rich low-temperature plasma. During the second step, atomic hydrogen generated by the plasma rapidly diffuses into the Mg lattice, forming particles with a significant fraction of MgH2. We find that hydrogenated Mg nanoparticles have an ignition temperature that is reduced by ∼200 °C when combusted with potassium perchlorate as an oxidizer, compared to the non-hydrogenated Mg material. This is due to the release of hydrogen from the fuel, jumpstarting its combustion. In addition, characterization of the plasma processes suggests that a careful balance between the dissociation of molecular hydrogen and heating of the nanoparticles must be achieved to avoid hydrogen desorption during production and achieve a significant degree of hydrogenation.

In-Situ Thermochemical Shock-Induced Stress at the Metal/Oxide Interface Enhances Reactivity of Aluminum Nanoparticles.

Although aluminum (Al) nanoparticles have been widely explored as fuels in energetic applications, researchers are still exploring approaches for tuning their energy release profile via microstructural alteration. In this study, we show that a nanocomposite (∼70 nm) of a metal ammine complex, such as tetraamine copper nitrate (Cu(NH3)4(NO3)2/TACN), coated Al nanoparticles containing only 10 wt. % TACN, demonstrates a ∼200 K lower reaction initiation temperature coupled with an order of magnitude enhancement in the reaction rate. Through time/temperature-resolved mass spectrometry and ignition onset measurements at high heating rates, we show that the ignition occurs due to a condensed phase reaction between Al and copper oxide (CuO) crystallized on TACN decomposition. TEM and XRD analyses on the nanoparticles at an intermediate stage show that the rapid heat release from TACN decomposition in-situ enhances the strain on the Al core with induction of nonuniformities in the thickness of its AlOx shell. The thinner region of the nonuniform shell enables rapid mass transfer of Al ions to the crystallized CuO, enabling their condensed phase ignition. Hence, the thermochemical shock from TACN coating induces stresses at the Al/AlOx interface, which effectively switches the usual gas phase O2 diffusion-limited ignition process of Al nanoparticles to become condensed phase Al ion transfer controlled, thereby enhancing their reactivity.

High-Temperature Interactions of Metal Oxides and a PVDF Binder.

Interactions between energetic material relevant nanoscale metal oxides (SiO2, TiO2, MgO, Al2O3, CuO, Bi2O3) and poly(vinylidene fluoride) (PVDF) at high temperature were investigated by temperature-jump/time-of-flight mass spectrometry (T-jump/TOFMS) and thermogravimetric-differential scanning calorimetry (TGA-DSC). Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used to characterize the morphology of the compositions, while X-ray diffraction (XRD) was utilized to analyze the condensed phase crystalline species at temperatures of interest. The exergonicity and exothermicity of HF gas with hydroxyl-terminated metal oxide surfaces make HF the likely fluorine-bearing moiety and primary mode of the fluorinating reactions, where terminal OH- configurations are replaced by F- in the formation of a stronger metal-fluorine bond. However, not all compositions produce corresponding stable metal fluoride. The results show that while some of the investigated metal oxide-PVDF compositions enhance PVDF decomposition and release HF in larger quantities than PVDF, others release HF in smaller quantities than PVDF and even retard PVDF decomposition. The former compositions demonstrate exothermic, multistep mass loss modes prior to neat PVDF mass loss, and the relative intensity of HF gas increases as the temperature of the release point decreases, implying a correlation between HF release and the progression of exothermic behavior. An interplay dynamic where surface interactions both lower the onset of HF release and engage exothermically with HF gas subsequently is proposed.

Vaporization-Controlled Energy Release Mechanisms Underlying the Exceptional Reactivity of Magnesium Nanoparticles.

Magnesium nanoparticles (NPs) offer the potential of high-performance reactive materials from both thermodynamic and kinetic perspectives. However, the fundamental energy release mechanisms and kinetics have not been explored due to the lack of facile synthetic routes to high-purity Mg NPs. Here, a vapor-phase route to surface-pure, core-shell nanoscale Mg particles is presented, whereby controlled evaporation and growth are utilized to tune particle sizes (40-500 nm), and their size-dependent reactivity and energetic characteristics are evaluated. Extensive in situ characterizations shed light on the fundamental reaction mechanisms governing the energy release of Mg NP-based energetic composites across particle sizes and oxidizer chemistries. Direct observations from in situ transmission electron microscopy and high-speed temperature-jump/time-of-flight mass spectrometry coupled with ignition characterization reveal that the remarkably high reactivity of Mg NPs is a direct consequence of enhanced vaporization and Mg release from their high-energy surfaces that result in the accelerated energy release kinetics from their composites. Mg NP composites also demonstrate mitigated agglomeration and sintering during reaction due to rapid gasification, enabling complete energy extraction from their oxidation. This work expands the compositional possibilities of nanoscale solid fuels by highlighting the critical relationships between metal volatilization and oxidative energy release from Mg NPs, thus opening new opportunities for strategic design of functional Mg-based nanoenergetic materials for tunable energy release.

Modelling and simulation of field directed linear assembly of aerosol particles.

Unlike liquid phase colloidal assembly, significantly changing the structure of fractal aggregates in the aerosol phase, is considered impractical. In this study, we discuss the possibility of applying external magnetic and electric fields, to tune the structure and fractal dimension (Df) of aggregates grown in the aerosol phase. We show that external fields can be used to induce dipole moments in primary nanoparticles. We found that an ensemble of particles with induced dipole moments will interact through directional attractive and repulsive forces, leading to the formation of linear, chain-like aggregates with Df ~ 1. The aggregate structure transition is dependent on the primary particle sizes, temperature and applied field strength which was evaluated by performing a hybrid ensemble/cluster-cluster aggregation Monte Carlo simulation. We demonstrate that the threshold magnetic field strength required to linearly assemble 10-500 nm particle sizes are practically achievable whereas the electric field required to assemble sub-100 nm particles are beyond the breakdown strength of most gases. To theoretically account for the enhanced coagulation rates due to attractive interactions, we have also derived a correction factor to both free molecular and transition regime coagulation kernel, based on magnetic dipolar interactions. A comparison has been made between the coagulation time-scales estimated by theory and simulation, with the estimated magnetization time-scales of the primary particles along with oscillation time period of the magnetic field, to demonstrate that sub-50 nm superparamagnetic primary particles can be magnetized and assembled at any temperature, while below the Curie temperature ferromagnetic particles of all sizes can be magnetized and assembled, given the applied field is higher than the threshold.

Silicon Nanoparticles for the Reactivity and Energetic Density Enhancement of Energetic-Biocidal Mesoparticle Composites.

Biocidal nanothermite composites show great potential in combating biological warfare threats because of their high-energy-release rates and rapid biocidal agent release. Despite their high reactivity and combustion performance, these composites suffer from low-energy density because of the voids formed due to inefficient packing of fuel and oxidizer particles. In this study, we explore the potential of plasma-synthesized ultrafine Si nanoparticles (nSi, ∼5 nm) as an energetic filler fuel to increase the energy density of Al/Ca(IO3)2 energetic-biocidal composites by filling in the voids in the microstructure. Microscopic and elemental analyses show the partial filling of mesoparticle voids by nSi, resulting in an estimated energy density enhancement of ∼21%. In addition, constant-volume combustion cell results show that nSi addition leads to a ∼2-3-fold increase in reactivity and combustion performance, as compared to Al/Ca(IO3)2 mesoparticles. Oxidation timescale analyses suggest that nSi addition can promote initiation due to faster oxygen transport through the oxide shell of Si nanoparticles. At nSi loadings higher than ∼8%, however, slower burning characteristics of nSi and sintering effects lead to an overall degradation of combustion behavior of the composites.

Magnetic-Field Directed Vapor-Phase Assembly of Low Fractal Dimension Metal Nanostructures: Experiment and Theory.

While gas-phase synthesis techniques offer a scalable approach to production of metal nanoparticles, directed assembly is challenging due to fast particle diffusion rates that lead to random Brownian aggregation. This work explores an electromagnetic-levitation technique to generate metal nanoparticle aggregates with fractal dimension (Df) below that of diffusion limited assembly. We demonstrate that in addition to levitation and induction heating, the external magnetic field is sufficient to compete with random Brownian forces, which enables the formation of altered fractals. Ferromagnetic metals (Fe, Ni) form chain-like aggregates, while paramagnetic Cu forms compact nanoparticle aggregates with higher Df values. We have also employed a Monte Carlo simulation to evaluate the necessary field strength to form linear chains in the gas phase.

In Situ Oxidation Studies of High-Entropy Alloy Nanoparticles.

Although high-entropy alloys (HEAs) have shown tremendous potential for elevated temperature, anticorrosion, and catalysis applications, little is known on how HEA materials behave under complex service environments. Herein, we studied the high-temperature oxidation behavior of Fe0.28Co0.21Ni0.20Cu0.08Pt0.23HEA nanoparticles (NPs) in an atmospheric pressure dry air environment by in situ gas-cell transmission electron microscopy. It is found that the oxidation of HEA NPs is governed by Kirkendall effects with logarithmic oxidation rates rather than parabolic as predicted by Wagner's theory. Further, the HEA NPs are found to oxidize at a significantly slower rate compared to monometallic NPs. The outward diffusion of transition metals and formation of disordered oxide layer are observed in real time and confirmed through analytical energy dispersive spectroscopy, and electron energy loss spectroscopy characterizations. Localized ordered lattices are identified in the oxide, suggesting the formation of Fe2O3, CoO, NiO, and CuO crystallites in an overall disordered matrix. Hybrid Monte Carlo and molecular dynamics simulations based on first-principles energies and forces support these findings and show that the oxidation drives surface segregation of Fe, Co, Ni, and Cu, while Pt stays in the core region. The present work offers key insights into how HEA NPs behave under high-temperature oxidizing environment and sheds light on future design of highly stable alloys under complex service conditions.

Ultrafast, scalable laser photothermal synthesis and writing of uniformly dispersed metal nanoclusters in polymer films.

This paper presents a fast CO2 laser synthesis and writing technique - laser photothermal synthesis and writing (LPSW) - to generate and write a high concentration of unaggregated, spherical sub-10 nm metal nanoparticles (sMNPs). The method is generic, and we demonstrate the fabrication of Ni, Cu, and Ag directly in polymer thin films. A partly IR-absorbing thin polymer film can be heated by the laser to high temperatures in a short time, triggering metal-reduction, nucleation, and growth. Rapid quenching of polymer films suppresses particle diffusion and traps the generated sMNPs in the polymer film. As a result, these particles are immobilized in the laser illuminated spot ("written" by the laser) on quenching. Here, Ag-polymer films are used as a model to demonstrate how laser parameters - pulse duration, laser energy flux, and number of pulses (pulsed thermal load) - can be varied to tune particle size distributions of metal sMNPs. Using this approach, we have been able to generate 4-12 nm Ag sMNPs with thermal pulses as short as 35 ms. Fast heating timescales employed in this approach allow for the scalable manufacturing of high yields of metal sMNPs, which we estimate to be around 1 g min-1. This rapid, general synthesis and writing technique may have potentially important applications in fast, large-scale additive manufacturing and patterning of metal-loaded polymer multilayers, flexible electronics, and sensors.