Initial stage of titanium oxidation in Ti/CuO thermites: a molecular dynamics study using ReaxFF forcefields.

The paper elucidates the main driving mechanisms at play during the early stage of the Ti/CuO thermite reaction using reactive forcefields in the frame of molecular dynamics calculations. Results show that TiO preferentially forms in immediate contact to pure Ti at temperatures as low as 200 K rather than TiO2. Increasing the temperature to 700 K, the 2 nm TiO2 in contact to Ti is found to be homogeneously depleted from half of its oxygen atoms. Also, the first signs of CuO decomposition are observed at 600 K, in correlation with the impoverishment in oxygen atom reaching the titanium oxide layer immediately in contact to CuO. Further quantification of the oxygen and titanium mass transport at temperatures above 700 K suggests that mostly oxygen atoms migrate from and across the titanium oxide interfacial layer to further react with the metallic titanium fuel reservoir. This scenario is opposed to the one of the Al/CuO system, for which the mass transport is dominated by the Al fuel diffusion across alumina. Further comparison of both thermites sheds light on the enhanced reactivity of the Ti-based thermite, for which CuO decomposition is promoted at lower temperature, and offers a novel understanding of thermite initiation at large.

Selecting Machine Learning Models to Support the Design of Al/CuO Nanothermites.

Novel properties associated with nanothermites have attracted great interest for several applications, including lead-free primers and igniters. However, the prediction of quantitative structure-energetic performance relationships is still challenging. This study investigates machine learning methods as tools to surrogate complex physical models to design novel nanothermites with optimized burning rates chosen for energetic performance. The study focuses on Al/CuO nanolaminates, for which nine supervised regressors commonly used in ML applied to materials science are investigated. For each, an ML model is built using a database containing a set of 2700 Al/CuO nanolaminate systems, specifically generated for this study. We demonstrate the superiority of the multilayer perceptron algorithm to surrogate conventional physical-based models and predict the Al/CuO nanolaminate microstructure-burn rate relationship with good efficiency: the burn rate is estimated with less than 1% error (0.07 m·s-1), which is very good for designing nano-engineered energetic materials, knowing that it typically varies from approximately 8-20 m·s-1. In addition, the optimization of the Al/CuO nanolaminate structure for burn rate maximization through machine learning takes a few milliseconds, against several days to achieve this task using a physical model, and months experimentally.

Elucidating the dominant mechanisms in burn rate increase of thermite nanolaminates incorporating nanoparticle inclusions.

It was experimentally found that silica and gold particles can modify the combustion properties of nanothermites but the exact role of the thermal properties of these additives on the propagating combustion front relative to other potential contributions remains unknown. Gold and silica particles of different sizes and volume loadings were added into aluminum/copper oxide thermites. Their effects on the flame front dynamics were investigated experimentally using microscopic dynamic imaging techniques and theoretically via a reaction model coupling mass and heat diffusion processes. A detailed theoretical analysis of the local temperature and thermal gradients at the vicinity of these two additives shows that highly conductive inclusions do not accelerate the combustion front while poor conductive inclusions result in the distortion of the flame front (corrugation), and therefore produce high thermal gradients (up to 1010K.m-1) at the inclusion/host material interface. This results in an overall slowing down of the combustion front. These theoretical findings contradict the experimental observations in which a net increase of the flame front velocity was found when Au and SiO2particles are added into the thermite. This leads to the conclusion that the faster burn rate observed experimentally cannot be fully associated with thermal effects only, but rather on chemical (catalytic) and/or mechanical mechanisms: formation of highly-stressed zones around the inclusion promoting the reactant mixing. One additional experiment in which physical SiO2particles were replaced by voids (filled with Ar during experiment) to cancel the potential mechanical effects while preserving the thermal inhomogeneity in the thermite structure confirms the hypothesis that instead of pure thermal conduction, it is the mechanical mechanisms that dominate the propagation velocity in our specific Al/CuO multilayered films.

The role of alkylamine in the stabilization of CuO nanoparticles as a determinant of the Al/CuO redox reaction.

We report on a new strategy to synthesize Al/CuO nanothermites from commercial Al and ultra-small chemically synthesized CuO nanoparticles coated with alkylamine ligands. These usual ligands stabilize the CuO nanoparticles and prevent them from aggregating, with the goal to enhance the interfacial contact between Al and CuO particles. Using a variety of characterization techniques, including microscopy, spectroscopy, mass spectrometry and calorimetry (ATG/DSC), the structural and chemical evolution of CuO nanoparticles stabilized with alkylamine ligands is analyzed upon heating. This enables us to describe the main decomposition processes taking place on the CuO surface at low temperature (<500 °C): the ligands fragment into organic species accompanied with H2O and CO2 release, which promotes CuO reduction into Cu2O and further Cu. We quantitatively discuss these chemical processes highlighting for the first time the crucial importance of the synthesis conditions that control the chemical purity of the organic ligands (octylamine molecules and derivatives such as carbamate and ammonium ions) in the nanothermite performance. From these findings, an effective method to overcome the ligand-induced CuO degradation at low temperature is proposed and the Al/CuO nanothermite reaction is analyzed, in terms of onset temperature and energy released. We produce original structures composed of aluminium nanoparticles embedded in CuO grainy matrices exhibiting an onset temperature ∼200 °C below the usual Al/CuO onset temperatures, having specific combustion profiles depending on the synthesis conditions, while preserving the total amount of energy released.

Controlled Growth and Grafting of High-Density Au Nanoparticles on Zinc Oxide Thin Films by Photo-Deposition.

The integration of high-purity nano-objects on substrates remains a great challenge for addressing scaling-up issues in nanotechnology. For instance, grafting gold nanoparticles (NPs) on zinc oxide films, a major step process for catalysis or photovoltaic applications, still remains difficult to master. We report a modified photodeposition (P-D) approach that achieves tight control of the NPs size (7.5 ± 3 nm), shape (spherical), purity, and high areal density (3500 ± 10 NPs/µm2) on ZnO films. This deposition method is also compatible with large ZnO surface areas. Combining electronic microscopy and X-ray photoelectron spectroscopy measurements, we demonstrate that growth occurs primarily in confined spaces (between the grains of the ZnO film), resulting in gold NPs embedded within the ZnO surface grains thus establishing a unique NPs/surface arrangement. This modified P-D process offers a powerful method to control nanoparticle morphology and areal density and to achieve strong Au interaction with the metal oxide substrate. This work also highlights the key role of ZnO surface morphology to control the NPs density and their size distribution. Furthermore, we experimentally demonstrate an increase of the ZnO photocatalytic activity due to high densities of Au NPs, opening applications for the decontamination of water or the photoreduction of water for hydrogen production.

DNA Grafting and Arrangement on Oxide Surfaces for Self-Assembly of Al and CuO Nanoparticles.

DNA-directed assembly of nano-objects as a means to manufacture advanced nanomaterial architectures has been the subject of many studies. However, most applications have dealt with noble metals as there are fundamental difficulties to work with other materials. In this work, we propose a generic and systematic approach for functionalizing and characterizing oxide surfaces with single-stranded DNA oligonucleotides. This protocol is applied to aluminum and copper oxide nanoparticles due to their great interest for the fabrication of highly energetic heterogeneous nanocomposites. The surface densities of streptavidin and biotinylated DNA oligonucleotides are precisely quantified combining atomic absorption spectroscopy with conventional dynamic light scattering and fluorometry and maximized to provide a basis for understanding the grafting mechanism. First, the streptavidin coverage is consistently below 20% of the total surface for both nanoparticles. Second, direct and unspecific grafting of DNA single strands onto Al and CuO nanoparticles largely dominates the overall functionalization process: ∼95% and 90% of all grafted DNA strands are chemisorbed on the CuO and Al nanoparticle surfaces, respectively. Measurements of hybridization efficiency indicate that only ∼5 and ∼10% of single-stranded oligonucleotides grafted onto the CuO and Al surfaces are involved in the hybridization process, corresponding precisely to the streptavidin coverage, as evidenced by the occupancy of 0.9 and 1.2 oligonucleotides per protein. The hybridization efficiency of single-stranded oligonucleotides chemisorbed on CuO and Al without streptavidin coating decreases to only ∼2%, justifying the use of streptavidin despite its poor surface occupancy. Finally, the structure of directly chemisorbed DNA strands onto oxide surfaces is examined and discussed.

Performance Enhancement via Incorporation of ZnO Nanolayers in Energetic Al/CuO Multilayers.

Al/CuO energetic structure are attractive materials due to their high thermal output and propensity to produce gas. They are widely used to bond components or as next generation of MEMS igniters. In such systems, the reaction process is largely dominated by the outward migration of oxygen atoms from the CuO matrix toward the aluminum layers, and many recent studies have already demonstrated that the interfacial nanolayer between the two reactive layers plays a major role in the material properties. Here we demonstrate that the ALD deposition of a thin ZnO layer on the CuO prior to Al deposition (by sputtering) leads to a substantial increase in the efficiency of the overall reaction. The CuO/ZnO/Al foils generate 98% of their theoretical enthalpy within a single reaction at 900 °C, whereas conventional ZnO-free CuO/Al foils produce only 78% of their theoretical enthalpy, distributed over two distinct reaction steps at 550 °C and 850 °C. Combining high-resolution transmission electron microscopy, X-ray diffraction, and differential scanning calorimetry, we characterized the successive formation of a thin zinc aluminate (ZnAl2O4) and zinc oxide interfacial layers, which act as an effective barrier layer against oxygen diffusion at low temperature.

General Strategy for the Design of DNA Coding Sequences Applied to Nanoparticle Assembly.

The DNA-directed assembly of nano-objects has been the subject of many recent studies as a means to construct advanced nanomaterial architectures. Although much experimental in silico work has been presented and discussed, there has been no in-depth consideration of the proper design of single-strand sticky termination of DNA sequences, noted as ssST, which is important in avoiding self-folding within one DNA strand, unwanted strand-to-strand interaction, and mismatching. In this work, a new comprehensive and computationally efficient optimization algorithm is presented for the construction of all possible DNA sequences that specifically prevents these issues. This optimization procedure is also effective when a spacer section is used, typically repeated sequences of thymine or adenine placed between the ssST and the nano-object, to address the most conventional experimental protocols. We systematically discuss the fundamental statistics of DNA sequences considering complementarities limited to two (or three) adjacent pairs to avoid self-folding and hybridization of identical strands due to unwanted complements and mismatching. The optimized DNA sequences can reach maximum lengths of 9 to 34 bases depending on the level of applied constraints. The thermodynamic properties of the allowed sequences are used to develop a ranking for each design. For instance, we show that the maximum melting temperature saturates with 14 bases under typical solvation and concentration conditions. Thus, DNA ssST with optimized sequences are developed for segments ranging from 4 to 40 bases, providing a very useful guide for all technological protocols. An experimental test is presented and discussed using the aggregation of Al and CuO nanoparticles and is shown to validate and illustrate the importance of the proposed DNA coding sequence optimization.

A computational chemist approach to gas sensors: modeling the response of SnO2 to CO, O2, and H2O gases.

A general bottom-up modeling strategy for gas sensor response to CO, O(2), H(2)O, and related mixtures exposure is demonstrated. In a first stage, we present first principles calculations that aimed at giving an unprecedented review of basic chemical mechanisms taking place at the sensor surface. Then, simulations of an operating gas sensor are performed via a mesoscopic model derived from calculated density functional theory data into a set of differential equations. Significant presence of catalytic oxidation reaction is highlighted.

Atomic Scale Insights into the First Reaction Stages Prior to Al/CuO Nanothermite Ignition: Influence of Porosity.

This theoretical work aims to understand the influence of nanopores at CuO-Al nanothermite interfaces on the initial stage of thermite reaction. ReaxFF molecular dynamics simulations were run to investigate the chemical and structural evolution of the reacting interface between the fuel, Al, and oxidizer, CuO, between 400 and 900 K and considering interfaces with and without a pore. Results show that the initial alumina layer becomes enriched with Al and grows primarily into the Al metal at higher temperatures. The modification of alumina is driven by simultaneous Al and O migration between metallic Al and the native amorphous Al2O3 layer. However, the presence of a pore significantly affects the growth kinetics and the composition of this alumina layer at temperatures exceeding 600 K, which impacts the initiation properties of the nanothermite. In the system without a pore, where Al is in direct contact with CuO, a ternary aluminate layer, a mixture of Al, O, and Cu, is formed at 800 K, which slows Al and O diffusion, thus compromising the nanothermite reactivity in fully dense Al/CuO composites. Conversely, the presence of a pore between Al and CuO promotes Al enrichment of the alumina layer above 600 K. At that temperature, any free oxygen molecules in the pore become attached to the reactive alumina surface resulting in a rapid oxygen pressure drop in the pore. This is expected to accelerate the reduction of the adjacent CuO as observed in experiments with Al/CuO composites with porosity at the CuO-Al interfaces.

Dominant role of OH- and Ti3+ defects on the electronic structure of TiO2 thin films for water splitting.

Anatase/rutile constituting TiO2 thin films were prepared by sputter deposition, and the influence of the post-annealing step with a narrow window at 200 °C revealed a gaining factor of 5 in H2 production. An in-depth analysis of the photocatalytic performance revealed the dominant role of intermediate states rather than the heterocrystalline nature and the mesoscale structure. Structural, chemical and optical investigations based on scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, UV-visible spectroscopy and photoluminescence supported by ab initio calculation correlated the H2 production with the dual presence of OH- and Ti3+ defects in the form of titanium interstitial atoms. In addition, steady-state photoluminescence measurements determined the chemically active role of ethanol, commonly used as a hole scavenger, in inducing deep hole traps upon dissociation on the surface. These results give new directions for the design of TiO2 based photocatalytic systems for light-driven H2 production through water splitting, guided by a detailed description of defects present on the electronic structure and their chemical identification.

Nanopatterning Si(111) surfaces as a selective surface-chemistry route.

Using wet-chemical self-assembly, we demonstrate that standard surface reactions can be markedly altered. Although HF etching of Si surfaces is known to produce H-terminated surfaces, we show that up to approximately 30% of a monolayer of stable Si-F bonds can be formed on atomically smooth Si(111) surfaces on HF reaction, when chemically isolated Si atoms are the target of the reaction. Similarly, approximately 30% Si-OH termination can be achieved by immersion of the partially covered F-Si(111) surface in water without oxidation of the underlying Si substrate. Such reactions are possible when H-terminated (111)-oriented Si surfaces are initially uniformly patterned with methoxy groups. These findings are contrary to the knowledge built over the past twenty years and highlight the importance of steric interactions at surfaces and the possibility to stabilize products at surfaces that cannot be obtained on chemically homogeneous surfaces.

The electrostatic probe: a tool for the investigation of the Aß(1-16) peptide deformations using the static modes.

We investigate the conformational changes of the Amyloid ß(1-16) peptide induced by moving Zn(2+) ions in the solvent, which we call the electrostatic probe. We use our recently developed approach of static modes which allows treating the flexibility of biological molecules at the atomic scale. Starting from an experimental apostructure, we find that several ion impacts allow the transition of the peptide toward its folded conformation, observed experimentally in the presence of Zn(2+) ions. This result shows the ability of our model and its associated software tool to describe properly the conformational changes and opens a new path toward the molecule/molecule docking problem.

High Areal Capacity Porous Sn-Au Alloys with Long Cycle Life for Li-ion Microbatteries.

Long-term stability is one of the most desired functionalities of energy storage microdevices for wearable electronics, wireless sensor networks and the upcoming Internet of Things. Although Li-ion microbatteries have become the dominant energy-storage technology for on-chip electronics, the extension of lifetime of these components remains a fundamental hurdle to overcome. Here, we develop an ultra-stable porous anode based on SnAu alloys able to withstand a high specific capacity exceeding 100 µAh cm-2 at 3 C rate for more than 6000 cycles of charge/discharge. Also, this new anode material exhibits low potential (0.2 V versus lithium) and one of the highest specific capacity ever reported at low C-rates (7.3 mAh cm-2 at 0.1 C). We show that the outstanding cyclability is the result of a combination of many factors, including limited volume expansion, as supported by density functional theory calculations. This finding opens new opportunities in design of long-lasting integrated energy storage for self-powered microsystems.

Self-Organized Al2Cu Nanocrystals at the Interface of Aluminum-Based Reactive Nanolaminates to Lower Reaction Onset Temperature.

Nanoenergetic materials are beginning to play an important role in part because they are being considered as energetic components for materials, chemical, and biochemical communities (e.g., microthermal sources, microactuators, in situ welding and soldering, local enhancement of chemical reactions, nanosterilization, and controlled cell apoptosis) and because their fabrication/synthesis raises fundamental challenges that are pushing the engineering and scientific frontiers. One such challenge is the development of processes to control and enhance the reactivity of materials such as energetics of nanolaminates, and the understanding of associated mechanisms. We present here a new method to substantially decrease the reaction onset temperature and in consequence the reactivity of nanolaminates based on the incorporation of a Cu nanolayer at the interfaces of Al/CuO nanolaminates. We further demonstrate that control of its thickness allows accurate tuning of both the thermal transport and energetic properties of the system. Using high resolution transmission electron microscopy, X-ray diffraction, and differential scanning calorimetry to analyze the physical, chemical and thermal characteristics of the resulting Al/CuO + interfacial Cu nanolaminates, we find that the incorporation of 5 nm Cu at both Al/CuO and CuO/Al interfaces lowers the onset temperature from 550 to 475 °C because of the lower-temperature formation of Al-Cu intermetallic phases and alloying. Cu intermixing is different in the CuO/Cu/Al and Al/Cu/CuO interfaces and independent of total Cu thickness: Cu readily penetrates into Al grains upon annealing to 300 °C, leading to Al/Cu phase transformations, while Al does not penetrate into Cu. Importantly, θ-Al2Cu nanocrystals are created below 63% wt Cu/Al, and coexist with the Al solid solution phase. These well-defined θ-Al2Cu nanocrystals seem to act as embedded Al+CuO energetic reaction triggers that lower the onset temperature. We show that ∼10 nm thick Cu at Al/CuO interfaces constitutes the optimum amount to increase both reactivity and overall heat of reaction by a factor of ∼20%. Above this amount, there is a rapid decrease of the heat of reaction.

Enhancing the Reactivity of Al/CuO Nanolaminates by Cu Incorporation at the Interfaces.

In situ deposition of a thin (∼5 nm) layer of copper between Al and CuO layers is shown to increase the overall nanolaminate material reactivity. A combination of transmission electron microscopy imaging, in situ infrared spectroscopy, low energy ion scattering measurements, and first-principles calculations reveals that copper spontaneously diffuses into aluminum layers (substantially less in CuO layers). The formation of an interfacial Al:Cu alloy with melting temperature lower than pure Al metal is responsible for the enhanced reactivity, opening a route to controlling the stochiometry of the aluminum layer and increasing the reactivity of the nanoenergetic multilayer systems in general.

Toward in silico biomolecular manipulation through static modes: atomic scale characterization of HIV-1 protease flexibility.

Probing biomolecular flexibility with atomic-scale resolution is a challenging task in current computational biology for fundamental understanding and prediction of biomolecular interactions and associated functions. This paper makes use of the static mode method to study HIV-1 protease considered as a model system to investigate the full biomolecular flexibility at the atomic scale, the screening of active site biomechanical properties, the blind prediction of allosteric sites, and the design of multisite strategies to target deformations of interest. Relying on this single calculation run of static modes, we demonstrate that in silico predictive design of an infinite set of complex excitation fields is reachable, thanks to the storage of the static modes in a data bank that can be used to mimic single or multiatom contact and efficiently anticipate conformational changes arising from external stimuli. All along this article, we compare our results to data previously published and propose a guideline for efficient, predictive, and custom in silico experiments.

Elementary surface chemistry during CuO/Al nanolaminate-thermite synthesis: copper and oxygen deposition on aluminum (111) surfaces.

The surface chemistry associated with the synthesis of energetic nanolaminates controls the formation of the critical interfacial layers that dominate the performances of nanothermites. For instance, the interaction of Al with CuO films or CuO with Al films needs to be understood to optimize Al/CuO nanolaminates. To that end, the chemical mechanisms occurring during early stages of molecular CuO adsorption onto crystalline Al(111) surfaces are investigated using density functional theory (DFT) calculations, leading to the systematic determination of their reaction enthalpies and associated activation energies. We show that CuO undergoes dissociative chemisorption on Al(111) surfaces, whereby the Cu and O atoms tend to separate from each other. Both Cu and O atoms form islands with different properties. Copper islanding fosters Cu insertion (via surface site exchange mechanism) into the subsurface, while oxygen islands remain stable at the surface. Above a critical local oxygen coverage, aluminum atoms are extracted from the Al surface, leading to oxygen-aluminum intermixing and the formation of aluminum oxide (γ-alumina). For Cu and O co-deposition, copper promotes oxygen-aluminum interaction by oxygen segregation and separates the resulting oxide from the Al substrate by insertion into Al and stabilization below the oxide front, preventing full mixing of Al, Cu, and O species.

Interfacial chemistry in Al/CuO reactive nanomaterial and its role in exothermic reaction.

Interface layers between reactive and energetic materials in nanolaminates or nanoenergetic materials are believed to play a crucial role in the properties of nanoenergetic systems. Typically, in the case of Metastable Interstitial Composite nanolaminates, the interface layer between the metal and oxide controls the onset reaction temperature, reaction kinetics, and stability at low temperature. So far, the formation of these interfacial layers is not well understood for lack of in situ characterization, leading to a poor control of important properties. We have combined in situ infrared spectroscopy and ex situ X-ray photoelectron spectroscopy, differential scanning calorimetry, and high resolution transmission electron microscopy, in conjunction with first-principles calculations to identify the stable configurations that can occur at the interface and determine the kinetic barriers for their formation. We find that (i) an interface layer formed during physical deposition of aluminum is composed of a mixture of Cu, O, and Al through Al penetration into CuO and constitutes a poor diffusion barrier (i.e., with spurious exothermic reactions at lower temperature), and in contrast, (ii) atomic layer deposition (ALD) of alumina layers using trimethylaluminum (TMA) produces a conformal coating that effectively prevents Al diffusion even for ultrathin layer thicknesses (∼0.5 nm), resulting in better stability at low temperature and reduced reactivity. Importantly, the initial reaction of TMA with CuO leads to the extraction of oxygen from CuO to form an amorphous interfacial layer that is an important component for superior protection properties of the interface and is responsible for the high system stability. Thus, while Al e-beam evaporation and ALD growth of an alumina layer on CuO both lead to CuO reduction, the mechanism for oxygen removal is different, directly affecting the resistance to Al diffusion. This work reveals that it is the nature of the monolayer interface between CuO and alumina/Al rather than the thickness of the alumina layer that controls the kinetics of Al diffusion, underscoring the importance of the chemical bonding at the interface in these energetic materials.

Atomic scale determination of enzyme flexibility and active site stability through static modes: case of dihydrofolate reductase.

A Static Mode approach is used to screen the biomechanical properties of DHFR. In this approach, a specific external stimulus may be designed at the atomic scale granularity to arrive at a proper molecular mechanism. In this frame, we address the issues related to the overall molecular flexibility versus loop motions and versus enzymatic activity. We show that backbone motions are particularly important to ensure DHFR domain communication and notably highlight the role of a α-helix in Met20 loop motion. We also investigate the active site flexibility in different bound states. Whereas in the occluded conformation the Met20 loop is highly flexible, in the closed conformation backbone motions are no longer significant, the Met20 loop is rigidified by new intra- and intermolecular weak bonds, which stabilizes the complex and promotes the hydride transfer. Finally, while various simulations, including I14 V and I14A mutations, confirm that Ile14 is a key residue in catalytic activity, we isolate and characterize at the atomic scale how a specific intraresidue chemical group makes it possible to assist ligand positioning, to direct the nicotinamide ring toward the folate ring.