John Okasinski

Ambient-stable tetragonal phase in silver nanostructures

Crystallization of noble metal atoms usually leads to the highly symmetric face-centred cubic phase that represents the thermodynamically stable structure. Introducing defective microstructures into a metal crystal lattice may induce distortions to form non-face-centered cubic phases when the lateral dimensions of objects decrease down to nanometre scale. However, stable non-face-centered cubic phases have not been reported in noble metal nanoparticles. Here we report that a stable body-centred tetragonal phase is observed in silver nanoparticles with fivefold twinning even at ambient conditions. The body-centered tetragonal phase originates from the distortion of cubic silver lattices due to internal strains in the twinned nanoparticles. The lattice distortion in the centre of such a nanoparticle is larger than that in the surfaces, indicating that the nanoparticle is composed of a highly strained core encapsulated in a less-strained sheath that helps stabilize the strained core.

Polymorphism in a high-entropy alloy

Polymorphism, which describes the occurrence of different lattice structures in a crystalline material, is a critical phenomenon in materials science and condensed matter physics. Recently, configuration disorder was compositionally engineered into single lattices, leading to the discovery of high-entropy alloys and high-entropy oxides. For these novel entropy-stabilized forms of crystalline matter with extremely high structural stability, is polymorphism still possible? Here by employing in situ high-pressure synchrotron radiation X-ray diffraction, we reveal a polymorphic transition from face-centred-cubic (fcc) structure to hexagonal-close-packing (hcp) structure in the prototype CoCrFeMnNi high-entropy alloy. The transition is irreversible, and our in situ high-temperature synchrotron radiation X-ray diffraction experiments at different pressures of the retained hcp high-entropy alloy reveal that the fcc phase is a stable polymorph at high temperatures, while the hcp structure is more thermodynamically favourable at lower temperatures. As pressure is increased, the critical temperature for the hcp-to-fcc transformation also rises.

In Operando Spatiotemporal Study of Li2O2 Grain Growth and its Distribution Inside Operating Li–O2 Batteries

Nanocrystalline lithium peroxide (Li2 O2 ) is considered to play a critical role in the redox chemistry during the discharge-charge cycling of the Li-O2 batteries. In this report, a spatially resolved, real-time synchrotron X-ray diffraction technique was applied to study the cyclic formation/decomposition of Li2 O2 crystallites in an operating Li-O2 cell. The evaluation of Li2 O2 grain size, concentration, and spatial distribution inside the cathode is demonstrated under the actual cycling conditions. The study not only unambiguously proved the reversibility of the Li2 O2 redox reaction during reduction and evolution of O2 , but also allowed for the concentration and dimension growths of the peroxide nanocrystallites to be accurately measured at different regions within the cathode. The results provide important insights for future investigation on mass and charge transport properties in Li2 O2 and improvement in cathode structure and material design.

In situ high-energy synchrotron X-ray diffraction studies and first principles modeling of α-MnO2 electrodes in Li–O2 and Li-ion coin cells

Despite their technological challenges, non-aqueous rechargeable lithium–oxygen cells offer extremely high theoretical energy densities and are therefore attracting much attention in a rapidly emerging area of electrochemical research. Early results have suggested that, among the transition metal oxides, alpha manganese dioxide (α-MnO2) appears to offer electrocatalytic properties that can enhance the electrochemical properties of Li–O2 cells, particularly during the early cycles. In this study, we have investigated the hybrid Li-ion/Li–O2 character of α-MnO2 electrodes in Li–O2 coin cells by in situ high-energy synchrotron X-ray diffraction, and compared the results with conventional Li/α-MnO2 coin cells assembled under argon. Complementary first principles density functional theory calculations have been used to shed light on competing lithium insertion and lithium and oxygen insertion reactions within the α-MnO2 tunnel structure during discharge, relative to lithium peroxide or lithium oxide formation.

In situ synchrotron X-ray diffraction studies of lithium oxygen batteries

Lithium oxygen batteries were studied in situ by synchrotron X-ray diffraction. Crystalline Li2O2 was shown to form reversibly on a plain carbon cathode under normal cycling conditions. However, if the cell was polarized to induce electrolyte decomposition before the oxygen reduction reaction was initiated, LiOH was found to cycle reversibly on the cathode instead. A mechanism linking the LiOH production to the electrolyte decomposition was proposed.

Quantifying the Nucleation and Growth Kinetics of Microwave Nanochemistry Enabled by in Situ High-Energy X-ray Scattering.

The fast reaction kinetics presented in the microwave synthesis of colloidal silver nanoparticles was quantitatively studied, for the first time, by integrating a microwave reactor with in situ X-ray diffraction at a high-energy synchrotron beamline. Comprehensive data analysis reveals two different types of reaction kinetics corresponding to the nucleation and growth of the Ag nanoparticles. The formation of seeds (nucleation) follows typical first-order reaction kinetics with activation energy of 20.34 kJ/mol, while the growth of seeds (growth) follows typical self-catalytic reaction kinetics. Varying the synthesis conditions indicates that the microwave colloidal chemistry is independent of concentration of surfactant. These discoveries reveal that the microwave synthesis of Ag nanoparticles proceeds with reaction kinetics significantly different from the synthesis present in conventional oil bath heating. The in situ X-ray diffraction technique reported in this work is promising to enable further understanding of crystalline nanomaterials formed through microwave synthesis.

Time-resolved x-ray diffraction techniques for bulk polycrystalline materials under dynamic loading

We have developed two techniques for time-resolved x-ray diffraction from bulk polycrystalline materials during dynamic loading. In the first technique, we synchronize a fast detector with loading of samples at strain rates of ~10(3)-10(4) s(-1) in a compression Kolsky bar (split Hopkinson pressure bar) apparatus to obtain in situ diffraction patterns with exposures as short as 70 ns. This approach employs moderate x-ray energies (10-20 keV) and is well suited to weakly absorbing materials such as magnesium alloys. The second technique is useful for more strongly absorbing materials, and uses high-energy x-rays (86 keV) and a fast shutter synchronized with the Kolsky bar to produce short (~40 μs) pulses timed with the arrival of the strain pulse at the specimen, recording the diffraction pattern on a large-format amorphous silicon detector. For both techniques we present sample data demonstrating the ability of these techniques to characterize elastic strains and polycrystalline texture as a function of time during high-rate deformation.

Synchrotron X-ray measurement techniques for thermal barrier coated cylindrical samples under thermal gradients.

Measurement techniques to obtain accurate in situ synchrotron strain measurements of thermal barrier coating systems (TBCs) applied to hollow cylindrical specimens are presented in this work. The Electron Beam Physical Vapor Deposition coated specimens with internal cooling were designed to achieve realistic temperature gradients over the TBC coated material such as that occurring in the turbine blades of aeroengines. Effects of the circular cross section on the x-ray diffraction (XRD) measurements in the various layers, including the thermally grown oxide, are investigated using high-energy synchrotron x-rays. Multiple approaches for beam penetration including collection, tangential, and normal to the layers, along with variations in collection parameters are compared for their ability to attain high-resolution XRD data from the internal layers. This study displays the ability to monitor in situ, the response of the internal layers within the TBC, while implementing a thermal gradient across the thickness of the coated sample. The thermal setup maintained coating surface temperatures in the range of operating conditions, while monitoring the substrate cooling, for a controlled thermal gradient. Through variation in measurement location and beam parameters, sufficient intensities are obtained from the internal layers which can be used for depth resolved strain measurements. Results are used to establish the various techniques for obtaining XRD measurements through multi-layered coating systems and their outcomes will pave the way towards goals in achieving realistic in situ testing of these coatings.

Strain response of thermal barrier coatings captured under extreme engine environments through synchrotron X-ray diffraction

The mechanical behaviour of thermal barrier coatings in operation holds the key to understanding durability of jet engine turbine blades. Here we report the results from experiments that monitor strains in the layers of a coating subjected to thermal gradients and mechanical loads representing extreme engine environments. Hollow cylindrical specimens, with electron beam physical vapour deposited coatings, were tested with internal cooling and external heating under various controlled conditions. High-energy synchrotron X-ray measurements captured the in situ strain response through the depth of each layer, revealing the link between these conditions and the evolution of local strains. Results of this study demonstrate that variations in these conditions create corresponding trends in depth-resolved strains with the largest effects displayed at or near the interface with the bond coat. With larger temperature drops across the coating, significant strain gradients are seen, which can contribute to failure modes occurring within the layer adjacent to the interface.

Silver chlorobromide nanocubes with significantly improved uniformity: synthesis and assembly into photonic crystals

Silver chlorobromide (AgClxBr1−x, 0 < x < 1) nanocubes with a highly uniform size, morphology, and crystallinity have been successfully synthesized through a co-precipitation of Ag+ ions with both Cl− and Br− ions in ethylene glycol containing polyvinyl pyrrolidone at mild temperatures. Compositions of the synthesized nanocubes can be easily tuned by controlling the molar ratio of Cl− to Br− ions in the reaction solutions. The size of the nanocubes is determined by varying a number of parameters including the molar ratio of Cl− to Br− ions, injection rate of Ag+ ions, and reaction temperature. The real-time formation of colloidal AgClxBr1−x nanocubes has been monitored, for the first time, by in situ high-energy synchrotron X-ray diffraction. The time-resolved results reveal that a fast injection rate of Ag+ ions is critical for the formation of AgClxBr1−x nanocubes with a highly pure face-centered cubic crystalline phase. The improved uniformity of the AgClxBr1−x nanocubes is beneficial for assembling them into order superlattices (e.g., photonic crystals) even by simply applying centrifugation forces. The stop band of the resulting photonic crystals can be easily tuned from the ultraviolet to the infrared region by using AgClxBr1−x nanocubes with different sizes. The variation of the dielectric constant of AgClxBr1−x associated with the change of the relative concentration of halide ions provides an additional knob to tune the optical properties of photonic crystals.