WAXD Research Articles

Fluid Structure of Molten LiCl-Li Solutions.

Molten mixtures of lithium chloride and metallic lithium (LiCl-Li) play an essential role in the electrolytic reduction of various metal oxides. These mixtures possess unique high temperature physical and chemical properties that have been investigated for decades. However, due to their extreme chemical reactivity, no study to date has been capable of definitively proving the basic physical nature of Li dissolution in molten LiCl. In this study, the evolution of the structure of molten LiCl-Li is probed as metallic Li is electrochemically introduced into the melt in situ, using synchrotron radiation experiments based on high energy wide-angle X-ray scattering (WAXS) and small-angle X-ray scattering (SAXS). The time-resolved scattering results indicate the formation of transient Cl- ion cages surrounding low-density voids with a periodicity of ∼8.3 Å, which suggests the formation of metastable Li nanocluster. The structure of the LiCl-Li nanoclusters in the solution is modeled using ab initio molecular dynamics (AIMD) simulations. The simulation results are in agreement with the X-ray diffraction measurement and suggest the nanoclusters are predominantly Li8, along with smaller clusters.

Antituberculosis Drug Interactions with Membranes: A Biophysical Approach Applied to Bedaquiline.

This work focuses on the interaction of the novel and representative antituberculosis (anti-TB) drug bedaquiline (BDQ) with different membrane models of eukaryotic and prokaryotic cells. The effect of BDQ on eukaryotic cell membrane models was assessed using liposomes, namely, multilamellar vesicles (MLVs) made of 1,2-dimyristoyl-rac-glycero-3-phosphocholine (DMPC) and also a mixture of DMPC and cholesterol (CHOL) (8:2 molar ratio). To mimic the prokaryotic cell membrane, 1,2-dimyristoyl-sn-glycero-3-phospho-rac-(1-glycerol) (DMPG) and 1,1′2,2′-tetra-oleoyl-cardiolipin (TOCL) were chosen. Powerful biophysical techniques were employed, including small-angle X-ray scattering (SAXS) and wide-angle X-ray scattering (WAXS), to understand the effect of BDQ on the nanostructure of the membrane models. The results showed that BDQ demonstrated a pronounced disordering effect in the bacterial cell membrane models, especially in the membrane model with cardiolipin (CL), while the human cell membrane model with large fractions of neutral phospholipids remained less affected. The membrane models and techniques provide detailed information about different aspects of the drug–membrane interaction, thus offering valuable information to better understand the effect of BDQ on their target membrane-associated enzyme as well as its side effects on the cardiovascular system.

Formic Acid Regenerated Mori, Tussah, Eri, Thai, and Muga Silk Materials: Mechanism of Self-Assembly.

Flexible and water-insoluble regenerated silk materials have caught considerable interest due to their mechanical properties and numerous potential applications in medical fields. In this study, regenerated Mori (China), Thai, Eri, Muga, and Tussah silk films were prepared by a formic acid-calcium chloride (FA) method, and their structures, morphologies, and other physical properties were comparatively studied through Fourier transform infrared spectroscopy (FTIR), wide-angle X-ray scattering (WAXS), scanning electron microscopy (SEM), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and thermogravimetric analysis (TGA). FTIR results demonstrated that the secondary structures of those five types of silk films are different from those of their respective natural silk fibers, whose structures are dominated by stacked rigid intermolecular β-sheet crystals. Instead, intramolecular β-sheet structures were found to dominate these silk films made by FA method, as confirmed by WAXS. We propose that silk I-like structures with intramolecular β-sheets lead to water insolubility and mechanical flexibility. This comparative study offers a new pathway to understanding the tunable properties of silk-based biomaterials.

Atomistic-scale insights into the crosslinking of polyethylene induced by peroxides

Dicumyl peroxide (DCP) is the most commonly used peroxide crosslinking agent for polyethylene (PE) in high voltage power cables. The DCP reactions in the PE matrix lead to the formation of a range of byproducts, some of which remain in the final crosslinked polyethylene (XLPE) product and may have adverse effects on the cable function and its long-term properties. In this study, we utilized ReaxFF based molecular dynamics (MD) simulations and experimental techniques including Fourier transform infrared (FTIR) mapping and wide-angle X-ray scattering (WAXS) to obtain detailed atomistic scale insight into peroxide-induced crosslinking of PE. Our results indicate that a moderate curing temperature rise to 500 K leads to an increased crosslinking extent, however, temperature rise above 500 K may have adverse effects on the PE crosslinking. Additionally, our results indicate that elevating the density improves the PE crosslinking. Our study showed that a high ratio of DCP to PE can increase the amount of generated byproducts but may not necessarily lead to an increased amount of XLPE. Our MD results also indicate that the presence of an external electric field had almost no effect on crosslinking and that di-(1-decyl-1-phenylundecyl) peroxide, may not be as efficient as DCP in XLPE production. These results indicate that ReaxFF based molecular dynamics, validated by experiments, is an efficient tool for analyzing – and improving – the conditions of polymerization chemistry.

Tailoring the isothermal crystallization kinetics of isodimorphic poly (butylene succinate-ran-butylene azelate) random copolymers by changing composition

A detailed isothermal crystallization study of biobased and biodegradable isodimorphic poly (butylene succinate-ran-butylene azelate) random copolyesters (PBS-ran-PBAz) with a wide composition range has been carried out to determine nucleation kinetics, spherulitic growth rates and overall crystallization kinetics. Differential Scanning Calorimetry (DSC) and Polarized Light Optical Microscopy (PLOM) analysis show that for the PBS-rich phase, the incorporation of BAz comonomer leads to a significant increase in nucleation density and a decrease in spherulitic growth. On the contrary, for the PBAz-rich phase, an antinucleating effect of the incorporation of BS comonomer has been observed. Both effects agree with the thermodynamic analysis of the equilibrium melting point depression as a function of composition, which predicts that only a small amount of BAz comonomer is included within the PBS-rich crystals and a larger amount of comonomer is included in PBAz-rich crystals. In addition, the enthalpy of melting of 100% crystalline PBS and PBAz were determined by a different practical approach: extrapolating real time synchrotron Wide Angle X-ray Scattering (WAXS) isothermal crystallization data and isothermal DSC data.

Conformational Differences among Metarhodopsin I, Metarhodopsin II, and Opsin Probed by Wide-Angle X-ray Scattering.

Among the photoproducts of vertebrate rhodopsin, only metarhodopsin II (Meta-II) preferentially adopts the active structure in which transmembrane helices are rearranged. Light-induced helical rearrangement of rhodopsin in membrane-embedded form was directly monitored by wide-angle X-ray scattering (WAXS) using nanodiscs. The change in the WAXS curve for the formation of Meta-II was characterized by a peak at 0.2 Å-1 and a valley at 0.6 Å-1, which were not observed in metarhodopsin I and opsin. However, acid-induced active opsin (Opsin*) showed a 0.2 Å-1 peak, but no 0.6 Å-1 valley. Analyses using the model structures based on the crystal structures of dark state and Meta-II suggest that the outward movement of helix VI occurred in Opsin*. However, the displaced helices III and V in Meta-II resulting from the disruption of cytoplasmic ionic lock were restored in Opsin*, which is likely to destabilize the G-protein-activating structure of opsin.

Destruction and Reorganization of Physically Cross-Linked Network of Thermoplastic Polyurethane Depending on Its Glass Transition Temperature

The mechanical behavior and morphological variation of thermoplastic polyurethanes (TPUs) with different hard segment contents (HSCs) deformed at different temperatures are investigated using tensile machine, small-angle X-ray scattering (SAXS), and wide-angle X-ray scattering (WAXS) techniques. The average constraint molecular weight ⟨Mc⟩ between the hard domains, calculated from the stress–strain curve, increases with the increasing deformation temperature and decreases with the increasing HSC. The increased ⟨Mc⟩ is also confirmed by the increased long spacing calculated from the SAXS peak. The intensity increase of the SAXS peak at high deformation temperature indicates that the induced hard domains exhibit higher density. The WAXS patterns indicate the induction of crystal form III at the deformation temperature above the Tg of the hard domains. The starting true stress of the generation of form III lies in the interval between 20 and 35 MPa. The orientation degree of chain segments at high temperatur...

Internal Structure of Nanometer-Sized Droplets Prepared by Antisolvent Precipitation

Antisolvent precipitation (AP) is a low-cost and less-invasive preparation alternative for organic nanoparticles compared to top-down methods such as high-pressure homogenization or milling. Here we report on particularly small organic nanoparticles (NPs) prepared by AP. It has been found for various materials that these NPs in their liquid state exhibit a significant degree of molecular order at their interface toward the dispersion medium including ubiquinones (coenzyme Q10), triglycerides (trimyristin, tripalmitin), and alkanes (tetracosane). This finding is independent of the use of a stabilizer in the formulation. While this is obviously a quite general interfacial structuring effect, the respective structural details of specific NPs systems might differ. Here, a detailed structural characterization of very small liquid coenzyme Q10 (Q10) NPs is presented as a particular example for this phenomenon. The Q10 NPs have been prepared by AP in the presence of two different stabilizers, sodium dodecyl sulfate (SDS) and pentaethylene glycol monododecyl ether (C12E5), respectively, and without any stabilizer. The NPs' size is initially analyzed by photon correlation spectroscopy (PCS). The SDS-stabilized Q10 NPs have been studied further by differential scanning calorimetry (DSC), small-angle X-ray and neutron scattering (SAXS, SANS), wide-angle X-ray scattering (WAXS), and cryogenic transmission electron microscopy (CryoTEM). A simultaneous analysis of SAXS and contrast variation SANS studies revealed the molecular arrangement within the interface between the NPs and the dispersion medium. The Q10 NPs stabilized by SDS and C12E5, respectively, are small (down to 19.9 nm) and stable (for at least 16 months) even when no stabilizer is used. The SDS-stabilized Q10 NPs reported here, are therewith, to the best of our knowledge, the smallest organic NPs which have been reported to be prepared by AP so far. In particular, these NPs exhibit a core-shell structure consisting of an amorphous Q10 core and a surrounding shell, which is mainly composed of oriented Q10 molecules and aligned SDS molecules. This structure suggests a significant amphiphilic behavior and a rather unexpected stabilizing role of Q10 molecules.

Structural evolution of cellulose triacetate film during stretching deformation: An in-situ synchrotron radiation wide-angle X-Ray scattering study

Structural evolutions of cellulose triacetate (CTA) film during uniaxial stretching process at different temperatures were studied by in-situ synchrotron radiation wide-angle X-ray scattering (WAXS) combined with dynamic mechanical analysis (DMA) and differential scanning calorimetry (DSC). The results show that four temperature regions can be divided for the CTA film stretching, in which different structural evolutions and deformation mechanisms will be observed. The structural evolutions of CTA film at temperatures between 60 and 125 °C (region I) are seriously influenced by the absorbed moisture, resulting in a large variation of the crystallinity (χc). At temperatures around Tg (195 °C), stretch-induced orientations for crystal can be achieved more easily although χc and crystal size have no large change compared with the flexible-chain semi-crystalline polymers like polyethylene. Interestingly, the CTA film presents various deformation mechanisms including the elongation of amorphous and slipping, formation, destruction and recrystallization of crystals during stretching at different temperatures, which are often observed for the flexible-chain semi-crystalline polymers. These results can provide valuable guidance for the hot-stretching processing and application of CTA retardation film.

Modelling of simultaneously obtained small and wide angle synchrotron-radiation scattering depth profiles of ordered titania nanotube thin films

Thin-films of vertically aligned titanium dioxide nanotubes are key constituents of charge transfer layers in 3rd generation photovoltaics. The beneficial charge transport primarily occurs due to the favourable microstructural features, i.e. the large effective surface-to-volume ratio. Here measuring methods are selected which are sensitive to microstructural features: Simultaneous Grazing Incidence Small and Wide Angle X-Ray Scattering (GISWAXS) and Scanning Electron Microscopy (SEM). Further, a model is developed for the simulation and explanation of the GISWAXS experimental data. Titanium nanotube arrays were investigated, which were previously successfully produced by electrochemical anodization of titanium thin film evaporated onto a zinc-oxide coated glass substrate. The developed model was shown to be appropriate to describe the obtained samples, which consist of arrays of single nanotubes with a diameter of 40–80 nm, and a titanium dioxide layer with a porosity of 30–50%. Within this work, we presented simultaneous GISWAXS as a comparable tool to SEM for the fast and successful study of the average nanotubes’ diameters in nanotubes arrays.

Simultaneous study of anionic polymerization of ε-caprolactam and crystallization of polyamide 6 in an isothermal process by in situ WAXS

We directly observed the polymerization and crystallization of polyamide 6 (PA6) via anionic polymerization with a combination of in situ wide-angle X-ray scattering (WAXS), temperature measurements, and real-time visualization. In situ WAXS discriminated polymerization and the crystallization of PA6. The peak temperatures produced by exothermic polymerization and crystallization were identified during the temperature measurements. Visual observations were consistent with the WAXS spectral changes. The WAXS results indicated that the molding process consisted of three stages: (1) polymerization induction, (2) polymerization, and (3) crystallization. We compared the polymerization rate, crystallization rate, and crystallinity at each molding temperature. Both polymerization and crystallization were slow at temperatures below 127 °C. Polymerization was fast at temperatures exceeding 166 °C, but PA6 was gelated, and the crystallization rate and crystallinity were low. In contrast, polymerization was fast at 139, 148, and 155 °C, and crystallization was faster at 148 and 155 °C than at 139 °C. Therefore, the total molding time of PA6 was shorter at 148 and 155 °C than at other temperatures. The crystallinity of PA6 decreased with increasing temperature due to increasing molecular weights. We concluded that molding temperatures between 148 and 155 °C were suitable for providing PA6 with high productivities and good properties. The polymerization and crystallization of polyamide 6 (PA6) via anionic polymerization was observed using a combination of in situ wide-angle X-ray scattering (WAXS), temperature measurement, and real-time visualization at 119–182 °C. In-situ WAXS discriminated between polymerization and the crystallization of PA6. The WAXS results indicated that polymerization was fast at 139–155 °C, and crystallization was fast at 148–155 °C. The crystallinity of PA6 decreased with increasing temperature. We concluded that molding temperatures between 148 and 155 °C were suitable for high productivities of PA6 with good properties.

Combinatorial Tuning of Structural and Optoelectronic Properties in CuxZn1−xS

Summary P-type transparent conductors (TCs) are important enabling materials for optoelectronics and photovoltaics, but their performance still lags behind n-type counterparts. Recently, semiconductor CuxZn1−xS has demonstrated potential as a p-type TC, but it remains unclear how properties vary with composition. Here, we investigate CuxZn1−xS across the entire alloy space (0 ≤ x ≤ 1) using combinatorial sputtering and high-throughput characterization. First, we find a metastable wurtzite alloy at an intermediate composition between cubic endpoint compounds, contrasting with solid solutions or cubic composites (ZnS:CuyS) from the literature. Second, structural transformations correlate with shifts in hole conductivity and absorption; specifically, conductivity increases at the wurtzite phase transformation (x ≈ 0.19). Third, conductivity and optical transparency are optimized within a "TC regime" of 0.10

High Energy SAXS-Waxs Studies on the Fluid Structure of Molten LiCl-Li Solutions

Molten mixtures of lithium chloride and metallic lithium (LiCl-Li) play an essential role in the electrolytic reduction of various metal oxides. These mixtures possess unique high temperature physical and chemical properties that have been researched for decades. However, due to their extreme chemical reactivity, no study to date has been capable of definitively proving the basic physical nature of Li dissolution in molten LiCl. In this study, the evolution of structures of the molten LiCl-Li, as metallic Li is electrochemically introduced into the melt, is investigated in situ using synchrotron radiation based high energy wide angle X-ray scattering (WAXS) and small-angle X-ray scattering (SAXS). The scattering results indicate the presence of Cl- ion “cages” with size of approximately 7.9Å, which suggests the formation of Li nanoclusters as previous reported. The structure factor of the melt derived from the SAXS results is in agreement with that obtained from ab-initio molecular dynamics (AIMD) simulation of lithium nanoclusters (Li4, Li6 and Li8) in LiCl. A physical model based on the formation and suspension of metallic Li nanocluster in lithium chloride is proposed to explain various phenomena exhibited by these solutions that were previously unexplainable. The submitted abstract has been created by UChicago Argonne, LLC, Operator of Argonne National Laboratory (“Argonne”). Argonne, a U.S. Department of Energy Office of Science laboratory, is operated under Contract No. DE-AC02-06CH11357. The U.S. Government retains for itself, and others acting on its behalf, a paid-up nonexclusive, irrevocable worldwide license in said article to reproduce, prepare derivative works, distribute copies to the public, and perform publicly and display publicly, by or on behalf of the Government. The Department of Energy will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan. http://energy.gov/downloads/doe-public-access-plan

Elaboration and Characterization of Active Films Containing Iron-Montmorillonite Nanocomposites for O2 Scavenging.

Iron particles of sizes between 6 and 20 nm forming aggregates of 57 ± 17 nm were synthesized by chemical reduction of iron precursors on the surface of montmorillonite (MMT). This active MMT-Fe powder was then uniformly distributed in a linear low-density polyethylene (LLDPE) matrix by extrusion at atmospheric conditions, as confirmed by wide-angle X-ray scattering (WAXS), which also detected a partial exfoliation of the nanoclays. Thermogravimetric analysis (TGA) did not detect any significant modification of the degradation temperature between nanocomposites and active nanocomposites. 57Fe Mössbauer spectroscopy evidenced the formation of a majority of iron boride in MMT-Fe as well as in the active film containing it. The LLDPE.Fu15.MMT-Fe3.75 and LLDPE.Fu15.MMT-Fe6.25 films had oxygen-scavenging capacities of 0.031 ± 0.002 and 0.055 ± 0.009 g(O2)/g(Fe), respectively, while the neat powder had an adsorption capacity of 0.122 g(O2)/g(Fe). This result confirms that the fresh film samples were partially oxidized shortly after thermomechanical processing (60% of oxidized species according to Mössbauer spectroscopy). No significant difference in oxygen permeability was observed when MMT-Fe was added. This was related to the relatively small film surface used for measuring the permeability. The reaction–diffusion model proposed here was able to reproduce the observed data of O2 adsorption in an active nanocomposite, which validated the O2 adsorption model previously developed for dried MMT-Fe powder.

Reduction of shear localization through structural rejuvenation in Zr–Cu–Al bulk metallic glass

The effect of high-pressure torsion (HPT) on the structure and mechanical behavior of Zr50Cu40Al10 bulk metallic glass was investigated using calorimetry, density measurement, high-energy X-ray scattering and nanoindentation. Increase in rotation number, and thus plastic deformation, lowers the hardness and elastic modulus, as well as the critical strain rate for suppressing the shear localization. Strain-softening induced by plastic deformation is attributed to the structural rejuvenation. Wide-angle X-ray scattering (WAXS) measurements suggest that HPT deformation reduces and broadens the peaks in the pair distribution function indicative of pronounced structural disordering and enabling structural rejuvenation. Measured excess free volume of 0.8% for samples deformed by HPT with a maximum structural relaxation enthalpy of 29.5 J/g in the sample with 20 and 50 revolutions.

Exploring the collagen nanostructure of dermal tissues after injury

Scar often occurred during wound repair. It was known that there were differences in collagen structure in dermal tissues at millimeter scale and micron scale, however, it was not known whether there were differences in collagen structure in dermal tissues at nanoscale during wound repair. In order to compare the difference at nanoscale, skin samples from patients were selected, the control groups were the normal skin from the same patients. These samples were tested by the small angle X-ray scattering techniques (SAXS) and wide angle X-ray scattering (WAXS) techniques. The transmission electron microscopy (TEM) was used as a comparison. The results showed that there were not only significantly differences between the normal tissue and scar tissue, but also between the center and the margin of the scar tissue at nanoscale by SAXS and WAXS, which was not demonstrated by other studies. These findings demonstrated that the SAXS and WAXS were excellent tools to detect the collagen structure at nanoscale and the orientation of the collagen alignment, which was beneficial for skin tissue engineering and skin regenerative medicine.

Cellulose nanocrystals-starch nanocomposites produced by extrusion: Structure and behavior in physiological conditions

Different amounts of cellulose nanocrystals (CNCs) were added to glycerol-plasticized thermoplastic starch (TPS) to obtain bio-based nanocomposites. First, nanocomposites are prepared by extrusion and their structure is studied at different scales using WAXS (Wide Angle X-ray Scattering) and solid-state NMR (Nuclear Magnetic Resonance) for local/crystalline organization, AF4 (Asymmetrical Flow Field-Flow Fractionation) for molecular weight and chain length, and SEM (Scanning Electron Microscopy) for the morphology at a larger scale. Then, relevant mechanical properties and behavior in physiological conditions (swelling, enzymatic degradation) are characterized. The results show that the incorporation of cellulose nanocrystals up to 2.5 wt% causes a mechanical reinforcement as determined by DMTA (Dynamic Mechanical Thermal Analysis) and reduces the swelling and the enzymatic degradation of the materials compared to reference TPS. This could be linked to the formation of starch-cellulose hydrogen and hydroxyl bonds. Conversely, above 5 wt% CNC content nanocrystals seem to aggregate which in turn worsens the behavior in physiological conditions.

Crystallization Kinetics of Poly(ethylene oxide) under Confinement in Nanoporous Alumina Studied by in Situ X-ray Scattering and Simulation.

While a relatively complete understanding of the nucleation and orientation of polymers under confinement in one-dimensional nanochannels has been achieved, crystallization kinetics investigation of confined polymers is still rare. In this work, we investigated the crystallization kinetics of poly(ethylene oxide) confined in anodic alumina oxide templates with different pore sizes using in situ wide-angle X-ray scattering (WAXS). The crystallization kinetics results were fitted with the Avrami equation. The Avrami index was determined by both "isothermal step crystallization" and in situ WAXS. The crystallization process of polymers under one-dimensional nanopore confinement was simulated by a "one-dimensional lattice model". Based on this model, it is shown that homogeneous nucleation with the simultaneous growth of multiple crystal planes with drastically different growth rates could result in Avrami indexes lower than 1.

Proceeding toward the development of poly(ɛ-caprolactone)/cellulose microfibrils electrospun biocomposites using a novel ternary solvent system

In the current study, a mixture of formic acid (FA), acetic acid (AA), and acetone was used, for the first time, as a ternary solvent system to dissolve poly(ɛ-caprolactone) (PCL). In addition, as a biomaterial reinforcement, various amounts of cellulose microfibrils (CMF) (1.5, 3, and 5 wt.%), extracted from rice husk, were added to PCL solution, and subsequently the prepared suspensions were individually electrospun. Adding acetone to FA/AA solvent system led to fabrication of uniform electrospun nanofibers with the average diameter of 178 ± 38 nm. Upon CMF incorporation, the mean electrospun fiber diameter was increased to 320 ± 132 nm at 5 wt.% CMF mostly due to the solution viscosity rise. In addition, scanning electron microscopy (SEM) confirmed wider diameter distribution in the presence of CMF. The electrospun fibers were also analyzed via wide angle X-ray scattering (WAXS) and differential scanning calorimetry (DSC) to study the supermolecular structure and thermal behavior of fibrous bionanocomposites, respectively. Both the characterizations positively affect the PCL crystallinity as a result of CMF incorporation. The DSC measurements showed the highest crystallinity (70.11%) at 1.5 wt.% CMF incorporation. The effect of CMF addition on the hydrophilicity of PCL was also investigated by contact angle measurement, where a decreasing trend in contact angle was observed upon CMF loading. Moreover, in vitro degradability of the bionanocomposite nonwoven mats was studied in PBS solution. The rate of degradation was enhanced in the presence of CMF. Moreover, tensile mechanical analysis was carried out and CMF inclusion had a reinforcing impact on electrospun PCL. The highest modulus (19.17 ± 0.8 MPa) and ultimate tensile strength (UTS) (4.45 ± 0.32 MPa) were achieved at 1.5 wt.% CMF addition to PCL.

Comparative Microstructural Analysis of Nongraphitic Carbons by Wide-Angle X-ray and Neutron Scattering

Non-graphitic carbons (NGCs) represent the most abundant class of sp2-hybridized carbon, materials (coal char coal, activated carbon, etc.). These carbons consist of small graphene layer stacks pos...