Optical Synchrotron Research Articles

From irregular to regular eutectic growth in the Al-Al3Ni system: In situ observations during directional solidification

We investigate the irregular eutectic growth dynamics of the Al-Al3Ni alloy, in which one of the solid phases (Al3Ni) grows faceted from the liquid. Leveraging in situ optical microscopy and synchrotron transmission x-ray microscopy, we address the question of the degree of coupling between Al and Al3Ni at the growth front and that of the shape of the microstructures left behind in the bulk solid during directional solidification. Real-time optical observations bring evidence for a morphological transition from a eutectic-grain dependent, irregular eutectic growth at low solidification velocity V (typically 1μms−1), to a weakly anisotropic, regular growth at higher V (reaching 10μms−1). Unprecedented x-ray nano-imaging of the solid–liquid interface, and 3D characterization of the growth patterns, were made possible by a new DS setup at Brookhaven National Laboratory’s NSLS-II. At low V, the leading tips of partly faceted Al3Ni crystals are observed to grow not far ahead of the Al growth front. Correlating in situ images and postmortem 3D tomographic reconstructions reveals that the presence of faceted and non-faceted regions of Al3Ni crystals in the solid is a direct consequence of coupling and decoupling during DS, respectively. Upon increasing V, the lead distance of Al3Ni vanishes, and the shape of Al3Ni ceases to be governed by faceted growth. These observations cast light onto the basic mechanisms (faceted growth, diffusive coupling, and the dynamics of trijunctions) governing a faceted to rod-like transition upon increasing V in the Al3Ni system, with broad implications to a large class of irregular eutectics.

Modulation of Tannic Acid on the Cholesteric Structure of Cellulose Nanocrystals.

The chiral nematic phase structure, formed by the self-assembly of cellulose nanocrystals (CNCs) in an aqueous suspension and maintained in a solid film, shows great potential for optical applications. To achieve complex structures in optical devices, it is crucial to subject CNCs to specific shearing processes, such as spinning and printing. Understanding the structural and property changes of the CNC liquid crystal phase in these processes is of utmost importance. In this study, we investigated the effect of adding tannic acid (TA) on the rheological properties and cholesteric phase structures of CNCs/TA mixed suspensions. By calculating the surface site interaction points, we observed that TA can adsorb onto the surface of CNC rods in suspensions through hydrogen bonding. Through characterization techniques, such as polarized optical microscopy, rheology, and synchrotron SAXS, we examined the effects of TA addition on the microstructure and rheological properties of the CNC liquid crystal phase and clarified the change relating to the system composition. Under the same CNC concentration, the volume fraction of the anisotropic phase, the pitch, and the rod spacing of the cholesteric phase were not significantly affected by the addition of TA. However, the system viscosity was significantly reduced with the appropriate amount of TA (2 wt %), in a wide range of CNC concentrations (up to 15 wt % CNCs). The flow indexes (n) in Region I and Region III of steady-state shear curves of CNCs/TA systems (11-15 wt % CNCs) were compared. Moreover, we introduced the well-established theoretical models for liquid crystal polymers to tentatively interpret Region I of the CNCs/TA cholesteric phase and realized that increased numbers of smaller cholesteric-phase domains in the CNCs/TA system and interfacial modification by TA may contribute to the fluidity change. The feature of the domain texture of CNCs/TA systems is verified by polarized optical microscopy observations.

New insights into the mechanism of ultrasonic atomization for the production of metal powders in additive manufacturing

Ultrasonic atomization is one of the promising technologies for producing metal powders for additive manufacturing, where precise control of particle size and morphology is essential. In this study, we coupled an ultrasonic transducer with a carbon fiber plate and atomized liquid droplets and films under different vibration amplitudes. Water, glycerol, and pure aluminum melt were used to study the atomization mechanism and the resulting droplet/powder characteristics, respectively. High-speed optical and ultrafast synchrotron X-ray imaging were used to study in situ the ultrasonic atomization dynamics, including pulsation and clustering of cavities inside the liquid layer/films, development of capillary waves, and formation of liquid droplets. For the first time, we observed and captured the occurrence of cavitation during the atomization of resting drops, films and impact droplets. The inertial cavitation events interfered with the capillary waves across the interphase boundary, puncturing and breaking the boundary to produce atomized mist. The in situ observation revealed the intricate dynamics of ultrasonic atomization and underscored the pivotal role of cavitation events throughout the entire atomization process. We also conducted experiments on ultrasonic atomization of liquid aluminum, producing particles of perfectly spherical shape. The particle size tended to decrease with reduced vibration amplitude Our work has demonstrated the important processing strategies on how to tailor the particle size while ensuring consistent particle shape and morphology, which is the key processing capability for producing high quality powders for additive manufacturing applications.

Nano-FTIR spectroscopy reveals SiO2 densification within fs-laser induced nanogratings.

This study explores the structural transformations induced by femtosecond (fs) laser inscriptions in glass, with a focus on type II modifications (so-called nanogratings), crucial for advanced optical and photonic technologies. Our novel approach employs scattering-type scanning near-field optical microscopy (s-SNOM) and synchrotron radiation nanoscale Fourier-transform infrared spectroscopy (nano-FTIR) to directly assess the nanoscale structural changes in the laser tracks, potentially offering a comprehensive understanding of the underlying densification mechanisms. The results reveal the first direct nanoscale evidence of densification driven by HP-HT within fs-laser inscribed tracks, characterized by a significant shift of the main infrared (IR) vibrational structural band of silica glass. It reveals moreover a complex interplay between type I and type II modifications.

Combined operando and ex-situ monitoring of the Zn/electrolyte interface in Zn-ion battery systems

Operando optical microscopy enables imaging at the interface between the Zn electrode and the electrolyte of 1 M ZnSO4(aq) in the symmetrical Zn/Zn cells assembled as the pouch cells with the mechanical load of 0.8 MPa. The imaging was executed during cycling of Zn plating and stripping at the different current densities of 0.5, 1.0, 2.0, and 4.0 mA cm−2, and the areal capacity of 2 mAh·cm−2. When the current densities are below 4.0 mA cm−2, no intense Zn dendrites are observed. However, at 4.0 mA cm−2, the severe Zn dendrites can penetrate through the separator and cause short-circuiting. From the electrochemical perspective, the voltage profile of such system drops to almost zero volt. Both operando optical and ex-situ synchrotron X-ray imaging further prove the appearance of the Zn dendrites. By Raman spectroscopy and X-ray diffraction, the cycled Zn electrode surface contains passivation species of Zn4(OH)6SO4, ZnO, and Zn(OH)2 that could limit the active surface area for the Zn plating/stripping, accelerating the localized current density and favoring the growth of Zn dendrites. With the SiO2 additive of 0.5% w/v in 1 M ZnSO4(aq), the severe Zn dendrites disappear, as well as the cycled Zn/electrolyte interface becomes close to the pristine state; low degree of the Zn electrode roughness and the Zn surface passivation is noticed. The appearance of the claimed Zn surface morphology was also confirmed by Scanning Electron Microscopy (SEM). In turn, too low or too high SiO2 content in the electrolyte does not generate desirable effects. A high level of Zn dendrites and short circuiting are still recognized. Hence, both the operando and ex-situ characterizations can mutually validate the phenomena at the Zn/electrolyte interface.

Correlation between Emission-line Luminosity and Gamma-Ray Dominance in the Blazar 3C 279

Despite numerous studies, the origin of the γ-ray emission from blazars is still debated, in particular whether it is produced by leptonic or hadronic processes. In this study, we are testing the leptonic scenario for the flat-spectrum radio quasar 3C 279, assuming that the γ-ray emission is generated by inverse Compton scattering of external target photons from the broad-line region (IC-BLR scenario). For this purpose we use a 10 yr data set of the source consisting of the optical spectroscopy data from the Steward Observatory blazar monitoring program and Fermi Large Area Telescope γ-ray data. We search for a possible correlation between the Compton dominance and the emission-line luminosity using the discrete correlation function analysis. As a result, we find no significant correlation between these two quantities at any time lag value, while the emission-line luminosity displays a moderate correlation with the γ-ray flux at a zero time lag. We also reveal that the optical synchrotron continuum flux shows a pronounced correlation with the γ-ray flux, and therefore we interpret these results within the leptonic IC-BLR scenario where the variations in Compton dominance are primarily induced by changes in the magnetic field, rather than in the emission-line luminosity.

A rapid optical and X-ray timing study of the neutron star X-ray binary Swift J1858.6−0814

ABSTRACT We present a rapid timing analysis of optical (HiPERCAM and ULTRACAM) and X-ray (NICER) observations of the X-ray transient Swift J1858.6−0814 during 2018 and 2019. The optical light curves show relatively slow, large amplitude (∼1 mag in gs) ‘blue’ flares (i.e. stronger at shorter wavelengths) on time-scales of ∼minutes as well as fast, small amplitude (∼0.1 mag in gs) ‘red’ flares (i.e. stronger at longer wavelengths) on time-scales of ∼seconds. The ‘blue’ and ‘red’ flares are consistent with X-ray reprocessing and optically thin synchrotron emission, respectively, similar to what is observed in other X-ray binaries. The simultaneous optical versus soft- and hard-band X-ray light curves show time- and energy-dependent correlations. The 2019 March 4 and parts of the June data show a nearly symmetric positive cross-correlations (CCFs) at positive lags consistent with simple X-ray disc reprocessing. The soft- and hard-band CCFs are similar and can be reproduced if disc reprocessing dominates in the optical and one component (disc or synchrotron Comptonization) dominates both the soft and hard X-rays. A part of the 2019 June data shows a very different CCFs. The observed positive correlation at negative lag in the soft band can be reproduced if the optical synchrotron emission is correlated with the hot flow X-ray emission. The observed timing properties are in qualitative agreement with the hybrid inner hot accretion flow model, where the relative role of the different X-ray and optical components that vary during the course of the outburst, as well as on shorter time-scales, govern the shape of the optical/X-ray CCFs.

Illustrating papyrus in Ancient Egypt

Illustrated papyruses from Ancient Egypt have survived across millennia, depicting with vivid colors numerous stories and practices from a distant past. We have investigated a series of illustrated papyruses from Champollion’s private collection showing scenes from the Book of the Dead, a document essential to prepare for the afterlife. The nature of the different pigments and their distribution are revealed by combining optical microscopy, Raman spectroscopy, and synchrotron X-ray powder diffraction and fluorescence. The standardized three-step process from the New Kingdom period was used, comprising a preparatory drawing made of red hematite, a coloring step using pigments from the Egyptian palette, and a final black contour drawn with a carbon-based ink. Interestingly, specific pigment mixes were deliberately chosen to obtain different shades. In some parts, the final contour significantly differs from the preliminary drawing, revealing the artist’s creativity. These results enhance our knowledge of illustrative practices in Ancient Egypt.

Do Aqueous Suspensions of Smectite Clays Form a Smectic Liquid-Crystalline Phase?

Bottom-up strategies for the production of well-defined nanostructures often rely on the self-assembly of anisotropic colloidal particles (nanowires and nanosheets). These building blocks can be obtained by delamination in a solvent of low-dimensionality crystallites. To optimize particle availability, determination of the delamination mechanism and the different organization stages of anisotropic particles in dispersion is essential. We address this fundamental issue by exploiting a recently developed system of fluorohectorite smectite clay mineral that delaminates in water, leading to colloidal dispersions of single-layer, very large (≈20 μm) clay sheets at high dilution. We show that when the clay crystallites are dispersed in water, they swell to form periodic one-dimensional stacks of fluorohectorite sheets with very low volume fraction (<1%) and therefore huge (≈100 nm) periods. Using optical microscopy and synchrotron X-ray scattering, we establish that these colloidal stacks bear strong similarities, yet subtle differences, with a smectic liquid-crystalline phase. Despite the high dilution, the colloidal stacks of sheets, called colloidal accordions, are extremely robust mechanically and can persist for years. Moreover, when subjected to AC electric fields, they rotate as solid bodies, which demonstrates their outstanding internal cohesion. Furthermore, our theoretical model captures the dependence of the stacking period on the dispersion concentration and ionic strength and explains, invoking the Donnan effect, why the colloidal accordions are kinetically stable over years and impervious to shear and Brownian motion. Because our model is not system specific, we expect that similar colloidal accordions frequently appear as an intermediate state during the delamination process of two-dimensional crystals in polar solvents.

The first fossil immature of Elmidae: an unusual riffle beetle larva preserved in Baltic amber.

Elmidae, riffle beetles, have both adult and immature stages that show specializations for water environments. Fossils of adults of Elmidae are already known from amber, however a record of immatures was so far lacking. We report here the first fossil larva of Elmidae, preserved in Baltic amber. To be able to access details of the body hidden by inclusions and “Verlumung” we conducted, in addition to optical documentation methods, micro-CT and synchrotron documentation methods. The larva is characterised by prominent dorso-lateral and lateral processes and a plate-like ventral operculum at the end of the abdomen. The new fossil has similarities in the general body shape and the prominent characters with some modern larvae of Elmidae. The posterior protrusions on the trunk end possibly represent gills, which would imply that fossil larvae of Elmidae also led a water-related life style similar to modern representatives.

Focus on software, data acquisition, and instrumentation

Focus on software, data acquisition, and instrumentation

Nanoscale chemical heterogeneity dominates the optoelectronic response of alloyed perovskite solar cells.

Halide perovskites perform remarkably in optoelectronic devices. However, this exceptional performance is striking given that perovskites exhibit deep charge-carrier traps and spatial compositional and structural heterogeneity, all of which should be detrimental to performance. Here, we resolve this long-standing paradox by providing a global visualization of the nanoscale chemical, structural and optoelectronic landscape in halide perovskite devices, made possible through the development of a new suite of correlative, multimodal microscopy measurements combining quantitative optical spectroscopic techniques and synchrotron nanoprobe measurements. We show that compositional disorder dominates the optoelectronic response over a weaker influence of nanoscale strain variations even of large magnitude. Nanoscale compositional gradients drive carrier funnelling onto local regions associated with low electronic disorder, drawing carrier recombination away from trap clusters associated with electronic disorder and leading to high local photoluminescence quantum efficiency. These measurements reveal a global picture of the competitive nanoscale landscape, which endows enhanced defect tolerance in devices through spatial chemical disorder that outcompetes both electronic and structural disorder.

Combining Optical Microscopy and X-ray Computed Tomography Reveals Novel Morphologies and Growth Processes of Methane Hydrate in Sand Pores

Understanding the mechanisms involved in the formation and growth of methane hydrate in marine sandy sediments is crucial for investigating the thermo-hydro-mechanical behavior of gas hydrate marine sediments. In this study, high-resolution optical microscopy and synchrotron X-ray computed tomography were used together to observe methane hydrate growing under excess gas conditions in a coarse sandy sediment. The high spatial and complementary temporal resolutions of these techniques allow growth processes and accompanying redistribution of water or brine to be observed over spatial scales down to the micrometre—i.e., well below pore size—and temporal scales below 1 s. Gas hydrate morphological and growth features that cannot be identified by X-ray computed tomography alone, such as hollow filaments, were revealed. These filaments sprouted from hydrate crusts at water–gas interfaces as water was being transported from their interior to their tips in the gas (methane), which extend in the µm/s range. Haines jumps are visualized when the growing hydrate crust hits a water pool, such as capillary bridges between grains or liquid droplets sitting on the substrate—a capillary-driven mechanism that has some analogy with cryogenic suction in water-bearing freezing soils. These features cannot be accounted for by the hydrate pore habit models proposed about two decades ago, which, in the absence of any observation at pore scale, were indeed useful for constructing mechanical and petrophysical models of gas hydrate-bearing sediments.

High-resolution longitudinal profile diagnostics for ultralow charges stored in a ring

Observations of optical synchrotron radiation emitted over millions of passes from a few electrons circulating in the particle accumulator ring at the Advanced Photon Source were performed with a digital CMOS camera and a synchroscan streak camera operating at 117.3 MHz. Discrete changes of integrated counts in the CMOS image region of interest are ascribed to single electron steps in a 10-s sensor integration time. Circulations of a single electron at 375 and at 425 MeV were demonstrated in the 12-bit digital CMOS camera images. The streak camera operating at the 12th harmonic of the fundamental revolution frequency at 9.77 MHz was used to measure the bunch length from 0.5-nC circulating charge down to tens of electrons or $&lt;10\text{ }\text{ }\mathrm{aC}$. The measurements were performed with $\ensuremath{\sim}8\text{\ensuremath{-}}\mathrm{ps}$ temporal resolution uniquely at such ultralow charges. These results also serve as a proof-of-principle longitudinal profile diagnostic for the predicted effects of optical stochastic cooling at low charge in commissioning experiments at the Fermilab Integrable Optics Test Accelerator ring.

Spectroscopic evidence for a gold-coloured metallic water solution.

Insulating materials can in principle be made metallic by applying pressure. In the case of pure water, this is estimated1 to require a pressure of 48megabar, which is beyond current experimental capabilities and may only exist in the interior of large planets or stars2-4. Indeed, recent estimates and experiments indicate that water at pressures accessible in the laboratory will at best be superionic with high protonic conductivity5, but not metallic with conductive electrons1. Here we show that a metallic water solution can be prepared by massive doping with electrons upon reacting water with alkali metals. Although analogous metallic solutions of liquid ammonia with high concentrations of solvated electrons have long been known and characterized6-9, the explosive interaction between alkali metals and water10,11 has so far only permitted the preparation of aqueous solutions with low, submetallic electron concentrations12-14. We found that the explosive behaviourof the water-alkali metal reaction can be suppressed by adsorbing water vapour at a low pressure of about 10-4millibar onto liquid sodium-potassium alloy drops ejected into a vacuum chamber. This set-up leads to the formation of a transient gold-coloured layer of a metallic water solution covering the metal alloy drops. The metallic character of this layer, doped with around5×1021electrons per cubic centimetre, is confirmed using optical reflection and synchrotron X-ray photoelectron spectroscopies.

High-Pressure Structural Evolution of Disordered Polymeric CS2.

Carbon disulfide is an archetypal double-bonded molecule belonging to the class of group IV-group VI, AB2 compounds. It is widely believed that, upon compression to several GPa at room temperature and above, a polymeric chain of type (-(C═S)-S-)n, named Bridgman's black polymer, will form. By combining optical spectroscopy and synchrotron X-ray diffraction data with ab initio simulations, we demonstrate that the structure of this polymer is different. Solid molecular CS2 polymerizes at ∼10-11 GPa. The polymer is disordered and consists of a mixture of 3-fold (C3) and 4-fold (C4) coordinated carbon atoms with some C═C double bonds. The C4/C3 ratio continuously increases upon further compression to 40 GPa. Upon decompression, structural changes are partially reverted, while the sample also undergoes partial disproportionation. Our work uncovers the nontrivial high-pressure structural evolution in one of the simplest molecular systems exhibiting molecular as well as polymeric phases.

Joining tungsten with steel for DEMO: Simultaneous brazing by Cu-Ti amorphous foils and heat treatment

Abstract Development of a reliable technology to join tungsten with steel is essential for DEMO application; however, it is difficult due to large differences in their physical properties. To solve this problem, high-temperature brazing was carried out. Cu-Ti brazing alloys, which were rapidly solidified into foil, were used together with a compensating vanadium interlayer, so the EK-181 steel/Cu-28Ti/V/Cu-50Ti/W and EK-181/Cu-50Ti/V/Cu-50Ti/W brazed joints were obtained. The microstructures of the seams were investigated by optical microscopy, SEM (EDX, EBSD) and synchrotron XRD. Thermocycling and shear strength tests showed that Cu-28Ti wt. % brazing alloy ensures a firmer joint compared to Cu-50Ti wt. %. The Cu-28Ti wt. % brazing alloy was used to perform high-temperature brazing in the brazing mode equivalent to traditional EK-181 steel heat treatment. It showed that every step of the heat treatment affected the microstructures and the shear strength.

Biomimetic Gemcitabine-Lipid Prodrug Nanoparticles for Pancreatic Cancer.

Gemcitabine (Gem) is a key drug for pancreatic cancer, yet limited by high systemic toxicity, low bioavailability and poor pharmacokinetic profiles. To overcome these limitations, Gem prodrug amphiphiles were synthesised with oleyl, linoleyl and phytanyl chains. Self-assembly and lyotropic mesophase behaviour of these amphiphiles were examined using polarised optical microscopy and Synchrotron SAXS (SSAXS). Gem-phytanyl was found to form liquid crystalline inverse cubic mesophase. This prodrug was combined with phospholipids and cholesterol to create biomimetic Gem-lipid prodrug nanoparticles (Gem-LPNP), verified by SSAXS and cryo-TEM to form liposomes. In vitro testing of the Gem-LPNP in several pancreatic cancer cell lines showed lower toxicity than Gem. However, in a cell line-derived pancreatic cancer mouse model Gem-LPNP displayed greater tumour growth inhibition than Gem using a fraction (<6 %) of the clinical dose and without any systemic toxicity. The easy production, improved efficacy and low toxicity of Gem-LPNP represents a promising new nanomedicine for pancreatic cancer.

Increasing photoluminescence yield of CsPbCl3 nanocrystals by heterovalent doping with Pr3+

CsPbCl3 perovskite nanocrystals are doped with heterovalent Pr3+ using hot-injection method. These Pr3+-doped CsPbCl3 nanocrystals exhibit a dramatically improved absolute photoluminescence quantum yield (PLQY) compared to the undoped CsPbCl3, reaching 78.9 % PLQY at 9 % Pr-substitution. The crystal structure modification upon Pr3+ doping and luminescence mechanism are investigated using conventional optical spectroscopy and synchrotron X-ray spectroscopy (i.e., X-ray absorption fine structure and X-ray excited optical luminescence). Both the Pr3+ and Cl− are found contributing to the luminescence enhancement, and their individual roles in luminescence enhancement are analyzed.

Multiwavelength behaviour of the blazar 3C 279: decade-long study from γ-ray to radio

ABSTRACT We report the results of decade-long (2008–2018) γ-ray to 1 GHz radio monitoring of the blazar 3C 279, including GASP/WEBT, Fermi and Swift data, as well as polarimetric and spectroscopic data. The X-ray and γ-ray light curves correlate well, with no delay $\gtrsim 3$ h, implying general cospatiality of the emission regions. The γ-ray–optical flux–flux relation changes with activity state, ranging from a linear to a more complex dependence. The behaviour of the Stokes parameters at optical and radio wavelengths, including 43 GHz Very Long Baseline Array images, supports either a predominantly helical magnetic field or motion of the radiating plasma along a spiral path. Apparent speeds of emission knots range from 10 to 37c, with the highest values requiring bulk Lorentz factors close to those needed to explain γ-ray variability on very short time-scales. The Mg ii emission line flux in the ‘blue’ and ‘red’ wings correlates with the optical synchrotron continuum flux density, possibly providing a variable source of seed photons for inverse Compton scattering. In the radio bands, we find progressive delays of the most prominent light-curve maxima with decreasing frequency, as expected from the frequency dependence of the τ = 1 surface of synchrotron self-absorption. The global maximum in the 86 GHz light curve becomes less prominent at lower frequencies, while a local maximum, appearing in 2014, strengthens toward decreasing frequencies, becoming pronounced at ∼5 GHz. These tendencies suggest different Doppler boosting of stratified radio-emitting zones in the jet.