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Owing to their exceptional properties, hard materials such as advanced ceramics, metals and composites have enormous economic and societal value, with applications across numerous industries. Understanding their microstructural characteristics is crucial for enhancing their performance, materials development and unleashing their potential for future innovative applications. However, their microstructures are unambiguously hierarchical and typically span several length scales, from sub-ångstrom to micrometres, posing demanding challenges for their characterization, especially for in situ characterization which is critical to understanding the kinetic processes controlling microstructure formation. This review provides a comprehensive description of the rapidly developing technique of ultra-small angle X-ray scattering (USAXS), a nondestructive method for probing the nano-to-micrometre scale features of hard materials. USAXS and its complementary techniques, when developed for and applied to hard materials, offer valuable insights into their porosity, grain size, phase composition and inhomogeneities. We discuss the fundamental principles, instrumentation, advantages, challenges and global status of USAXS for hard materials. Using selected examples, we demonstrate the potential of this technique for unveiling the microstructural characteristics of hard materials and its relevance to advanced materials development and manufacturing process optimization. We also provide our perspective on the opportunities and challenges for the continued development of USAXS, including multimodal characterization, coherent scattering, time-resolved studies, machine learning and autonomous experiments. Our goal is to stimulate further implementation and exploration of USAXS techniques and inspire their broader adoption across various domains of hard materials science, thereby driving the field toward discoveries and further developments.

In many food applications, the mechanical properties of fats play a critical role in determining the processing performance of fat-rich products. In fact, fat crystal networks form a particular class of soft materials that exhibit viscoelastic properties. The uniqueness of the mechanical response is intricately linked to the hierarchical nature of the system, as fats possess a complex architecture encompassing features at different scale levels (i.e., length scales). Since the discovery of crystalline nanoplatelets (CNPs), it has been hypothesized that CNPs are the basic building blocks of lipid networks and that CNPs are the responsible units for the mechanical properties of fats. This hypothesis, however, has only been partially tested. In this article, we examine which units could be responsible (e.g., lamellae, CNP, CNP aggregates) for the mechanical breakdown of fat crystal networks, through Rheo-USAXS in beamline ID02 (ESRF, Grenoble, France). Time-resolved USAXS profiles were acquired during the three steps of a three-interval thixotropy test (3iTT), namely, pre-shear, shear and recovery. The results were then utilized to evidence which specific length scale is arranged (i.e., orientated) during rheological breakdown. The findings suggest that, at the tested shear rates, orientation is only visible from 250 nm onwards, suggesting that the rheological breakdown of triglycerides is primarily driven by the orientation, and possible disruption, of CNP aggregates. These results reveal the critical role of CNP aggregates in the mechanical properties of fats. In the longer term, we believe this study will steer future research toward a more focused understanding of CNP aggregation and disaggregation dynamics. [ABSTRACT FROM AUTHOR]

Palm oil (PO), a semi-solid fat at room temperature, is a popular food ingredient. To steer the fat functionality, sucrose esters (SEs) are often used as food additives. Many SEs exist, varying in their hydrophilic-to-lipophilic balance (HLB), making them suitable for various food and non-food applications. In this study, a stearic–palmitic sucrose ester with a moderate HLB (6) was studied. It was found that the SE exhibited a complex thermal behavior consistent with smectic liquid crystals (type A). Small-angle X-ray scattering revealed that the mono- and poly-esters of the SE have different packings, more specifically, double and single chain-length packing. The polymorphism encountered upon crystallization was repeatable during successive heating and cooling cycles. After studying the pure SE, it was added to palm oil, and the crystallization behavior of the mixture was compared to that of pure palm oil. The crystallization conditions were varied by applying cooling at 20 °C/min (fast) and 1 °C/min (slow) to 0 °C, 20 °C or 25 °C. The samples were followed for one hour of isothermal time. Differential scanning calorimetry (DSC) showed that nucleation and polymorphic transitions were accelerated. Wide-angle X-ray scattering (WAXS) unraveled that the α-to-β′ polymorphic transition remained present upon the addition of the SE. SAXS showed that the addition of the SE at 0.5 wt% did not significantly change the double chain-length packing of palm oil, but it decreased the domain size when cooling in a fast manner. Ultra-small-angle X-ray scattering (USAXS) revealed that the addition of the SE created smaller crystal nanoplatelets (CNPs). The microstructure of the fat crystal network was visualized by means of polarized light microscopy (PLM) and cryo-scanning electron microscopy (cryo-SEM). The addition of the SE created a finer and space-filling network without the visibility of separate floc structures. [ABSTRACT FROM AUTHOR]

This article describes a correction procedure for the removal of indirect background contributions to measured small‐angle X‐ray scattering patterns. The high scattering power of a sample in the ultra‐small‐angle region may serve as a secondary source for a window placed in front of the detector. The resulting secondary scattering appears as a sample‐dependent background in the measured pattern that cannot be directly subtracted. This is an intricate problem in measurements at ultra‐low angles, which can significantly reduce the useful dynamic range of detection. Two different procedures are presented to retrieve the real scattering profile of the sample. [ABSTRACT FROM AUTHOR]

Palm oil (PO) is still widely used for the production of all types of food products. Due to its triacylglycerol (TG) composition, PO is semisolid at ambient temperature, offering possibilities for many applications. In order to tailor the fat crystal network for certain applications, it remains imperative to understand the structural build-up of the fat crystal network at the full-length scale and to understand the effect of processing conditions. In this study, PO was crystallized under four temperature protocols (fast (FC) or slow (SC) cooling to 20 °C or 25 °C) and was followed for one hour of isothermal time. A broad toolbox was used to fundamentally unravel the structural build-up of the fat crystal network at different length scales. Wide-angle and small-angle X-ray scattering (WAXS and SAXS) showed transitions from α-2L to β'-2L over time. Despite the presence of the same polymorphic form (β'), chain length structure (2L), and domain size, ultra-small-angle X-ray scattering (USAXS) showed clear differences in the mesoscale. For all samples, the lamellar organization was confirmed. Both cooling speed and isothermal temperature were found to affect the size of the crystal nanoplatelets (CNPs), where the highest cooling speed and lowest isothermal temperature (FC and 20 °C) created the smallest CNPs. The microstructure was visualized with polarized light microscopy (PLM) and cryo-scanning electron microscopy (cryo-SEM), showing clear differences in crystallite size, clustering, and network morphology. Raman spectroscopy was applied to confirm differences in triglyceride distribution in the fat crystal network. This study shows that both cooling rate and isothermal temperature affect the fat crystal network formed, especially at the meso- and microscale. [ABSTRACT FROM AUTHOR]

Recent technical developments and the performance of the X-ray photon correlation spectroscopy (XPCS) method over the ultra-small-angle range with the Extremely Brilliant Source (EBS) at the ESRF are described. With higher monochromatic coherent photon flux (∼1012 photons s−1) provided by the EBS and the availability of a fast pixel array detector (EIGER 500K detector operating at 23000 frames s−1), XPCS has become more competitive for probing faster dynamics in relatively dilute suspensions. One of the goals of the present development is to increase the user-friendliness of the method. This is achieved by means of a Python-based graphical user interface that enables online visualization and analysis of the processed data. The improved performance of XPCS on the Time-Resolved Ultra-Small-Angle X-ray Scattering instrument (ID02 beamline) is demonstrated using dilute model colloidal suspensions in several different applications.

The microstructure of a compressed explosive solid is closely related to its shock sensitivity and mechanical properties. In this study, ultra-small-angle and small-angle X-ray scattering (USAXS and SAXS) techniques were combined to explore the hierarchical microstructure of die-pressed 2,4,6-trinitro-1,3,5-benzenetriamine (TATB) discs obtained from nanostructured TATB (nano-TATB) powder as the precursor. Using the Guinier-Porod model, the pseudo-invariants, and Porod's law, this study analyzed the microstructures of the materials on a nanometer scale to track the changes in void size, porosity, and interfacial area, which reflected the response of TATB under applied pressures of 1, 2, 5, 10, 15 ​kN and 30 ​kN. Results show that there existed three populations of voids in the measured q range. The intergranular voids with sizes of tens of nanometers were sensitive to low pressures (15 ​kN), as indicated by the decrease in the volume fractal dimension. Porosities of the voids with sizes of 1–900 ​nm, which were determined by the pseudo-invariants obtained from the scattering data, decreased from 6% to 1% as the pressures increased from 1 ​kN to 30 ​kN. The response of these structural parameters to external pressures implies that the main densification mechanisms under die compression include the flow, fracturing, and plastic deformation of the TATB granules. This study provides a direct insight into the structural evolution of TATB during compression.

Recent technical developments and the performance of the X-ray photon correlation spectroscopy (XPCS) method over the ultra-small-angle range with the Extremely Brilliant Source (EBS) at the ESRF are described. With higher monochromatic coherent photon flux (~1012 photons s-1) provided by the EBS and the availability of a fast pixel array detector (EIGER 500K detector operating at 23000 frames s-1), XPCS has become more competitive for probing faster dynamics in relatively dilute suspensions. One of the goals of the present development is to increase the user-friendliness of the method. This is achieved by means of a Python-based graphical user interface that enables online visualization and analysis of the processed data. The improved performance of XPCS on the Time-Resolved Ultra-Small-Angle X-ray Scattering instrument (ID02 beamline) is demonstrated using dilute model colloidal suspensions in several different applications. [ABSTRACT FROM AUTHOR]

Three oleogelator molecules (Triacontane (TC), Stearic acid (SA), and Behenyl Lignocerate (BL)) were studied individually, in pairs, or all together to make an oleogel using triolein as the oil. WAXS, SAXS and USAXS were used to elucidate the solid structures from angstroms to a few micrometers. A two‐dimensional mapping of atomic positions for each molecule was carried out to understand the crystalline multilayer structures formed. We assumed that the molecules were rigidly extended and that they underwent no significant (hindered) rotations so that the free energy is determined by the Lennard‐Jones interactions of closely packed multilayers. TC molecules were predicted to form a tilt angle of θt≈33°, yielding a SAXS line at q≈0.194 Å─1, in acceptable agreement with the measured q=0.181Å−1. For SA crystals θt≈33° (predicted) yielding a SAXS line at q=0.150Å−1 compared to q=0.159Å−1 (observed). No mixed crystals were observed for any pair of molecules or when all three were used. USAXS data showed that SA forms large nanocrystals compared to TC and BL. All three combinations of molecular pairs showed basic scatterers smaller or similar to those of individual molecules. The theory presented here, together with the experimental results, showed why no mixed crystals are formed from two or all three molecules. Data from the USAXS region suggested that, when using all three molecules, a more compact fractal structure was obtained, compared with those if one or two of the molecules were used. [ABSTRACT FROM AUTHOR]

In many food applications, the mechanical properties of fats play a critical role in determining the processing performance of fat-rich products. In fact, fat crystal networks form a particular class of soft materials that exhibit viscoelastic properties. The uniqueness of the mechanical response is intricately linked to the hierarchical nature of the system, as fats possess a complex architecture encompassing features at different scale levels (i.e., length scales). Since the discovery of crystalline nanoplatelets (CNPs), it has been hypothesized that CNPs are the basic building blocks of lipid networks and that CNPs are the responsible units for the mechanical properties of fats. This hypothesis, however, has only been partially tested. In this article, we examine which units could be responsible (e.g., lamellae, CNP, CNP aggregates) for the mechanical breakdown of fat crystal networks, through Rheo-USAXS in beamline ID02 (ESRF, Grenoble, France). Time-resolved USAXS profiles were acquired during the three steps of a three-interval thixotropy test (3iTT), namely, pre-shear, shear and recovery. The results were then utilized to evidence which specific length scale is arranged (i.e., orientated) during rheological breakdown. The findings suggest that, at the tested shear rates, orientation is only visible from 250 nm onwards, suggesting that the rheological breakdown of triglycerides is primarily driven by the orientation, and possible disruption, of CNP aggregates. These results reveal the critical role of CNP aggregates in the mechanical properties of fats. In the longer term, we believe this study will steer future research toward a more focused understanding of CNP aggregation and disaggregation dynamics.

ZnO inverse opals combine the outstanding properties of the semiconductor ZnO with the high surface area of the open-porous framework, making them valuable photonic and catalysis support materials. One route to produce inverse opals is to mineralize the voids of close-packed polymer nanoparticle templates by chemical bath deposition (CBD) using a ZnO precursor solution, followed by template removal. To ensure synthesis control, the formation and growth of ZnO nanoparticles in a precursor solution containing the organic additive polyvinylpyrrolidone (PVP) was investigated by in situ ultra-small- and small-angle X-ray scattering (USAXS/SAXS). Before that, we studied the precursor solution by in-house SAXS at T = 25 °C, revealing the presence of a PVP network with semiflexible chain behavior. Heating the precursor solution to 58 °C or 63 °C initiates the formation of small ZnO nanoparticles that cluster together, as shown by complementary transmission electron microscopy images (TEM) taken after synthesis. The underlying kinetics of this process could be deciphered by quantitatively analyzing the USAXS/SAXS data considering the scattering contributions of particles, clusters, and the PVP network. A nearly quantitative description of both the nucleation and growth period could be achieved using the two-step Finke–Watzky model with slow, continuous nucleation followed by autocatalytic growth. [ABSTRACT FROM AUTHOR]

Palm oil (PO) is still widely used for the production of all types of food products. Due to its triacylglycerol (TG) composition, PO is semisolid at ambient temperature, offering possibilities for many applications. In order to tailor the fat crystal network for certain applications, it remains imperative to understand the structural build-up of the fat crystal network at the full-length scale and to understand the effect of processing conditions. In this study, PO was crystallized under four temperature protocols (fast (FC) or slow (SC) cooling to 20 °C or 25 °C) and was followed for one hour of isothermal time. A broad toolbox was used to fundamentally unravel the structural build-up of the fat crystal network at different length scales. Wide-angle and small-angle X-ray scattering (WAXS and SAXS) showed transitions from α-2L to β’-2L over time. Despite the presence of the same polymorphic form (β’), chain length structure (2L), and domain size, ultra-small-angle X-ray scattering (USAXS) showed clear differences in the mesoscale. For all samples, the lamellar organization was confirmed. Both cooling speed and isothermal temperature were found to affect the size of the crystal nanoplatelets (CNPs), where the highest cooling speed and lowest isothermal temperature (FC and 20 °C) created the smallest CNPs. The microstructure was visualized with polarized light microscopy (PLM) and cryo-scanning electron microscopy (cryo-SEM), showing clear differences in crystallite size, clustering, and network morphology. Raman spectroscopy was applied to confirm differences in triglyceride distribution in the fat crystal network. This study shows that both cooling rate and isothermal temperature affect the fat crystal network formed, especially at the meso- and microscale.

Self-propelled particulate systems manifest certain collective behavior of living matter, which have been the subject of intense research over the past decades. One of the elegant methods for realizing such active motions is by means of custom synthesized Janus particles suspended in a catalytic medium that can be triggered upon illumination by ultraviolet light. In this work, the evolution of the particle dynamics from passive diffusive to active ballistic behavior upon light illumination was probed by multispeckle x-ray photon correlation spectroscopy (XPCS). This technique enables not only studying the emergence of active motions in three dimensions (3D) but also deciphering different contributions to the overall dynamics. Using a combination of homodyne and heterodyne analysis, the ensemble averaged mean velocity, velocity fluctuations and diffusion coefficient of particles were determined in the thermodynamic limit. Results revealed a gradual transition from diffusive to ballistic dynamics with systematic increase of the catalytic activity. At the intermediate region, the dynamics is dominated by Gaussian velocity fluctuations and an enhanced relaxation rate with a weaker wave vector dependence similar to superdiffusive behavior. For the highest activity, the dynamics became purely ballistic with Lorentzian-like distribution of velocity fluctuations. Presented results demonstrate that different aspects of active dynamics can be investigated in 3D over a broad range of PĂ©clet numbers and other control parameters by means of multispeckle XPCS. [ABSTRACT FROM AUTHOR]

Determination of the orientation of microfibrils within ultra-high molecular weight polyethylene (UHMWPE) fibers is considered to be an important method in evaluating the mechanical properties of the fibers. Four commonly used orientation evaluation methods are summarized and used to evaluate UHMWPE fibers at different drawing stages in the industrial line, and the results exhibit certain limitations. To overcome these limitations, a new evaluation method for quantitive characterization of UHMWPE fiber properties is proposed. Meanwhile, in situ small-angle X-ray scattering data of an UHMWPE fiber drawn at 100 °C were used to perform a Pearson correlation coefficient test, and the results show a very strong correlation between the strain ratio and the evaluated coefficient. [ABSTRACT FROM AUTHOR]

ZnO inverse opals combine the outstanding properties of the semiconductor ZnO with the high surface area of the open-porous framework, making them valuable photonic and catalysis support materials. One route to produce inverse opals is to mineralize the voids of close-packed polymer nanoparticle templates by chemical bath deposition (CBD) using a ZnO precursor solution, followed by template removal. To ensure synthesis control, the formation and growth of ZnO nanoparticles in a precursor solution containing the organic additive polyvinylpyrrolidone (PVP) was investigated by in situ ultra-small- and small-angle X-ray scattering (USAXS/SAXS). Before that, we studied the precursor solution by in-house SAXS at T = 25 °C, revealing the presence of a PVP network with semiflexible chain behavior. Heating the precursor solution to 58 °C or 63 °C initiates the formation of small ZnO nanoparticles that cluster together, as shown by complementary transmission electron microscopy images (TEM) taken after synthesis. The underlying kinetics of this process could be deciphered by quantitatively analyzing the USAXS/SAXS data considering the scattering contributions of particles, clusters, and the PVP network. A nearly quantitative description of both the nucleation and growth period could be achieved using the two-step Finke–Watzky model with slow, continuous nucleation followed by autocatalytic growth.

[Display omitted] Self-assembled lyotropic phases are important in a variety of applications, in particular microemulsions are essential for formulation science. A spectacular situation arises when microemulsions are made to swell by systematically increasing the bending modulus of the surfactant film separating the oil and water regions. In an attempt to realize such extremely swollen microemulsion phases, Peter et al. [ Phys. Rev. Lett. , 76 (1996) 3866] found a variety of lyotropic phases including a long-range ordered three-dimensional cubic phase over a narrow section of the complex phase diagram of a pseudo-quaternary system composed of decane, brine, octanol, and sodium dodecyl sulfate. In this work, the same region of the phase diagram was reinvestigated using high-resolution small-angle X-ray scattering (HR-SAXS) and rheo-SAXS, which is an important technical aspect for homogenizing the sample and orienting the structural units. Whilst the formation of a swollen two-dimensional hexagonal phase was observed, the structural features of a cubic phase were not detected. The long correlation lengths noted prior were also seen here, over 2000 nm for the hexagonal phase, taken from rheo-SAXS measurements. Based on the measurements covering more than three orders of magnitude in scattering vector, the structure appeared to be an organization of elongated swollen emulsion droplets, which could form an interconnected structure, dense liquid-like order, or further order into a hexagonal morphology with unusually large lattice spacings for a surfactant system. [ABSTRACT FROM AUTHOR]

The new technical features and enhanced performance of the ID02 beamline with the Extremely Brilliant Source (EBS) at the ESRF are described. The beamline enables static and kinetic investigations of a broad range of systems from ångström to micrometre size scales and down to the sub‐millisecond time range by combining different small‐angle X‐ray scattering techniques in a single instrument. In addition, a nearly coherent beam obtained in the high‐resolution mode allows multispeckle X‐ray photon correlation spectroscopy measurements down to the microsecond range over the ultra‐small‐ and small‐angle regions. While the scattering vector (of magnitude q) range covered is the same as before, 0.001 ≤ q ≤ 50 nm−1 for an X‐ray wavelength of 1 Å, the EBS permits relaxation of the collimation conditions, thereby obtaining a higher flux throughput and lower background. In particular, a coherent photon flux in excess of 1012 photons s−1 can be routinely obtained, allowing dynamic studies of relatively dilute samples. The enhanced beam properties are complemented by advanced pixel‐array detectors and high‐throughput data reduction pipelines. All these developments together open new opportunities for structural, dynamic and kinetic investigations of out‐of‐equilibrium soft matter and biophysical systems. [ABSTRACT FROM AUTHOR]

Currently, the actual mechanical properties of carbon fibers (CF) differ significantly from the theoretical values. This is primarily attributed to significant limitations imposed by structural defects, greatly hindering the widespread application of CF. To solve this problem, we used in situ growth of zeolitic imidazolate framework-8 (ZIF-8) and γ rays to modulate the core-shell of CF in this study. For the surface structure of CF during the process of γ irradiation, the organic structure within ZIF-8 gradually degrades and forms a cross-linking structure with the surface defects of the CF. This process significantly enhances the binding strength between inorganic material from the postdecomposition of ZIF-8 and the carbon layer on the surface of CF, repairing the surface defects. For the internal structure of CF, γ irradiation can improve the orientation of the internal micropores of CF and increase the degree of internal graphitization of CF. In this paper, an in-depth analysis of CF before and after repair was conducted by using characterization techniques such as nanoindentation and ultrasmall angle X-ray scattering (USAXS). Compared to unmodified CF, its mechanical properties improved by approximately 19.99%, which exceeds that in approximately 95% of similar works in the field.

Owing to their exceptional properties, hard materials such as advanced ceramics, metals and composites have enormous economic and societal value, with applications across numerous industries. Understanding their microstructural characteristics is crucial for enhancing their performance, materials development and unleashing their potential for future innovative applications. However, their microstructures are unambiguously hierarchical and typically span several length scales, from sub-ångstrom to micrometres, posing demanding challenges for their characterization, especially for in situ characterization which is critical to understanding the kinetic processes controlling microstructure formation. This review provides a comprehensive description of the rapidly developing technique of ultra-small angle X-ray scattering (USAXS), a nondestructive method for probing the nano-to-micrometre scale features of hard materials. USAXS and its complementary techniques, when developed for and applied to hard materials, offer valuable insights into their porosity, grain size, phase composition and inhomogeneities. We discuss the fundamental principles, instrumentation, advantages, challenges and global status of USAXS for hard materials. Using selected examples, we demonstrate the potential of this technique for unveiling the microstructural characteristics of hard materials and its relevance to advanced materials development and manufacturing process optimization. We also provide our perspective on the opportunities and challenges for the continued development of USAXS, including multimodal characterization, coherent scattering, time-resolved studies, machine learning and autonomous experiments. Our goal is to stimulate further implementation and exploration of USAXS techniques and inspire their broader adoption across various domains of hard materials science, thereby driving the field toward discoveries and further developments., (open access.)

Applications of small-angle scattering (SAS) in structural biology have benefited from continuing developments in instrumentation, tools for data analysis, modeling capabilities, standards for data and model presentation, and data archiving. The interplay of these capabilities has enabled SAS to contribute to advances in structural biology as the field pushes the boundaries in studies of biomolecular complexes and assemblies as large as whole cells, membrane proteins in lipid environments, and dynamic systems on time scales ranging from femtoseconds to hours. This review covers some of the important advances in biomolecular SAS capabilities for structural biology focused on over the last 5 years and presents highlights of recent applications that demonstrate how the technique is exploring new territories. [Display omitted] This review highlights how recent technical advances in small-angle X-ray and neutron scattering with contrast variation have contributed to our expanding knowledge of biomolecular complexes and assemblies as large as whole cells, membrane proteins in lipid environments, lipid structures, and dynamic systems on time scales ranging from femtoseconds to hours. [ABSTRACT FROM AUTHOR]

The solvent composition of the catalyst ink profoundly impacts both the porous structure and the efficiency of the mass-production process of the catalyst layer for polymer electrolyte fuel cells. However, the underlying mechanism remains far from elucidated. Here, we present the size of aggregate and the fractal dimension of the agglomerate structure as determined by ultra-small X-ray scattering (USAXS) of the catalyst inks with varied solvent composition. By examining the correlations between the structural properties provided by USAXS, rheological properties, and the quantity of ionomer adsorbed on the Pt/C, we elucidate the solvent's influence on the agglomerate structure. In highly polar solvents, akin to water, a considerable number of amphiphilic ionomers adsorb to the Pt/C particles, resulting in the formation of dispersed Pt/C aggregate particles approximately 200 nm in size that cannot be subdivided further into smaller particles even with the use of a homogenizer. As the polarity diminishes with the addition of alcohol content, ionomers desorb, and the affinity between the aggregates and the solvent decreases, leading to the evolution of agglomerates. The observed solvent effect can be rationally characterized by one of Hansen's solubility parameters, which specifies the polar interaction. [Display omitted] • Formation mechanism of the agglomerate structure in the catalyst ink of PEFC was investigated. • USAXS reveals changes in the agglomerate structure with varied solvent compositions. • In low-polarity solvents, ionomers desorb from Pt/C, facilitating agglomerate evolution. • Increased polarity leads to ionomer adsorption and dispersion of agglomerates into aggregates. • The observed solvent effects can be rationally characterized by HSP- δ P. [ABSTRACT FROM AUTHOR]

Ultra‐SAXS can enhance the capabilities of existing synchrotron SAXS/WAXS beamlines. A compact ultra‐SAXS module has been developed, which extends the measurable q‐range with 0.0015 ≤ q (nm−1) ≤ 0.2, allowing structural dimensions in the range 30 ≤ D (nm) ≤ 4000 to be probed in addition to the range covered by a high‐end SAXS/WAXS instrument. By shifting the module components in and out on their respective motor stages, SAXS/WAXS measurements can be easily and rapidly interleaved with USAXS measurements. The use of vertical crystal rotation axes (horizontal diffraction) greatly simplifies the construction, at minimal cost to efficiency. In this paper, the design considerations, realization and synchrotron findings are presented. Measurements of silica spheres, an alumina membrane, and a porous carbon catalyst are provided as application examples. [ABSTRACT FROM AUTHOR]

A previously reported multi‐scale model for (ultra‐)small‐angle X‐ray (USAXS/SAXS) and (very) small‐angle neutron scattering (VSANS/SANS) of live Escherichia coli was revised on the basis of compositional/metabolomic and ultrastructural constraints. The cellular body is modeled, as previously described, by an ellipsoid with multiple shells. However, scattering originating from flagella was replaced by a term accounting for the oligosaccharide cores of the lipopolysaccharide leaflet of the outer membrane including its cross‐term with the cellular body. This was mainly motivated by (U)SAXS experiments showing indistinguishable scattering for bacteria in the presence and absence of flagella or fimbrae. The revised model succeeded in fitting USAXS/SAXS and differently contrasted VSANS/SANS data of E. coli ATCC 25922 over four orders of magnitude in length scale. Specifically, this approach provides detailed insight into structural features of the cellular envelope, including the distance of the inner and outer membranes, as well as the scattering length densities of all bacterial compartments. The model was also successfully applied to E. coli K12, used for the authors' original modeling, as well as for two other E. coli strains. Significant differences were detected between the different strains in terms of bacterial size, intermembrane distance and its positional fluctuations. These findings corroborate the general applicability of the approach outlined here to quantitatively study the effect of bactericidal compounds on ultrastructural features of Gram‐negative bacteria without the need to resort to any invasive staining or labeling agents. [ABSTRACT FROM AUTHOR]

Self-propelled particulate systems manifest certain collective behavior of living matter, which have been the subject of intense research over the past decades. One of the elegant methods for realizing such active motions is by means of custom synthesized Janus particles suspended in a catalytic medium that can be triggered upon illumination by ultraviolet light. In this work, the evolution of the particle dynamics from passive diffusive to active ballistic behavior upon light illumination was probed by multispeckle x-ray photon correlation spectroscopy (XPCS). This technique enables not only studying the emergence of active motions in three dimensions (3D) but also deciphering different contributions to the overall dynamics. Using a combination of homodyne and heterodyne analysis, the ensemble averaged mean velocity, velocity fluctuations and diffusion coefficient of particles were determined in the thermodynamic limit. Results revealed a gradual transition from diffusive to ballistic dynamics with systematic increase of the catalytic activity. At the intermediate region, the dynamics is dominated by Gaussian velocity fluctuations and an enhanced relaxation rate with a weaker wave vector dependence similar to superdiffusive behavior. For the highest activity, the dynamics became purely ballistic with Lorentzian-like distribution of velocity fluctuations. Presented results demonstrate that different aspects of active dynamics can be investigated in 3D over a broad range of Péclet numbers and other control parameters by means of multispeckle XPCS.

Crystal collimation offers a viable alternative to the commonly used pinhole collimation in small‐angle X‐ray scattering (SAXS) for specific applications requiring highest angular resolution. This scheme is not affected by the parasitic scattering and diffraction‐limited beam broadening. The Darwin width of the rocking curve of the crystals mainly defines the ultimate beam divergence. For this purpose, a dispersive Si‐111 crystal collimation set‐up based on two well conditioned pseudo channel‐cut crystals (pairs of well polished, independent parallel crystals) using a higher‐order reflection (Si‐333) has been developed. The gain in resolution is obtained at the expense of flux. The system has been installed at the TRUSAXS beamline ID02 (ESRF) for reducing the horizontal beam divergence in high‐resolution mesurements. The precise mechanics of the system allows reproducible alignment of the Bragg condition. The high resolution achieved at a sample–detector distance of 31 m is demonstrated by ultra‐small‐angle X‐ray scattering measurements on a model system consisting of micrometre‐sized polystyrene latex particles with low polydispersity. A dispersive Si‐111 crystal collimation set‐up based on two well conditioned pseudo channel‐cut crystals using higher‐order reflections has been developed and installed at the TRUSAXS beamline ID02 at the ESRF. This scheme is not limited by either the scattering or the diffraction by the slits, offering the highest angular resolution at the expense of flux for ultra‐small‐angle X‐ray scattering (USAXS) applications. The performance is demonstrated by USAXS measurements on micrometre‐sized spherical particles with low polydispersity. [ABSTRACT FROM AUTHOR]

X-ray phase contrast imaging (XPCI) methods give access to contrast mechanisms that are based on the refractive properties of matter on top of the absorption coefficient in conventional x-ray imaging. Ultra small angle x-ray scattering (USAXS) is a phase contrast mechanism that arises due to multiple refraction events caused by physical features of a scale below the physical resolution of the used imaging system. USAXS contrast can therefore give insight into subresolution structural information, which is an ongoing research topic in the vast field of different XPCI techniques. In this study, we quantitatively compare the USAXS signal retrieved by the beam tracking XPCI technique with the gold standard of the analyzer based imaging XPCI technique using a synchrotron x-ray source. We find that, provided certain conditions are met, the two methods measure the same quantity., Competing Interests: The authors have no conflicts to disclose., (© 2023 The Author(s). Published by IOP Publishing Ltd.)

This article presents the main technical features and performance of the upgraded beamline ID02 at the ESRF. The beamline combines different small‐angle X‐ray scattering techniques in one unique instrument, enabling static and kinetic investigations from ångström to micrometre size scales and time resolution down to the sub‐millisecond range. The main component of the instrument is an evacuated detector tube of length 34 m and diameter 2 m. Several different detectors are housed inside a motorized wagon that travels along a rail system, allowing an automated change of the sample–detector distance from about 1 to 31 m as well as selection of the desired detector. For optional combined wide‐angle scattering measurements, a wide‐angle detector is installed at the entrance cone of the tube. A scattering vector (of magnitude q) range of 0.002 ≤ q ≤ 50 nm−1 is covered with two sample–detector distances and a single‐beam setting for an X‐ray wavelength of 1 Å. In the high‐resolution mode, two‐dimensional ultra‐small‐angle X‐ray scattering patterns down to q < 0.001 nm−1 can be recorded, and the resulting one‐dimensional profiles have superior quality as compared to those measured with an optimized Bonse–Hart instrument. In the highest‐resolution mode, the beam is nearly coherent, thereby permitting multispeckle ultra‐small‐angle X‐ray photon correlation spectroscopy measurements. The main applications of the instrument include the elucidation of static and transient hierarchical structures, and nonequilibrium dynamics in soft matter and biophysical systems. The technical features and performance of a new instrument for time‐resolved ultra‐small‐angle and coherent X‐ray scattering are presented. The instrument enables static and kinetic investigations from ångström to micrometre size scales and time resolution down to the sub‐millisecond range. Applications include elucidation of static and transient hierarchical structures in soft matter and biophysical systems. [ABSTRACT FROM AUTHOR]

Successful implementation of the single‐photon‐counting Eiger 500k pixel array detector for sub‐millisecond X‐ray photon correlation spectroscopy (XPCS) measurements in the ultra‐small‐angle scattering region is reported. The performance is demonstrated by measuring the dynamics of dilute silica colloids in aqueous solvents when the detector is operated at different counter depths, 4, 8 and 12 bit. In the fastest mode involving 4 bit parallel readout, a stable frame rate of 22 kHz is obtained that enabled measurement of intensity–intensity autocorrelation functions with good statistics down to the 50 µs range for a sample with sufficient scattering power. The high frame rate and spatial resolution together with large number of pixels of the detector facilitate the investigation of sub‐millisecond dynamics over a broad length scale by multispeckle XPCS. This is illustrated by an example involving phoretic motion of colloids during the phase separation of the solvent. The performance of the high‐resolution fast‐photon‐counting Eiger 500k detector for sub‐millisecond X‐ray photon correlation spectroscopy measurement is demonstrated. [ABSTRACT FROM AUTHOR]

A three‐image algorithm is proposed in order to retrieve the absorption, refraction and ultra‐small‐angle X‐ray scattering (USAXS) properties of the object in X‐ray analyzer‐based imaging. Based on the Gaussian fitting to the rocking curve, the novel algorithm is theoretically derived and presented, and validated by synchrotron radiation experiments. Compared with multiple‐image radiography, this algorithm only requires a minimum of three intensity measurements, and is therefore advantageous in terms of simplified acquisition procedure and reduced data collection times, which are especially important for specific applications such as in vivo imaging and phase tomography. Moreover, the retrieval algorithm can be specialized to particular cases where some degree of a priori knowledge on the object is available, potentially reducing the minimum number of intensity measurements to two. Furthermore, the effect of angular mis‐alignment on the accuracy of the retrieved images was theoretically investigated, which can be of use in image interpretation and optimization of the data acquisition procedure. [ABSTRACT FROM AUTHOR]

An experimental study of the influence of multiple‐scattering events on data acquired by small‐angle X‐ray scattering (SAXS) and X‐ray photon correlation spectroscopy (XPCS) techniques in the ultra‐small‐angle range is presented. Both techniques rely on the single‐scattering assumption and any deviation may lead to erroneous interpretation of structural and dynamical results. Typical effects of multiple scattering on measured static and dynamic scattering from model colloidal suspensions are presented, and it is demonstrated that the same information content as in a single‐scattering experiment can be extracted after applying appropriate corrections. The perturbations induced by multiple scattering on resolution, photon statistics and speckle visibility are evaluated and the required optimal experimental conditions are discussed. In many cases, multiple scattering might be tolerable to a certain extent, especially if any shortcomings are outweighed by beneficial effects from counting statistics, acquisition time and signal‐to‐background ratio. The presented study may help to optimize future experiments and serve as a guide for data evaluation for this type of system. [ABSTRACT FROM AUTHOR]

The physical mechanisms characterizing the breakup of a diesel spray into droplets are still unknown. This gap in knowledge has largely been due to the challenges of directly imaging this process or quantitatively measuring the outcomes of spray breakup, such as droplet size. Recent x-ray measurements by Argonne National Laboratory, utilized in this work, provide needed information about the spatial evolution of droplet sizes in selected regions of the spray under a range of injection pressures (50–150 MPa) and ambient densities (7.6–22.8 kg/m 3 ) relevant for diesel operating conditions. Ultra-small angle x-ray scattering (USAXS) measurements performed at the Advanced Photon Source are presented, which quantify Sauter mean diameters ( SMD ) within optically thick regions of the spray that are inaccessible by conventional droplet sizing measurement techniques, namely in the near-nozzle region, along the spray centerline, and within the core of the spray. To quantify droplet sizes along the periphery of the spray, a complementary technique is proposed and introduced, which leverages the ratio of path-integrated x-ray and visible laser extinction (SAMR) measurements to quantify SMD . The SAMR and USAXS measurements are then utilized to evaluate current spray models used for engine computational fluid dynamic (CFD) simulations. We explore the ability of a carefully calibrated spray model, premised on aerodynamic wave growth theory, to capture the experimentally observed trends of SMD throughout the spray. The spray structure is best predicted with an aerodynamic primary and secondary breakup process that is represented with a slower time constant and larger formed droplet size than conventionally recommended for diesel spray models. Additionally, spray model predictions suggest that droplet collisions may not influence the resultant droplet size distribution along the spray centerline in downstream regions of the spray. [ABSTRACT FROM AUTHOR]

Nanoparticle electrodeposition is a simple and scalable approach to synthesizing supported nanoparticles. Used with a deep eutectic solvent (DES), surface nanoparticles can be assembled and exhibit unique surface charge separation when the DES is adsorbed on the nanoparticle surface. Key to understanding and controlling the assembly and the capacitance is a thorough understanding of surface particle mobility and charge screening, which requires an in-situ approach. In this study, Pb particle formation, size, shape and capacitance are resolved in a 1:2 choline Cl − : urea deep eutectic solvent whilst sweeping the cell potential in the range: 0.2 V to −1.2 V (vs. Ag/AgCl). These system parameters were resolved using a complementary suite of sample-rotated small angle X-ray scattering (SR-SAXS) and electrochemical impedance spectroscopy (EIS), which are presented and discussed in detail. This approach is able to show that both particle and ion transport are impeded in the DES, as aggregation occurs over the course of 6 minutes, and dissolved Pb ions accumulate and remain near the surface after a nucleation pulse is applied. The DES-Pb interactions strongly depend on the cell potential as evidenced by the specific differential capacitance of the Pb deposit, which has a maximum value of 2.5 +/− 0.5 F g −1 at −1.0 V vs. Ag/AgCl. Altogether, the SR-SAXS-EIS approach is able to characterize the unique nanoparticle capacitance, mobility and ion mobility in a DES and can be used to study a wide range of nanoparticle deposition systems in-situ . [ABSTRACT FROM AUTHOR]

The combination of nanostructured fluids (NSFs), such as micellar solutions or microemulsions and highly-retentive hydrogels, such as PVA-based cryogels, represents nowadays a promising and innovative approach in the field of conservation of cultural heritage, as it enables the highest control available during cleaning interventions. However, at present, little is known about the confinement of NSFs into PVA-based cryogels. In the present work, small-angle X-ray scattering (SAXS) and ultra-small-angle X-ray scattering (USAXS), combined with fluorescence correlation spectroscopy (FCS), were used to address this issue. Two significantly different NSFs were selected for this purpose, based on anionic or nonionic surfactants, and they were confined into four different gels: two single PVA and two PVA/PVA "twin-chain polymer networks" (TC-PNs). The analysis of the experimental results shows that surfactant nature is crucial in determining the interaction of NSFs with the gels' polymer network. Moreover it was demonstrated that loading NSFs on PVA-based cryogels does not significantly affect the short-range nanostructure of neither the NSFs nor the gels, preserving the cleaning performances of the combined system. [Display omitted] • Nanostructured fluids (NSFs) confined in cryogels represent a powerful cleaning tool. • USAXS and FCS were used to study the nanostructure of PVA cryogels/NSFs systems. • USAXS allowed the study of the PVA cryogels' nanostructure on a larger length scale. • NSFs induced minor changes in the gels' nanostructure, i.e. a slight increase in crystallites' size. • FCS clarified that surfactant's nature is key to determine NSF/gel interactions. [ABSTRACT FROM AUTHOR]

The application of small-angle X-ray scattering (SAXS) to whole Escherichia coli cells is challenging owing to the variety of internal constituents. To resolve their contributions, the outer shape was captured by ultra-small-angle X-ray scattering and combined with the internal structure resolved by SAXS. Building on these data, a model for the major structural components of E. coli was developed. It was possible to deduce information on the occupied volume, occurrence and average size of the most important intracellular constituents: ribosomes, DNA and proteins. E. coli was studied after treatment with three different antibiotic agents (chloramphenicol, tetracycline and rifampicin) and the impact on the intracellular constituents was monitored. [ABSTRACT FROM AUTHOR]

Structural arrest in an aging colloid-polymer mixture of charged colloidal disks and weakly interacting polymers is primarily governed by the spatial arrangement of microstructural domains in the system. Here we present a detailed ultra-small angle x-ray scattering (USAXS) study of the polymer induced microstructural changes occurring in systems containing laponite ® and poly(ethylene oxide) (PEO). Laponite ® suspensions are known to transition from a homogeneous fluid to an arrested phase as a function of time. USAXS results show that when polymer chains are added to this colloidal system, the microstructural changes are found to depend on (i) polymer-colloid size ratio, (ii) particle and polymer concentration. Large length scale structures (300–1000 nm) of non-uniformly varying size appear with increasing concentration of high molecular weight PEO ( R g / R ∼ 2.4). However with shorter PEO chains ( R g / R ∼ 0.5), we observe the formation of intermediary structures with a characteristic length scale of 50–60 nm. With increasing particle concentration, we observe a more compact structure for the high molecular weight PEO and no signature of a percolating network in the case of the low molecular PEO. We believe that these results add to our understanding of the complex aging behavior of clay-polymer systems. [ABSTRACT FROM AUTHOR]

ABSTRACT Cavitation behavior in poly(4-methyl-1-pentene) upon stretching below glass transition temperature was investigated by in situ ultra-small angle X-ray scattering technique. Strong stress-whitening was observed indicating an extensive occurrence of cavitation in the material during tensile deformation below Tg. The X-ray scattering patterns suggest oriented disc-shaped cavities with normal mostly parallel to the stretching direction occurred. Structural parameters of such cavities such as thickness, radius, and tilting angle of the normal of the disc with respect to the stretching direction have been successfully calculated using a model fitting procedure. The results exhibited a two-step process of cavitation that small amount of large cavities appeared first and then small cavities were triggered extensively in the samples at larger strains. This two-step cavitation phenomenon can be weakened after the quenched sample was annealed or the sample was prepared by slow cooling. This peculiar two-step cavitation process can be understood as a result of high frozen in internal stress in quenched sample that led to local failure of the materials. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016, 54, 2007-2014 [ABSTRACT FROM AUTHOR]

Multi-speckle X-ray photon correlation spectroscopy (XPCS) measurements in the ultra-small-angle range are performed using a long pinhole collimation instrument in combination with two-dimensional photon-counting and high-sensitivity imaging detectors. The feasibility of the presented setup to measure dynamics on different time and length scales pertinent to colloidal systems is shown. This setup offers new research opportunities, such as for example in the investigation of non-equilibrium dynamics in optically opaque, complex systems over length scales from tens of nanometres to several micrometres. In addition, due to the short duration of the X-ray exposure involved in the ultra-small-angle range, possible radiation-induced effects are alleviated. Furthermore, the performance of two different detectors, a photon-counting Pilatus 300K and an integrating FReLoN CCD, are compared, and their applicability for accurate XPCS measurements is demonstrated. [ABSTRACT FROM AUTHOR]

In this contribution, the composition-temperature phase diagram of a swollen microemulsion system was investigated using high resolution small-angle X-ray scattering to explore the morphological landscape over the selected region of interest. As the oil content was increased, the morphology transformed from a bicontinuous microemulsion, X D < 0.6, to a disordered emulsified-microemulsion, X D > 0.6, consisting of a dense packing of microemulsion droplets, and a hexagonal phase at X D = 0.6. During the heating from room temperature up to the highest temperature, T = 304 K, each composition transitioned into the disordered emulsified-microemulsion morphology, however, while cooling more complex structural changes were observed. Interestingly, for each composition the same sequence of phase transitions was observed during the cooling process, first there was a transition to the emulsified hexagonal phase and then to the bicontinuous microemulsion, likely due to further expulsion of oil, resulting in a composition that would favour a bicontinuous morphology. The dynamics of the microemulsion droplets were probed using X-ray photon correlation spectroscopy, which revealed two relaxation modes, typically found in dense colloidal systems below their glass transition. These results demonstrate the importance of a combined structural and dynamical approach in the studies of dense microemulsion systems, relevant for many industrial applications. [Display omitted] [ABSTRACT FROM AUTHOR]