Metal–organic frameworks such as ZIF-8, grown in situ on nanocellulose (NC), have gained significant attention in recent years due to the versatility of the processing route and multifaceted application in the field of environmental remediation and biomedical applications. However, insights into the interactions between NC and MOF precursors and MOF structure evolution during in situ synthesis are limited or nonexistent. We report the kinetics of ZIF-8 formation on a nanocellulose (NC) aqueous suspension and in water at room temperature, monitored in real time after the addition of ZIF-8 precursors. This is the first study revealing the mechanism of ZIF-8 formation in the presence of nanocellulose. A combination of synchrotron-based small-angle (SAXS) and wide-angle X-ray scattering (WAXS) enabled us to compare the time evolution of the radius of gyration obtained from SAXS and the extent of crystallization determined by WAXS. Based on the SAXS data, we propose a new model that accounts for the initial rapid formation of primary particles, which subsequently evolve into medium-range structures before growing into the final product. Scanning electron microscopy images supported this mechanism, showing smaller particles at the beginning of the reaction and confirmed interparticle interactions, showing nanocellulose particles decorating the surface of the final ZIF-8 crystals. We demonstrate that the concentration of the starting metal salt significantly influences the kinetics of the reaction but has little effect on the ZIF-8 particle size. In contrast, increasing the NC concentration led to a reduction in the final ZIF-8 particle size, while having a negligible impact on the reaction rate and affording a minor decrease in surface area and micropore volume. We show that at the lower NC concentration that was studied the ZIF-8 particles were covered by NC, and no reduction in porosity was observed. Moreover, the kinetics of formation was shown to be independent of the NC functional group and morphology under the conditions used in this study.

Thermochemical treatments like nitrocarburizing and gas nitriding form hardened surface layers of iron nitrides and carbides, improving wear, fatigue, and corrosion resistance in loaded components made of steel. This study employs micro-focused X-ray diffraction (µXRD) imaging at a synchrotron facility to characterize the microstructure of nitrocarburized and gas-nitrided steel surfaces in three steel grades (46MnVS3, 34CrNiMo6, 16CrMnNiMo9–5–2). Through line profile analysis with fine-step mesh grid scanning, we spatially resolve phase distributions and elastic strains in the compound layer. The ε-phase exhibits isotropic residual strain, transitioning from expansion to compression with depth, while the γ’-phase displays anisotropic strain, expanding perpendicular to the surface and compressing parallel to it. These findings highlight µXRD’s potential for detailed structural analysis, enabling optimization of surface hardening processes.

This article elucidates the dissolution of cellulose from different raw materials in NaOH aqueous solution via the combination of synchrotron-radiation-based SAXS/WAXS characterization. The X-ray measurements probed the mesostructure of the cellulose samples during the freeze-thawing cycle allowing tracking the initial swelling of the structure, the kinetics of disintegration of the cellulose crystallites as well as controlling the final state of the cellulose solution, i.e. presence or absence of cellulose aggregates. The individual SAXS and WAXS measurements were fitted and modelled to enable visualisation and tracking of the changes in the structure in relation to temperature during cooling and warming phases. To further increase the understanding of the parameters affecting dissolution different cellulose samples and solution compositions were considered. For this purpose the effect of increasing the concentration of NaOH and adding Zn2+ has been carefully investigated as well as the importance of the cellulose origin. We found consistent development that the dissolution occurs faster at higher concentrations of NaOH and with Zn2+ regardless the origin. Nevertheless, SAXS data show that materials with a larger amount of cellulose I show more apparent swelling in mesoscopic structure than bleached agricultural containing cellulose II. Despite few crystalline residues after the complete cooling-heating cycle shown by WAXS, some cellulose was not completely dissolved as some network structure remained in the samples under the test condition as suggested by SAXS. © The Author(s) 2024.

Superinsulating nanofibrillar cellulose foams have the potential to replace fossil-based insulating materials, but the development is hampered by the moisture-dependent heat transport and the lack of direct measurements of phonon transport. Here, inelastic neutron scattering is used together with wide angle X-ray scattering (WAXS) and small angle neutron scattering to relate the moisture-dependent structural modifications to the vibrational dynamics and phonon transport and scattering of cellulose nanofibrils from wood and tunicate, and wood cellulose nanocrystals (W-CNC). The moisture interacted primarily with the disordered regions in nanocellulose, and WAXS showed that the crystallinity and coherence length increased as the moisture content increased. The phonon population derived from directional-dependent phonon density of states (GDOS) increased along the cellulose chains in W-CNC between 5 and 8 wt% D2O, while the phonon population perpendicular to the chains remained relatively unaffected, suggesting that the effect of increased crystallinity and coherence length on phonon transport is compensated by the moisture-induced swelling of the foam walls. Frequency scaling in the low-energy GDOS showed that materials based on hygroscopic and semicrystalline nanocellulose falls in between the predicted behavior for solids and liquids. Phonon-engineering of hygroscopic biopolymer-based insulation materials is promoted by the insights on the moisture-dependent phonon transport.

Regenerated cellulose fibers have been considered as potential precursor fibers for carbon fibers because of their balanced cost and performance. Increased attention has been paid to blending lignin with the regenerated cellulose to generate precursor fibers which render good mechanical properties and higher carbon yield. The mechanical properties of carbon fibers have been found closely correlated to the structure of precursor fibers. However, the effects of lignin blending on molecular- and morphological structure of the precursor are still unclear. This study aims at clarifying the structural information of lignin–cellulose precursor fibers from molecular level to mesoscale by scanning X-ray microdiffraction. We present the existence of a skin–core morphology for all the precursor fibers. Increase of lignin content in precursor fiber could reduce the portion of skin and cause obvious disorder of the meso- and molecular structure. By correlating structural variations with lignin blending, 30% lignin blending has been found as a potential balance point to obtain precursor fibers maintaining structural order together with high yield rate. 

In recent years, there has been extensive research into the development of cheaper and more sustainable carbon fiber (CF) precursors, and air-gap-spun cellulose-lignin precursors have gained considerable attention where ionic liquids have been used for the co-dissolution of cellulose and lignin. However, ionic liquids are expensive and difficult to recycle. In the present work, an aqueous solvent system, cold alkali, was used to prepare cellulose-lignin CF precursors by wet spinning solutions containing co-dissolved dissolving-grade kraft pulp and softwood kraft lignin. Precursors containing up to 30 wt% lignin were successfully spun using two different coagulation bath compositions, where one of them introduced a flame retardant into the precursor to increase the CF conversion yield. The precursors were converted to CFs via batchwise and continuous conversion. The precursor and conversion conditions had a significant effect on the conversion yield (12–44 wt%), the Young’s modulus (33–77 GPa), and the tensile strength (0.48–1.17 GPa), while the precursor morphology was preserved. Structural characterization of the precursors and CFs showed that a more oriented and crystalline precursor gave a more ordered CF structure with higher tensile properties. The continuous conversion trials highlighted the importance of tension control to increase the mechanical properties of the CFs. © 2022 by the authors.

Small-angle X-ray scattering (SAXS) is a useful technique for nanoscale structural characterization of materials. In SAXS, structural and spatial information is indirectly obtained from the scattering intensity in the spectral domain, known as the reciprocal space. Therefore, characterizing the structure requires solving the inverse problem of finding a plausible structure model that corresponds to the measured scattering intensity. Both the choice of structure model and the computational workload of parameter estimation are bottlenecks in this process. In this work, we develop a framework for analysis of SAXS data from disordered materials. The materials are modeled using Gaussian Random Fields (GRFs). We study the case of two phases, pore and solid, and three phases, where a third phase is added at the interface between the two other phases. Further, we develop very fast GPU-accelerated, Fourier transform-based numerical methods for both structure generation and SAXS simulation. We demonstrate that length scales and volume fractions can be predicted with good accuracy using our machine learning-based framework. The parameter prediction executes virtually instantaneously and hence the computational burden of conventional model fitting can be avoided. Copyright © 2022 Röding, Tomaszewski, Yu, Borg and Rönnols.

Cellulose nanofibrils (CNFs) with carboxylated surface ligands are a class of materials with tunable surface functionality, good mechanical properties, and bio-/environmental friendliness. They have been used in many applications as scaffold, reinforcing, or functional materials, where the interaction between adsorbed moisture and the CNF could lead to different properties and structures and become critical to the performance of the materials. In this work, we exploited multiple experimental methods to study the water movement in hydrated films made of carboxylated CNFs prepared by TEMPO oxidation with two different surface charges of 600 and 1550 μmol·g-1. A combination of quartz crystal microbalance with dissipation (QCM-D) and small-angle X-ray scattering (SAXS) shows that both the surface charge of a single fibril and the films' network structure contribute to the moisture uptake. The films with 1550 μmol·g-1 surface charges take up twice the amount of moisture per unit mass, leading to the formation of nanostructures with an average radius of gyration of 2.1 nm. Via the nondestructive quasi-elastic neutron scattering (QENS), a faster motion is explained as a localized movement of water molecules inside confined spheres, and a slow diffusive motion is found with the diffusion coefficient close to bulk water at room temperature via a random jump diffusion model and regardless of the surface charge in films made from CNFs.

Structural transformations and lattice expansion of oleate-capped iron oxide nanocube superlattices are studied by time-resolved small-angle X-ray scattering (SAXS) during solvent removal. The combination of conductor-like screening model for real solvents (COSMO-RS) theory with computational fluid dynamics (CFD) modeling provides information on the solvent composition and polarity during droplet evaporation. Evaporation-driven poor-solvent enrichment in the presence of free oleic acid results in the formation of superlattices with a tilted face-centered cubic (fcc) structure when the polarity reaches its maximum. The tilted fcc lattice expands subsequently during the removal of the poor solvent and eventually transforms to a regular simple cubic (sc) lattice during the final evaporation stage when only free oleic acid remains. Comparative studies show that both the increase in polarity as the poor solvent is enriched and the presence of a sufficient amount of added oleic acid is required to promote the formation of structurally diverse superlattices with large domain sizes. © 2022 The Authors. 

Small angle X-ray scattering (SAXS) is extensively used in materials science as a way of examining nanostructures. The analysis of experimental SAXS data involves mapping a rather simple data format to a vast amount of structural models. Despite various scientific computing tools to assist the model selection, the activity heavily relies on the SAXS analysts’ experience, which is recognized as an efficiency bottleneck by the community. To cope with this decision-making problem, we develop and evaluate the open-source, Machine Learning-based tool SCAN (SCattering Ai aNalysis) to provide recommendations on model selection. SCAN exploits multiple machine learning algorithms and uses models and a simulation tool implemented in the SasView package for generating a well defined set of datasets. Our evaluation shows that SCAN delivers an overall accuracy of 95%-97%. The XGBoost Classifier has been identified as the most accurate method with a good balance between accuracy and training time. With eleven predefined structural models for common nanostructures and an easy draw-drop function to expand the number and types training models, SCAN can accelerate the SAXS data analysis workflow.