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Biphasic transition is an important behavior of starch caused by heat-moisture treatment (HMT). Starch may change from typical single endotherm to biphasic endotherm (G1, G2) by HMT which corresponded to two viscosity peaks (PV 1 and PV 2 ) in pasting analysis. During PV 1 , remarkable disruption of birefringence occurred in the inner region of starch granules, accompanied by a decreased relative crystallinity from 20.59 to 14.73%. Native starch completely lost their birefringence at 73 °C, while the HMT starch still showed strong birefringence in granule periphery. The HMT starch only lost crystallites at 80 °C (PV 2 ). A crystallite stability hypothesis was developed that G1 was mainly due to the gelatinization of the inner crystalline lamellae of starch granule, and the newly formed G2 was caused by the peripheral ones enhanced by HMT. This work also provided details on the mechanism of HMT and a potential method for the thermal transition study on starch., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Tuning of crystal structures and shapes of submicrometer-sized noble metals have revealed fascinating catalytic, optical, electrical, and magnetic properties that enable developments of environmentally friendly and durable nanotechnological applications. Several attempts have been made to stabilize Au, knowing its extraordinary stability in its conventional face-centered cubic (fcc) lattice, into different lattices, particularly to develop Au-based catalysis for industry. Here, we report the results from scanning X-ray diffraction microscopy (SXDM) measurements on an ambient-stable penta-twinned bipyramidal Au microcrystallite (about 1.36 μm in length and 230 nm in diameter) stabilized in noncubic lattice, exhibiting catalytic properties. With more than 82% of the crystal volume, the majority crystallite structure is identified as body-centered orthorhombic (bco), while the remainder is the standard fcc. A careful analysis of the diffraction maps reveals that the tips are made up of fcc, while the body contains mainly bco with very high strain. The reported structural imaging technique of representative single crystallite will be useful to investigate the growth mechanism of similar multiphase nano- and micrometer-sized crystals.

The innovative Incremental Sheet Forming (ISF) process affects the post-forming properties of thermoplastic polymers. However, the effects of degree of plastic strain, and the orientation and size of specimen on the mechanical properties are still unknown. In the present study, therefore, the ISF process is performed on a polymer sheet by varying the plastic strain ranging from 6% to 108%. The corresponding effects on the properties and associated polymer structure are quantified by conducting a variety of mechanical and structural tests. The results reveal that the post-ISF tensile properties like yield stress, ultimate stress, drawing stress, elastic modulus and elongation decrease from 26.6 to 10 MPa, 30.5 to 15.4 MPa, 18.9 to 9.9 MPa, 916 to 300 MPa and 1107% to 457%, respectively, as the strain increases in the investigated range. The value of post-ISF relaxation properties, contrary to the tensile properties, increases with increasing strain up to 62%. Particularly, reductions in stress, strain and modulus increase from 41% to 202%, 37% to 51%, and 41% to 202%. As regard the orientation effect, the sheet in the feed direction shows greater strength than the transverse direction (up to 142% in yield stress and 72% in ultimate stress). Moreover, the smaller sample offers greater strength than the larger one (up to 158% in yield stress and 109% in ultimate stress). The analysis of the post-ISF tensile properties and structural results lead us to conclude that the drop in the tensile properties due to increasing strain occurs due to corresponding increase in the voids area fraction (1.25% to 31%) and a reduction in the crystallinity (38% to 31%).

Nowadays, improvement of the surface finish of parts manufactured by fused deposition modelling is a well-studied topic. Chemical post-treatments have proven to be the best technique in terms of time consumption and smoothness improvement. However, these treatments modify the structure of the material and, consequently, its mechanical properties. This relationship was studied in this work. In this case, on the basis of a previous study on crystallisation, polylactic acid pieces were subjected to different post-treatments to evaluate their effects on the sample's mechanical properties, i.e., tensile strength and hardness. Models were obtained according to their percentage of crystallisation, which was related to the different treatments, as well as immersion time. Dramatic changes were obtained within a wide range of material behaviour with some treatments. Specifically, changes were obtained in the maximum stress (from 55 to 20 MPa), in elongation (from 3% to 260%), and in the hardness scale (Shore D to A).

In this study, TiO₂⁻ZnFe₂O₄ (ZFO) core-shell nanorods with various ZFO crystallite thicknesses were synthesized through sputtering-deposited ZFO thin films onto the surfaces of TiO₂ nanorods. By coupling the ZFO narrow bandgap oxide with TiO₂, an enhanced photodegradation efficiency of methylene orange under irradiation was achieved. Structural analyses revealed that ZFO crystallites fully covered the surfaces of the TiO₂ nanorods. The sputtering-deposited ZFO crystallites on the head region of the composite nanorods were markedly thicker than those covering the lateral region of the composite nanorods. The coverage of ZFO crystallites on the TiO₂ nanorods led to an improved light harvesting, a decrease in the hole⁻electron recombination rate, as well as the enhanced photodegradation activity of the TiO₂⁻ZFO heterostructures under irradiation. The optimized ZFO thickness on the head region of the composite nanorods was approximately 43 nm on average and that at the lateral region of the composite nanorods was 15 nm, which exhibited superior photodegradation ability to methylene orange and retained a stable photodegradation efficiency of approximately 97% after cycling tests. The results herein demonstrate that sputtering deposition of ZFO crystallite with tunable thickness is a promising approach to designing TiO₂⁻ZFO composite nanorods with various ZFO coverage sizes and to adjust their photodegradation ability toward organic dyes.

A hybrid catalyst was prepared using cellulose nanofibrils and magnetite to degrade organic compounds. Cellulose nanofibrils were isolated by mechanical defibrillation producing a suspension used as a matrix for magnetite particles. The solution of nanofibrils and magnetite was dried and milled resulting in a catalyst with a 1:1 ratio of cellulose and magnetite that was chemically and physically characterized using light, scanning electron and transmission electron microscopies, specific surface area analysis, vibrating sample magnetometry, thermogravimetric analysis, Fourier transform infrared spectroscopy, X-ray diffraction, catalytic potential and degradation kinetics. Results showed good dispersion of the active phase, magnetite, in the mat of cellulosic nanofibrils. Leaching and re-use tests showed that catalytic activity was not lost over several cycles. The hybrid material produced was tested for degradation of methylene blue dye in Fenton-like reactions resulting in a potential catalyst for use in degradation of organic compounds., (Published by Elsevier Ltd.)

Spin-crossover (SCO) triazole-based coordination polymers can be synthesized by micelle techniques, which almost always lead to rod-shaped nanoparticles. In order to notably reach new morphologies, we explore here the potentiality of the spray-drying (SD) method to get SCO materials. Three SCO coordination polymers and a mononuclear complex are investigated. In all cases, the SD method obtains particles definitely showing SCO. The features of the latter are yet always different from those of the referenced materials, in the sense that SCO is more gradual and incomplete, in adequacy with the poor crystallinity of the powders obtained by SD. In the case of coordination polymers, the particles are preferentially spherical. Indications of possible polymorphism and/or new materials induced by the use of the SD method are evidenced. In the case of the mononuclear complex, the SD method has allowed reproducing, in a quick and easy way, the well-known bulk compound. This exploratory work demonstrates the relevance of the concept and opens the way to a systematic scrutiny of all the experimental parameters to tune the size, morphology, and properties of the SD-synthesized SCO particles.

Graphene-based nanostructured systems and van der Waals heterostructures comprise a material class of growing technological and scientific importance. Joining materials with vastly different properties, polymer/graphene heterosystems promise diverse applications in surface and nanotechnology, including photovoltaics or nanotribology. Fundamentally, molecular adsorbates are prototypical systems to study confinement-induced phase transitions exhibiting intricate dynamics, which require a comprehensive understanding of the dynamical and static properties on molecular time and length scales. Here, we investigate the dynamics and the structure of a single polyethylene chain on free-standing graphene by means of molecular dynamics simulations. In equilibrium, the adsorbed polymer is orientationally linked to the graphene as two-dimensional folded-chain crystallite or at elevated temperatures as a floating solid. The associated superstructure can be reversibly melted on a picosecond time scale upon quasi-instantaneous substrate heating, involving ultrafast heterogeneous melting via a transient floating phase. Our findings elucidate time-resolved molecular-scale ordering and disordering phenomena in individual polymers interacting with solids, yielding complementary information to collective friction and viscosity, and linking to recent experimental observables from ultrafast electron diffraction. We anticipate that the approach will help in resolving nonequilibrium phenomena of hybrid polymeric systems over a broad range of time and length scales.

Silk fibroin, a natural multi-domain protein, has attracted great attention due to its superior mechanical properties such as ultra-high strength and stretchability, biocompatibility, as well as its versatile biodegradability and processability. It is mainly composed of β-sheet crystallites and amorphous domains. Although its strength is well known to be controlled by the dissociation of protein chains from β-sheet crystallites, the way that water as the solvent affects its strength and the reason that its theoretically predicted strength is several times higher than experimental measurement remain unclear. We perform all-atom molecular dynamics simulations on a β-sheet crystallite of Bombyx mori silk. We find that water solvent reduces the number and strength of hydrogen bonds between β-chains, and thus greatly weakens the strength of silk fibroin. By dissociating protein chains at different locations from the crystallite, we also find that the pulling strength for the interior chains is several times higher than that for the surface/corner chains, with the former being consistent with the theoretically predicted value, while the latter on par with the experimental value. It is shown that the weakest rupture strength controls the failure strength of silk fibre. Hence, this work sheds light on the role of water in the strength of silk fibroin and also provides clues on the origin of the strength difference between theory and experiment.

Biominerals have complex and heterogeneous architectures, hence diffraction experiments with spatial resolutions between 500 nm and 10 μm are extremely useful to characterize them. X-ray beams in this size range are now routinely produced at many synchrotrons. This chapter provides a review of the different hard X-ray diffraction and scattering techniques, used in conjunction with efficient, state-of-the-art X-ray focusing optics. These include monochromatic X-ray microdiffraction, polychromatic (Laue) X-ray microdiffraction, and microbeam small-angle X-ray scattering. We present some of the most relevant discoveries made in the field of biomineralization using these approaches., (© 2013 Elsevier Inc. All rights reserved.)

In this work, untreated bovine cortical bones (BCBs) were exposed to a range of heat treatments in order to determine at which temperature the apatite develops an optimum morphology comprising porous nano hydroxyapatite (nanoHAp) crystals. Rectangular specimens (10 mm × 10 mm × 3-5 mm) of BCB were prepared, being excised in normal to longitudinal and transverse directions. Specimens were sintered at up to 900 °C under ambient pressure in order to produce apatites by two steps sintering. The samples were characterized by thermogravimetric analysis, X-ray diffraction (XRD), and scanning electron microscopy (SEM) attached to an energy-dispersive X-ray spectroscopy detector. For the first time, morphology of the HAp particles was predicted by XRD, and it was verified by SEM. The results show that an equiaxed polycrystalline HAp particle with uniform porosity was produced at 900 °C. It indicates that a porous nanoHAp achieved by sintering at 900 °C can be an ideal candidate as an in situ scaffold for load-bearing tissue applications.