scholarly journals Facile investigation of reversible nanostructure changes in flexible crystals

2020 ◽  
Author(s):  
Shotaro Hayashi

Abstract Detailed investigation of macroscopic deformation and nanoscopic structural changes in flexible organic crystals pose challenges for investigators. Herein, applied stress and subsequent relaxation of elastic organic crystals resulted in reversible macroscopic crystal deformation. X-ray diffraction with a curved jig revealed reversible nanoscopic structural changes in the crystal structure under the bending stress and relaxation. The crystal lattice changed quantitatively under the applied macroscopic stress-strain (%). This method enables quantitative monitoring of the dynamic nanoscopic structural changes in detail associated with crystal deformation through the use of standard laboratory X-ray diffraction analysis. Importantly, the developed method offers a way of quantitatively measuring reversible structural changes, without synchrotron X-ray analysis. Moreover, the analysis derives Poisson’s ratio, i.e., the ratio of the change in the width per unit width of materials. It is important in materials science, normally has a positive value in the range of 0.2–0.5. However, the crystals show not only the "Poisson effect" but also the unusual "negative Poisson effect". This novel approach for investigation generates unprecedented opportunities for understanding dynamic nanostructure changes in flexible organic crystals.

Author(s):  
G.E. Ice

The increasing availability of synchrotron x-ray sources has stimulated the development of advanced hard x-ray (E≥5 keV) microprobes. With new x-ray optics these microprobes can achieve micron and submicron spatial resolutions. The inherent elemental and crystallographic sensitivity of an x-ray microprobe and its inherently nondestructive and penetrating nature will have important applications to materials science. For example, x-ray fluorescent microanalysis of materials can reveal elemental distributions with greater sensitivity than alternative nondestructive probes. In materials, segregation and nonuniform distributions are the rule rather than the exception. Common interfaces to whichsegregation occurs are surfaces, grain and precipitate boundaries, dislocations, and surfaces formed by defects such as vacancy and interstitial configurations. In addition to chemical information, an x-ray diffraction microprobe can reveal the local structure of a material by detecting its phase, crystallographic orientation and strain.Demonstration experiments have already exploited the penetrating nature of an x-ray microprobe and its inherent elemental sensitivity to provide new information about elemental distributions in novel materials.


IAWA Journal ◽  
1996 ◽  
Vol 17 (4) ◽  
pp. 393-403 ◽  
Author(s):  
Yuki Kondo ◽  
Tomoyuki Fujii ◽  
Yoshioki Hayashi ◽  
Atsushi Kato

Organic crystals were found in tracheid lumina of some samples of Torreya yunnanensis Chen ' L. K. Fu imported from Yunnan, China. Tracheids with crystals were found in short to long tangential bands along the growth ring boundaries. Because the crystals were rapidly dissolved with ethanol and xylene, cross and tangential sections were mounted in de-ionized water without staining and observed by biological, polarised light, and phase-contrast microscopy. The crystals were sublimated under vacuum during routine sample preparation for conventional SEM and only the peripheral parts remained. With the aid of low vacuum-SEM and modified cryo-SEM procedure, the shape of the crystals was revealed. Some were styloid and large enough to fill tracheid lumina, while others were stacked appearing as slates filling tracheid lumina. X-ray diffraction applied to sections and isolated crystals showed that they were single crystals and orientated along the cell wall. UV spectra on isolated crystals and methanol dissolution of crystals suggested that they were composed of phenolic compounds. Crystals that were recrystallized from methanol were analysed by 1H and l3C nuclear magnetic resonance spectroscopy. These two techniques revealed that the major and minor components were o-methoxy cinnamic acid and o-methoxy cinnamic aldehyde.


2014 ◽  
Vol 70 (a1) ◽  
pp. C94-C94
Author(s):  
Pawel Kuczera ◽  
Walter Steurer

The structure of d(ecagonal)-Al-Cu-Rh has been studied as a function of temperature by in-situ single-crystal X-ray diffraction in order to contribute to the discussion on energy or entropy stabilization of quasicrystals (QC) [1]. The experiments were performed at 293 K, 1223 K, 1153 K, 1083 K, and 1013 K. A common subset of 1460 unique reflections was used for the comparative structure refinements at each temperature. The results obtained for the HT structure refinements of d-Al-Cu-Rh QC seem to contradict a pure phasonic-entropy-based stabilization mechanism [2] for this QC. The trends observed for the ln func(I(T1 )/I(T2 )) vs.|k⊥ |^2 plots indicate that the best on-average quasiperiodic order exists between 1083 K and 1153 K, however, what that actually means is unclear. It could indicate towards a small phasonic contribution to entropy, but such contribution is not seen in the structure refinements. A rough estimation of the hypothetic phason instability temperature shows that it would be kinetically inaccessible and thus the phase transition to a 12 Å low T structure (at ~800 K) is most likely not phason-driven. Except for the obvious increase in the amplitude of the thermal motion, no other significant structural changes, in particular no sources of additional phason-related configurational entropy, were found. All structures are refined to very similar R-values, which proves that the quality of the refinement at each temperature is the same. This suggests, that concerning the stability factors, some QCs could be similar to other HT complex intermetallic phases. The experimental results clearly show that at least the ~4 Å structure of d-Al-Cu-Rh is a HT phase therefore entropy plays an important role in its stabilisation mechanism lowering the free energy. However, the main source of this entropy is probably not related to phason flips, but rather to lattice vibrations, occupational disorder unrelated to phason flips like split positions along the periodic axis.


2003 ◽  
Vol 802 ◽  
Author(s):  
R. G. Haire ◽  
S. Heathman ◽  
T. Le Bihan ◽  
A. Lindbaum ◽  
M. Iridi

ABSTRACTOne effect of pressure on elements and compounds is to decease their interatomic distances, which can bring about dramatic perturbations in their electronic nature and bonding, which can be reflected in changes in physical and/or chemical properties. One important issue in the actinide series of elements is the effect of pressure on the 5f-electrons. We have probed changes in electronic behavior with pressure by monitoring structure by X-ray diffraction, and have studied several actinide metals and compounds from thorium through einsteinium. These studies have employed angle dispersive diffraction using synchrotron radiation, and energy dispersive techniques via conventional X-ray sources. The 5f-electrons of actinide metals and their alloys are often affected significantly by pressure, while with compounds, the structural changes are often not linked to the involvement of 5 f-electron. We shall present some of our more recent findings from studies of selected actinide metals, alloys and compounds under pressure. A discussion of the results in terms of the changes in electronic configurations and bonding with regard to the element's position in the series is also addressed.


2012 ◽  
Vol 730-732 ◽  
pp. 925-930
Author(s):  
Daniela Nunes ◽  
Vanessa Livramento ◽  
Horácio Fernandes ◽  
Carlos Silva ◽  
Nobumitsu Shohoji ◽  
...  

Nanostructured copper-diamond composites can be tailored for thermal management applications at high temperature. A novel approach based on multiscale diamond dispersions is proposed for the production of this type of materials: a Cu-nDiamond composite produced by high-energy milling is used as a nanostructured matrix for further dispersion of micrometer sized diamond. The former offers strength and microstructural thermal stability while the latter provides high thermal conductivity. A series of Cu-nDiamond mixtures have been milled to define the minimum nanodiamond fraction suitable for matrix refinement and thermal stabilization. A refined matrix with homogenously dispersed nanoparticles could be obtained with 4 at.% nanodiamond for posterior mixture with mDiamond and subsequent consolidation. In order to define optimal processing parameters, consolidation by hot extrusion has been carried out for a Cu-nDiamond composite and, in parallel, for a mixture of pure copper and mDiamond. The materials produced were characterized by X-ray diffraction, scanning and transmission electron microscopy and microhardness measurements.


2005 ◽  
Vol 38 (5) ◽  
pp. 749-756 ◽  
Author(s):  
Ulrich Gesenhues

The polygonization of 200 nm rutile crystals during dry ball-milling at 10gwas monitored in detail by means of transmission electron microscopy (TEM) and X-ray diffraction (XRD). The TEM results showed how to modify the Williamson–Hall method for a successful evaluation of crystal size and microstrain from XRD profiles. Macrostrain development was determined from the minute shift of the most intense reflection. In addition, changes in pycnometrical density were monitored. Accordingly, the primary crystal is disintegrated during milling into a mosaic of 12–35 nm pieces where the grain boundaries induce up to 1.2% microstrain in a lower layer of 6 nm thickness. Macrostrain in the interior of the crystals rises to 0.03%. The pycnometrical density, reflecting the packing density of atoms in the grain boundary, decreases steadily by 1.1%. The results bear relevance to our understanding of plastic flow and the mechanism of phase transitions of metal oxides during high-energy milling.


Metals ◽  
2021 ◽  
Vol 11 (5) ◽  
pp. 800
Author(s):  
Vladimír Girman ◽  
Maksym Lisnichuk ◽  
Daria Yudina ◽  
Miloš Matvija ◽  
Pavol Sovák ◽  
...  

In the present study, the effect of wet mechanical alloying (MA) on the glass-forming ability (GFA) of Co43Fe20X5.5B31.5 (X = Ta, W) alloys was studied. The structural evolution during MA was investigated using high-energy X-ray diffraction, X-ray absorption spectroscopy, high-resolution transmission electron microscopy and magnetic measurements. Pair distribution function and extended X-ray absorption fine structure spectroscopy were used to characterize local atomic structure at various stages of MA. Besides structural changes, the magnetic properties of both compositions were investigated employing a vibrating sample magnetometer and thermomagnetic measurements. It was shown that using hexane as a process control agent during wet MA resulted in the formation of fully amorphous Co-Fe-Ta-B powder material at a shorter milling time (100 h) as compared to dry MA. It has also been shown that substituting Ta with W effectively suppresses GFA. After 100 h of MA of Co-Fe-W-B mixture, a nanocomposite material consisting of amorphous and nanocrystalline bcc-W phase was synthesized.


Polymers ◽  
2021 ◽  
Vol 13 (7) ◽  
pp. 1034
Author(s):  
Oladipo Folorunso ◽  
Yskandar Hamam ◽  
Rotimi Sadiku ◽  
Suprakas Sinha Ray ◽  
Neeraj Kumar

In this study, a hybrid of graphene nanoplatelets with a polypyrrole having 20 wt.% loading of carbon-black (HGPPy.CB20%), has been fabricated. The thermal stability, structural changes, morphology, and the electrical conductivity of the hybrids were investigated using thermogravimetric analyzer, differential scanning calorimeter, X-ray diffraction analyzer, scanning electron microscope, and laboratory electrical conductivity device. The morphology of the hybrid shows well dispersion of graphene nanoplatelets on the surface of the PPy.CB20% and the transformation of the gravel-like PPy.CB20% shape to compact spherical shape. Moreover, the hybrid’s electrical conductivity measurements showed percolation threshold at 0.15 wt.% of the graphene nanoplatelets content and the curve is non-linear. The electrical conductivity data were analyzed by comparing different existing models (Weber, Clingerman and Taherian). The results show that Taherian and Clingerman models, which consider the aspect ratio, roundness, wettability, filler electrical conductivity, surface interaction, and volume fractions, closely described the experimental data. From these results, it is evident that Taherian and Clingerman models can be modified for better prediction of the hybrids electrical conductivity measurements. In addition, this study shows that graphene nanoplatelets are essential and have a significant influence on the modification of PPy.CB20% for energy storage applications.


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