Anisotropy in the mechanical properties of organic crystals: temperature dependence

The nanoindentation technique has recently been utilized for quantitative evaluation of the mechanical properties of molecular materials successfully, including their temperature (T) dependence. In this paper, we examine how the mechanical anisotropy varies with T in saccharin and L-alanine single crystals. Our results show that elastic modulus (E) decreases linearly in all the cases examined, with the T-dependence of E being anisotropic. Correspondence between directional dependence of the slopes of the E vs. T plots and the linear thermal expansion coefficients was found. The T-dependence of hardness (H), on the other hand, was found to be nonlinear and significant when (100) of saccharin and (001) of L-alanine are indented. While the anisotropies in E and H of saccharin and E of L-alanine enhance with T, the anisotropy in H of L-alanine was found to reduce with T. Possible mechanistic origins of these variations are discussed.

Structure-mechanical property correlations in mechanochromic luminescent crystals of boron difluoride dibenzoylmethane derivatives

The structure and mechanical properties of crystalline materials of three boron difluoride dibenzoylmethane (BF(2)dbm) derivatives were investigated to examine the correlation, if any, among mechanochromic luminescence (ML) behaviour, solid-state structure, and the mechanical behaviour of single crystals. Qualitative mechanical deformation tests show that the crystals of BF(2)dbm(Bu-t)(2) can be bent permanently, whereas those of BF(2)dbm(OMe)(2) exhibit an inhomogeneous shearing mode of deformation, and finally BF(2)dbmOMe crystals are brittle. Quantitative mechanical analysis by nanoindentation on the major facets of the crystals shows that BF(2)dbm(Bu-t)(2) is soft and compliant with low values of elastic modulus, E, and hardness, H, confirming its superior suceptibility for plastic deformation, which is attributed to the presence of a multitude of slip systems in the crystal structure. In contrast, both BF(2)dbm(OMe)(2) and BF(2)dbmOMe are considerably stiffer and harder with comparable E and H, which are rationalized through analysis of the structural attributes such as the intermolecular interactions, slip systems and their relative orientation with respect to the indentation direction. As expected from the qualitative mechanical behaviour, prominent ML was observed in BF(2)dbm(Bu-t)(2), whereas BF(2)dbm(OMe)(2) exhibits only a moderate ML and BF(2)dbmOMe shows no detectable ML, all examined under identical conditions. These results confirm that the extent of ML in crystalline organic solid-state fluorophore materials can be correlated positively with the extent of plasticity (low recovery). In turn, they offer opportunities to design new and improved efficient ML materials using crystal engineering principles.

Microhardness Studies of Vapour Grown Tin (II) Sulfide Single Crystals

Earth abundant tin sulfide (SnS) has attracted considerable attention as a possible absorber material for low-cost solar cells due to its favourable optoelectronic properties. Single crystals of SnS were grown by physical vapour deposition (PVD) technique. Microindentation studies were carried out on the cleaved surfaces of the crystals to understand their mechanical behaviour. Microhardness increased initially with the load, giving sharp maximum at 15 g. Quenching effect has increased the microhardness, while annealing reduced the microhardness of grown crystals. The hardness values of as-grown, annealed and quenched samples at 15 g load are computed to be 99.69, 44.52 and 106.29 kg/mm(2) respectively. The microhardness of PVD grown crystals are high compared to CdTe, a leading low-cost PV material. The as-grown faces are found to be fracture resistant.

Crystal structure of a tripeptide containing aminocyclododecane carboxylic acid: a supramolecular twisted parallel -sheet in crystals

The crystal structure of a tripeptide Boc-Leu-Val-Ac(12)c-OMe (1) is determined, which incorporates a bulky 1-aminocyclododecane-1-carboxylic acid (Ac(12)c) side chain. The peptide adopts a semi-extended backbone conformation for Leu and Val residues, while the backbone torsion angles of the C-,C--dialkylated residue Ac(12)c are in the helical region of the Ramachandran map. The molecular packing of 1 revealed a unique supramolecular twisted parallel -sheet coiling into a helical architecture in crystals, with the bulky hydrophobic Ac(12)c side chains projecting outward the helical column. This arrangement resembles the packing of peptide helices in crystal structures. Although short oligopeptides often assemble as parallel or anti-parallel -sheet in crystals, twisted or helical -sheet formation has been observed in a few examples of dipeptide crystal structures. Peptide 1 presents the first example of a tripeptide showing twisted -sheet assembly in crystals. Copyright (c) 2016 European Peptide Society and John Wiley & Sons, Ltd.

Anomalous re-entrant glassy magnetic phase in LaMn0.5Co0.5O3 single crystals

We report an anomalous re-entrant glassy magnetic phase in (l00) oriented ferromagnetic LaMn0.5Co0.5O3 single crystals. The characterization is fortified with conventional magnetometry, like linear as-well-as non-linear ac susceptibility and specific heat. As the sample is cooled below the ferromagnetic transition temperature, it reenters a glassy magnetic phase whose dynamics have little resemblance with the conventional response. The glassy transition shifts to a higher temperature with increasing frequency of the applied ac field. But it does not respond to the dc biasing or memory experiment. Specific heat as well as non-linear ac susceptibility data also do not relate to the conventional glassy response. Unusually low magnetic entropy indicates the lack of long range magnetic ordering. The results demonstrate that the glassy phase in LaMn0.5Co0.5O3 is not due to any of the known conventional origins. We infer that the competing ferromagnetic and antiferromagnetic interaction due to high B-site disorder is responsible for this anomalous re-entrant glassy phase. (C) 2016 AIP Publishing LLC.

Crystal structure of a tripeptide containing aminocyclododecane carboxylic acid: a supramolecular twisted parallel -sheet in crystals

The crystal structure of a tripeptide Boc-Leu-Val-Ac(12)c-OMe (1) is determined, which incorporates a bulky 1-aminocyclododecane-1-carboxylic acid (Ac(12)c) side chain. The peptide adopts a semi-extended backbone conformation for Leu and Val residues, while the backbone torsion angles of the C-,C--dialkylated residue Ac(12)c are in the helical region of the Ramachandran map. The molecular packing of 1 revealed a unique supramolecular twisted parallel -sheet coiling into a helical architecture in crystals, with the bulky hydrophobic Ac(12)c side chains projecting outward the helical column. This arrangement resembles the packing of peptide helices in crystal structures. Although short oligopeptides often assemble as parallel or anti-parallel -sheet in crystals, twisted or helical -sheet formation has been observed in a few examples of dipeptide crystal structures. Peptide 1 presents the first example of a tripeptide showing twisted -sheet assembly in crystals. Copyright (c) 2016 European Peptide Society and John Wiley & Sons, Ltd.

Anomalous re-entrant glassy magnetic phase in LaMn0.5Co0.5O3 single crystals

We report an anomalous re-entrant glassy magnetic phase in (l00) oriented ferromagnetic LaMn0.5Co0.5O3 single crystals. The characterization is fortified with conventional magnetometry, like linear as-well-as non-linear ac susceptibility and specific heat. As the sample is cooled below the ferromagnetic transition temperature, it reenters a glassy magnetic phase whose dynamics have little resemblance with the conventional response. The glassy transition shifts to a higher temperature with increasing frequency of the applied ac field. But it does not respond to the dc biasing or memory experiment. Specific heat as well as non-linear ac susceptibility data also do not relate to the conventional glassy response. Unusually low magnetic entropy indicates the lack of long range magnetic ordering. The results demonstrate that the glassy phase in LaMn0.5Co0.5O3 is not due to any of the known conventional origins. We infer that the competing ferromagnetic and antiferromagnetic interaction due to high B-site disorder is responsible for this anomalous re-entrant glassy phase. (C) 2016 AIP Publishing LLC.

Facile synthesis of Graphene Oxide/Double-stranded DNA composite liquid crystals and Hydrogels

Investigation of the interactions between graphene oxide (GO) and biomolecules is very crucial for the development of biomedical applications based on GO. This study reports the first observation of the spontaneous formation of self-assembled liquid crystals and three-dimensional hydrogels of graphene oxide with double-stranded DNA by simple mixing in an aqueous buffer media without unwinding double-stranded DNA to single-stranded DNA. The GO/dsDNA hydrogels have shown controlled porosity by changing the concentration of the components. The strong binding between dsDNA and graphene is proved by Raman spectroscopy.

Optical Diagnostic and Modeling Solution Growth Process of Sodium Chlorate Crystals

Both a real time optical interferometric experiment and a numerical simulation of two-dimension non-steady state model were employed to study the growth process of aqueous sodium chlorate crystals. The parameters such as solution concentration distribution, crystal dimensions, growth rate and velocity field were obtained by both experiment and numerical simulation. The influence of earth gravity during crystal growth process was analyzed. A reasonable theory model corresponding to the present experiment is advanced. The thickness of concentration boundary layer was investigated especially. The results from the experiment and numerical simulation match well.

Growth of Silicon Carbide Bulk Crystals by Physical Vapor Transport Method and Modeling Efforts in the Process Optimization

Silicon carbide bulk crystals were grown in an induction-heating furnace using the physical vapor transport method. Crystal growth modeling was performed to obtain the required inert gas pressure and temperatures for sufficiently large growth rates. The SiC crystals were expanded by designing a growth chamber having a positive temperature gradient along the growth interface. The obtained 6H-SiC crystals were cut into wafers and characterized by Raman scattering spectroscopy and X-ray diffraction, and the results showed that most parts of the crystals had good crystallographic structures.

Growth of bulk single crystals beta-FeSi2 by chemical vapour deposition

Bulk single crystals b-FeSi2, as a new photoelectric and thermoelectric material, has been successfully grown using chemical vapor transport technique by using iodine as transport agent in a sealed ampoule. The effects of crystal growth condition on quality and morphologies of the single crystals were studied. Both needle-like and grain-like single crystals were gained. By changing substrate temperature, tetrahedral high quality a-FeSi2 single crystals were also obtained.

Thermoelastic Stresses in SiC Single Crystals Grown by the Physical Vapor Transport Method

A finite element-based thermoelastic anisotropic stress model for hexagonal silicon carbide polytype is developed for the calculation of thermal stresses in SiC crystals grown by the physical vapor transport method. The composite structure of the growing SiC crystal and graphite lid is considered in the model. The thermal expansion match between the crucible lid and SiC crystal is studied for the first time. The influence of thermal stress on the dislocation density and crystal quality is discussed.

Numerical Simulation of the Flow Field and Concentration Distribution in the Bulk Growth of Silicon Carbide Crystals

The physical vapor transport (PVT) method is being widely used to grow large-size single SiC crystals. The growth process is associated with heat and mass transport in the growth chamber, chemical reactions among multiple species as well as phase change at the crystal/gas interface. The current paper aims at studying and verifying the transport mechanism and growth kinetics model by demonstrating the flow field and species concentration distribution in the growth system. We have developed a coupled model, which takes into account the mass transport and growth kinetics. Numerical simulation is carried out by employing an in-house developed software based on finite volume method. The results calculated are in good agreement with the experimental observation.