Effect of Stress and Interface defects on Photo Luminescence of Si nano-crystals embedded in SiO2

Effect of stress and interface defects on photo luminescence property of a silicon nano-crystal (Si-nc) embedded in amorphous silicon dioxide (a-SiO2) are studied in this paper using a self-consistent quantum-continuum based modeling framework. Si-ncs or quantum dots show photoluminescence at room temperature. Whether its origin is due to Si-nc/a-SiO2 interface defects or quantum confinement of carriers in Si-nc is still an outstanding question. Earlier reports have shown that stresses greater than 12 GPa change the indirect energy band gap structure of bulk Si to a direct energy band gap structure. Such stresses are observed very often in nanostructures and these stresses influence the carrier confinement energy significantly. Hence, it is important to determine the effect of stress in addition to the structure of interface defects on photoluminescence property of Si-nc. In the present work, first a Si-nc embedded in a-SiO2 is constructed using molecular dynamics simulation framework considering the actual conditions they are grown so that the interface and residual stress in the structure evolves naturally during formation. We observe that the structure thus created has an interface of about 1 nm thick consisting of 41.95% of defective states mostly Sin+ (n = 0 to 3) coordination states. Further, both the Si-nc core and the embedding matrix are observed to be under a compressive strain. This residual strain field is applied in an effective mass k.p Hamiltonian formulation to determine the energy states of the carriers. The photo luminescence property computed based on the carrier confinement energy and interface energy states associated with defects will be analysed in details in the paper.

Experimental study of fracture behavior of magnesium single crystals

In this work, the fracture behavior of magnesium single crystals is studied by conducting experiments with notched three point bend specimens of three crystallographic orientations. In the first and second orientations, the c-axis is along the normal to the flat surface of the notch, while in the third it is aligned with the notch front. For all the orientations, in situ electron back scattered diffraction observations made around the notch root show profuse tensile twinning of {10 (1) over bar2} type. Further, in the first two orientations basal and prismatic slip traces are identified from optical metallography. The width of the most prominent twin saturates at around 120-150 mu m, while twins continue to nucleate farther away to accommodate plastic deformation. In all the orientations, crack initiation occurs before the attainment of peak load and the crack grows stably along twin-matrix interface before deflecting at twin-twin intersections. Results show that profuse tensile twinning is an important energy dissipating mechanism that enhances the fracture toughness. (C) 2013 Elsevier B.V. All rights reserved.

Kinematic and Mechanical Profile of the Self-Actuation of Thermosalient Crystal Twins of 1,2,4,5-Tetrabromobenzene: A Molecular Crystalline Analogue of a Bimetallic Strip

A paradigm shift from hard to flexible, organic-based optoelectronics requires fast and reversible mechanical response from actuating materials that are used for conversion of heat or light into mechanical motion. As the limits in the response times of polymer-based actuating materials are reached, which are inherent to the less-than-optimal coupling between the light/heat and mechanical energy in them, 1 a conceptually new approach to mechanical actuation is required to leapfrog the performance of organic actuators. Herein, we explore single crystals of 1,2,4,5-tetrabromobenzene (TBB) as actuating elements and establish relations between their kinematic profile and mechanical properties. Centimeter-size acicular crystals of TBB are the only naturally twinned crystals out of about a dozen known materials that exhibit the thermosalient effect-an extremely rare and visually impressive crystal locomotion. When taken over a phase transition, crystals of this material store mechanical strain and are rapidly self-actuated to sudden jumps to release the internal strain, leaping up to several centimeters. To establish the structural basis for this colossal crystal motility, we investigated the mechanical profile of the crystals from macroscale, in response to externally induced deformation under microscope, to nanoscale, by using nanoindentation. Kinematic analysis based on high-speed recordings of over 200 twinned TBB crystals exposed to directional or nondirectional heating unraveled that the crystal locomotion is a kinematically complex phenomenon that includes at least six kinematic effects. The nanoscale tests confirm the highly elastic nature, with an elastic deformation recovery (60%) that is far superior to those of molecular crystals reported earlier. This property appears to be critical for accumulation of stress required for crystal jumping. Twinned crystals of TBB exposed to moderate directional heating behave as all-organic analogue of a bimetallic `strip, where the lattice misfit between the two crystal components drives reveriible deformation of the crystal.

Tuning solubility and stability of hydrochlorothiazide co-crystals

Hydrochlorothiazide (HCT), C7H8ClN3O4S2, is a diuretic BCS (Biopharmaceutics Classification System) class IV drug which has primary and secondary sulfonamide groups. To modify the aqueous solubility of the drug, co-crystals with biologically safe co-formers were screened. Multi-component molecular crystals of HCT were prepared with nicotinic acid, nicotinamide, succinamide, p-aminobenzoic acid, resorcinol and pyrogallol using liquid-assisted grinding. The co-crystals were characterized by FT-IR spectroscopy, powder X-ray diffraction (PXRD) and differential scanning calorimetry. Single crystal structures were obtained for four of them. The N-H center dot center dot center dot O sulfonamide catemer synthons found in the stable polymorph of pure HCT are replaced in the co-crystals by drug-co-former heterosynthons. Isostructural co-crystals with nicotinic acid and nicotinamide are devoid of the common sulfonamide dimer/catemer synthons. Solubility and stability experiments were carried out for the co-crystals in water (neutral pH) under ambient conditions. Among the six binary systems, the co-crystal with p-aminobenzoic acid showed a sixfold increase in solubility compared with pure HCT, and stability up to 24 h in an aqueous medium. The co-crystals with nicotinamide, resorcinol and pyrogallol showed only a 1.5-2-fold increase in solubility and transformed to HCT within 1 h of the dissolution experiment. An inverse correlation is observed between the melting points of the co-crystals and their solubilities.

Micropillar and macropillar compression responses of magnesium single crystals oriented for single slip or extension twinning

Uniaxial compression experiments were conducted on two magnesium (Mg) single crystals whose crystallographic orientations facilitate the deformation either by basal slip or by extension twinning. Specimen size effects were examined by conducting experiments on mu m- and mm-sized samples. A marked specimen size effect was noticed, with micropillars exhibiting significantly higher flow stress than bulk samples. Further, it is observed that the twin nucleation stress exerts strong size dependence, with micropillars requiring substantially higher stress than the bulk samples. The flow curves obtained on the bulk samples are smooth whereas those obtained from micropillars exhibit intermittent and precipitous stress drops. Electron backscattered diffraction and microstructural analyses of the deformed samples reveal that the plastic deformation in basal slip oriented crystals occurs only by slip while twin oriented crystals deform by both slip and twinning modes. The twin oriented crystals exhibit a higher strain hardening during plastic deformation when compared to the single slip oriented crystals. The strain hardening rate, theta, of twin oriented crystals is considerably greater in micropillars compared to the bulk single crystals, suggesting the prevalence of different work hardening mechanisms at these different sample sizes. (C) 2013 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

C-11/C-9 Helices in Crystals of alpha beta Hybrid Peptides and Switching Structures between Helix Types by Variation in the alpha-Residue

Close-packed helices with mixed hydrogen bond directionality are unprecedented in the structural chemistry of alpha-polypeptides. While NMR studies in solution state provide strong evidence for the occurrence of mixed helices in (beta beta)(n) and (alpha beta)(n) sequences, limited information is currently available in crystals. The peptide structures presented show the occurrence of C-11/C-9 helices in (alpha beta)(n) peptides. Transitions between C-11 and C-11/C-9 helices are observed upon varying the alpha-amino acid residue.

Finite element simulations of notch tip fields in magnesium single crystals

Recent experiments using three point bend specimens of Mg single crystals have revealed that tensile twins of {10 (1) over bar2}-type form profusely near a notch tip and enhance the fracture toughness through large plastic dissipation. In this work, 3D finite element simulations of these experiments are carried out using a crystal plasticity framework which includes slip and twinning to gain insights on the mechanics of fracture. The predicted load-displacement curves, slip and tensile twinning activities from finite element analysis corroborate well with the experimental observations. The numerical results are used to explore the 3D nature of the crack tip stress, plastic slip and twin volume fraction distributions near the notch root. The occurrence of tensile twinning is rationalized from the variation of normal stress ahead of the notch tip. Further, deflection of the crack path at twin-twin intersections observed in the experiments is examined from an energy standpoint by modeling discrete twins close to the notch root.

Combinatorial effect of rolling and carbonaceous nanoparticles on the evolution of crystallographic texture and structural properties of ultra high molecular weight polyethylene

Ultra high molecular weight polyethylene (PE) is a structural polymer widely used in biomedical implants. The mechanical properties of PE can be improved either by controlled crystalline orientation (texture) or by the addition of reinforcing agents. However, the combinatorial effect has not received much attention. The objective of this study was to characterize the structure and mechanical properties of PE composites incorporating multiwall carbon nanotubes (MWCNT) and reduced graphene oxide (RGO) subjected to hot rolling. The wide angle X-ray diffraction studies revealed that mechanical deformation resulted in a mixture of orthorhombic and monoclinic crystals. Furthermore, the presence of nanoparticles resulted in lower crystallinity in PE with smaller crystallite size, more so in RGO than in MWCNT composites. Rolling strengthened the texture of both orthorhombic and the monoclinic phases in PE. Presence of RGO weakened the texture of both phases of PE after rolling whereas MWCNT only mildly weakened the texture. This resulted in a reduction in the elastic modulus of RGO composites whereas moduli of neat polymer and the MWCNT composite increased after rolling. This study provides new insight into the role of nanoparticles in texture evolution during polymer processing with implications for processing of structural polymer composites.

Tuning Mechanical Properties of Pharmaceutical Crystals with Multicomponent Crystals: Voriconazole as a Case Study

Crystals of voriconazole, an antifungal drug, are soft in nature, and this is disadvantageous during compaction studies where pressure is applied on the solid. Crystal engineering is used to make cocrystals and salts with modified mechanical properties (e.g., hardness). Cocrystals with biologically safe coformers such as fumaric acid, 4-hydroxybenzoic acid, and 4-aminobenzoic acid and salts with hydrochloric acid and oxalic acid are prepared through solvent assisted grinding. The presence (salt) or absence (cocrystal) of proton transfer in these multicomponent crystals is unambiguously confirmed with single crystal X-ray diffraction. All the cocrystals have 1:1 stoichiometry, whereas salts exhibit variable stoichiometries such as HCl salt (1:2) and oxalate salts (1:1.5 and 1:1). The nanoindentation technique was applied on single crystals of the salts and cocrystals. The salts exhibit better hardness than the drug and cocrystals in the order salts drug cocrystals. The molecular origin of this mechanical modulation is explained on the basis of slip planes in the crystal structure and relative orientations of the molecules with respect to the nanoindentation direction. The hydrochloride salt is the hardest solid in this family. This may be useful for tableting of the drug during formulation and in drug development.

Designing Elastic Organic Crystals: Highly Flexible Polyhalogenated N-Benzylideneanilines

The intermolecular interactions and structural features in crystals of seven halogenated N-benzylideneanilines (Schiff bases), all of which exhibit remarkable flexibility, were examined to identify the common packing features that are the raison d'etre for the observed elasticity. The following two features, in part related, were identified as essential to obtain elastic organic crystals: 1)A multitude of weak and dispersive interactions, including halogen bonds, which may act as structural buffers for deformation through easy rupture and reformation during bending; and 2)corrugated packing patterns that would get interlocked and, in the process, prevent long-range sliding of molecular planes.

Structural studies on Mycobacterium tuberculosis RecA: Molecular plasticity and interspecies variability

Structures of crystals of Mycobacterium tuberculosis RecA, grown and analysed under different conditions, provide insights into hitherto underappreciated details of molecular structure and plasticity. In particular, they yield information on the invariant and variable features of the geometry of the P-loop, whose binding to ATP is central for all the biochemical activities of RecA. The strengths of interaction of the ligands with the P-loop reveal significant differences. This in turn affects the magnitude of the motion of the `switch' residue, Gln195 in M. tuberculosis RecA, which triggers the transmission of ATP-mediated allosteric information to the DNA binding region. M. tuberculosis RecA is substantially rigid compared with its counterparts from M smegmatis and E. coli, which exhibit concerted internal molecular mobility. The interspecies variability in the plasticity of the two mycobacterial proteins is particularly surprising as they have similar sequence and 3D structure. Details of the interactions of ligands with the protein, characterized in the structures reported here, could be useful for design of inhibitors against M. tuberculosis RecA.

Do carboximide-carboxylic acid combinations form co-crystals? The role of hydroxyl substitution on the formation of co-crystals and eutectics

Carboxylic acids, amides and imides are key organic systems which provide understanding of molecular recognition and binding phenomena important in biological and pharmaceutical settings. In this context, studies of their mutual interactions and compatibility through co-crystallization may pave the way for greater understanding and new applications of their combinations. Extensive co-crystallization studies are available for carboxylic acid/amide combinations, but only a few examples of carboxylic acid/imide co-crystals are currently observed in the literature. The non-formation of co-crystals for carboxylic acid/imide combinations has previously been rationalized, based on steric and computed stability factors. In the light of the growing awareness of eutectic mixtures as an alternative outcome in co-crystallization experiments, the nature of various benzoic acid/cyclic imide combinations is established in this paper. Since an additional functional group can provide sites for new intermolecular interactions and, potentially, promote supramolecular growth into a co-crystal, benzoic acids decorated with one or more hydroxyl groups have been systematically screened for co-crystallization with one unsaturated and two saturated cyclic imides. The facile formation of an abundant number of hydroxybenzoic acid/cyclic carboximide co-crystals is reported, including polymorphic and variable stoichiometry co-crystals. In the cases where co-crystals did not form, the combinations are shown invariably to result in eutectics. The presence or absence and geometric disposition of hydroxyl functionality on benzoic acid is thus found to drive the formation of co- crystals or eutectics for the studied carboxylic acid/imide combinations.

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.

Hardness Alternation in alpha,omega-Alkanedicarboxylic Acids

The variation of hardness as a function of the number of carbon atoms in alpha,omega-alkanedicarboxylic acids, CNH2N-2O4 (4 <= N <= 9), was examined by recourse to nanoindentation on the major faces of single crystals. Hardness exhibits odd-even alternation, with the odd acids being softer and the even ones harder; the differences decrease with increasing chain length. These variations are similar to those seen for other mechanical, physical, and thermal properties of these diacids. The softness of odd acids is rationalized due to strained molecular conformations in them, which facilitate easier plastic deformation. Relationships between structural features, such as interplanar spacing, interlayer separation distance, molecular chain length, and signatures of the nanoindentation responses, namely, discrete displacement bursts, were also examined. Shear sliding of molecular layers past each other during indentation is key to the mechanism for plastic deformation in these organic crystals.

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.