Structures and elastic properties of OsN2 investigated via first-principles density functional calculations

The structure, elastic, and electronic properties of OsN2 at various space groups: cubic Fm-3m, Pa-3, and orthorhombic Pnnm were studied by first-principles calculations based on density functional theory. Our calculation indicates that the structure in orthorhombic Pnnm phase is energetically more stable compared with cubic systems. It is metallic, mechanically stable and contains diatomic N-N units with the bond distance 1.418 A. These characters are consistent with experimental facts that OsN2 is orthorhombic and metallic. The calculated bulk modulus 394 GPa is also the highest among the considered space groups, slightly larger than previous value 358 GPa. The calculated elastic anisotropic factors and directional bulk modulus showed that OsN2 possess high elastic anisotropy.

Daunomycin binding to detergent micelles: A model system for evaluating the hydrophobic contribution to drug-DNA interactions

The interaction of daunomycin with sodium dodecyl sulfate and Triton X-100 micelles was investigated as a model for the hydrophobic contribution to the free energy of DNA intercalation reactions. Measurements of visible absorbance, fluorescence lifetime, steady-state fluorescence emission intensity, and fluorescence anisotropy indicate that the anthraquinone ring partitions into the hydrophobic micelle interior. Fluorescence quenching experiments using both steady-state and lifetime measurements demonstrate reduced accessibility of daunomycin in sodium dodecyl sulfate micelles to the anionic quencher iodide and to the neutral quencher acrylamide. Quenching of daunomycin fluorescence by iodide in Triton X-100 micelles was similar to that seen with free daunomycin. Studies of the energetics of the interaction of daunomycin with micelles by fluorescence and absorbance titration methods and by isothermal titration calorimetry in the presence of excess micelles revealed that association with sodium dodecyl sulfate and Triton X-100 micelles is driven by a large negative enthalpy. Association of the drug with both types of micelles also has a favorable entropic contribution, which is larger in magnitude for Triton X-100 micelles than for sodium dodecyl sulfate micelles.

Low-compressibility and hard materials ReB2 and WB2: Prediction from first-principles study

First-principle calculations are performed to investigate the structural, elastic, and electronic properties of ReB2 and WB2. The calculated equilibrium structural parameters of ReB2 are consistent with the available experimental data. The calculations indicate that WB2 in the P6(3)/mmc space group is more energetically stable under the ambient condition than in the P6/mmm. Based on the calculated bulk modulus, shear modulus of polycrystalline aggregate, ReB2 and WB2 can be regarded as potential candidates of ultra-incompressible and hard materials. Furthermore, the elastic anisotropy is discussed by investigating the elastic stiffness constants. Density of states and electron density analysis unravel the covalent bonding between the transition metal atoms and the boron atoms as the driving force of the high bulk modulus and high shear modulus as well as small Poisson's ratio.

Synthesis, crystal structure and magnetic properties of a chain coordination polymer {[Cu4L2(H2O)] center dot H2O}(n)

A chain coordination polymer with the chemical formula {[Cu4L2(H2O)] (.) H2O)(n), has been synthesized by the assembly reaction of K(2)CuL(.)1.5H(2)O and Cu(OAC)(2)(H2O)-H-. with a 1:1 mole ratio in methanol., where H4L=2-hydroxy-3-[(E)-({2-[(2-hydroxybenzoyl)imino]ethyl I imino)methyl] benzoic acid, OAC(-) = CH3COO-. The crystal structure was determined by single-crystal X-ray diffraction analysis, the compound has chain molecular structure formed by dissymmetrical tetranuclear units. The magnetic measurements showed that Cu-Cu of the complex exhibit antiferromagnetic interactions, and satisfactory fittings to the observed magnetic susceptibility data were obtained by assuming a binuclear system, and further using molecular field approximation to deal with magnetic exchange interactions between binuclear systems.

In situ study of nanostructure and morphological development during the crystal-mesophase transition of poly(di-n-hexylsilane) and poly(di-n-butylsilane) by X-ray and hot-stage AFM

Nanostructure and morphology and their development of poly(di-n-hexylsilane) (PDHS) and poly(di-n-butylsilane) (PDBS) during the crystal-mesophase transition are investigated using small angle X-ray scattering (SAXS), wide angle X-ray diffraction and hot-stage atomic force microscopy. At room temperature, PDHS consists of stacks of lamellae separated by mesophase layers, which can be well accounted using an ideal two-phase model. During the crystal-mesophase transition, obvious morphological changes are observed due to the marked changes in main chain conformation and intermolecular distances between crystalline phase and mesophase. In contrast to PDHS, the lamellae in PDBS barely show anisotropy in dimensions at room temperature. The nonperiodic structure and rather small electronic density fluctuation in PDBS lead to the much weak SAXS. The nonperiodic structure is preserved during the crystal-mesophase transition because of the similarity of main chain conformation and intermolecular distances between crystalline phase and mesophase.

Nanostructure and mechanical measurement of highly oriented lamellae of melt-drawn HDPE by scanning probe microscopy

Scanning probe microscopy was used to simultaneously determine the molecular chain structure and intrinsic mechanical properties, including anisotropic elastic modulus and friction, for lamellae of highly oriented high-density polyethylene (HDPE) obtained by the melt-drawn method. The molecular-scale image of the highly oriented lamellae by friction force microscopy (FFM) clearly shows that the molecular chains are aligned parallel to the drawing direction, and the periodicities along and perpendicular to the drawing direction are 0.26 and 0.50 nm, respectively. The results indicate that the exposed planes of the lamellae resulting from the melt-drawn method are (200), which is consistent with results of transmission electron microscopy and electron diffraction. Because of the high degree of anisotropy in the sample, coming from alignment of the molecular chains along the drawing direction, the measured friction force, F, determined by FFM is strongly dependent on the angle, theta, between the scanning direction and the chain axis. The force increases as theta is increased from 0 degrees (i.e., parallel to the chain axis) to 90 degrees (i.e., perpendicular to the chain axis). The structural anisotropy was also found to strongly influence the measurements of the transverse chain modulus of the polymer by the nanoindentation technique. The measured value of 13.8 GPa with transverse modulus was larger than the value 4.3 GPa determined by wide-angle X-ray diffraction, which we attributed to anisotropic deformation of the lamellae during nanoindentation measurements that was not accounted for by the elastic treatment we adopted from Oliver and Pharr. The present approach using scanning probe microscopy has the advantage that direct correlations between the nanostructure, nanotribology, and nanomechanical properties of oriented samples can be determined simultaneously and simply.

Molecular and supramolecular deformations and disclinations in a liquid crystalline copolyether thin films under an electrostatic field

An alignment study of a liquid crystalline copolyether TPP-7/11(5/5) thin films has been carried out in a 10 kV . cm(-1) electrostatic field parallel to the thin film surface normal. This copolyether possesses a negative dielectric anisotropy. The chain molecules are homogeneously aligned in the electric field and they form two-dimensionally ordered lamellae in a tilted columnar phase when the samples were cooled to room temperature. It is observed that the chain molecules are splayed to form bent lamellae and the chain direction is perpendicular to the tangential direction of the lamellar surfaces. These lamellae thus become replicas of the chain orientation, Due to the flexoelectric effect and density fluctuation on the thin film free surface, disclinations having topological strength s = 1, c = pi /4 and defect walls form. These s = 1 disclinations possesses both left- and right-handednesses. Discussion of the defect formations have been attempted.

Experimental measurement of polyethylene chain modulus by scanning force microscopy

Nanoindentation technique and scanning force microscopy have been used to measure directly the polyethylene modulus along the chain axis. Single crystals of polyethylene were employed in order to obtain well-aligned chain segments. To minimize effects of scanner creep, a Z scan rate of 3 Hz was employed. The "X Rotate" value of 25 degrees was selected to eliminate effects of lateral tip motion. The results were analyzed by the Oliver -Pharr method for which direct observation and measurement of the contact area are not required. Considering the influence of tip roundness on the projected contact area, the nanoindentation results were analyzed by the Sawa method. The chain modulus obtained from the thinner polyethylene single crystal sample was 204 +/- 21 GPa by the Oliver-Pharr method and 168 +/- 17 GPa by the Sawa method. The lower values than expected were due to substrate effects and anisotropy of chain deformation during nanoindentation. An extrapolation of the chain modulus obtained by various strains to zero nanoindentation eliminated the effect of substrate and anisotropy of chain deformation. The corresponding chain modulus obtained from the thicker sample was 278 GPa by the Oliver-Pharr method and 267 GPa by the Sawa method, respectively, in better agreement with the value of 340 Cpa determined theoretically. (C) 2001 Elsevier Science Ltd. All rights reserved.

Electrostatic-field-induced chain alignment of liquid crystalline copolyether TPP thin films

A liquid crystalline (LC) copolyether has been synthesized from 1-(4-hydroxy-4'-biphenyl)-2-(4-hydroxyphenyl)propane with 1,7-dibromoheptane and 1,11-dibromoundecane with a 50/50 (both in %) equal composition of the 7- and 11-methylene monomers [coTPP-7/11(5/5)]. A mono-domain with a homeotropic alignment can be induced by a thin film surface in the LC phase. When an electrostatic field is applied to the surface-induced mono-domains parallel to the thin film surface normal, the molecular alignment undergoes a change from the homeotropic to uniaxial homogeneous arrangement. However, when the field is applied to a direction perpendicular to the thin film surface normal. the molecular alignment is about 10 degrees -tilt with respect to the homeotropic alignment toward the a*-axis. This is because the permanent dipole moment of the copolyether is not right vertical to the molecular direction. The calculation of molecular dipoles indicates that the permanent dipole moment of this copolyether is about 70 degrees away from the molecular axis, which leads to a negative dielectric anisotropy. It is speculated that the 10 degrees- rather than 20 degrees -tilt is due to a balance between the alignment induced by the electrostatic field and the surface. In the electrostatic field, molecules are subjected to a torque tau, which is determined by the permanent dipole moment P and the electrostatic field E: tau = P x E. The molecular realignment in both parallel and perpendicular directions to the thin film surface normal is determined by satisfying the condition of tau = P x E = 0. (C) 2001 Elsevier Science Ltd. All rights reserved.

A comparative study of insoluble and soluble polyimide thin films

Physical properties of thin films of soluble and insoluble aromatic polyimides were compared by d.s.c., u.v.-visible and fluorescence spectroscopy, and prism coupler technique. D.s.c. results showed that the thermal properties of insoluble polyimides are superior to those of soluble ones, owing to the specific molecular interactions of insoluble polyimides, revealed by fluorescence spectroscopy. However, the specific molecular interactions sacrifice the transparency in their thin films, shown by u.v.-visible transmission spectra. Negative birefringence of thin films, not only for soluble polimides but also for polyamic acids of insoluble polyimides, was confirmed by prism coupler, while thin films of insoluble polyimides thermally imidized lack high levels of negative birefringence. It is regarded that thin films of insoluble polyimides thermally imidized are likely to be isotropic because of molecular relaxation above their glass transition temperatures (T-g) in the course of thermal imidization, according to Flory's principle. On the contrary, thin films of insoluble poyimide chemically imidized keep the same levels of negative birefringence as those of the relevant polyamic acid thin films. Judging from the opposite cases, it is recognized that molecular relaxation above T-g weakens the optical anisotropy of polyimide thin films. (C) 1998 Elsevier Science Ltd. All rights reserved.

Optical properties of organo-soluble polyimide thin films and their applications in liquid crystal displays

Three organo-soluble polyimide powders have been synthesized. Their imidization was verified by Fourier transform infrared (FTIR) and thermal gravimetric analysis (TGA) techniques. The amorphous morphology of their thin films were confirmed by X-ray diffraction. Polyimide thin films were prepared by solution casting or spin coating. UV-visible transmission spectra of thin films revealed that they are almost transparent in the range of visible light. With in-plane orientation, revealed by FTIR spectra, negative birefringence (Delta n) of thin films were observed, and refractive indices of the thin films along the film plane (n(TE)) and normal to the plane (n(TM)) were measured by a prism coupler. Because of negative birefringence of the thin films, they tan be substituted for the compensation films for twisted nematic liquid crystal displays (TN-LCDs) to extend their viewing angles. In this paper, a 90 degrees C TN-LCD and 120 degrees C TN-LCD were taken as examples to show the compensation effect of thin films of a qualified polyimide. (C) 1998 Elsevier Science S.A. All rights reserved.

Study of molecular order in organo-soluble polyimide thin films

The changes in refractive indices (n(TE) and n(TM)) in a direction normal to the plane of thin films of an organo-soluble polyimide based on 1,4-bis(3,4-dicarboxyphenoxy) benzene dianhydride and 2,2'-dimethyl-4,4'-methylene dianiline were measured by a prism coupler. The results implied that the molecules near the substrate-polyimide interface were much ordered, while those near the polyimide-air interface were less ordered, judging from the variation in the level of negative birefringence with the depth of the films. The molecules are more condensed near the substrate surface, as seen by the average refractive index increasing from the polyimide-air interface to the substrate-polyimide interface, which implies that the condensed states of polyimide molecules change gradually in the depth direction. (C) 1997 Elsevier Science B.V.

Synthesis of a series of chiral copolymers with azo groups and investigations of reversible liquid crystalline alignment induced by the LB films of these materials

A series of liquid crystalline copolymers, poly{2-hydroxyethyl methacrylate}-co-{6-[4-(S-2-methyl-1-butyloxycarbonylphenylazo)phenoxy]hexyl methacrylate} with an azobenzene moiety as photoreactive mesogenic unit, was prepared and investigated by using DSC, polarized optical microscopy and X-ray diffraction. The results show that these polymers exhibit smectic phases. Z-type Langmuir-Blodgett films of these copolymers were successfully deposited onto calcium fluoride and quartz. Reversible homeotropic and planar liquid crystal alignments were induced by using the photochromism of the LB films of one of the copolymers containing 20.6 mol % of the azo unit.

The effect of formulated molecular weight on temperature resistance and mechanical properties in polyimide based composites

This experimental study examines the role of formulated molecular weight between crosslink sites on the temperature resistance and mechanical properties of composites based on a polyimide containing a diphenyl thioether unit (PTI). The composites are fabricated by in situ polymerization of monomer reactants (PMR) using three monomeric ingredients: bis(3,4-dicarboxyphenyl) sulfide dianhydride (TDPA); 4,4'-methylene dianiline (MDA); and the monomethyl ester of norbornene anhydride (NE). By changing monomeric molar ratio, three formulations are prepared, in which formulated molecular weight between crosslink sites varies from 1487 to 3446 g mol(-1). Unidirectional composite laminates from each formulation and T300 carbon fibres are compression moulded and cut into a series of test specimens. By measuring the glass transition temperature (T-g), Mode I interlaminar fracture toughness (G(IC)) and other mechanical properties at room and elevated temperatures, the influences of formulated molecular weight on the temperature resistance and mechanical properties of PTI-based composites are investigated.

INTERLAMINAR FRACTURE OF CARBON THERMOPLASTIC POLYIMIDE COMPOSITES

Mode I interlaminar fracture of a novel amorphous thermoplastic polyimide reinforced with unidirectional carbon fibre has been studied experimentally using double cantilever beam specimens and scanning electron microscopy. Three kinds of composite were ma