Observation of twisting growth of branched polyethylene single crystals formed from the melt

The twisting growth of a branched polyethylene single crystal formed from the melt was observed directly by means of transmission electron and atomic force miscroscopy. The surface stress asymmetry arising from the asymmetry of the surface-fold structure and, chain tilting resulted in the twisting growth of the single crystals. The handedness of the twisting lamellae was consistent With the chain-tilting direction. When multilayer lamellae piled up in a thicker film, the lamellar twist would be inevitably causing screw dislocations.

Effect of branch content on the transition of crystalline structure and morphology of metallocene-catalyzed branched polyethylene

Transition of crystalline structure and morphology of metallocene-catalyzed butyl branched polyethylene with branch content has been studied. It was found that the long periods of the branched polyethylene were controlled by crystallization conditions for the lower branch content samples and by branch contents for the higher branch content samples. When the branch content increased to a critical value the branched polyethylene had no long period because the crystalline morphology was changed from folded chain crystal to a bundled crystal. The TEM observations supported the results. The transition of the crystalline morphology resulted from the reduction of lamellar thickness with increasing of branch content since the branches were rejected from the lattice. The reduction of lamellar thickness with increasing of branch content also resulted in lattice expansion and decrease of melt temperature of the branched polyethylene. (C) 2001 Kluwer Academic Publishers.

A comparative study on the electroluminescence properties of some terbium beta-diketonate complexes

By comparing the phosphorescence spectra of Gd(acac)(3) (acac=acetylacetone), Gd(TFacac)3 (TFacac=1,1,1-trifluoroacetylacetone), the effects of fluorine replacement of hydrogen on the triplet state energy of the ligands were revealed. Fluorine can lower the triplet state energy of Hacac and make it more suitable for energy transfer towards the D-5(4) state of terbium. Organic electroluminescent devices (OELDs) with the corresponding trivalent terbium complexes as emissive layers were fabricated. Triple-layer-type devices with a structure of glass substrate/ITO (indium tin oxide)/PVK [poly(N-vinylcarbazole)]/PVK : Tb complex: PBD [2-(4-biphenyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole]/PBD/Al exhibit bright green luminescence upon applying a dc voltage. The luminance of a device with Tb(TFacac)(3)phen (1,10-phenanthroline) and Tb( TFacac) 3 as emissive layer is higher than that of the corresponding devices with Tb(acac)(3)(phen) and Tb(acac)(3) as emissive layers. The EL device with Tb(TFacac)(3)(phen) as emitter exhibits characteristic emission of Tb3+ ions with a maximum luminance of 58 cd m(-2) at 25 V.

Influence of short chain branches on crystallization and melting behavior of low molecular weight polyethylenes

The crystallization and melting behavior of mellocene-catalized branched and linear polyethylenes of low molecular weight was studied. It was found that the crystalline lattice of branched polyethylene is larger than that of linear polyethylene because of the existence of branched chains. The melting behavior of branched polyethylene is similar to that of linear polyethylene since the branched chains can not enter the lattice. However, the crystalline behavior of low molecular weight branched polyethylene is the same as that of high molecular weight linear polyethylene, but different with that of low molecular weigh linear polyethylene. Kinetics theory analysis evidenced that the transition temperature of growth regime of the branched polyethylene is about 20 degreesC lower than that of linear polyethylene with the same molecular weight. It may be attributed to the existence of short branched chains.

Formation of mesophase mono-domains and micro-structures in thin films of a series of copolyethers containing both odd-numbered methylene units

The structural and morphological evolution of mono-domains in thin films has been investigated for a series of liquid crystalline (LC) copolyethers. The copolyethers studied were synthesized by the reaction of 1-(4-hydroxy-4 ' -biphenylyl)-2-(4-hydroxyl-phenyl)propane (TPP) with 1,7-dibromoheptane and 1,11-undecane at different compositions (coTPPs-7/11). In contrast to the solution-cast thin films without annealing, which exhibit the isotropic homogeneous molecular orientation, mono-domains with a homeotropic alignment were found in coTPP-7/11(5/5) after the thin films were annealed in the high-temperature columnar phase (Phi '). Similar to the nucleation process in polymer crystallization, transmission electron microscopic observations show that small mono-domains appear in the initial stage of annealing, where molecules form a uniaxial in-plane chain orientation. With increasing annealing time, the molecular orientation gradually became tilted with respect to the substrate surface, and finally, a uniaxial homeotropic molecular orientation was achieved after a prolonged annealing time. The lateral size of mono-domains was found to increase continuously with annealing time and grew into a circular shape, indicating an isotropic lateral growth scheme which implies a hexagonal molecular packing proved by the electron diffraction experiments.

Thermal influence on excimer-laser-induced electrical conductivity on polyimide film surfaces

The thermal influence on the electrical conductivity of polyimide film surfaces induced by KrF-laser irradiation was investigated, The formation of conducting phases was demonstrated to be highly temperature sensitive, as evidenced by strong dependence of the electrical conductivity on repetition rate and ambient temperature. XPS and Raman studies showed that the efficiency of the formation of conducting phases could be enhanced by the increase of temperature on irradiated polyimide film surfaces. After the disruption of polymeric chain, the carbon-enriched clusters remained on the irradiated polyimide film surfaces organized into polycrystalline graphite-like clusters responsible for electrical conductivity. The resulting dangling bonds from the decomposition process of polyimide acted as centers for the rearrangement of carbon-enriched clusters. It is suggested that the motion of radicals was promoted with increasing the temperature. Therefore the formation of polycrystalline graphite-like clusters benefited from high remaining temperature on the irradiated polyimide film surfaces. These results revealed that thermal influence played a dominant role on the formation of conducting phases.

Study of elastic modulus and yield strength of polymer thin films using atomic force microscopy

Nanometer-scale elastic moduli and yield strengths of polycarbonate (PC) and polystyrene (PS) thin films were measured with atomic force microscopy (AFM) indentation measurements. By analysis of the AFM indentation force curves with the method by Oliver and Pharr, Young's moduli of PC and PS thin films could be obtained as 2.2 +/- 0.1 and 2.6 +/- 0.1 GPa, respectively, which agree well with the literature values. By fitting Johnson's conical spherical cavity model to the measured plastic zone sizes, we obtained yield strengths of 141.2 MPa for PC thin films and 178.7 MPa for PS thin films, which are similar to2 times the values expected from the literature. We propose that it is due to the AFM indentation being asymmetric, which was not accounted for in Johnson's model. A correction factor, epsilon, of similar to0.72 was introduced to rescale the plastic zone size, whereupon good agreement between theory and experiment was achieved.

Direct measurement of plowing friction and wear of a polymer thin film using the atomic force microscope

Nanometer-scale plowing friction and wear of a polycarbonate thin film were directly measured using an atomic force microscope (AFM) with nanoscratching capabilities. During the nanoscratch tests, lateral forces caused discrepancies between the maximum forces for the initial loadings prior to the scratch and the unloading after the scratch. In the case of a nanoscratch test performed parallel to the cantilever probe axis, the plowing friction added another component to the moment acting at the cantilevered end compared to the case of nanoindentation, resulting in an increased deflection of the cantilever. Using free-body diagrams for the cases of nanoindentation and nanoscratch testing, the AFM force curves were analyzed to determine the plowing friction during nanoscratch testing. From the results of this analysis, the plowing friction was found to be proportional to the applied contact force, and the coefficient of plowing friction was measured to be 0.56 +/- 0.02. Also, by the combination of nanoscratch and nanoindentation testing, the energetic wear rate of the polycarbonate thin film was measured to be 0.94 +/- 0.05 mm(3)/(N m).

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.

Morphologies of metallocene-catalyzed short chain branched polyethylene single crystals formed from the melt at higher temperature

Metallocene-catalyzed short chain branched polyethylene single crystals, formed from the melt at a higher crystallization temperature of 114 degreesC, were obtained. Highly elongated lamellae were formed, which are different from truncated lozenge or lenticular shaped single crystals formed at a lower crystallization temperature. It was found that there existed a definite line in the lamellae along the longitudinal growth direction and two regions were separated by the definite line. The lateral habits of both the regions were asymmetrical about the b-axis due to the chain tilting, which was the same as that at a lower crystallization temperature. Generally, the highly elongated lamellae were not straight, but curved towards the opposite direction with chain tilting direction due to a series of edge dislocation within a lamella. The inner side of a lamella was serrated and the outer side was smooth due to the lamellar curvature. The thickness of both regions of a lamella was different, the broader region was thicker than the narrower region, which was different from the uniform thickness of the lamellae formed at a lower crystallization temperature. The different thicknesses within a lamella were considered as the result of the initial thickness difference and the impact of isothermal thickening. (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.

Structural studies of excimer laser-induced percolative phase transition on polyimide thin film surfaces

The behavior of electrical conductivity for excimer laser irradiated polyimide films in the vicinity of the critical number of laser shots was described by three-dimensional percolative phase transition model. It is: found that electrical conductivity changed more rapidly than that predicted by the percolation model. Thus, the change in microstructure with increasing number of laser shots was analyzed by FT-IR Raman spectrometry and laser desorption time-of-flight mass spectrometry. It is demonstrated that not only the number but also the average size of graphite particles on the irradiated polyimide film surfaces increased with increasing number of laser shots. These results were helpful to better understand the critical change in electrical conductivity on the irradiated polyimide film surfaces. (C) 2001 Elsevier Science B.V. All rights reserved.

Diffusion-limited kinetics modeling of one-step polyimide formation

A diffusion-limited kinetic model was developed to describe the imidization of one-step polythioetherimide formation based on an endgroup diffusion model. The changes of conversion and viscosity during the imidization were monitored with thermogravimetric analysis and dynamic stress rheometry, respectively. It was observed that the imidization rate began to decelerate after a fast early stage, whereas the viscosity in the system increased dramatically after a period of low value. Amic acid and imide formations concurrently take place in the one-step polyimide formation, but the formation of amic acid is much slower than that of imide and is the rate-limiting step of imidization. When a second-order kinetic model was used to describe the imidization, the effect of viscosity on the diffusion resistance of reactive groups needed to be included. In order to predict the change of viscosity during the imidization, the Lipshitz-Macosko model was modified and introduced into the diffusion-limited kinetic model by the Stokes-Einstein equation. The comparison of the modeled results with experimental data indicated that the diffusion-limited kinetic model and the modified Lipshitz-Macosko model were able to efficiently predict the changes of conversion and viscosity with temperature and time during the one-step polythioetherimide formation. (C) 2001 John Wiley & Sons, Inc.

Phase structure and transitions in a poly(methyloctadecylsilane) oligomer

A poly(methyloctadecylsilane) oligomer was synthesized by a typical Wurtz coupling reaction. Upon cooling, three transitions were observed at temperatures of 39.9, 37.5 and 33.9 degreesC at a rate of 2.5 degreesC/min in differential scanning calorimetry (DSC). The first transition, with enthalpy change of 0.47 kT/mol and supercooling of 0.2 degreesC, was characteristic of the conformational change in the Si-Si backbone into an all-trans conformation, which was detected by temperature-dependent Fourier transform infrared (FT-FR) spectroscopy. The second and the third transitions with large supercooling were identified as the formation of two-dimensional hexagonal crystal packing and three-dimensional two-chain orthorhombic crystal packing, respectively. The crystal structure was determined by the combination of WAXD and transmission electron microscopy (TEM) experiments. (C) 2000 Elsevier Science Ltd. All rights reserved.