Single-chain single crystals of gutta-percha

Single-chain single crystals of gutta-percha have been observed by transmission electron microscopy of atomizer-sprayed particles deposited from a very dilute solution in chloroform onto a carbon film which had a filter paper wetted with ethanol in contact with its under side. Selected-area electron diffraction patterns of crystals having no definite crystal profiles showed that the crystals were of the low-melting crystalline form and that the chain segments in the single crystals were standing up from the substrate during crystallization. In cases of single crystals showing sharply defined crystal profiles, electron diffraction patterns showed that they were neither of the low-melting form nor the high-melting form. The structure of this new crystalline modification needs further studies.

Crystallization process and morphology structure of poly(aryl ether ether ketone ketone) containing meta-phenyl links

The crystallization process and morphology of poly(aryl ether ether ketone ketone) containing meta-phenyl links (PEEKmK) have been investigated by transmission electron microscopy and electron diffraction. The results indicate that the thin films of PEEKmK isothermally crystallized from both the glassy state and the melt at the temperature range of 180 similar to 250 degrees C consist of two kinds of morphological forms, i. e. large (order of mu m), flat-on single crystals and narrow, lath-like, edge-on lamellae, The latter consists of the spherulites. Meanwhile, the growing process of the two kinds of morphological forms has been discussed.

Crystallization of syndiotactic polypropylene (sPP) from oriented melts

The influence of the syndiotacticity on the crystallization behaviour of syndiotactic polypropylene (sPP) has been investigated. The syndiotacticity has been measured by C-13-NMR spectroscopy and the phase formation has been observed by electron diffraction of oriented samples. It is shown that the crystal phase formation depends strongly on the perfection of the tacticity of the macromolecules.

Effect of lamellar thickness on the epitaxial crystallization of PE on oriented iPP films

The effects of lamellar thickness on the epitaxial crystallization of polyethylene on the oriented isotatic polypropylene have been studied by means of transmission electron microscopy. The results obtained from the bright field electron microscopy and electron diffraction show that the epitaxial orientation of the PE crystals on the iPP substrate depends not only on the thickness of the oriented iPP lamellae, but also on the lamellar thickness of PE crystals. No epitaxial orientation relationship between PE crystal and iPP substrate can be found, when the PE crystals are thicker than the lamellar thickness of iPP along the matching direction. This suggests, that the epitaxial nucleation of PE in the PE/iPP epitaxial system is controlled not only by the chain-row matching, but also by a secondary nucleation process.

The crystal structure and drawing-induced polymorphism in poly(aryl ether ketone)s .1. Poly(oxybiphenyl-4-4'-diyloxy-1,4-phenylenecarbonyl-1,3-phenylenecarbonyl-1,4-phenylene)

Crystal structure and polymorphism induced by uniaxial drawing of a poly(aryl ether ketone) [PEDEKmK] prepared from 1,3-bis(4-fluorobenzoyl)benzene and biphenyl-4,4'-diol have been investigated by means of transmission electron microscopy (TEM), electron diffraction (ED), wide-angle X-ray diffraction (WAXD), and differential scanning calorimetry (DSC) techniques. The melting and recrystallization process in the temperature range of 250-260 degrees C, far below the next melting temperature (306 degrees C), was identified and found to be responsible for the remarkable changes in lamellar morphology. Based on WAXD and ED patterns, it was found that crystal structure of isotropic-crystalline PEDEKmK obtained under different crystallization conditions (melt-crystallization, cold-crystallization, solvent-induced crystallization, melting-recrystallization, and crystallization from solution) keeps the same mode of packing, i.e., a two-chain orthorhombic unit cell with the dimensions a = 0.784 nm, b = 0.600 nm, and c = 4.745 nm (form I). A second crystal modification (form II) can be induced by uniaxial drawing above the glass transition temperature, and always coexists with form I. This form also possesses an orthorhombic unit cell but with different dimensions, i.e., a = 0.470 nm, b = 1.054 nm, c = 5.064 nm. The 0.32 nm longer c-axis of form II as compared with form I is attributed to an overextended chain conformation due to the expansion of ether and ketone bridge bond angles during uniaxial drawing. The temperature dependence of WAXD patterns for the drawn PEDEKmK suggests that form II can be transformed into the more stable form I by relaxation of overextended chains and relief of internal stress at elevated temperature in absence of external tension.

Recrystallization of HDPE in HDPE/iPP quenched films

Epitaxial crystallization behavior of HDPE/iPP double layers under quenching and annealing conditions has been studied by means of transmission electron microscopy (TEM). The results obtained from bright field TEM observations indicate that in the as-quenched state the HDPE that is in direct contact with the surface of the oriented iPP substrate recrystallizes in the form of oriented crystallites dispersed on the iPP substrate. The electron diffraction results show that besides the two normally observed epitaxial orientations between HDPE and iPP, there is also a special orientation with [001](HDPE)parallel to[001](iPP). The HDPE which is in contact with the clean surface of a glass slide crystallizes in small lamellae with random orientation. In the boundary region, the epitaxially crystallized HDPE small lamellae stop right on the boundary of the oriented iPP film. If the quenched samples are annealed at 128 degrees C (below T-m of HDPE) for 2 h, the small HDPE crystals grow to thick lamellae in both areas. But only the epitaxial orientation of HDPE with [001](HDPE)parallel to[101](iPP) has been observed.

Epitaxial crystallization in the sPP/nylon-12 semicrystalline polymer system

The epitaxial crystallization behaviour of syndiotactic polypropylene (sPP) on highly oriented nylon-12 substrates has been investigated by means of transmission electron microscopy. The results obtained from bright field electron microscopy and electron diffraction indicate that sPP crystals grow epitaxially on the oriented nylon-12 substrate with their c-axes +/- 37 degrees apart from the chain axis of the nylon-12 substrate. The contact planes of the sPP crystals are the (100) lattice planes. Moreover, the epitaxial crystallization of nylon-12 on highly oriented sPP substrates from a dilute solution in cyclohexanone has also been studied using optical microscopy. The results show that the nylon-12 crystals grow epitaxially on the oriented sPP substrate with the oriented nylon-12 lamellae forming large, anisotropic domains. Copyright (C) 1996 Elsevier Science Ltd.

Morphological studies on a novel poly(aryl ether ketone)

The morphology of a novel poly(aryl ether ketone) [PEDEKmK] was investigated via polarizing optical microscopy (POM), TEM, DSC, SAXS and electron diffraction (ED). A distinct change in lamellar thickness, orientation, and spherulitic morphology was observed due to crystal melting and recrystallization. However, the crystal packing mode is found to be identical before and after the recrystallization process.

THE USE OF LIGHT-MICROSCOPY FOR INVESTIGATIONS OF EPITAXIAL-GROWTH OF POLYMERS ON POLYMERIC SUBSTRATES

In order to study the oriented (epitaxial) crystallization of thermoplastic polymers on oriented polymer substrates, generally the transmission electron microscopy (TEM) is used. With this instrument, the crystallized material can easily be resolved and orientation relationships can be monitored by electron diffraction. Disadvantages are the time consuming sample preparations and difficulties in the in-situ observations of the crystallization events, because of the radiation sensitivity of the polymer crystals. It is demonstrated that these disadvantages of the TEM can be eleminated by the use of different methods of light optical contrasts under specific preparation conditions of the samples and that the optical microscopy being a supplementary method to the TEM for investigations of epitaxial crystallization.

EPITAXIAL CRYSTALLIZATION OF TRANS-1,4-POLYBUTADIENE ON HIGHLY ORIENTED ISOTACTIC POLY(PROPYLENE) FILMS

Epitaxial crystallization of trans-1,4-polybutadiene (PBD) on highly oriented isotactic poly(propylene) (iPP) has been investigated at different crystallization temperatures and rates. From electron microscopy and electron diffraction, it is confirmed that epitactic growth of the low-temperature modification (monoclinic) with microcrystals of PBD on the iPP films takes place with their chain directions about +/- 50-degrees apart. No epitaxial relationship occurs between the high-temperature modification (hexagonal) of PBD and the iPP substrate. Thermal analyses of PBD-PP layered films indicate that the epitaxy has an important effect on the formation of the high-temperature modification of PBD.

EPITAXIAL CRYSTALLIZATION OF SYNDIOTACTIC POLYPROPYLENE ON UNIAXIALLY ORIENTED POLYETHYLENE

The epitaxial crystallization of syndiotactic polypropylene (sPP) on uniaxially oriented polyethylene (PE) has been investigated by electron microscopy and electron diffraction. It is found that the sPP lamellae grow epitaxially on the PE substrate film with the preference in sPP for the b axis as the fast growth direction. Instead of 50-degrees as in the system of isotactic polypropylene with PE, the molecular chains of the sPP crystals are approximately +/- 37-degrees inclined to the chain direction of PE.

EPITAXIAL CRYSTALLIZATION OF HDPE ON IPP IN HDPE/IPP BLENDS

Unique crystalline morphologies of solution-cast films of HDPE/iPP blends were investigated by means of transmission electron microscopy (TEM), electron diffraction, metal shadowing and specimen-tilt techniques. The unique morphologies come from an epitaxial crystallization of HDPE on iPP. The contact planes of the two kinds of crystals are (100) of HDPE and (010) of iPP, while the intercrossing angle between their chain axes is about 50-degrees. The HDPE existed with different crystalline morphologies in the two kinds of crystalline regions of iPP spherulites, i.e. cross-hatched and single-crystal-type structures. Based on structural analysis, two models of epitaxial growth of HDPE on iPP are proposed.

Preparation of Dendritic Copper Nanostructures and Their Characterization for Electroreduction

Dendritic copper nanostructures of different morphologies were synthesized by a surfactant-free electrochemical method. Single crystal nature of the nanostructures was revealed from their X-ray diffraction and electron diffraction patterns. Mechanism of dendrite formation was discussed from thermodynamic aspects using the concept of supersaturation. Supersaturation of the copper metal reduced on the surface of the electrode was the crucial factor for the generation of different morphologies. Effects of applied potential, temperature, and the solution concentration on the supersaturation were studied. The NO3- and H2O2 electroreduction ability of the dendritic materials was tested. Use of copper dendrite-modified electrode as NO3- sensor was demonstrated.

Ultrasonic synthesis of silica-alumina nanomaterials with controlled mesopore distribution without using surfactants

A novel sol-gel process has been developed for the synthesis of amorphous silica-aluminas with controlled mesopore distribution without the use of organic templating agents, e.g., surfactant molecules. Ultrasonic treatment during the synthesis enables production of precursor sols with narrow particle size distribution. Atomic force microscopy analysis shows that these sol particles are spherical in shape with a narrow size distribution (i.e., 13-25 nm) and their aggregation during the gelation creates clusters containing similar sized interparticle mesopores. A nitrogen physiadsorption study indicates that the mesoporous materials containing different Si/Al ratios prepared by the new synthesis method has a large specific surface area (i.e., 587-692 m(2)/g) and similar pore sizes of 2-11 nm. Solid-state Al-27 magic angle spinning (MAS) NMR shows that most of the aluminum is located in the tetrahedral position. A transmission electron microscopy (TEM) image shows that the mesoporous silica-alumina consists of 12-25 nm spheres. Additionally, high-resolution TEM and electron diffraction indicate that some nanoparticles are characteristic of a crystal, although X-ray diffraction and Si-29 MAS NMR analysis show an amorphous material.

Structure and properties of samarium overlayer and Sm/Rh surface alloy on Rh(100)

The structure and properties of Sm overlayer and Sm/Rh surface alloy have been investigated with Auger electron spectroscopy (AES), low energy electron diffraction (LEED), X-ray photoelectron spectroscopy (XPS), and temperature programmed desorption spectroscopy (TDS). The growth of Sm on Rh(100) at room temperature (RT) appears following the Stranski-Krastanov growth mode and only the trivalent state Sm is observed from XPS results. Thermal treatment of the Sm film at 900 K leads to the formation of ordered surface alloy which shows the c(5 root2 x root2)R45 degrees and c(2 x 2) LEED patterns. Annealing the Sm film at temperature above 400 K makes the binding energy (B.E.) of Sm 3d(5/2) shift to higher energy by 0.7 eV, which indicates charge transfer from Sm to Rh(100) substrate, causing the increase of CO desorption temperature.