Transport properties of dichloromethane in glassy polymers. II. Amorphous syndiotactic polystyrene films

Sorption and diffusion of dichloromethane vapor were measured in amorphous syndiotactic polystyrene films, obtained with different cooling conditions and after controlled aging times at different temperatures. The diffusional behavior, at the temperature of 25°C, was characterized by three stages, depending on penetrant activity. In the first stage, at low activity, the diffusion coefficient was independent of vapor concentration; the second stage was characterized by concentration-dependent diffusion, whereas in the third stage, at high activity, the strong interaction solvent–polymer increased the mobility, allowing the polymer crystallization. The different cooling conditions neither have an effect on the diffusional behavior nor on the sorption curve. The aging, both at room temperature and at 70°C, did not change the diffusion parameters, but led to the appearance of more and more anomalous sorption behavior. The sorption curve, as a function of vapor activity, did not show any difference for the fresh and the aged-at-room temperature samples, whereas the samples aged at 70°C presented a lower sorption at low activity. The presence of ordered domains, impermeable to the penetrant at low activity, was suggested on the basis of sorption results. The solvent-induced crystallization was investigated for all the samples. Crystallization was induced at an activity of 0.45 for the fresh and the aged-at-room temperature samples; at variance, the samples aged at 70°C crystallize at a slightly higher activity, reaching, nevertheless, a higher level of crystallinity. © 1993 John Wiley & Sons, Inc.     

Vapour induced ordering phenomena in syndiotactic polystyrene amorphous films

Summary Films of amorphous syndiotactic polystyrene were exposed to dichloromethane vapour at varying activity, up to a=1. Infrared analysis and wide angle X-ray scattering were used to follow the development of ordered structures, induced by the vapour. It has been found that characteristic bands in the infrared spectrum appear after activity a=0.45, whereas X-rays show that the sample is still amorphous. The appearance of the crystalline reflections occurs at higher activities and a continuous improvement up to a=1 in the X-ray pattern is observed.     

IMITATION LEARNING AND ANCHORING THROUGH CONCEPTUAL SPACES

In order to have a robotic system able to effectively learn by imitation and not merely reproduce the movements of a human teacher, the system should have the capability to deeply understand the perceived actions to be imitated. This paper deals with the development of a cognitive architecture for learning by imitation in which a rich conceptual representation of the observed actions is built. The purpose of the following discussion is to show how the same conceptual representation can be used both in a bottom-up approach, in order to learn sequences of actions by imitation learning paradigm, and in a top-down approach, in order to anchor the symbolical representations to the perceptual activities of the robotic system. Experiments concerned with the problem of teaching a humanoid robotic system simple manipulative tasks are reported.     

Autophagy as an ultrastructural marker of heavy metal toxicity in human cord blood hematopoietic stem cells

Stem cells are a key target of environmental toxicants, but little is known about their toxicological responses. We aimed at developing an in-vitro model based on adult human stem cells to identify biomarkers of heavy metal exposure. To this end we investigated the responses of human CD34+ hematopoietic progenitor cells to hexavalent chromium (Cr[VI]) and cadmium (Cd). Parallel cultures of CD34+ cells isolated from umbilical cord blood were exposed for 48 h to 0.1 microM and 10 microM Cr(VI) or Cd. Cultures treated with 10 microM Cr(VI) or Cd showed marked cell loss. Ultrastructural analysis of surviving cells revealed prominent autophagosomes/autophagolysosomes, which is diagnostic of autophagy, associated with mitochondrial damage and replication, dilatation of the rough endoplasmic reticulum and Golgi complex, cytoplasmic lipid droplets and chromatin condensation. Treated cells did not show the morphologic hallmarks of apoptosis. Treatment with 0.1 microM Cr(VI) or Cd did not result in cell loss, but at the ultrastructural level cells showed dilated endoplasmic reticulum and evidence of mitochondrial damage. We conclude that autophagy is implicated in the response of human hematopoietic stem cells to toxic concentrations of Cr(VI) and Cd. Autophagy, which mediates cell survival and death under stress, deserves further evaluation to be established as biomarker of metal exposure.     

Model for the a.c. hall effect of high-T c superconductors

The sign of the Cooper pairs in the superconducting state of the currently found high-T _c superconductors can be best measured by utilizing the so-called a.c. Hall effect. In this experiment a d.c. magnetic field is applied normal to the surface of the superconductor and a planar electromagnetic wave perpendicularly polarized incident upon the sample surface. By measuring the reflected electric field polarized in the incident plane, one could determine the sign as well as the magnitude of the a.c. Hall coefficient. The measurement provides a direct means to determine the sign and density of the Cooper pairs in the superconducting state of the high-T _c superconducting sample.     

Propagation properties of ferromagnetic insulator guide

In order to realize new ferrite planar devices for applications at millimeter-wavelength frequencies, the authors have developed nonreciprocal ferrite devices schemes for incorporating ferromagnetic layers in dielectric insulator guide geometries. Their research program involves both the calculation and the measurement of device characteristics. For the calculation, a method of effective permeability, in which the permeability is a tensor, is introduced to characterize the ferrite material. The propagation properties of the insular guide are calculated by using a single-mode approach. The calculated results for dispersion, dielectric, and conductivity losses show resonant behavior with the application of a magnetic bias field for a guide configuration in which the ferrite replaces the insular dielectric. Ferrite phase shifters, filters, isolators, and circulators are potential applications of this guide configuration. For the experimental part of the study, wave dispersion and attenuation were measured in a purely dielectric insular guide from 26.5 to 40GHz. In addition to these experiments wave attenuation was measured as a function of magnetic bias field for the case where a hexagonal ferrite platelet was mounted on the ground plane near the insulator guide. General agreement is found between calculated and measured attenuation     

Elastic and viscoelastic behavior of ethylene–propylene copolymers

The viscoelastic behavior of an ethylene–propylene copolymer is analyzed. Two different vulcanization procedures were followed; in the first a binary mixture of initiator-polymer was used, while in the second the polymer was diluted by a solvent. The networks thus obtained show a different viscoelastic behavior depending on the different vulcanization procedure used. Results, analyzed in terms of supramolecular organization being present in the amorphous material, give some important information about the molecular nature of the C₂ coefficient of the Mooney-Rivlin equation, and therefore about the well-known deviations from the Gaussian theory shown by all rubber-like networks.     

Synthesis and Microstructural Investigations of Organometallic Pd(II) Thiol-Gold Nanoparticles Hybrids

In this work the synthesis and characterization of gold nanoparticles functionalized by a novel thiol-organometallic complex containing Pd(II) centers is presented. Pd(II) thiol, trans, trans-[dithiolate-dibis(tributylphosphine)dipalladium(II)-4,4′-diethynylbiphenyl] was synthesized and linked to Au nanoparticles by the chemical reduction of a metal salt precursor. The new hybrid made of organometallic Pd(II) thiol-gold nanoparticles, shows through a single S bridge a direct link between Pd(II) and Au nanoparticles. The size-control of the Au nanoparticles (diameter range 2–10 nm) was achieved by choosing the suitable AuCl₄ ⁻/thiol molar ratio. The size, strain, shape, and crystalline structure of these functionalized nanoparticles were determined by a full-pattern X-ray powder diffraction analysis, high-resolution TEM, and X-ray photoelectron spectroscopy. Photoluminescence spectroscopy measurements of the hybrid system show emission peaks at 418 and 440 nm. The hybrid was exposed to gaseous NO _x with the aim to evaluate the suitability for applications in sensor devices; XPS measurements permitted to ascertain and investigate the hybrid –gas interaction.