Isothermal and non‐isothermal crystallization of poly(L‐lactic acid)/poly(butylene terephthalate) blends

Isothermal and non‐isothermal crystallization kinetics of poly(l ‐lactic acid)/poly(butylene terephthalate) (PLLA/PBT) blends containing PLLA as major component is detailed in this contribution. PLLA and PBT are not miscible, but compatibility of the polymer pair is ensured by interactions between the functional groups of the two polyesters, established upon melt mixing. Crystal polymorphism of the two polyesters is not influenced by blending, as probed by wide‐angle X‐ray analysis. The addition of PLLA does not affect the temperature range of crystallization kinetics of PBT, nor the crystallinity level attained when the blends are cooled from the melt at constant rate. Conversely, PBT favors crystallization of the biodegradable polyester. The addition of PBT results in an anticipated onset of crystallization of PLLA during cooling at a fixed rate, with a sizeable enhancement of the crystal fraction. Isothermal crystallization analysis confirmed the faster crystallization rate of PLLA in the presence of PBT. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40372.     

Dynamics of SiO2 Buried Layer Removal from Si-SiO2-Si and Si-SiO2-SiC Bonded Substrates by Annealing in Ar

Silicon-on-silicon-carbide substrates could be ideal for high-power and radiofrequency silicon devices. Such hybrid wafers, when made by wafer bonding, contain an intermediate silicon dioxide layer with poor thermal characteristics, which can be removed by high-temperature annealing in an inert atmosphere. To understand the dynamics of this process, removal of 2.4-nm-thick SiO₂ layers from Si-SiO₂-Si and Si-SiO₂-SiC substrates has been studied at temperatures ranging from 1100°C to 1200°C. The substrates were analyzed by transmission electron microscopy, electron energy-loss spectroscopy, secondary-ion mass spectroscopy, and ellipsometry, before and after annealing. For oxide thickness less than 2.4 nm, the activation energy for oxide removal was estimated to be 6.4 eV, being larger than the activation energy reported for removal of thicker oxides (4.1 eV). Under the same conditions, the SiO₂ layer became discontinuous. In the time domain, three steps could be distinguished: bulk diffusion, bulk diffusion with void formation, and bulk diffusion with disintegration. The void formation, predominant here, has an energetic cost that could explain the larger activation energy. The oxide remaining after prolonged annealing corresponds to one layer of oxygen atoms.     

Poly(L‐lactic acid) with added α‐tocopherol and resveratrol: optical,physical, thermal and mechanical properties

Poly(L ‐lactic acid) (PLLA) films containing various concentrations of two natural antioxidants, α‐tocopherol and resveratrol, were fabricated by a melt compounding and compression molding process. The influence of the antioxidants on the optical properties such as color and UV‐visible light transmission was analyzed. The thermal, mechanical, rheological and physical properties of PLLA films with added antioxidants were assessed. PLLA films with added α‐tocopherol and resveratrol showed a yellowish brown color and the lightness was influenced by the presence of the antioxidants. The glass transition and melting temperatures were significantly reduced with the addition of antioxidants while enhanced thermal stability was observed, which could be a benefit and important for processing and production. PLLA films with added antioxidants were slightly more hydrophobic than neat PLLA. The combination effect of plasticizing and enhancement of the elastic modulus with differing concentrations of two antioxidants played a critical role in the mechanical and thermomechanical properties of PLLA films. The melt viscosity of the PLLA films with added antioxidants was substantially higher than that of neat PLLA. The higher melt viscosity and G′(ω) could be an indication of formation of entanglement between PLLA and the two antioxidants. Copyright © 2012 Society of Chemical Industry     

Peculiar crystallization kinetics of biodegradable poly(lactic acid)/poly(propylene carbonate) blends

Binary blends of poly(lactic acid) (PLA) and poly(propylene carbonate) (PPC) were found to display a peculiar crystallization kinetics. The two biodegradable polymers were blended by melt mixing, to obtain binary blends at various compositions. Temperature‐modulated calorimetry and dynamic‐mechanical analysis indicated that the blend components are partially miscible, and display two separate glass transitions, at temperatures intermediate to those of the plain polymers. Electron microscopy analysis disclosed the morphology of PLA/PPC blends, made of PPC‐rich particles finely dispersed within the PLA‐rich matrix. The possible establishment of interactions between the functional groups of the two polymers upon melt mixing has been hypothesized as the reason for partial miscibility and compatibility of the two biodegradable polymers. The PLA/PPC blends display good mechanical properties, with enhanced performance at rupture compared with plain PLA. Most importantly, the addition of PPC affects also the crystallization kinetics of PLA, since the more mobile PPC chains favor diffusion of the stiffer PLA chain segments towards the growing crystals, which fastens the spherulite growth rate of PLA. Such positive influence of an amorphous polymer on crystal growth rate has been demonstrated here for the first time in blends that display phase‐separation in the melt. POLYM. ENG. SCI., 55:2698–2705, 2015. © 2015 Society of Plastics Engineers     

Effect of chlorine dioxide gas on physical,thermal, mechanical,and barrier properties of polymeric packaging materials

The effects of gaseous chlorine dioxide (ClO₂) on properties and performance of 10 selected polymeric packaging materials, including polyethylene (PE), biaxially oriented poly(propylene), polystyrene, poly(vinyl chloride), poly(ethylene terephthalate) (PET), poly(lactic acid), nylon, and a multilayer structure of ethylene vinyl acetate (EVA)/ethylene vinyl alcohol (EVOH), were evaluated. Physical, mechanical, barrier, and color properties as well as infrared (IR) spectra were assessed before and after polymer samples were exposed to 3600 ppmV ClO₂ gas at 23°C for 24, 168, and 336 h. The IR spectra of the ClO₂‐treated samples revealed many changes in their chemical characteristics, such as the formation of polar groups in the polyolefin, changes in functional groups, main chain scission degradation, and possible chlorination of several materials. The ClO₂‐treated PE samples showed a decrease in tensile properties compared with the untreated (control) films. Decreases in moisture, oxygen, and/or carbon dioxide barrier properties were observed in the treated PE, PET, and multilayer EVA/EVOH/EVA samples. A significant increase (P < 0.05) in the barrier to O₂ was observed in the ClO₂‐treated nylon, possibly the result of molecular reordering, which was found through an increase in the crystallinity of the material. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

The dynamic response of end-clamped sandwich beams with a Y-frame or corrugated core

The dynamic response of end-clamped monolithic beams and sandwich beams has been measured by loading the beams at mid-span using metal foam projectiles. The AISI 304 stainless-steel sandwich beams comprise two identical face sheets and either prismatic Y-frame or corrugated cores. The resistance to shock loading is quantified by the permanent transverse deflection at mid-span of the beams as a function of projectile momentum. The prismatic cores are aligned either longitudinally along the beam length or transversely. It is found that the sandwich beams with a longitudinal core orientation have a higher shock resistance than the monolithic beams of equal mass. In contrast, the performance of the sandwich beams with a transverse core orientation is very similar to that of the monolithic beams. Three-dimensional finite element (FE) simulations are in good agreement with the measured responses. The FE calculations indicate that strain concentrations in the sandwich beams occur at joints within the cores and between the core and face sheets; the level of maximum strain is similar for the Y-frame and corrugated core beams for a given value of projectile momentum. The experimental and FE results taken together reveal that Y-frame and corrugated core sandwich beams of equal mass have similar dynamic performances in terms of rear-face deflection, degree of core compression and level of strain within the beam.     

Switching Device Based on a Thin Film of an Azo-Containing Polymer for Application in Memory Cells

Results obtained on a conductive multilevel device realized with a 100 nm azo-polymer film are reported. The capability to switch between three different conductance states makes the device versatile both for Write Once Read Many and Write Many Read Many memory cell application. The analysis of the - curves indicates that the hysteretic conductance change with the external voltage can be explained in terms of different hopping distances existing between the nearest neighbors intervening in the two conformational states of the molecular structure.     

Sympathetic neurotransmission in isolated rat atria after sensory-motor denervation by neonatal treatment with capsaicin

Long-term interactions between sympathetic and sensory-motor nerves have been shown in several tissues. Previous investigations in this laboratory have demonstrated an increase in cardiac sensory-motor innervation after neonatal sympathectomy by guanethidine and an increase of perivascular sympathetic neurotransmission after neonatal treatment by capsaicin. The present study evaluated the effects of sensory-motor denervation on sympathetic neurotransmission in the heart. Newborn rats were injected with capsaicin or its vehicle (Tween 80). Sympathetic neurotransmission was studied in isolated atria driven at a constant rate (4 Hz) by measuring cardiac responses to electrical field stimulation, in the presence of atropine 1 microM. Inotropism of tyramine, norepinephrine and calcitonin gene-related peptide was also tested. Neonatal capsaicin treatment did not affect cardiac responses to trains of an increasing number (2-32) of field pulses. Moreover, inotropic responses to tyramine did not differ between control, capsaicin- and Tween 80-treated preparations. Neither maximal effect nor pD2 values were significantly different between the groups. Similarly, the inotropism of calcitonin gene-related peptide was comparable in all groups of atrial preparations. In marked contrast to earlier papers on blood vessels, this study shows a lack of effect of sensory-motor denervation by neonatal capsaicin treatment on cardiac sympathetic neurotransmission. The different neuronal plasticity of vascular and cardiac sensory innervation will be discussed. The present results also indicate that capsaicin-induced sensory-motor denervation is not associated with changes in cardiac responsiveness to calcitonin gene-related peptide.     

Molecular-Level Characterization of Heterogeneous Catalytic Systems by Algorithmic Time Dependent Monte Carlo

Monte Carlo algorithms and codes, used to study heterogeneous catalytic systems in the frame of the computational section of the NANOCAT project, are presented along with some exemplifying applications and results. In particular, time dependent Monte Carlo methods supported by high level quantum chemical information employed in the field of heterogeneous catalysis are focused. Technical details of the present algorithmic Monte Carlo development as well as possible evolution aimed at a deeper interrelationship of quantum and stochastic methods are discussed, pointing to two different aspects: the thermal-effect involvement and the three-dimensional catalytic matrix simulation. As topical applications, (i) the isothermal and isobaric adsorption of CO on Group 10 metal surfaces, (ii) the hydrogenation on metal supported catalysts of organic substrates in two-phase and three-phase reactors, and (iii) the isomerization of but-2-ene species in three-dimensional supported and unsupported zeolite models are presented.     

Personality disorders and psychiatric symptoms in psoriasis

Two groups of psoriatic outpatients (ns = 192 and 119) were given, respectively, the Million Clinical Multiaxial Inventory-II and Foulds' Delusions-Symptoms-States Inventory. They were compared with dental (n = 192) and with general surgical (n = 190) patients. The psoriatic group presented clearly higher mean scores and frequencies on most of the personality disorder scales. On Foulds' inventory, psoriatic patients showed higher frequencies of neurotic and psychotic class allocations. A cluster analysis of personality scores provided evidence for 4 different personality clusters of patients with psoriasis: (a) Avoidant, Dependent, Schizoid, and Self-defeating (32.2%), (b) Compulsive, Narcissistic, and Aggressive (30.7%), (c) no personality disorder (18.2%), (d) Borderline, Paranoid, and Schizotypal, etc. (18.8%).