Microstructure and properties of poly(urethane-siloxane)s based on hyperbranched polyester of the fourth pseudo generation

Poly(urethane-siloxane) networks based on hydroxyethoxy propyl terminated poly(dimethylsiloxane) (PDMS) as the soft segment and 4,4′-methylenediphenyl diisocyanate (MDI) and two hyperbranched polyesters with different core as the hard segments were characterized by swelling experiments, thermal analyses (DSC and TG), thermomechanical analysis (DMTA), X-ray scattering studies, SEM and AFM analyses, water contact angle and water absorption measurements, as well as surface free energy determination. From these studies, structure–property relationships were elucidated. Hyperbranched polyesters based on 2,2-bis(hydroxymethyl)propionic acid and ethoxylated pentaerythritol or di-trimethylolpropane as core (BH-40 and HBP-4) were used as crosslinkers for the samples of different series. Both series are composed of samples having different PDMS (i.e., soft segment) content. The crosslinking density and extent of hydrogen bonding showed an influence on the polyurethane (PU) properties. It was found that higher crosslinking density and better thermal stability of PUs based on BH-40 compared to HBP-4 based PUs are due to the less dense structure of BH-40. DMTA experiments revealed that the networks exhibit two glass transition temperatures, of the soft and hard segments, and one secondary relaxation process. The crosslinking density and extent of the microphase separation increased and thermomechanical properties were improved with decreasing content of PDMS. With increasing PDMS content, the surface of the polyurethane networks became more hydrophobic, the surface free energy decreased and thermal stability was improved. The obtained results revealed that synthesized PUs have good thermal and thermomechanical properties, which can be tailored for the potential use in the coating technology by changing the type of hyperbranched polyester or PDMS content.     

Nanocomposite materials based on zinc sulfide nanoparticles reinforced chlorinated styrene butadiene rubber

The effect of zinc sulfide (ZnS) nanoparticles in chlorinated styrene‐butadiene rubber (Cl‐SBR) was analyzed by X‐ray diffraction analysis (XRD), scanning electron microscopy (SEM), Differential Scanning Calorimetry, and impedance analyzer. The cure time, mechanical properties, and solvent transport of petroleum fuels through the Cl‐SBR/ZnS nanocomposites at different temperatures were evaluated. XRD and SEM studies showed that ZnS nanoparticles were well‐placed in the polymeric structure of Cl‐SBR. The increased glass transition temperature of the composite with the loading of nanoparticles indicated the increased molecular rigidity. Rheometric torque, alternating current conductivity, dielectric property, tensile strength, tear resistance, modulus, hardness, abrasion resistance, heat build‐up, and compression set were increased with the loading of nanoparticles, however, cure and scorch time, elongation at break, and resilience were reduced with the loading of nanoparticles. The diffusion results have been explained in terms of the size of liquid molecules and the diffusion mechanism was found to follow the anomalous trend. The activation energy for diffusion, sorption and permeation process was evaluated. These activation energy parameters were increased with the size of the penetrant molecules and also with the loading of nanoparticles. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46538.     

Synthesis and characterization of copolymers based on poly(butylene terephthalate) and ethylene oxide‐poly(dimethylsiloxane)‐ethylene oxide

A series of thermoplastic elastomers based on ethylene oxide‐poly(dimethylsiloxane)‐ethylene oxide (EO‐PDMS‐EO), as the soft segment, and poly(butylene terephthalate) (PBT), as the hard segment, were synthesized by catalyzed two‐step, melt transesterification reaction of dimethyl terephthalate (DMT) with 1,4‐butanediol (BD) and α,ω‐dihydroxy‐(EO‐PDMS‐EO). Copolymers with a content of hard PBT segments between 40 and 90 mass % and a constant length of the soft EO‐PDMS‐EO segments were prepared. The siloxane prepolymer with hydrophilic terminal EO units was used to improve the miscibility between the polar comonomers, DMT and BD, and the nonpolar PDMS. The molecular structure and composition of the copolymers were determined by ¹H‐NMR spectroscopy, whereas the effectiveness of the incorporation of α,ω‐dihydroxy‐(EO‐PDMS‐EO) into the copolymer chains was verified by chloroform extraction. The effects of the structure and composition of the copolymers on the melting temperatures and the degree of crystallinity, as well as on the thermal degradation stability and some rheological properties, were studied. It was demonstrated that the degree of crystallinity, the melting and crystallization temperatures of the copolymers increased with increasing mass fraction of the PBT segments. The thermal stability of the copolymers was lower than that of PBT homopolymer, because of the presence of thermoliable ether bonds in the soft segments. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Melt rheology of aliphatic hyperbranched polyesters

Rheological behavior in melt of aliphatic hyperbranched polyesters (AHBP), synthesized using pseudo‐one‐step and one‐step procedure, was investigated in this work. Three commercially available AHBP were also examined. Because of the presence of relatively strong hydrogen bonds between numerous end hydroxyl groups, AHBP of lower generation number, as well as the sample of tenth pseudo generation, show non‐Newtonian behavior in the entire investigated frequency and temperature region. However, for other examined AHBP, the slope of the frequency dependence of complex viscosity (η* = f(ω)) becomes smaller with the temperature increase. Therefore, samples of fourth, fifth, and sixth pseudo generations show Newtonian behavior at temperatures higher than 70°C. Value of glass transition temperature, melt flow activation energy, fractional free volume, and thermal expansion coefficient were determined for the investigated AHBP. The influence of the type of end groups on rheological properties of AHBP was also examined. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Optimizing performances of photovoltaics in Reunion Island—tilt angle

As in Reunion Island, France, around 61% of electricity is produced by using coal and fuel oil with high greenhouse emissions, it is beneficial to the environment to produce electricity from solar energy. Therefore, there is a large push to generate electricity from solar energy by use of photovoltaic (PV) arrays. However, it is important to have high efficiency of electricity generation, that is, to locate PV arrays in an optimal direction. The investigated PV systems may take 1, 2, 4, and 12 tilts per year. For the PV arrays facing the north–south direction, this paper reports investigations of their optimum tilts and the maximum amounts of generated electricity. The investigated PV arrays are located in the towns of Saint‐Benoit, Les Avirons, Piton Saint‐Leu, and Petite‐France in Reunion Island. To obtain optimal tilt of the PV arrays for electricity production from solar energy, EnergyPlus software and GenOpt software are used with Hooke–Jeeves optimization routine. For the investigated PV arrays, the percentage gains in energy, exergy, avoided fossil energy, and the percentage decrease in CO₂ emission are around 5% when compared with that of the PV array that takes only one optimum tilt per year. Copyright © 2011 John Wiley & Sons, Ltd.     

The Carbon Cost of Work—Impacts of Office Building and Commuting Energy in Sydney Workplaces

We investigate greenhouse emissions of office workers in Sydney, drawing on census data, national building energy benchmarks as well as journey-to-work and energy data from two study buildings. Comparing work locations in the central business district (CBD) and Macquarie Park Corridor with metro-wide averages, we find that building emissions dominate over commuting emissions across the city, but commuting is increasingly important as building energy efficiency increases. Furthermore, our results indicate that efforts to improve a building's energy efficiency at Macquarie Park are largely negated by high reliance on car travel despite the introduction of the Epping–Chatswood train line. We conclude that improving building energy efficiency, office space utilisation and network connectivity (currently evident only in the CBD) delivers the best opportunity to reducing the carbon cost of workplaces.     

DSC study of the cure kinetics during nanocomposite formation: Epoxy/poly(oxypropylene) diamine/organically modified montmorillonite system

The effect of an organically modified montmorillonite (OMMT) on the curing kinetics of a thermoset system based on a bisphenol A epoxy resin and a poly(oxypropylene)diamine curing agent were studied by means of differential scanning calorimetry (DSC) in isothermal and dynamic (constant heating rate) conditions. Montmorillonite and prepared composites were characterized by X‐ray diffraction analysis (XRD) and simultaneous differential scanning calorimetry–thermogravimetric analysis (DSC–TGA). Analysis of DSC data indicated that the presence of the filler has a very small effect on the kinetics of cure. A kinetic model, arising from an autocatalyzed reaction mechanism, was applied to the DSC data. Fairly good agreement between experimental and modeling data was obtained. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 550–557, 2006     

Isothermal and nonisothermal cure kinetics of an epoxy/poly(oxypropylene)diamine/octadecylammonium modified montmorillonite system

The effect of an octadecylammonium‐exchanged montmorillonite on the curing kinetics of a thermoset system based on a bisphenol A epoxy resin and a poly(oxypropylene)diamine curing agent were studied with differential scanning calorimetry (DSC) in isothermal and dynamic (constant‐heating‐rate) conditions. Montmorillonite and the prepared composites were characterized by X‐ray diffraction analysis and simultaneous DSC and thermogravimetric analysis. The analysis of the DSC data indicated that the intercalated octadecylammonium cations catalyzed the epoxy–amine polymerization. A kinetic model, arising from an autocatalyzed reaction mechanism, was applied to the DSC data. Fairly good agreement between the experimental data and the modeling data was obtained. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1765–1771, 2006     

Drying of solids; estimation of the mathematical model parameters

In order to determine physical meaning of a thin‐layer mathematical model parameter, the Page model was modified and tested on numerous experimental data. Applicability of the model was tested on the drying kinetics data, X(t), of 11 different types of the porous materials and dried in a convective, vacuum and/or microwave dryers under the predetermined external process conditions. During the entire drying time the drying kinetics of all the investigated materials and heating methods were successfully correlated with the modified Page model. The evaluated values of a new parameter, t_k, corresponded to the time at which diffusion, as a governing mechanism of moisture movement through the material, started. The results were confirmed by the pore size distribution of some materials.