Thiol‐ene photopolymerization for efficient curing of vinyl esters

Monomers for radical photopolymerization based on vinyl esters (VEs) have recently been identified as suitable alternatives to (meth)acrylates on account of their low irritancy and cytotoxicity. The drawback of most VEs with abstractable hydrogens is their relatively low reactivity compared with (meth)acrylates. Within this article, we proved by photo‐differential scanning calorimetry measurements and real‐time Fourier transform infrared spectroscopy that the thiol‐ene concept is able to improve the photoreactivity of these VEs to a large extent to a level between those of acrylates and methacrylates. Other VEs have now a reactivity of at least the level of similar acrylates. Mechanical properties as determined by Dynamic Mechanical Analysis and Charpy impact tests showed significant toughening of these materials. Furthermore, we were able to confirm low toxicity of all components by osteoblast cell culture experiments. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Correlation of charge transport with structural order in highly ordered melt‐crystallized poly(3‐hexylthiophene) thin films

A series of well‐defined poly(3‐hexylthiophene)s (P3HT) of different molecular weight (MW) and high regioregularity was investigated for charge transport properties in as‐cast and melt‐crystallized films. The semicrystalline structure of the P3HT was characterized by X‐ray scattering and Atomic force microscopy. Crystallization by cooling from the melt led to a substantial increase in crystallinity and a stronger alignment of the crystals in comparison to as‐cast films. The increase in crystallinity went along with an increase in hole mobility of up to an order of magnitude as measured by the space charge limited current method. Additionally, the hole mobility depended on the long period of P3HT lamellae and consequently on the MW. In compliance with the long period, the charge carrier mobility first increased with the MW before decreasing again at the onset of chain folding. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013 , 51, 943–951     

Fluoropolyethers end‐capped by polar functional groups. III. Kinetics of the reactions of hydroxy‐terminated fluoropolyethers and model fluorinated alcohols with cyclohexyl isocyanate catalyzed by organotin compounds

The kinetics of the dibutyltin dilaurate (DBTDL)‐catalyzed urethane formation reactions of cyclohexyl isocyanate (CHI) with model monofunctional fluorinated alcohols and fluoropolyether diol Z‐DOL H‐1000 of various molecular weights (100–1084 g mol^?1) in different solvents were studied. IR spectroscopy and chemical titration methods were used for measuring the rate of the total NCO disappearance at 30–60 °C. The effects of the reagents and DBTDL catalyst concentrations, the solvent and hydroxyl‐containing compound nature, and the temperature on the reaction rate and mechanism were investigated. Depending on the initial reagent concentration and solvent, the reactions could be well described by zero‐order, first‐order, second‐order, or more complex equations. The reaction mechanism, including the formation of intermediate ternary or binary complexes of reagents with the tin catalyst, could vary with the concentration and solvent and even during the reaction. The results were treated with a rate expression analogous to those used for enzymatic reactions. Under the explored conditions, the rate of the uncatalyzed reaction of fluorinated alcohols with CHI was negligible. Moreover, there was no allophanate formation, nor were there other side reactions, catalysis by urethane in the absence of DBTDL, or a synergetic effect in the presence of the tin catalyst. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3771–3795, 2002     

The Ternary System Li2O-Al2O3-B2O3: Compounds and Phase Relations

The ternary system Li₂O-Al₂O₃-B₂O₃ is reinvestigated with solid-state reaction and X-ray powder diffraction technique to clarify some long-standing uncertainties. The phase relations are constructed based on the phase identifications of 51 ternary samples. Six ternary compounds, Li₂AlB₅O₁₀, LiAlB₂O₅, Li₃AlB₂O₆, Li₂AlBO₄, LiAl₇B₄O₁₇ and a compound with a composition close to 0.66Li₂O·0.06Al₂O₃·0.28B₂O₃, are observed or confirmed in this system, and the thermal stability of these ternary compounds is also discussed on the basis of DTA experimental results.     

H-, C-NMR and ethylene polymerization studies of zirconocene/MAO catalysts: effect of the ligand structure on the formation of active intermediates and polymerization kinetics

Using ¹H- and ¹³C-NMR spectroscopies, cationic intermediates formed by activation of L₂ZrCl₂ with methylaluminoxane (MAO) in toluene were monitored at Al/Zr ratios from 50 to 1000 (L₂ are various cyclopentadienyl (Cp), indenyl (Ind) and fluorenyl (Flu) ligands). The following catalysts were studied: (Cp-R)₂ZrCl₂ (R=Me, 1,2-Me₂, 1,2,3-Me₃, 1,2,4-Me₃, Me₄, Me₅, n-Bu, t-Bu), rac-ethanediyl(Ind)₂ZrCl₂, rac-Me₂Si(Ind)₂ZrCl₂, rac-Me₂Si(1-Ind-2-Me)₂ZrCl₂, rac-ethanediyl(1-Ind-4,5,6,7-H₄)₂ZrCl₂, (Ind-2-Me)₂ZrCl₂, Me₂C(Cp)(Flu)ZrCl₂, Me₂C(Cp-3-Me)(Flu)ZrCl₂ and Me₂Si(Flu)₂ZrCl₂. Correlations between spectroscopic and ethene polymerization data for catalysts (Cp-R)₂ZrCl₂/MAO (R=H, Me, 1,2-Me₂, 1,2,3-Me₃, 1,2,4-Me₃, Me₄, Me₅, n-Bu, t-Bu) and rac-Me₂Si(Ind)₂ZrCl₂ were established. The catalysts (Cp-R)₂ZrCl₂/AlMe₃/CPh₃⁺B(C₆F₅)₄⁻ (R=Me, 1,2-Me₂, 1,2,3-Me₃, 1,2,4-Me₃, Me₄, n-Bu, t-Bu) were also studied for comparison of spectroscopic and polymerization data with MAO-based systems. Complexes of type (Cp-R)₂ZrMe⁺←Me⁻-Al≡MAO (IV) with different [Me-MAO]⁻ counteranions have been identified in the (Cp-R)₂ZrCl₂/MAO (R=n-Bu, t-Bu) systems at low Al/Zr ratios (50-200). At Al/Zr ratios of 500-1000, the complex [L₂Zr(μ-Me)₂AlMe₂]⁺[Me-MAO]⁻ (III) dominates in all MAO-based reaction systems studied. Ethene polymerization activity strongly depends on the Al/Zr ratio (Al/Zr=200-1000) for the systems (Cp-R)₂ZrCl₂/MAO (R=H, Me, n-Bu, t-Bu), while it is virtually constant in the same range of Al/Zr ratios for the catalytic systems (Cp-R)₂ZrCl₂/MAO (R=1,2-Me₂, 1,2,3-Me₃, 1,2,4-Me₃, Me₄) and rac-Me₂Si(Ind)₂ZrCl₂/MAO. The data obtained are interpreted on assumption that complex III is the main precursor of the active centers of polymerization in MAO-based systems.     

The systems Zr(Nb,Ti)(R)O2−δ, R=Yb, Ca—optimization of mixed conductivity and comparison with results of other systems (R=Y and Gd)

In this work we address the optimization of mixed conductivity in fluorite compounds based on zirconia. Phase relations of the new systems YbO_1.5-NbO_2.5-ZrO₂, and CaO-NbO_2.5-ZrO₂ are presented. The limit of the cubic defect fluorite phase in YbO_1.5-NbO_2.5-ZrO₂ closely resembles that of the system YO_1.5-NbO_2.5-ZrO₂, whilst in CaO-NbO_2.5-ZrO₂ is narrow extending to include composition Ca_0.255Nb_0.15Zr_0.595O_1.82 at 1500°C. The influence of dopant ion size, charge and composition on ionic conduction is assessed and parallels are drawn with the systems YO_1.5-NbO_2.5-ZrO₂ and YO_1.5-TiO₂-ZrO₂. Comparison of these results with published data on the Ti containing systems CaO-TiO₂-ZrO₂, GdO_1.5-TiO₂-ZrO₂ shows that the highest mixed conducting compositions can only be offered in the system YO_1.5-TiO₂-ZrO₂ out of all the systems here studied.     

Effect of the structure of titanium–magnesium catalysts on the morphology of polyethylene produced

The structure and formation of polyethylene (PE) particles on supported titanium–magnesium catalysts having different structural characteristics (sizes of microcrystallites, mesopores, and subparticles) were studied for the first time. Scanning electron microscopy was used to identify structural elements of the polymer particles formed over such catalysts and to reveal morphological changes in the growing polymer particles when the yield was increased from approximately 0.2 g PE/g catalyst to approximately 13 kg PE/g catalyst. A relationship was found between structural characteristics of the porous catalyst particles, morphology of the nascent polymer particles, and bulk density of the polymer powder. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2298–2308     

Dependence of electrical performance on structural organization in polymer field effect transistors

Organic semiconductors (OSCs) are strong contenders for use in printed, flexible electronics. Although organic electronic materials have been studied for many years, the physics of charge transport is still under investigation. This is in part due to variability resulting from the large variety of molecules that can be synthesized and inconsistency in electrical characterization due to device and processing conditions. Molecular ordering in OSCs is known to alter the charge transport characteristics and attention to long range and short range ordering provides clues as to the nature of transport pathways. Here, we study ordered regioregular poly(3‐hexylthiophene‐2,5‐diyl) films carefully prepared to obtain a set of three samples with incrementally increasing order on identical transistor architectures. Ordering was characterized using a variety of short and long range techniques to probe the coherence and number of crystallites formed during processing, and the correlation between these different measures of order are quantified. We observe three changes in transistor behavior that show a shift from non‐ideal to more textbook‐like characteristics with increasing order: reduction of the contact resistance, shift to field‐independent mobility, and a shift from a diode‐like (S‐shaped) to linear response at low lateral fields. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 1063–1074     

Geometric Design of Anode-Supported Micro-Tubular Solid Oxide Fuel Cells by Multiphysics Simulations

High volumetric power density (VPD) is the basis for the commercial success of micro-tubular solid oxide fuel cells (mtSOFCs). To find maximal VPD (MVPD) for anode-supported mtSOFC (as-mtSOFC), the effects of geometric parameters on VPD are analyzed and the anode thickness, t_an, and the cathode length, l_ca, are identified as the key design parameters. Thermo-fluid electrochemical models were built to examine the dependence of the electrical output on the cell parameters. The multiphysics model is validated by reproducing the experimental I-V curves with no adjustable parameters. The optimal l_ca and the corresponding MVPDs are then determined by the multiphysics model for 20 combinations of r_in, the inner tube radius, and t_an. And all these optimization are made at 1073.15 K. The results show that:(i) significant performance improvement may be achieved by geometry optimization, (ii) the seemingly high MVPD of 11 and 14 W/cm³ can be easily realized for as-mtSOFC with single-and double-terminal anode current collection, respectively. Moreover, the variation of the area specific power density with l_ca2(2 mm, 40 mm) is determined for three representative (r_in, t_an) combinations. Besides, it is demonstrated that the current output of mtSOFC with proper geometric parameters is comparable to that of planar SOFC.     

The theory of non-linear molecular orientation and stress in polymer fluids

Non-linear stress, and orientation characteristics for polymer fluids (melts, solutions) composed of chain macromolecules of finite length have been derived. Freelyjointed chains with inverse Langevin statistics have been assumed, and their behaviour in potential hydrodynamic fields analyzed. Numerical calculations have been performed for uniaxial extensional flow in a wide range of flow rates (and stresses). In the range of small stresses, orientation is a linear function of stress. At higher stresses, orientation factor levels off, asymptotically approaching unity.Flow orientation characteristics significantly differ from those derived from affine deformation of polymer networks. This difference is a natural consequence of constraints imposed by network junctions on chain deformation.This work is dedicated to Professor Hanns-Georg Kilian on his 60th birthday in appreciation of his contribution to Polymer Physics.