Bonding at Compatible and Incompatible Amorphous Interfaces of Polystyrene and Poly(Methyl Methacrylate) Below the Glass Transition Temperature

Abstract

Films of high‐molecular‐weight amorphous polystyrene (PS, M _w = 225 kg/mol, M _w/M _n = 3, T _g‐bulk = 97°C, where T _g‐bulk is the glass transition temperature of the bulk sample) and poly(methyl methacrylate) (PMMA, M _w = 87 kg/mol, M _w/M _n = 2, T _g‐bulk = 109°C) were brought into contact in a lap‐shear joint geometry at a constant healing temperature T _h, between 44°C and 114°C, for 1 or 24 hr and submitted to tensile loading on an Instron tester at ambient temperature. The development of the lap‐shear strength σ at an incompatible PS–PMMA interface has been followed in regard to those at compatible PS–PS and PMMA–PMMA interfaces. The values of strength for the incompatible PS–PMMA and compatible PMMA–PMMA interfaces were found to be close, both being smaller by a factor of 2 to 3 than the values of σ for the PS–PS interface developed after healing at the same conditions. This observation suggests that the development of the interfacial structure at the PS–PMMA interface is controlled by the slow component, i.e., PMMA. Bonding at the three interfaces investigated was mechanically detected after healing for 24 hr at T _h = 44°C, i.e., well below T _g‐bulks of PS and PMMA, with the observation of very close values of the lap‐shear strength for the three interfaces considered, 0.11–0.13 MPa. This result indicates that the incompatibility between the chain segments of PS and PMMA plays a negligible negative role in the interfacial bonding well below T _g‐bulk.     

pH‐sensing nanostar probe using surface‐enhanced Raman scattering (SERS): theoretical and experimental studies

Local pH environment has been considered to be a potential biomarker for tumor diagnosis because solid tumors contain highly acidic environments. A pH‐sensing nanoprobe based on surface‐enhanced Raman scattering (SERS) using nanostars under near‐infrared excitation has been developed for potential biomedical applications. To theoretically investigate the effect of protonation state on SERS spectra of p‐mercaptobenzoic acid (pMBA), we used the density functional theory (DFT) with the B3LYP functional to calculate Raman vibrational spectra of pMBA‐Au/Ag complex in both protonated and deprotonated states. Vibrational spectral bands were assigned with DFT calculation and used to investigate SERS spectral changes observed from experiment when varying pH value between five and nine. The SERS peak position of pMBA at ~1580 cm⁻¹ was identified to be a novel pH‐sensing index, which has small but noticeable downshift with pH increase. This phenomenon is confirmed and well‐explained with theoretical simulation. The study demonstrates that SERS is a sensitive tool to monitor minor structural changes due to local pH environment, and DFT calculations can be used to investigate Raman spectra changes associated with minor differences in molecular structure. Copyright © 2013 John Wiley & Sons, Ltd.     

Raman spectroscopy of very small Cd1−xCoxS quantum dots grown by a novel protocol: direct observation of acoustic‐optical phonon coupling

Glass‐embedded Cd_1−xCo_xS quantum dots (QDs) with mean radius of R ≈ 1.70 nm were successfully synthesized by a novel protocol on the basis of the melting‐nucleation synthesis route and herein investigated by several experimental techniques. Incorporation of Co²⁺ ions into the QD lattice was evidenced by X‐ray diffraction and magnetic force microscopy results. Optical absorption features with irregular spacing in the ligand field region confirmed that the majority of the incorporated Co²⁺ ions are under influence of a low‐symmetry crystal field located near to the Cd_1−xCo_xS QD surface. Electron paramagnetic resonance data confirmed the presence of Co²⁺ ions in a highly inhomogeneous crystal field environment identified at the interface between the hosting glass matrix (amorphous) and the crystalline QD. The acoustic‐optical phonon coupling in the Cd_1−xCo_xS QDs (x ≠ 0.000) was directly observed by Raman measurements, which have shown a high‐frequency shoulder of the longitudinal optical phonon peak. This effect is tuned by the size‐dependent sp‐d exchange interaction due to the magnetic doping, causing variations in the coupling between electrons and longitudinal optical phonon. Copyright © 2013 John Wiley & Sons, Ltd.     

Further results on large sets of disjoint group‐divisible designs with block size three and type 2n41

Large sets of disjoint group‐divisible designs with block size three and type 2ⁿ4¹ were first studied by Schellenberg and Stinson because of their connection with perfect threshold schemes. It is known that such large sets can exist only for n ≡0 (mod 3) and do exist for all odd n ≡ (mod 3) and for even n=24m, where m odd ≥ 1. In this paper, we show that such large sets exist also for n=2^k(3m), where m odd≥ 1 and k≥ 5. To accomplish this, we present two quadrupling constructions and two tripling constructions for a special large set called ^*LS(2ⁿ). © 2002 Wiley Periodicals, Inc. J Combin Designs 11: 24–35, 2003; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/jcd.10032     

Construction of graphs with given circular flow numbers

Suppose r ≥ 2 is a real number. A proper r‐flow of a directed multi‐graph is a mapping such that (i) for every edge , ; (ii) for every vertex , . The circular flow number of a graph G is the least r for which an orientation of G admits a proper r‐flow. The well‐known 5‐flow conjecture is equivalent to the statement that every bridgeless graph has circular flow number at most 5. In this paper, we prove that for any rational number r between 2 and 5, there exists a graph G with circular flow number r. © 2003 Wiley Periodicals, Inc. J Graph Theory 43: 304–318, 2003     

Operator–valued Fourier multiplier theorems on Besov spaces

We investigate analytical properties of a measure geometric Laplacian which is given as the second derivative w.r.t. two atomless finite Borel measures μ and ν with compact supports supp μ ? supp ν on the real line. This class of operators includes a generalization of the well‐known Sturm‐Liouville operator as well as of the measure geometric Laplacian given by . We obtain for this differential operator under both Dirichlet and Neumann boundary conditions similar properties as known in the classical Lebesgue case for the euclidean Laplacian like Gauß‐Green‐formula, inversion formula, compactness of the resolvent and its kernel representation w.r.t. the corresponding Green function. Finally we prove nuclearity of the resolvent and give two representations of its trace.     

Planar and Nonplanar Shock Waves in a Degenerate Quantum Plasma

The nonlinear propagation of modified electron‐acoustic (mEA) shock waves in an unmagnetized, collisionless, relativistic, degenerate quantum plasma (containing non‐relativistic degenerate inertial cold electrons, both nonrelativistic and ultra‐relativistic degenerate hot electron and inertial positron fluids, and positively charged static ions) has been investigated theoretically. The well‐known Burgers type equation has been derived for both planar and nonplanar geometry by employing the reductive perturbation method. The shock wave solution has also been obtained and numerically analyzed. It has been observed that the mEA shock waves are significantly modified due to the effects of degenerate pressure and other plasma parameters arised in this investigation. The properties of planar Burgers shocks are quite different from those of nonplanar Burgers shocks. The basic features and the underlying physics of shock waves, which are relevant to some astrophysical compact objects (viz. non‐rotating white dwarfs, neutron stars, etc.), are briefly discussed. (© 2015 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Investigations of Droplet‐Plasma Interaction using Multi‐Dimensional Coupled Model

Recently developed multi‐dimensional coupled fluid‐droplet model is used to investigate the behavior of complex interaction between the liquid precursor droplets and atmospheric pressure plasma (APP). The significance of this droplet‐plasma interaction is not well understood under diverse realm of working conditions in two‐phase flow. In this study, we explain the implication of vaporization of liquid droplets in APP which are subsequently responsible to control major characteristics of surface coating depositions. Coalescence of water droplets is more dominant than Hexamethyldisiloxane (HMDSO) droplets because of its sluggish rate of evaporation. A disparity in the performance of evaporation is identified in two independent mediums, such as gas mixture and discharge plasma using HMDSO precursor. The length of evaporation of droplets is amplified by an increment of gas flow rate indicating with a reduction in the gas temperature and electron mean energy. In particular, the spatio‐temporal density distributions of charged particles show a clear pattern in which the typical nitrogen impurity ions are primarily effective as compared to other helium ionic species along the pulse of droplets in APP. Finally, we contrast the behavior of discharge species in the pure helium and He‐N2 gas mixtures revealing the importance of stepwise and Penning ionization processes. (© 2015 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

A New Scheme for High‐Intensity Laser‐Driven Electron Acceleration in a Plasma

We propose a new approach to high‐intensity relativistic laser‐driven electron acceleration in a plasma. Here, we demonstrate that a plasma wave generated by a stimulated forward‐scattering of an incident laser pulse can be in the longest acceleration phase with injected relativistic beam electrons. This is why the plasma wave has the maximum amplification coefficient which is determined by the acceleration time and the breakdown (overturn) electric field in which the acceleration of the injected beam electrons occurs. We must note that for the longest acceleration phase the relativity of the injected beam electrons plays a crucial role in our scheme. We estimate qualitatively the acceleration parameters of relativistic electrons in the field of a plasma wave generated at the stimulated forward‐scattering of a high‐intensity laser pulse in a plasma. (© 2015 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Gas‐phase elimination kinetics of selected aliphatic α,β‐unsaturated aldehydes catalyzed by hydrogen chloride

The gas‐phase elimination of 2‐methyl‐2‐propenal catalyzed by HCl yields propene and CO gas, while E‐2‐pentenal with the same catalyst gives butene and CO gas. The kinetics determinations were carried out in a static system with the reaction vessels deactivated with allyl bromide and the presence of the free radical inhibitor toluene. Temperature and pressure ranges were 350.0–410.0 °C and 34–76 Torr. The elimination reactions are homogeneous and unimolecular, and follow a first‐order rate law. The rate coefficients for the reactions are expressible by the following Arrhenius equations: Data from the kinetic and thermodynamic parameters of these catalyzed elimination reactions implies a mechanism of a concerted five‐membered cyclic transition state structure for the formation of the corresponding olefin and carbon monoxide. Copyright © 2015 John Wiley & Sons, Ltd.