On the nature of phase separation of polymer solutions at high extension rates

Experiments with stretching moderately concentrated polymer solutions have been carried out. Model experiments were carried out for poly(acrylonitrile) solutions in dimethyl siloxane. Just the choice of concentrated solutions allowed for a clear demonstration of a demixing effect with the formation of two separate phases—an oriented polymer fiber and solvent drops sitting on its surface. An original experimental device for following all subsequent stages in the demixing process was built. It combined two light beams, one transverse to the fiber and a second directed along (inside) the fiber, the latter played the role of an optical line. This gives a unique opportunity to observe processes occurring inside a fiber. The process of demixing starts from the volume phase separation across the whole cross section of a fiber at some critical deformation and the propagation of the front of demixing along the fiber. Then a solvent cylindrical skin appears which transforms into a system of separate droplets. New experimental data are discussed based on a comparison of the current different points of view on the phenomenon of deformation‐induced phase separation: thermodynamic shift of the equilibrium phase transition temperature, growth of stress‐induced concentration fluctuations in two‐component fluids, and mechanically pressing a solvent out from a polymer network. The general belief is that a rather specific (so‐called “beads‐on‐a‐string”) structure of a filament is realized in stretching dilute solutions: beads of a polymer solution connected by oriented polymer bridges forming a single object. The situation in stretching moderately concentrated solutions appears quite different: real phase separation was observed. So, the alternative phenomenon to the formation of the “beads‐on‐a‐string” structure has been experimentally proven. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 559–565     

Instrumental correction of time dependent counting losses in high rate gamma-ray spectrometry

A CAMAC system was installed for pulse height analysis and correction of counting losses due to the dead-time of a multichannel analyzer and the pulse pile-up. A computer program was developed to control the whole system, and to collect and store data in both conventional and cyclic measurement modes.     

Effect of high temperature in determination of the mathematical dead time and the constants of the n-alkane retention time curve in gas chromatography

In gas liquid chromatography, the column dead time and the constants of the n-alkane retention time curve are calculated by the multiparametric least-squares regression iterative method at high temperature between 180 and 270°C. The method was applied to two types of columns. The first group includes eight packed columns (seven OV polymethylphenylsiloxane and Apolane-87), while the second includes five glass capillary columns (four methylsilicone with different film thicknesses and Apolane-87). The calculated tM and b values were compared with those obtained by Guardino's, Grobler's, and Kaiser's methods. The influences of coating thickness and temperature thereon were investigated.     

On the nature of carbon-hydrogen bond activation at rhodium and related reactions

Over the past 20 years, substantial progress has been made in the understanding of the activation of C-H and other strong bonds by reactive metal complexes in low oxidation states. This paper will present an overview of the use of pentamethylcyclopentadienyl and trispyrazolylborate rhodium complexes for the activation of arene and alkane C-H bonds. Insights into bond strengths, kinetic and thermodynamic selectivities, and the nature of the intermediates involved will be reviewed. The role of eta-2 arene complexes will be shown to be critical to the C-H activation reactions. Some information about the fleeting alkane sigma-complexes will also be presented. In addition, use of these complexes with thiophenes has shown the ability to cleave C-S bonds. Mechanistic information has been obtained indicating coordination through sulfur prior to cleavage. Relevant examples of nickel-based C-S cleavage will also be given.     

Polymer permeability and time lag at high concentrations of sorbate

A recently proposed theory of polymer sorption derived from thermodynamic analysis, was used to develop general analytical expressions for permeability, time lag and steady-state profile under non-linear Types I and II sorption equilibrium observed in glassy polymer membranes and Type III equilibrium observed in rubbers. Useful subclasses of these general analytical expressions are explored in order to demonstrate their utility for characterisation.     

Applications of pulse radiolysis and flash photolysis to some problems related to the chemistry of cancer therapy

The semireduced form (Adr) of the anti-tumour agent adriamycin is implicated in cardiotoxic side effects. Adr, prepared by reduction with e _aq ^– and CO ₂ ^– , has pK values at 2.9 and 9.2. In the pH range 6–11, Adr is relatively stable, existing in equilibrium with Adr and the hydroquinone, the latter subsequently losing the sugar within 100 ms. The E ₇ ¹ of Adrais –328 mV, so at equilibrium the reaction O ₂ ^– + AdrO₂ + Adr lies well over to the left. The relative yields of O₂(¹g) formed via energy transfer from triplet excited components of haematoporphyrin derivative, the drug used in photodynamic therapy, have been measured by observations of the phosphorescence emission at 1270 nm. The measurements suggest that the most active component, dihaematoporphyrin ether or ester, is comparatively ineffective itself photodynamically, but may serve as a pool for the more effective haematoporphyrin and hydroxyethylvinylporphyrin to act inside the cancer cell. One-electron oxidation of dopa, through N ₃ ^. or photoionization, leads to the melanin precursor dopachrome via dopasemiquinone and dopaquinone. The latter reacts with cysteine to form cysteinyldopa, a marker for malignant melanoma metastasis. N ₃ ^. —initiated oxidation of cysteinyldopa proceeds via a different mechanism involving the corresponding semiquinone, quinone and a quinone-imine which rearranges to a more stable benzothiazole.     

Adsorption of gases on adsorbents of various nature and porous structure at high pressures

The isotherms of excess adsorption of argon, nitrogen, and carbon dioxide on adsorbents with various porous structures (active carbon AU-71, polymeric sorbent MN-200, and synthetic zeolite NaA) were measured on the precision volumetric-gravimetric device in the pressure range of 0.1—150 MPa and at temperatures 300—400 K. The results of determination of the adsorption volumes of the studied adsorbents were compared using two methods. The first method is based on the Dubinin-Radushkevich equation, whereas the second one involves a conditional division of the weight of the substance in an ampule into the adsorbed portion and the part existing in the gas phase. The behavior of the adsorbed substance is described by the equation of adsorption of complete content corresponding to the physics of the adsorption process. The relation of the parameters of the empirical Dubinin—Radushkevich equation to the energy characteristics of the system was established.     

Dynamic property and constitutive model of polyvinyl butaral material at high strain rates

The polyvinyl butaral (PVB) interlayer of automotive windshield plays an important role in the protection of both pedestrian and passenger, the mechanical property of PVB material should be in‐depth studied. In this article, the systematical uniaxial tensile experiments of PVB material under high strain rates are conducted, the strain rates range from 125.6 to 3768 s^?1. The results of experiments show that there exists a phenomenon of stress spurt caused by the stress hardening in the final stage of tension, and the strain rate exerts great influence on mechanical property of PVB material. Further, the data fitting basing on Mooney–Rivlin model is carried out, it is found that the fitting results are consistent with the experiment data, which means that the Mooney–Rivlin constitution model can describe the large deformation behavior of PVB material. At last, the rate‐dependent mechanical behavior of the PVB material is further investigated in this article. On the basis of the experiment results and Johnson–Cook model, a rate‐dependent constitutive model is proposed to describe the tensile mechanical property of PVB material under high strain rates. This work will be beneficial to the simulation and analysis of automotive collision safety and pedestrian safety protection, which are related to damage of automotive windshield. Copyright © 2014 John Wiley & Sons, Ltd.     

The prediction of the peak width at half height in HPLC

The prediction of the peak width at half height is an important aspect in the optimization of the chromatographic operating conditions. In this paper, a linear relationship, between the peak widths at half height and the retention values with various isocratic elution is observed. In gradient elution, however, the relationship between the peak widths at half height and the so-called invented retention values that correspond to the mobile phase composition by eluting the solute from the column end is developed. We believe that there is almost the same band width at half height inside the column (in unit of length) for different solutes. The peak width at half height in the chromatogram (in unit of time) is mainly determined by the capacity factor of the solute when it is eluted from the column end. The larger the capacity factor of a solute eluted from the column end, the more slowly will be the solute eluted from the column end and the wider will be the peak width at half height. It is possible to predict the peak width at half height in various isocratic and gradient elutions by using this linear relationship.     

Mechanical behavior of basalt and glass textile composites at high strain rates: A comparison

The aim of this paper is to study and compare the mechanical behavior of woven basalt and woven glass epoxy composites at high strain rates, in order to assess the possibility of replacing glass fiber composites with basalt fiber composites for aircraft secondary structures, such as radomes, fairings, wing tips, etc. Both composites were produced using the same epoxy matrix, the same manufacturing technique, and with comparable densities, fiber volume fractions, and static stiffnesses. Dynamic tensile and shear experiments were performed using a split Hopkinson tension bar, in addition to reference quasi-static experiments to compare both material behaviors over a wide range of strain rates. Normalized results with respect to the material density and fiber volume fraction showed that basalt epoxy composite had higher elastic stiffness, ultimate tensile strength, ultimate tensile strain, and absorbed energy in tension compared to glass epoxy composite. This suggests a promising potential in replacing glass fibers composites with basalt fiber composites in aircraft secondary structures and, more generally, components prone to impact. However, for the basalt epoxy composite, improvements in the fiber-matrix adhesion and in the manufacturing technique are still required to enhance their shear properties compared to glass fiber composites, and fully exploit the potential of basalt epoxy composites in aeronautical applications.     

Monolayers of twisted binaphthyls for aromatic crystallization at low nucleation densities and high growth rates

Monolayers of 1,1'-bi-2-naphthol (BN) derivatives, of which the two naphthalene rings are twisted along the carbon(1)-carbon(1') single bond, were studied for their conformational effect on the growth of pentacene crystals on their monolayer surface. BN monolayers with H and Br at 6,6'-positions (H-BN and Br-BN) were prepared by immersion-coating in toluene solution of the corresponding BNSiCl2. Pentacene was thermally evaporated onto the H-BN and Br-BN monolayers, silica, octadecylsilyl (ODTS) SAM, and a micropattern of H-BN and ODTS SAM. Pentacene crystals were also grown on the SAMs of 1-naphthylsilyl(NPh), phenylsilyl(Ph), and diphenylsilyl (DPh) groups, which are aromatic and have contact angle values similar to those of the the BN monolayers. AFM images of the crystals at the early stage of growth indicated that the BN monolayers suppressed the nucleation while facilitating the growth of nuclei to larger crystals. The low nucleation density and high growth rate are accounted for by the amorphous nature of the twisted BN monolayer surface where the intermolecular interaction between neighboring adsorbates is likely to be suppressed. The results offer new insights into designing surfaces for controlling the crystallization kinetics of organic materials.     

Distributions of ionic concentrations and electric field around the three-phase contact at high rates of Langmuir-Blodgett deposition

A mathematical problem is formulated and numerically solved for addressing the electric field and ionic concentration distributions developing around the three-phase contact line during the Langmuir-Blodgett deposition of charged monolayers. Compared to a previous paper dealing with the same effect (J. Phys. Chem. B 2004, 108, 13449), the present analysis is not restricted to the case of low deposition rates and small concentration changes. The obtained results show that, for sufficiently high deposition rates, the subphase composition substantially changes in the immediate vicinity of the three-phase contact line. It is shown that the predicted changes in the subphase composition can drastically affect the adhesion work and the dynamic contact angle. On this basis, the influence of the concentration polarization effect on meniscus behavior is discussed.     

Polymerizability and related problems in the anionic polymerization of lactams

The anionic polymerization of lactams at low temperatures is not governed by thermodynamic equilibrium between the cyclic monomer and the linear polymer. On the basis of our reaction mechanism we propose therefore a new criterion (in contrast to the thermodynamic one) for estimating the chemical polymerizability of lactam: k_endo/k_lactam, where k_lactam is the rate constant of alkaline hydrolysis of the lactam and k_endo that of the endocyclic imide bond in the corresponding N-acyl lactam. The value thus found for α-piperidone and giving the theoretical polymerizability of this lactam accounts, however, only partially for its low polymerizability. Finally, the behavior of α-piperidone derivatives in α-pyrrolidone polymerization, as well as that of α-pyrrolidone and α-piperidone in polymerization in the presence of inorganic salts such as LiCl and LiSCN, shows that the unusually low ability of this lactam to polymerize could be explained in terms of the hydrogen-bond-rich structure of the resulting polymer appearing at a lower stage of conversion than that of other lactams and which might encage the active site situated at the end of the growing chain and thus hinder the access of lactam anion.     

Fast growth rates of polyethylene single crystals grown at high temperatures and their relevance to crystallization theories

The rates of growth of polyethylene single crystals grown from dilute solution in hexadecane and tetradecanol have been measured over the temperature range T_c = 98–120°C by following the change in turbidity during crystallization of a suspension of crystals of known shape and final size. The rates decrease similarly with T_c in each solvent, but for a given supercooling crystals grow much faster in tetradecanol where the corresponding crystallization temperature is higher. Similarly, the rates are much higher in hexadecane than those previously reported from xylene at equivalent supercoolings but lower T_c. Changes in the corresponding crystal morphologies as T_c is raised are quantified in terms of the axial ratio and the degree of curvature of the nominally {100} faces, both of which increase with T_c. The results can be interpreted as showing a transition from regime I to regime II growth in both solvents, which agrees both qualitatively and quantitatively with the predictions of the nucleation-based kinetic theories. Such a transition has never before been reported for solution crystallization. Using this analysis, reasonable values are obtained for the crystal side-surface energy σ of 7.4–7.5 erg cm^?2 and for the regime I substrate length L of 0.14 μm. No correlation is found between crystal morphology and growth rate and there are no discontinuous changes in morphology at the proposed transition points. The occurrence of curved crystal edges raises the fundamental issue of how to reconcile noncrystallographic growth surfaces with nucleation-controlled growth. A new approach to polymer crystal growth based on equilibrium surface roughening, which does not require nucleation, is therefore very pertinent in this respect and this is discussed.     

On determination of formaldehyde in air by differential pulse polarography and related techniques

Summary Formaldehyde collection efficiency from air and its determination by DC and DP polarography and linear sweep voltammetry at mercury electrode in basic and acidic solutions are scrutinized. Some statements from older literature about this subject are found to be too conservative. The experimental conditions and reliable procedure for formaldehyde sampling from air, standardization and determination from solution using polarographic and related techniques are presented. Detection limits of formaldehyde determination by these techniques are estimated.

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Bestimmung von Formaldehyd in Luft mittels differentieller Puls-Polarographie und ähnlichen Verfahren

Zusammenfassung Die Anreicherung von Formaldehyd aus Luft und dessen Bestimmung mittels DC-und DP-Polarographie sowie mittels linearer Voltammetrie an der Quecksilber-Elektrode in basischem und saurem Milieu wurde eingehend geprüft. Gewisse Feststellungen in der älteren Literatur erwiesen sich als ungeeignet. Die experimentellen Voraussetzungen zur Probenahme, die Standardisierung und Bestimmung aus Lösung mit Hilfe polarographischer und ähnlicher Verfahren wurden angegeben. Die Nachweisgrenzen wurden ermittelt.