On the electrical polarization of polymer single crystals in suspension

A model is proposed for the electrical polarization that causes the orientation and, hence, the electric birefringence of a suspension containing single crystals of a poly(ethylene oxide)–polystyrene diblock copolymer or a poly(ethylene oxide) homopolymer. It serves to describe how an electric dipole moment lying in the plane of the single crystal can be induced by protons migrating in poly-(ethylene oxide). The resulting Kerr effect is calculated up to saturating fields, and the observed dispersion of the polarization in high frequency fields is explained as a space charge relaxation phenomenon. The estimated relaxation time agrees satisfactorily with published experimental data.     

Molecular dynamic study of dielectric polarization and ferroelectricity in a model polar polymer

Molecular dynamics simulations are used to explore the polarization response of a lamellar crystal consisting of folded chains of a highly simplified model polar polymer. The system is based on a united atom model of polyethylene with constrained bond lengths and bond angles, and it is endowed with artificial partial charges placed on the united atoms to give it a simple polar character. Simulations performed with various temperatures, electric field directions, and electric field application histories reveal a complicated sequence of reorientation processes, including pronounced ferroelectric behavior. The sequence includes a weak, temperature‐independent prompt response, and a slow‐rising delay regime with stretched exponential behavior and thermally‐activated reorientation parameters consistent with trans‐gauche (TG) barrier crossings in the amorphous phase. When the delay regime has progressed sufficiently, a primary large‐amplitude response due to organized rotation of large subsegments in the crystalline phase occurs in a rapid manner that requires relatively few TG barrier crossings. A final, extremely slow rise in residual polarization completes the sequence. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 740–759     

Effect of external electrical field on phase behavior and morphology development of polymer dispersed liquid crystal

Phase diagrams for mixtures of liquid crystal (LC)/monomer with and without an external electrical field applied have been established using polarized light microscope (PLM).The (isotropic + nematic) coexistent phase region and (isotropic + isotropic) phase boundary of LC/monomer mixtures were observed to shift upward to higher temperatures when the external electrical field exists. It was found that the electrical field applied during the cross-linking polymerization has a significant influence on the phase diagrams for the LC/polymer mixtures by rendering the coexistent phase regions shift upward to higher temperatures. The influence of the external electrical field on the processes of the isotropic-isotropic phase separation and liquid crystal ordering in PDLC formation has also been investigated. The results revealed that both the processes could be highly accelerated by the electrical field.     

Effect of nanoparticle network formation on electromagnetic properties and cell morphology of microcellular polymer nanocomposite foams

Adding high loadings of nanoparticles can remarkably alter the functionality of polymer nanocomposite foams. Therefore, this dramatic change was studied at the percolation threshold as a point to predict the properties of foamed nanocomposites using the viscoelastic characteristics of un-foamed ones. In this research, the effect of incorporating 10–40 wt% of ZnO nanoparticles on rheological properties of PS/ZnO samples was investigated. Then, these samples were foamed at processing temperatures of 80 and 120 °C to study morphology and electromagnetic properties. First, the rheological study showed that the storage modulus of nanocomposites increased significantly above 20 wt% of nanoparticles. A connected network of nanoparticles altered the microstructure of nanocomposite at this rheological percolation. The morphological results show a higher cell density for foamed samples above the rheological percolation. From electromagnetic properties, the effect of ZnO connected network is obvious on the absorption enhancement for 30 and 40 wt% and only for 40 wt% of ZnO at 80 and 120 °C, respectively. Therefore, the viscoelastic properties of samples are still dominant at the lower temperature, but the foam structure became more important at the higher temperatures. This shows that the role of the filler network faded at the higher temperature and electromagnetic properties were changed with the foam structure. The microstructure expansion results in the decrease of filler amount at a fixed volume of foams, so more filler fraction is required to form a connected network of nanoparticles.     

Effect of temperature and solvent on polymer tacticity in the free‐radical polymerization of styrene and methyl methacrylate

The effect of temperature and solvent on polymer tacticity in free‐radical polymerization of styrene and methyl methacrylate was studied by ¹³C and ¹H NMR, respectively. Polystyrene shows a mild syndiotactic tendency (P_m = 0.36 ± 0.02) that is independent of temperature over a wide range (?10 to 120 °C), while poly(methyl methacrylate) shows a stronger syndiotactic tendency (P_m = 0.17 ± 0.01 at 30 °C) that decreases as temperature is increased (P_m = 0.22 ± 0.02 at 80 °C). None of the polymerization solvents studied (bulk, THF, DMF, DMSO, acetonitrile, and acetone) had a significant effect on polymer tacticity in either system. The triad fractions of both polymers showed deviations from the Bernoulli model, implying that the antepenultimate unit affects the propagation reaction. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 3351–3358     

Effect of the polymer matrix on the formation of silver nanoparticles in polymer–silver salt complex membranes

When polymer–silver salt complex membranes were exposed to UV irradiation, the separation performances of both the permeance and selectivity for propylene–propane decreased, which was primarily attributed to the reduction of the silver ions in the membranes to silver nanoparticles. Here, the effect of the polymer matrix on the formation of silver nanoparticles in the polymer–silver salt complex membranes was investigated. This effect was assessed for the complexes of two kinds of silver salts (AgBF₄ and AgCF₃SO₃) with several polymeric ligands containing three different carbonyl groups, including poly(vinyl pyrrolidone) (PVP) with an amide group, poly(vinyl methyl ketone) (PVMK) with a ketone group, and poly(methyl methacrylate) (PMMA) with an ester group. UV–vis spectra and transmission electron microscopy (TEM) images clearly indicated that the reduction rate of the silver ions has the following order in the various polymer matrices: PVP > PVMK > PMMA, whereas the size and the distribution of the nanoparticles exhibited the reverse order. The tendency to form silver nanoparticles was explained in terms of the differences between the comparative strengths of the interactions of the silver ions with the different carbonyl oxygens in the matrices, as well as that of the silver ions with counteranions, which was characterized by X‐ray photoelectron spectroscopy (XPS) and FT‐Raman spectroscopy. It was concluded that when the concentration of free silver ions was low due to weak polymer–silver ion and strong silver ion–anion interactions, as found with PMMA, the reduction rate of silver ions to silver nanoparticles was slow. Therefore, the PMMA–silver complex membranes were less sensitive to decreases in separation performance upon UV irradiation than compared to the PVP membranes. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1168–1178, 2006     

Effect of polymer polarity on the positronium formation

Positron annihilation lifetime spectra have been measured on styrene–methyl methacrylate, styrene–acrylonitrile, and styrene–butyl methacrylate copolymers. The results show that the longest lifetime τ₃ remains constant during extended PALS measurement in all experiment copolymers, and relative intensity I₃ decreases to a certain extent with measured time in weak polar copolymers and remain almost unchanged in strong polar copolymers as well as ST–BMA copolymers. The observed decrease in I₃ have been found to be unrelated to the microstructural change of copolymers, and, instead, to be more likely a result of the buildup of an electric field inside the copolymers during the prolonged PALS measurement. The field effect can result in the decrease of I₃ due to the increase in the positrons and electrons diffusing out of the spur, but the influence of the electric field on I₃ decrease with increasing the polarity of the copolymers and the softness of side groups of macromolecular chains in the copolymers. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 435–442, 2000     

Effect of thickness of the PPO membranes on the surface morphology

The effect of membrane thickness on surface morphology has been studied for the case of polyphenylene oxide (PPO) membranes cast from solutions of PPO in trichloroethylene (TCE). Both roughness and nodule size decrease with increasing membrane thickness up to a certain point after which they begin to increase. Minima in roughness and nodule size are observed for 9–11 μm thick films. These minima depend on initial polymer concentration in the casting solution. At a membrane thickness greater than 11 μm, super nodular aggregates are formed. A mechanism based on Marangoni and Rayleigh number is presented.     

Effect of coagulating agent viscosity on the kinetics of formation,morphology, and transport properties of cellulose nanofiltration membranes

Low-viscous coagulating agents are tradionally used to precipitate polymers from their solutions and obtain films and fibers from them; they represent, as a rule, the combinations of solvent and nonsolvent of the polymer used. At the same time, since the structure of the precipitated polymer is formed under non-equilibrium conditions, the influence of the coagulant viscosity can be quite substantial. The influence of the viscosity of the medium on the formation of structure, morphology, and transport characteristics of the precipitated polymer is studied by example of forming of the cellulose membranes from solution in N-methyl-morpholine N-oxide using some proton-donor coagulants. In this regard, the interdiffusion processes proceeding at the contact of cellulose solutions and coagulating agents (water, propylene glycol, glycerin) are explored using the laser interferometry method. Varying the precipitator viscosity allows one to change the rate of formation and correspondingly the morphology of the cellulose films. In turn, the membrane structure determines its transport characteristics, which were assessed by the filtration of aprotic media with anionic dyes—Orange II and Remazol Brilliant Blue R. The application of the low-viscous precipitator provides the formation of a uniform film structure in the bulk, but leads to development of defects close to the surface, while a viscous medium promotes the formation of a relatively thin dense shell on the films.     

Effect of the procedure for preparing porous membranes based on interpolyelectrolyte complexes on their structure,surface morphology,and surface electrical properties

Ultrafiltration membranes based on interpolyelectrolyte complexes of sulfonate-containing aromatic copolyamide, acrylonitrile–N,N-dimethyl-N,N-diallylammonium chloride copolymer, and poly-N,N-dimethyl-N,N-diallylammonium chloride were prepared. Their structure and surface electrical properties were studied. The correlation between the procedure for performing the interpolymer reaction, the degree of conversion, the composition of the resulting complex, and the membrane characteristics was revealed. The electrokinetic potential of the membrane specimens varies in the interval from–35.2 to +3.1 mV. The interpolymer compound composition, surface electrical properties of the membranes, and their activity in sorption of base and acid dyes correlate with each other. Therefore, it is appropriate to use these dyes as test systems for determining the nature and concentration of free ionic groups. The effect of the membrane preparation procedure on the charge distribution pattern on the membrane separation surface is considered.     

Effect of annealing on the electrical properties and morphology of a conducting polymer used as an anode in organic light‐emitting devices

The surface sheet resistance of conducting films of glycerol‐doped poly(3,4‐ethylenedioxy‐thiophene)–poly(styrene sulfonate) is largely dependent on the annealing temperature. The presence of free glycerol in insufficiently baked films, as indicated by infrared spectra and thermogravimetric analysis, results in conducting polymer films with poor morphology and low electrical conductivity. The device performance of organic light‐emitting diodes using this modified poly(3,4‐ethylenedioxy‐thiophene)–poly(styrene sulfonate) as an anode is also greatly affected by the baking conditions of the conducting films. The maximum light output, current density, and luminous power efficiency are observed from devices using anodes baked at a high temperature close to the boiling point of glycerol. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2522–2528, 2003     

Effect of the composition of binary polar solvent mixtures on dye adsorptivity in the polymer matrix

Sorption and diffusion processes of 1-mercapto-2-naphthol nickel complex in a polymer matrix upon surface dyeing of polymethyl methacrylate are studied by near-IR spectroscopy as a function of dye solution composition and technological parameters of the process. The optimum solution composition and technological regime are selected. The diffusion coefficient is evaluated.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1289–1293, July, 1995.The authors express their gratitude to Dr. Chem. Sci. N. O. Mchedlov-Petrosyan for a series of valuable remarks in his discussion of this work.This work was carried out with financial support from the International Science Foundation (Grant U2V000).     

Effect of macro-RAFT agent on the morphology of polymer dispersed liquid crystals

In this study, macro-(RAFT) reversible additional fragmental chain transfer agent prepared by reversible additional fragmental chain transfer polymerisation has been incorporated into polymer dispersed liquid crystals (PDLCs). The effects of concentration, molecular weight and glass transition temperature of macro-RAFT agent were studied in terms of morphology, polymerisation kinetics, molecular weight of polymer matrix and electro-optical properties of the films. It was found that the key factor influencing morphology was the mobility of macro-RAFT agent chain rather than polymerisation rate and molecular weight of polymer matrix. Furthermore, the decrease in the mobility of macro-RAFT agent chain caused less liquid crystal nematic fraction, smaller liquid crystal domain size and greater driving voltage.     

Effect of matrix bidispersity on the morphology of polymer-grafted nanoparticle-filled polymer nanocomposites

We present a simulation study showing the effect of bidispersity in matrix homopolymer length on the wetting/dewetting of homopolymer-grafted nanoparticles and the morphology of polymer nanocomposites where the graft and matrix polymer chemistries are identical. In a bidisperse matrix with equal number of short and long chains and average matrix length greater than the monodisperse graft length, the densely grafted polymer layer is preferentially wet by the short chains and relatively dewet by the long chains. This is driven by a larger gain in entropy of mixing between graft and matrix for short matrix chains than long matrix chains. Despite the preferential wetting of the short and dewetting of long chains, matrix length bidispersity does not significantly change the overall wetting of the grafted layer. Unlike graft length bidispersity that significantly improves particle dispersion, matrix length bidispersity slightly increases particle aggregation in the polymer matrix. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 1661–1668     

Effect of polymer molecular weight on the fiber morphology of electrospun mats

In this work, different fractions of solvent-induced polymer degraded solution were mixed with freshly prepared solution of same polymer, and its effect on fiber morphology of electrospun mats was investigated. Nylon-6 solution in formic acid was allowed to degrade for 3 weeks and different fractions of it were mixed with freshly prepared nylon-6 solution to get the electrospun mats. FE-SEM images of the mats indicated that the a large amount of sub-nanofibers (<50 nm in diameter) in the form of spider-net like structures were achieved by tailoring the amount of solvent degraded polymer solution in the freshly prepared nylon-6 solution. Large quantity of these ultrafine sub-nanofibers present in electrospun nylon-6 mats could increase its hydrophilicity and mechanical strength. The decreased average pore diameter and increased BET surface area of the mat, caused by spider-net like structure, can make it as a potential candidate for air/water filtration.     

Effect of the surface modification of polymer membranes on their microbiological fouling

Composite polymer membranes with chemically different surfaces are prepared by the photochemical modification of Millipore microfiltration poly(vinylidene fluoride) and polysulfone membranes using 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-hydroxyethyl methacrylate, and 2-(dimethylamino)ethyl methacrylate quaternized with methyl chloride. It is shown that, during the filtration of an E. coli suspension, the membrane flux substantially decreases with time owing to the fouling of the membrane surface by bacterial cells. The membranes with the hydrophilic surface are less susceptible to fouling than hydrophobic membranes, while the ability to recover the performance upon washing is higher for the membranes with a chemically neutral surface than for charged membranes. It is shown that the susceptibility of membranes to microbiological fouling reduces with a decrease in the roughness of the membrane surface. It is established that the membranes modified with the quaternized 2-(dimethylamino)ethyl methacrylate possess antibacterial properties. These membranes proved to be the most efficient in the filtration of natural surface water in a noncontinuous regime, a result that is explained by the ability of membranes to prevent the formation of a fouling biofilm on their surfaces.     

Effect of filler on the in situ formation of linear polymer blends

The kinetics of component formation and phase separation for the in situ preparation of aerosil-filled blends of linear PU and linear PS is studied. The introduction of a filler into the PU-PS system increases the rate of PS formation. This feature distinguishes this system from the previously studied PU-PMMA system, where the introduction of aerosil reduces the rate of PMMA formation. This effect may be associated with a decrease in the mobility of blend components that is related to introduction of the filler, which leads to more viscous systems, and with differences in conditions of the in situ polymerization of styrene and methyl methacrylate in the blend with the PU being formed. The acceleration of phase separation in the PU-PS system with an increase in the PS content may be explained by the preferential adsorption of PU on aerosil.     

Effect of thermochemical treatment on the surface morphology and hydrophobicity of heterogeneous ion-exchange membranes

A comparative analysis is performed on the effect thermochemical treatment in aqueous, alkali, and acid media has on the surface morphology and hydrophobicity of swelling heterogeneous ion-exchanged membranes. A correlation between changes in surface morphology and hydrophobicity is established. It is shown that under prolonged (50 h) membrane thermal treatment above room temperature, hydrophobicity is reduced due to substantial enlargement of cavities and cracks resulting from the partial destruction of inert binder (polyethylene) and reinforcing poly-?-caproamide fabric (capron).     

Effect of micelle composition on the formation of surfactant-templated polymer films

Surfactant-templated polymer films prepared from polyethylenimine (PEI), cetyltrimethylammonium bromide (CTAB), and octaethylene glycol monohexadecyl ether (C(16)E(8)) were examined and the effect of increasing the percentage of nonionic surfactant in the micelles measured using both surface and bulk-sensitive techniques. It was found that there is a strong interaction between CTAB and C(16)E(8), although no interaction between the C(16)E(8) and PEI was observed. Generally, increasing the percentage of C(16)E(8) in the micelles decreases both the thickness and degree of order in the films; however, it was observed, depending on the conditions, that films could still be formed with as little as 20% cationic surfactant. Experiments on the CTAB/Brij56/PEI system were also performed and these indicate that it is similar to the CTAB/C(16)E(8)/PEI system.