On a nonexponential transformation equation for spherulitic crystallization

An equation has been derived for the development of crystallinity from heterogeneously nucleated spherulites which impinge with a small number of neighboring but randomly centered spherulites. The crystallization-time dependence calculated from the equation conforms to an Avrami equation with initial fractional values for the n exponent, and the equation appears to be a better fit of the initial time dependence of the crystallization of polyethylene than the Avrami equation itself. It appears to account satisfactorily for the observation of fractional n values in the analysis of the crystallization curves of this polymer. The derivation of the equation only accounts for the impingement of spherulites in pairs and does not allow for multiple impingements. This limits its fit to less than the total primary crystallization. The effect on nonrandom centering of spherulites is discussed.     

Melting and crystallization of a polyphosphate

Lithium polyphosphate crystals produced by crystallization during polymerization and crystallization from the polymer melt were analyzed by thermal analysis. The glass-transition and melting temperature, heat of fusion, and entropy of fusion were found to be 336°C, 651.5°C, 21 kJ/mole, and 23 J/deg mole, respectively. Crystallization from the macromolecular melt was followed by thermal analysis, x-ray diffraction, and electron and optical microscopy. It could be shown that chain folding may be the first step to crystallization from the macromolecular melt. Oligomers could not effectively nucleate crystallization. Lithium polyphosphate is shown to present a prime example of the processes involved in crystallization during polymerization and macromolecular melt crystallization.     

Spectroscopic and conformational study of phenyl benzoate

IR spectra of phenyl benzoate (PB) have been studied at various temperatures. On the basis of the calculation of the frequencies and forms of the normal phenyl benzoate molecule, the complete assignment of vibrational spectra was achieved. A conformational analysis of PB was carried out using molecular mechanics calculations. It was shown that the relative orientation of the benzene rings varies with temperature and phase state.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 459–463, March, 1995.     

Melting and homogeneous crystallization of a Lennard-Jones system

Melting and homogeneous crystallization in a Lennard-Jones system of 10,976 atoms in a model box with periodic boundary conditions were investigated by the molecular dynamics method in an NVE ensemble. Crystal melting occurs by arbitrary generation and growth of local defects transformed into regions of a disordered phase. These defects gradually span the entire space of the sample, absorbing the residual islands of crystal. Homogeneous crystallization of a liquid starts with generation of crystal nuclei which grow into defective crystals. The resulting crystal varies in structure between different realizations of the model. Face-centered cubic (fcc) structures prevail. A hexagonal close packing (hcp) structure is present on the boundaries of fcc regions and arises from disordering in alternation of atomic planes. Multiple twinning of the fcc structure is observed, and aggregates with fivefold symmetry have been found.     

Gradient flexoelectric switching response in a nematic phenyl benzoate

We report on the inverse flexoelectric effects observed in a nematic liquid crystal with a small positive dielectric anisotropy subject to static and very low frequency (<1 Hz) a.c. fields. The Bobylev–Pikin flexobands appear at a temperature‐dependent d.c. threshold. Under square wave excitation, a new type of transient optical response occurs soon after each polarity reversal, and we ascribe it to the gradient flexoelectric distortion explicable on the basis of the presence of intrinsic double layers. This instability is characterized by a threshold voltage that decreases with temperature. Its maximum amplitude increases linearly with voltage close to threshold, and occurs after polarity reversal at a time τ_m that scales inversely as the voltage; τ_m decreases exponentially with frequency and temperature. After each polarity change, the ionic current following the charging current decreases almost exponentially to a non‐zero value; the residual current increases monotonically with the applied bias.     

Melting and crystallization of tetrafluoroethylene-ethylene copolymers

The melting and crystallization of copolymers of tetrafluoroethylene with ethylene, synthesized in bulk and in suspension by semi-flow method, were studied by DSC. X-ray diffractions and infrared spectra of the copolymers were measured and new crystalline reflections different from those of the homopolymers were observed. The melting temperature of the copolymers synthesized in bulk depends strongly on the composition and exhibits several maxima. A certain small decrease in the melting temperature within the range of the alternating composition is observed. For alternating copolymers synthesized in suspension, the peaks are monomodal indicating a higher structural and chemical homogeneity of the copolymer. The nonisothermal crystallization kinetics in the temperature interval from 260 to 255°C of the alternating copolymer prepared in suspension can be described by a modified Avrami equation. The mechanism of nucleation and nuclei growth during the nonisothermal crystallization of the tetrafluoroethylene-ethylene copolymer is close to that of polyethylene.     

Melting behaviors,crystallization kinetics,and spherulitic morphologies of poly(butylene succinate) and its copolyester modified with rosin maleopimaric acid anhydride

This article investigated the melting behaviors, crystallization kinetics, and spherulitic morphologies of poly(butylene succinate) (PBS) and its copolyester (PBSR) modified with rosin maleopimaric acid anhydride, using wide‐angle X‐ray diffraction, differential scanning calorimeter (DSC), and polarized optical microscope. Subsequent DSC scans of isothermally crystallized PBS and PBSR exhibited two melting endotherms, respectively, which was due to the melt‐recrystallization process occurring during the DSC scans. The equilibrium melting point of PBSR (125.9 °C) was lower than that of PBS (139 °C). The commonly used Avrami equation was used to describe the isothermal crystallization kinetics. For nonisothermal crystallization studies, the model combining Avrami equation and Ozawa equation was employed. The result showed a consistent trend in the crystallization process. The crystallization rate was decreased, the perfection of crystals was decreased, the recrystallization was reduced, and the spherulitic morphologies were changed when the huge hydrogenated phenanthrene ring was added into the chain of PBS. The activation energy (ΔE) for the isothermal crystallization process determined by Arrhenius method was 255.9 kJ/mol for PBS and 345.7 kJ/mol for PBSR. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 900–913, 2006     

Monolayer behaviour of a nematogenic phenyl benzoate at the air-water interface

The pressure-area characteristics of the monolayers of butyl p-(p--ethoxy-phenoxycarbonyl) phenyl carbonate (BPC) have been studied at various temperatures in the range 10°-31°C. With compression, the film passes from the gaseous (G) to the multilayer (M) state, via the liquid condensed (L) state. The transitions from G to L and L to M states occur over wide plateau regions at lower temperatures. The widths of these regions and also the molecular areas at which they begin decrease linearly with elevation in temperature. A remarkable feature of the isotherms is that, in the G and L regions, as the temperature is lowered, they shift in the direction of higher pressure. This is explained by taking into account the possible molecular orientations with respect to the substrate. The overall surface behaviour of BPC differs from that of some other phenyl benzoates studied earlier. In particular, BPC does not form liquid-crystal-like multilayers. The paper also includes certain results on the surface behaviour of mixtures of BPC and cholesterol; the condensing effect of cholesterol is briefly discussed.     

Chiral liquid-crystalline copolyacrylates with biphenyl and phenyl benzoate side groups

The phase behavior and structure of liquid-crystalline phases of three series of copolymers with mesogenic units belonging to the families of biphenyls and phenyl benzoates have been studied, with the former mesogenic units containing a chiral center in a flexible spacer. A variation in the isotropization temperature as a function of composition is well described by the additivity rule, whereas the tilt angle of mesogenic groups in smectic layers changes nonlinearly. This angle decreases beginning from homopolymers and attains the minimum value for the copolymers of the equimolar composition, which show the highest ferroelectric activity among the polymer systems under study.     

Mechanism of reaction of phenyl glycidyl ether with phenyl benzoate in the presence of water

The reaction of phenyl glycidyl ether with phenyl benzoate in the presence of water was investigated by adsorption liquid chromatography.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 131–133, January, 1990.     

Non-isothermal crystallization behaviors and spherulitic morphology of poly(lactic acid) nucleated by a novel nucleating agent

Journal of Thermal Analysis and Calorimetry - The effect of cadmium phenylmalonate (PMA-Cd) as a novel nucleating agent on the crystallization behaviors and spherulitic morphology of poly(lactic...     

Photochemical rearrangement of phenyl benzoate in the presence of cyclodextrins and amylose

The photorearrangement of phenyl benzoate in aqueous medium is changed in the presence of cyclodextrins or amylose; the ortho/para migration ratio is altered in favor of the para position.     

Initiation of the internal-conversion process in the phenyl benzoate molecule

The INDO and CNDO/S methods were used to calculate changes in the energy of the ground state and the energy of the first singlet-singlet transition of phenyl benzoate permitted with respect to its multiplet nature with consistent rotation of phenyl groups of the molecule in the cis conformation. It was found that in the lowest excited singlet state of the phenyl benzoate molecule an adiabatic photoreaction can occur, as a result of which the energy of the S₀-S₁ electron transition decreases to values of 2 eV. With motion of the molecular system along the coordinate of the photoreaction, an internal-conversion process is initiated, which leads to the experimentally observed absence of luminescence of phenyl benzoate solutions.Translated from Teoreticheskaya i Eksperimental'naya Khimiya, Vol. 21, No. 3, pp. 365–367, May–June, 1985.     

Synthesis of graphislactones A-D through a palladium-mediated biaryl coupling reaction of phenyl benzoate derivatives

The chemical synthesis of graphislactones A-D was achieved through the Pd-mediated intramolecular biaryl coupling reaction of phenyl benzoate derivatives.     

New liquid-crystalline homo-and copolymers with phenyl benzoate side groups and a chiral center in a flexible spacer

The phase behavior and structure of liquid-crystalline homo-and copolymers based on structurally isomeric units belonging to the family of phenyl benzoates that differ in orientation of an ester link situated between benzene rings have been studied with X-ray diffraction, scanning calorimetry, and polarization optical microscopy. The orientation of this link in the monomer unit affects the temperature of phase transition, the type of the smectic phase, and the packing mode of side mesogenic groups in smectic layers of homopolymers. When monomer units commensurable with the monomer units of the basic component in terms of geometry but not identical to them in terms of smectogenity are randomly incorporated into macromolecules of the LC polymer, the resulting copolymer is characterized by layered packing not typical of either of the components.     

Instabilities across the isotropic conductivity point in a nematic phenyl benzoate under AC driving

We characterize the sequence of bifurcations generated by ac fields in a nematic layer held between unidirectionally rubbed ITO electrodes. The material, which possesses a negative dielectric anisotropy epsilona and an inversion temperature for electrical conductivity anisotropy sigmaa, exhibits a monostable tilted alignment near TIN, the isotropic-nematic point. On cooling, an anchoring transition to the homeotropic configuration occurs close to the underlying smectic phase. The field experiments are performed for (i) negative sigmaa and homeotropic alignment, and (ii) weakly positive sigmaa and nearly homeotropic alignment. Under ac driving, the Freedericksz transition is followed by bifurcation into various patterned states. Among them are the striped states that seem to belong to the dielectric regime and localized hybrid instabilities. Very significantly, the patterned instabilities are not excited by dc fields, indicating their possible gradient flexoelectric origin. The Carr-Helfrich mechanism-based theories that take account of flexoelectric terms can explain the observed electroconvective effects only in part.     

A novel crystalline structure - poly(tetrafluoroethylene) spherulitic crystal and its crystallization kinetics

Spherulitic crystals of Poly(tetrafluoroethylene) (PTFE), for the first time, are observed in a kind of PTFE composite, and are verified by polarized optic microscopy (POM). Differential scanning calorimetry (DSC) is used to study the isothermal crystallization kinetics of PTFE matrix at different temperatures. The result shows that Avrami parameter is near 3, which may be elucidated that PTFE crystallizes three-dimensionally from preexisting nuclei. The result is in accordance with scanning electric microscopy (SEM) and POM observation of the crystalline morphology of PTFE. Compared with the rate of one-dimension crystallization, the rate of three-dimension crystallization is lower. So the three-dimension crystallization is easier to control than the one-dimension crystallization of PTFE.     

Melting and crystallization of poly(ethylene terephthalate) under pressure

A piston-cylinder-type high-pressure dilatometer has been built and the effect of pressure on melting behavior of poly(ethylene terephthalate) (PET) has been studied. The melting temperature increases but the rate of change of the melting temperature decreases with increasing pressure. Poly(ethylene terephthalate) crystallized from the melt at elevated pressure and temperature was studied by thermal analysis, and wide-angle and small-angle x-ray diffraction and electron microscopy. Chain-extended PET crystals were observed for the first time and some of their properties are described. A similarity to extended-chain polyethylene is suggested.