Showing papers in "Journal of Polymer Science Part B in 1978"

Raman spectroscopic method for determining the crystallinity of polyethylene

Abstract: The Raman spectrum of partially crystalline polyethylene can be described as a superposition of three components, which originate from the orthorhombic crystalline phase, a meltlike amorphous phase, and a disordered phase of anisotropic nature, where chains are stretched but have lost their lateral order. The mass fractions involved in the three phases can be derived directly from the integral intensities of characteristic bands without an additional calibration procedure. A comparison of the results obtained for a variety of samples shows agreement with the crystallinities derived from the density, and the small-angle and wide-angle x-ray diagrams. Data indicate that the disordered anisotropic phase is located at a transition zone between crystalline and amorphous layers. Application of the method in a temperature-dependence experiment permits a detailed examination of partial melting.

On the theory of the excluded‐volume effect of a polyelectrolyte in a 1‐1 electrolyte solution

Abstract: An excluded-volume theory of polyelectrolytes is presented based on the concept of a Kuhn statiscal segment depending on the concentration of added salt. The polyion is viewed as a wormlike chain bearing charges which interact according to a Debye–Huckel potential. It is shown that it is consistent to split up the screened Coulomb potential into two parts: a short-range interaction giving rise to a so-called electrostatic persistence length which depends on the Debye–Huckel radius, and a long-range interaction denoting the excluded-volume effect. The mean-square radius of the polyelectrolyte is derived, and this deviates markedly from expressions based on a constant Kuhnsegment length. Furthermore, certain polyelectrolytes exhibit negligible excluded-volume effects and behave as wormlike chains with a persistence length equal to the sum of the bare persistence length and the electrostatic persistence length. In addition, an expression for the polyion–polyion contribution to the second virial coefficient is obtained.

CO2 sorption in poly(ethylene terephthalate) above and below the glass transition

Abstract: High-pressure CO2 sorption data in semicrystalline poly(ethylene terephthalate) (PET) are presented for temperatures ranging from 25 to 115°C. The results are described by Henry's law above the glass-transition temperature of PET, while a dual-mode sorption model comprised of a Henry's law and a Langmuir isotherm applies in the glassy state. The disappearance of the Langmuir capacity of the polymer above Tg presumably results from the elimination of regions of localized lower density which are frozen into the glass upon quenching from the rubbery state. Exposure of PET to a high CO2 pressure produced a systematic variation in the apparent sorption equilibria. Correlation of the Langmuir capacity of PET with the dilatometric parameters of the polymer provides a useful framework for understanding the origin of the Langmuir sorption mode and for interpreting annealing and conditioning effects in glassy polymers.

Equilibrium melting parameters of poly(ethylene terephthalate)

Abstract: The equilibrium melting temperature, volume, and enthalpy and entropy changes on melting of poly(ethylene terephthalate) have been analyzed and heats of fusion have been newly measured with an automated scanning calorimeter to yield the following data: 553°K, 16.9 cm3/mole, 2.69 kJ/mole, and 48.6 J/deg/mole, respectively. A more detailed discussion of annealed samples obtained from etched starting materials shows that the density of the noncrystalline regions may be variable.

Molecular motions, the α relaxation, and chain transport in polyethylene crystals

Abstract: Conformational energy calculations are used to investigate molecular motions in polyethylene crystals. From these a model is derived for the motion that accomplishes the net rotation translation that is believed to underlie the nuclear magnetic resonance (NMR) and dielectric α processes in polyethylenes and paraffins (and their dipole decorated derivatives). The resulting model is found to incorporate features of a number of previous models but differs significantly from all of them. The rotation is accomplished by means of a twisted (by 180°) region that propagates smoothly along the chain across the crystal. It differs from previous rotational models in that the twisted region is found to be rather localized (to ∼12 CH2 units). A dependence of activation energy on chain length (paraffins) or crystal thickness (polyethylenes), with the activation energy becoming independent of thickness in thick crystals, results not from the rotational lattice mismatch of the twisted region per se but from the translational lattice mismatch induced by the 180° rotation of one stem relative to the other. The twist differs from a stable point-defect twist previously proposed (Reneker defect) in that the chain torsion is relatively uniform through the twist and there is no shortening of the chain accompanying it. Further, the twist propagates smoothly without local barriers to its advance. Thus the propagating twist is to be through of as a transition state rather than a hopping defect. Detailed atomistic conformational energy calculations on C22H46 crystals were combined with a simplified elastic theory for translational stem mismatch in longer chains. From the combined calculations the activation parameters for twist propagation as a function of chain length or crystal thickness could be calculated. The results were compared with experiment for the dielectric α relaxation in paraffins containing dissolved ketones and polyethylenes containing carbonyl groups. The agreement is quite good, especially considering the paucity of adjustable parameters in the model. There is only some slight uncertainty in the calculated entropy of activation and a scattering correction was made a posteriori to account for a slow continued drop-off in relaxation rate in very thick crystals.

Fourier transform infrared studies on the thermal degradation of polyacrylonitrile

Abstract: Fourier transform infrared studies of the thermal degradation of polyacrylonitrile (PAN) conducted at 200°C in air and under reduced pressure are presented. The spectra are markedly superior to those published previously. A mechanism consistent with the infrared results obtained under reduced pressure is advanced, and assignments for the infrared bands occuring in the spectrum of both the reduced pressure and air degraded PAN are given.

Synthesis and properties of a new polydiacetylene: Poly[1,6‐di(N‐carbazolyl)‐2,4‐hexadiyne]

Abstract: The solid-state synthesis and properties are reported for a new polydiacetylene: poly(1,6-di(N-carbozolyl)-2,4-hexadiyne). The monomer crystals polymerize quantitatively with ..gamma.. irradiation or thermal annealing. An autocatalytic effect is observed in both ..gamma..-ray polymerization and thermal polymerization and is attributed to an increase in chain propagation length at about 5% conversion. The activation energy for thermal polymerization is about 25 kcal/mole, independent of the degree of conversion to polymer. The exceptional thermal stability of the polymer crystals allowed a thermomechanical analysis over a large temperature range, -50 to 300/sup 0/C. With increasing temperature, the polymer contracts in the chain direction linearly with temperature over the entire range, yielding a thermal expansion coefficient of (-2.32 +- 0.02) x 10/sup -50/C/sup -1/. Photoconductivity action spectra are reported for the polymer crystals. The energies for the photoconductivity onset (ca. 2.3 eV) and for the lowest energy optical transition (1.89 eV) are the lowest reported for the polydiacetylenes. The photoconduction onset is blue-shifted with respect to optical absorption--a result which is consistent with the excitonic assignment for the lowest energy optical transition in the polydiacetylenes.

Transient and steady‐state permeation in poly(ethylene terephthlate) above and below the glass transition

Abstract: Transient and steady-state permeation data are reported for CO2 in semicrystalline poly(ethylene terephthalate) for temperatures ranging from 25 to 115°C over the pressure range from 1 to 20 atm. The pressure dependency of the time lag and permeability disappears completely above the glass transition of the polymer, and Fick's law with a concentration-independent diffusion coefficient applies. In the glassy state, a concentration-dependent diffusion coefficient is necessary to describe the data. The form of this concentration dependence is described well by the partial immobilization transport model that attributes a different mobility to each of the two populations of sorbed gas which exist in local equilibrium with each other in glassy polymers. The importance of reporting the pressure used in transport experiments involving glassy polymers is emphasized by comparing the difference in the activation energy of the apparent diffusivity calculated from the measured time lag at 1 and 20 atm. Also, the magnitude of the observed slope discontinuity at Tg in Arrhenius plots of these apparent diffusities is shown to be a function of the upstream pressure used in the experiment. The independently measured time lags are compared with the predicated values calculated from various transport models and found to be described best by the partial immobilization model.

Solid‐state polymerization of a diacetylene crystal: Thermal, ultraviolet, and γ‐ray polymerization of 2,4‐hexadiyne‐1,6‐diol bis‐(p‐toluene sulfonate)

Abstract: Results are presented for the thermal, ultraviolet, and γ-ray polymerization of 2,4-hexadiyne-1,6-diol bis-(p-toluene sulfonate) (PTS). Monomer extraction is used to obtain polymer conversion-vs.-time curves at 30, 50, and 80°C. In agreement with previous work over a narrower temperature range, the curves all display a dramatic autocatalytic effect with an onset at about 10% conversion to polymer. Although the polymerization rate undergoes a 200-fold change over this temperature range, the shape of the conversion curves does not change. These data yield an activation energy (E) of 22.2 ± 0.4 kcal/mole when interpreted in terms of the time required to reach 50% polymer. An annealing technique is used to provide a closer look at the autocatalytic region. In that case, E = 22.5 ± 0.8 kcal/mole is determined from measurements of the time required to go from 10 to 50% polymer at temperatures ranging from 23 to 80°C (a 500-fold change in rate). Thermal polymerization rates measured in the low-conversion limit using a spectroscopic method based on diffuse reflectance yield E = 22.8 ± 0.6 kcal/mole. Thus E is independent of polymer conversion and the autocatalytic effect can be best understood as arising from a large increase in the propagation length of the polymer chains. The autocatalytic effect is shown to be present in both UV and γ-ray polymerization. In the case of γ-ray polymerization, conversion-vs.-time and spectroscopic measurements are consistent with inhomogeneities in the polymer concentration caused by particle tracks. Activation energies for UV and γ-ray polymerization are quite low (2-3 kcal/mole) and confirm that the chain initiation event makes the major energetic contribution to E. The polymerization mechanism is discussed in detail. The photopolymerization experiments can be consistently interpreted with a model based on the triplet excited state of the diacetylene monomer as the chain initiation species.

Effect of particle shape at finite concentration on the elastic moduli of filled polymers

Abstract: The elegant approach of Eshelby, developed for dilute dispersions, is generalized to include the interaction of filler with filler. It is then utilized to determine the five elastic moduli of filled polymer containing aligned ellipsoidal particles at finite concentrations φ. The anisotropic particle shape is characterized by an aspect ratio ρ of an ellipsoid. The present theory compares well with available experiments in the literature. The experimentally verified Kerner equation for spherical particles and rule of mixtures for the longitudinal Young's modulus at ρ → ∞ are special cases of our new results.

Structural relaxation in poly(vinyl acetate)

Abstract: Structural relaxation in poly(vinyl acetate) (PVAc) in and slightly above the glass-transition region has been studied by monitoring the time dependence of enthalpy using differential scanning calorimetry and the frequency dependence of electric polarization by dielectric loss measurements. The results have been analyzed to yield the kinetic parameters characterizing the structural relaxation and are compared with similar analyses of previously published shear compliance and volume relaxation experiments. Relaxation of enthalpy, electric polarization, volume, and shear stress in PVAc all appear to be characterized by somewhat different relaxation times. The difference between the volume and enthalpy relaxation times, coupled with the fact that PVAc exhibits a Prigogine–Defay ratio greater than unity, is evidence for a previously proposed connection between the thermodynamics and kinetics of structural relaxation in terms of an order parameter model.

Melting and crystallization of poly(vinylidene fluride) under high pressure

Abstract: Precise melting and crystallization temperatures of extended-chain and folded-chain crystals of form I and folded-chain crystals of form II poly(vinylidene fluoride) under high pressure have been obtained by microdifferential thermal analysis (DTA). Upon heating at pressures above 4000 kg/cm2, the micro-DTA thermogram of form II crystallized from the melt at atmospheric pressure shows melting of the form II structure and the melting of the folded-chain and extended-chain crystals of form I, formed through recrystallization processes. These features were clarified by supplemental methods. The bandwidth seen in electron micrographs of the extended-chain crystal of form I obtained by crystallization under high pressure was in the range of 1500 to 2000 A. At atmospheric pressure, the extended-chain crystal of form I melted at 207°C, approximately 17°C higher than the folded-chain crystal of form I and 31°C higher than the folded-chain crystal of form II.

Crystal structure of isotactic poly(4‐methyl‐1‐pentene)

Abstract: The crystal structure of isotactic poly(4-methyl-1-pentene) was determined by x-ray analysis. The unit cell is tetragonal, P4b2, with α = 18.70 A and c (fiber axis) = 13.68 A; it contains four molecular chains each consisting of seven monomeric units in the fiber period. The molecular conformation is essentially a (7/2) helix, but deviates slightly from the uniform (7/2) helix. The unusual low density is discussed from the structural point of view.

Hydrostatic extrusion of linear polyethylene: Effects of molecular weight and product diameter

Abstract: Oriented rods of linear polyethylene have been prepared by hydrostatic extrusion at 100°C. Materials having a range of different molecular weights were investigated and their behavior was found to correlate well with the melt flow index. The differences in extrusion process characteristics for large- and small-diameter products are discussed. In this context the effect of deformational heating is important and criteria are suggested for determining its significance and also for determining the stability of the process in terms of a critical extrusion pressure.

Crystallization and melting of aqueous gelatin

Abstract: Gelation and melting of aqueous gelatin were investigated by differential scanning calorimetry. This phenomenon can be analyzed as a conventional crystallization process assuming predetermined primary nucleation and unidirectional growth. The results were interpreted in terms of the fringed micelle model. Calculated values of the diameter of the rematured collagen fibril were found to be in excellent agreement with those determined previously by electron microscopy.

Structure of the quenched form of polypropylene

Abstract: X-ray diffraction has been used to further investigate the quenched form of polypropylene. The diffractometer traces were analyzed by a mathematical peak separation procedure which assumed a combined Cauchy and Gaussian shape for the peaks. The results confirmed that the quenched form contains about 60% of amorphous polypropylene. In the remainder, the x-ray diffraction peak positions indicate that the chain helices are arranged in a square array and a cubic or tetragonal symmetry is proposed for this phase. The shape of the x-ray diffractometer peaks indicates a degree of strain in the structure. Crystallite sizes, determined from peak breadths, have been estimated as approximately 30 A.

High‐speed aqueous gel‐permeation chromatography

Abstract: High-speed gel-permeation chromatography (GPC) of water-soluble polymers has been investigated by using TSK-GEL, type-PW columns packed with small porous particles. Being semirigid, the column packing could be operated under high pressure and, therefore, it was possible to achieve high-speed GPC. A resolution higher than that of ordinary GPC in organic solvent system was attained when the measurement of one sample was completed within 40 min with a 6-ft column set. Samples with a wide range of molecular weights, from oligomers to polymers having a molecular weight greater than 106, could be fractionated. Dextran, polyethylene glycol, polyacrylamide, poly(vinyl alcohol), and poly(vinyl pyrrolidone) were separated according to molecular size with no evidence of adsorption. Investigation of other water soluble polymers is now in progress.

Nature of melt rheological transition in a styrene–butadiene–styrene block copolymer

Abstract: Our laboratory previously reported the observation of a high temperature, melt rheological transition in a styrene–butadiene–styrene (S:7 × 103 and B:43 × 103) block copolymer from the highly elastic, nonlinear viscous behavior typical of a multiphase structure to linear viscous behavior with insignificant elasticity typical of a single-phase structure. We have investigated the precise nature of this melt rheological transition in the 7S-43B-7S sample by measuring the dynamic viscoelastic properties at more than 11 temperatures, including several in the transition region. A new procedure was developed for accurately measuring the sample temperature in a Weissenberg rheogoniometer. The transition is found to start at about 140°C and proceed over a narrow transition region from 140 to about 150°C. Data at all temperatures superimpose onto a single master curve only at high reduced frequencies. At low reduced frequencies, two characteristic branches of the master curve are formed. The data at temperatures below the transition region superimpose onto the upper branch where the dynamic viscosity η′(ω) is a strong function of ω, whereas the data at temperatures above the transition region superimpose onto the lower branch where η′(ω) is independent of ω. The data at temperatures within the transition region fall between the upper and lower branches, ordered according to their temperature positions. The apparent flow activation energy is found to be constant at about 22.8 kcal/mole below the transition region, but appears to decrease to about 17.4 kcal/mole above the transition region. The narrowness of the rheological transition far above the glass transition temperature of the polystyrene domains and the limiting linear viscoelastic behavior at low frequencies above the transition suggest an accompanying morphological transition rather than a gradual weakening of the polystyrene domains.

Specific volume of polysulfone as a function of temperature and pressure

Abstract: The pressure–volume–temperature (PVT) properties of a commercial polysulfone derived from bisphenol A and 4,4′-dichlorodiphenylsulfone are studied experimentally and theoretically in the temperature range 30–370°C and for pressures to 2000 kg/cm2. PVT surfaces are determined for an annealed glass, formed under zero pressure, and for the melt. Two glass-transition lines must be distinguished: T(P) which is the intersection of the glass and melt PVT surfaces, and Tg(P), which is obtained by pressurizing the melt isothermally. The application of Ehrenfest-type equations to these transitions are discussed. The Prigogine–Defay ratio r = ΔkΔCp/TV(Δα)2 at P = 0 is found to be equal to 0.95 (±20%), using ΔCp data determined on identical samples. The melt data is compared with the Simha–Somcynski hole theory, using the reducing parameters V* = 0.788 cm3/g, T* = 12,560°K, P* = 10,875 bar. The hole fraction appearing in the theory is found to be constant along T(P), but the glass PVT relationship cannot be reproduced by using the Simha–Somcynsky theory together with the assumption that the hole fraction remains constant in the glass. At P = 0 the hole fraction must be allowed to decrease with decreasing temperature, but at a slower rate than in the melt.

Intramolecular excimer formation in macromolecules. I. Energy migration and excimer formation in copolymers exhibiting nearest‐neighbor excimer interactions

Abstract: Energy migration and intramolecular excimer formation have been studied in a series of copolymers comprising 1-vinylnaphthalene, 2-vinylnaphthalene, and styrene with methyl methacrylate. The technique of fluorescence depolarization was used to characterize energy migration in glassy solutions of the copolymers. The extent of energy migration in these copolymers is determined by the mean sequence length of aromatic species la. Assuming that excimer formation occurs as a result of nearest-neighbor interactions, the concentration of excimer sites in the macromolecule will be proportional to the fraction of links between aromatic species faa. It is proposed that these sites are populated via energy migration from the site of absorption. Proportionality between the ratio of excimer to monomer emission intensities and the function la·faa was predicted. Good agreement with this relationship was obtained in each of the copolymer systems studied. Reactivity ratios of methyl methacrylate (rm) in copolymerization at 70°C with the aromatic monomers (ra) were determined as: 1-vinylnaphthalene—rm = 0.43, ra = 1.71: 2-vinylnaphthalene—rm = 0.37, ra = 4.46; styrene-rm = 0.45, ra = 0.58.

Study of the molecular motions of polyethylene by line‐shape analysis of broad‐line proton NMR spectra

Abstract: The broad-line proton NMR spectra of polyethylene are separated into three components (broad, medium, and narrow) corresponding to the crystalline and two kinds of amorphous protons, respectively. All amorphous protons are found to be mobile above 210°K. The unusually low molecular mobility in the amorphous regions of polyethylene compared to purely amorphous and other partially crystalline polymers is considered to be adequately described by the network model of Edwards and De Gennes. In this model the chain motions are anisotropic and restricted to small tubular volumes. The medium and the narrow component are believed to result from two different modes of chain motion within these tubes, depending on the free volume available. Two motions in the crystalline regions are observed. One at temperatures below 110°K involves 2%–5% of the protons, depending on the crystallinity of the material, and the other beginning at 290°K involves all crystalline protons (α-process). Coupling of the amorphous and crystalline motions is found above 290°K. Several line shapes have been tested as representations of the three components. Of these the low-temperature spectrum, the Gauss–Lorentz product curve, and the Lorentz curve proved to be the most suitable shapes for the broad, medium, and narrow component, respectively. Using these line shapes, the best fit of the experimental spectra and the expected agreement of the broad and the crystalline fraction are obtained over a very broad temperature range. Above 310°K the low-temperature spectrum must be replaced by the convolution of a Gauss curve and a rectangular function to take into account the line-shape transition of the α-process. The modulation broadening of all components is considered, and this allows line-shape analysis close to the melting point.

Hydrostatic extrusion of polyoxymethylene

Abstract: The hydrostatic extrusion behavior of polyoxymethylene (POM) is described. Extrusions were performed at 164°C for a range of different molecular weight grades. Excellent unflawed lengths of extrudate were obtained with axial Young's moduli, measured at room temperature, reaching values as high as 24 GPa. The extrusion characteristics are discussed in terms of the very strong dependence of the flow stress of POM on strain and strain rate and pressure. In addition to measurements of Young's modulus over a wide temperature range, data for shear modulus and transvers modulus are also presented. A limited amount of other structural measurements is presented.

Effect of hydrogen bonding and ionic aggregation on the melt rheology of an ethylene–methacrylic acid copolymer and its sodium salt

Abstract: A study has been made of the dynamic and steady shear melt theology of an ethylene-methacrylic acid copolymer, its methyl ester, and 70% neutralized sodium salt. Measurements were made with a Rheometrics mechanical spectrometer using the eccentric rotating disks and cone-and-plate geometries over a temperature range of 120–180°C and frequency range of 10−3 to 102 rad/sec. Correspondence was found between steady shear viscosity and the complex dynamic viscosity for the ester and acid materials. Over the temperature and frequency range studied the time-temperature superposition principle was applicable to G′ data for each of the derivatives and a supermaster curve could be constructed from the three individual master curves. Time-temperature superposition was found not applicable to G″ data for the sodium salt. Differences in rheological response between the ester and acid copolymers are explained by differences in Tg. It is suggested that differences in temperature shifts ΔT required to produce G′ superposition between the three derivatives reflect differences in ΔH for interchain interactions. A mechanism for flow of clustered ionomers is consisting of an initiation and a propagation step.

Solubility of carbon dioxide in cellulose acetate at elevated pressures

Abstract: The solubility of carbon dioxide in symmetric (dense) cellulose 2.4-acetate has been measured at temperatures from 0 to 70°C and pressures up to 45 atm. The polymer samples were prepared by slowly drying asymmetric reverse osmosis membranes. The solubility isotherms can be described satisfactorily up to 60°C by the “dual-sorption” model for glassy polymers. The model cannot represent the experimental data above 60°C, possibly because of a second-order transition in the polymer between 60 and 70°C. An analysis of the dual-sorption parameters and of the heats of solution and “hole filling” suggests that the polymer samples contained a relatively large volume of microcavities. Gas solution appears to occur predominantly in microcavities, a large fraction of the penetrant moleculers being immobilized or partially immobilized. The solubilities obtained in this work are compared with similar data computed from time-lag measurements of other investigators, and the validity of the dual-sorption model is examined for the present case.

The effect of pressure on the volume and the dielectric relaxation of linear polyethylene

Abstract: The effects of pressure on the α (ca. 70°C, 1 kHz) and γ (ca. −100°C, 1 kHz) relaxations of linear polyethylene were studied dielectrically between 0 and 4 kbar. Equation of state (PVT) data were also determined in the range of interest of these relaxations. The sample was rendered dielectrically active through oxidation (0.8 C0 per 1000 CH2). The α process (which occurs in the crystalline fraction) could be studied over a much wider temperature range than heretofore possible due to the effect of pressure in increasing the melting point. Examination of relaxation strength from 50 to 150°C showed that there must be two crystalline relaxation processes: the well-known α relaxation plus a competing one. The α relaxation is believed to be due to a chain twist–rotation–translation mechanism that results in rotation–translation of an entire chain in the crystal. The relaxation strength of the α process decreases and therefore indicates the presence of a second (faster and not directly observed) process that increases in intensity with increasing temperature. It is postulated that the second process is due to motion of defects that become more numerous through thermal injection at higher temperatures. Analysis of the relaxation data along with the PVT data allowed the constant volume activation energy for the α relaxation to be determined. It was found to be 19.4 ± 0.5 kcal/mole. The constant volume activation energy is important in modeling calculations of the crystal motions and is significantly smaller than the atmospheric constant pressure activation energy of 24.9 kcal/mole. The effect of pressure on the activation parameters and shape of the γ process was also determined. There has been controversy over whether the γ process occurs only in the amorphous fraction or in both the amorphous and crystalline phases. Since the two phases have quite different compressibilities, increasing the pressure should change the shape of the loss curves (versus frequency and temperature) if the process occurs in both phases. The shape (but not location) of the loss curves was found to be remarkably independent of pressure. This finding strengthens the view that the γ process is entirely amorphous in origin.

Small‐angle x‐ray scattering by nylon 6

Abstract: Small-angle x-ray scattering (SAXS) of isotropic or uniaxially oriented nylon 6 was investigated as a function of thermal and mechanical history. In addition to the peak position and linewidth of the SAXS maximum, the integrated SAXS intensity was measured. It was found that the radial intensity distributions of isotropic or arced patterns are controlled to some extent by the small width of the semicrystalline macrolattice, rendering the conventional long period and line shape analysis inapplicable to these patterns. A two-dimensional analysis is possible with well-oriented fibers; the major structural changes which are seen in fibers after annealing above 190°C are associated with melting and recrystallization. Extensive cold drawing and subsequent annealing cause rather modest (ca. ∼30%) changes in the integrated SAXS intensity. These effects are consistent with the generation of homogeneous interfibrillar regions during the latter stages of plastic deformation. On annealing a quenched film on nylon 6, the transformation of the crystals from a pseudohexagonal to a monoclinic habit occurs above 170°C.

Laser Raman scattering in uniaxially oriented atactic polystyrene

Abstract: Raman polarization measurements of atactic polystyrene (APS) films were recorded after uniaxial stretching. Twelve different polarization directions were observed by varying the direction and polarization of the laser and scattered radiation. The polarization behavior of several vibration modes were shown clearly in the Raman spectra. On the basis of these polarization properties and previous vibrational studies of model compounds of polystyrene as well as of monosubstituted benzene derivatives, a reassignment of some of the vibrational modes of APS is made and discussed.