The stability of neck propagation and its oscillatory mode have been studied for the cold drawing of poly(ethylene terephthalate) films. On the basis of Barenblatt's model considering a temperature rise at the neck, the stability has been analysed for neck propagation at constant speed and at constant load. It is shown that the stability is directly connected to the sign of the slope of the stress-drawing rate plot; unstable neck propagation should be in the region of negative slope. It is argued that the unstable mode changes to an oscillatory neck propagation for drawing at constant speed, while the mode in drawing at constant load is transformed to the other stable region. Experimental study has confirmed the unstable drawing at constant load and the transition of neck propagation rate. Oscillatory neck propagation has also been examined by a numerical calculation of non-linear differential equations based on Barenblatt's model. The limits of Barenblatt's model are also discussed.
The strength of impact-modified polystyrene is related to the volume of craze matter generated in fracture. In the Izod test, crazes tend to initiate and propagate between interacting neighbours. The efficiency of craze termination is also critical to toughness, and depends upon the particle morphology. Using computer simulations of crazes propagating through an array of model particles, it has been possible to quantitatively model the crazing process and predict strength. The model is applicable to materials having a wide range of particle sizes, rubber phase volumes, and either solid or occluded particles. Predictions are in good agreement with data obtained for experimental blends as well as commercial HIPS.
In size exclusion chromatography (s.e.c.) analysis both the universal calibration curve (UCC) and the secondary calibration curve (molecular weight calibration) can be constructed using the Mark-Houwink-Sakurada (MHS) relation,  = KM". Over a very wide range of molecular weights neither K nor a is constant; therefore, the interpretation of results using one set of K and a values may not be correct (i.e. in the case of commercial resins). An alternative model which relates molecular weight (MW) to It/] over a very wide range of molecular weights is [q]=KoMrl/2+K'Mw where K o and K' do not change. The intrinsic viscosities of polystyrene standards with MWs of 10 3 to 2 X 106 were measured and the results were used to establish a UCC for a multi-detector s.e.c, system. From the UCC two calibration curves were established using the MHS relation and the alternative model. Commercial polystyrene and polyethylene resins were analysed using the same analytical system. At the higher molecular weight end one observes a deviation between the results from absolute MWdetectors and the calibration curve based on a particular set of K and a values. On the other hand, MWs obtained from the calibration curve using the alternative model were consistent with results from absolute molecular weight detectors. This indicates that the use of the alternative model will provide a more accurate calibration for s.e.c, analysis when the molecular weight distribution is relatively wide.
The spherulitic growth rate ofisotactic polypropylene in dotriacontane was studied using optical microscopy. Polymer concentration was varied from 100 to 10 wt% iPP in 10 wt% intervals. Crystallization temperature was varied from 372 to 429 K in 1 K intervals. The influence of these variables on polymer spherulitic growth rate and regime transitions was analysed using the Lauritzen-Hoffman and Toda nucleation theories
Bulk crystallization rates, nucleation density, general morphological features, equilibrium melting point and absolute crystalline percentage of linear and star-branched nylon-6 have been studied as a function of branch-point functionality and temperature. Overall bulk crystallization rates were described in terms of the Avrami equation and crystallization half-times. No significant differences in bulk crystallization rates as a function of crystallization temperature or absolute crystalline percentage were observed between linear, three-arm and six-arm samples with identical thermal history. Equilibrium melting points obtained by Hoffman Weeks analysis were reduced in star-branched nylon-6 compared to the linear polymer of comparable molecular weight. In order to deconvolute the effects of a decreased thermodynamic driving force for formation of crystals of branched polymers, crystallization half-times were measured as a function of supercooling. The crystallization half-times of star-branched nylon-6 as a function of supercoolin9 were reduced compared to those of linear nylon-6 of comparable molecular weight. The general spherulitic superstructure appeared unaffected by increasing branch-point functionality up to six. However, irregularities in lamellar structure were implied by SAXS experiments on samples with branch-point functionality as low as three.
A dynamic mechanical analysis has been performed on three thermotropic polydibenzoates, designated PDEB, PTEB and PTTB, synthesized from p,p'-dibenzoic acid and di-, tri- or tetraethylene glycol, respectively. The isotropization temperature decreases greatly as the length of the spacer increases, and the mesophase of PTTB is not detected at all. Three dynamic mechanical relaxations are found for each polymer in the temperature range from - 150 to 100°C. The a relaxation corresponds to the glass transition of the polydibenzoates, the fl relaxation is typical of polyesters and the 7 relaxation has its origins in the crankshaft motions of the oxyethylene units in the spacer, i.e. the oxygen atom can cooperate in this movement when substituting for a methylenic unit.
A linear correlation function is found for cloudpoint composition curves of ternary systems consisting of one polymer, one solvent and one non-solvent. The conditions for validity of this correlation function appear to be that the polymer is strongly incompatible with the non-solvent, and that only liquid-liquid demixing occurs. The linearized cloudpoint (LCP) curve is interpreted in terms of the various parameters occurring in the Flory-Huggins theory. The slope of the LCP line appears to be only dependent on the molar volumes of the components. Information about the binary Flory-Huggins interaction parameters and their concentration dependence can be obtained from the intercept of the linearized curve. Cloudpoints induced by crystallization do not follow the correlation. This gives an opportunity to distinguish between crystallization and liquid-liquid demixing without any additional experiments.
Monodisperse linear polytetrahydrofuran (PTHF) chains with unreactive end groups were mixed with PTHF chains with reactive ends. The concentration of the linear unreactive chains was dilute, approximately 3 wt%. The phase behaviour as well as the single chain conformation of the unreactive chains was investigated after the reactive chains were end-linked via either a tetrafunctional crosslinker or a free radical polyaddition reaction. The results were found to depend strongly on the difference in the molecular weights between the reactive chains and the unattached linear chains.
Several investigations show that the unperturbed dimensions of a given polymer in any solvent do not depend on the nature of the solvent, as far as the solvent has no influence on the rotation of the chain segments. In this case K o is a constant. The evaluation of K e from [t/]-M data by application of the classical Burchard-Stockmayer-Fixman (BSF) theory often results in different values, with dependence on solvent power and, with mixed solvents, on solvent composition. This is mainly due to the non-linearity of the relationship, especially with high molar mass polymers in good solvents. Better results are obtained by non-linear graphical treatment of the BSF plot, or by application of a modified equation proposed by Tanaka, which takes into account the general ~5 z relationship between molecular expansion factors and the excluded volume parameter z. Plots of ([q]/M°'5) 5/3 versus M °5 show linearity over nearly the entire range of molar mass studied and evaluation of unperturbed dimensions results in a quasi unique value of K o for a given polymer.
Swelling experiments were carried out with three cationic polyelectrolyte gels of N-n-butyl-4-vinylpyridinium bromide (BPyBr), N-n-butyl-N,N-dimethyl-4-vinylanilinium bromide (BAnBr) and N-n-butyl-N,Ndimethyl-( N'-acryloyl-3-aminopropyl)ammonium bromide (BAPABr). The swelling equilibria of the gels were measured in aqueous solutions of inorganic electrolytes: HBr, NaBr, KBr, NaCI and NaI. The swelling ratios of the gels did not depend on the cationic species of the electrolytes examined but depended strongly on the anionic species. Volume phase transitions were not observed with the BPyBr and BAnBr gels in aqueous solutions of NaC1 and NaBr whereas a phase transition was observed in an aqueous solution of NaI. The NaI concentration at which the phase transition occurred was raised with an increase in temperature. On the other hand, no discontinuous change was observed in the swelling equilibria of the BAPABr gel, even in the NaI aqueous solution. Comparison of the present results for the BAPABr gel with previous results for a polyelectrolyte gel verified the importance of hydrophobic interactions, which enhance the occurrence of volume phase transitions.