For film blowing of polyethylene it has been shown previously that melt elongation is very powerful for polymer characterization. With two types of rheometers, simple (also called “uniaxial”) elongational tests as well as creep tests can be performed homogeneously. In simple elongation, the melts of branched polyethylene show a remarkable strain hardening. With respect to their advantages and disadvantages, these rheometers complement each other. For multiaxial elongations the various modes of deformation can be performed by means of the rotary clamp technique. With the strain rate components ordered such that \documentclass{article}\pagestyle{empty}\begin{document}$ \dot \varepsilon $\end{document}11 ? \documentclass{article}\pagestyle{empty}\begin{document}$ \dot \varepsilon $\end{document}22 ≥ \documentclass{article}\pagestyle{empty}\begin{document}$ \dot \varepsilon $\end{document}33, the ratio m = \documentclass{article}\pagestyle{empty}\begin{document}$ \dot \varepsilon $\end{document}22/\documentclass{article}\pagestyle{empty}\begin{document}$ \dot \varepsilon $\end{document}11 characterizes the test mode. The Stephenson definition of the elongational viscosities makes use of the linear viscoelastic material equation and proves to be very efficient because the linear shear viscosity (t) (“stressing” viscosity) can act as the reference for the nonlinear behavior in elongation. Results are given for polyisobutylene measured not only in simple, equibiaxial, and planar elongations, but also in new test modes with a change of m during the deformation. This allows one to investigate the consequences of a deformation-induced anisotropy of the rheological behavior. 相似文献
The kinetics of the reaction have been studied at 25°C. in strong acid solution; the effects of acidity, chloride, chlorate and chlorine are reported. A mechanism is postulated to interpret the peculiar features of this reaction as well as the stoichiometry and some of the kinetics of the parallel reaction The mechanism involves HClO2 and HOCl as intermediates General rate expressions are derived for the formation of chlorine dioxide and chlorine, and the individual rate constants are calculated. An expression is obtained for the relationship between the ratio of chlorine dioxide to chlorine produced and the ratio of chlorate to chloride. 相似文献
Summary: It is well known that the weight‐average molecular weight ( ) is strictly dependent on conversion in step‐growth polymerizations performed in batch and that the is very sensitive to impurities and molar imbalance. This makes the work of controlling a non trivial job. In this paper a new methodology is introduced for in‐line monitoring and control of conversion and of polyurethanes produced in solution step‐growth polymerizations, based on near‐infrared spectroscopy (NIRS) and torquemetry. A calibration model based on the PLS method is obtained and validated for monomer conversion, while the weight‐average molecular weight is monitored indirectly with the relative shear signal provided by the agitator. Control procedures are then proposed and implemented experimentally to avoid gelation and allow for maximization of . The proposed monitoring and control procedures can also be applied to other step growth polymerizations.
In this article the kinetics of chemical-controlled radical-chain copolymerization have been reduced to pseudohomopolymerization kinetics by introducing the apparent rate constants, The methods for the determinations of the values of the apparent rate constants, mode of termination, and the methods for the calculation of molecular weights and distributions are proposed. The data required for these determinations and calculations are simply obtained by the usual steady-state method. According to the traditional kinetics along with the definitions of the apparent rate constants, these apparent rate constants as functions of traditional rate constants, monomer compositions, and copolymer compositions are derived. Further utilizing the theoretical expressions obtained, we show that the apparent rate constants are the general rate constants for both radical chain homo- and copolymerizations. The bulk radical copolymerizations of methyl methacrylate and styrene at various monomer feed compositions at 60°C are used to test the proposed model. The empirical apparent rate constants obtained are described well, by the following expressions, and and the mode of termination on the combination termination is where K and K denote the apparent rate constants of propagation and termination, respectively. The term f1(= 1 ? f2) stands for the mole fraction of styrene in the monomer solution fed. F1 is the copolymer composition produced at f1. β is the mode of termination. 相似文献
Empirical correlations of flow properties of poly(vinyl chloride) were made using data reported by a number of investigators. Correlation was made by plotting the reduced variable viscosity η/η0 versus \documentclass{article}\pagestyle{empty}\begin{document}$ (\eta _0 \dot \gamma \bar M_w )/(_\rho RT) $\end{document} or \documentclass{article}\pagestyle{empty}\begin{document}$ (\eta _0 \dot \gamma \bar M_w ^{0.5} )/(_\rho RT) $\end{document} for unplasticized PVC and versus \documentclass{article}\pagestyle{empty}\begin{document}$ (\eta _0 \dot \gamma \bar M_w ^{0.5} )/(_\rho RTW_2 ^a ) $\end{document} with polymer concentration, W2, for PVC containing plasticizer. 相似文献
The complex Young's modulus, E*(ω), and the complex strain-optical coefficient, O*(ω), of poly(ether sulfone) (PES), polysulfone (PSF), and polyethermide (PEI), were measured over the frequency range 1 to 130 Hz. The data were analyzed with a modified stress-optical rule: The Young's modulus was decomposed into two complex functions, E(ω) and E(ω); the modified stress-optical coefficient, CR and CG, associated with the rubber (R) and glass (G) components, respectively, were determined. The results for six polymers, including polystyrene, poly(α-methyl styrene), and bisphenol A polycarbonate were compared with each other. One of the coefficients, CR, equivalent to the stress-optical coefficient in melts, mainly depended on the way in which phenyl groups were connected to the chain. The other, CG, was in the range of 20 to 40 Brewsters, and did not strongly depend on the details of polymer structure. The component function, E(ω), which was located in the glassy region and originated from the high glassy modulus, was almost the same in shape when plotted against ω with double logarithmic scales. The R component, E(ω), located at the long time end of the glass-to-rubber transition zone, was slightly sensitive to the molecular structure of polymers. 相似文献
Different values are reported in the literature for the intrinsic birefringence of the crystalline (Δn) and the amorphous (Δn) phases in nylon 6. Mostly, these values have either been determined by extrapolation (and then it is assumed that Δn = Δn) or calculated theoretically. In this study, intrinsic birefringence values Δn and Δn for nylon 6 were determined using the Samuels two-phase model which correlates sonic modulus with structural parameters. Three series of fiber samples were used: (1) isotropic samples of different degrees of crystallinity for estimation of E and E moduli at two temperatures. The following modulus values were obtained: 1.62 × 109 and 6.66 × 109 N/m2 for 28.5°C, and 1.81 × 109 and 6.71 × 109 N/m2 for ?20°C; (2) anisotropic, amorphous fiber samples for estimation of Δn = 0.076 and E = 1.63 × 109 N/m2 at 28.5°C; (3) semicrystalline samples of various draw ratios for estimations of Δn = 0.089 and Δn = 0.078. All measurements were carried out with carefully dried samples to avoid erroneous results caused by moisture. 相似文献
The viscoelastic properties of a rubber–resin blend, which influences performance of the blend as a pressure-sensitive adhesive, depend upon the structure of the resin as well as its molecular weight. The effect of the concentration of a compatible resin in the blend was examined using a mechanical spectrometer. Four types of resins were used. These are the rosin esters, polyterpenes, pure monomer resins such as polystyrene and poly(vinyl cyclohexane), and petroleum stream resins. Each was examined in blends with both natural rubber and styrene–butadiene rubber over a range of concentrations. It is shown that the temperature of the tan δ peak for compatible systems can be predicted by the Fox equation, T = W1T + W2T, where W1 and W2 are the weight fractions of the resin and rubber, respectively, and the Tg's are the tan δ peak temperatures in K. The plateau modulus G for a blend can be identified as the G′ value in the rubbery plateau at the point where tan δ is at a minimum. The relationship between G and G, the plateau modulus for the undiluted elastomer, is shown to be proportional to the volume fraction of the elastomer raised to the 2.3–2.4 power for natural rubber with six different compatible resins. The exponent for styrene–butadiene rubber is 2.5–2.6 with four different resins. Using these relationships, both the tan δ peak temperature and plateau modulus can be predicted for a rubber–resin system from data on the unmodified elastomer and on one typical rubber–resin blend. 相似文献
It is the object of the present study to obtain clear knowledge of the relations in the polypropylene melt between its linear viscoelasticity and its nonlinear steady capillary flow, paying particular attention to the elastic properties in its capillary flow. By representing the linear viscoelasticity numerically with zero-shear viscosity, η0, and steady-state compliance, J, evaluation has been made of the properties concerning the elasticity of polymer melt in the capillary flow, such as non-Newtonianity, the entrance pressure loss, the end correction, the Barus effect, and the melt fracture. The steady flow viscosity η, the entrance pressure loss P0, the critical shear stress, τc, and the critical shear rate $\dot \gamma _c$ at which melt fracture begins to occur are subject to η0 as follows: From the well-known relationship between η and the weight-average molecular weight M?w, these quantities are governed by M?w. Meanwhile, for such quantities as structural viscosity index N, end correction coefficient ν, and elastic pressure loss ratio P0/P, following correlations hold: As η0 and J are respectively determined mainly by M?w and the molecular weight distribution MWD, these quantities are governed by both M?w and MWD. Physical meanings of η0·J and η02 · J are, respectively, mean relaxation time and a measure of stored energy in steady flow. The Barus effect has a positive correlation to J, ν, and P0/P. (The symbol ∝ employed here means positive correlation.) 相似文献
Commercial high density polyethylene (HDPE), low density polythylene (LDPE), and linear low density polyethylene (LLDPE) resins were tested at 150, 170, and 190°C in steady state, dynamic, and extensional modes. Within the low rates of deformation \documentclass{article}\pagestyle{empty}\begin{document}$ \dot \gamma $\end{document} = ω ≤ 0.3, the steady state and dynamic functions agreed: η = η′ and N1 = 2G′; at the higher rates, the steady state parameters were larger. The elongational viscosity, ηe, was measured under a constant rate, \documentclass{article}\pagestyle{empty}\begin{document}$ \dot \varepsilon $\end{document}, or stress, σ, condition. In the first case for LLDPE, the transient η reached an equilibrium plateau value, ηe. For HDPE, η increased up to the break point. For LDPE, stress hardening was recorded. Under constant stress the ηe, could always be determined; its value, within experimental error, agreed with the maximum value of η determined in a constant \documentclass{article}\pagestyle{empty}\begin{document}$ \dot \varepsilon$ \end{document} experiment. The maximum strain at break was only ε = 1.5 for HDPE and 3, to 4 for LDPE and LLDPE. The rate of deformation dependence of the η (or η′) and ηn may be discussed in terms of the Trouton ratio, RT = ηe/3η at \documentclass{article}\pagestyle{empty}\begin{document}$ \dot \gamma $\end{document} = ω = \documentclass{article}\pagestyle{empty}\begin{document}$ \dot \varepsilon$ \end{document}: RT ≤ 1.2 for LLDPE, RT ≤ 2.5 for HDPE, and RT ≤ 15 for LDPE. The PE resins were extruded at 190°C through a laboratory extruder equipped with a slit or rod die. The rotational speed of the screw varied from 0 to 90 rpm. Extrusion pressure, output, and energy were measured and correlated with the rheological parameters of the resins. 相似文献
The present paper is a case study of an application of sensitivity analysis in chemical kinetics. Emphasis is laid upon chemical interpretation of sensitivity information and on identification of the most important model important model parameters. The kinetic model for reforming of C6 hydrocarbons proposed by Mobil [14] is extended to the analysis of the behavior of n-hexane conversion in an adiabatic reactor. The importance of six initial conditions (feed composition and initial temperature) is analyzed by the computation of normalized first order sensitivity gradients (y/y) (δyi/δy). The relative importance of 21 model parameters αj is estimated by the computation of normalized sensitivity gradients of the type (αj/yi) (δyi/δαj). The influence of the decisive model parameters ΔH and ΔH (activation enthalpies of benzene hydrogenation and methyl cyclopentane isomerization, respectively) as well as operating parameters is presented. The problem of uncertainly in the value of ΔH and its influence on the model solution is also sown. Finally, some advantages of the application of normalized gradients of the explanation of process behavior are discussed. 相似文献
Viscosity measurements made by a cone-plate viscometer on polyisobutylene in decalin solutions at different concentrations and their corresponding glass bead suspensions with filler loadings up to 40% by volume are reported. The range of shear rate $ \dot \gamma $ investigated is between 0.1 and 1000 sec?1. The solutions show shear-thinning behavior, and the relative viscosity ηr of the slurries generally decreases with increasing shear rate. The results indicate two different types of mechanism, respectively at high and low shear rates. At low $ \dot \gamma $, the relative viscosity can be correlated extending relations already well known for suspensions in Newtonian liquids which are based on the mechanism of aggregate disruption. The behavior at high $ \dot \gamma $ values is believed to be due to the influence of the filler on the flow properties of macromolecules, in particular on relaxation time. Through a shifting procedure, an increase in relaxation time which depends on filler content and not on polymer concentration is shown. 相似文献
The tensile behavior of polyethylene/ethylene vinyl acetate (PE/EVA) polymer blends filled with calcium carbonate (CaCO3) was studied using tensile and viscoelastic tests. The relations between tensile properties (modulus, strength, etc) of oriented and unoriented PE/EVA-CaCO3, and void volume of polymer/CaCO3 interface, PE/EVA blend ratio, and CaCO3 content were investigated. The results indicated that the tensile strength and elongation of PE/EVA-CaCO3 decreased with CaCO3 content and PE blend ratio for unoriented PE/EVA-CaCO3 systems. In the case of oriented samples, the relative modulus (E/E, where E and E are the modulus of oriented composites and the modulus of oriented matrix, respectively) of PE/EVA-CaCO3 is larger than that of PE/CaCO3 by increasing the EVA content relative to PE and CaCO3. The value of E/E can be simply expressed as the function of void volume and CaCO3 modulus to polymer matrix modulus. 相似文献