Effect of sub-Tg annealing on CO2 sorption in polycarbonate

High pressure CO₂ sorption data in polycarbonate (PC) are reported as a function of temperature and thermal history. The bulk physical structural changes produced by annealing at 125 and 135°C were monitored by density and thermal property changes. The sorption data are analyzed by the dual sorption model which assumes the sorption isotherm to consist of Henry's law and Langmuir sorption terms; The Langmuir capacity term C of PC can be grossly correlated with the reported volumetric parameters of the polymer. This excess volume interpretation of C has found support in the good correlation between C and the corresponding enthalpy relaxation from parallel Differential Thermal Analysis of the samples. Density measurements provide gross evidence of the free volume interpretation of C. The experimental uncertainties in the data compromise a more critical test of the relationship between C and the density of annealed samples.     

Numerical and experimental investigation of three-dimensional flow in extrusion dies

The univariant element, Q₁ P₀, and the multivariant elements, QP₀ and R P₀, are compared for the numerical simulation of the flow in extrusion dies. The pressure distribution obtained by using the Q₁ P₀ element was found to be afflicted with the checkerboard pressure mode. On the other hand, the multivariant elements, Q P₀ and R P₀, gave accurate and physically reasonable velocity and pressure distributions. The computed values of the pressure drop across extrusion dies matched well with the pressure drop determined experimentally.     

Characterization of crystallinity,orientation, and mechanical properties in biaxially stretched poly(p-phenylene sulfide) films

In this paper, we describe the preparation and structural characterization of biaxially oriented poly(p-phenylene sulfide) (PPS) films. These films were prepared in a biaxial stretching machine at various stretching temperatures, rates, and stretching ratios. Selected samples were constrained annealed at elevated temperatures. The state of orientation was determined by wide angle X-ray diffraction (pole figure determination) and birefringence measurements. The results are expressed in terms of the biaxial orientation functions (?,?). Mechanical properties (tensile modulus, tensile strength, and elongation to break) were obtained as a function of processing conditions and direction in the plane of the films.     

A quantitative description for the optical properties of crystalline polymers applied to polyethylene

A quantitative model which described the microscopic and macroscopic refractive index properties of uniaxially oriented crystalline polymers has been extended in relation to molecular bond polarizabilities in this work. Application of this extended modeling methodology in analyzing measured refractive index data for a series of unoriented and oriented samples of linear polyethylene provided Δ = 0.0585 and Δ = 0.194 as the most probable crystalline and noncrystalline intrinsic birefringences for samples exhibiting spherulitic morphology. With these intrinsic birefringences, noncrystalline orientation functions were determined from the optical measurements coupled to the model and the results compared to values obtained from infrared measurements. This comparison of noncrystalline orientation functions, as well as from low density polyethylene reported by other investigators, provided experimental justification for our modeling methodology to examine the possibility of changing intrinsic birefringences for polyethylene as a function of orientation and morphology. The results of this examination demonstrated that values for Δ = 0.0585 and Δ = 0.12 should be used for both low and high density polyethylene samples oriented above the spherulitic to fibrillar transition region.     

Highly oriented polyacetylene: Structures and electrical conductivity of the compounds doped with alkali metals and selected oxidants

Films of polyacetylene synthesized according to Akagi method present a high degree of crystallinity. A 6-7 times stretching of these films results in the orientation of the polymer fibers: The mosaic was ± 5 degrees. Such highly oriented polyacetylene (HOPA) films were chemically doped by heavy alkali metals in the vapor state and electrochemically with GaCl anion in nitromethane medium. The evolution of the structures and the variation of the electrical conductivity upon doping were examined in both cases. Doping with alkali metal leads to the appearance of different intercalated phases: The commensurability of these phases is discussed as a function of the nature and the concentration of the intercalated alkaline ion. The electrical maximum room temperature conductivity, which depends on the nature of the alkali metal, is maximum for K-doped materials. In the case of GaCl doping, the unique intercalated phase observed is poorly organized except in the chain direction where a GaCl ion is found every 4.5 (CH) units. The room temperature electrical conductivity measured along the chain axis is equal to 15 000 S/cm, one order of magnitude higher than the value observed in Shirakawa unoriented polyacetylene.     

Viscoelasticity of some engineering plastics analyzed with the modified stress-optical rule

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, C_R and C_G, 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, C_R, equivalent to the stress-optical coefficient in melts, mainly depended on the way in which phenyl groups were connected to the chain. The other, C_G, 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.     

Molecular weight and molecular weight distribution from dynamic measurements of polymer melts

A method for determining the molecular weight distribution (MWD) of a polymer melt has been developed using the dynamic elastic modulus (G'), plateau modulus (G), and zero shear complex viscosity (η). The cumulative MWD was found to be proportional to a plot of (G'/G)^0.5 vs. measurement frequency (ω). Frequency (ω) was found to be inversely proportional to (MW)^3.4, as expected. Results were scaled to absolute values using the empirical relationship η ∝ (M?_w)^3.4, where M?_w is the weight-average MW. M?_w, M?_n (number-average MW) and M?_w/M?_n calculated from melt measurements were found to agree with size exclusion chromatography usually well within 10 percent for broad and bimodal distribution samples. M?_w/M?_n tended to be approximately 20 percent higher for narrow distribution samples (M?_w/M?_n < 1.2) because we did not account for a finite distribution of relaxation times from a collection of monodisperse polymer chains. We also did not account for the plasticizing effect of short chains mixed with long ones which caused peak positions to be closer together for Theological vs, size exclusive chromatography (SEC) determinations of MW for bimodal distribution blends.     

Strain-induced crystallization,Part III: Theory

A nucleation theory for strain-induced crystallization is formulated to explain and to predict the effects of molecular strain on crystallization kinetics and crystallite size. Unlike any current theories that have based their formulations on some assumed extended-chain line nuclei or folded-chain crystals, the present theory avoids all assumptions concerning the crystal morphology. It is based on experimental findings which indicate limited crystal growth in the strain direction, following a reciprocal dependence of crystal thickness on supercooling ΔT. (ΔT = T, ? T, where the equilibrium melting temperature, T, is a variable dependent on degree of molecular strain prior to strain-induced crystallization.) It is predicted that the logarithm of the nucleation rate, N^o, is dependent on (T)²/T(ΔT) or T/T(ΔT), and that the critical nucleus thickness l^*o is shown to be proportional to T/ΔT. In addition, expressions are also presented, including examples, to show the dependence of N^o, l^*o and T^o_m on degree of molecular strain, ?, or melt entropy reduction, Δs′. Our analysis predicts that, on comparing a polyethylene crystallized in the presence of strain to one crystallized in the absence of strain at 130°C, an increase in “coil” dimension of less than about 50 percent can bring about a 10⁴ fold increase in heterogeneous nucleation rate, a 30–40 percent reduction in critical nucleus thickness and a 10°C increase in equilibrium melting temperature. These results will be discussed and compared with available experimental evidence.     

Corona-discharge treatment of polyethylene films. I. Experimental work and physical effects

Corona treatment of films, mainly polyethylene, was studied at commercial levels in a small continuous treater. Degree of treatment was characterized by measuring polar and dispersion components of surface energy, ASTM Wipe and ASTM Adhesion Ratio (“peel adhesion”). The chief factors studied were corona current, applied frequency, web speed, dielectric thickness and air-gap thickness between electrode and film. Other factors less intensively investigated were type of film, film additives, aging time after treatment, humidity and corona atmosphere. The polar component of surface energy, γ, is the key to understanding the changes in adhesive behavior of the films during treatment. We found that, for the equipment used, γ is accurately given by the equation where D = dielectric thick ness and G = air gap, both in mils; S = web speed, ft/min; I = corona current, ma, and γ is in dyne-cm/cm². A similarly structured equation describes ASTM Wipe. Using measured surface-energy components for the pressure-sensitive tape used in the peel adhesion test, it was possible to calculate an adhesion interaction for each film on which peel adhesion was measured and to show that it closely correlates with peel strength. Humidity changes in the moderate-humidity range, number of electrodes used and corona frequency had little effect on properties. Slip additives inhibited development of adhesion until treatment levels became high; adhesion properties gradually diminished upon aging of films stored at ambient conditions.     

Several features of vinyl chloride–diallyl phthalate suspension copolymerization

Vinyl chloride–diallyl phthalate (VC–DAP) suspension copolymerization was carried out in a 5‐L autoclave and 200‐mL stainless steel vessel at 45°C. The apparent reactivity ratios of VC–DAP suspension copolymerization system were calculated as r_VC = 0.77 and r_DAP = 0.37. It shows that VC–DAP copolymer contains no gel when the feed concentration of DAP (f) is lower than a critical concentration (f_cr, inside the range of 0.466–0.493 mmol/mol VC at 80–85% conversion), the polymerization degree (DP) of copolymer increases with the increase of f and conversion. VC–DAP copolymer is composed of gel and sol fractions when f is larger than f_cr. The DP of sol fraction decreases as f increases, but the gel content and the crosslinking density of gel increase. The gel content also increases as conversion increases. The results also show that the index of polydispersity of molecular weight of sol changes with f, a maximum value appears when f is close to f_cr. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 156–162, 2000     

Electron sensitive negative resists of vinylaromatic polymers

Electron resist properties of three vinylaromatic polymers, polystyrene, polyvinylcarbazole and poly(3-bromo-N-vinylcarbazole) have been examined. Polystyrene and polyvinylcarbazole are high contrast resists of high dry etch resistance, but for adequate sensitivity (D ? ca. 10 μC/cm² at 25 kV) high molecular weights are needed (M _w ? 10⁶). Poly(3-brotno-N-vinylearbazole) has a much higher sensitivity (D = ca. 2 μC/cm²) than the unsubstituted polymer. The sensitivity of polystyrene and polyvinylcarbazole is increased appreciably by addition of organic bisazides as crosslinking agents, e.g. a sensitivity increase of almost an order of magnitude was found upon addition of 3% 4, 4′-diazidostilbene to polystyrene, high contrast being maintained.     

Uniaxial and biaxial orientation development and mechanical properties of polystyrene films

Uniaxially and biaxially oriented polystyrene films were prepared in a biaxial stretching machine. The state of orientation was determined by birefringence measurements and represented in terms of a set of biaxial orientation factors ?. The data are plotted on an isosceles triangular diagram whose coordinates represent the orientation factors ?, ?. Tensile force–elongation curves were obtained on the films in the machine stretching direction (MSD) and at various angles to the MSD in the plane of the film. The isotropic film is brittle, while uniaxial films yield in the machine direction but are brittle in the transverse direction. The biaxially oriented films exhibit ductile yielding in all directions in the plane of the film.     

Contribution of polyalkyl(meth)acrylates to the design of PVC melt viscosity

The shear viscosity of poly(vinylchloride) (PVC) at 200°C can be decreased by at least one order of magnitude by the addition of as little as 5 wt% poly n-alkyl-(meth)acrylates (PMA) of a much lower dynamic viscosity than PVC. For this effect to be observed, the polymeric additive must be immiscible with PVC at 200°C. The average size of the dispersed phases is observed in the range of 0.5 to 5 μm; size fluctuation in this domain has no significant effect. When these conditions are met, there is a linear increase in the shear viscosity ratio η_blend/η_PVC from 0.2 to 1.0 with increasing logarithmic values of the dynamic viscosity ratio of the additive over PVC [(log(η/η)) from −4 to −1].     

The influence of inclusion geometry on the elastic properties of discontinuous fiber composites

Simplifying assumptions are used to reduce micromechanical treatments to compact expressions which directly reveal the role of the inclusion shape and aspect ratio in establishing the elastic behavior of heterogeneous materials. Attention is directed to the comparison of aligned ellipsoidal and cylindrical inclusions that exhibit transversely isotropic behavior characterized by five independent elastic constants. These comparisons show that the effective transverse in-plane moduli (E, k* and G) are essentially independent of inclusion shape for aspect ratio greater than ～ 20; ellipsoidal inclusions provide higher longitudinal reinforcement than cylindrical inclusions of equivalent aspect ratio. Comparison of predictions with measured elastic moduli shows that both the cylindrical and ellipsoidal shape models for isolated inclusions overpredict longitudinal elastic constants for systems which exhibit evidence of inclusion agglomeration. The notion of an effective aspect ratio based on clusters of filaments responding as a coherent unit appears to provide a means for reconciling a wide range of experimental observations.     

Intrinsic birefringence of nylon 6

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.     

The apparent rate constant model for kinetics of radical chain copolymerization: Chemical-controlled process

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.     

Forced oscillations in continuous flow stirred tank reactors with nonlinear step growth polymerization

The self-step growth polymerization of RA_f monomers in homogeneous, continuous flow stirred tank reactors (HCSTRs) is simulated under conditions of periodic feed concentration (with frequency ω and amplitude α). By having periodic operation, the polydispersity index of the polymer is found to increase by about 35% over the values at steady state. Periodic operation of HCSTRs is found to lead to gelation only for certain values of the frequency and the dimensionless residence time τ^*. Gelling envelopes have been obtained to give conditions under which HCSTRs should be operated. These envelopes can be described in terms of two critical dimensionless residence times, τ and τ such that nongelling operation is always ensured when τ^* < τ. For τ^* > τ, periodic operation always leads to gelation, and HCSTRs cannot be used. For τ < τ^* < τ, the gelling behavior is found to depend on the functionality f, amplitude α, and the dimensionless residence time τ^*.     

Thermal properties of poly(vinyl cyclohexane)

Isotactic poly(vinyl cyclohexane) (PVCH) was studied by thermal analysis. The deduced equilibrium melting point, T, is 405°C (678 K). The heat of fusion, Δ H was found to be 50.82 J/g (5.60 kJ/mol) and Δ C_p at T_g, is 0.273 J/(gK) [30.1 J/(molK)]. The glass transition temperature, T_g, of the amorphous PVCH is 80°C (353 K). In semicrystalline samples, T_g increases up to 165°C (438 K) for crystallinities > 40%. Beside crystalline and flexible amorphous, a rigid amorphous phase is postulated in the semicrystalline polymer.     

Spherulitic crystallization behavior of linear low‐density polyethylene

In this study the crystallization behavior of linear low‐density polyethylenes (LLDPEs) (ethylene‐α‐olefin copolymers) was studied by polarized light microscopy. A modified Hoffman‐Lauritzen (MHL) expression is proposed whereby the equilibrium melting temperature, T (T), is replaced with the melting temperature of the crystal stem is replaced with the maximum possible stem length, T. It successfully describes the crystalline spherulitic growth kinetics for both homogeneous and heterogeneous LLDPEs. In addition to regimes III and II, another regime (IM) was found in the high crystallization temperature range. Linear growth behavior of crystalline spherulites was observed in regime III, and nonlinear growth behavior was found in regimes II and IM. The basal surface free energy can be estimated from the short chain branching polydispersity (SCBP) for LLDPEs with excluded comonomers. Polym. Eng. Sci. 45:74–83, 2005. © 2004 Society of Plastics Engineers.     

Tearing mode interlaminar fracture toughness of composite materials

The Simplified Split Cantilever Beam (SSCB) is proposed in this work and compared with the Split Cantilever Beam (SCB) to obtain the tearing mode interlaminar fracture toughness. The materials considered are single‐fiber system composites and interply hybrid composites. For interply hybrid composites, three different types of stacking sequence for SSCB specimens, which are [0/0//0],[0/0//0]. and [0/0//0], are tested to compare their suitability. Finite element analysis combined with a modified crack closure integral has been applied to separate the different components of the strain‐energy release rate. In addition, the method of compliance calibration was used to calculate Gc values. The effects of crack growth, initial crack length, specimen width, and number of glass fiber plies were also studied. The results show that SSCB testing has a more dominant Mode III component and more stable Gc values than SCB testing. For SSCB testing, the crack growth and the specimen width for the range considered have no clear effects on the interlaminar fracture toughness, but the initial crack length should be carefully selected to obtain corrected values. The tearing mode interlaminar fracture toughness of interply hybrid composites is higher than that of carbon/epoxy composites, and the three different types of stacking sequence considered are all suitable to approximate the Mode III interlaminar fracture toughness for interply hybrid composites.