Showing papers in "Polymer Engineering and Science in 1976"

The Halpin-Tsai Equations: A Review

Abstract: The Halpin-Tsai equations are based upon the “self-consistent micromechanics method” developed by Hill. Hermans employed this model to obtain a solution in terms of Hill's “reduced moduli”. Halpin and Tsai have reduced Hermans' solution to a simpler analytical form and extended its use for a variety of filament geometries. The development of these micromechanic's relationships, which form the operational bases for the coniposite analogy of Halpin and Kardos for semi-crystalline polymers, are reviewed herein.

Methods for predicting the thermal conductivity of composite systems: A review

Abstract: The thermal conductivity of a solid or gas filled polymer is used in processing or end use application calculations. Numerous theoretical and empirical correlations are found in the literature. A careful review of these models indictes that no one correlation or technique accurately predicts the thermal conductivity of all types of composites. The investigation indicated that for solid filled composites the Lewis and Nielsen equation fitted the experimental data best for the range of fillers tested. However, for a gas filled polymer, none of the theoretical models proved adequate. The semi-empirical approach of Harding showed considerable merit.

An experimental study of the kinetics of polymer crystallization during shear flow

Abstract: Some principles of rheology are applied to the study of the shear-induced crystallization of molten polymers. A new technique is described for measuring crystallization kinetics during isothermal flow at constant shear rate in a parallel plate rheometer. The crystallization rate is characterized by the time elapsed from the start of shearing until the rise in melt viscosity due to crystallization. The measured-viscosity and induction time for crystallization are shown to be independent of sample geometry. Kinetic data are presented for crystallization of three linear polyethylenes at shear rates of 0.03 – 30 sec−1. It is shown that shear flow has a strong accelerating effect on crystallization when the deformation rate exceeds a critical value. Comparison of results for the different polyethylenes reveals that higher molecular weight materials crystallize faster at a given shear rate and temperature. Finally, shear-induced crystallization of propylene polymers is shown to be unaffected by the presence of either a carbon black additive or a heterogeneous nucleating agent. It is concluded that the hydrodynamic origin of the shear-induced crystallization is elastic chain extension due to entanglement couplings between molecules. Furthermore, it is suggested that transient orientation effects during the startup of shear flow may have a dominant influence on the observed phenomena.

Transition behavior of poly(vinylidene fluoride)/poly(ethyl methacrylate) blends

Abstract: Previous work has shown evidence that PMMA and PEMA are miscible with PVF2. The present paper examines in detail the behavior of PEMA/PVF2 blends by thermal analysis and dynamic mechanical testing. All transitions and relaxations are affected by blond composition but in a complex manner owing to the crystallization of PVF2 from blends rich in this component. Inadequacies of the simple two-phase picture of semi-crystalline polymers is believed responsible for some of the transitional behavior observed here. The melting point depression observed for PVF2 was found to be consistent with an exothermic heat of mixing for this pair comparable in value to that found for PPMA/PVF2/All evidence here are consistent with the previous conclusion of miscibility for these systems.

Rheological changes during a urethane network polymerization

Abstract: Trifunctional poly-e-caprolactone polyol was polymerized with a chain-extended 1,6-hexane diisocyanate, and the rheology followed by cone and plate flow. Viscosity was found to be independent of shear rate up to at least 102 N.s/m2 (103 poise) and 30s−1. Extent of reaction was monitored by a periodic titration for isocyanate groups. Using branching theory, viscosity was related to extent of reaction and temperature. Such relations should be useful for process models. Normal force data for the curing system are also reported.

Residual stresses in polymers and their effect on mechanical behavior

Abstract: Plates of bisphenol-A polycarbonate and poly(methyl methacrylate) have been quenched in ice water from temperatures slightly above their glass transition temperatures. Residual stresses are thus created, Measurement of these residual stresses has been accomplished by the “layer removal” method and the stress distributions through the thickness are presented. Compressive stresses, approximately 3000 psi, exist at the surface while tensile stresses-of at least 1000 psi exist in the interior. It is shown that these residual stresses can influence the notched Izod impact strengths for polycarbonates. The mechanism is thought to be suppression of craze initiation in advance of the notch due to the presence of residual compressive stresses for specimens notched prior to quenching. In the case of poly(methyl methacrylate), it is shown that compressive residual stresses at the surface can cause plastic yielding to occur in bending experiments resulting in permanent deformation and greater energy absorption.

Properties, environmental stability, and molding characteristics of polyphenylene sulfide

Abstract: Polyphenylene sulfide is a new engineering plastic characterized by a unique combination of useful environmental, mechanical, and flame resistant properties. This paper presents a variety of new developments in molding methods and long term properties of polyphenylene sulfide. Optimum conditions for fabrication by injection molding, compression molding, and free sintering techniques are described along with a comprehensive tabulation of mechanical, factional, and electrical properties of various filled and unfilled compositions. The effect of injection molding conditions and post-treatments, such as annealing, on mechanical behavior is discussed. Long term stability of molded specimens of the polymer to a variety of chemical environments as well as oven aging studies are reported. The significance of these properties is illustrated by a discussion emphasizing new applications for various compositions based on polyphenylene sulfide.

Poly-para-xylelene: its chemistry and application in coating technology.

Abstract: The chemistry of p-xylelene and of its analogues has been reviewed. Its modes of formation and polymerization to poly-p-xylelene have been described, and the initiation and hypothetical termination steps have been discussed. The reactions taking place in the gas phase and in the deposited film are contrasted with those taking place in solutions. The problems of crystallization of the polymer simultaneously proceeding with its growth have been stressed. Finally, the properties of poly-p-xylelenes and their application in the coating industry have been described in some detail, emphasizing the special advantages of gas-deposition leading directly to a solid and coherent film. Some future fields of application of this technique have been outlined.

Crystallization from a strained melt or solution

Abstract: The elongation and orientation of randomly coiled macromolecules in a strained melt or solution reduces their entropy and thus increases the crystallization or melting temperature of the ideal lattice. At any given temperature of experiment this enhances nucleation and crystal growth rate. As a rule, linear primary nuclei are formed. They contain more or less extended chains. The existence of row nuclei reduces the local gradient in the liquid to such an extent that further crystallization proceeds by epitaxial overgrowth of folded chain lamellae. Densely packed cylindrites are formed with the ribbon-like lamellae radiating from the central row nucleus. The irregular shish-kebab structure observed in stirred or sonicated solutions seems to be formed by subsequent exial deformation of cylindrites in the flow field. It displaces the lamellae irregularly and thus produces a great many microfibrillar elements parallel to the original row nuclei. The almost completely extended chains in the shish yield a high elastic modulus and tensile strength for exial loading. The shish-kebab morphology in fibers as spun does not affect to a great extent the mechanical properties obtainable by subsequent drawing. The lamellae are transformed into microfibrils in very much the same manner as in spherulitic samples. But the highly regular orientation of lamellae seems to result in a more uniform drawing and hence a stronger fiber. In an extremely high temperature and pressure gradient, the melt extrusion produces hard elastomers where the lamellae of the cylindrites seem to be locally stapled. Upon application of tensile load in the extrusion direction, the intervening sections bend like beams, thus forming thin holes extending in the direction perpendicular to the load. The holes enormously enhance the permeability for gases and liquids. The elastic bending of lamellae yields the high recoverable strain and low tensile modulus.

The effect of molecular weight on the physical and mechanical properties of ultra-drawn high density polyethylene

Abstract: A study has been made on the effects of molecular weight on the physical and mechanical properties of cold-extruded high density polyethylene. Prior data indicate that such ultra-drawn strands contain a significant fraction of extended-chain crystals. Four samples, spanning the molecular weight range of 59,000 to 147,000, were cold-extruded under the same conditions and were examined with respect to their melting point, degree of crystallinity, linear expansion coefficient, Young' modulus, strain to break, and tensile strength. The degree of crystallinity, linear expansion coefficient, and modulus did not change significantly with molecular weight. The melting point, strain to break, and tensile strength do increase with increasing molecular weight. This leads to the conclusion that the amount of extended-chain crystals is invariant with molecular weight. Higher molecular weight polymers are seen as providing a greater number of the chains, thus giving the fiber a higher tensile strength.

Impact strength of polymers: 1. The effect of thermal treatment and residual stress

Abstract: The effect of thermal annealing and quenching on the notched Izod impact strength of several polymers has been studied. Primary emphasis was placed on polycarbonate, but ABS, PVC, polysulfone, and polymethylmethacrylate were also studied. It was determined that residual stresses created by thermal quenching from above the glass transition temperature can have a great effect on impact strength for the polycarbonate, PVC, and polysulfone polymers studied. In fact, it is shown that the thickness transition observed in impact strength for polycarbonates is governed by the residual stresses and not by thickness. In polycarbonates, quenched sheets up to 3/8 in. in thickness have shown impact strengths of 18 ft-lb/in. whereas sheets 1/8 in. in thickness can be embrittled by annealing, showing an impact strength of 2 ft-lb/in. However, it has been shown that this embrittlement results from the absence of residual stress. Residual stresses having maximum values up to 3000 psi (in Compression) have been determined at the polycarbonate sheet surface using birefringence measurement techniques. The existence of these compressive stresses is postulated to restrict the extent of craze growth at the notch tip, and the impact specimen can yield rather than fail in a brittle manner if the stress state is sufficient.

A dynamic melting model for a single-screw extruder†

Abstract: A new theoretical concept is given which provides an efficient and consistent method for predicting flow and heat transfer characteristics of the melting zone for a large single-screw extruder. In contradistinction to previous, theories, significant melt accumulation in the molten films as observed experimentally is considered, instead of postulating the melt accumulation in the “melt pool”. The mathematical model has been obtained by the simultaneous solution of the momentum and energy equation of the melt flow and. solid bed, allowing for the existence of the pressure gradient: The theory is supplemented by a numerical example which shows good agreement with experimental data obtained on a 90 mm extruder with polypropylene, where the down-channel pressure profile and me profile of the solid bed Were taken as yardsticks for the melting process. For exact determination of the area for applicability of this theory, more experimental information is required.

The SPE international award address—1975 polymerization by oxidative coupling—an historical review

Abstract: The history of PPO®, polymers of 2,6-dimethylphenol, and Noryl® resins is described from the initial discovery through commercialization. The scope of oxidative polymerization as applied principally to phenols and acetylenes is outlined as well as the chemical reactions which can be performed on the resulting polymers.

Studies on multilayer film coextrusion I. The rheology of flat film coextrusion

Abstract: Multilayer blown film coextrusion was studied, both experimentally and theoretically. For the experimental study, an annular die with a feed-port system was designed and multilayer blown films were produced by rotating the inner mandrel with a one horsepower variable-speed drive at speeds from nearly 2 to 6 rpm, and by inflating the tubular molten film with air. The die has 16 feed slots and melt pressure transducers are mounted along the axial direction of the outer wall of the annular flow channel. The transducers were used to determine the pressure gradient in the annular flow channel, which then permitted determination of the reduction in pressure drop when different combinations of two polymer systems were coextruded. Polymers used for b own film coextrusion were: (1) low-density polyethylene with ethylene-vinyl acetate; (2) low-density polyethylene with high-density polyethylene; (3) low-density polyethylene with polypropylene; (4) high-density polyethylene with ethylene-vinyl acetate. For the theoretical study, stratified helical flow was analyzed using a power-law non-Newtonian model. A computational procedure was developed to predict the number of layers, layer thickness, and the volumetric flow rate as functions of certain processing variables (namely, the pressure drop in the die, and the angular speed of rotation of the inner mandrel of the die) and the rheological parameters of the individual polymers concerned. Comparison was made of the theoretical prediction of volumetric flow rate with experimental ones. Some representative results are presented of the theoretically predicted axial and angular velocity distributions, shear stress profiles, and shear rate profiles.

Rheological properties of incompatible blends of two elastomers

Abstract: Mold flows and melt viscosities of an incompatible bi-component EPDM and “Viton” fluoroelastormer system were examined. A marked reduction in the melt viscosities of either component was observed when a small amount of the other component was present. It was speculated that the phenomenon was a result of a slippage between the polymer and the coated capillary surface due to the presence of a minor amount of the incompatible polymer. Evidence is given to indicate that this effect cannot be accounted for using the “melt structural heterogeneity” mechanism proposed for a different system by Andtrianova.

The preparation of ultra-high modulus polypropylene films and fibres

Abstract: Following the discovery that linear polyethylene can be drawn to very high draw ratios to produce oriented fibres and films with ultra-high initial moduli, a similar study has been undertaken for polypropylene. In particular, the modulus/draw ratio relationship has been obtained for a range of polymers of different molecular weight and molecular weight distribution. The effects of thermal history and draw temperature were studied, and it was shown that under optimum conditions material with an initial modulus at room temperature of 1.9 × 1010 Nm−2 (205 gdtex, 3 × 106 psi) can be obtained. This value is at least 50 percent greater than those previously recorded for drawn fibres and about one half of the theoretical modulus.

Characterization and piezoelectric activity, of stretched and poled poly(vinylidene fluoride). Part I: Effect of draw ratio and poling conditions†

Abstract: A number of investigators have reported on the high degree of piezoelectricity manifested by oriented films of poly(vinylidene fluoride) (PVF2) To develop applications for this piezoelectric effect, our laboratory is involved in a systematic investigation of the factors responsible for this remarkable behavior of PVF2 In a unique high-speed process, commercial PVF2 film was uniaxially stretched to a series of draw ratios ranging up to 7/1 The resulting films were characterized by techniques involving infrared spectroscopy, density, birefringence, sonic modulus, X-ray diffraction, and dynamic mechanical response The films were then poled at various electric field strengths, temperatures, and times Correlations have been made between draw ratio, physical properties, poling conditions, and piezoelectric activity of the films It was found that the piezoelectric activity increased to limiting values with draw ratio, poling voltage, poling temperature, and poling time It was evident that for PVF2 film a significant amount of oriented phase I crystalline material is required for high degrees of piezoelectric activity The Appendix gives the apparent rate dependence observed for the piezoelectric effect when signal is measured with a voltage sensor of relatively low input impedance

Finite Element Analysis of Calendering

Abstract: The general equations describing the flow of Newtonian and non-Newtonian fluids in the gap of two calender rolls were simplified by making use of the lubrication approximation. The resulting equations were solved by the finite element method. The results are in excellent agreement with existing analytical solutions for Newtonian fluids. New results were obtained for pressure, velocity profiles and sheet thickness of non-Newtonian fluids for symmetric and asymmetric calendering (different roll diameters, different roll speeds). The solution of this problem demonstrated the great possibilities offered by the finite element method in solving Theological problems of practical significance, particularly whenever complicated wall boundaries or free surfaces are involved.

Unlimited flex life in the molded‐in hinge in polypropylene: A structural hypothesis

Abstract: Injection molded hinges of polypropylene possess uniquely unlimited flex life. Polypropylene when crystallized from the melt under extensional flow (as in injection, molded hinges), shows a unique morphology characterized by a planar row structure of lamellae accompanied by a bimodal distribution of the unit cells having the alpha crystal phase. This bimodal orientation consists of two apparently independent orientations of the unit cells with respect to the flow direction: one with the c-(chain) axis parallel to and one with the a′-axis parallel to the flow direction. (The a′-axis is a vector normal to (100) and thus parallel to a* in reciprocal space.) Experimental data on the morphology of polypropylene crystallized under extensional flow are interpreted in terms of two components. The c-axis component corresponds to those molecules in the planar row structure. The a′-component is attributed to secondary crystallization in which small crystallites are finely dispersed between the lamellae of the row structure. These small crystallites act as a “morphological plasticizer” protecting the load-bearing row structure from destructive stress during flexure.

A review of techniques for processing ultra-high modulus polymers

Abstract: Linear crystalline polymers can be processed to high degrees of orientation sufficient to produce dramatic increases in tensile strength and modulus. Three processes have been identified for inducing such orientation: cold drawing, hydrostatic extrusion, and solution spinning. All three processes utilize a high elongational velocity gradient in a critical temperature range to produce a high strength crystalline morphology. Although the molecular superstructure may differ in each case, the mechanical properties are similar, An increase in strength is achieved either through the creation of new tie molecules between crystal lamellae or through the creation of an extended chain crystal substructure. Temperature and molecular weight are the prime variables in determining which morphology will develop. The optimum processing temperature for many of the specific techniques is the crystalline dispersion temperature. At this temperature, the crystal structure is particularly adaptable to forming a new crystal morphology. Ul-tradrawn polymers are more Hookean in behavior than isotropic polymers and have properties similar to steel and glass. Polyoxymethylene has been processed most closely to its theoretical strength. Polyethylene, which is the most difficult to process, has achieved the highest modulus of any common polyolefin polymer, about 7 × 1010 Pa.

Jetting phenomena in injection mold filling mold filling

Abstract: Experimental studies of injection molding of polymer melts have classified two regimes of mold filling–simple filling and jetting. In this paper we have examined a wide range of polymer melts and mold designs in an attempt to devise a criterion for the transition between these regimes. This criterion is found to be related to the extrudate swell d, gate diameter D, and small cavity dimension at the gate h. For isothermal mold filling, if d/h exceeds 1.0, the-melt will contact the mold, stick to it, and induce a simple mold filling regime. The variation in behavior in vertical and horizontal mold filling is considered, as is the influence of barriers near the gate. For the non-isothermal mold case, the manner of filling is similar, and the criterion for jetting remains the same, The die swell behavior in the non-isothermal case is complex.

Influence of long‐chain branching on the viscoelastic properties of low‐density polyethylenes

Abstract: Melt How data has been determined for a series of fractionated and whole low density polyethylenes which has been characterized in terms of their molecular weights and degree of long-chain branching, (LCB). The resulting data indicate that low LCB influences melt flow both through a reduction in molecular size and an increased level of intermolecular interaction. Die swell measurements on whole polymers indicate an increase in melt elasticity with increase in degree of LCB for samples of similar melt flow (MI). Comparison of GPC data with observed die swell characteristics indicates that die swell is a molecular size dependent property and independent of intermolecular entanglement effects, suggesting that the measurement of elastic properties of LDPE melts will provide a means of determining relative degrees of LCB for commercial resins.

Mechanical properties of oriented polyethylene/polystyrene blends

Abstract: Incompatible blends comprised of polystyrene and various high density polyethylenes were processed into tapes, in which both the phase and molecular orientations were parallel to the machine direction, by a combination of extrusion and mechanical stretching of the melt prior to quenching. Machine direction tensile yield strengths and ultimate elongations were found to be considerably higher than those obtained for comparable compression molded samples throughout the range of blend compositions and processing conditions investigated. Transverse tape properties were consistently poor due to poor interfacial adhesion. An optimum in machine direction properties was observed as the stretch ratio was increased at various melt temperatures. This optimum is likely due to a competition between morphological and molecular orientation rates during the stretching process and is a complex function of stretching rate and melt temperature as well as blend composition, relative phase viscosities, polyethylene crystallinity, and interfacial adhesion. Tapes stretched at high melt temperatures tended to show decreasing ductility and increasing tensile strength as room temperature storage time increased. This is believed to be due to secondary crystallization of the polyethylene phase. Oriented tapes were found to be easily fibrillated by mechanical heating to form a pulp. This material may prove suitable as a high grade replacement for cellulose pulp in paper making and could be formed at low cost from waste plastic feed stock.

Morphological changes during oriented polymer crystallization

Abstract: A theory of the stress-induced crystallization of polymeric networks is presented which takes into account 1) the free energy of fusion, 2) crystal surface energies and 3) entropic changes in the amorphous sections of crystallizing chains. It is assumed that the vector running from one end to the other of the crystallite is oriented in the direction of network extension, irrespective of crystal morphology, thus minimizing the free energy of crystallization. Assuming that the network assumes the crystal morphology which minimizes the free energy of the network at a given degree of crystallinity and that the crystallization proceeds along this lowest free energy path, it is predicted for simple network extension that growth of a perfectly oriented extended-chain crystal occurs initially, changing to a one-fold crystal oriented perpendicular to extension at low extension and to a two-fold crystal having nearly perfect orientation at High extension. The stress is predicted to decay initially and then to rise as the network chains switch from an extended-to a folded-chain morphology. Spatial factors which may trap chains in the ex tended-chain morphology or prematurely stopping the crystallization process can result in a mixed crystal morphology. At high extension, the structure is similar to that of the shish kebab.

Flow-induced crystallization of linear polyethylene above its normal melting point

Abstract: The phenomenon of flow-induced crystallization was investigated using a linear polyethylene above its normal melting point flowing continuously in a Biconical Rheometer. It was found that the resin crystallized in the superheated state at rates which increased with increasing shear rate and decreasing temperature. A method of analysis of the temperature dependence of the various stages of flow induced crystallization is proposed. It deals with and attempts to explain the experimental fact that a higher viscosity enhances the rate of flow-induced crystallization in contrast to the effect of viscosity on the rate of quiescent crystallization. Some of the flow-induced crystallization samples were transparent and exhibited a high DSC thermogram “tail”.

Strain‐induced crystallization I. Limiting extents of strain‐induced nuclei

Abstract: This paper points out that interpretations from stress changes alone during oriented crystallization have led to widely different proposed chain conformations and consequently very different crystallization mechanisms for strain-induced crystallization (SIC). Many of the proposals, including the one by Keller and Machin which takes into account some electron microscopy and X-ray observations, show varying degrees of incompatibility with existing stress relaxation, kinetic or morphological data on SIC. Another problem lies in the difficulty with proper interpretation of observed morphology on samples which have been Subjected to additional thermally-induced crystallization (TIC) after SIC, especially, in the absence of prior characterization of SIC crystallites, the finding of a fibrillar-to-lamellar transformation in stretched polymers upon additional TIC (Part H) also indicates that the generally-observed oriented lamellar morphology has a much more subtle origin than-that depicted by most crystallization models. Part I discusses our previously published morphological data on the characteristics of SIC crystallites from the melt, which includes: (a) their melting point elevation, (Tm » T°m), (b) their nearly perfect crystalline orientation function (fc ∼ 1), (c) their fast rates of crystallization (t1/2 < 1 sec), and (d) their fibrillar morphology and limited dimensions along the fibrillar stretch axis (∼100A). Examples of morphology of SIC from the glass and from stirred solution are also included to show the overall similarity of fibrillar morphology brought about by stretching.

A generalized melt viscosity-temperature dependence for styrene and styrene-acrylonitrile based polymers

Abstract: The dependence of the melt flow of polymers on temperature is of both theoretical and commercial importance. A useful representation of the temperature dependence of the shear-dependent viscosity, based on superposition of flow curves at various temperatures, has previously been presented by the author for several olefin polymers. This method is extended in the current work to styrene and styrene-acrylonitrile based polymers. The melt viscosity-temperature dependence of a broad range of styrenic polymers and copolymers, ranging from polystyrene to 82 percent AN styrene-acrylonitrile copolymer, with and without rubber inclusions, was investigated. Flow curves at the various temperatures were found to be superimposable, as had earlier been found to be the case for olefin polymers, and a unique quantitative relationship between the superposition shift factors and temperature was found applicable to the entire family of polymers. The resultant energy of activation for viscous flow is in excellent agreement with previously published results for polystyrene Newtonian viscosities, and the magnitude of the shift factors is consistent with a limited set reported for ABS polymers. Independent tests of the derived relationships provided excellent prediction of measured viscosities. Thus, it is considered that a general viscosity-temperature relationship has been defined for this family of polymers, independent of molecular structural detail.

Predictions of limiting mechanical performance for anisotropic crystalline polymers

Abstract: A four-stage synthesis of molecular, micromechanical, and macromechanical models is used to predict the dependence of the longitudinal and transverse Young's moduli and the axial and transverse shear moduli of anisotropic polyethylene on percent crystallinity and the state of molecular orientation. Variational methods are employed to establish the upper and lower limits for anisotropic elastic response. The difference between lower and upper bound limits is interpreted as the potential for improving mechanical performance. A modified form of the Tsai-Halpin equation is used to examine parametric ranging (via a contiguity factor, ξ) between the lower and Tupper bound limits. In this application, the contiguity factor is interpreted as a characteristic of the internal stress-strain distribution which is dependent upon the size, shape, packing geometry, and elastic properties of the crystalline and amorphous regions. The potential for achieving high modulus polymeric materials is illustrated by treating percent crystallinity, molecular orientation, and contiguity as materials design variables subject to control by processing conditions. Optimum property trade-offs, necessary for balancing the over all mechanical behavior of anisotropic materials, are illustrated through the control of orientation and contiguity, The theoretical predictions for the moduli of anisotropic polyethylene are in good agreement with values reported for material processed by traditional procedures as well as ultra-oriented polyethylene.

Annealing effect on the microstructure of poly(vinyl chloride)

Abstract: The effect of annealing on the microstructure of commercial grade poly(vinyl chloride) was investigated by calorimetric, X-ray and viscoelastic measurements. The degree of crystallinity increases with increasing annealing temperature from above the glass transition temperature up to 130°C, at which point the degree of crystallinity takes on a maximum value. Also, the crystal melting temperature increases with increasing annealing temperature. Thermal analysis and X-ray study suggest that the crystallite of poly (vinyl chloride) decomposes by thermal degradation when annealed, above 170°C. The isothermal crystallization process is analyzed using Avrami's equation employing the degree of crystallinity as a function of annealing time at various annealing temperatures. The crystallization rate has a maximum value at around 140°C. It is expected that the crystalline texture grows in the shape of a lineal-like habit, judging from the magnitude of Avrami's constant and from a study of the X-ray intensity distribution. The αf-transition was observed to occur at temperatures 5 to 10°C lower than the crystalline melting temperatures for annealed specimens of poly(vinyl chloride) using a dynamic spring analysis. The αf-transition may be attributed to thermal molecular motions with a long time scale, resulting from the cross-link points introduced by the small crystallites.

Rotational molding heat transfer—an update

Abstract: In earlier works, a complicated circulation model was chosen to describe heat transfer to powder in a rotating mold. In order to satisfy the model, an experimentally-determined empty mold temperature response was used. An alternate heat transfer model, in which the powder is assumed to be in static contact with the mold surface at all times, shows significant temperature deviation from the earlier model. The predicted time for complete sinter-melting is much closer to earlier experimental data than the predicted times from the circulation model. The melting time is seen to follow the form given by the Goodman penetration model. Complete heating and cooling profiles are more easily generated using this static model, and a new interpretation of the air cooling step in the heat transfer cycle results.