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Two-dimensional time-domain 1H NMR was used to investigate annealed isotactic polypropylene in the solid phase. The spin–lattice relaxation in the laboratory frame and in the rotating frame were correlated with the shape of the free induction decay to identify and characterize relaxation components over the temperature range −120 to 120 °C. Several phase transitions were observed, and three distinct solid phases, with different chain mobilities, were detected. Two of these phases were identified as regions with different mobilities within the crystalline phase. The third phase was characterized by a high degree of isotropy in molecular motion. This phase, identified as the amorphous phase, appeared as the polymer was heated above a low-temperature (−45 °C) phase transition. All transitions observed at higher temperatures occurred exclusively in this phase. About one-third of the polymer chains reside between crystalline lamellae, whereas the majority form amorphous regions outside fibrils of multilamellar structure. Furthermore, the glass-to-rubber transition, occurring above −15 °C, consists of three stages. During the first stage, between −15 °C and 15 °C, regions with an increased segment mobility (labeled intermediate phase) appear gradually within the amorphous phase. At 15 °C, the intermediate phase consists of ∼10% of the polymer units, or one-third of the polymer units constituting the amorphous phase. Between 15 °C and 25 °C, the intermediate phase increases rapidly to 18%. This is associated with the appearance of semiliquid and liquid regions, likely within the intermediate phase. Polymer chain segments (and possibly entire chains) involved in the liquidlike phases exhibit heterogeneous molecular motion with a correlation frequency higher than 106 Hz. These two stages of glass-to-rubber transition occur within amorphous regions outside multilamellar structures. The third stage of the glass transition, appearing above 70 °C, is associated with the upper glass transition and occurs within the interlamellar amorphous phase. Finally, on a timescale of 100 ms or less, spin diffusion does not couple the amorphous regions outside fibrils with crystalline and amorphous regions within multilamellar fibrils. However, on a timescale of hundreds of milliseconds to seconds, all different regions within isotactic polypropylene are partially coupled. It is proposed that the relative magnitude of the crystalline magnetization, as observed in the T1ρ experiment, is a good measure of polymer crystallinity. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2487–2506, 2000

The intensities and lifetimes of positrons annihilating in low and high density poly(ethylene) (LDPE and HDPE) were measured. As expected the orthopositronium (oPs) pick-off lifetime and intensity increases with temperature; the relative values of the intensity are consistent with differential scanning calorimetry (DSC) results. Two other components with shorter lifetimes were deconvoluted from the complex exponential decay profiles. Detailed studies were carried out on quenched and annealed samples of LDPE and HDPE in an attempt to correlate the two shorter components with crystallization; both CsF and plastic scintillators were used. DSC analyses were also carried out. We conclude that the shortest lifetime component is caused by a combination of parapositronium (pPs) decay and the annihilation of free positrons in the crystalline regions and that the second longest lived component can also be associated with crystalline regions especially the crystalline/amorphous boundary.

The mechanical properties of blends of isotactic polypropylene and high-density polyethylene with a postconsumer resin (recycled dairy containers) were investigated over the entire composition range. Modification of these blends with an ethylene/propylene/diene copolymer or an ethylene/vinyl acetate copolymer was also investigated. Isotactic polypropylene/postconsumer resin blends have satisfactory impact and tensile properties at postconsumer resin contents of less than 50% for certain applications. At higher postconsumer resin contents, the tensile properties were adversely affected. The impact properties remained satisfactory. Addition of an ethylene/propylene/diene copolymer improved the mechanical properties of these blends to levels equal to or greater than those for neat isotactic polypropylene. Ethylene/vinyl acetate copolymers were also able to improve the mechanical properties, but not as efficiently as did the ethylene/propylene/diene copolymer. Blends of high-density polyethylene and a postconsumer resin had poor impact and tensile properties. Although the ethylene/propylene/diene copolymer and ethylene/vinyl acetate copolymers were able to improve these properties, the improvement was insufficient for general recycling, except at lower (≤25%) postconsumer resin contents. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 2081–2095, 1998

In this report, we present the results of our investigation into the crystallization behaviour of polyproplene. The crystallization process was followed by hot-stage optical microscopy, differential scanning calorimetry, and dynamic mechanical methods. As well, nuclear magnetic resonance spin-spin relaxation techniques were employed to probe the morphology of the polypropylene. Nucleation in this isotactic polypropylene was athermal and appeared to be heterogeneous. The dependence of the onset temperature of crystallization on the annealing temperature and on the annealing time indicated that PP nuclei were able to survive the melting process. Nuclear magnetic resonance spin-spin relaxation experiments indicated that the PP melt contained a significant proportion of regions of high segment density. It was postulated that these ‘ordered’ regions acted as nucleation sites for PP crystallization, and that the number and size of these regions was determined by the annealing time and temperature. Addition of HDPE to PP resulted in melting-point depression and plasticization of the PP phase at lower HDPE contents. HDPE was able to penetrate the PP phase sufficiently at lower HDPE contents to reduce the number and size of regions of high segment density, thereby delaying the nucleation and subsequent crystallization of the PP phase.

With two-dimensional time-domain NMR analysis in the proton spin rotating frame, three phases are identifiable in the solid polyethylene. The major proton magnetization fraction is due to the polymer's crystalline region, where the motion is least isotropic and slowest. A magnetization fraction with intermediate relaxation rate is also intermediate in magnitude. This component is proposed to comprise chain loops on the surfaces of crystallites and effectively entangled chain segments. The most mobile fraction, which is most liquid-like with a T2 of near 1 ms at 120°C, is also the smallest. It is proposed that it is due to polymer chains in the amorphous phase. In the crystalline phase the chain motion is an unexpectedly effective relaxation mechanism at ∼50 KHz. This process, which involves propagation of a twisted region along the crystallite, as has been suggested before, is either not present in the other two phases of the HDPE or is less efficient because of the lower polymer density. The activation energies for the crystalline, intermediate and amorphous phases are estimated to be 34 ± 3, 13 ± 3, and 8 ± 2 Kcal/mol, respectively. The frequencies of the relaxation process at 120°C are 43 KHz, 350 KHz, and 1.5 MHz, respectively. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 2551–2558, 1997

The basic features of a three-step experimental process to produce supermicron polymer particles are described. First, a submicron emulsifier-free latex is prepared by a well-known technique. Second, the latex is aggregated by destabilizing with cetyl pyridinium chloride under constant stirring conditions, to yield roughly spherical clusters of 6-12 μ diameter. Third, the aggregates are stabilized with poly(vinyl alcohol) and internally coalesced by heating at or above the glass transition temperature. The final product particles have relatively smooth surfaces. Results are qualitatively interpreted in terms of a dynamic equilibrium where the aggregate size is determined by a balance between attractive interparticle potentials and stirring shear forces. Bimodal aggregate size distributions suggest the aggregate break-up mechanism may involve the erosion of individual latex particles and small fragments from the surface of aggregates. © 1996 John Wiley & Sons, Inc.

The mechanical properties of high-density polyethylene (HDPE)-rich i-PP/HDPE blends were studied. Two grades of HDPE were investigated, one with a melt viscosity close to that of the polypropylene (PP) and the other having a much lower melt viscosity. Compatibilization of the 10/90 i-PP/HDPE blend with three copolymers (an ethylene/propylene/diene [EPDM] copolymer and two ethylene/vinylacetate [EVA] copolymers, differing in their VA content) was also investigated. Blends of PP with the low melt viscosity HDPE displayed poor mechanical properties. It was not possible to improve these properties sufficiently with EPDM or EVA. In the case where viscosity matching was achieved between PP and HDPE, addition of i-PP (up to 30%) to HDPE resulted in a large drop in the impact strength of the blends, compared to that of the neat HDPE. A large drop (>50%) was also observed in the ultimate tensile elongation. However, the flexural modulus, yield stress, and ultimate tensile strength all increased with the introduction of i-PP into HDPE. Modification of these blends with an EPDM resulted in the return of all properties to values very close to those of the neat HDPE. The ultimate tensile elongation of the EPDM-modified i-PP/HDPE blend even exceeded that of the virgin HDPE. It was also found that although EVAs can be used to compatibilize these blends these additives were not as effective as was the EPDM. © 1996 John Wiley & Sons, Inc.

A low-density polyethylene was shear modified by repeated extrusions. These operations resulted in no detectable changes in the polymer molecular weight distribution. The apparent melt viscosity and elasticity decreased after extrusion, as is commonly observed in shear modification. These rheological effects were fully reversible by annealing the melt. Transverse proton relaxation measurements showed the existence of four identifiable different regions in the polymer melt. The range of relaxation times encompassed two orders of magnitude. These reflect the existence of regions with different degrees of conformational order. Shear modification results in the breakup of a minor proportion of the most constrained regions, which have the shortest relaxation times. The apparent “entanglements” that are inferred from rheological measurements probably reflect the coexistence of segments of more than one macromolecule in chain-folded domains, as indicated by molecular dynamics calculations. These results are evidence that the equilibrium state of LDPE is not a chain-entangled, highest entropic condition, but rather a lowest free energy state in which chain folding is favored. They are consistent with other longstanding observations, such as the failure of experiments to produce amorphous polyethylene and the apparent lack of mixing of HDPE and LDPE on a molecular level.

Three commercially produced polymer samples (polyethylene, polypropylene, and polystyrene) have been analyzed in the melt state using proton nuclear magnetic resonance (NMR) T 2 relaxation methods using the Carr-Purcell-Meiboom-Gill (CPMG) spin-echo pulse sequence. Samples were run with exposure to air and again after extensive degassing at a vacuum of 10 -4 mmHg for periods of not less than 96 h. The comparison is made by initially considering the presence of microscopic voids in the samples as a source of local field inhomogeneity and how they affect the T 2 relaxation behavior. For PP and PS samples, degassing caused a decrease in all T 2 time constants associated with the multicomponent decays. The component intensities each of the time constants was also significantly altered. For the PE sample, degassing caused a decrease in the time constants associated with the amorphous material in the molten polymer. Examination of the fastest relaxing component of the three component decay showed approximate invariance in the T 2 decay constant. This result supports our previously reported model in which that fast relaxing component is attributable to regions of local order or high segmental density within the molten polyethylene, a remnant of the crystalline material which exists in the premelting bulk polymer. The results of this research are of particular significance to those who wish to use this NMR technique as a quantitative method of determination of NMR distinct morphological regions within heterogeneous polymers

Past work has shown that addition of high-density polyethylene (HDPE) to polypropylene (PP) resulted in a significant reduction in the elongation at break and in the gate-region impact strength of injection molded articles. In this study, we report on the compatibilization of these blends with ethylene/propylene/diene monomer (EPDM) or ethylene/vinyl acetate (EVA) copolymers. EPDM is effective at improving the impact strength and gate puncture resistance of a 90/10 PP/HDPE blend. EVA, on the other hand, is effective at improving the impact strength and the elongation at break of this material. It was also found that EVA is a better impact modifier for PP than is EPDM. DSC analysis indicated that EPDM, when blended with PP, caused a significant reduction in the degree of crystallinity of the PP. This was not observed in the case of EVA/PP blends. Further, our results indicate that care must be taken in designating a particular material as a better compatibilizer than some other material. It is crucial that conditions be attached to the label compatibilizer, indicating in particular the desired mechanical properties of the blend. © 1996 John Wiley & Sons, Inc.

The amount of divinylbenzene (DVB) that can be incorporated in a one-shot dispersion copolymerization with styrene to form a coagulum-free latex is low (

An ethylene–octene linear low-density polyethylene (LLDPE) was treated with peroxide in a reactive extrusion system. A counterrotating nonintermeshing twin-screw extruder (System 2) was contrasted with a corotating intermeshing twin-screw machine (System 1). In System 2, the peroxide solution was pumped into the melted polymer, while it entered with the polymer pellets in the feed section of System 1. Molecular structure changes and the rheological behavior of peroxide-modified resins are similar in both operations but System 2 is much more effective. Much lower peroxide levels were needed in System 2. However, reactions in this setup were also more difficult to control. The presence of microgel was clearly evident in System 2 products but not in those made in System 1. The results of such reactive extrusion processes depend critically on the method of the peroxide feed and mixing conditions. Reaction conditions that favor optimum economy and peroxide efficiency are those which may compromise product homogeneity. © 1996 John Wiley & Sons, Inc.

The effects of reactive extrusion with peroxide have been compared for two linear low-density polyethylenes (LLDPEs). Resin C is a butene copolymer, while Resin B is an octene-ethylene copolymer. Both have similar molecular weight distributions, but Resin B is significantly richer in terminal vinyl groups. Under the same reactive extrusion conditions, Resin B is much more reactive. Resin C is easier to process in this system, producing products clean of microgel. Concurrently, however, a given peroxide level produces less molecular weight enhancement and long-branch formation in Resin C. Reactive extrusion with peroxide is suitable to effect improvements in the processability of LLDPEs for film applications, provided that the choice of peroxide and the process details are tailored to the characteristics of the particular LLDPE.

Matrix assisted laser desorption/ionisation time-of-flight mass spectrometry (MALDI-TOF MS) is used to mass characterise several low molecular weight, commercially available PS, PMMA and PEG samples. In addition, the utility of the technique for the study of polymer synthesis is demonstrated; different initiation and termination mechanisms leave dead chains with characteristic end groups which, in many cases, can be rapidly identified mass spectrometrically. There is broad agreement between MWDs derived from MALDI spectra and those obtained from conventional GPC analysis, but in some instances the differences are significant. Polydispersities obtained mass spectrometrically are invariably lower than those determined by GPC.

Commercial ethylene–octene linear low-density polyethylenes (LLDPEs) were reactively extruded with low levels of a peroxide [2,5-dimethyl-2,5-di(t-butylperoxy)hexane] to modify polymer molecular structure and processing properties. Peroxide levels were kept low to avoid crosslinking. This article reports the effects of this reactive extrusion on viscoelastic properties. Rheological properties are more sensitive than are molecular structure characteristics to the changes produced by reactions of very low peroxide concentrations. Complex viscosity increases are seen, especially at low frequencies. Shear-thining behavior is also accentuated. The crossover between G′ and G″ moves to lower frequencies. A modified Cole–Cole presentation of these data shows that the elastic component is more predominant for extrusion-reacted materials. Peroxide-modified materials all have higher Bagley end correction values than those of barefoot resins. The former exhibit lower power indices (more shear thinning). All these properties indicate more long-chain branching and higher melt elasticity. However, die swell decreased as a function of peroxide concentration. Peroxide treatment results in an enhancement of elongational viscosity, both under isothermal and cooling conditions, along with a decrease in drawdown ability. The rheological changes parallel those reported earlier in molecular characteristics but are more sensitive and suitable to evaluate the effects of reactive processing. The effectiveness of the reactive extrusion process for improving processability of LLDPEs depends critically on the extrusion conditions. © 1995 John Wiley & Sons, Inc.

The emulsion polymerization of large monodisperse MMA/BA copolymer particles by surfactant-free means at high solids content is described. A series of sequential seeded growth reactions were used to obtain monodisperse particles with diameters of at least 3 microns. A combination of an oil-soluble initiator, AIBN, and a water-soluble initiator, ammonium persulfate (AP), was used. The AIBN initiated the bulk of the polymerization and the AP provided the stabilization for the polymer particles through its charged endgroups. The amount of AP initiator to be used in each growth step was calculated empirically using a criterion of a constant ratio of moles of sulfate groups to the polymer particle surface area. © 1995 John Wiley & Sons, Inc.

Mechanical and rheological properties of blends of polypropylene (PP) and linear polyethylene (PE) were studied, with particular attention to the effects of aging of such mixtures. These two olefin polymers are basically incompatible. In PP-rich blends, addition of highdensity PE (HDPE) causes only a slight decrease in tensile properties and impact resistance of injection-molded specimens. In all cases, annealed specimens have higher moduli and lower impact strength than as-molded products. While none of these changes are very drastic, the addition of small amounts of HDPE was observed to result in a serious decrease of gate-region impact resistance of thin-walled moldings. Blends with 10–20% HDPE exhibited an unexpected interaction in tensile, thermal, and melt-flow properties as well as in crystallization behavior. © 1995 John Wiley & Sons, Inc.

In this article, we report the results of molecular dynamics simulations for models of poly(ethylene), isotactic poly(propylene), and mixtures of the two to understand the possible origin of melt state incompatibility. At temperatures well above the crystal melting points of the homopolymers, isolated poly(ethylene) and poly(propylene) chains formed high-density collapsed states. The poly(ethylene) and poly(propylene) chains were found to segregate into distinct domains even when the initial state was highly interpenetrating. The poly(ethylene) phase shows a significant amount of local order at the simulation temperature. In the case of poly(propylene), some helical segments were found in the collapsed structure. We speculate that the immiscibility of these two nonpolar polymers, in the melt state, may be due to the differences in local morphology that are present in the melt state.

A “surfactant-free” emulsion polymerization of methyl methacrylate was conducted at 80°C with ammonium persulfate initiator. The water-soluble MMA-based oligomers re-maining were isolated and analyzed both as-produced and after hydrolysis. NMR analysis revealed that the mole ratio of MMA repeat units to sulfate end groups in the former is 6.5. Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry and gel permeation chromatography both showed that the mean number of MMA repeat units comprising the extracted material is 8–9. The hydrolysis procedure rids the oligomers of their terminal groups and converts some of the methyl ester groups to acid, greatly sim-plifying the mass spectrum. This appears to be the first direct measurement of “surfactants” produced in situ from monomer and persulfate initiator. © 1995 John Wiley & Sons, Inc.

The emulsion polymerization of large MMA/BA copolymer particles with narrow particle size distributions and core-shell structure is described. A series of sequential seeded growth emulsion polymerizations were used to obtain monodisperse particles with diameters of at least 3 μm, at 30% solids contents. Because the core and shell polymers used here were chemically similar, core-shell structures could not be verified by differential staining tech-niques. Core-shell structure was demonstrated by minimum film-forming temperature studies and by scanning electron microscopy in conjunction with energy dispersive x-ray analysis, using chlorine-labeled core polymers. © 1995 John Wiley & Sons, Inc.

It is well known that the amount of surfactant must be carefully controlled during starve-fed emulsion polymerization processes. Too little surfactant leads to emulsion instability and coagulation, while too much surfactant leads to secondary particle formation. Although these relationships are qualitatively understood in the art, there is little quantitative basis to guide the synthetic chemist, especially in multistep starve-fed emulsion polymerization processes to make larger supermicron particles. We have developed a method, which will be described in a companion article, to control the surfactant level by monitoring the surface tension during polymerization. In order to quantitatively predict how much surfactant to add at any given time, one needs to know in advance the adsorption characteristics of the soap. Further complicating the matter is the formation of “in situ” or oligomeric surfactant during polymerization with aqueous initiators such as ammonium persulfate. This work demonstrates how to prepare surface-active oligomers and how to make latex particles using them as surfactant. First, we established the mass balance for the initiator-derived sulfate groups in seed latexes by conductometric, potentiometric, and iodometric titrations. Based on the characterization of seed latexes, a method for determining the effective sulfate concentration has been developed. When surface-active oligomers were used as the only surfactant, we obtained a series of monodisperse, supermicron copolymer latex particles with diameters up to 3.22 μm. This is a similar result to that obtained with a commercially made anionic surfactant. © 1995 John Wiley & Sons, Inc.

In a multidetector SEC system it is necessary to match the outputs of the detectors that sense eluant concentration with those that are molecular weight dependent. There are several methods to accomplish this. The most common is to determine the interdetector volume or time difference between detectors. The difficulty with this technique is that with detector systems where the column eluent is split, the interdetector time difference varies with solution viscosity. Two new techniques were implemented on a high temperature SEC/DRI/LALLS/VISC system which take into account changes in solution viscosity due to high molecular weight polymers. Both techniques use calibration curves of hydrodynamic volume versus elution volume for the different detectors to determine the instantaneous time difference between the detectors as it varies with solution viscosity. Either method provides the correct interdetector time lag information. We note also that in multidetector systems the configuration of the detectors should be such as to maximize solvent flow rates through each detector and hence to minimize band broadening effects. © 1995 John Wiley & Sons, Inc.

A commercial linear low density polyethylene (1-hexene comonomer) was reacted with dicumyl peroxide at appropriate levels to initiate chain extension without crosslinking. The peroxide modification was carried out both in the presence and absence of a common hindered phenolic antioxidant. Thermal treatment of the resin was also completed with and without antioxidant present to evaluate the contribution of classical thermooxidative degradation to the peroxide modification process. In terms of pure thermal degradation, the phenolic antioxidant was found to be effective in prevention of reduction of molecular weights at the high end of the molecular weight distribution, as reflected in changes in M z . At the low end of the distribution, the opposite effect is seen, where the removal of the antioxidant actually allows an increase in the value of M n , through chain coupling reactions. Processing of the resin with addition of the organic peroxide significantly increases the molecular weights of both antioxidant containing and antioxidant free resins. Increasing the reaction temperature increases the rate of degradative chain scission and nonenlarging disproportionation reactions. At low temperatures, the presence of the antioxidant acts negatively with respect to chain enlargement reactions, and an overall reduction is seen in the efficiency of the peroxide in its role of increasing molecular weights. As the reaction temperature is increased, chain scission reactions become more predominant, and the antioxidant free resin shows very substantial decreases in molecular weight. Retention of the antioxidant at higher reaction temperatures is beneficial to maintaining high molecular weights, both with and without peroxide present. As in the peroxide free case, branching is essentially unchanged by the absence of antioxidant in peroxide modification. © 1995 John Wiley & Sons, Inc.

The dominant species in the early stages of an emulsifier-free emulsion polymerization of styrene has been found to be an oligomer of two to three monomer units using a novel trapping technique. This involved the intercalation of charged primary oligomers between the layers of a hydrotalcite, [Mg4Al2(OH)12]2+[A]2- (where A = dianion). Hydrotalcites are an important class of lamellar, inorganic compounds whose interlayer spacing can be mod-ified by anion exchange. Our approach first involved preparing a hydrotalcite precursor in which the layers were propped apart by an organic dianion (terephthalate = TA). This material was then used to capture the negatively charged polystyrene oligomers from the emulsion polymerization reaction mixture. We found that TA was rapidly ion-exchanged for the charged oligomers. The resulting pillared hydrotalcite material was characterized using XRD and SEC. We found that the interlayer spacing between the hydroxide layers increased to 23.2 A on exposure to the emulsion reaction mixture. This represents an interlayer expansion of 18.3 A (after subtraction of the hydroxide layer contribution), which is cnsistent with intercalation of oligomers with two to three monomer units arranged in a bilayer. This size estimate was confirmed by the results of size exclusion chromatography. © 1995 John Wiley & Sons, Inc.

Inverse gas chromatography of alkanes has been used to assess the degree of fusion of rigid polyvinyl chloride (PVC) extrudates. The relative degree of fusion is provided by ratios of the retention volumes of the alkane probe molecules in the bulk of the PVC. This method is nonintrusive and can be used to measure degree of fusion quantitatively if a completely fused reference material can be provided. The present analysis involves evaluations of the contributions to the overall retention volume of the alkane probes, resulting from adsorption and from bulk diffusion. The diffusivity of the alkanes was clearly dependent on the processing history of the PVC extrudate. A direct variation was observed between the size of the diffusing molecules and their residence time as adsorbates on the polymer surface. © 1995 John Wiley & Sons, Inc.

This review focusses on processes in which emulsion polymerizations are carried out in stages so that previously formed particles are either overcoated in subsequent polymerization stages or engulf the second and later stage polymers. These products are often called “core-shell” particles. Basically, the most stable state of the final system is the one with the lowest net interfacial energy. In the case of a two-stage emulsion polymerization there can be three interfacial tensions to consider. Several mutually consistent, effective thermodynamic treatments have been published. At present, they serve primarily to predict when the morphology of multi-stage polymerization products may not be a simple reflection of the synthesis sequences. It is possible, and frequently desirable, however to produce particle structures that appear at first glance to be thermodynamically forbidden. This is achieved either by changing the surface characteristics of a polymer from those of the bulk material or by employing kinetic factors to anchor energetically unprofitable morphologies. This paper summarizes methods of both types that have been reported to control the texture of structured latex particles in order to produce designed morphologies.

Low-density polyethylene (LDPE) and also linear low-density polyethylene (LLDPE) resins can be characterized by the degree of strain hardening and down-gaging during elongation. A new method for the determination of the apparent elongational flow characteristics is presented. In a small scale apparatus, a molten monofilament is stretched under nonisothermal conditions similar to those found in tubular film extrusion. Measurement of resistance to elongational flow and apparent elongational strain rates permit the comparison of the process-ability of different resins under specified conditions. The effect of melt temperature and extension ratio are examined. The importance of the molecular structure of both LDPE and LLDPE resins on these properties is also outlined.

Mixtures of film grade LLDPE, LDPE, and PP may occur in recy cle streams. Household plastic films collected through a recycling program were found to contain less than 2 per cent PR The present study concerns the effects of minor amounts of polypropylene on the film properties of such mix tures. Polypropylene enhances film stiffness slightly and has no deleterious ef fect on other PE film properties at levels up to 5 per cent PP However, consider able degradation of tear and impact strength occurs with higher polypropylene concentrations. These problems are alleviated by addition of a vinyl acetate EVA film grade polymer of 28% VA content, which will permit PP levels ap proaching 20 per cent without negative impact on film properties. Good proper ties were observed in 85/15 LLDPE/PP mixtures by addition of 5 per cent of this EVA, based on the total polyolefin content. This report gives a detailed descrip tion of the mechanical properties of the extruded films.

A comprehensive model of film formation that was proposed in an earlier article by the present authors was evaluated for latexes having a wide range of physical properties. In this model, capillary force and interfacial forces act in tandem to promote film coalescence. The emulsion polymers studied were all based on poly(methyl methacrylate-co-butyl acrylate). The viscoelastic nature of the copolymer was varied by the addition of molecular weight modifiers (CBr4 chain-transfer agent and ethylene glycol dimethacrylate cross-linking monomer) during synthesis. In contrast to the simplifications of the previous analysis, the experimental system was well characterized. The effect of water plasticization was investigated. The surface energetics of the system were studied. Also, drying kinetics were considered. Results showed that the degree of coalescence ranged from complete fusion to superficial fusion. The minimum film temperature was found to increase with increasing polymer rigidity, as is expected. Comparison of the model predictions and experimental observations validated the model. © 1994 John Wiley & Sons, Inc.

Studies on the crystallization of polymers are usually carried out by dilatometry, differential scanning calorimetry (d.s.c.) and optical microscopy. These methods have been widely used in the analysis of crystallization kinetics using the Avrami equation. Direct determination of nucleation rate and density is only possible by the optical microscope technique. We have employed a new technique for studying the crystallization behaviour of polymers by using a dynamic mechanical method. This method is capable of detecting the onset of nucleation. Semiquantitative data on the nucleation density and the initial crystallization rate may also be deduced by this method. Results from the dynamic mechanical method are cross-compared with d.s.c. and optical microscope data for polypropylene, polyethylene and their blends, and are shown to be mutually consistent.

In this paper we address the aspects associated with shear modification of low density polyethylene by extrusion. By successive passes of the polymer through an extruder it can be shown that both the melt viscosity and melt elasticity are reduced by shear modification. These reversible variations are not accompanied by significant changes in molecular weight distribution. The major effects of extrusion are to decrease the amount of elastically effecitve material. Study of proton relaxation times at 150°C shows that the melt comprises regions of relatively ordered, entangled, and unentangled polymer. Shearing reduces the proportion of more ordered material. The elastically effective anchors that are reduced by shearing are regions with restricted segmental mobility rather than conventional entanglements or intermolecular knots. Successive extrusions produce a relatively small decrease in the number of such constraints to molecular motion. Repeated shearing has a diminishing effect on the proportion of more ordered material in the polyethlene melt. This parallels observations of the effects of repeated shear modification on the properties of polyethylene films and other extrudates.

The influences of initiator concentration, ionic strength of the aqueous phase and styrene sulfonic acid sodium salt comonomer on the average particle size and particle uniformity of latexes generated via emulsifier-free emulsion polymerization of styrene has been studied. It was found that the average particle size increased with increasing initiator concentration in reactions where the ionic strength was not controlled. The uniformity of the latex particles decreased as the initiator concentration increased. It was also found that at a minimum initiator concentration of 1.5 × 10−3 M at a temperature of 80°, adequate conversion could not be obtained. This limited the range of particle sizes which could be produced without adding additional surfactants. It was also found that smaller particles, 0.135 μm diameter, could be formed by copolymerizing styrene sulfonic acid sodium salt with styrene. The effects of ionic strength on particle size was also investigated and it was found that the particle size increased with increasing ionic strength. At constant ionic strength, it was found that particle size decreased with increasing initiator concentration as expected theoretically.

Conversion of analytical TREF data to accurate branching distributions of polyethylene requires a calibration of branching frequency as a function of elution temperature. It has been found that the elution temperature of a semicrystalline polymer such as polyethylene depends on molecular weight, branch content, branch length, and branch clustering. It stands to reason that every polymer will have its own unique relation of branch frequency and elution temperature. Ideally, the polymer would be fractionated by a preparative TREF technique and the fractions analyzed by NMR or IR to determine branch frequency with respect to elution temperature. This method is tedious and time-consuming. An alternative method is described here to determine the relation between branch frequency and TREF elution temperature and to generate a calibration from analytical TREF data only. A twodetector system is used to simultaneously measure both concentration and branching frequency as a function of elution temperature. Each polymer is analyzed using analytical TREF data alone, eliminating the need for preparative TREF fractionation and NMR analysis of the fractions. © 1994 John Wiley & Sons, Inc.

A major stream of post-consumer plastics is a commingled blend of polyethylenes and polypropylenes, which usually exhibits lower performance compared with that of the homopolymers due to the incompatible nature of polyethylenes and polypropylenes. Various studies have been carried out to characterize the structure, morphology, mechanical, thermal, and rheological behavior of this blend. The effect of processing, modification, and compatibilization have also been studied by various workers. This article is a review of the work done on polyethylene–polypropylene blends to help in the understanding of this important blend. © 1994 John Wiley & Sons, Inc.

Blends of t-butylaminoethyl methacrylate grafted polyethylene (PE-g-tBAEMA) with methyl methacrylate-methacrylic acid copolymer (PMMA-MAA) and polymethyl methacrylate (PMMA) were prepared in a Banbury type batch mixer. The effects of component proportions and processing conditions on the melt flow index, morphology, impact, and tensile properties of the resulting polymer blends were investigated. The interfacial chemical reaction was studied using Fourier transform infrared (FTIR) technique. It was observed that the melt index of the blends was reduced with increasing melt processing temperature and mixing time, indicating the formation of PE-g-PMMA block copolymer. New IR bands at 1554, 1628, 1800, and 1019 cm−1 were observed only for PE-g-tBAEMA/PMMA-MAA, the reactive blends, but not for PE-g-tBAEMA/PMMA, the nonreactive blend. These IR bands were attributed to the amide, carboxylate anion and methacrylimide formation resulting from the chemical reaction between the secondary amine on the PE-g-tBAEMA/PMMA moiety and the carboxylic acid on PMMA-MAA segment. The morphology of the blends in various compositions was examined using scanning electron microscopy (SEM) and related to their mechanical properties. All of the blends have a domain structure whose morphology is strongly dependent on the concentration of the dispersed phase. Furthermore, the PE-g-tBAEMA/PMMA-MAA reactive blends were shown to have much finer morphology than the corresponding nonreactive blends. For the reactive polymer blends consisting of brittle particles dispersed in the ductile matrices, the PE-g-tBAEMA/PMMA-MAA, impact and tensile result higher than predicted by the additivity rule were observed. The toughening of polyethylene by PMMA was explained by a “cold-drawing” mechanism. The Young's modulus of the blends and the extent of interfacial adhesion were analyzed with Takayanagi and Sato-Furukawa's theories. © 1993 John Wiley & Sons, Inc.

A commercial-grade LLDPE resin was cross-linked using three different dialkyl peroxides, at three different concentrations. The peroxides were ranked in order of their Cross-linking efficiency and their effectiveness at increasing the storage modulus of the virgin resin at the cure temperature. The chemical mechanism by which the cross-linking occurs is shown to be closely related to the changes in concentrations of reactive vinyl species on the polyethylene molecules, which follows well with proposed mechanisms of previous publications. Finally, a direct relationship is shown to exist between the rate of peroxide decomposition and the rate of increase in storage modulus of the rubbery modified resin during the curing reaction. © 1993 John Wiley & Sons, Inc.

The performance of acrylic (50:50 MMA/BuA) latexes was investigated as a function of fusion level using high speed tensile testing. The structure of the copolymer was varied via the addition of molecular weight modifiers to the emulsion polymerizations. Chain transfer agent (CBr4) was used to reduce the copolymer modulus, and crosslinker (EGDM, ethylene glycol dimethacrylate) was added to increase the modulus. The resulting materials exhibited a wide range of viscoelastic behavior (G* varied from ∼ 107 dyne cm−2 to ∼ 109 dyne cm−2). Fracture energy and peak force at break were measured as a function of the complex modulus. It was found that both of these parameters showed a maximum with respect to G* that corresponded to intermediate levels of crosslinking. This observation was explained in terms of the degree of coalescence of the films. Fully fused films (excess CBr4) were brittle and performed poorly, conceivably because of insufficient entanglement to support stress. Marginally fused films also exhibited inferior, brittle behavior. The films cast from latexes synthesized with low levels of molecular weight modifiers showed intermediate fusion levels and superior tensile performance. The quantitative results were rationalized using scanning electron microscopy (SEM) of both the virgin films and the fracture surfaces. For comparison, the same materials were tested in a fully fused state following hot pressing. The behavior paralleled that expected for vulcanized rubbers in which lightly crosslinked materials exhibit the highest tensile strength. © 1993 John Wiley & Sons, Inc.

The effect of several variables relevant to film formation in 49 : 49 : 2 poly(methyl methacrylate-co-butyl acrylate-co-methacrylic acid) latexes were studied. Plasticization of the terpolymer by both an anionic [sodium dodecyl benzene sulphonate (NaDBS)] and a nonionic [nonyl phenol ethylene oxide adduct (NP40), forty ethylene oxide units on average] surfactant were investigated. Dynamic mechanical measurements indicated that NP40 plasticized the polymer, whereas NaDBS did not. This was attributed to the compatibility of the nonionic emulsifier and the polymer. The influence of the surfactants on the film formation process was studied using minimum film temperature (MFT) measurements and scanning electron microscopy (SEM). As expected, the MFT was independent of NaDBS concentration. However, the MFT was also independent of NP40 concentration. Film formation was further investigated using SEM. The series of micrographs at varying NaDBS concentrations showed no effect on the degree of film fusion. However, surface exudates were observed. The micrographs revealed that increasing NP40 content resulted in an apparently greater degree of film coalescence. That is, there was bridging of the particles in the interstitial regions. This was attributed to localized plasticization of the polymer in these regions by NP40. The effect of water plasticization of the latex polymer was studied using dynamic mechanical measurements. The physical character of the terpolymer was varied using mol wt modifiers (CBr4 chain transfer agent and ethylene glycol dimethacrylate crosslinker). It was found that all of the polymers were plasticized by water. Finally, the film forming behavior was investigated as a function of latex pH. MFT measurements indicated an independence of pH. © 1993 John Wiley & Sons, Inc.

The effect of particle size in high-impact polystyrene (HIPS) is difficult to determine because of a size polydispersity and changes in particle morphology during the HIPS synthesis process. In this study, poly(n-butyl acrylate) rubber core/polystyrene shell particles were made by emulsion polymerization methods such that the only difference was in particle diameter, which ranged from 0.4 to 6.2 μm. The latexes were subsequently incorporated into a polystyrene matrix to form a toughened composite that acted as a simple model for HIPS. Charpy impact energies (notched and unnotched) of the composites showed that there was no toughening for particle sizes less than 2μm in diameter. The optimal impact energy was obtained with particle diameters in the region of 2–3 μm at 8 wt % rubber loading. The results imply that craze stabilization is the most important aspect of the toughening process. A simple toughening model based on the crack opening displacement of craze breakdown between adjacent rubber particles is suggested, with interparticle distance as the most important variable. © 1993 John Wiley & Sons, Inc.

The viscoelastic responses of some molten polymers, and particularly of low density polyethylene (LDPE), are known to vary with processing history. Reasons for the variations include the effects of shear history on morphological states of the polymer, or on its molecular weight parameters. A typical low density polyethylene has been used to test the shear-history dependence concept following a variety of processing steps. The polymer was sheared in single-screw and twin-screw extruders, and in a high speed melter / mixer (Gelimat). Samples also were precipitated from very dilute solutions in trichlorobenzene and in p-xylene. GPC analyses showed that, in general, these procedures did not affect the various moments of molecular weight. An exception was the Gelimat-mixed sample, for which mild reductions in Mn and Mw were noted. In contrast, melt viscosity and elasticity readings, the former from low shear evaluations and the latter from extrudate swelling, were affected by the various procedures. A drop in melt viscosity and in elasticity was observed, being most pronounced for precipitated and twin-screw extruded versions of the LDPE. Reductions also were observed in the specimen sheared in the Gelimat instrument. Following conditioning at the test extrusion temperature (170°C), viscous and elastic responses tended to revert to those of the unsheared control sample, the exception again being the sample sheared in the Gelimat melter / mixer. Of the various mechanisms proposed in the literature to account for transient property changes such as those reported, temporary changes in the degree of chain entanglement appear the most satisfactory explanation. Irreversible alterations in viscoelastic properties may be associated with changes in molecular weights due to processing at high shear.

Analysis of analytical temperature rising elution fractionation (TREF) data involves conversion of elution temperature information to branching information via a calibration curve relating the two. The curve is generated by analysis of polymer fractions recovered using preparative TREF techniques. In preparative TREF a stepwise temperature ramp is used to recover these fractions so that samples with sharp branching distributions are obtained. A continuous temperature ramp, as in analytical TREF, produces samples that differ in branching properties from the stepwise ramp at the same temperatures. The analytical TREF data can be corrected for these differences by an iterative computer program so that a calibration curve generated by preparative techniques can be used to convert the analytical TREF data to branching distributions. Analytical TREF results should be corrected for fraction overlap before relating these data to polymer properties. © 1993 John Wiley & Sons, Inc.

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, [η] = KMa. 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 [η] over a very wide range of molecular weights is [η] = K π M r 1 2 + K′ M w were Kθ and K′ do not change. The intrinsic viscosities of polystyrene standards with MWs of 103 to 2 × 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 MW detectors 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.

Thermally initiated crosslinking reactions have been studied in a linear low-density polyethylene, and an ethylene—propylene rubber. The polymers contained conventional thermal stabilizers or one of three surface-coated rutile pigments. Enthalpies of crosslinking and reaction kinetics depended on the degree of terminal vinyl unsaturation in the polymers, that characteristic being greater in the rubber than in the polyethylene. The presence of thermal stabilizers did not exert any measurable influence on measured parameters of the crosslinking processes. The effects of rutile varied, depending on their surface acidity or basicity, as determined from chromatographic measurements. Basic rutile was found to reduce heats and to slow rates of reaction, while acidic rutiles did not affect the reactions. These observations may be attributed to interaction between the basic pigment surface and acidic moieties involved in the crosslinking reaction. © 1992 John Wiley & Sons, Inc.

Latex particles of up to 2 μm can be made by standard emulsion polymerization methods, but attempts at larger sizes usually results in a crop of smaller particles or coagulation of the latex. In this work, it is shown that use of an oil-soluble initiator (2,2′ azodiisobutyronitrile [AIBN]) provides a means by which large (6 μm diameter) polybutyl acrylate latex particles can be made by sequential core-shell polymerizations. It is suggested that the limited water solubility of AIBN decreases the formation of secondary particles and that the lower ionic strength of the water phase enhances stability of the latex compared to a conventional persulfate initiator. To further minimize formation of secondary particles, long reaction times and progressively larger proportions of seed latex are used in successive reactions. © 1992 John Wiley & Sons, Inc.

Direct grafting of polystyrene onto polyethylene has been carried out in a twin screw extruder with an organic peroxide and a crosslinking co-agent. The reaction extruded blends exhibited enhancement in impact properties at an optimum level of peroxide and co-agent. Further improvement was achieved by introducing styrene monomer into the system during reactive extrusion. The structure and morphology of the blends were studied using differential scanning calorimetry, scanning electron microscopy, infrared spectroscopy, and size exclusion chromatography

Molecular weights of polyethylenes have been characterized using differential refractometer (DRI), continuous viscometer (CV), and low-angle laser light (LALLS) detection. In normal operation with the latter two detectors, the DRI is also employed as a concentration detector. The intrinsic viscosity of the whole polymer can be derived from the CV without use of a DRI concentration detector. If one calibrates the size exclusion chromatography (SEC) columns using the CV detector, it is possible to use this universal calibration relation and the CV detector to calculate number average molecular weight (Mn) of the polymer. Weight average molecular weight (Mw) of the sample can be calculated using data from the LALLS alone, without reference to the DRI. These variations of the analysis were tested and the advantages and limitations of the different detectors were compared using standard reference polyethylene samples in solution in 1,2,4-trichlorobenzene at 145°C. © 1992 John Wiley & Sons, Inc.

Proton NMR spin-spin relaxation measurements were made on three commercial-grade polyethylenes in the melt state. All samples exhibit a three-component relaxation behavior, with components being assigned to amorphous low-molecular weight material (non-network fraction), amorphous entangled network fraction, and an ordered or high-segmental-density fraction, in order of decreasing relaxation times. Sample thermal history is shown to have a considerable effect on the overall relaxation behavior, and therefore on the relative amounts of each of the three components in the melt

A DSC method for assessing degree of fusion of rigid PVC compounds has been improved, so as to make the technique more precise and objective. Analysis of conventional pipe samples provides assessments of gelation level that accord with solvent resistance and practical experience. However, thermal analysis techniques prove to be unreliable for compounds that contain no filler or more than about 13% filler. At least about 1% filler appears to be necessary for the phenomena that are the basis of this technique. Filler may affect crystallization of PVC compounds.

Core-shell polymer composites made by two-stage emulsion polymerizations are useful in many applications. In systems involving a hydrophilic/hydrophobic polymer pair, a core-shell arrangement is thermodynamically unfavorable and may be difficult to achieve. To counteract the thermodynamic forces in such a system, the mobility of the phases can be reduced to such an extent that a core-shell morphology is achieved. This was accomplished in a PMMA/PS two-stage system by lowering the second-stage polymerization temperature to room temperature using a redox initiator. At this relatively low temperature, a core-shell morphology was obtained even when the second-stage was carried out as a batch polymerization. © 1992 John Wiley & Sons, Inc.

A model, developed to account for the concentration dependence of the dimensions of dissolved polymers over a wide concentration range, has been combined with very simple hard sphere statistical mechanical relations to predict transport properties of polymer solutions. Diffusion and sedimentation coefficients are estimated accurately and Newtonian solution viscosity can also be predicted up to fairly high concentrations.