Structural changes in solvent-induced crystallization of quenched isotactic polypropylene

Solvent-induced crystallization of quenched isotactic polypropylene (iPP) films in dichloromethane, cyclohexane, carbon tetrachloride, and chloroform has been investigated.WAXD, density, and DSC measurements indicate that smectic iPP films undergo a complex rearrangement of the structure in these liquids, leading to a process of crystallization.Transport properties of the dried samples, after the solvent treatment, show that the first stage of crystallization involves, in addition to the smectic phase, a fraction of amorphous phase, while further crystallization regards only the smectic phase.The morphology of the crystallized samples has been investigated by transmission electron microscopy following permanganic etching. No change in the basic morphology is found, although local organization showing splaying and branching appears clearer in the solvent crystallized samples than in the starting smectic sample.     

Drawing behavior of cross-linked isotactic polypropylene

The drawing behavior of cross-linked isotactic polypropylene was analysed. The crystallinity and the composition of the crystalline phase are affected by cross-linking. Structural and topological features play a significant role in the drawing behavior. The yielding, the necking phenomenon, and the ultimate properties, i.e., stress and strain at the fracture, can be correlated with the sample structure. The general picture agrees well with Peterlin's model of cold drawing.     

Mixed spherulites of alpha and gamma phases in gamma-irradiated and thermal-treated isotactic polypropylene

Samples of commercial bulk gamma irradiated i-PP are recrystallized at various temperatures. Optical microscopy, (SALS), and (DSC) are used. All common types of PP spherulites are observed. Investigation shows that number of dendritic spherulites and their positive birefringences increase with doses. It is supposed that spherulites observed consist of twins built up of triclinic and monoclinic crystallites of i-PP. A mechanism of their growth is proposed.     

Effects of uniaxial stretching and shrinkage on proton spin-lattice and spin-spin relaxation times of isotactic polypropylene

An isotactic polypropylene film was stretched at 120 °C in poly(ethylene glycol) and thermally shrunk at various temperatures. Proton spin-lattice,T ₁, and spin-spin,T ₂, relaxation times were measured using a broad line pulse spectrometer operating at 19.8 MHz in the temperature range 40 °C–100 °C. The temperature ofT ₁ minimum shifts to higher temperatures and the value ofT ₁ minimum increases in magnitude as the stretching ratio is increased. In contrast the temperature ofT ₁ minimum shifts to lower temperatures as shrinkage is increased, whereas the value ofT ₁ minimum increases in magnitude because of the increase in crystallimty during shrinkage. T_2a, the longestT ₁ associated with the mobile amorphous regions, increases during shrinkage, indicating that chain mobility in the amorphous regions increases substantially during shrinkage. It was found that an orientation function of the amorphous regions,f _a, correlates well withT _2a .Presented in part at the 52nd Annual Meeting of the Japan Chemical Society, Kyoto, April 1986.     

Morphology and mechanical properties of ultrahigh molecular weight polypropylene prepared by gelation/crystallization at various temperatures

Films of ultrahigh molecular weight (5.4×10⁶) polypropylene were produced by gelation/crystallization at various temperatures from dilute decalin solutions according to the method of Smith and Lemstra. The temperatures chosen were 20°, 30°, 50°, and 60°C. With increasing the temperature, the long period and crystallinity of the resultant gel film increased. By contrast, when the films were stretched up to 50 } 60 times, the increases in Young's modulus and crystallinity become more significant, as the temperature of the gelation/crystallization became lower. This interesting phenomenon is thought to be due to the dependence of the number of entanglements on the temperatures concerning gelation/crystallization and evaporation of solvent from the gel to form a film.     

Melt drawing as a route to high performance polyethylene

Well established routes for obtaining stiff and strong polyethylene (PE) involve solid state drawing either of solution crystallized gel films or melt crystallized spherulitic PE. The aim of this work is to show the potential of melt deformation as an alternative route for obtaining highly oriented products. Our previous work on the melt deformation route showed that oriented PE fibers could be directly extruded under appropriately controlled conditions [8,9]. Here, we show that PE films (or filaments) can also be melt drawn in the temperature window 130–160 °C, thus yielding oriented products. The advantage of melt drawing over direct melt extrusion is that it allows a wider operational latitude and thus does not require such carefully controlled conditions.The morphology produced by melt deformation is different from solid state deformation and consists of extended chain fibrils with platelet overgrowths. The relative amount of fibrils and platelets depends on operating parameters. The temperature window of PE melt drawing is identified with the regime where some flow induced crystallization takes place. The conditions for melt drawability are of wider generality for crystallizable flexible chain polymers. They are: (i) adequate strain rate to overcome entropie resistance to chain extension, (ii) but not high enough to activate the elastic response of the transient networks in the entangled system, (iii) sufficient strain to fully extend the chain, (iv) appropriate temperature for flow-induced crystallization and strain hardening, and (v) cooling to freeze the oriented structure.Ultra high molecular weight PEs were not the most suitable for melt drawing due to their high recoverable elongation in the melt (melt elasticity) in addition to added limitations imposed by their nascent grain systeme. Our work suggests that an optimum molecular weight for melt drawing is¯M _w(400–900)×10³ with further possibilities for improvement through multimodal distributions.     

Crystallization kinetics of isotactic polypropylene blended with atactic polystyrene

Crystallization kinetic parameters, such as spherulitic growth rates, nucleation densities, and Avrami-exponents, have been determined by optical microscopy for isotactic polypropylene blended with atactic polystyrene. It is found that the crystallization of iPP is strongly influenced by the presence of polystyrene. With increasing PS concentration in the blend, the nucleation densities decrease, while the spherulitic growth rates as well as the positions of thermal peaks, measured by DSC, remain independent of sample composition. Due to the formation of interfaces as a consequence of increasing dispersion of polystyrene the nucleation changes from preferentially thermal to athermal.     

Thermochromism of polypropylene gels

It is found that polypropylene gels in some solvents of benzene-derivatives show a striking change of colour. The colour changes from blue to yellow as the temperature rises from the melting point of the solvent to around 70–80 °C. The apparent characteristic of the phenomenon resembles the thermochromism of cholesteric liquid crystals although polypropylene itself is colourless and has no asymmetric carbons in the molecules. Polypropylene flakes swelled in these solvents also show similar thermochromism.     

Grafting onto ultrafine ferrite particles: Reaction of isocyanate-capped polypropylene glycol with hydroxyl groups on the surface

The grafting of polypropylene glycol (PPG) onto an ultrafine ferrite by the reaction of hydroxyl groups on the surface with isocyanate-capped PPG (PPG-NCO), prepared by the reaction of an equimolecular amount of PPG with tolylene 2,4-diisocyanate, was investigated. When PPG-NCO (M _n=2.5×10³) was heated with the ferrite in bulk, the percentage of grafting onto the ferrite at 120 °C was increased up to 18.5%. On the contrary, the grafting by the reaction of PPG with hydroxyl groups on the ferrite at 120°C was scarcely observed. The grafted PPG onto the ferrite was removed by hydrolysis with a dilute methanol solution of potassium hydroxide. Therefore, it was considered that PPG was grafted onto the ferrite surface with urethane bond. The grafting of PPG onto the surface was also confirmed by infrared spectra. The reaction of PPG-NCO with the ferrite was accelerated by the addition of-picoline as a catalyst. PPG-grafted ferrite was found to produce a stable colloidal dispersion in organic solvents. Furthermore, the effect of molecular weight of PPG-NCO on the grafting onto the ferrite was discussed.     

Discussion of craze formation and growth in amorphous polymers in terms of the multiplicity of glass transition at low temperatures

A craze, the typical deformation zone in an amorphous polymer, can be divided into a precraze and a proper craze. A better understanding of the two corresponding formation processes is possible in terms of glass transition multiplicity.The precraze is associated with the molecular mobility in the confined flow zone, which is part of the main transition. The proper craze corresponds to the mobility in the flow transition zone (terminal zone for shear). A negative pressure generated by nonuniaxial stress is considered to be important for the maintainance of the molecular mobility in these zones belowT _g . The behavior of the zones at negative pressure and low temperatures Tg is considered using a pressure-temperature diagram. The fibril structure of crazes is discussed by a defect diffusion model for the proper glass transition; it is correlated with the sequential physical aging of the corresponding frozen structural defects. Typical mode lengths of the molecular mobilities in the different zones are compared with typical craze parameters. The structure of the craze material is considered to result from confined flow processes which cannot percolate because in the main transition the flow is confined by entanglements, and in the flow transition zone the flow is stopped by releasing the negative pressure due to crack propagation.     

Viscoelastic behaviour during gelation of various molar-mass polyvinylchloride solutions and polymerization temperatures

The gel formation of various 10% molar-mass polyvinyl-chloride (PVC) sample solutions and polymerization temperatures in di-(2-ethylhexyl)phthalate (DOP) was studied by measuring dynamic moduli as functions of gelation (or ageing) time and frequency. The propensity to form gels increases with increasing molar mass and decreasing polymerization temperature. Extraction of a commercial PVC with acetone separates it into a relatively highly crystalline and a nearly non-crystalline polyvinyl chloride.     

Distribution of emulsified monomers with different water solubility

The location and distribution of acrylic acid and styrene in emulsions made with a cationic surfactant, cetyltrimethylammonium bromide (CTAB), or an anionic surfactant, sodium dodecylsulfate (SDS), were determined with ultra-violet spectroscopy, conductivity, and potentiometry. In these systems, the acrylic acid remains in the aqueous phase near the micelle surface, whereas the styrene is located in the micelles or in emulsified droplets. In the absence of acrylic acid, some of the styrene is solubilized in the micelle interior and some is adsorbed at the micelle inner surface. Upon addition of acrylic acid, all the styrene is displaced to the center of the micelles. The interaction between acrylic acid and CTAB micelles is stronger than that between acrylic acid and SDS micelles. With CTAB, acrylic acid is adsorbed at the micelle surface, whereas with SDS, acrylic acid remains in the intermicellar solution. These differences can account for the differences reported in the emulsion copolymerization of acrylic acid and styrene using CTAB or SDS.     

Studies of thermally stimulated current in polypropylene/calcium carbonate/surfactant systems

Thermally stimulated polarization (TSP) and depolarization (TSD) experiments have been performed with two grades of polypropylene and some respective CaCO₃-filled composites containing small amounts of nonionic surfactant (0–2 wt%). The effects of electrode blocking, electrode materials on the thermally stimulated currents, and reproducibility of the measurements have been studied. The effect of water vapor adsorbed from the ambient air on the AC dielectric properties and on the thermally stimulated polarization behavior has been determined.The addition of either CaCO₃ or surfactant to PP decreases the intensity of the _c depolarization current peak in the pre-melting region, while the presence of both components increases the current. Partial discharges are present in poly propylene/CaCO₃ composites under high voltages if neither water vapor nor a coherent surfactant layer is present at the matrix/filler interface.A short literature survey is presented on the TSC studies of polyolefins and their composites, and various mechanisms responsible for the observed changes are discussed, including interfacial polarization, trap redistribution through nucleation, and oriented adsorption.     

Interaction of nitrophenols with lipids at the air/water interface

The uptake of ortho and para nitrophenol to charged and neutral lipid monolayers spread at the air/solution interface was studied by reflection spectroscopy. The adsorption characteristics of the two nitrophenols have been studied by measuring the surface pressure and surface potential as a function of molecular area of the different lipid monolayers in the presence of nitrophenols in the subphase. The results have been interpreted in terms of the electrostatic interaction between the negatively charged dissociated phenolate ions and the positively charged head group of dioctadecyldimethylammonium bromide monolayers.     

Microstructure and lateral diffusion in monolayers of polymerizable amphiphiles

Lipid analogue amphiphilic molecules containing polymerizable units were investigated in monolayers at the air/water interface by using film balance measurements, fluorescence microscopy, and photobleaching techniques. The polymerizable groups (diene-, diyne-, and methacrylate units) were introduced into the hydrophobic alkyl chains or into the polar head of the amphiphilic molecules.In the case of the diene- and diyne-containing compounds the polymerizable units are incorporated into the hydrophobic alkyl chains, enabling them to form a two-dimensional network. Due to the free chain flexibility of the monomers the lateral mobility was comparable to that of saturated lipid analogues and decreases upon polymerization proportionally to the dose of UV irradiation. In addition, fluid/solid phase transitions of compounds with polymerizable groups in the hydrophobic part tend to vanish during the formation of the polymers. However, the direct observation of the growth of polymeric crystalline domains can be followed by using diacetylene lipid analogues.In the case of the methacrylate derivatives the polymerizable unit was coupled to the polar part via a flexible spacer. For these systems the characteristics of the monomeric phase transition are retained after polymerization. However, it shows a significant, strong decrease of the in-plane mobility already in the fluid-expanded phase of the polymer. The quantitative measurements of the lateral diffusion in the monolayers can be correlated with fluorescence microscopic images of their structure.     

Phase diagram of the system dihexadecylphosphatidylcholine/dihexadecyl-phosphatidic acid/water/NaOH at pH=14

Differential-scanning-calorimetry, freeze-fracture electron microscopy, and³¹P-NMR spectroscopy were used to study the lyotropic and thermotropic properties of the system dihexadecylphosphatidylcholine/dihexadecylphosphatidic acid/water/ NaOH in dispersion with excess water at pH=14. The phase diagram showed that both phospholipids are demixed nearly completely in the gel phase. The coexistence of theP and theB -phase in the mixtures was pointed out in the freeze-fracture electron micrographs by the ripple structure (P -phase) and by the lamellar structure (B -phase).     

Study of the polymer latex coalescence by dielectric measurements at microwave frequency—feasibility of the method

The measurement of the complex dielectric constant ( ^*=–j) in the dipolar absorption domain of the free water molecule (microwave region) permits us to follow quasi-specifically and precisely the water circulation during the coalescence process of a latex. Weight losses and dielectric constants variations have been simultaneously recorded upon latex drying, in a resonant cavity at 5 and 9 GHz and under controlled atmosphere and temperature. Two different latexes were studied (polybutylacrylate (PBuA) and polystyrene (PS)) from which the glass transition temperature effect was investigated. It is found that the harder the polymer particles, the more clearly evidenced the flocculation and packing points are. This method appears to be quite reliable for discriminating the various steps in the film formation process of latexes.     

FTIR spectroscopic and NMR studies of hard elastic polypropylene

The variation of amorphous orientation and crystalline regularity of hard elastic polypropylene (HEPP) films during cyclic deformation and stress relaxation processes were studied using a FTIR spectrometer. The result proves entropic elasticity and shows the orientational hysteresis in the amorphous region or within the microfibrils, and also shows that the amorphous orientation increases, but that the crystalline regularity decreases with the increase of extension rate.Three spin-spin relaxation timesT _2f,T _2m, andT _2s and associated mass fractionsF _f,F _m, andF _s of HEPP fibers were measured with a solid echo of NMR method at different elongations and after relaxation or recovery for a long time A new possible interpretation was proposed that, while the microfibrils are formed in HEPP, the medium decay component should be ascribed to inner molecules of the microfibrils, and the slow decay component to the surface molecules of the microfibrils. According to this interpretation, the results implied that subfibrillation is the main process when HEPP is stretched up to 15% strain, and that at above 15% strain thinning and lengthening of the microfibrils become the main process. Thickening of the microfibrils was found in the recovery and relaxation processes.     

Cubic phases as structures of disclinations

We look for possible ordered geometrical configurations with bicontinuous or cellular topologies, optimizing the frustration of a periodic system of frustrated fluid films. The solutions found have the same symmetries as those observed for cubic phases of amphiphilic molecules. This agreement leads to consider cubic structures as structures of defects of rotation, or disclinations.This paper was presented at the workshop Ringing gels and Cubic phases, University of Bayreuth, October 25–26th, 1988.     

Phase and miscibility behavior of binary lipid systems

Differential scanning calorimetry was applied to study the phase diagrams of the following binary lipid systems: myristic acid (C₁₃COOH) / pentadecanoic acid (C₁₄COOH); palmitic acid methyl ester (C₁₅COOMe) / heptadecanoic acid methyl ester (C₁₆COOMe); palmitic acid methyl ester (C₁₅COOMe) / stearic acid methyl ester (C₁₇COOMe); palmitic acid methyl ester (C₁₅COOMe) / arachidic acid methyl ester (C₁₉COOMe). A distinct succession in the phase diagram types and phase regions was observed, according to the chemical structure of the mixing components.In the systems C₁₃COOH/C₁₄COOH; C₁₅COOMe/C₁₆COOMe and C₁₆COOMe/ C₁₇COOMe, both components are completely miscible in the low- and high-temperature phase. Contrasting with these three binary lipid systems, the system C₁₅COOMe/ C₁₄COOMe shows complete miscibility only in the high-temperature phase, but almost complete demixing in the solid state. In the phase diagram an incongruent melting 11 complex is built up. This complex forms an eutectic mixture with the phase of C₁₅COOMe and a peritectic system with C₁₉COOMe.