The morphology of irradiated isotactic polypropylene

The research in this article explores the response of semicrystalline isotactic polypropylene to gamma radiation in air, and relates the morphological changes of the polymer to corresponding changes in mechanical properties. The effect of the initial morphology of the polymer on its response to irradiation is considered using infrared spectroscopy (FTIR), small‐ and wide‐angle X‐ray scattering, dynamic mechanical thermal analysis (DMTA), and mechanical testing. The extent of chain scission and crosslinking is dependent on the dose but not the initial starting morphology. These chemical changes cause the crystallinity to increase slightly, and the glass transition temperature to rise by a few degrees in all samples, but the overall morphology is only subtly changed. In contrast, a major deterioration in mechanical properties is caused. The effects of the irradiation observed under these conditions are similar in each material and the ultimate properties determined by the properties seen in the original material. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2234–2242, 1999     

ESR study on molecular motion of peroxy radicals of polytetrafluoroethylene

Temperature variations of the line shapes of e.s.r. spectra from the peroxy radicals of polytetrafluoroethylene ( ) were investigated in detail and the results were quantitatively analysed based on Kneubühl's theory on the line shape. It was found that there were two kinds of rapid molecular motions, of which the correlation times were about 10⁻⁹ s, for the peroxy radicals of ; one was the rotational motion related to the peroxy chain radical, the other was the three dimensional motion associated with the peroxy end radical. The activation energies of these molecular motions were estimated as 0·52 kcal/mol and 0·26 kcal/mol for the rotational motion and the three dimensional motion, respectively. Origins of such rapid motions were discussed in connection with the other molecular motions of polymers, which were found by other experimental methods.     

ESR studies of photoirradiated cellulose on radical formation and decay

The ESR spectra of untreated samples and photosensitized samples of rayon cellulose, amorphous cellulose, and wood cellulose irradiated with ultraviolet light were studied. Generally, several kinds of spectra were established, and ferric ion photosensitizer increased the yield of free radicals in celluloses on irradiation. The observed five-line spectrum was resolved to be a superposition of single-line, two-line, and three-line spectra. The decay of free radicals of celluloses at ambient temperature was also examined for changes of the pattern and the intensities of ESR spectra. Based on the changes of spectra induced by a warm-up process, three kinds of radicals which gave three components of the five-line spectrum were identified. During the warm-up process, phenomena of radical migration and formation of new radicals synchronized with the decay of radicals were recognized on photosensitized samples of rayon cellulose and amorphous cellulose.     

Determination of the effect of pressure on viscosity of an isotactic polypropylene

Despite the importance of the effect of pressure on the flow properties of a polymeric material, it is often overlooked also because of the difficulties involved in the experimental measurements. In this study, the effect of pressure on viscosity for an isotactic polypropylene was characterized in both a direct and an indirect method. In particular, a homemade device was adopted to obtain data of viscosity under high pressure and high shear rates. In addition, an indirect method based on the Simha–Somcynsky equation of state was adopted to obtain the dependence of free volume on temperature and pressure on the basis of experimental specific volume measurements; the Doolittle equation was then applied to verify the dependence of viscosity on free volume. The two methods provided similar results, confirming that, at least for polypropylene, the indirect method based on specific volume measurements can be used instead of the more complex direct measurement of the viscosity under pressure.     

A study on multiple melting of isotactic polypropylene

Multiple melting characteristics of a highly isotactic polypropylene (iPP) were studied by means of differential scanning calorimetry (DSC). Double melting characteristics were observed on melting iPP crystallized isothermally at temperatures ranging from 110 to 140°C. iPP crystallized below and above 125°C exhibited different double melting characteristics from each other. For iPP crystallized below 125°C, the single melting peak split into two peaks during slow DSC heating scans without changing the total crystallinity in the polymer. On the other hand, the double melting endotherm of iPP crystallized above 125°C seemed to come from two preexisting crystal fractions having different T_m. There existed an optimum annealing temperature range where the five-minute annealing of iPP raised T_m of the polymer significantly. The treatment also increased the crystallinity of iPP crystallized isothermally at 110°C by 12%.     

High pressure d.t.a. study on the melting and crystallization of isotactic polypropylene

The melting and crystallization behaviour of isotactic polypropylene (iPP) in the (monoclinic) and γ (triclinic) crystalline modifications has been studied by differential thermal analysis (d.t.a.) under high pressure. The d.t.a. melting thermograms of the sample prepared by slow cooling from the melt at atmospheric pressure ( form) and high pressure (γ form) show single endothermic peaks up to about 4600 bar in isobaric measurements. Two isolated melting point curves, corresponding to the melting of the and γ modifications, were obtained and the melting points were fitted to a quadratic equation as a function of the pressure (bar). The slope of the curve at atmospheric pressure has been determined accurately for each crystalline form. Two curves were observed for the pressure dependence of the crystallization peak temperature in the d.t.a. curve. The origin of the separated crystallization curves is discussed in relation to the degradation of the iPP melt-crystallized under high pressure.     

Power law of molecular weight dependence of lateral growth rate of isotactic polypropylene

Molecular weight (M) dependence of the lateral growth rate (V) of α form crystal of isotactic polypropylene (iPP) was studied. Reliable equilibrium melting temperature determined in our previous study was used for the analysis of supercooling dependence of V. A power law of M of V, , was obtained, where H is a small constant (H = 0.7). The small H, which is similar to that of the hexagonal phase of polyethylene (H = 0.7) in comparison with the value of H = 1.7 for the orthorhombic phase of polyethylene, confirmed our prediction of smaller H for “rod like” chain polymers because of easier chain sliding within the interface between the crystalline phase and the melt. Thus, the universality of the important role of topological nature in polymer crystallization was confirmed. Lateral surface free energy (σ) of the α form of iPP was obtained as σ ≅ 1.59 × 10⁻⁶ J/cm².     

Physical aging in isotactic polypropylene

Physical aging studies were made using commercial and laboratory samples of isotactic polypropylene. Linear and nonlinear viscoelastic responses were measured after quenching the glass from above the glass transition temperatures to below the glass transition. Results show that aging is not eliminated by large mechanical deformations; rather, the time required for the glass to age into equilibrium is independent of the applied stress. Results obtained are purely kinetic and interpreted as the effects accompanying the process of glass formation in a semicrystalline polymer. © 1996 John Wiley & Sons, Inc.     

Atomic force microscopy study of the lamellar growth of isotactic polypropylene

The growth behaviors of cross-hatched and lath-like lamellae of α-form spherulites and flat-on lamellae of β-form pherulites of isotactic polypropylene were studied with a high-temperature atomic force microscopy in situ and in real time. The growth rates of crystal lamellae in types I, II and mixed α-form spherulites and in β-form spherulites, as well as the spatial frequency of tangential branching, were measured. The frequency of tangential branching increases with decreasing crystallization temperature, while the growth rates of leading radial and tangential lamellae are approximately the same at a given temperature. Observations of as-crystallized materials demonstrated that the spacing and length of transverse lamellae is sufficient to differentiate among spherulite types. Height measurements in the melt near the growth surface indicate roles of molecular transport in the crystallization process.     

Influence of β nucleation on the mechanical properties of isotactic polypropylene and rubber modified isotactic polypropylene

The tensile and fracture behaviour of neat α and β nucleated isotactic polypropylene and rubber-modified α and β nucleated isotactic polypropylene has been investigated at test speeds of 0.0001-10 ms⁻¹ in the temperature range −30 to +60 °C. The presence of the β phase had little effect at low temperature. However, at +25 and +60 °C, it increased the speeds corresponding to the ductile-brittle transition in the neat polymer by more than three decades. This behaviour has been linked to changes in microdeformation mechanisms observed at the lamellar and spherulitic level, an increase in cavitational deformation in tensile tests and an increase in the strength of the β relaxation in dynamic mechanical spectra. In the blends, the presence of the β phase led to somewhat higher energy dissipation in regimes of ductile fracture. However, the ductile-brittle transitions were not significantly affected. The modifier phase was therefore inferred to control the initiation and propagation of the plastic zone ahead of the crack tip during fracture.     

ESR study of the radical polymerization of styrene

Summary The absolute rate constant of propagation (k_p) in styrene polymerization was determined on the basis of ESR detection of the polymer radical in the temperature range of 0 to 130°C. The Arrhenius plot of k_p gave a good linear relationship and the activation energy of the propagation was evaluated to be 39.7 KJ/mol. The termination rate constants over the same temperature range were also obtained by using the k_p values according to the standard kinetics of radical polymerization. Apparent activation energy of the termination was estimated to be 15.6 KJ/mol.     

Fabrication and morphology development of isotactic polypropylene nanofibers from isotactic polypropylene/polylactide blends

The excellent characteristics of polymeric nanofibers with diameters less than 1 μm such as the enormous specific surface result in a dramatic increase in a variety of functional applications. In this article, polymer blends of isotactic polypropylene (iPP) and polylactide (PLA) were fabricated through a twin‐screw extruder. The extrudates were prepared at various processing conditions and the iPP nanofibers were obtained by removal of the PLA matrix from the drawn samples. The influences of drawing ratio, the processing temperature, and the blend ratio of iPP/PLA on the morphology development of iPP phase were investigated by scanning electron microscopy. It was found that the uniformed iPP nanofibers with averaged diameters less than 500 nm were fabricated by the suitable processing parameters. Otherwise, the processing immiscibility and rheological behavior of iPP/PLA blends were studied by means of dynamic mechanical analysis and capillary rheometer. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Luminescence emission of isotactic polypropylene

In order to elucidate the origin of luminescent species in unstabilized commercial isotactic polypropylene (IPP), effects of hexane extraction and exposure of the extracted IPP film to the atmosphere on both fluorescence and phosphorescence emissions were examined. Fluorescence emission from the unextracted IPP film disappeared by the extraction, and only a very weak phosphorescence emission was found. During the exposure of the extracted IPP film to the atmosphere, both fluorescence and phosphorescence emissions appeared again. The intensity of the spectra increased with the exposure time and finally almost reached that from the unextracted IPP film. The results indicated that main fluorescent species in IPP are foreign impurities originating from an ambient atmosphere, and that contribution of a very minor amount of phosphorescence species such as carbonyl groups incorporated with the polymer was scarce.     

In situ optical microscope study of the shear-induced crystallization of isotactic polypropylene

The shear-induced crystallization behavior of isotactic polypropylene (i-PP) has been investigated by in situ optical microscope under various thermal and shear histories. A shish-kebab structure during growth was observed under a well controlled, however, weak shear field. According to our results under these weak shear and thermal history, a modified model was proposed for the growing process of melt shear-induced crystallization of i-PP. Furthermore, many physical insights were provided on several still unsettled issues such as extended chain crystals, row nuclei, and smectic ordering questions.     

ESR study on radical polymerization of styrene

Summary Propagation rate constant (k_p) for styrene was evaluated at different chain lengths of the polymer radical based on the steady-state concentration of the polymer radical determined by means of ESR spectroscopy at 70°C. Over a range of degree of polymerization of the polymer radical from 40 to 410, the value of k_p, 480±10 L/mol·s, remained constant. A considerable increase in viscosity of the polymerization mixture did not affect this value.     

Globules of microparacrystals in nascent isotactic polypropylene

SAXS and TEM measurements were used in studying the morphology of nascent isotactic polypropylene (PP) polymerized with a high-yield heterogeneous Ziegler-Natta MgCl₂ supported catalyst. In contrast to the melt- or solution- crystallized isotactic PP cases, the SAXS datam obtained here using Kratky-camera and TEM diagrams, show the characteristic scattering of globules (～ 1100Å in diameter) and a remarkably small polydispersity of 0.14. TEM observations also show sometimes the presence of smaller globular particles of about 300Åin diameter whose amount is below the resolving power of SAXS. Due to the lack of interparticle interference, lamellae do not exist and therefore no mention of an amorphous phase is required. WAXS can be analysed as a series of overlapping reflections with paracrystalline (liquid-like) distortions at g = 5%. These microparacrystals (mPC's) have in accordance with the α*-law, a mean size of (α*/g)²d¯=60Å and constitute the globules. From line profile analysis one finds that their polydispersity g_N is 0.4 and this agrees well with a relation between N and g_N which is deduced theoretically for microparacrystal-ensembles in the equilibrium state. A new relation between the polydispersity g^N of microparacrystals and the size of globules is derived from TEM observations. These observations sometimes show clearly separated spherical particles whose size distribution is in the range of the SAXS results, but varies from micrograph to micrograph. The morphology of the nascent PP is greatly influenced by the distribution of the active centres on the catalyst's carrier and this excludes the regular chain-folding in a crystalline phase and the existence of larger disordered chain segments in an amorphous phase. The whole volume is therefore filled with microparacrystals.     

Character of crystallization nuclei in isotactic polypropylene

Examination of the isothermal crystallization and the effect of melting conditions on samples of isotactic polypropylene and its composite with talc, combined with electron-microscopic observation, has shown two types of heterogeneous nuclei effective in the crystallization process: (1) metastable nuclei, representing the unmelted crystalline phase of polypropylene, stabilized by solid heterogeneities, and operating after melting at relative low melting temperature and/or short melting time; and (2) stable crystallization nuclei, associated with solid heterogeneities, being probably catalyst residues. On the surface of these nuclei isotactic polypropylene tends to crystallize in an ordered fashion.     

SAXS study on structure formation from the uniaxially oriented glass in isotactic polypropylene

The structure formation of isotactic polypropylene from the uniaxially oriented glass into the smectic mesophase has been studied by small-angle X-ray scattering. Remarkable anisotropy between the directions parallel and perpendicular to the chain axis is found in the development of structure formation. Below −20 °C is observed a structure with density variation having the wave vector, perpendicular to the chain axis with a period of 5 to 6 nm. Between −20 and +25 °C, the density variations with both parallel and perpendicular to the chain axis develop. Above +25 °C, the density variation with perpendicular to the chain axis develops but disappears eventually, while that parallel to the chain axis keeps on growing.     

聚丙烯复合材料的非等温结晶动力学

采用差示扫描量热仪研究了β成核剂和水滑石(LDH)/β成核剂复配的成核剂对聚丙烯(PP)非等温结晶动力学及熔融行为的影响。结果表明:加入成核剂后,PP中晶体分布不均匀且分散度增大。莫志深方法采用F(θ)表征聚合物在单位时间内达到某一结晶度时所需的冷却(或加热)速率,结晶度达到40%时,纯PP的F(θ)为3.82,加入β成核剂的PP的F(θ)为3.30,加入LDH/β成核剂的PP的F(θ)为2.49。与纯β成核剂相比,LDH/β成核剂能更好地提高PP的结晶温度、结晶速率,增强PP的β晶熔融峰,减弱β晶和α晶共存熔融峰和α晶熔融峰。