The spherulitic and lamellar morphology of melt-crystallized isotactic polypropylene

A study is presented concerning the basic morphology of melt-crystallized isotactic polypropylene (iPP). Involved within, is the coordinated application of optical and electronmicroscopy on a range of commercial iPP-s, crystallized in the temperature range 100°C–150°C. For electron microscopy in particular, the permanganic etching technique has been used throughout, providing the simultaneous combination of both real space microstructures with electron diffraction information. The investigation itself has centred on the five different spherulite types, as identified optically, which were then correlated with the details of their particular lamellar morphology. It was found that each spherulite type is characterized by virtue of the arrangement of its constituent lamellae, in terms of orientation, habit type and crystal structure. Thus, specific correlations were obtained between the structural entities on all scales of the structure hierarchy.     

Dependence of electrical breakdown on spherulite size in isotactic polypropylene

A self-seeding technique, coupled with isothermal crystallization, was used to prepare isotactic polypropylene specimens of varying spherulite size, but of constant crystallinity and lamellar thickness. The latter quantities were also varied by changing the isothermal crystallization temperature. The electrical lifetime at constant applied voltage, in a point-plane geometry, was measured. It was found that the electrical lifetime decreased with increasing spherulite size and, more weakly, with decreasing crystallinity (at a given spherulite size).     

On the lamellar morphology of melt-crystallized isotactic polystyrene

The lamellar morphology of melt-crystallized isotactic polystyrene has been investigated by extending the technique of permanganic etching for electron microscopy. This paper reports on objects grown at 220°C which are comparatively uncomplicated, being aggregates of hexagonal lamellae, with smooth facets and distinguishable internal sectors, organized into axialites. To a first approximation only, hexagonal lamellae splay apart about a common diagonal presenting three characteristic projections in orthogonal directions. These are hexagonal, sheaflike and an array of approximately parallel lamellae. In reality the term axialite is an oversimplification. Splaying is not restricted to a single axis but occurs in three dimensions making these objects incipient spherulites. Polystyrene spherulites grown as low as 180°C the temperature of maximum growth rate are also constructed on the same principles as are spherulites of polyethylene and isotactic polypropylene. These are that a framework is established by individual dominant lamellae which branch and splay apart leaving interstices to be filled by later-crystallizing subsidiary lamellae. There is evidence that subsidiary lamellae contain shorter molecules on average than do dominant lamellae. The dominant/subsidiary construction is not what had been assumed in the Keith and Padden theory of spherulitic growth nor is there evidence of cellulation or local diffusion influencing development even though crystal sizes exceed the Keith and Padden parameter · by two orders of magnitude. We conclude that polymer spherulites can form independently of the mechanism proposed by Keith and Padden¹⁴. It is suggested that the cause of lamellae splaying apart is a mutual repulsion due to uncrystallized portions of molecules between dominant lamellae.     

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.     

低等规聚丙烯的研制Ⅴ.粘性聚合物的分离技术

采用液相本体法生产的粘性低等规聚丙烯在排放输送和分离回收时易堵塞阀门和管道。模试结果表明：控制聚合时丙烯转化率为20％～50％,同时预先在闪蒸釜中加人表面分散剂质量分数约0．3％的液体介质及预先充人丙烯单体可以有效地解决这一问题。介绍了采用乙醇-水溶液作为分散介质的分离技术特征,并可用深度冷冻法或吸附极性分子法从回收体系中除去乙醇。     

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.     

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.     

The physical aging of isotactic polypropylene

The microstructural changes in isotactic polypropylene (PP), subsequent to quench from the melt to around T_g were studied using dynamic mechanical loss, volume dilatometry, small and wide angle X-ray scattering, infrared and NMR spectroscopy. The β-transition loss tangent and the specific volume decreased linearly with logarithm of aging time. Dynamic mechanical loss and NMR spectroscopy results established that amorphous chain mobility reduced during aging. X-ray and IR techniques showed that the crystallinity, the crystalline density, and the average chain conformation do not change during aging. Tensile tests indicated that diffusion of air or moisture into the polymer is not a competitive mechanism for the aging phenomenon. A simple free-volume model is quantitatively consistent with these observations. The fraction of the material which cannot age increased as the quench temperature decreased. Further, at lower temperatures a portion of the nonageable fraction is shown to reside in the amorphous fraction.     

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。     

固相氯化法氯化等规聚丙烯结构分析

借助ＤＳＣ,ＩＲ,＾１Ｈ－ＮＭＲ方法对搅拌式固相氯化制备的氯化等规聚丙烯的宏观氯原子分布和微观氯原子分布进行了分析。结果表明,搅拌式固相氯化法能够迅速破坏等规聚丙烯的结晶,从而得到宏观氯原子分布均匀的ＣＩＰＰ。此方法制备的ＣＩＰＰ主要为等丙烯分子链上的仲氢原子被取代的产物。     

Radiation-induced oxidative degradation of isotactic polypropylene

Gas evolution, oxygen consumption, and change of mechanical properties were studied for the γ-ray irradiation of isotactic polypropylene from ⁶⁰Co under various conditions, such as vacuum, air, and oxygen at room temperature. For irradiation under vacuum, G(H₂) = 2.9 and G (CH₄) = 0.09; the G values for other gases were very small. In the presence of oxygen, G(H₂) was the same, and the G values for other hydrocarbons were two times those under vacuum. The G values of oxidative products and oxygen consumption were G(CO₂) = 2.5, G(CO) = 1.1, and G(O₂) = 50 at oxygen pressure of 500 torr and were dependent on oxygen pressure. With irradiation under vacuum at 2–3 Mrad, mechanical properties scarcely changes immediately after irradiation but degrade gradually with storage time in air at room temperature.     

Uniaxial roll-drawing of isotactic polypropylene sheet

The process described as “roll-drawing” has been applied to commercial extruded sheets of isotactic polypropylene (M?_n = 70,900). Preheated billets were drawn into thin, clear, transparent sheets in a single pass, producing uniaxial orientation of the polymer molecules in the draw direction. At the maximum draw ratio of 20, the ultimate tensile strength and Young's modulus in the draw direction were 0.5 GPa and 20 GPa respectively. The mechanical properties transverse to the draw direction were virtually unchanged. The theory of fiber reinforcement for unidirectional anisotropic plates was applied to interpret the orientation dependence of the stress-strain behavior of the drawn sheets. From these results, it was estimated that the mechanical properties of biaxially laminated polypropylene sheets equaled the performance of aramid and carbon fiber composites, The roll-drawing process appears to be economically attractive for the production of ultra-high modulus crystalline thermoplastics in sheet form having excellent uniaxial or biaxial properties.     

Thermal stability of additivated isotactic polypropylene

Summary Isotactic polypropylene stabilised with fullerene [C60], its adduct with methyl levopimarate, carbon black, p-t-butylcalix[4]arene, p-t-butylcalix[6]arene, Irganox 1076 or Topanol OC was investigated by means of oxygen uptake method under isothermal (165^°C) and isobaric (normal pressure) conditions. Oxidation investigations were performed in air as degradation environment. Additive concentration was 0.25 % (w/w). Kinetic parameters, oxidation induction and oxidation rate are compared with similar characteristics of additive-free i-PP. Effect of γ-irradiation on thermal oxidation is also presented. Three γ-exposure doses (50, 100 and 150 kGy) were selected. The influence of radiation treatment on the efficiency of studied compounds and some mechanistic aspects are also presented. Received: 5 June 2002/Revised version: 10 August 2002/ Accepted: 12 September 2002 Correspondence to Traian Zaharescu     

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     

Some crystallization kinetics of isotactic polypropylene

Infra-red evidence is presented that the building of helices in the crystallization process from the glassy (or smectic) phase or from the melt are second order or zero-th order respectively. The observation coupled with data from density and X-ray diffraction measurements is interpreted in molecular structural terms.     

Crystallization features of oxidized isotactic polypropylene

The effect of the initial molecular weight parameters of polypropylene on the kinetics of isothermal polymerization is shown. It is found that the feed polymer with a wider molecular weight distribution (P-1) is characterized by lower values of the half-crystallization time as compared to the polymer with a narrower molecular weight distribution (P-2). Comparison between the crystallization parameters and the kinetics of accumulation of oxidation products showed that as the degree of oxidation of the polypropylene increases, the crystallization rate for both samples decreases and the concentration of the oxidation products increases. In this case, the degradation of tie chains accelerates the formation of crystallites. It is shown that P-1 has a higher nucleation energy as compared with P-2 and that this parameter increases during the oxidation of both polymers.     

Thermal characteristics and crystallinity of Ziegler–Natta isotactic polypropylene/metallocene isotactic polypropylene polyblended fibers

Ziegler–Natta isotactic polypropylene (ZN‐iPP) and metallocene isotactic polypropylene (m‐iPP) were extruded (in ratios of 75/25, 50/50, and 25/75) from one melt twin‐screw extruder to produce three ZN‐iPP/m‐iPP polyblended polymers and, subsequently, spin fibers. In this study, we examined the rheology of the ZN‐iPP/m‐iPP polyblended polymers and the thermal characteristics and crystallinity of the ZN‐iPP/m‐iPP polyblended fibers using gel permeation chromatography, rheometry, differential scanning calorimetry (DSC), wide‐angle X‐ray diffraction, density gradient analysis, and extension stress–strain measurement. The apparent melt viscosity of the ZN‐iPP/m‐iPP polyblended polymers revealed positive‐deviation blends. The 50/50 blend of ZN‐iPP/m‐iPP had the highest apparent melt viscosity. For five samples, the complex melt viscosity decreased with the angular frequency, which represented typical non‐Newtonian behavior. The Cole–Cole plot, which consisted of the imaginary part of the complex melt viscosity versus the real part of the complex melt viscosity plot, of the ZN‐iPP/m‐iPP polyblended polymers showed a semicircular relationship with the blend ratios. It indicated that the ZN‐iPP/m‐iPP polyblended polymers were miscible. We analyzed the shear modulus data (G′ vs G″) by plotting them on a log–log scale. The plot revealed almost the same slopes for the ZN‐iPP/m‐iPP polyblended polymers, which indicated a good miscibility between the ZN‐iPP and m‐iPP polymers. The experimental DSC results demonstrate that the ZN‐iPP and m‐iPP polymers constituted a miscible system. The crystallinity and tenacity of the ZN‐iPP/m‐iPP polyblended fibers initially increased and then fell as the m‐iPP content increased. Meanwhile, the 50/50 blend of ZN‐iPP/m‐iPP had the highest crystallinity and tenacity. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effects of thermal history on isotactic polypropylene

The effect of past thermal history on the melting behavior of isotactic polypropylene is investigated in some detail. It is shown that a series of stepwise annealing treatments at steadily increasing temperatures will raise the final melting point and will result in a double endothermic peak if the final anneal temperature is at or close to 160°C. It is also shown that a series of stepwise annealing treatments at steadily decreasing temperature will lead to multiple DSC peaks. The number of such separate peaks is equal to or greater than the number of annealing steps. Even low-temperature anneals (100–130°C) affect the melting endotherm, while high-temperature anneals have a marked effect on both the degree of crystallinity of the sample and the final melting temperature. For a 3-min anneal, the highest degree of crystallinity is produced by an anneal temperature of 155°C. The highest melting temperature (～182°C) is produced by a 30-min, or longer, anneal at about 160°C. The implications of these results in terms of crystal thickening and perfection are discussed.     

Electrospun-fiber induced transcrystallization of isotactic polypropylene matrix

To reveal the influences of fiber diameter and characteristics on the surface-induced matrix crystallization, four different fibers, i.e. syndiotactic polystyrene (sPS), Nylon 6, and polyhydroxyamide (PHA) and poly(p-phenylene benzobisoxazole) (PBO) fibers, were used to study their nucleating abilities towards isotactic polypropylene (iPP) matrix. Among them, micron-sized PBO fibers were obtained from the supplier, whereas submicron-sized fibers of sPS, Nylon 6 and PHA were prepared by the solution electrospinning process developed in this laboratory. To resolve the observation difficulty due to the fast nucleation rate and crystal growth at high supercooling degrees (>60 °C), a high speed camera was mounted on the polarized optical microscope equipped with a hot stage to successfully snapshot the corresponding processes at various crystallization temperatures (T_c) in the range of 96-120 °C. For all the active fibers, only α-form iPP transcrystallites were observed at the fiber/matrix interface. Two crucial parameters were proposed for characterizing the fiber nucleating ability, i.e. the interfacial free energy difference (Δσ) based on the heterogeneous nucleation from a thermodynamic point of view, and the maximum temperature for transcrystalline layer observed (T_max) based on a kinetic consideration. Values of Δσ for different fibers were derived on the basis of the tertiary nucleation taking place in the selective “grooves” at the fiber surface. It was found that the nucleating rate of sPS fibers was scaled with the fiber diameter, and Δσ showed a negligible diameter dependence, but T_max slightly increased with increasing fiber diameter. For all the fibers investigated, an intimate relation between the Δσ and T_max was derived and used to compare their nucleating abilities.