Further study on double‐melting endotherms of isotactic polypropylene

The origins of the single‐ and double‐melting endotherms of isotactic polypropylene crystallized at different temperatures were studied carefully by differential scanning calorimetry, wide‐angle X‐ray diffraction, and small‐angle X‐ray scattering. The experimental data show that spontaneous crystallization occurs when the crystallization temperature is lower than 117°C; thus the lamellae formed are imperfect. At a lower heating rate, the recrystallization or reorganization of these imperfect lamellae leads to double endotherms. On the other hand, when the crystallization temperature is higher than 136°C, two major kinds of lamellae with different thickness are developed during the isothermal process, which also results in the double‐melting endotherms. In the intermediate temperature range the lamellae formed are perfect, and there is only a single peak in the distribution of lamellar thickness. This explains the origin of the single‐melting endotherm. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 163–170, 2000     

Effect of orientation on melting of isotactic polypropylene

The effect of uniaxial orientation on the melting of a commercial grade of isotactic polypropylene has been investigated by thermal analytical techniques. Orientation progressively shifts the onset of and the observed melting point to higher temperatures and increases the peak heights of differential scanning calorimetric (DSC) endotherms. The increase in melting point with orientation is attributed to the increase in configurational entropy of the extended melt into which the polymer crystallites melt.     

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.     

Effect of β-nucleating agents on crystallization and melting behavior of isotactic polypropylene

Two kinds of β-nucleating agents, named a rare earth complex (WBG) and a N,N′-dicyclohexylterephthalamide (TMB5), were introduced into isotactic polypropylene (iPP), and their effect on crystallization and melting behavior of iPP was comparatively investigated. Wide angle X-ray diffraction measurements revealed that both the two additives were highly effective in inducing β modification. At their respective optimum concentrations of 0.08 wt % for WBG and 0.06 wt % for TMB5, the relative amount of β-form calculated by Turner-Jones equation both exceeds 92%. However, the isothermal crystallization kinetics investigated by differential scanning calorimetry demonstrated that WBG had more pronounced effect than TMB5 in accelerating the overall crystallization rate. The Lauritzen–Hoffman theory analysis also revealed that WBG was more effective not only in increasing the nucleus number but also in accelerating the growth rate of crystallization. After completing isothermal crystallization process, the subsequent melting behavior examination suggested that the addition of WBG expanded the upper limit temperature of forming β modification, and therefore was more effective in delaying the β-α transformation than TMB5. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Morphology,crystallization and melting properties of isotactic polypropylene blended with lignin

The influence of lignin (L) on the thermal properties and kinetics of crystallization of isotactic polypropylene (PP) is reported in this article. PP blends containing 5 and 15 wt % of L were prepared by mixing the components in a screw mixer. An increase of the thermal degradation temperature of the blends was observed as a function of L content. The crystallization and thermal behavior of the pure PP and of the PP/L blends were analyzed by differential scanning calorimetry (DSC). Isothermal crystallization kinetics were described by means of the Avrami equation, which suggests a three‐dimensional growth of crystalline units, developed by heterogeneous nucleation. The isothermal growth rate of PP spherulites was studied using a polarizing optical microscope. The enhancement of PP crystallization rate for the PP/L blends was observed and ascribed to the nucleating action of lignin particles. Non‐isothermal crystallization kinetics were applied, according to the results elaborated by Ziabicki and the method modified by Jeziorny. The kinetic crystallizability of the PP is not influenced by the L present in the blend. In the presence of L, PP can simultaneously crystallize in both the α and β crystalline forms, and the ratio between the α and β forms was determined by X‐ray diffraction analysis. Two melting peaks relative to the two crystalline form of PP were observed for the PP/L blends, for all isothermal crystallization temperatures investigated by means of DSC. The equilibrium melting temperature for α‐form of pure PP was obtained. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1435–1442, 2004     

Influence of the conformational order of glassy isotactic polypropylene on its crystallization and melting behaviour

The influence of conformational order of glassy isotactic polypropylene (iPP) on its crystallization and melting behaviour was studied by wide‐angle X‐ray diffraction (WAXD), Fourier‐transform infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC). The glassy iPP samples with various conformational orders were prepared by freeze‐drying procedure from very dilute solution. WAXD and FTIR results suggest that although freeze‐dried samples are non‐crystalline, their conformational order is rather high and increases with decreasing concentration of parent solutions. With increasing conformational order of glassy samples, the cold crystallization peak shifts to lower temperature, indicating acceleration of crystallization. At low fusion temperature, the conformational order of melt obtained from freeze‐dried samples is high so that the relaxation time of single‐ and pauci‐chains to re‐entangle is long and the interpenetration between single‐ and pauci‐chain collective particles is slow. However, at high fusion temperature, the interpenetration process can be completed very quickly. Copyright © 2004 Society of Chemical Industry     

Morphological features and melting behavior of nanocomposites based on isotactic polypropylene and multiwalled carbon nanotubes

Nanocomposites based on low molar mass isotactic polypropylene (iPP) and a low concentrations (1–2 wt %) of multiwalled carbon nanotubes (MWCNTs) were studied using thermal analysis, optical and electronic microscopy, and X‐ray diffraction/scattering techniques. It was first determined that MWCNT decrease induction time and act as nucleating agents of the iPP crystals during nonisothermal crystallization. One of the consequences of the nucleation effect was that the original spherulitic morphology of iPP was transformed into a fibrillar‐like. The corresponding long period of the original well‐defined lamellar structure slightly increased suggesting the formation of thicker crystals in samples containing MWCNT. The nature of the α‐iPP crystalline structure was not affected by MWCNT. After nonisothermal crystallization, two melting endotherms were present during thermal scanning of the iPP/MWCNT nanocomposites their proportion changing with the heating rate. After resolving the total DSC signal in its components using MDSC, the overall evolution of such behavior could be explained in terms of the melting/recrystallization mechanism. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

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。     

A SAXS–WAXD study on the mesomorphic-α transition of isotactic polypropylene

The smectic-α transition of iPP was studied by wide angle X-ray diffraction (WAXD) and small angle X-ray scattering (SAXS). WAXD and SAXS patterns were taken at different temperatures during the transition. Two different approaches were taken in the analysis of SAXS data: the correlation function and a fitting method based on theoretical distribution models. Up to 80°C just smectic phase was observed, whereas beyond that temperature α lamellae appeared and the two populations of lamellae were found to coexist in the sample. The new α phase population stemmed from within the preexistent smectic stacks, according to a lamellar insertion model. α lamellae thickened to a larger extent than the smectic phase, that just underwent thermal expansion. Results were consistent with a mechanism of transformation involving a rearrangement of the chains without a melting-recrystallization process. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

The effect of nanoclays on the nucleation,crystallization, and melting mechanisms of isotactic polypropylene

The influence of organomodified nanoclay (montmorillonite) on the crystallization and melting mechanisms of isotactic polypropylene (iPP) was studied. Films of both neat polymer and clay nanocomposites were prepared after molecular weight optimization through melt extrusion. Products exhibited the tactoidlike morphology since no compatibilizers were used. The effect of introduction of nanoclay within the polymer was studied through isothermal crystallization and linear heating. The results indicated that low nanoclay concentrations induce the formation of the β‐crystalline structure, its formation being inhibited with high nanoclay contents. Dynamic nonisothermal bulk crystallization experiments indicated that nanoclays act as nucleating agents of iPP. Isothermal, bulk crystallization studies indicated that the crystallization process (induction time and crystallization kinetics) is proportionally accelerated by the nanoclay presence. There was also an accelerated formation of secondary crystallization when nanoclays were present in high concentrations. POLYM. ENG. SCI., 47:1889–1897, 2007. © 2007 Society of Plastics Engineers     

Crystallization and melting behavior in syndiotactic polypropylene: Origin of multiple melting phenomenon

The melting behavior of syndiotactic polypropylene (s‐PP) after isothermal crystallization from the melt state was studied using differential scanning calorimetry (DSC) and wide‐angle X‐ray diffraction (WAXD) techniques. Three melting endotherms were observed for isothermal crystallization at high degrees of undercooling. The minor endotherm, located closed to the corresponding crystallization temperature, was postulated to be the melting of the secondary crystallites formed at the crystallization temperature. The low‐temperature melting peak was found to be the melting of the primary crystallites formed, and the high‐temperature melting peak was a result of the melting of the crystallites recrystallized during a heating scan. The triple‐melting behavior observed in subsequent melting endotherms of s‐PP was therefore described as contributions from melting of the secondary crystallites and their recrystallization, partial melting of the less stable fraction of the primary crystallites and their recrystallization, melting of the primary crystallites, and remelting of the recrystallized crystallites formed during the heating scan. In addition, determination of the equilibrium melting temperature for this s‐PP resin according to the linear and nonlinear Hoffman–Weeks extrapolations provided values of 143.1 and 185.6°C, respectively. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1083–1097, 2001     

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.     

Influences of the chemical defects on the crystal thickness and their melting of isothermally crystallized isotactic polypropylene

Ziegler-Natta and Metallocene Catalysis isotactic polypropylene with different chemical defects were isothermally crystallized at various crystallization temperatures. The crystal thickness and their corresponding melting behavior were studied using small angle X-ray scattering, atomic force microscopy, optical microscopy, and differential scanning calorimetry. The equilibrium melt temperature of the samples was calculated from the Hofmann-Weeks extrapolation for the supercooling. Two lamellar populations were distinctly observed in all cases during the crystallization process. Relatively thicker and stable lamellar crystals which melt at higher temperatures were observed with lowering the supercooling and found catalysis dependence in these crystals. During melting, no significant recrystallization of the samples has been detected for higher crystallization temperature where recrystallization processes enhance the lamellae thickness. The melting of the crystals has found strong dependence with the crystallization temperatures, the catalysis process and the nature of the defects present in the isotactic polypropylene. The increase of the crystal lamellae thickness and their melting temperature might be presumably related with the chain folding mechanism as well as the stability of the crystals formed during the isothermal crystallization process. A combined plot of SAXS and DSC results is demonstrated for the equilibrium melting temperature followed by critical analysis of the results.     

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.     

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.     

A deformation induced order-disorder transition in isotactic polypropylene

In this study, isotactic polypropylene (i-PP) has been deformed by uniaxial compression to draw ratios up to 16×, and at draw temperatures from 30°C to 140°C. An order-disorder transition in the crystals is observed at draw temperatures well above the stability limit, 70°C, reported for the disordered phase; Furthermore, this disordered phase (called smectic) is found to induce ductility and improve the efficiency of draw. The deformation induced smectic phase has been characterized using WAXS, DSC, and on-line compression load versus draw ratio measurements. In consequence, a set of process conditions are offered to optimize draw. A mechanism for plastic deformation of i-PP is also suggested, using the smectic phase as a probe.     

Formation and behaviour of low‐temperature melting peak of quenched and annealed isotactic polypropylene

The process of low‐melting point (LMP) α‐phase formation in a quenched and annealed isotactic polypropylene (iPP) was studied by means of differential scanning calorimetry. The influence of preparation conditions (quenching and annealing temperatures, annealing times and sample thickness), together with the measurement parameters (heating and cooling rates), on the iPP melting behaviour are analysed. The results reveal a constant yield of LMP crystals over a wide range of quenching temperatures. This study also suggests that the LMP α‐crystals originate from the crystallization of polymer portions, which are somewhere between the amorphous and the smectic phase on the macromolecular scale of order. © 2001 Society of Chemical Industry     

Effects of substituted aromatic heterocyclic phosphate salts on properties,crystallization, and melting behaviors of isotactic polypropylene

Nucleation effects of 2,2′‐methylene‐bis (4,6‐di‐tert‐butylphenyl) phosphate metal salts as a nucleating agent for isotactic polypropylene (iPP) were investigated with differential scanning calorimeter and polarized optical microscope, and their effects on mechanical, optical, and heat resistance properties of iPP were also studied. The results showed that monovalent metal salts of substituted aromatic heterocyclic phosphate such as sodium salt, lithium salt, and potassium salt had a good performance. With 0.2 wt % of sodium salt, lithium salt, or potassium salt incorporated into iPP, the crystallization peak temperature of iPP could be increased by 13.5, 13.6, and 15.0°C, respectively; the mass fraction of crystallinity of iPP could be increased by about 5%; and crystallization rate was enhanced increasingly. Meanwhile the tensile strength and flexural modulus of iPP could be increased by about 10 and 30%, respectively, and the clarity and heat distortion temperature of iPP could also be improved significantly. But bivalent and trivalent metal salts of substituted aromatic heterocyclic phosphate had little effect on properties of iPP. Meanwhile the morphology study showed that the addition of monovalent sodium salt could decrease the spherulite size of iPP significantly. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4868–4874, 2006     

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.