Crystallization characteristics of isotactic polypropylene with and without nucleating agents

Nucleation effects of two sorbitol derivatives on the crystallization of isotactic polypropylene (iPP) were studied by means of differential scanning calorimetry (DSC) and polarized optical microscopy (POM). A nonisothermal crystallization kinetic equation was employed to analyze the crystallization characteristics of iPP with or without the nucleating agents from DSC crystallization thermograms. The equilibrium melting temperature of iPP necessary for the kinetic study was obtained by the extrapolation method to be 209°C. The nonisothermal crystallization kinetic analysis for the unnucleated iPP at different cooling rates was possible by assuming the spherulite growth initiated simultaneously by heterogeneous and homogeneous nucleation. On the other hand, the crystallization kinetics of the nucleated iPP could be described by the heterogeneous nucleation and growth process alone. The addition of the nucleating agents up to their saturation concentrations in iPP increased the crystallization peak temperature by 17°C, and the number of effective nuclei by three orders of magnitude. A high concentration of the nucleating agents caused agglomeration of the agents to lower the number of effective nuclei.     

Effect of nano-nucleating agent addition on the isothermal and nonisothermal crystallization kinetics of isotactic polypropylene

Using differential scanning calorimetry (DSC) technique, a comparative study has been made of the isothermal and nonisothermal crystallization kinetics of nonnucleated isotactic polypropylene (iPP) and of nucleated iPP with 0.5 wt% of single-walled carbon nanotubes (SWCNTs) as a nucleating agent. The Avrami exponents (n) of iPP and nucleated iPP are close to 3.0 for isothermal crystallization. These results indicate that the addition of nucleating agents did not change the crystallization growth patterns of the neat polymer and that crystal growth was heterogeneous three-dimensional spherulitic. The results show that the addition of SWCNTs can shorten the crystallization half-time (t _1/2) and increase the crystallization rate of iPP. In the nonisothermal crystallization process, the Ozawa model failed to describe the crystallization behavior of nucleated iPP. The Cazé–Chuah model successfully described the nonisothermal crystallization process of iPP and its nanocomposite. A kinetic treatment based on the Ziabicki theory is presented to describe the kinetic crystallizability, in order to characterize the nonisothermal crystallization kinetics of iPP and nucleated iPP. Polarized light microscopy (PLM) experiments reveal that SWCNTs served as nucleating sites, resulting in a decrease of the spherulite size.     

Effect of nucleating agent addition on crystallization of isotactic polypropylene

The isothermal and nonisothermal crystallization kinetics of nonnucleated and nucleated isotactic polypropylene (iPP) were investigated by DSC and a polarized light microscope with a hot stage. Dibenzylidene sorbitol (DBS) was used as a nucleating agent. It was found that the crystallization rate increased with the addition of DBS. The influence of DBS on fold surface energy, σ_e, was examined by the Hoffman and Lauritzen nucleation theory. It showed that σ_e decreased with the addition of DBS, suggesting that DBS is an effective nucleating agent for iPP. Ozawa's theory was used to study the nonisothermal crystallization. It was found that the crystallization temperature for the nucleated iPP was higher than that for nonnucleated iPP. The addition of DBS reduced the Ozawa exponent, suggesting a change in spherulite morphology. The cooling crystallization function has a negative exponent on the crystallization temperature. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 2089–2095, 1998     

Influence of a particulate nucleating agent on the quiescent and flow-induced crystallization of isotactic polypropylene

Flow induced crystallization of commercial isotactic polypropylene (iPP) and its blends with sodium 2,2′-methylene bis-(4,6-di-tert-butylphenyl) phosphate (also known as NA11) is studied by means of in-situ time resolved small-angle X-ray scattering (SAXS). The isothermal crystallization at 145 °C (i.e. well below melting temperature of polymer) is performed after the application of steady shear to probe the anisotropic structure formation. In order to separate the influence of shear rate and shear time on polymer crystallization, four different shear conditions (60 s⁻¹ for 1 s, 30 s⁻¹ for 2 s, 15 s⁻¹ for 4 s and 6 s⁻¹ for 10 s) are applied while maintaining the same imposed strain in the polymer melt. Further the effect of different concentration of nucleating agent on the crystallization kinetics of iPP is examined both under quiescent and shear flow conditions. For instance, under quiescent condition, the crystallization half-time (τ_1/2) decreases with the increasing concentration of nucleating agent in the polymer. Under shear flow conditions, our observations are as follows: In the case of neat iPP, τ_1/2 decreases significantly at higher shear rates (≥30 s⁻¹). Compared to the neat iPP, for the same concentration of NA11 in the NA11/iPP blends differences in τ_1/2 with the increase in applied shear rates are significantly smaller. In other words, the crystallization kinetics is dominated by the amount of nucleating agent in the NA11/iPP blends as opposed to shear rates in the neat iPP. The present study shows that the critical value of shear rate required for chain orientation in the molten polymer is lower in the presence of the nucleating agent compared to neat iPP. The self-nucleation process investigated with the aid of differential scanning calorimetry (DSC), indicates that the nucleating efficiency of NA11 on iPP is around 60%.     

Anomalous molecular orientation of isotactic polypropylene sheet containing N,N′-dicyclohexyl-2,6-naphthalenedicarboxamide

Small amount of N,N′-dicyclohexyl-2,6-naphthalenedicarboxamide as a β-form nucleating agent is dissolved beyond 280 °C in a molten isotactic polypropylene (iPP) and appears as needle crystals around at 240 °C during cooling procedure. Further, iPP molecules crystallize on the surface of the needle crystals, in which c-axis of the β-form iPP crystals grows perpendicular to the long axis of the needle crystals. Under flow field at extrusion processing, the needle crystals orient to the flow direction prior to the crystallization of iPP. As a result, c-axis of the β-form iPP crystals orients perpendicular to the applied flow direction with a small amount of α-form iPP. Moreover, the vertical molecular orientation of the extruded sheet sample is responsible for unique mechanical anisotropy; the fracture occurs along the transversal direction.     

A novel highly efficient β‐nucleating agent for isotactic polypropylene

A novel highly efficient β‐nucleating agent for isotactic polypropylene (iPP), hexahydrophthalic barium (HHPA‐Ba), was found and its effects on the mechanical properties, the β‐phase content, and crystallization behavior of iPP were investigated, respectively. The results show that the β‐phase content of nucleated iPP (k_β value) can reach 80.2% with 0.4 wt % HHPA‐Ba. The impact strength and crystallization peak temperature of nucleated iPP are greatly increased. Compared with pure iPP, the impact strength of nucleated iPP can increase 2.4 times. Meanwhile, the spherulite size of nucleated iPP is dramatically decreased than that of pure iPP. The Caze method was used to investigate the nonisothermal crystallization kinetics of nucleated iPP and the crystallization active energy was achieved by Kissinger method. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Fast isothermal calorimetry of modified polypropylene clay nanocomposites

Calorimetric experiments at cooling rates comparable to those during injection molding, as an example, are needed to study phase transitions under conditions relevant for processing. Ultra fast scanning calorimetry is a technique which provides a means to analyze the materials of interest under rapid cooling conditions and it is a promising technique by which the crystallization behavior of composite systems based on fast crystallizing polymers like isotactic polypropylene (iPP) can be studied. By combining conventional DSC and ultra fast chip calorimetry isothermal crystallization experiments were performed in the whole temperature range between glass transition and melting temperature of iPP. Because of the very small time constant of the calorimeter, isothermal crystallization processes with peak times down to 100 ms were investigated after cooling the sample from the melt at 2000 K/s. iPP grafted with maleic anhydride (PPgMA) - montmorillonite clay nanocomposites were studied. The influence of various clay loadings on the crystallization behavior of PPgMA at different temperatures was followed by ultra fast isothermal calorimetry. PPgMA clay nanocomposites showed a variation in crystallization peak times with different clay loadings at crystallization temperatures between 70 °C and 100 °C. No influence of clay loading was observed at lower crystallization temperatures. At these temperatures, where the mesophase is formed and homogeneous nucleation is expected, the contribution of the clay as a nucleating agent is negligible. For crystallization at about 80 °C, where the α-phase is formed, the nucleating effect of the clay is observed yielding complex crystallization kinetics. In the temperature range 75-85 °C in some nanocomposites a double peak during isothermal crystallization was observed corresponding to a fast and a slow crystallization processes occurring simultaneously. At higher temperatures, above 120 °C, the clay slightly retards the crystallization process.     

Influence of a nucleating agent on the crystallization behaviour of isotactic polypropylene and elastomer blends

The influence of a nucleating agent on the crystallization behaviour of isotactic polypropylene (iPP), in their blends with poly(styrene-b-ethylene butylene-b-styrene) (SEBS), and a metallocenic ethylene-octene copolymer (EO) was investigated by DSC, optical microscopy and real-time small and wide angle X-ray scattering (SAXS and WAXS) experiments using synchrotron radiation. In non-nucleated iPP/SEBS blends, the crystallization of the iPP matrix occurred in the presence of the styrenic domains which induced a nucleating effect on the process, as observed in the synchrotron experiments. The metallocenic elastomer did not affect the crystallization behaviour of iPP in the iPP/EO blends in non-isothermal experiments, however, the development of crystallinity in the elastomer was restricted. In the nucleated isotactic polypropylene/elastomer blends a significant increase in the crystallinity and the crystallization rate of the iPP matrix was observed due to the presence of the nucleating agent. However, the nucleating efficiency of the additive was strongly affected by the nature and content of the elastomeric component. The nucleating agent efficiency was higher in the presence of the ethylene-octene component than the styrenic elastomer.     

Phase behavior of semicrystalline polymer blends

The phase behavior of the semicrystalline polymer blend composed of isotactic polypropylene (iPP) and linear low density polyethylene (PE) was studied using small angle X-ray scattering (SAXS) and optical microscopy (OM). Based on the random phase approximation, the iPP/PE interaction parameter, χ, was obtained, and used to construct the iPP/PE phase diagram. The χ values reported in this study are lower than the χ values for deuterium-labeled moieties, measured by small angle neutron scattering (SANS). The predicted phase diagram has upper critical solution temperature (UCST) behavior with a critical temperature of 143 °C for the molecular weights used in this study. OM was used to locate cloud points and the results are consistent with the predicted phase diagram. Since iPP melts above the critical point, care was taken to distinguish phase separation from iPP crystallization by studying the kinetics of iPP crystallization, and the iPP crystallization was discerned from dewetting. In PE-rich blends, the iPP crystallization was suppressed and no dewetting was observed.     

Halloysite nanotubes as a novel β-nucleating agent for isotactic polypropylene

The nucleating ability of halloysite nanotubes (HNTs) towards isotactic polypropylene (iPP) was investigated by differential scanning calorimetry (DSC), X-ray diffraction (XRD), polarized optical microscopy (POM) and scanning electron microscopy (SEM). HNTs are identified to have dual nucleating ability for α-iPP and β-iPP under appropriate kinetics conditions. The formation of β-iPP is dependent on the HNTs loading in the iPP/HNTs composites. The composite with 20 phr of HNTs is found to have the highest content of β-iPP. Under non-isothermal crystallization the content of β-iPP increases with decreasing of the cooling rate. The maximum β-crystal content is obtained at cooling rate of 2.5 °C/min. The supermolecular structure of the β-iPP is identified as β-hedrites with flower-cup-like and axialite-like arrangements of the lamellae. Under isothermal crystallization the β-crystal can be formed in the temperature range of 115-140 °C. Outside the temperature range, no β-iPP can be observed. The content of β-crystal reaches the maximum value at crystallization temperature of 135 °C. The formation of the β-iPP in the composites is correlated to the unique surface characteristics of the HNTs.     

A highly active novel β-nucleating agent for isotactic polypropylene

A highly active novel β-nucleating agent for isotactic polypropylene (iPP), cadmium bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate (BCHE30), was found and its effects on the mechanical properties, the content of β-crystal, and crystallization behavior of iPP were investigated, respectively. The results show that the impact strength and crystallization peak temperature of nucleated iPP are greatly increased, while the spherulite size of nucleated iPP is dramatically decreased than that of pure iPP. The content of β-form of nucleated iPP (k_β value) can reach 87% with 0.1 wt% BCHE30. The Caze method was used to study the non-isothermal crystallization kinetics of nucleated iPP and the crystallization active energy was achieved by Kissinger method.     

Ductile-brittle transition controlled by isothermal crystallization of isotactic polypropylene and its blend with poly(ethylene-co-octene)

The correlation between crystalline morphology development and tensile properties of isotactic polypropylene (iPP) and its blend with poly(ethylene-co-octene) (PEOc) was investigated to study the ductile-brittle transition (DBT) in fracture modes. The sample processing strategy and the scientific observations have never been reported previously. The samples were first isothermally crystallized at 130 °C, 123 °C or 115 °C for a wide range of crystallization times, and then quenched to 35 °C for characterization. It was found that the crystallization conditions including crystallization temperature and time governed the crystalline morphology and even the tensile properties of iPP and the iPP/PEOc (80/20) blend. The lower the crystallization temperature, the shorter the crystallization time was needed for the occurrence of DBT, and the sharper the transition would be. The addition of the elastomer component delayed the DBT occurrence for the iPP/PEOc blend in terms of the crystallization time, owing to the fact that the existence of PEOc domains between the iPP lamellar stack regions or at the iPP spherulitic boundaries enhanced the ductility of the blend. The X-ray diffraction results displayed the oriented and destroyed crystalline structure characterizing the ductile fracture, while unoriented structure describing the brittle failure. The DBT is closely related to the crystal perfection, and factors such as the crystallization temperature and time and the compositions have been proven to be significant variables in determining the DBT occurrence.     

等规聚丙烯/顺丁橡胶合金的结晶和抗冲击性能

研究了熔融共混法制备的不同共混比的等规聚丙烯(iPP)／顺丁橡胶(PcBR)合金的结晶特性及抗冲击性能。结果显示,随着(?)(PcBR)从0增至40％,iPP球晶的完整程度逐渐下降,球晶间的边界模糊化,球晶不断细化; PcBR的加入诱导了iPP的β晶型生成,其含量的增加导致合金中的微晶尺寸减小,晶面间距值基本不变,而长周期则明显增加;同时,合金的结晶峰所对应的温度有所升高,结晶速率明显增大,而相对结晶度减小,PcBR对iPP的结晶起到异相成核剂的作用;PcBR对iPP有显著的增韧效果。     

基于六氢邻苯二甲酸盐的α/β复合成核剂对聚丙烯性能的影响

将α成核剂六氢邻苯二甲酸钙和β成核剂六氢邻苯二甲酸锌复合得到α/β复合成核剂体系,研究了其对等规聚丙烯（iPP）力学性能和结晶性能的影响,并用Avrami理论研究了成核iPP的等温结晶动力学。结果表明,α/β复合成核剂以特定比例复合可以同时提高iPP的刚性和韧性,其中在复合比例为7∶3时,拉伸强度提升了6.7 %,弯曲模量提升了21.8 %,冲击强度提升了108.2 %。进一步研究了复合成核剂在iPP中的浓度效应,随着总添加量的增加,iPP的结晶温度逐渐增加,力学性能趋于稳定,在添加量达到0.4 %（质量分数,下同）时基本不变,此时冲击强度提升了175.3 %,弯曲模量提升了15.0 %,拉伸强度提升了6.5 %。等温结晶动力学的结果表明,复合成核剂体系的加入可以明显缩短iPP的结晶时间并且降低结晶所需的表面能。     

Rheologically determined negative influence of increasing nucleating agent content on the crystallization of isotactic polypropylene

Dibenzylidene sorbitol (DBS) exists in the form of fibril and usually acts as an effective nucleating agent to facilitate crystallization of polyolefin during manufacturing. In this research, the isothermal crystallization of isotactic polypropylene (iPP) containing different amounts of DBS was followed by dynamic rheometry, and described upon a viewpoint of viscoelastic property evolution. Since the adopted temperatures within the entire sample preparation and characterization process were below the melting point of DBS, the DBS additives played a role of only solid nucleating agent, thus the possible effect of a changed miscibility between iPP and DBS on the viscoelastic properties as change of temperature could be ignored. Although saturation of nucleating iPP was observed at 0.1% DBS concentration, a negative influence with further increasing DBS content on the crystallization of iPP was determined for the first time via time sweep of G′ upon a single angular frequency and application of “inverse quenching” protocol within a wide range of angular frequency. Even more, a largely increased G′ and viscosity were observed in the melt as decreasing the temperature of iPP containing 0.1% DBS, suggesting a strong quasi-solid like behavior before iPP crystallization. A complement for well understanding the crystallization of iPP containing nucleating agent was discussed based on the formation of the DBS fibrils' network, the interfacial tension between crystalline/amorphous phase, and the consistency of crystallizing lamellae. Our study demonstrates clearly that the crystalline characteristic upon saturation of heterogeneous nucleating is difficult to be detected by traditional means, but could be followed reasonably by rheological measurements which is much sensitive to the microstructural changes.     

Temperature dependence of the nucleation effect of sorbitol derivatives on polypropylene crystallization

The temperature dependence of the nucleation effect of three sorbitol derivatives on the crystallization of isotactic polypropylene (iPP) was studied by means of isothermal crystallization kinetic analysis. Isothermal crystallization thermograms obtained by differential scanning calorimetry (DSC) were analyzed based on the Avrami equation. The Avrami analysis for the nucleated iPP was carried out with DSC data collected to 35% relative crystallinity, and the rate constants were corrected assuming the heterogeneous nucleation and three dimensional growth of iPP spherulites. A semi-empirical equation for the radial growth rate of iPP spherulites was given as a function of temperature and was used to determine the number of effective nuclei at different temperatures. The number of effective nuclei in the nucleated samples was estimated to be 3 × 10² ∽ 10⁵ times larger than that in the neat iPP. The logarithmic numbers of the effective nuclei decreased linearly with decreasing degree of supercooling in the range of crystallization temperatures tested. The temperature dependence of the effect of the nucleating agents on iPP crystallization was given quantitatively in terms of the deactivation factor defined as a fraction of the particles that are active at a particular temperature but inert at the temperature one degree higher. The nucleation activity and its temperature dependence are considered to be cooperative effects of many factors, including the dispersion and the physical or chemical nature of the agent as well as the interaction between the agent and the polymer. It is suggested that the temperature dependence of the effect of a nucleating agent should be treated as a characteristic of a given polymer/ nucleating agent mixture.     

Thermal and morphological characteristics of polypropylene/smectic polyester blends

Several blends of isotactic polypropylene, iPP, and the liquid crystalline polymer poly(triethylene glycol p,p′-bibenzoate), PTEB, have been prepared with different compositions, and analyzed by scanning electron microscopy, polarizing optical microscopy, infrared spectroscopy, X-ray diffraction with synchrotron radiation, and thermal methods (thermogravimetric analysis and differential scanning calorimetry). The results show a good adhesion matrix-dispersed phase when a maleic anhydride-grafted PP is used as compatibilizer, MA-g-PP. The calorimetric and synchrotron experiments indicate higher crystallization temperatures for the iPP component in the blends when compared with those of pure iPP. The higher crystallization temperature seems to be associated with a crystallinity increase. Optical microscopy results point out the nucleating effects of both PTEB and MA-g-PP on the iPP spherulites. The synchrotron experiments reveal that, on cooling from the isotropic melt, a SmA mesophase is formed first from the PTEB component, followed by its transformation into a tilted SmC mesophase. The isotropic-SmA transition is clearly affected in the blends with higher contents in iPP.     

Improving crystallization behaviors of isotactic polypropylene via a new POSS‐sorbitol compound

A new compound was synthesized by chemical combination of (3‐mercapto)propyl‐heptaisobutyl polyhedral oligomeric silsesquioxane (POSS‐SH) and 1,3:2,4‐bis(3,4‐dimethylbenzylidene) sorbitol (DMDBS) via epichlorohydrin while hydroxyl groups were still retained in the product POSS‐DMDBS. The prepared POSS‐DMDBS was introduced into isotactic polypropylene (iPP) to improve crystallization behaviors of iPP and obtain nanocomposites with suitable mechanical properties. Crystallization and mechanical properties of iPP/POSS‐DMDBS were systematically investigated by wide‐angle X‐ray diffraction, polarization microscopy, atomic force microscopy, differential scanning calorimetry, and tensile tests. The spherulite size of the modified iPP was obviously decreased with the addition of POSS‐DMDBS, while the crystallization temperature was increased by 5°C to 9°C depending on the content of POSS‐DMDBS incorporated. POSS‐DMDBS exhibited relatively higher nucleating efficiency on iPP which is similar to that of DMDBS, confirmed by the increased crystallization temperature. It was also found that the tensile modulus of iPP after adding POSS‐DMDBS increased significantly with respect to pristine iPP, but the elongation values decreased. Introduction of POSS‐DMDBS in content less than 1 wt% could bring about effective influence on the crystallization behaviors of iPP, demonstrating its potential applications . POLYM. ENG. SCI., 57:357–364, 2017. © 2016 Society of Plastics Engineers     

Influence of thermal history on crystalline morphologies of isotactic polypropylene in its miscible blends with polybutene‐1

The miscibility behaviors in blends of isotactic polypropylene (iPP) and polybutene‐1 (PB) have been studied using in‐situ FTIR imaging. The heterogeneous melt of 3/7 iPP/PB blends were formed at 250, 220, and 180°C and then quenched to the same crystallization temperature of iPP at 125°C, respectively. Evolution processes of composition distribution during crystallization were monitored according to their characteristic peaks, and the results suggest a trend from local concentration to uniform dispersion of PB fraction. Further studies of the PB fraction as the distance from the growth front of iPP spherulite indicate an irreversible phase behavior with the progress of thermal history. The cyclic melting and crystallization favor the mixing of iPP/PB blend. Meanwhile, the nonlinear growth rate of iPP spherulite is mainly responsible for compatible promotion of iPP/PB blend, which hinders the transportation of iPP chains to its growth front. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43282.     

Highly active thermally stable β‐nucleating agents for isotactic polypropylene

Calcium salts of suberic (Ca‐Sub) and pimelic (Ca‐Pim) acids were synthesized and implemented as in different grades of isotactic polypropylene (iPP). Propylene homopolymer, as well as random and block copolymers containing these additives, crystallized iPP into pure or nearly pure β modification in the isothermal and nonisothermal crystallization experiments. Recently, Ca‐Sub proved to be the most effective β‐nucleating agent of iPP. The Ca‐Sub nucleating agent widens the upper crystallization temperature range of pure β‐iPP formation up to 140°C. In this study the effect of the these additives on the crystallization, melting characteristics, and structure of the PP were studied. The degree of crystallinity of β‐iPP was markedly higher than that of α‐iPP. A widening in the melting peak of the samples crystallized in a high temperature range was first observed and discussed in regard to literature results of the same phenomenon for α‐iPP. The morphology of the β‐iPP samples was revealed by scanning electron microscopy. Independent of the type of polymer or nucleating agent, hedritic structures were found in the early stages of growth of the β‐spherulites. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2357–2368, 1999