Substrate effect on the crystallization of isotactic polypropylene

The evolution of storage modulus measured by a rotational rheometer shows that the isothermal crystallization of isotactic polypropylene (iPP) melts in contact with aluminum plates (PP-Al) are considerably faster than that with stainless-steel plates (PP-SS). The difference is bigger at higher temperatures, and this behavior is opposite to that expected by our numerical simulation considering uniform bulk phase transition and substrate's ability to remove the latent heat. Polarized optical observations and surface energy evaluations via contact angle measurement indicate that surface energy of the substrates, including the effects of submicrometer morphology and roughness, should be the key factor to affect the crystallization of iPP. Transcrystallization zones, in which the nucleation density is controlled by the surface energy of substrates, were observed to grow toward the bulk with the thickness of about 0.2 mm for iPP to affect the global crystallization behavior. The critical value of surface energy of substrate to promote the interfacial crystallization of a polymer melt is derived, in terms of which the aluminum and stainless steel as well as optical glass, promote the surface nucleation with respect to the bulk nucleation of iPP. As a consequence, the conventional differential scanning calorimetry measurement mainly gives the heat fluxes of interfacial crystallization rather than the bulk crystallization due to the large surface-to-volume ratio of the specimen and the aluminum pan used which is a high surface energy substrate. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Isothermal crystallization behavior of polyamide 6,6/multiwalled carbon nanotube nanocomposites

The good dispersion of functionalized multiwalled carbon nanotube (f‐MWCNT) in polyamide 6,6 (PA 6,6) matrix was prepared by solution mixing techniques. The crystalline structure and crystallization behaviors of PA 6,6 and PA 6,6/f‐MWCNT nanocomposites were studied by X‐ray diffraction (XRD), differential scanning calorimetry (DSC), and polarized optical microscopy (POM) analysis. DSC isothermal results revealed that the overall isothermal crystallization rates of PA 6,6 increased as well as the activation energy of PA 6,6 extensively decreased by adding f‐MWCNT into PA 6,6, suggesting that the addition of f‐MWCNT probably induces the heterogeneous nucleation. The effect of f‐MWCNT on the chain arrangement for the crystallization of PA 6,6/f‐MWCNT nanocomposites was also discussed. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Isothermal and nonisothermal crystallization kinetics of isotactic polypropylene nucleated with substituted aromatic heterocyclic phosphate salts

The crystallization kinetics of isotactic polypropylene (iPP) and nucleated iPP with substituted aromatic heterocyclic phosphate salts were investigated by means of a differential scanning calorimeter under isothermal and nonisothermal conditions. During isothermal crystallization, Avrami equation was used to describe the crystallization kinetics. Moreover, kinetics parameters such as the Avrami exponent n, crystallization rate constant Z_t, and crystallization half‐time t_1/2 were compared. The results showed that a remarkable decrease in t_1/2 as well as a significant increase in overall crystallization rate was observed in the presence of monovalent salts of substituted aromatic heterocyclic phosphate, while bivalent and trivalent salts have little effect on crystallization rate of iPP. The addition of monovalent metal salts could decrease the interfacial free energy per unit area perpendicular to PP chains σ_e value of iPP so that the nucleation rate of iPP was increased. During nonisothermal crystallization, Caze method was used to analyze the crystallization kinetics. It also showed that monovalent metal salts had better nucleation effects than bivalent and trivalent metal salts. From the obtained Avrami exponents of iPP and nucleated iPP it could be concluded that the addition of different nucleating agents changed the crystal growth pattern of iPP. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3307–3316, 2006     

Isothermal crystallization behavior of isotactic polypropylene blended with small loading of polyhedral oligomeric silsesquioxane

The isothermal crystallization kinetics and morphology development of isotactic polypropylene (iPP) blended with small loading of nanostructure of polyhedral oligomeric silsesquioxane (POSS) were studied with differential scanning calorimetry (DSC), polarized optical microscopy (POM), and wide-angle X-ray diffraction (WAXD). The crystallization behaviors of iPP/POSS composites presented an unusual crystallization behavior during isothermal and nonisothermal crystallization conditions. The exothermic morphologies of isothermal and nonisothermal crystallization of iPP/POSS composites changed remarkably with increasing POSS. Moreover, the developments of spherulitic morphology for iPP/POSS composites showed that the major dispersed POSS molecules became nanocrystals first and then aggregated together forming thread- or network-like morphologies, respectively, depending on POSS content, which was observed. It implies that these major POSS nanocrystals' morphologies appeared as an effective nucleating agent and promoted the nucleation rate of iPP, whereas the minor dispersed POSS molecules that had slight miscibility between iPP retarded the nucleation and growth rates of iPP in the remaining bulk region. Therefore, the isothermal crystallization showed a single exothermic peak at pure iPP and POSS-1.0, whereas at POSS-2.0 and POSS-3.0, displayed the multi-exothermic peaks during isothermal crystallization. These faces indicated that POSS molecules were both influence on the transport of iPP chain in the melted state and on the free-energy of formation the critical nuclei of iPP assisted by the POSS structures were observed. Therefore, we postulated that the crystallization mechanisms of multi-exothermic peaks in isothermal crystallization may proceed to combine the “nucleating agent inducing nucleation of iPP event assisted by the POSS domains” that the nucleation of iPP does occur preferentially on the surfaces of the POSS “threads” or “networks” structures, and “nucleation and growth of iPP in the remaining bulk melted iPP region retarded by dispersed POSS molecules”. Therefore, effects of POSS content on the isothermal and nonisothermal crystallization behaviors of iPP/POSS composites due to the POSS molecules partially miscible with iPP, at very small loading of POSS molecules, promoted or retarded the rates of nucleation and growth of iPP depending on the POSS content and crystallization temperature were discussed.     

Influence of different β‐nucleating agent on crystallization behavior,morphology, and melting characteristic of multiwalled carbon nanotube‐filled isotactic polypropylene nanocomposites

To obtain isotactic polypropylene (iPP) nanocomposites with high β‐crystal content, TMB5, calcium pimelate and calcium pimelate supported on the surface of nano‐CaCO₃ were used as β‐nucleating agent and MWCNT filled β‐nucleated iPP nanocomposites were prepared. The effect of different β‐nucleating agent and MWCNT on the crystallization behavior and morphology, melting characteristic and β‐crystal content of β‐nucleated iPP nanocomposites were investigated by DSC, XRD and POM. The results indicated that addition of MWCNT increased the crystallization temperature of iPP and MWCNT filled iPP nanocomposites mainly formed α‐crystal. The β‐nucleating agent can induce the formation of β‐crystal in MWCNT filled iPP nanocomposites. The β‐nucleating ability and β‐crystal content in MWCNT filled β‐nucleated iPP nanocomposites decreased with increasing MWCNT content and increased with increasing β‐nucleating agent content due to the nucleation competition between MWCNT and β‐nucleating agents. It is found that the calcium pimelate supported on the surface of inorganic particles as β‐nucleating agent has stronger heterogeneous β‐nucleation than calcium pimelate and TMB5. The MWCNT filled iPP nanocomposites with high β‐crystal content can be obtained by supported β‐nucleating agent. POLYM. COMPOS., 36:635–643, 2015. © 2014 Society of Plastics Engineers     

Investigation of the crystallization behavior of isotactic polypropylene polymerized with different Ziegler‐Natta catalysts

Detailed characterization of the crystallization behavior is important for obtaining better structure property correlations of the isotactic polypropylene (iPP), however, attributed to the complexity in ZN‐iPP polymerization, the relationship between crystallization behavior and the stereo‐defect distribution of iPP is still under debate. In this study, the crystallization kinetics of the primary nucleation, crystal growth and overall crystallization of two iPP samples (PP‐A and PP‐B) with nearly same average isotacticity but different stereo‐defect distribution (the stereo‐defect distribution of PP‐B is more uniform than PP‐A) were investigated. The results of isothermal crystallization kinetics showed that the overall crystallization rate of PP‐A was much higher than that of PP‐B; but the analysis of self‐nucleation isothermal crystallization kinetics and the polarized optical microscopy (POM) observation indicated that the high overall crystallization rate of PP‐A was attributed to the high primary nucleation rate of the resin. The stereo‐defect distribution plays an important role in determining both the nucleation kinetics and crystal grow kinetics, and thus influence the overall crystallization kinetics. A more uniform distribution of stereo‐defects restrains the crystallization rate of iPP, moreover, it has more influence on nucleation kinetics, comparing with the crystal growth. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Improved conductivity and thermal stability by the formation of a charge‐transfer complex in β‐nucleation‐agent‐nucleated and MWCNT‐filled iPP composites

In this study, the influence of β‐nucleation agent (β‐NA) on the morphology and properties of multi‐walled carbon nanotube (MWCNT) filled isotactic polypropylene (iPP) composites was explored in details. The results show that the incorporation of β‐NA has promoted the dispersion of MWCNT in the iPP matrix, which is profitable for improving the thermal stability and conductivity properties of MWCNT‐iPP composites. Besides, the 0.05 wt % β‐NA nucleated samples exhibit higher impact toughness than that of un‐β‐NA‐nucleated ones. Further SEM observations show that the morphology of MWCNT changes from large agglomerations to small clusters with doping of β‐NA. The main reason is that the incorporation of β‐NA (TMB‐5) in MWCNT filled iPP matrix has led to the formation of a charge‐transfer complex. Some of these clusters act as nucleation sites for inducing crystallization of α spherulites, which have a compete growth with β‐NA induced β crystals. Meanwhile, other clusters exist in the inter‐lamella amorphous phase of β crystals, some of them even combine two adjacent β spherulites. Accordingly, a large conductive network comes into being. Based on the investigated results, a mechanism model is proposed. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Fluctuation-assisted nucleation in the phase separation/crystallization of iPP/OBC blends

This work mainly focused on the nucleation behavior in iPP/OBC (isotactic polypropylene/polyolefin block copolymers) blends with two distinct OBCs. The influence of composition and molecular structure of the OBC component on the crystallization kinetics of the blends was investigated systematically with the aim to better understand the interplay between the two coupled phase transitions in the blends: macrophase separation and crystallization. The isothermal crystallization kinetics showed component and composition dependence in iPP/OBC blends. All the blends in the studied range have enhanced nucleation ability of iPP than the pure iPP under identical conditions. Furthermore, the distinct macrophase separation morphology resulting from the different compatibility between the various OBCs and iPP caused remarkable diversity between the blends: the nuclei density is qualitatively higher (or the nucleation rate is qualitatively faster) in the more compatible blends, and this enhancement of nucleation can be depressed by imposing a macrophase separation process before crystallization. The crystal nuclei from the phase separated matrix were preferentially formed at the interface of the phase domains, and then grew toward and into the iPP-rich phase. It is postulated that the increased nuclei density and/or nucleation rate followed the fluctuation-assisted nucleation mechanism: the enhanced concentration fluctuation at the interfacial area created by the spinodal decomposition played an important role in the nucleation behavior of iPP/OBC blends. The decreased interface areas with increased domain sizes after deeper phase separation, coupled with a more depressed concentration fluctuation, are responsible for lower nuclei density after long time annealing for phase separation.     

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     

Post-yield fracture behaviour of PA-6/LDPE-g-MA/nanoclay ternary nanocomposites: semiductile-to-ductile transition

The relationship between the stereo-defect distribution and the crystallization behavior of Ziegler-Natta isotactic polypropylene (ZN-iPP) is an important issue, which has not been clearly studied up to now. In this work, the crystallization behavior of a series of iPP samples with similar average isotacticity but different stereo-defect distribution, polymerized with the same Ziegler-Natta catalyst system, was studied by means of differential scanning calorimetry (DSC) and polarized optical microscopy (POM) observation. The results of isothermal crystallization kinetics indicated that, as the distribution of stereo-defects becomes more uniform, the overall crystallization rate decreases gradually. Meanwhile, the results of self-nucleation isothermal crystallization kinetics showed that, the crystal growth rate decreases gradually and the energy barrier of crystal growth increases. Moreover, the POM observation illustrated that not only the crystal growth rate, but also the nucleation rate decrease gradually as the stereo-defect distribution becomes more uniform. The results above indicated that for iPP polymerized with the same Ziegler-Natta catalyst system, stereo-defect distribution plays an important role in determining the nucleation kinetics, crystal growth kinetics and the overall crystallization kinetics of the resin.     

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.     

Unique nucleation of multi-walled carbon nanotube and poly(ethylene 2,6-naphthalate) nanocomposites during non-isothermal crystallization

Multi-walled carbon nanotube (MWCNT) and poly(ethylene 2,6-naphthalate) (PEN) nanocomposites are prepared by a melt blending process. There are significant dependence of non-isothermal crystallization behavior and kinetics of PEN/MWCNT nanocomposites on the MWCNT content and cooling rate. The incorporation of MWCNT accelerates the mechanism of nucleation and crystal growth of PEN, and this effect is more pronounced at lower MWCNT content. Combined Avrami and Ozawa analysis is found to be effective in describing the non-isothermal crystallization of the PEN/MWCNT nanocomposites. The MWCNT in the PEN/MWCNT nanocomposites exhibits much higher nucleation activity than any nano-scaled reinforcement. When a vary small quantity of MWCNT was added, the activation energy for crystallization is lower, then gradually increased, and becomes higher than that of pure PEN above 1.0 wt% MWCNT content. The incorporation of MWCNT improves the storage modulus and loss modulus of PEN/MWCNT nanocomposites.     

Variation of non‐isothermal crystallization behavior of isotactic polypropylene with varying β‐nucleating agent content

The non‐isothermal crystallization behavior, the crystallization kinetics, the crystallization activation energy and the morphology of isotactic polypropylene (iPP) with varying content of β‐nucleating agent were investigated using differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). The DSC results showed that the Avrami equation modified by Jeziorny and a method developed by Mo and co‐workers could be successfully used to describe the non‐isothermal crystallization process of the nucleated iPPs. The values of n showed that the non‐isothermal crystallization of α‐ and β‐nucleated iPPs corresponded to a tridimensional growth with homogeneous and heterogeneous nucleation, respectively. The values of crystallization rate constant showed that the rate of crystallization decreased for iPPs with the addition of β‐nucleating agent. The crystallization activation energy increased with a small amount (less than 0.1 wt%) of β‐nucleating agent and decreased with higher concentration (more than 0.1 wt%). The changes of crystallization rate, crystallization time and crystallization activation energy of iPPs with varying contents of β‐nucleating agent were mainly determined by the ratio of the content of α‐ and β‐phase in iPP (α‐PP and β‐PP) from the DSC investigation, and the large size and many intercrossing lamellae between boundaries of β‐spherulites for iPPs with small amounts of β‐nucleating agent and the small size and few intercrossing bands among the boundaries of β‐spherulites for iPPs with large amounts of β‐nucleating agent from the SEM examination. Copyright © 2010 Society of Chemical Industry     

Crystallization behavior and mechanical strength of poly(butylene succinate‐co‐ethylene glycol)‐based nanocomposites using functionalized multiwalled carbon nanotubes

Biodegradable poly(butylene succinate‐co‐ethylene glycol) (PBSG)/multiwalled carbon nanotube (MWCNT) nanocomposites were successfully prepared through physical blending and silication between PBSG and acyl aminopropyltriethoxysilane functionalized multiwalled carbon nanotube (MWCNT‐APTES). Nuclear magnetic resonance (NMR) spectra observations revealed that the PBSG chains were covalently attached to the MWCNT‐APTES by hydrolysis. PBSG/MWCNT‐APTES nanocomposites after hydrolysis showed excellent interfacial compatibility between PBSG and MWCNT‐APTES, which was helpful for the dispersion of MWCNT in the PBSG matrix. The incorporation of MWCNT‐APTES accelerated the crystallization of PBSG in the nanocomposites for both approaches of physical blending and hydrolysis due to the heterogeneous nucleation effect of MWCNT while the crystal structure of PBSG was remained. Furthermore, the crystallization rate of PBSG in PBSG/MWCNT‐APTES nanocomposites after hydrolysis was slower than that in the nanocomposite by physical blend. The tensile strength and modulus of the nanocomposites increased about 6% and 11% with the addition of only 1 wt% MWCNT‐APTES compared with that of neat PBSG, and was larger for the PBSG/MWCNT‐APTES nanocomposites after hydrolysis. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Crystallization behavior and crystallization kinetic studies of isotactic polypropylene modified by long‐chain branching polypropylene

In this article, we discuss the crystallization behavior and crystallization kinetics of isotactic polypropylene (iPP) modified by long‐chain‐branching (LCB) high‐melt‐strength iPP over a wide composition range, that is, LCB‐iPP from 10 to 50 wt %. Over the entire range we investigated, the presence of LCB‐iPP accelerated crystallization in both the isothermal crystallization process and nonisothermal crystallization process, even when the LCB‐iPP content was as low as 10%, and both crystallization processes were enhanced more significantly as the LCB‐iPP content increased. Hoffman–Lauritzen theory analysis revealed that the fold‐free energy decreased effectively with the occurrence of the LCB structure, although the growth rate of spherulites was depressed, as shown by polarized optical microscopy. Meanwhile, the regime III–regime II transition temperature was about 15° higher for all of the LCB‐iPP compositions than that of iPP because the LCB structure reduced the mobility of the polypropylene chains. Furthermore, the γ‐form crystal structure was favored by LCB compared to the β form, which was supported by wide‐angle X‐ray diffraction. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effect of phenol functionalized carbon nanotube on mechanical,dynamic mechanical,and thermal properties of isotactic polypropylene nanocomposites

In this work, multiwall carbon nanotubes (MWCNT) were functionalized with phenol and characterized by using Fourier transform infrared spectroscopy (FTIR). Isotactic polypropylene (iPP)/MWCNT composites of both the unfunctionalized and functionalized MWCNT were prepared by melt blending in a miniextruder at different loadings of nanotubes (i.e., 0.1, 0.25, 1.0, and 5.0 wt%). The tensile properties of the composites were found to increase with increase in nanotube loading with a maximum in Young's modulus being achieved at 1.0 wt% loading of phenol functionalized MWCNT. The differential scanning calorimetry (DSC) studies reveal the nucleating effect of MWCNT on the crystallization of iPP. Percentage crystallinity was found to increase on phenol functionalization of MWCNT. Results of X‐ray diffraction studies of the composites are in conformity with that of DSC studies. Dynamic mechanical studies reveal that the functionalized MWCNT causes many fold increase in the storage modulus, and the effect is pronounced in the case of functionalized MWCNT. POLYM. ENG. SCI. 2012. © 2011 Society of Plastics Engineers     

Interfacial crystallization and its mechanism in in-situ dynamically vulcanized iPP/POE blends

The effect of in-situ crosslinking of poly (ethylene-co-octene) (POE) rubber phase on the interfacial crystallization of isotactic polypropylene (iPP) in dynamically vulcanized iPP/POE blends was studied. The results showed that in situ crosslinking of POE obviously increased the interfacial crystallization of iPP in the dynamically vulcanized blends, comparing with that of pure iPP and the unvulcanized blend. The interfacial crystallization of iPP was further increased with the increase in crosslink degree. After annealing, the obvious interfacial crystallization was still obtained in the blend with high crosslink degree. Based on the fluctuation assisted nucleation mechanism in solution blended iPP/polyolefin block copolymer (OBC) blends, we proposed for the first time the interfacial crystallization mechanism in dynamically vulcanized blends: the oriented chains of iPP formed by concentration fluctuation at the interface during phase separation or shearing stress during melt mixing can be maintained because of the in situ crosslinking of POE phase, resulting in the enhancement of nucleation density at the iPP/POE interface. Our study proposes a new interfacial crystallization mechanism, and provides guidance for the preparation of high performance thermoplastic vulcanizates (TPVs) product by tailoring the interfacial crystallization of TPVs.     

Effects of dodecyl amine functionalized graphene oxide on the crystallization behavior of isotactic polypropylene

Dodecyl amine functionalized graphene oxide (DA‐GO)/isotactic polypropylene (iPP) nanocomposites were prepared via solution mixing method. Fourier transform infrared (FTIR), thermogravimetric analysis (TGA), and X‐ray photoelectron spectroscopy (XPS) verified that the DA was successfully grafted onto the surface of graphene oxide. The crystallization behavior of iPP/DA‐GO nanocomposites was investigated by differential scanning calorimetry (DSC) and polarized optical microscope (POM). The DSC results of both isothermal and non‐isothermal crystallization process indicated that the addition of DA‐GO can decrease the half‐time crystallization (t_1/2) and elevate crystallization peak temperature (T_p) of iPP. The results of isothermal crystallization kinetics showed that the overall crystallization rates of iPP/DA‐GO nanocomposites, especially with higher DA‐GO content, were much faster than that of neat iPP. During the non‐isothermal crystallization process, the nucleation ability (Φ) of nanocomposites containing 0.05, and 0.5 wt % DA‐GO were 0.83 and 0.69, respectively. And the crystallization activation energy of iPP decreased from 348.7 (neat iPP) to 309.2 and 283.1 kJ/m 2 by addition of 0.05 and 0.5 wt % DA‐GO, respectively. The decrease of Φ and indicated DA‐GO has strong heterogeneous nucleation effect and can promote the crystallization of iPP significantly. Additionally, POM micrographs showed the DA‐GO in iPP matrix can form more nucleation sites for the spherulite growth. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 40000.     

The influence of rubber-matrix interfaces on the crystallization kinetics of isotactic polypropylene blended with ethylene-propylene-diene terpolymer (EPDM)

Blends of isotactic polypropylene with amorphous and slightly crystalline ethylene-propylene-diene terpolymer (EPDM), prepared by solution blending, have been investigated by optical microscopy and differential scanning calorimetry. Nucleation and crystallization kinetic parameters, such as nucleation rates, nucleation half times, Avrami-exponents and spherulitic growth rates, have been determined. It has been found that the dispersion of crystalline EPDM in iPP is different from that of amorphous EPDM. Both EPDMs are incorporated into the spherulites, causing a decrease of the maximum growth rate of the iPP spherulites. The surface free energy of the iPP crystals is diminished on adding EPDM to iPP and is accompanied by a higher secondary nucleation rate. From the decrease observed in the Avrami exponent with increasing EPDM concentration in the blend, it has been concluded that nucleation becomes predominantly heterogeneous, as there is a proportional increase in the interfacial area between the two components.     

Isothermal crystallization and melting behavior of polypropylene with lanthanum complex of cyclodextrin derivative as a β‐nucleating agent

A novel highly active β‐nucleating agent, β‐cyclodextrin complex with lanthanum (β‐CD‐MAH‐La), was introduced to isotactic polypropylene (iPP). Its influence on isothermal crystallization and melting behavior of iPP was investigated by differential scanning calorimeter (DSC), wide‐angle X‐ray diffraction (WAXD), and polarized light microscopy (PLM). WAXD results demonstrated that β‐CD‐MAH‐La was an effective β‐nucleating agent, with β‐crystal content of iPP being strongly influenced by the content of β‐CD‐MAH‐La and the isothermal crystallization temperature. The isothermal crystallization kinetics of pure iPP and iPP/β‐CD‐MAH‐La was described appropriately by Avrami equation, and results revealed that β‐CD‐MAH‐La promoted heterogeneous nucleation and accelerated the crystallization of iPP. In addition, the equilibrium melting temperature (T) of samples was determined using linear and nonlinear Hoffman‐Weeks procedure. Finally, the Lauritzen‐Hoffman secondary nucleation theory was applied to calculate the nucleation parameter (K_g) and the fold surface energy (σ_e), the value of which verify that the addition of β‐CD‐MAH‐La reduced the creation of new surface for β‐crystal and then led to faster crystallization rate. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011