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.     

Thermoplastic elastomers from iPP/EPR blends: Crystallization and phase structure development

The phase morphology and structure of thermoplastic elastomers obtained from isotactic polypropylene (iPP) and ethylene—propylene random copolymer (EPR) blends by means of the dynamic curing of EPR rubbery component carried out during its melt mixing with iPP in a Banbury mixer at 180°C were investigated. Samples obtained by compression molding and by using isothermal crystallization conditions of the iPP phase were analyzed by means of differential scanning calorimetry, of optical, scanning, and transmission electron microscopy, and of wide-angle and small-angle X-ray diffraction. The influence of cooling below the melting point and of EPR molecular structure on the kinetic and thermodynamic parameters related to crystallization process of the iPP phase was also studied. It was found that the process of dynamic curing of the EPR component dramatically affects the development of the phase morphology and structure in the material. As a matter of fact, the blend containing the uncured EPR is characterized by the presence of iPP domains randomly distributed in the EPR rubbery matrix, whereas in the blend containing the cured EPR the iPP phase becomes the continuous phase crystallizing in a structure that resembles a cobweb tending to surround the EPR cured particles; moreover such an iPP cobweb appears to be contituted by row structures of stacked lamellae. It was found that the addition of EPR phase interferes dramatically with the crystallization process of the iPP, thus inducing drastic modification in its intrinsic morphology (size, neatness, regularity of spherulites, inner structure of spherulites, etc.). Such interference was found to be comparatively stronger when the iPP phase crystallizes in presence of cured EPR. The elastic behavior of the thermoplastic elastomer material was accounted for by applying the “leaf spring model” to the morphology and structure of the iPP phase crystallized in presence of cured EPR. © 1994 John Wiley & Sons, Inc.     

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。     

Isothermal crystallization kinetics of AB<Subscript>3</Subscript> hyperbranched polymer (HBP)/polypropylene (PP) blends

In this paper, the isothermal crystallization kinetics of pure isotactic polypropylene (iPP) and iPP with 5% AB₃ hyperbranched polymer (HBP) added had been investigated by differential scanning calorimetry (DSC). During isothermal crystallization, the crystallization rate of the blends was higher than those of iPP remarkably. Moreover, the value of t _½ became smaller with increasing the HBP molecular weight in blends, however, the crystallization rate of the blend decreased when the higher molecular weight HBP (\( \bar{M}_{n} \) = 12,500) was added. The crystallization rate of the blends was more sensitive to temperature than that of iPP. An increase in the Avrami exponent may be attributed to the fractal structure of hyperbranched polymer.     

Spherulite nucleation in blends of isotactic polypropylene with isotactic poly(butene-1)

The phase morphology and the influence of composition on the primary nucleation of isotactic polypropylene in isotactic polypropylene/isotactic poly(butene-1) (iPP/iPB) blends were investigated by electron and light microscopy and small-angle light scattering. It was found that iPP and iPB are miscible but the thermal treatment induces partial phase separation of components and the formation of iPP-rich and iPB-rich phases. The complete phase separation needs high temperatures and/or a long time of melt annealing. In samples crystallized isothermally at low undercooling the heterogeneous primary nucleation in blends is depressed as compared to plain iPP. In blends the less active heterogeneities lose their activity because of an increase of the energy barrier for critical size nucleus formation due to phase separation of blend components during crystallization. For the same reason the rate of homogeneous nucleation in blends decreases, as observed in samples crystallized at very high undercooling. At very high undercooling iPP and iPB are able to crystallize with similar rates, which results in the formation of a fraction of iPB spherulites in addition to iPP spherulites. Consequently the number of spherulites in the blend is larger than that in plain iPP, in spite of the decrease in the homogeneous nucleation rate of iPP in the blend. © 1994 John Wiley & Sons, Inc.     

Nonisothermal crystallization of isotactic polypropylene blended with poly(α-pinene). I. Bulk crystallization

The influence of a natural terpene resin, poly(α-pinene) (PαP), on the nonisothermal crystallization process of isotactic polypropylene (iPP) was investigated. The solidification process strongly depends on cooling rate, composition, and miscibility of the system. For the blends containing PαP up to 30 wt %, the overall nonisothermal crystallization rate is depressed with respect to plain iPP. This is probably the result of the diluting effect of the polyterpene because the two components are miscible. The 50/50 blend presents, instead, two amorphous phases: an iPP-rich phase and a PαP-rich phase. For this composition, solidification starts at temperatures higher than those for plain iPP and blends with lower PαP content, given that the diluting effect of PαP in the iPP-rich phase is counterweighted by an increased number of nuclei that originate from the polyterpene-rich phase domains. PαP also influences the morphology of iPP spherulites, which are spherical in plain iPP and become more irregular with increasing PαP content. The number and dimension of iPP spherulites depend on blend composition and miscibility of the components. Moreover, the nonisothermal crystallization kinetics of iPP/PαP blends was analyzed with the Ozawa equation. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 358–367, 2001     

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.     

Effect of nylon 6 inclusions on the crystalline morphology of polypropylene–nylon 6 blends

Crystallization behavior and crystalline morphology of plain polypropylene (PP) and its blend with 0 to 30 wt % nylon 6 were studied by the hot‐stage polarized light microscopy method. Radial growth rate and the size and number of PP spherulites were measured as a function of both the isothermal crystallization temperature and the nylon 6 content of the blend. The study revealed that a reduction in the isothermal crystallization temperature from 135 to 120°C, for both the plain PP and its blend with nylon 6, leads to the formation of a large number of fast‐growing, small spherulites. Moreover, the size and growth rate of PP spherulites decreased on increasing the nylon 6 content of the blend; whereas the number of PP spherulites decreased sharply on initial addition of 10% nylon 6 and, thereafter, increased slightly by further addition of nylon 6. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1769–1775, 2000     

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     

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     

超支化聚合物对聚丙烯等温结晶动力学的影响

采用示差扫描量热仪(DSC)研究聚合物结晶动力学,讨论了添加5%超支化聚合物对聚丙烯结晶行为的影响,结果表明,少量超支化聚合物可使聚丙烯的结晶速度显著提高,Avrami指数明显增加。偏光显微镜照片显示,超支化聚合物的引入使体系晶核数目急剧增加,球晶的半径明显变小。     

Isothermal crystallization kinetics and morphology development of isotactic polypropylene blends with atactic polypropylene

The crystallization kinetics and morphology development of pure isotactic polypropylene (iPP) homopolymer and iPP blended with atactic polypropylene (aPP) at different aPP contents and the isothermal crystallization temperatures were studied with differential scanning calorimetry, wide‐angle X‐ray diffraction, and polarized optical microscopy. The spherulitic morphologies of pure iPP and larger amounts of aPP for iPP blends showed the negative spherulite, whereas that of smaller amounts of aPP for the iPP blends showed a combination of positive and negative spherulites. This indicated that the morphology transition of the spherulite may have been due to changes the crystal forms of iPP in the iPP blends during crystallization. Therefore, with smaller amounts of aPP, the spherulitic density and overall crystallinity of the iPP blends increased with increasing aPP and presented a lower degree of perfection of the γ form coexisting with the α form of iPP during crystallization. However, with larger amounts of aPP, the spherulitic density and overall crystallinity of the iPP blends decreased and reduced the γ‐form crystals with increasing aPP. These results indicate that the aPP molecules hindered the nucleation rate and promoted the molecular motion and growth rate of iPP with smaller amounts of aPP and hindered both the nucleation rate and growth rate of iPP with larger amounts of aPP during isothermal crystallization. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1093–1104, 2007     

Miscibility in crystalline polymer blends: Isotactic polypropylene and linear low‐density polyethylene

The phase behavior and the crystallization kinetics of blends composed of isotactic polypropylene (iPP) and linear low‐density polyethylene (LLDPE) were investigated by differential scanning calorimetry. The phase behavior indicates the formation of separate crystals of iPP and LLDPE at each investigated blend composition. The crystallization trace reveals that iPP crystallizes in its normal range of temperatures (i.e., at temperatures higher than that of LLDPE), when its content in the blend is higher than 25% by weight. In the blend whose iPP content is as high as 25%, at least a portion of iPP crystallizes at temperatures lower than that of LLDPE. This behavior has been proposed by Bassett to be attributed to a change in the kind of nucleation from heterogeneous to homogeneous. From the Avrami analysis of the isothermal crystallization of iPP in the presence of molten LLDPE, n values close to 2 are always obtained. According to our previously proposed interpretation of the Avrami coefficient, it can be related to the crystallite fractal dimension, through d = n + 1, which gives values close to 3, according to the spherulitic observed morphology. The kinetics parameter, i.e., the half‐time of crystallization, and the kinetic constant k show that a decrease in the overall rate of crystallization of iPP occurs on blending. Optical microscopy photographs, taken during the cooling of the samples from the melt, confirm the above results and show increasingly less resolved spherulite texture on increasing LLDPE content in the blend. The diffusion parameters evaluated for the neat polymers and for the blends in dichloromethane, which give information on the miscibility in the amorphous state, show that the diffusional behavior of the blends is governed by iPP, suggesting a two‐phase amorphous state. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3338–3346, 2003     

Crystallization behaviour of isotactic polypropylene/linear low density polyethylene blends

Crystallization behaviour of isotactic polypropylene/linear low density polyethylene (iPP/LLDPE) blends has been investigated by optical microscopy and DSC. Crystallization of iPP depends upon blend composition and thermal history. When blended with LLDPE, the crystallization temperature of iPP, T_c, decreased slightly. Crystallinity did not change in the range 0-80wt% LLDPE; there were only slight changes in the crystalline structure, but LLDPE seemed to resist forming the β type of spherulites. Below 80 wt% of LLDPE, iPP was a continuous phase. The iPP spherulite growth rate was almost constant; however, overall crystallization decreased due to decreasing primary nuclei density.     

Stereochemical composition-properties relationships in isotactic polypropylenes obtained with different catalyst systems

The influence of stereochemical composition of the radial growth rate of spherulites, the nucleation density, the overall rate of crystallization and the thermal behaviour of fractions of iPP samples synthesized with different catalyst systems (low, high and very high yield) was investigated. The study used ¹³C n.m.r., differential scanning calorimetry (d.s.c.) and optical microscopy. The ¹³C n.m.r. analysis showed that due to the presence of catalytic sites with different stereoregulating capability the catalyst system produces polypropylene with different stereoregularity. It was found that the growth rate of spherulites and the overall rate of crystallization are strictly related to the stereochemical structure of the polypropylene. Moreover, for the low yield iPP, phenomena of secondary crystallization were observed by Avrami analysis of the overall kinetics. Values of the equilibrium melting temperature (T_m), energy of nucleation (Δø1) and surface free energy of folding (σe) of iPP lamellar crystals have been determined according to the kinetic theory of polymer crystallization. The values of such thermodynamic quantities as well as the thermal behaviour of various iPP are strongly dependent upon the amount and distribution of configurational irregularities existing along the chains and upon the molecular mass distribution.     

Morphology of a melt crystallized iPP/HDPE/hydrogenated hydrocarbon resin blend

The structure, phase structure, morphology, crystallization and melting behavior of isotactic polypropylene (iPP) blended with a master batch (MB), formed by high density polyethylene and hydrogenated hydrocarbon resin (iPP/MB), have been in details investigated by using X-ray diffraction, optical microscopy and differential scanning calorimetry. It was found that the structure and morphology depend on crystallization conditions. A new family of α spherulites of iPP (type I spherulites) can be activated using appropriate crystallization conditions. Nucleation of these spherulites has been explained by using the approach of nucleus migration in polymer blends. Type I spherulites present specific morphological, kinetic and thermal behaviors. In particular it was found that the growth rate of type I spherulites, at a given T_c, is higher than the growth rate of spherulites grown from plain iPP.     

Role of multi-wall carbon nanotube network in composites to crystallization of isotactic polypropylene matrix

The composites (iPP/CNTs) made of isotactic polypropylene (iPP) and multi-wall carbon nanotubes (CNTs) were prepared by solution blending. To improve compatibility between CNTs and iPP and to enhance dispersion of CNTs in iPP matrix, CNTs were chemically modified by grafting alkyl chains. The chemically modified CNTs had about 6 wt% grafted alkyl chains. Rheological measurements indicated that CNTs caused gelation in iPP/CNTs due to CNT network formation and the critical gelation CNT concentration was about 7.4 wt%, which was considered to be high due to the low CNT aspect ratio in this study. Crystallization behaviors of iPP/CNTs were studied by using optical microscopy (OM) and differential scanning calorimetry (DSC). Radial growth rates of spherulites during isothermal crystallization of iPP/CNTs with CNT concentrations less than 2.0 wt% measured by using OM showed decreasing trends with increasing CNT concentration. Avrami analysis of the exothermic heat flow curves during isothermal crystallization of iPP/CNTs measured by DSC indicated that crystallization rates were accelerated when CNT concentrations were lower than the critical gelation concentration, because CNTs mainly functioned as nucleating agents for crystallization, while crystallization rates did not change obviously when CNT concentrations were higher than the critical gelation concentration, because CNT network could form and mainly functioned to provide restriction to mobility and diffusion of iPP chains to crystal growth fronts.     

Correlation of miscibility and mechanical properties of polypropylene/olefin block copolymers: Effect of chain composition

This study examines the miscibility and mechanical properties of isotactic polypropylene (iPP) and olefin block copolymer (OBC) blends (70/30 wt %). The blends exhibit phase-separated morphology. The OBC domain size decreases with increasing the 1-octene content in the soft segment. The crystallization, melting behavior, and the long spacing of the iPP component in the blends are nearly the same as those of neat iPP, while the T_g of the iPP component shifts slightly to lower temperature. “Blocky” OBC is immiscible with iPP, while the soft segment rich polymers in OBC could be partially miscible with iPP. The impact strength of the blends is greatly increased with increasing the 1-octene content in the OBC soft segment. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

A novel β‐nucleating agent for isotactic polypropylene

The nucleating ability of p‐cyclohexylamide carboxybenzene (β‐NA) towards isotactic polypropylene (iPP) was investigated by differential scanning calorimetry, X‐ray diffraction, polarized optical microscopy and scanning electron microscopy. β‐NA is identified to have dual nucleating ability for α‐iPP and β‐iPP under appropriate kinetic conditions. The formation of β‐iPP is dependent on the content of β‐NA. The content of β‐phase can reach as high as 96.96% with the addition of only 0.05 wt% β‐NA. Under non‐isothermal crystallization the content of β‐iPP increases with increasing cooling rate. The maximum β‐crystal content is obtained at a cooling rate of 40 °C min^–1. The supermolecular structure of the β‐iPP is identified as a leaf‐like transcrystalline structure with an ordered lamellae arrangement perpendicular to the special surface of β‐NA. Under isothermal crystallization β‐crystals can be formed in the temperature range 80–140 °C. The content of β‐crystals reaches its maximum value at a crystallization temperature of 130 °C. © 2012 Society of Chemical Industry     

Morphology and thermal properties in the binary blends of poly(propylene-co-ethylene) copolymer and isotactic polypropylene with polyethylene

The morphology and thermal properties of isothermal crystallized binary blends of poly(propylene-co-ethylene) copolymer (PP-co-PE) and isotactic polypropylene (iPP) with low molecular weight polyethylene (PE) were studied with differential scanning calorimeter (DSC), dynamic mechanical analysis (DMA), polarized optical microscopy (POM) and wide-angle X-ray diffraction (WAXD). In PP-co-PE/PE binary blends, however, the connected PE acted as a phase separating agent to promote phase separation for PP-co-PE/PE binary blends during crystallization. Therefore, the thermal properties of PP-co-PE/PE presented double melting peaks of PE and a single melting temperature of PP during melting trace; on the other hand, at cooling trace, the connected PE promoted crystallization rate because of enhanced segmental mobility of PP-co-PE during crystallization. At isothermal crystallization temperature between the melting points of iPP and PE, the binary blend was a crystalline/amorphous system resulting in persistent remarkable molten PE separated domains in the broken iPP spherulite. And then, when temperature was quenched to room temperature, the melted PE separated domains were crystallized that presented a crystalline/crystalline system and formed the intra-spherulite segregation morphology: these PE separated domains/droplet crystals contained mixed diluent PE with connected PE components. On the other hand, in the iPP/PE binary blends, the thermal properties showed only single melting peaks for both PE and iPP. Moreover, the glass transition temperature of iPP shifted to lower temperature with increasing PE content, implying that the diluent PE molecules were miscible with iPP to form two interfibrillar segregation morphologies: iPP-rich and PE-rich spherulites. In this work, therefore, we considered that the connected PE in PP-co-PE functioned as an effective phase separating agent for PP and diluent PE may be due to the miscibility between connected PE and diluent PE larger than that between PP and dispersed PE.