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%.     

Shear-induced orientation in the crystallization of an isotactic polypropylene nanocomposite

Isothermal crystallization of isotactic polypropylene (iPP)/organic montmorillonite (OMMT) binary composite under shear field was investigated by in situ polarized optical microscopy, rheometry and transmission electron microscopy. When shear strain was small, shear flow could enhance the crystallization of iPP, and the crystallizing entity was spherulitic in iPP/OMMT composite in which the OMMT content was below the percolation threshold. With shear strain increasing, the orientation extent became stronger and cylindrites and strings of spherulites appeared in these samples. However, for iPP/OMMT composite with OMMT content higher than the percolation threshold, when the shear strain was not big enough to destroy the fillers network in the matrix, the crystallization of iPP was similar with that of the un-sheared sample. When shear strain was large enough, the fillers network was destroyed and clay layers were aligned along the flow direction. There formed oriented crystals including cylindrites and strings of spherulites, which were much smaller in size than those formed in the previous case, because the aligned clay layers acted as heterogeneous nucleation agents to promote crystallization of iPP.     

Influence of crystallization temperature on the morphologies of isotactic polypropylene single-polymer composite

The supermolecular structures of iPP fiber/matrix composites as a function of crystallization temperature were studied by means of optical microscopy. The results show that, even though partial melting of the iPP fibers is in favor of initiating the β-iPP crystal growth, the interfacial morphology of iPP single-polymer composites induced by its own fiber depends strongly on the crystallization temperature. It was found that transcrystalline structures of negative radial β_III-iPP or banded β_IV-iPP can be produced within the crystallization temperature range 105-137 °C, while transcrystallization zone of pure negative radial α_II-iPP crystals is observed at higher crystallization temperature, e.g. 141 °C. On the other hand, the surrounding iPP spherulites grown from the bulk are composed of α-iPP in the whole crystallization temperature range. However, the optical character of the spherulites is controlled by the thermal condition.     

Cavitation during isothermal crystallization of isotactic polypropylene

Cavitation during isothermal crystallization of thin films of isotactic polypropylene was investigated systematically by light microscopy. Cavitation results from the negative pressure buildup due to density change during crystallization in the pockets of melts occluded by impinging spherulites. The morphology of such areas was also studied by SEM. The value of the negative pressure at the moment of cavitation was calculated from the drop of the spherulite growth rate. It was shown that the process of cavitation and the value of the negative pressure causing cavitation depend on the crystallization temperature. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 2439–2448, 2001     

Orientated crystallization in discontinuous aramid fiber/isotactic polypropylene composites under shear flow conditions

Melt blends of short aramid fibers (AF) and isotactic polypropylene (iPP) are subjected to shear at 145°C and the structural evolution and final morphology are examined by in situ synchrotron X‐ray scattering/diffraction and high‐resolution scanning electron microscopy, respectively. The results indicate that the presence of short AFs significantly enhances the crystallization of iPP. It is argued that shear flow in this system exerts a twofold orientating action, namely, on the bulk iPP molecules and on the short AFs. The resultant crystalline morphology reflects the combined effects of crystallization on orientated iPP molecules to facilitate a shish kebab morphology and at the interface of the aligned fibers, to form transcrystallinity. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1113–1118, 2005     

Shear-induced crystallization in isotactic polypropylene containing ultra-high molecular weight polyethylene oriented precursor domains

Melt blends of short ultra-high molecular weight polyethylene (UHMWPE) fibers and isotactic polypropylene (iPP) were subjected to shear at 145 °C, above the melting point of polyethylene (PE). Structural evolution and final morphology were examined by in situ synchrotron X-ray scattering/diffraction as well as ex situ microbeam X-ray diffraction and high resolution scanning electron microscopy, respectively. Results indicate that the presence of oriented UHMWPE molten domains significantly facilitated the crystallization of iPP and enhanced the initial ‘shish-kebab’ structure leading to the final cylindritic morphology. It is argued that shear flow aligns the fibrillar UHMWPE domains, where the interfacial frictions between PE and iPP effectively retards the relaxation of iPP chains, allowing the aligned iPP chains to create a shish-like structure. Nucleation on the iPP shish initiates the folded chain lamellae (kebabs), which grow perpendicularly to the iPP/PE interface.     

Effect of lanthanum-modified magnesium silicate on isotactic polypropylene crystallization in composite materials during shear flow

The activity of isotactic polypropylene (iPP) nucleating additives during shear flow of composite materials is still not entirely explained. In current work the sol-gel method was employed to synthesize MgO·SiO₂ filler, surface-modified with trivalent lanthanum. The crystallization of commercial iPP in the presence of 0.5% by weight La³⁺ modified or unmodified silicates was analyzed. The wide angle X-ray scattering analysis proved that the presence of even small amount of filler influences significantly on supermolecular structure of iPP. The results of microscope observations confirmed that the lanthanum-modified filler shows the nucleating ability for iPP. In that case a significant reduction of crystallization induction time was noticed. The investigation of iPP crystallization in composites after shear treatment confirmed that the increase of shear rate reduces the nucleating ability of additives. Moreover, the flow of filler particles during shearing may impede the shear-induced crystallization phenomenon.     

Modeling of flow‐induced crystallization in blends of isotactic polypropylene and poly(ethylene‐co‐octene)

Poly(ethylene‐co‐octene) (PEOc) has been shown to provide a high toughening contribution to isotactic polypropylene (iPP). The theoretical modeling of flow‐induced crystallization (FIC) of blends of iPP and PEOc is not much reported in the literature. The aim of the present work is to clarify the FIC of iPP upon addition of PEOc in terms of theoretical modeling. The crystallization of iPP and PEOc blends in flow is simulated by a modified FIC model based on the conformation tensor theory. Two kinds of flow fields, shear flow and elongational flow, are considered in the prediction to analyze the influence of flow field on the crystallization kinetics of the polymer. The simulation results show that the elongation flow is much more effective than shear flow in reducing the dimensionless induction time of polymer crystallization. In addition, the induction time of crystallization in the blends is sensitive to the change of shear rate. In comparison with experimental data, the modified model shows its validity for the prediction of the induction time of crystallization of iPP in the blends. Moreover, the simulated relaxation time for the blends becomes longer with increasing percentage of PEOc in the blends. Copyright © 2012 Society of Chemical Industry     

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     

The influence of stem conformation on the crystallization of isotactic polypropylene

The influence of stem conformation on the crystallization of i-PP is studied by growing α-form lamellae in melts of β-form lamellae at different temperatures. The melting of β-form lamellae and the crystallization of α-form lamellae is observed in situ at the interface of α- and β-form spherulites by AFM. The growth rate of α-form lamellae in the melt of β-form lamellae is much lower than that in the isotropic melt due to the stem conformation barrier, which originates from the difference in the α and β unit cell packing models.     

Flow‐induced crystallization during isotactic polypropylene film casting

In this work, a previously proposed model for flow‐induced crystallization of polymers was slightly modified and successfully applied in describing film casting experiments performed working with isotactic polypropylene. In this process, the melt experiences flowing conditions, during the cooling. The effect of flow on crystallization kinetics was accounted for by the entropic increase of melting point because of the orientation effect of the flow. The orientation of the macromolecules was described by means of a nonlinear dumbbell model, and the entropic shift was calculated on the basis of the rubber elasticity theory. The flow‐induced crystallization model, using reasonable values for relaxation time, was proved able to quantitatively predict the enhancement effect of the flow as an increase of spherulite nuclei density and growth rate, in presence of low‐level flows (Deborah number <1–10). The morphology changes due to higher level of flow (fine grained, fibrils, shish‐kebab) were not predicted by this approach. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

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     

In situ optical microscope study of the shear-induced crystallization of isotactic polypropylene

The shear-induced crystallization behavior of isotactic polypropylene (i-PP) has been investigated by in situ optical microscope under various thermal and shear histories. A shish-kebab structure during growth was observed under a well controlled, however, weak shear field. According to our results under these weak shear and thermal history, a modified model was proposed for the growing process of melt shear-induced crystallization of i-PP. Furthermore, many physical insights were provided on several still unsettled issues such as extended chain crystals, row nuclei, and smectic ordering questions.     

Structure, morphology and non-isothermal crystallization behavior of polypropylene catalloys

The structure, morphology and non-isothermal crystallization behavior of polypropylene catalloys (PP-cats) as well as pure polypropylene were investigated via differential scanning calorimeter (DSC), wide angle X-ray diffraction (WAXD) and real-time hot-stage optical microscopy (OM). The results reveal that the crystalline structures of PP-cats change with variations of the crystallization conditions and composition. The crystalline phase might consist of α-PP, β-PP and PE crystals. The content of β-PP increases with the increase of EP copolymer content and the cooling rate. At lower cooling rates, the morphologies of all non-isothermal crystallized PP-cats show spherulitic structure, and the decrease of crystal perfection and the increase of nucleation density of PP-cats system could be evidently observed. Considering the compositions of PP-cats, these indicated that the interactions between propylene homopolymer and the ethylene-propylene copolymers (both random and block ones) are in favor of the enhancement of the nucleation ability of α-form as well as β-form. In comparison with pure PP, the overall crystallization rates of the PP-cats increase dramatically, while the growth rates of the spherulites in all PP-cats decrease distinctly under the given cooling conditions. These experimental results were explained on the basis of diluting effect and obstructing effect on the mobility of PP chains in the ethylene-propylene copolymer.     

Polymorphism of syndiotactic polystyrene: γ phase crystallization induced by bulky non-guest solvents

The crystallization of amorphous syndiotactic polystyrene (s-PS) films when induced by bulky solvents, whose molecules are too big to be enclosed as guest of s-PS clathrate phases, generally leads to the formation of γ-phase. This kind of solvent induced crystallization in amorphous films generates a preferential (200) uniplanar orientation of the γ-crystalline phase. Moreover, the presence of highly boiling solvents in the amorphous phase of these γ-form samples can induce a γ→β phase transition, as a consequence of thermal annealing procedures at atmospheric pressure. A comparison with literature data suggests that the formation of the thermodynamically stable β-phase is generally favored with respect to the formation of the kinetically favored α-phase, by any s-PS dilution.     

Hydrogenated petroleum resin effect on the crystallization of isotactic polypropylene

The influence of the hydrogenated petroleum resin P125 on the crystallization behavior, crystallization kinetics, and optical properties of polypropylene (PP) were investigated. The results of differential scanning calorimetry, successive self‐nucleation, and annealing fractionation demonstrated that P125 reduced the interaction between the PP molecules, decreased the crystallization, prevented PP from forming thick lamellae, and encouraged the formation of thin lamellae. The isothermal crystallization kinetics, self‐nucleation isothermal crystallization kinetics, and polarized optical microscopy observations showed that P125 slightly decreased the nucleation rate, significantly decreased the crystal growth rate, generally reduced the overall crystallization rate, and effectively deceased the crystallite sizes of PP. The optical properties studies showed that P125 effectively decreased the haze and increased the surface glossiness and yellowness index of PP. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

β-Crystal formation of isotactic polypropylene induced by N, N’-dicyclohexylsuccinamide

N, N’-dicyclohexyl succinamide (DCS) was found to be a new β-nucleating agent for isotactic polypropylene (iPP) by means of wide angle X-ray diffraction (WAXD) and polarized light microscopy (PLM) measurements for the first time. The maximum proportion of β-form within iPP specimen was 79.1% with addition of 0.05% DCS. With increasing crystallization time, the proportion of β-form changed slightly when the nucleated iPP specimens crystallized at 120°C and 130°C for more than 20 min; but at 140°C, the content of β-form markedly decreased because β-α solid to solid transformation occurred. The analysis of the cell parameters of DCS and β-form iPP showed good lattice matching relationship between them.     

Rheological studies on the quasi-quiescent crystallization of polypropylene nanocomposites

Isothermal crystallization of isotactic polypropylene (iPP)/organic montmorillonite (OMMT) binary nanocomposite and iPP/OMMT/poly(ethylene-co-octene) (PEOc) ternary nanocomposites has been investigated by polarized optical microscopy (POM), rheometry and scanning electron microscopy (SEM). At the stage of nucleation the heterogeneous nucleation effect of OMMT was much greater than the concentration fluctuation assisted nucleation effect in the ternary nanocomposite. Besides, PEOc played a role of inhibitor of OMMT nucleation agents at the nucleation stage because many of OMMT layers were distributed around PEOc-rich domains. At stage II of the crystal growth process, the entanglement effect of PEOc greatly affected the rheological response (storage modulus (G′) and its growth rate) due to the long side chains of PEOc component. In stage III of the growth process, OMMT layers and the entanglement of PEOc chains limited the motion of polypropylene chains. So the growth rate of G′ was slowed down. During the shrinkage and cooling process after isothermal crystallization, some fibril links between the spherulites, consisting of PEOc chains and iPP chains, were formed from the amorphous phases surrounding the spherulites.     

氯化聚乙烯橡胶改性聚丙烯的非等温结晶行为研究

用示差扫描量热仪(DSC)对氯化聚乙烯橡胶(CM)改性聚丙烯(PP)的非等温结晶行为进行了研究。结果表明,随着降温速度上升,样品结晶温度下降,结晶速度上升。在以15k/min与20k/min速度降温时,发现两者的结晶行为相一致。采用TCHC交联剂的1#样品的结晶温度与速度都大于采用DCP交联剂的2#样品,前者的硫化效率低,对结晶影响小。本文又通过求解非等温结晶动力学参数与结晶活化能,进一步解释了1#与2#样品的结晶行为。     

Isothermal crystallization behavior of metallocene‐catalyzed isotactic polypropylene

Isothermal crystallization behavior of isotactic polypropylene (iPP) synthesized using metallocene catalyst was investigated in this work. The isotacticity of the polypropylene was characterized by ¹³C‐NMR spectroscopy. It was found that the melting temperature (T_m) of the iPP is 123.51°C and the crystallization temperature (T_c) is 93°C. The iPP synthesized in this work did not show a general increase of T_m with an increase of crystallization temperature T_c, due to the short crystallization time of 20 min and low molecular weight (number average molecular weight = 6,300). The iPP showed a tendency of increasing heat of fusion (ΔH_f) with decreasing crystallization temperature. All the spherulites of iPP samples showed negative birefringence. For the iPP sample crystallized at the highest T_c (= 123°C, just below T_m), the spherulite showed a pronounced Maltese Cross and a continuous sheaf‐like texture aligning radially, which suggests that R‐lamellaes are dominant in this spherulite. The crystalline structure of the iPP was also investigated by X‐ray diffraction. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 231–237, 2005