Isothermal melt crystallization and melting behaviour of syndiotactic polypropylene

The lamellar morphological information and subsequent melting behaviour of syndiotactic polypropylene (s‐PP) samples isothermally crystallized at crystallization temperatures ranging from 30 to 95 °C have been investigated using a combination of wide‐angle X‐ray diffraction (WAXD), small‐angle X‐ray scattering (SAXS) and differential scanning calorimetry (DSC) techniques. Three known methods for determining the equilibrium melting temperature T_m°, namely the Gibbs–Thomson extrapolation, the linear Hoffman–Weeks extrapolation and the non‐linear Hoffman–Weeks extrapolation, have been employed to evaluate this important thermodynamic parameter, and the results obtained are compared. Finally, an estimate of the equilibrium melting temperature for a perfect s‐PP sample (T_m°)_100% is given. © 2000 Society of Chemical Industry     

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

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

Unbiased evaluation of literature data on equilibrium melting temperature and enthalpy of fusion of perfectly syndiotactic polypropylene

The thermodynamic properties of highly syndiotactic polypropylene (PP) were reevaluated based on the data taken from the literature. The thermodynamic equilibrium melting temperature of a perfectly syndiotactic PP, which was estimated based on the Flory theory for the depression of the melting point in random copolymers, was 168.0°C. However, it was found to be 174.2°C when a linear extrapolation was attempted on a plot of the observed equilibrium melting temperature against the syndiotacticity level. The thermodynamic enthalpy of fusion of a perfect crystal of fully syndiotactic PP was estimated to be 8.7 kJ mol⁻¹, and the average value of the literature data was 7.8 kJ mol⁻¹. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1603–1609, 2001     

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

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

Influence of molten-state annealing on the phase structure and crystallization behaviour of high impact polypropylene copolymer

The phase structure evolution of high impact polypropylene copolymer (IPC) during molten-state annealing and its influence on crystallization behaviour were studied. An entirely different architecture of the IPC melt was observed after being annealed, and this architecture resulted in variations of the crystallization behaviour. In addition, it was found that the core-shell structure of the dispersed phase was completely destroyed and the sizes of the dispersed domains increased sharply after being annealed at 200 °C for 200 min. Through examination of the coarseness of the phase morphology using phase contrast microscopy (PCM), it was found that a co-continuous structure and an abnormal ‘sea-island’ structure generally appeared with an increase in annealing time. The original matrix PP component appeared as a dispersed phase, whereas the copolymer components formed a continuous ‘sea-island’ structure. This change is ascribed to the large tension induced by solidification at the phase interface and the great content difference between the components. When the temperature was reduced the structure reverted to its original form. With increasing annealing time, the spherulite profiles became more defined and the spherulite birefringence changed from vague to clear. Overall crystallization rates and nucleation densities decreased, but the spherulite radial growth rates remained almost constant, indicating that molten-state annealing mainly affects the nucleation ability of IPC, due to a coarsened microstructure and decreased interface area.     

Further study on double‐melting endotherms of isotactic polypropylene

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

Rheological and isothermal crystallization characteristics of neat and calcium carbonate‐filled syndiotactic polypropylene

Steady‐state and oscillatory shear behavior of three neat syndiotactic polypropylene (s‐PP) resins and a s‐PP resin (s‐PP#8) filled with CaCO₃ particles of varying content, size, and type of surface modification were investigated. All of the neat s‐PP resins investigated exhibited the expected shear‐thinning behavior. Both the storage and loss moduli increased with decreasing temperature. The shift factors used to construct the master curves were fitted well with both the Arrhenius and the Williams–Landel–Ferry (WLF) equations. The inclusion of CaCO₃ particles of varying content, size, and type of surface modification, to a large extent, affected both the steady‐state and oscillatory shear behavior of s‐PP/CaCO₃ compounds, with the property values being found to increase with increasing content, decreasing size, and surface coating of the CaCO₃ particles. Lastly, the effects of melt‐annealing and crystallization temperatures on isothermal crystallization behavior of s‐PP#8 filled with CaCO₃ particles of varying content, size, and type of surface modification were also investigated. The half‐time of crystallization of neat s‐PP#8 exhibited a strong correlation with the choice of the melt‐annealing temperature (T_f) when T_f was less than about 160 °C, while it became independent of T_f when T_f was greater than about 160 °C. On the other hand, the half‐time of crystallization of s‐PP#8/CaCO₃ compounds did not vary much with the T_f. Generally, the observed half‐time of crystallization decreased with increasing CaCO₃ content and increased with increasing CaCO₃ particle size. Finally, coating the surface of CaCO₃ particles with either stearic acid or paraffin reduced the ability of the particles to effectively nucleate s‐PP#8. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4515–4525, 2006     

Structure and crystallization behaviour of syndiotactic polystyrene/layered double hydroxide nanocomposites

Syndiotactic polystyrene (sPS) based polymer nanocomposites have been prepared using surfactant‐free layered double hydroxides (SF‐LDHs) by a modified solvent mixing method with different loadings of 1, 2.5, 5 and 10 wt%. The nanocomposite preparation process involves a wash treatment of as‐prepared SF‐LDHs in an appropriate organic solvent followed by gel formation in a non‐polar solvent. The gel was directly used to make highly dispersed polymer nanocomposites. The influence of highly dispersed SF‐LDH platelets on the crystallization, polymorphism, thermal stability and flame retardancy of sPS was examined. It was shown that SF‐LDHs significantly enhance the crystallization rate of sPS and favour the formation of the thermodynamically stable β form along with the α form of sPS. Moreover, highly dispersed SF‐LDHs decrease the heat release rate and total heat release of sPS indicating the enhancement of flame‐retardant properties of sPS. In this way, it was found that the dispersed SF‐LDH platelets act as a multifunctional nanofiller for sPS. © 2015 Society of Chemical Industry     

Crystallization and melting behaviour of polypropylene/barium sulfate composites

The effects of polypropylene (PP)–barium sulfate (BaSO₄) interfacial interaction on the crystallization and melting behaviour of PP/BaSO₄ composites were investigated by means of differential scanning calorimetry. The results show that BaSO₄ can act as nucleating agent and the nucleation activity increases when the PP–BaSO₄ interface is modified. Neat PP exhibits a single fusion endotherm after being non‐isothermally crystallized, whereas the PP/BaSO₄ composites show dual endotherms or a broad endotherm with a shoulder at the low temperature side, indicating that there are more crystallites with less perfection formed in the composite samples. It is shown that the hindrance of BaSO₄ particles on the transport of PP chains to the crystallization zone is responsible for the formation of the less perfect crystallites. Moreover, the melting patterns of the composites are different from sample to sample, which can be attributed to the different extents of deviation from equilibrium at which the crystallization processes proceeded. Copyright © 2004 Society of Chemical Industry     

茂金属间规聚丙烯的研发新进展

综述了茂金属间规聚丙烯(sPP)催化剂及聚合工艺的研究进展;从工业化的角度。对催化剂载体的选择、载体化方法以及聚合工艺实施方法进行了探讨。茂金属sPP结构新颖,性能独特,是一种新型热塑性树脂。具有广阔的应用前景。我国应加快sPP催化剂合成、聚合工艺以及加工性能的研究．尽快实现sPP产业化。     

Crystallization and melting behaviour of polypropylene ‘catalloys’

The crystallization and melting behaviour of polypropylene ‘catalloys’ (PP‐cats) as well as pure polypropylene (PP) were investigated using differential scanning calorimetry. The results showed that, for PP‐cats and PP, a single melting peak of PP appeared under slow cooling rate. When the cooling rate is fast enough in the non‐isothermal case, or the crystallization temperature is relatively high in the isothermal case, a shoulder peak appears in front of the melting peak with increasing ethylene content in PP‐cats. It is believed that this shoulder is induced by recrystallization of crystals initially formed during non‐isothermal or isothermal crystallization. When the ethylene component in PP‐cats reached a certain level, there existed a melting peak of polyethylene (PE) crystallized during the cooling process. Polarized optical microscopy (POM) showed that the spherulites formed by PP‐cats were much smaller and had less perfect morphology compared with that formed by pure PP at the same cooling rate. And with the increase of the cooling rate, the spherulites could not be clearly observed. Copyright © 2004 Society of Chemical Industry     

Effects of silver nanoparticles on the dynamic crystallization and physical properties of syndiotactic polypropylene

The effects of silver (Ag) nanoparticles on the physical properties of syndiotactic PP (sPP) were investigated concentrating on the isothermal melt crystallization behavior under shear. sPP with 5 wt % Ag nanoparticles presented higher crystallization temperature (T_c) and heat of crystallization (ΔH_c) than pure sPP. At 90°C, the Ag nanoparticles had little effect on the induction time of crystallization but a little increased the half‐time (t_1/2) for the crystallization. At 100°C, however, the induction time was decreased with increasing the Ag content and the t_1/2 was decreased up to the Ag content of 0.5 wt %. DSC melting endotherms exhibited double melting peaks when crystallized at 90°C under shear but a single melting peak when crystallized at 100°C. The WAXD patterns exhibited that the presence of Ag nanoparticles did not produce any change in the crystal structure of sPP. The tensile strength of sPP is little changed up to the Ag content of 0.1 wt % but it was decreased with further addition. In addition, the introduction of less than 0.1 wt % Ag increased the elongation at break, but further addition decreased it abruptly. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Influence of annealing temperature on the lamellar and connecting bridge structure of stretched polypropylene microporous membrane

The influence of annealing temperature on the lamellar and connecting bridge structure of stretched polypropylene microporous membrane was investigated using small‐angle X‐ray scattering, temperature‐modulated differential scanning calorimetry and scanning electron microscopy. It is found that with increasing annealing temperature from 105 to 145 °C, the main lamella melting peak combines with that from connecting bridges and a uniform pore arrangement is obtained in the microporous membrane. The annealed lamella thickness is increased and lamellar structure is improved, due to the occurrence of melting and recrystallization during annealing. At the same time, more secondary crystals are formed. The melting and recrystallization and secondary crystals contribute to the appearance of an annealing peak in the differential scanning calorimetry curve of annealed film. During the following cold and hot stretching, the secondary crystals disappear and convert to initial connecting bridges. The improved lamellar structure can support the scaffold of pore structure, resulting in a uniform connecting bridge arrangement. But further increasing the temperature to 150 °C degrades the initial lamellar structure, leading to a decrease of pore arrangement in the stretched microporous membrane. Annealing leads to the difference of lamellar structure: the initial lamellar structure is improved and some weak secondary crystals are formed in the amorphous region. © 2014 Society of Chemical Industry     

Nonisothermal melt‐crystallization kinetics of syndiotactic polypropylene compounded with various nucleating agents

Nonisothermal melt‐crystallization behavior of syndiotactic polypropylene (sPP) compounded with 5% by weight (wt %) of some inorganic fillers [i.e., kaolin, talcum, marl, titanium dioxide (TiO₂), and silicon dioxide (SiO₂)] and 1 wt % of some organic fillers, which are some sorbital derivatives (i.e., DBS, MDBS, and DMDBS) was investigated and reported for the first time. It was found that the ability of these fillers to nucleate sPP decreased in the following sequence: DBS > talcum > MDBS > SiO₂ ～ kaolin ～ DMDBS > marl > TiO₂, with DBS being able to shift the crystallization exotherm by ～ 18°C on average, while TiO₂ was able to shift the crystallization exotherm by only ～ 6°C on average, from that of neat sPP. The Avrami analysis revealed that the Avrami exponent for sPP compounds varied between 2.9 and 4.3, with the values for neat sPP varying between 3.1 and 6.8. Lastly, the Ziabicki's crystallizability of sPP compounds was greater than that of neat sPP, suggesting an increase in the crystallization ability of sPP as a result of the presence of these fillers. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 245–253, 2005     

Nonisothermal melt crystallization kinetics of syndiotactic polypropylene/alumina nanocomposites

Nonisothermal melt crystallization kinetics of syndiotactic polypropylene (sPP)/alumina nanocomposites were investigated via differential scanning calorimetry. The addition of alumina nanoparticles significantly increases the number of nuclei and promotes the crystallization rate of sPP. Nonisothermal melt crystallization kinetics was analyzed by fitting the experimental data to a Nakamura model using Matlab. The average values of Avrami exponent n are 1.7 for both sPP and sPP/Al₂O₃ nanocomposites during slow cooling, which implies a two‐dimensional growth is the predominant mechanism of crystallization following a heterogeneous nucleation. The two nanocomposites give n values equal to 2.3 during faster cooling, indicating that the main growth type taking place for sPP/alumina nanocomposites is also the two‐dimensional growth. The subsequent melting behavior shows that the presence of alumina nanoparticles changed both the cold crystallization and the recrystallization of sPP. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

聚丙烯（PP）／黏土复合材料熔融剂的研究

以马来酸酐（MAH）等为单体接枝聚丙烯作为聚丙烯（PP）／黏土复合材料熔融剂,考察了马来酸酐用量、引发剂过氧化苯甲酰（BPO）用量、反应时间、温度等因素对产物接枝率的影响,并通过红外光谱图对PP-g-MAH进行表征。结果表明,当m（PP）：m（复配单体）：m（BPO）=10．0：2．0：0．6、反应温度控制在120℃左右、复配单体为马来酸酐／苯乙烯时,熔融剂PP-g-MAH的接枝率可获得较大值3．9％。实验同时表明,反应时间对接枝率的影响不大;苯乙烯的加入对接枝率有较大的影响,与普通单体单一马来酸酐相比,加入苯乙烯的接枝率明显提高。     

Molding of syndiotactic polystyrene under its melting temperature

Syndiotactic polystyrene (SPS), a thermoplastic polymer that exhibits a high T_m in some crystalline forms, can be conveniently processed by a cold‐compaction technique. Processing temperatures in the range of 150–210°C, well below the T_m, gives rise to physicomechanical properties comparable and even better than those obtained by thermal compression or injection molding. The optimum treatment temperature seems to fall around 175°C. X‐ray diffraction analysis, thermal analysis, and density measurements suggest that such behavior is connected to phase transitions of SPS and favored by the presence of styrene included in the crystalline fraction. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 377–383, 2001     

Oriented crystallization in fiber formation: Inferences from the structure and properties of melt spun syndiotactic polypropylene filaments

In processes, such as melt spinning, the crystallization behavior of syndiotactic polypropylene (sPP) is found to be substantially different from that of most other linear polymers. The anisotropic stress field in such processes leads invariably to extension as well as alignment (orientation) of the chains in the melt, both of which contribute usually to dramatic enhancement in the rate of crystallization. However, since the primary structure of the sPP chain in its most preferred crystal form is comprised of a “coiled helical,” ? (T₂G₂)₂? , sequence, stress‐induced chain extension can lead to conformational sequences that are not favorable for crystallization in this form. As a consequence, process conditions that generate higher stress levels can cause a diminution in the rate of crystallization of this polymer. Such conformation‐related aspects of oriented crystallization of sPP have been addressed through an analysis of the structure and properties of melt‐spun fibers, produced over a range of spinning speeds. The results serve to identify a refinement that is needed in current models of oriented crystallization and also a mechanism to promote the nucleation of crystallization of sPP. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2305–2317, 2001     

Crystalline memory effects in isothermal crystallization of syndiotactic polypropylene

Isothermal crystallization behavior after partial or complete melting of syndiotactic polypropylene was investigated by differential scanning calorimetry (DSC). On partial melting, the total concentration of predetermined nuclei was found to decrease with increasing fusion temperature and increasing time period that the sample spent at a specific fusion temperature. A significant effect of the rate of heating to the fusion temperature was also observed. On complete melting, the total concentration of predetermined nuclei was found to approach a constant value, which is the concentration of infusible heterogeneous nuclei (e.g., impurities, catalyst residues) present originally in the sample. At a specific fusion temperature, the concentration of predetermined athermal nuclei was found to decrease exponentially with the time period spent in the melt. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 337–346, 2000