Melting behavior and nonisothermal crystallization kinetics of polyamide 6/polyamide 66 molecular composites via in situ polymerization

The melting behavior and nonisothermal crystallization kinetics of pure polyamide 6 (PA 6) and its molecular composites with polyamide 66 (PA 66) were investigated with differential scanning calorimetry. The PA 6/PA 66 composites had one melting peak, whereas the coextruded PA 6/PA 66 blends had two melting peaks. With the addition of PA 66 to PA 6 via in situ anionic polymerization, the melting temperature, crystallization temperature, and crystallinity of PA 6 in the composites decreased. The half‐time of nonisothermal crystallization increased for a PA 6/PA 66 molecular composite containing 12 wt % PA 66, in comparison with that of pure PA 6. The commonly used Ozawa equation was used to fit the nonisothermal crystallization of pure PA 6 and its composites. The Ozawa exponent values in the primary stage were equal to 1.28–3.03 and 1.28–2.97 for PA 6 and its composite with 12 wt % PA 66, respectively, and this revealed that the mechanism of primary crystallization of PA 6 and PA 6/PA 66 was mainly heterogeneous nucleation and growth. All the results indicated that the incorporation of PA 66 into PA 6 at the molecular level retarded the crystallization of PA 6. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2172–2177, 2005     

Melting behavior,nonisothermal crystallization kinetics,and morphology of PP/nylon 11/EPDM‐g‐MAH blends

The melting behavior, nonisothermal crystallization behavior, and morphology of pure polypropylene (PP) and its blends were investigated by differential scanning calorimetry and polarized optical microscopy. The nonisothermal crystallization kinetics was analyzed using the Avrami equation modified by Jeziorny and the equation combining the Avrami and Ozawa method. The surface fold free energy and the effective activation energy for both PP and its blends were obtained by Hoffman‐Lauritzen theory and Vyazovkin's approach, respectively. The results showed that the presence of nylon 11 hindered the mobility of PP chains but accelerated the overall crystallization rate. The POM observation confirmed that the addition of nylon 11 decreased the spherulites size of PP matrix. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Isothermal and nonisothermal crystallization kinetics of novel even‐odd nylon 10 11

Isothermal and nonisothermal crystallization kinetics of even‐odd nylon 10 11 were investigated by differential scanning calorimetry (DSC). Equilibrium melting point was determined to be 195.20°C. Avarmi equation was adopted to describe isothermal and nonisothermal crystallization. A new relation suggested by Mo was used to analyze nonisothermal crystallization and gave a good result. The crystallization activation energies have been obtained to be ?583.75 and ?270.06 KJ/mol for isothermal and nonisothermal crystallization, respectively. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1637–1643, 2005     

Phase stability and melting behavior of the α and γ phases of nylon 6

The phase stability and melting behavior of nylon 6 were studied by high‐temperature wide‐angle X‐ray diffraction and differential scanning calorimetry (DSC). The results show that most of the α phase obtained by a solution‐precipitation process [nylon 6 powder (Sol‐Ny6)] was thermodynamically stable and mainly melted at 221°C; the double melting peaks were related to the melt of α crystals with different degrees of perfection. The γ phase formed by liquid nitrogen quenching (sample LN‐Ny6) melted within the range 193–225°C. The amorphous phase converted into the γ phase below 180°C but into the high‐temperature α phase at 180–200°C. Both were stable over 220°C. α‐ and γ*‐crystalline structures were formed by annealing but were not so stable upon heating. Typical double melting peaks were shown on the DSC curve; melt recrystallization happened within the range 100–200°C. The peak at 210°C was mainly due to the melting of the less perfect crystalline structure of the γ phase and a fraction of the α phase; the one at 219°C was due to the high‐temperature α‐ and γ‐phase crystals. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Motion mode of poly(lactic acid) chains in film during strain‐induced crystallization

How stress and temperature impact the movement of poly(lactic acid) (PLA) chains in the process of tensile film stretching was studied. The motion mode of chains was investigated through the study of the strain‐induced crystallization and orientation through changes in the draw temperature (T_d), draw ratio, and draw rate. The crystallinity and orientation degrees of the PLA films were measured by differential scanning calorimetry, Fourier transform infrared spectroscopy, and polarized optical microscopy. According to the competition between the orientation caused by the stretching and relaxation of chains under the temperature field, the motion modes of PLA chains during strain were divided into four types, modes I–IV. When T_d was 100°C, the PLA chains acted in mode I, in which the relaxation rate of chains was so fast that no crystallinity or orientation could be obtained. Beyond a draw rate of 20 mm/min at a T_d of 90°C, the type of chain movement changed from mode I to II. In mode II, only crystallites could be reserved after unloading. Chains in the PLA film moved in mode III at a T_d of 80°C; then, both the crystallization and orientation were enhanced monophonically with increasing draw rate. Beyond the draw rate of 10 mm/min at a T_d of 70°C, the orientation rate of chains was much faster than the relaxation one, and the motion mode transformed from mode III to IV. Then, obvious decreases in the crystallinity and orientation were observed with further increases in the draw rate; this resulted from the destruction of the crystallites. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42969.     

Structure,mechanical, and thermal behavior of nylon 6‐polyisoprene block copolymers obtained via anionic polymerization

The structure and physicomechanical properties of nylon 6 (N‐6) modified with polyethylene oxide–polyisoprene–polyethylene oxide (PEO‐PI‐PEO) copolymers via activated anionic polymerization have been investigated by using differential scanning calorimetry (DSC), wide‐angle X‐ray diffraction (WAXD), thermogravimetric analysis (TGA), dynamic mechanical analysis (DTMA), and by optical microscopy. This study deals with the influence that the N‐6/PI ratio and the length of the PI segments have on the physicomechanical behavior, thermal stability, and the structural changes of the block copolymers. Literature does not report on previous investigations of this kind. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3251–3258, 2004     

On the nonisothermal melt crystallization kinetics of industrial batch crosslinked polyethylene

The chemical modification of commodity polymers such as polyethylene (PE) is a versatile synthetic approach for preparing materials that cannot be manufactured cost-effectively using conventional polymerization techniques. Aiming to improve PE character low contents of dicumyl peroxide (DCP), from 0% to 1.5% was added as crosslinker to an industrial batch (PEs mixture and additives). From tensile testing crosslinking provided higher elastic modulus most due to the restrained microstructure where XPEs macromolecular chains are interconnected also providing lower strain at break. Crosslinking effects on the nonisothermal melt crystallization rate (Cmax) and degree of crystallinity (Xc) were evaluated; Cmax increased with the cooling rates, whereas Xc increased upon DCP addition. The melt crystallization kinetics were thoroughly investigated applying Pseudo-Avrami, Ozawa, and Mo models. Ozawa failed to describe the crystallization most due to ignore the secondary crystallization and spherulites impingement at the end of crystallization while Pseudo-Avrami and Mo provided quite good fits. The activation energy was computed using Arrhenius' approach, crosslinked compounds presented higher energy consumption, whereas exception was verified for 0.5XPE which displayed the lowest energy and overall the best mechanical performance this is the most proper compound for industrial applications, such as packaging, and disposables as well as general goods.     

Morphology and crystallization behavior of nylon 6‐clay/neat nylon 6 bicomponent nanocomposite fibers

Nylon 6‐clay hybrid/neat nylon 6, sheath/core bicomponent nanocomposite fibers containing 4 wt % of clay in sheath section, were melt spun at different take‐up speeds. Their molecular orientation and crystalline structure were compared to those of neat nylon 6 fibers. Moreover, the morphology of the bicomponent fibers and dispersion of clay within the fibers were analyzed using scanning electron microscopy and transmission electron microscopy (TEM), respectively. Birefringence measurements showed that the orientation development in sheath part was reasonably high while core part showed negligibly low birefringence. Results of differential scanning calorimetry showed that crystallinity of bicomponent fibers was lower than that of neat nylon 6 fibers. The peaks of γ‐crystalline form were observed in the wide‐angle X‐ray diffraction of bicomponent and neat nylon 6 fibers in the whole take‐up speed, while α‐crystalline form started to appear at high speeds in bicomponent fibers. TEM micrographs revealed that the clay platelets were individually and evenly dispersed in the nylon 6 matrix. The neat nylon 6 fibers had a smooth surface while striped pattern was observed on the surface of bicomponent fibers containing clay. This was speculated to be due to thermal shrinkage of the core part after solidification of the sheath part in the spin‐line. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 39996.     

Isothermal and nonisothermal crystallization kinetics of MC nylon and polyazomethine/MC nylon composites

Crystallization kinetics of MC nylon (PA6) and polyazomethine (PAM)/MC nylon (PAM/PA6) both have been isothermally and nonisothermally investigated by different scanning calorimetry (DSC). Two stages of crystallization are observed, including primary crystallization and secondary crystallization. The Avrami equation and Mo's modified method can describe the primary stage of isothermal and nonisothermal crystallization of PA6 and PAM/PA6 composite, respectively. In the isothermal crystallization process, the values of the Avrami exponent are obtained, which range from 1.70 to 3.28, indicating an average contribution of simultaneous occurrence of various types of nucleation and growth of crystallization. The equilibrium melting point of PA6 is enhanced with the addition of a small amount of rigid rod polymer chains (PAM). In the nonisothermal crystallization process, we obtain a convenient method to analyze the nonisothermal crystallization kinetics of PA6 and PAM/PA6 composites by using Mo's method combined with the Avrami and Ozawa equations. In the meanwhile, the activation energies are determined to be ?306.62 and ?414.81 KJ/mol for PA6 and PAM/PA6 (5 wt %) composite in nonisothermal crystallization process from the Kissinger method. Analyzing the crystallization half‐time of isothermal and nonisothermal conditions, the over rate of crystallization is increased significantly in samples with a small content of PAM, which seems to result from the increased nucleation density due to the presence of PAM rigid rod chain polymer. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2844–2855, 2004     

Isothermal and nonisothermal crystallization kinetics of partially melting nylon 10 12

Nylon 10 12, a newly industrialized engineering plastic, shows a double‐melting phenomenon during melting. Partial melts were obtained when the sample was heated to the temperature between the two melting peaks. A differential scanning calorimeter was used to monitor the energies of the isothermal and nonisothermal crystallization from the partially melted samples. During isothermal crystallization, relative crystallinity develops with a time dependence described by the Avrami equation, with the exponent n = 1.0. For nonisothermal studies, kinetics treatments based on the Avrami and Ozawa equations are presented to describe the crystallization process. It was found that the two treatments can describe the nonisothermal crystallization from the partially melted samples. The derived Avrami and Ozawa exponents are all about 1.0, which means that the partially melted samples crystallize by one‐dimensional growth, which may cause thickening of the lamellae. We calculated the crystallization activation energies for isothermal and nonisothermal crystallization from the partially melted samples. It was found that the activation energy determined by the Kissinger method was not rational, which may be attributed to the free‐nucleation process for nonisothermal crystallization from partially melted samples. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1311–1319, 2003     

Effect of core‐shell morphology evolution on the rheology,crystallization, and mechanical properties of PA6/EPDM‐g‐MA/HDPE ternary blend

In this article, polyamide 6 (PA6), maleic anhydride grafted ethylene‐propylene‐diene monomer (EPDM‐g‐MA), high‐density polyethylene (HDPE) were simultaneously added into an internal mixer to melt‐mixing for different periods. The relationship between morphology and rheological behaviors, crystallization, mechanical properties of PA6/EPDM‐g‐MA/HDPE blends were studied. The phase morphology observation revealed that PA6/EPDM‐g‐MA/HDPE (70/15/15 wt %) blend is constituted from PA6 matrix in which is dispersed core‐shell droplets of HDPE core encapsulated by EPDM‐g‐MA phase and indicated that the mixing time played a crucial role on the evolution of the core‐shell morphology. Rheological measurement manifested that the complex viscosity and storage modulus of ternary blends were notable higher than the pure polymer blends and binary blends which ascribed different phase morphology. Moreover, the maximum notched impact strength of PA6/EPDM‐g‐MA/HDPE blend was 80.7 KJ/m² and this value was 10–11 times higher than that of pure PA6. Particularly, differential scanning calorimetry results indicated that the bulk crystallization temperature of HDPE (114.6°C) was partly weakened and a new crystallization peak appeared at a lower temperature of around 102.2°C as a result of co‐crystal of HDPE and EPDM‐g‐MA. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Crystallization behavior of PA‐6 clay nanocomposite hybrid

Polyamide‐6 (PA‐6)/clay (modified montmorillonite) hybrid was synthesized by melt blending at high shear stress. ²⁷Al‐NMR of solid state shows that the clay is not modified after melt blending. Using wide‐line ¹H‐NMR and TEM, it is demonstrated that the nanocomposite exhibits mainly an exfoliated structure. It is shown that the modified montmorillonite induces the crystallization of PA‐6 predominantly in γ‐form. The presence of clay in PA‐6 increases the polymer crystallization temperature, and decreases its melting point. These phenomena show that a certain number of interactions develop near the reinforcing material, and that the latter plays a particular role of nucleating agent. However, the crystallization is not spherulitic and the assumption of macromolecular orientation in the vicinity of the clay is demonstrated by the observations carried out in DSC and AFM. These particular properties of orientation will have a particular importance on the mechanical behavior of the nanocomposite material. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2416–2423, 2002     

A new method to prepare low melting point polyamide‐6 and study crystallization behavior of polyamide‐6/calcium chloride complex by rheological method

A new method to prepare low melting point polyamide‐6 (LPA6) by complex reaction of calcium chloride (CaCl₂) and polyamide‐6 (PA6) in a co‐rotating twin screw extruder was reported. We employed a new rheological method to study the crystallization behavior of PA6/CaCl₂ complex and the mechanism of confined crystallization of PA6. Compared with differential scanning calorimetry (DSC), this method was more capable of detecting crystalline information. What's more, it was also an effective method for studying mechanism of confined crystallization. From the results of X‐ray diffraction, DSC, infrared spectroscopy, rheology, and mechanical properties, the complex reaction of CaCl₂ with the carbonyl oxygen atom in the amide group disrupted the intermolecular hydrogen bonding and confined the mobility of PA6 molecules. This could significantly reduce the crystallinity and melting temperature of PA6, and improve tensile strength and notched Izod impact strength. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41513.     

Isothermal crystallization kinetics of high‐flow nylon 6 by differential scanning calorimetry

The isothermal crystallization kinetics have been investigated with differential scanning calorimetry for high‐flow nylon 6, which was prepared with the mother salt of polyamidoamine dendrimers and p‐phthalic acid, an end‐capping agent, and ε‐caprolactam by in situ polymerization. The Avrami equation has been adopted to study the crystallization kinetics. In comparison with pure nylon 6, the high‐flow nylon 6 has a lower crystallization rate, which varies with the generation and content of polyamidoamine units in the nylon 6 matrix. The traditional analysis indicates that the values of the Avrami parameters calculated from the half‐time of crystallization might be more in agreement with the actual crystallization mechanism than the parameters determined from the Avrami plots. The Avrami exponents of the high‐flow nylon 6 range from 2.1 to 2.4, and this means that the crystallization of the high‐flow nylon 6 is a two‐dimensional growth process. The activation energies of the high‐flow nylon 6, which were determined by the Arrhenius method, range from ?293 to ?382 kJ/mol. The activation energies decrease with the increase in the generation of polyamidoamine units but increase with the increase in the content of polyamidoamine units in the nylon 6 matrix. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Isothermal crystallization kinetics and melting behavior of multiwalled carbon nanotubes/polyamide‐6 composites

Pristine and functionalized multiwalled carbon nanotubes (MWNTs) were used to fabricate polyamide 6 (PA6) composites through melt blending. The functionalized MWNTs were obtained by grafting 1,6‐hexamethylenediamine (HMD) onto the pristine MWNTs to improve their compatibility with PA6 matrix. The effect of MWNTs on the isothermal crystallization and melting behavior of PA6 was investigated by differential scanning calorimetry (DSC) and X‐ray diffraction (XRD). The Avrami and Lauritzen–Hoffmann equations are used to describe the isothermal crystallization kinetics. The values of the Avrami exponent found for neat PA6, the pristine MWNTs/PA6 and functionalized MWNTs/PA6 composite samples are about 4.0, 1.7, and 2.3, respectively. The activation energies are determined by the Arrhenius method, which is lower for the composites, ?320.52 KJ/mol for pristine MWNTs/PA6 and ?293.83 KJ/mol for functionalized MWNTs/PA6, than that for the neat PA6 (?284.71 KJ/mol). The following melting behavior reveals that all the isothermally crystallized samples exhibit triple melting endotherms at lower crystallization temperature and double melting endotherms at higher crystallization temperature. The multiple melting endotherms are mainly caused by the recrystallization of PA6 during heating. The resulting equilibrium melting temperature is lower for the composites than for neat PA6. In addition, polarizing microscopy (PLM) and small angle light scanning (SALS) were used to study the spherulite morphology. The results show that the MWNTs reduce the spherulite radius of PA6. This reduction is more significant for pristine MWNTs. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Effects of UV‐irradiation on the nonisothermal crystallization kinetics of polypropylene

The influences of UV‐induced photodegradation on the nonisothermal crystallization kinetics of polypropylene (PP) were investigated by differential scanning calorimetry. The Avrami analysis modified by Jeziorny, Ozawa method, and a method modified by Liu were employed to describe the nonisothermal crystallization process of unexposed and photodegraded PP samples. Kinetics studies reveal that the rates of nucleation and growth may be affected differently by photodegradation. A short‐term UV‐irradiation may accelerate the overall nonisothermal crystallization process of PP, but a long‐term UV‐irradiation should impede it. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Fractionated crystallization in polyolefins–nylon 6 blends

The crystallization behavior of polyolefins–nylon 6 polymer blends was studied by differential scanning calorimetry (DSC) measurements. In these blends, the crystallization of the minor component often starts with distinctly deeper supercooling than that of the pure polymer, and proceeds in several separate steps. The origin of this phenomenon was studied and was related to the volume fraction of the dispersed phase and the compatibility between the dispersed phase and the matrix. © 1994 John Wiley & Sons, Inc.     

Strain‐induced crystallization in uniaxially drawn PETG plates

The copolyester poly(ethylene glycol‐co‐cyclohexane‐1,4‐dimethanol terephthalate) (PETG) is used industrially as an uncrystallizable polymer, whereas PET is an inherently crystallizable polymer. Nevertheless, a crystalline phase could appear in the material. To create a strain‐induced crystalline phase in an initially amorphous PETG material, plates were placed in the heating chamber of a tensile machine at 100°C and uniaxially drawn to obtain different samples with various draw ratios. During DSC analysis of highly drawn samples, perturbations of the baseline appear above the glass‐transition temperature, consisting of weak exothermic and endothermic phenomena. Comparison of DSC and X‐ray diffraction analysis of drawn PETG and PET shows that a strain‐induced crystalline phase appears in this copolyester. A spherulitic superstructure could also appear after lengthy annealing. Analysis of this semicrystalline material allowed estimation of the degree of crystallinity, about 3% after a drawing at high draw ratio and about 11% for undrawn annealed material. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 3405–3412, 2001     

Effect of the ionic liquid [bmim]PF6 on the nonisothermal crystallization kinetics behavior of poly(ether‐b‐amide)

Blending ionic liquid with crystalline polymer permits the design of new high‐performance composite materials. The final properties of these materials are critically depended on the degree of crystallinity and the nature of crystalline morphology. In this work, nonisothermal crystallization behavior of poly(ether‐b‐amide) (Pebax®1657)/room temperature ionic liquid (1‐butyl‐3‐methylimidazolium hexafluorophosphate, [bmim]PF₆) was investigated by differential scanning calorimetry. The presence of [bmim]PF₆ can retard the nucleation of Pebax®1657 and lead to the crystallization depression of the PA block and the crystalline disappearance of the PEO block. However, the dilution effect of the IL results in a higher growth rate of crystallization of PA block. The influence of [bmim]PF₆ content and cooling rate on crystallization mechanism and spherulitc structures was determined by the Avrami equation modified by Jeziorny and Mo's methods, whereas the Ozawa's approach fails to describe the nonisothermal crystallization behavior of Pebax®1657/[bmim]PF₆ blends. In the modified Avrami analysis, the Avrami exponent of PA blocks, n > 3, for pure Pebax®1657, while 3 > n > 2 for Pebax®1657/[bmim]PF₆ blends testifies the transformation of crystallization growth pattern induced by [bmim]PF₆ from three‐dimensional growth of spherulites to a combination of two‐ and three‐dimensional spherulitic growth. Further, lower activation energy for the nonisothermal crystallization of PA blocks of Pebax®1657 can be observed with the increase of [bmim]PF₆ content. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42137.     

Investigation of crystallization behavior in dynamically vulcanized EPDM–nylon copolymer blends

A thermoplastic vulcanizate (TPV) of a ethylene–propylene–diene terpolymer (EPDM) and nylon copolymer (PA) was prepared by dynamic vulcanization. Maleic anhydride (MAH)–grafted EPDM (EPDM–g–MAH), MAH‐grafted EPR (EPR–g–MAH), and chlorinated polyethylene (CPE) were used as compatibilizers. The effect of dynamic vulcanization and compatibilizer on the crystallization behavior of PA was investigated. Differential scanning calorimeter measurement results showed no pronounced shift in the crystallization temperature for PA in EPDM–PA TPV compared to that for PA in the neat state, whereas the crystallization temperature increased after adding compatibilizer. The decrease in the crystallinity of TPVs was a result of the crystallization occurring in confined spaces between rubber particles. The equilibrium melting temperature (Tm⁰) of the PA copolymer was measured and was determined to be 157°C. The isothermal crystallization kinetics of PA in the neat and TPV states also was investigated. The crystallization rate was highest in the compatibilized TPV and lowest in the neat PA, whereas it was intermediate in the uncompatibilized TPV unvulcanized blends. Compared with unvulcanized EPDM–PA blends, the dynamic vulcanization process seemed to cause an obvious increase in the crystallization rate of the PA copolymer, especially when a suitable compatibilizer was used. This occurred because the dynamic vulcanization introduced fine crosslinked rubber particles that could act as heterogeneous nucleating centers. In addition, the use of a suitable compatibilizer permitted the formation of finely dispersed vulcanized rubber particles and therefore increased the density of the nucleating centers. The complex morphology of the blends was investigated by atomic force microscopy to evaluate the effect of compatibilizer on the size of the dispersed rubber particles. Compared with the morphology of TPVs with the same dosage of EPDM–g–MAH compatibilizer, the morphology of TPVs using EPR–g–MAH as compatibilizer showed much smaller dispersed rubber particles, which may have contributed to the higher crystallization rate. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 824–829, 2003