Isothermal crystallization kinetics and melting behavior of nylon/saponite and nylon/montmorillonite nanocomposites

DSC thermal analysis and X‐ray diffraction have been used to investigate the isothermal crystallization behavior and crystalline structure of nylon 6/clay nanocomposites. Nylon 6/clay has prepared by the intercalation of ε‐caprolactam and then exfoliating the layered silicates by subsequent polymerization. The DSC isothermal results reveal that introducing saponite into the nylon structure causes strongly heterogeneous nucleation induced change of the crystal growth process from a two‐dimensional crystal growth to a three dimensional spherulitic growth. But the crystal growth mechanism of nylon/montmorillonite nanocomposites is a mixed two‐dimensional and three‐dimensional spherulitic growth. The activation energy drastically decreases with the presence of 2.5 wt % clay in nylon/clay nanocomposites and then slightly increases with increasing clay content. The result indicates that the addition of clay into nylon induces the heterogeneous nucleation (a lower ΔE) at lower clay content and then reduces the transportation ability of polymer chains during crystallization processes at higher clay content (a higher ΔE). The correlation among crystallization kinetics, melting behavior, and crystalline structure of nylon/clay nanocomposites is also discussed. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2196–2204, 2004     

Isothermal crystallization kinetics and melting behavior of modified high‐density polyethylene/barium sulfate nanocomposites

The melting/crystallization behavior and isothermal crystallization kinetics of high‐density polyethylene (HDPE)/barium sulfate (BaSO₄) nanocomposites were studied with differential scanning calorimetry (DSC). The isothermal crystallization kinetics of the neat HDPE and nanocomposites was described with the Avrami equation. For neat HDPE and HDPE/BaSO₄ nanocomposites, the values of n ranges from 1.7 to 2.0. Values of the Avrami exponent indicated that crystallization nucleation of the nanocomposites is two‐dimensional diffusion‐controlled crystal growth. The multiple melting behaviors were found on DSC scan after isothermal crystallization process. The multiple endotherms could be attributed to melting of the recrystallized materials or the secondary lamellae caused during different crystallization processes. Adding the BaSO₄ nanoparticles increased the equilibrium melting temperature of HDPE in the nanocomposites. Surface free energy of HDPE chain folding for crystallization of HDPE/BaSO₄ nanocomposites was lower than that of neat HDPE, confirming the heterogeneous nucleation effect of BaSO₄. POLYM. COMPOS., 2011. © 2010 Society of Plastics Engineers     

Crystallization and melting behavior of polyester/clay nanocomposites

Polyester/clay nanocomposites were prepared by melt compounding with different clay loadings. Comparing against neat polyester resins, the crystallization and multiple melting behavior of the nanocomposites was investigated by differential scanning calorimetry (DSC) and X‐ray diffraction (XRD). Nanoclay filler is an effective heterogeneous nucleating agent, as evidenced by a decrease and an increase in the crystallization temperature for both cold and melt crystallization of polyesters, respectively. The degree of crystallinity was found to increase with increasing clay content, due to heterogeneous nucleation effects by the addition of a nanofiller. For the annealed samples, multiple melting peaks were always observed for both neat polyester and its nanocomposites. The origins of the multiple melting behavior are discussed, based on the DSC and XRD results. Interestingly, an ‘abnormal’ high‐temperature endothermic peak (T_{m, 3}) at about 260 °C was observed when the nanocomposite samples were annealed at higher temperatures (eg ≥240 °C). The constrained polyester crystals formed within intercalated clay platelets due to confinement effects were probably responsible for this melting event at these higher temperatures. Copyright © 2004 Society of Chemical Industry     

Isothermal crystallization, melting behavior and crystalline morphology of syndiotactic polystyrene blends with highly-impact polystyrene

Syndiotactic polystyrene (sPS) blends with highly-impact polystyrene (HIPS) were prepared with a twin-screw extruder. Isothermal crystallization, melting behavior and crystalline morphology of sPS in sPS/HIPS blends were investigated by differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD) and polarized optical microscopy (POM). Experimental results indicated that the isothermal crystallization behavior of sPS in its blends not only depended on the melting temperature and crystallization temperature, but also on the HIPS content. Addition of HIPS restricted the crystallization of sPS melted at 320 °C. For sPS melted at 280 °C, addition of low HIPS content (10 wt% and 30 wt%) facilitated the crystallization of sPS and the formation of more content of α-crystal. However, addition of high HIPS content (50 wt% and 70 wt%) restricted the crystallization of sPS and facilitated the formation of β-crystal. More content of β-crystal was formed with increase of the melting and crystallization temperature. However, α-crystal could be obtained at low crystallization temperature for the specimens melted at high temperature. Addition of high HIPS content resulted in the formation of sPS spherulites with less perfection.     

Pre‐melting temperature effect on the isothermal melt crystallization and multiple melting behavior of syndiotactic polystyrene

This work examined how pre‐melting temperature (T_max) affects the isothermal melt crystallization kinetics, the resulting melting behavior and crystal structure of syndiotactic polystyrene (sPS) by using differential scanning calorimetry (DSC), polarized light microscopy (PLM) and the wide angle X‐ray diffraction (WAXD) technique. Experimental results indicated that raising T_max decreased the nucleation rate and the crystal growth rate of sPS. The Avrami equation was also used to analyze the overall crystallization kinetics. The Avrami exponent n and rate constant K were determined for different T_max specimens at various crystallization temperatures (T_c's). Our results indicated that the nucleation type of sPS is T_max and T_c dependent as well. Evaluation of the activation energy for the isothermal crystallization processes revealed that it increases from 375 kJmol^?1 to 485 kjmol ^?1 with an increase of T_max. From the melting behavior study, we believe that the T_max and T_c‐dependent multiple melting peaks are associated with different polymorphs as well as recrystallized crystals formed during heating scans. Moreover, the percentage content of α form in the crystals formed under different crystallization conditions was estimated through WAXD experiments.     

Morphology,crystallization and melting properties of isotactic polypropylene blended with lignin

The influence of lignin (L) on the thermal properties and kinetics of crystallization of isotactic polypropylene (PP) is reported in this article. PP blends containing 5 and 15 wt % of L were prepared by mixing the components in a screw mixer. An increase of the thermal degradation temperature of the blends was observed as a function of L content. The crystallization and thermal behavior of the pure PP and of the PP/L blends were analyzed by differential scanning calorimetry (DSC). Isothermal crystallization kinetics were described by means of the Avrami equation, which suggests a three‐dimensional growth of crystalline units, developed by heterogeneous nucleation. The isothermal growth rate of PP spherulites was studied using a polarizing optical microscope. The enhancement of PP crystallization rate for the PP/L blends was observed and ascribed to the nucleating action of lignin particles. Non‐isothermal crystallization kinetics were applied, according to the results elaborated by Ziabicki and the method modified by Jeziorny. The kinetic crystallizability of the PP is not influenced by the L present in the blend. In the presence of L, PP can simultaneously crystallize in both the α and β crystalline forms, and the ratio between the α and β forms was determined by X‐ray diffraction analysis. Two melting peaks relative to the two crystalline form of PP were observed for the PP/L blends, for all isothermal crystallization temperatures investigated by means of DSC. The equilibrium melting temperature for α‐form of pure PP was obtained. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1435–1442, 2004     

Isothermal crystallization of lightly sulfonated syndiotactic polystyrene/montmorillonite clay nanocomposites

Lightly sulfonated syndiotactic polystyrene (sPS) nanocomposites were prepared using a solution intercalation technique, and the effect of montmorillonite clay on the crystallization kinetics of sulfonated sPS ionomer nanocomposites was systematically studied. Wide angle X-ray diffraction (WAXD) and transmission electron microscopy (TEM) were used to evaluate the dispersion of clay platelets within sPS and sulfonated sPS ionomer (SsPS) matrices. Experimental results obtained from WAXD and TEM revealed a predominately exfoliated morphology within the SsPS ionomer containing 5 wt.% of organically-modified clay. The corresponding non-sulfonated sPS control exhibited a mixed morphological structure consisting of intercalated platelets and many platelets that were present as micron-sized agglomerates. Using differential scanning calorimetry (DSC), the Avrami approach was used to elucidate information related to nucleation and growth within the sPS and SsPS systems during the isothermal crystallization process. Pristine and organically-modified clays significantly increased the overall crystallization rate of the SsPS ionomer, while the nanoclays slightly decreased the crystallization rate of the non-ionic sPS. The mechanistic origins of increased crystallization rates within the SsPS ionomer clay nanocomposites were attributed to multiple phenomena including disruption of the ionomer electrostatic network and a nucleating effect due to the presence of well-separated, homogeneously dispersed clay platelets.     

Crystallization kinetics of poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate)/clay nanocomposites

The preparation and properties of nanocomposites, consisting of a poly(3‐Hydroxybutyrate‐co‐3‐hydroxyvalerate) and an organophilic clay are described. The effect of organophilic clay on the crystallization behavior of (PHBV) was studied. A differential scanning calorimeter (DSC) was used to monitor the energy of the crystallization process from the melt. During the crystallization process from the melt, the organophilic clay led to an increase in crystallization temperature (T_c) of PHBV compared with that for plain PHBV. During isothermal crystallization, dependence of the relative degree of crystallization on time was described by the Avrami equation. The addition of organophilic clay caused an increase in the overall crystallization rate of PHBV, but did not influence the mechanism of nucleation, and growth of the PHBV crystals and the increase caused by a small quantity of clay is move effective than that large one. The equilibrium melting temperature of PHBV was determined as 186°C. Analysis of kinetic data according to nucleation theories showed that the increase in crystallization rate of PHBV in the composite is due to the decrease in surface energy of the extremity surface. The mechanical test shows that the tensile strength of hybrid increased to 35.6 MPa, which is about 32% higher than that of the original PHBV with the incorporation of 3 wt % clay, and the tensile modulus was also increased. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 655–661, 2004     

Isothermal and nonisothermal crystallization kinetics of poly(ε‐caprolactone)/multi‐walled carbon nanotube composites

Differential scanning calorimeter (DSC) and polarized optical microscopy (POM) have been used to investigate the isothermal and nonisothermal crystallization behavior of poly(ε‐caprolactone) (PCL)/multi‐walled carbon nanotube (MWNT) composites. PCL/MWNT composites have been prepared by mixing the PCL polymer with carboxylic groups containing multi‐walled carbon nanotubes (c‐MWNTs) in tetrahydrofuran solution. Raman spectrum of c‐MWNT indicated the possible presence of carboxylic acid groups at both ends and on the sidewalls of the MWNTs. The TEM micrograph showed that the c‐MWNT is well separated and uniformly dispersed in the PCL matrix. DSC isothermal results showed that the introduction of c‐MWNT into the PCL initiates strongly heterogeneous nucleation, which induced a change of the crystal growth process. The activation energy of PCL significantly decreases by adding 0.25 wt% c‐MWNT into PCL/c‐MWNT composites and then increases as c‐MWNT content increases. The result demonstrates that the addition of c‐MWNT into PCL induces the heterogeneous nucleation at lower c‐MWNT content and then inhibits the polymer chain transportation ability during crystallization at higher c‐MWNT content. In this study, we have also studied the nonisothermal crystallization kinetics and melting behavior of PCL/c‐MWNT composites at various cooling rates. The correlation among isothermal and nonisothermal crystallization kinetics and melting behavior of PCL/c‐MWNT composites can be also discussed. POLYM. ENG. SCI., 46:1309–1317, 2006. © 2006 Society of Plastics Engineers     

Polymorphic behavior of nylon 6/saponite and nylon 6/montmorillonite nanocomposites

X‐ray diffraction methods and DSC thermal analysis have been used to investigate the structural change of nylon 6/clay nanocomposites. Nylon 6/clay has prepared by the intercalation of ε‐caprolactam and then exfoliaton of the layered saponite or montmorillonite by subsequent polymerization. Both X‐ray diffraction data and DSC results indicate the presence of polymorphism in nylon 6 and in nylon 6/clay nanocomposites. This polymorphic behavior is dependent on the cooling rate of nylon 6/clay nanocomposites from melt and the content of saponite or montmorillonite in nylon 6/clay nanocomposites. The quenching from the melt induces the crystallization into the γ crystalline form. The addition of clay increases the crystallization rate of the α crystalline form at lower saponite content and promotes the heterophase nucleation of γ crystalline form at higher saponite or montmorillonite content. The effect of thermal treatment on the crystalline structure of nylon 6/clay nanocomposites in the range between Tg and Tm is also discussed.     

Isoconversional kinetic analysis of DSC data on nonisothermal crystallization: Estimation of Hoffman-Lauritzen parameters and thermal transitions in PET/MMT nanocomposites

The differential isoconversional method of Friedman is applied to non-isothermal melt crystallization DSC data to obtain effective activation energy ΔE. In comparison to neat PET, ΔE of intercalated 93A MMT clay nanocomposites (PCNs) decreased and highly dependent on the clay content. Hoffman-Lauritzen (H–L) secondary nucleation theory parameters, K_g and U* were evaluated using isoconversional approach of Vyazovkin and Sbirrazzuoli. Crystallization regime transition from regime III is observed at 190°C for neat PET, which shifted to higher temperature range 200°C–208 °C for PCNs. The K_g parameters for both regimes for PET are consistent with our isothermal experiments and reported in literature. However, the K_g values of nanocomposites are highly sensitive to the temperature dependent nucleation activity and ΔE of PET chain motion in melt and are not very much comparable with our isothermal results. Nevertheless, the observed results clearly indicate that the 93AMMT clay layers predominantly act as heterogeneous nucleating sites.     

Crystal morphology and crystallization kinetics of polyamide‐11/clay nanocomposites

Polyamide‐11 (PA11)/clay nanocomposites were prepared by in situ intercalative polymerization. The crystal morphology and crystallization kinetics of these nanocomposites were investigated via polarized light microscopy (PLM), small‐angle laser scattering (SALS) and differential scanning calorimetry (DSC). PA‐11 can crystallize into well‐formed spherulites, while only very tiny crystallites were observed by PLM and SALS for the nanocomposites. Both isothermal and non‐isothermal crystallization methods were employed to investigate the crystallization kinetics by DSC. Both techniques showed an increased crystallization rate with the addition of clay. However, the Avrami exponent decreased with the addition of clay in isothermal crystallization but showed a wide range of values depending on the cooling rate in the non‐isothermal crystallization. The changes in crystal morphology and crystallization kinetics can be understood as being due to the ‘supernucleating’ effect of the nanodispersed clay layers. Copyright © 2004 Society of Chemical Industry     

Isothermal crystallization kinetics and melting behavior of polyamide 11/silica nanocomposites prepared by in situ melt polymerization

Polyamide 11 (PA 11)/silica nanocomposites were prepared via in situ melt polymerization by the dispersion of hydrophobic silica in 11‐aminoundecanoic acid monomer. Their isothermal crystallization process and melting behaviors were analyzed by differential scanning calorimetry. The isothermal crystallization kinetics was analyzed by the Avrami equation. The obtained data showed that the model of nucleation and growth of PA 11 was not affected after the incorporation of silica and was a mixture with two‐dimensional, circular, three‐dimensional growth with thermal nucleation. Double and single melting peaks were observed depending on the crystallization temperature. The equilibrium melting point of samples was evaluated, and the spherulites growth kinetics parameters and fold surface free energy were further calculated according to the classical theories. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Crystallization and melting behavior of 1,2‐syndiotactic polybutadiene

1,2‐Syndiotactic polybutadiene was synthesized at ?30°C using the catalyst system CrCl₂(dmpe)₂‐MAO. The syndiotactic index of the butadiene sequences, expressed as a percentage of syndiotactic pentads [rrrr], was evaluated by ¹³C‐NMR measurements. WAXD and SAXS techniques were employed to characterize the crystalline structure of the polymer. The thermal behavior of the polybutadiene was investigated by differential scanning calorimetry. The isothermal crystallization kinetics were described by means of the Avrami equation, which suggested a three‐dimensional growth of crystalline units, developed by heterogeneous nucleation, followed by a secondary crystallization stage. Polybutadiene isothermally crystallizes from the melt according to regime II of crystallization described by Lauritzen–Hoffman secondary nucleation theory. Nonisothermal crystallization kinetics were elaborated using the Ziabicki and Avrami methods modified by Jeziorny. The equilibrium melting temperature was calculated. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1680–1687, 2004     

Isothermal crystallization behavior of poly(L‐lactic acid)/organo‐montmorillonite nanocomposites

The isothermal crystallization behavior of poly(L ‐lactic acid)/organo‐montmorillonite nanocomposites (PLLA/OMMT) with different content of OMMT, using a kind of twice‐functionalized organoclay (TFC), prepared by melt intercalation process has been investigated by optical depolarizer. In isothermal crystallization from melt, the induction periods (t_i) and half times for overall PLLA crystallization (100°C ≤ T_c ≤ 120°C) were affected by the temperature and the content of TFC in nanocomposites. The kinetic of isothermal crystallization of PLLA/TFC nanocomposites was studied by Avrami theory. Also, polarized optical photomicrographs supplied a direct way to know the role of TFC in PLLA isothermal crystallization process. Wide angle X‐ray diffraction (WAXD) patterns showed the nanostructure of PLLA/TFC material, and the PLLA crystalline integrality was changed as the presence of TFC. Adding TFC led to the decrease of equilibrium melting point of nanocomposites, indicating that the layered structure of clay restricted the full formation of crystalline structure of polymer. The specific interaction between PLLA and TFC was characterized by the Flory‐Huggins interaction parameter (B), which was determined by the equilibrium melting point depression of nanocomposites. The final values of B showed that PLLA was more compatible with TFC than normal OMMT. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Crystallization Behaviors of amino-terminated polyurethane (ATPU)-grafted polypropylene

Summary A melt-grafting approach was employed to prepare a novel functional polypropylene(FPP)—amino-terminated polyurethane grafted polypropylene (PP-g-ATPU). The crystallization behaviors of PP and PP/FPP blends were characterized using differential scanning calorimetry (DSC), wide angle X-ray scattering (WAXS) and polarized optical microscopy (POM). The effects of FPP composition on crystallization behavior, crystal transformation, and morphology of PP/FPP crystalline were investigated. The results showed that at a low dosage (<2.0 wt%) ATPU acted as a heterogeneous nucleation agent during the crystallization of PP/FPP blends. However, when the content of ATPU reached 2.0 wt% or higher, ATPU deteriorated the crystallization of PP or PP/FPP blends. The crystallite size decreased and the number of crystallites increased as the ATPU content increased. The Avrami analysis was adopted to describe the isothermal crystallization process. The difference in the exponent n between PP and PP/FPP suggested that the isothermal crystallization kinetics of PP/FPP blends followed a three-dimensional growth via heterogeneous nucleation. In terms of the half-time of the crystallization, t_1/2, the crystallization rate of functional PP blends was faster than that of PP homopolymer at a given crystallization temperature.     

sPS/PBA-aPS共混物的结晶与熔融行为

通过熔融共混法制备了间规立构聚苯乙烯/聚丙烯酸丁酯无规立构聚苯乙烯核壳乳胶粒子（sPS/PBA-aPS）共混物,采用差示扫描量热仪、X射线衍射仪和偏光显微镜研究了PBA-aPS对sPS结晶性能、结晶形态的影响,以及共混物在不同降温速率下、等温结晶条件下所得试样的熔融行为。结果表明, PBA-aPS的引入对sPS的结晶起阻碍作用,sPS及其共混物存在明显熔融重结晶再熔融现象,sPS平衡熔点为293.2 ℃,共混物的平衡熔点随PBA-aPS含量增加而降低,sPS形成β型大球晶完善性变差,sPS/PBA-aPS共混物的冲击强度明显提高,sPS/PBA-aPS质量比为80:20时,冲击强度提高了117 %。     

Synthesis and material properties of syndiotactic polystyrene/organophilic clay nanocomposites

Syndiotactic polystyrene (sPS)/organophilic clay nanocomposites were fabricated by direct‐melt intercalation method. To overcome the thermal instability of organophilic clay at high‐melt processing temperatures of sPS, an organophilic clay modified by alkyl phosphonium was adopted, which is known to be thermally stable. By using the newly synthesized clay, we could fabricate sPS intercalated nanocomposites. The microstructures of nanocomposites were confirmed by X‐ray diffraction (XRD) and transmission electron microscopy (TEM). The crystallization rate of nanocomposites investigated by differential scanning calorimetry (DSC) does not increase despite the presence of clay, which may be due to the physical hindrance of organic modifiers in the clay dispersion. Nanocomposites exhibited enhanced mechanical properties such as strength and stiffness relative to the virgin polymer. In addition, thermal stability was confirmed to be improved by thermogravimetric analysis (TGA). © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2144–2150, 2004     

Crystallization kinetics of chain extended poly(lactic acid)/clay nanocomposites

The poly(lactic acid)/clay nanocomposites (PLACNs) were prepared by melt mixing method, then multiepoxide chain extender (CE) was added into PLACNs to induce the branched structure of poly(lactic acid) (PLA) chains. The nonisothermal cold crystallization and isothermal melting crystallization of PLA, PLACNs, and chain extended PLACNs (CEPLACNs) were characterized by DSC and studied by Avrami analysis. The results showed that the inducing of clay and CE affected the crystallization behavior of PLA in different way. Adding CE increased the overall crystallinity of PLA at cooling process, but clay had an opposite effect. Besides that, the addition of CE and clay increased the crystal nuclei number due to the heterogeneous nucleation mechanism. According to the crystallization kinetics study, the inducing of clay almost no effect on the crystal growth rate of PLA, but the branched structure had a pronounced effect for improving crystal growth rate of PLA. POLYM. COMPOS., 36:2123–2134, 2015. © 2014 Society of Plastics Engineer     

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