Crystallization behavior of poly(ε‐caprolactone)/layered double hydroxide nanocomposites

Poly(?‐caprolactone) (PCL)/layered double hydroxide (LDH) nanocomposites were prepared successfully via simple solution intercalation. The nonisothermal melt crystallization kinetics of neat PCL and its LDH nanocomposites was investigated with the Ozawa, Avrami, and combined Avrami–Ozawa methods. The Ozawa method failed to describe the crystallization kinetics of the studied systems. The Avrami method was found to be useful for describing the nonisothermal crystallization behavior, but the parameters in this method do not have explicit meaning for nonisothermal crystallization. The combined Avrami–Ozawa method explained the nonisothermal crystallization behavior of PCL and its LDH nanocomposites effectively. The kinetic results and polarized optical microscopy observations indicated that the addition of LDH could affect the mechanism of nucleation and growth of the PCL matrix. The Takhor model was used to analyze the activation energies of nonisothermal crystallization. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation and characterization of biodegradable poly(ϵ‐caprolactone) self‐reinforced composites and their crystallization behavior

Self‐reinforced poly(?‐caprolactone) (PCL) composites were prepared by dispersing a homologous nucleating agent within the PCL matrix through melt mixing. Coalesced PCL, featuring more orderly chain arrangements, acted as the nucleating agent leading to improvement of crystallization for the melt PCL matrix. Non‐isothermal melt crystallization behavior, isothermal melt crystallization kinetics, spherulitic morphology and the crystal structure of neat PCL and the PCL self‐reinforced composites were studied in detail. The results indicated that both non‐isothermal and isothermal melt crystallization of PCL composites were enhanced significantly by the homologous nucleating agent, while the crystallization mechanism and crystal structures remained unchanged. The results of tensile mechanical tests showed that the Young's modulus of the composites was improved by up to 77% with the incorporation of 20 wt% nucleating agent. Biocompatibility tests demonstrated that the cells could adhere to and proliferate well on the surface of the self‐reinforced PCL composites. © 2017 Society of Chemical Industry     

Nonisothermal crystallization behavior and mechanical properties of poly(butylene succinate)/silica nanocomposites

Silica nanoparticles and poly(butylene succinate) (PBS) nanocomposites were prepared by a melt‐blending process. The influence of silica nanoparticles on the nonisothermal crystallization behavior, crystal structure, and mechanical properties of the PBS/silica nanocomposites was investigated. The crystallization peak temperature of the PBS/silica nanocomposites was higher than that of neat PBS at various cooling rates. The half‐time of crystallization decreased with increasing silica loading; this indicated the nucleating role of silica nanoparticles. The nonisothermal crystallization data were analyzed by the Ozawa, Avrami, and Mo methods. The validity of kinetics models on the nonisothermal crystallization process of the PBS/silica nanocomposites is discussed. The approach developed by Mo successfully described the nonisothermal crystallization process of the PBS and its nanocomposites. A study of the nucleation activity revealed that the silica nanoparticles had a good nucleation effect on PBS. The crystallization activation energy calculated by Kissinger's method increased with increasing silica content. The modulus and yield strength were enhanced with the addition of silica nanoparticles into the PBS matrix. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Miscibility and crystallization behavior of biodegradable poly(ε‐caprolactone)/tannic acid blends

Miscibility, isothermal melt crystallization kinetics, spherulitic morphology and growth rates, and crystal structure of completely biodegradable poly(ε‐caprolactone) (PCL)/tannic acid (TA) blends were studied by differential scanning calorimetry, polarized optical microscopy, and wide angle X‐ray diffraction in detail in this work. PCL and TA are miscible as evidenced by the single composition dependent glass transition temperature over the whole compositions range and the depression of equilibrium melting point of PCL in the PCL/TA blends. Isothermal melt crystallization kinetics of neat PCL and an 80/20 PCL/TA blend was investigated and analyzed by the Avrami equation. The overall crystallization rates of PCL decrease with increasing crystallization temperature for both neat PCL and the PCL/TA blend; moreover, the overall crystallization rate of PCL is slower in the PCL/TA blend than in neat PCL at a given crystallization temperature. However, the crystallization mechanism of PCL does not change despite crystallization temperature and the addition of TA. The spherulitic growth rates of PCL also decrease with increasing crystallization temperature for both neat PCL and the PCL/TA blend; moreover, blending with TA reduces the spherulitic growth rate of PCL in the PCL/TA blend. It is also found that the crystal structure of PCL is not modified in the PCL/TA blend. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Crystallization behavior of poly(ϵ‐caprolactone)/Tio2 nanocomposites obtained by in situ polymerization

Poly(?‐caprolactone) (PCL)/titanium dioxide (TiO₂) nanocomposites were prepared by in situ polymerization of ?‐caprolactone in the presence of modified‐TiO₂ nanoparticles as initiators. The molecular weight of PCL matrix was dependent on the amount of the TiO₂ fillers. The incorporation of TiO₂ did not significantly affect the crystalline structure of PCL. Moreover, a tendency of the nanoparticles to form aggregates was observed, especially at higher fillers contents. The analysis of the crystallization process showed that the addition of TiO₂ nanoparticles accelerated the crystallization rate of PCL, and the crystallization rates increased by increasing the filler content. The crystallization activation energy dependence on the filler content observed here is probably the consequence of the two competing factors. The tendency of activation energy obtained by nonisothermal crystallization is similar to that of isothermal crystallization. POLYM. ENG. SCI., 2012. © 2011 Society of Plastics Engineers     

Crystallization behavior of polyamide 11/multiwalled carbon nanotube composites

Differential scanning calorimetry (DSC) was used to investigate the isothermal and nonisothermal crystallization kinetics of polyamide11 (PA11)/multiwalled carbon nanotube (MWNTs) composites. The Avrami equation was used for describing the isothermal crystallization behavior of neat PA11 and its nanocomposites. For nonisothermal studies, the Avrami model, the Ozawa model, and the method combining the Avrami and Ozawa theories were employed. It was found that the Avrami exponent n decreased with the addition of MWNTs during the isothermal crystallization, indicating that the MWNTs accelerated the crystallization process as nucleating agent. The kinetic analysis of nonisothermal crystallization process showed that the presence of carbon nanotubes hindered the mobility of polymer chain segments and dominated the nonisothermal crystallization process. The MWNTs played two competing roles on the crystallization of PA11 nanocomposites: on the one hand, the MWNTs serve as heterogeneous nucleating agent promoting the crystallization process of PA11; on the other hand, the MWNTs hinder the mobility of the polymer chains thus retarding the crystal growth process of PA11. The activation energies of PA11/MWNTs composites for the isothermal and nonisothermal crystallization are lower than neat PA11. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

Nonisothermal crystallization kinetics of high‐density polyethylene/barium sulfate nanocomposites

The high‐density polyethylene (HDPE)/barium sulfate (BaSO₄) nanocomposites had been successfully prepared by melt‐blending. Nonisothermal melt‐crystallization kinetics of neat HDPE and HDPE/BaSO₄ nanocomposites was investigated with differential scanning calorimetry under different cooling rates. The nonisothermal crystallization behavior was analyzed by Ozawa, Avrami, and combined Ozawa–Avrami methods. It was found that the Ozawa method failed to describe the nonisothermal crystallization behavior of neat HDPE and HDPE/BaSO₄ nanocomposites. The modified Avrami method by Jeziorny was only valid for describing the middle stage of crystallization but was not able to describe the later stage of neat HDPE and HDPE/BaSO₄ nanocomposites crystallization. The value of Avrami exponent n for neat HDPE ranged from 3.3 to 5.7 and for HDPE/BaSO₄ nanocomposites ranged from 1.8 to 2.5. It is postulated that the values of n close to 3 are caused by spherulitic crystal growth with heterogeneous nucleation, whereas simultaneous occurrence of spherulitic and lamellar crystal growth with heterogeneous nucleation account for lower values of n. The combined Ozawa–Avrami method by Mo and coworkers (Polym. Eng. Sci., 37(3) , 568 (1997)) was able to satisfactorily describe the crystallization behavior of neat HDPE and HDPE/BaSO₄ nanocomposites. In addition, the activation energy of nonisothermal crystallization was determined using the Kissinger (J. Res. Natl. Bur. Stand., 57(4) , 217 (1956)) method, showing that the crystallization activation energy of HDPE/BaSO₄ nanocomposites was lower than that of neat HDPE. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Rheology,mechanical properties,and biodegradation of poly(ε‐caprolactone)/silica nanocomposites

Biodegradable poly(ε‐caprolactone) (PCL)/silica nanocomposites containing 1–9 wt% silica nanoparticles were prepared by melt compounding in this work. The rheology, mechanical properties, and biodegradation were investigated. PCL/silica nanocomposite shows a high percolation threshold, which is between 7 and 9 wt%. Once percolation network structure forms, the long‐range motion of PCL chains is highly restrained. From the results of mechanical tests, the tensile strength, modulus, and yield strength of the nanocomposites are enhanced by the incorporation of silica nanoparticles. Moreover, it is interesting to find that the biodegradation rates have been enhanced obviously in the PCL/silica nanocomposites than in neat PCL, which may be of great use for the practical application of PCL. POLYM. COMPOS., 34:1620–1628, 2013. © 2013 Society of Plastics Engineers     

Epoxy/poly(ɛ‐caprolactone) nanocomposites: Effect of transformations of structure on crystallization

The influence of morphology of the epoxy/poly(?‐caprolactone) (PCL) system and corresponding nanocomposites with organophilized layered silicate on PCL crystallization was studied by differential scanning calorimetry, scanning, and transmission electron microscopy. The results obtained indicate a significant affecting of nonisothermal PCL crystallization by phase morphology brought about by the reaction‐induced phase separation (RIPS) influenced either by various nanoclay contents or the epoxy/PCL ratio. Dispersed morphology of PCL matrix with epoxy globules induces crystallization at higher temperatures. The inverse dispersed morphology of epoxy matrix with PCL inclusions causes crystallization at lower temperature. The co‐continuous morphology induces crystallization in both steps. Rate of the second crystallization step is substantially higher than that in the first step. No nucleation effect has been found in the nanocomposites with the added nanofiller. Multicomponent samples show retarded crystallization, i.e., lower crystallinities and lower overall crystallization rate compared with neat PCL. The results obtained suggest that it is primarily morphological/interfacial effects that play a decisive role in the crystallization behavior of PCL in the epoxy/PCL/clay system. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3197–3204, 2013     

Nonisothermal crystallization kinetics and thermomechanical properties of multiwalled carbon nanotube‐reinforced poly(ε‐caprolactone) composites

BACKGROUND: The technological development of poly(ε‐caprolactone) (PCL) is limited by its short useful lifespan, low modulus and high crystallinity. There are a few papers dealing with the crystallization behavior of carbon nanotube‐reinforced PCL composites. However, little work has been done on the crystallization kinetics of melt‐compounded PCL/multiwalled carbon nanotube (MWNT) nanocomposites. In this study, PCL/MWNT nanocomposites were successfully prepared by a simple melt‐compounding method, and their morphology and mechanical properties as well as their crystallization kinetics were studied. RESULTS: The MWNTs were observed to be homogeneously dispersed throughout the PCL matrix. The incorporation of a very small quantity of MWNTs significantly improved the storage modulus and loss modulus of the PCL/MWNT nanocomposites. The nonisothermal crystallization behavior of the PCL/MWNT nanocomposites exhibits strong dependencies of the degree of crystallinity (X_c), peak crystallization temperature (T_p), half‐time of crystallization (t_1/2) and Avrami exponent (n) on the MWNT content and cooling rate. The MWNTs in the PCL/MWNT nanocomposites exhibit a higher nucleation activity. The crystallization activation energy (E_a) calculated with the Kissinger model is higher when a small amount of MWNTs is added, then gradually decreases; all the E_a values are higher than that of pure PCL. CONCLUSION: This paper reports for the first time the preparation of high‐performance biopolymer PCL/MWNT nanocomposites prepared by a simple melt‐compounding method. The results show that the PCL/MWNT nanocomposites can broaden the applications of PCL. Copyright © 2008 Society of Chemical Industry     

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     

Crystallization behavior of biodegradable poly(L‐lactide)/multiwalled carbon nanotubes nanocomposites from the amorphous state

Crystallization behavior of biodegradable poly(L ‐lactide) (PLLA) and its nanocomposites at different carboxyl‐functionalized multiwalled carbon nanotubes (f‐MWNTs) contents from the amorphous state was studied in detail in this work. For the isothermal cold crystallization, the presence of f‐MWNTs enhances the isothermal cold crystallization of PLLA in the nanocomposites compared with that of neat PLLA at the same crystallization temperature; moreover, the overall cold crystallization rate of PLLA increases with increasing the f‐MWNTs content in the PLLA matrix while the crystallization mechanism does not change. For the nonisothermal crystallization, the f‐MWNTs also accelerate the crystallization process of PLLA. In addition, the activation energies of nonisothermal cold crystallization process were calculated using both the Kissinger and Friedman methods. The cold crystallization activation energies of PLLA are higher in the nanocomposites than in neat PLLA, indicating that the addition of f‐MWNTs into the PLLA matrix acts as a physical hindrance to retard crystallization. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Biodegradable poly(butylene succinate‐co‐butylene adipate)/multiwalled carbon nanotube nanocomposites: Preparation,morphology, and crystallization behavior

Biodegradable poly(butylene succinate‐co‐butylene adipate) (PBSA)/multiwalled carbon nanotubes (MWCNTs) nanocomposites were prepared via a simple melt‐compounding method at low MWCNTs contents. Scanning and transmission electron microscopy observations revealed a relatively nice dispersion of MWCNTs throughout the PBSA matrix. Both the nonisothermal and isothermal melt crystallizations of PBSA were enhanced significantly in the nanocomposites relative to neat PBSA because of the presence of MWCNTs; however, the crystal structure of PBSA remained unchanged. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Nonisothermal crystallization behavior of melt‐intercalated polyethylene‐clay nanocomposites

The influence of nanoclay particles on the nonisothermal crystallization behavior of intercalated polyethylene (PE) prepared by melt‐compounding was investigated. It is observed that the crystallization peak temperature (T_p) of PE/clay nanocomposites is slightly but consistently higher than the neat PE at various cooling rates. The half‐time (t_0.5) for crystallization decreased with increase in clay content, implying the nucleating role of nanoclay particles. The nonisothermal crystallization data are analyzed using the approach of Avrami (Polymer 1971, 12, 150), Ozawa (Polym Eng Sci 1997, 37, 443), and Mo and coworkers (J Res Natl Bur Stand 1956, 57, 217), and the validity of the different kinetic models to the nonisothermal crystallization process of PE/clay nanocomposites is discussed. The approach developed by Mo and coworkers successfully explains the nonisothermal crystallization behavior of PE and PE/clay nanocomposites. The activation energy for nonisothermal crystallization of neat PE and PE/clay nanocomposites is determined using the Kissinger (J Res Natl Bur Stand 1956, 57, 217) method. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3809–3818, 2006     

聚酰胺11/白炭黑纳米复合材料的非等温结晶动力学研究

采用原位聚合法制备了聚酰胺11（PA11）及PA11/白炭黑纳米复合材料,利用差示扫描量热仪研究了PA11及其纳米复合材料的非等温结晶过程,用经Jeziorny修正的Avrami方程、Mo法对其非等温结晶动力学进行了研究,计算并得到了非等温结晶动力学参数。结果表明,Avrami方程和Mo法都适用于处理PA11及其纳米复合材料的非等温结晶过程;在其非等温结晶过程中,PA11及其纳米复合材料都包括初期结晶和二次结晶两个阶段;Mo法表明,复合材料的结晶速率比PA11的小。此外,用Huffman-Lauritzen理论计算了PA11及其纳米复合材料非等温结晶的结晶活化能,结果表明,纳米复合材料的结晶活化能的绝对值小于PA11。     

Multiwalled carbon nanotube nucleated crystallization behavior of biodegradable poly(butylene succinate) nanocomposites

Poly(butylene succinate) (PBS) nanocomposites with multiwalled carbon nanotubes (MWNTs) prepared by melt compounding were studied for the effect of MWNT dispersion on the modulus and crystallization kinetics. The nucleating effect of the addition of 0.1 wt % MWNT to PBS was clearly demonstrated. Differential scanning calorimetry nonisothermal crystallization studies showed a clear decrease in the half‐time of crystallization with increasing MWNT content in PBS/MWNT nanocomposites. It was observed with the Ozawa method that the Ozawa parameter values for the nanocomposites were lower than those for neat PBS, and this indicated that the crystal morphology was different. The storage modulus of the nanocomposites increased about 23% with the addition of only 0.1% MWNT in comparison with neat PBS, whereas the glass‐transition temperature was unaltered. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Nonisothermal crystallization behavior of poly(ϵ‐caprolactone)/attapulgite nanocomposites by DSC analysis

Nanocomposites based on biodegradable poly(ε‐caprolactone) (PCL) and attapulgite (AT) were prepared by solution mixing. The nonisothermal crystallization of the pure PCL and PCL/AT nanocomposites at different AT contents and different cooling rates were investigated by differential scanning calorimetry (DSC). There are significant dependence of nonisothermal crystallization behavior and kinetics of PCL/AT nanocomposites on the AT content and cooling rate. The Jeziorny method has been employed to analyze the DSC data. The results show that Jeziorny method could describe this system well. It can be concluded that AT can be used as an effective nucleating agent and has effects on the growth of crystallites in the crystallization process of PCL matrix. POLYM. ENG. SCI., 47:460–466, 2007. © 2007 Society of Plastics Engineers.     

Heterogeneous bubble nucleation in PCL/clay nanocomposite foams

Abstract

Nanocomposites based on biodegradable polycaprolactone (PCL) and organically modified layered silicates (organoclay) have been prepared by melt mixing. The isothermal crystallisation of polycaprolactone/clay nanocomposites showed that the well-dispersed organoclay platelets acted as nucleating agents in the PCL matrix, as confirmed by a remarkable reduction of the crystallisation half-time t_1/2. The nanocomposites showed much higher complex viscosity than that of the neat PCL and pseudosolid-like behaviour in the low frequency range. The foaming process of PCL/clay nanocomposites containing 2%wt and 5%wt of clay were investigated by using a batch process. The results showed that the presence of clay resulted in an increase in cell density and a reduction of cell size compared to pure PCL and higher densities due to the higher viscosity of the melt.     

Understanding the effect of silica nanoparticles and exfoliated graphite nanoplatelets on the crystallization behavior of isotactic polypropylene

This study explores how the presence of nanofillers with different structural and chemical characteristics, specifically silica nanoparticles and exfoliated graphite nanoplatelets (GNP), alters the crystallization behavior and polymorphism of a semicrystalline polymer, such as polypropylene (PP). The main focus of this research is to investigate how silica and GNP affect the nucleation and growth of PP crystals during isothermal crystallization. The nonisothermal crystallization behavior, including crystal structures, crystallization temperature, and rate, is also determined. PP composites with nanomaterial content up to 7 wt% were produced by melt mixing and injection molding. Both silica and graphite were found to be effective nucleating agents, significantly increasing the crystallization rate during isothermal crystallization, with greater changes observed in case of GNP composites. The effect of filler type and amount on the PP polymorphism and lamella thickness was studied by X‐ray diffraction and modulated differential scanning calorimetry. Both silica and graphite were found to be effective nucleating agents for the less common β‐phase of PP crystals even at low nanomaterial concentration. α‐?crystal perfection and the recrystallization of the β‐form in the α‐form and/or at the transcrystalline regime were found to be responsible for the recrystallization occurring upon melting in nanocomposites at high silica or medium GNP content. POLYM. ENG. SCI., 55:672–680, 2015. © 2014 Society of Plastics Engineers     

Crystallization,morphology, and mechanical properties of poly(butylene succinate)/poly(ethylene oxide)‐polyhedral oligomeric silsesquioxane nanocomposites

The biodegradable poly(butylene succinate) (PBS)/poly(ethylene oxide)‐polyhedral oligomeric silsesquioxane (PEO‐POSS) nanocomposites were prepared by the solution blending and melt‐injection methods. The effect of PEO‐POSS on the non‐isothermal and isothermal crystallization, morphology, as well as mechanical properties of PBS was carefully investigated. The PEO‐POSS nanoparticles dispersed well in the PBS matrix, with the diameters around 30 nm. From isothermal crystallization analysis, the incorporation of PEO‐POSS enhanced the crystallization of PBS due to the heterogeneous nucleation effect while the crystal structure of PBS remained. PBS/PEO‐POSS nanocomposites showed of higher glass transition temperatures than that of neat PBS, attributing to the existence of PEO‐POSS decreasing the flexibility of PBS chains. The elongation at break of the PBS/PEO‐POSS nanocomposites reached the maximum value with PEO‐POSS content of 5 wt%. However, the elastic modulus of PBS decreased after the incorporation of PEO‐POSS. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers