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     

Nonisothermal crystallization behavior of a luminescent conjugated polymer,poly(9,9‐dihexylfluorene‐alt‐2,5‐didodecyloxybenzene)

The nonisothermal crystallization kinetics of poly(9,9‐dihexylfluorene‐alt‐2,5‐didodecyloxybenzene) (PF6OC12) from the melt were investigated using differential scanning calorimetry under different cooling rates. Several analysis methods were used to describe the nonisothermal crystallization behavior of PF6OC12. It was found that the modified Avrami method by Jeziorny was only valid for describing the early stage of crystallization but was not able to describe the later stage of PF6OC12 crystallization. Also, the Ozawa method failed to describe the nonisothermal crystallization behavior of PF6OC12. However, the method developed by combining the Avrami and Ozawa equations could successfully describe the nonisothermal crystallization kinetics of PF6OC12. According to the Kissinger method, the activation energy was determined to be 114.9 kJ mol^?1 for the nonisothermal melt crystallization of PF6OC12. Copyright © 2006 Society of Chemical Industry     

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     

Nonisothermal melt and cold crystallization kinetics of poly(aryl ether ether ketone ketone)

Analysis of the nonisothermal melt and cold crystallization kinetics of poly(aryl ether ether ketone ketone) (PEEKK) was performed by using differential scanning calorimetry (DSC). The Avrami equation modified by Jeziorny could describe only the primary stage of nonisothermal crystallization of PEEKK. And, the Ozawa analysis, when applied to this polymer system, failed to describe its nonisothermal crystallization behavior. A new and convenient approach for the nonisothermal crystallization was proposed by combining the Avrami equation with the Ozawa equation. By evaluating the kinetic parameters in this approach, the crystallization behavior of PEEKK was analyzed. According to the Kissinger method, the activation energies were determined to be 189 and 328 kJ/mol for nonisothermal melt and cold crystallization, respectively.     

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     

Preparation and nonisothermal crystallization behavior of polypropylene/layered double hydroxide nanocomposites

Polypropylene (PP)/layered double hydroxide (LDH) nanocomposites were prepared via melt intercalation using dodecyl sulfate anion modified LDH and maleated PP as compatibilizing agent. Evidently the interlayer anions in LDH galleries react with maleic anhydride groups of PP-g-MA and lead to a finer dispersion of individual LDH layers in the PP matrix. The nanostructure was characterized by XRD and TEM; the examinations confirmed the nanocomposite formation with exfoliated/intercalated layered double hydroxides well distributed in the PP matrix. The nonisothermal crystallization behavior of resulting nanocomposites was extensively studied using differential scanning calorimetry (DSC) technique at various cooling rates. In nonisothermal crystallization kinetics, the Ozawa approach failed to describe the crystallization behavior of nanocomposites, whereas the Avrami analysis and Jeziorny method well define the crystallization behavior of PP/LDH nanocomposite. Combined Avrami and Ozawa analysis (Liu model) also found useful. The results revealed that very small amounts of LDH (1%) could accelerate the crystallization process relative to the pure PP and increase in the crystallization rates was attributed to the nucleating effect of the nanoparticles. Polarized optical microscopy (POM) observations also support the DSC results. The effective crystallization activation energy was estimated as a function of the relative degree of crystallinity using the isoconversional analysis. Overall, results indicated that the LDH particles in nanometer size might act as nucleating agent and distinctly change the type of nucleation, growth and geometry of PP crystals.     

Nonisothermal melt and cold crystallization kinetics of poly(aryl ether ketone ether ketone ketone)

Nonisothermal melt and cold crystallization kinetics of poly(aryl ether ketone ether ketone ketone) (PEKEKK) were investigated by differential scanning calorimetry (DSC). The Avrami equation modified by Jeziorny could only describe the primary stage of nonisothermal crystallization kinetics of PEKEKK. Also, the Ozawa equation could not describe its nonisothermal crystallization behavior. A convenient and reasonable kinetic approach was used to describe the nonisothermal crystallization behavior. The crystallization activation energy were estimated to be −264 and 370 KJ/mol for nonisothermal melt and cold crystallization by the Kissinger method. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2865–2871, 2000     

Isothermal and nonisothermal crystallization kinetics of a semicrystalline copolyterephthalamide based on poly(decamethylene terephthalamide)

The isothermal and nonisothermal crystallization kinetics of a semicrystalline copolyterephthalamide based on poly(decamethylene terephthalamide) (PA‐10T) was studied by differential scanning calorimetry. Several kinetic analyses were used to describe the crystallization process. The commonly used Avrami equation and the one modified by Jeziorny were used, respectively, to describe the primary stage of isothermal and nonisothermal crystallization. The Avrami exponent n was evaluated to be in the range of 2.36–2.67 for isothermal crystallization, and of 3.05–5.34 for nonisothermal crystallization. The Ozawa analysis failed to describe the nonisothermal crystallization behavior, whereas the Mo–Liu equation, a combination equation of Avrami and Ozawa formulas, successfully described the nonisothermal crystallization kinetics. In addition, the value of crystallization rate coefficient under nonisothermal crystallization conditions was calculated. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 819–826, 2004     

Crystallization kinetics of poly(L‐lactide)/carbonated hydroxyapatite nanocomposite microspheres

Microspheres consisting of carbonated hydroxyapatite (CHAp) nanoparticles and poly(L ‐lactide) (PLLA) have been fabricated for use in the construction of osetoconductive bone tissue engineering scaffolds by selective laser sintering (SLS). In SLS, PLLA polymer melts and crystallizes. It is therefore necessary to study the crystallization kinetics of PLLA/CHAp nanocomposites. The effects of 10 wt% CHAp nanoparticles on the isothermal and nonisothermal crystallization behavior of PLLA matrix were studied, using neat PLLA for comparisons. The Avrami equation was successfully applied for the analysis of isothermal crystallization kinetics. Using the Lauritzen‐Hoffman theory, the transition temperature from crystallization Regime II to Regime III was found to be around 120°C for both neat PLLA and PLLA/CHAp nanocomposite. The combined Avrami‐Ozawa equation was used to analyze the nonisothermal crystallization process, and it was found that the Ozawa exponent was equal to the Avrami exponent for neat PLLA and PLLA/CHAp nanocomposite, respectively. The effective activation energy as a function of the relative crystallinity and temperature for neat PLLA and PLLA/CHAp nanocomposite under the nonisothermal crystallization condition was obtained by using the Friedman differential isoconversion method. The Lauritzen‐Hoffman parameters were also determined from the nonisothermal crystallization data by using the Vyazovkin‐Sbirrazzuoli equation. CHAp nanoparticles in the composite acted as an efficient nucleating agent, enhancing the nucleation rate but at the same time reducing the spherulite growth rate. This investigation has provided significant insights into the crystallization behavior of PLLA/CHAp nanocomposites, and the results obtained are very useful for making good quality PLLA/CHAp scaffolds through SLS. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Nonisothermal crystallization behavior and nucleation of LDPE/Al nano- and microcomposites

The nonisothermal crystallization and melting behavior of LDPE and LDPE/Al nano- and microcomposites prepared from melt compounding were studied using differential scanning calorimetry (DSC). The DSC results show that the Al nanoparticles can either facilitate or hinder the crystallization of LDPE, depending on the dispersion of the nanoparticles in LDPE. The well-dispersed Al nanoparticles do not have nucleating effects and mainly act as obstacles in the crystallization process, but the agglomerates of Al nanoparticles can act as nucleating agents and slightly accelerate the crystallization process of LDPE. The Al microparticles have nucleating effect and facilitate the crystallization process of LDPE. The combined Avrami–Ozawa equation was used to describe the nonisothermal crystallization process. It was found that the combined Avrami–Ozawa method can successfully describe the nonisothermal crystallization process. The melting behavior indicates that the lamellar thickness distribution of the nanocomposites and microcomposites is not significantly changed in comparison with the neat LDPE. POLYM. ENG. SCI., 47:1052–1061, 2007. © 2007 Society of Plastics Engineers     

Plasticized and unplasticized PLA/organoclay nanocomposites: Short‐ and long‐term thermal properties,morphology, and nonisothermal crystallization behavior

The short‐ and long‐term thermal properties, organoclay dispersion state, and the nonisothermal crystallization kinetics of organoclay based nanocomposites of poly(lactic acid) (PLA) and poly(ethylene glycol) (PEG) plasticized PLA were investigated. Differential scanning calorimetry analyses showed that plasticization of PLA/PEG blend was diminished due to physical aging by the time. The change in thermal properties such as glass transition temperature, cold crystallization temperature, and melting temperature was monitored. It was revealed from X‐ray diffraction analyses that in long term, the exfoliated and/or intercalated organoclay structure of nanocomposites observed in short term (just after processing) was differentiated to a tactoidal form (i.e., nonseparated clays). The nonisothermal crystallization behavior and kinetics were examined by using Avrami, Ozawa, and combined Avrami–Ozawa models. Moreover, the nucleating effect of clays was investigated in terms of Gutzow and Dobrewa approaches. It was found out that clays did not act as nucleating agents in plasticized PLA nanocomposites, which was also in good agreement with activation energy values obtained from Kissinger and Takhor models. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Isothermal and nonisothermal crystallization kinetics of fully bio‐based polyamides

We studied the crystallization behaviors of bio‐based BDIS polyamides synthesized from the following biomass monomers: 1,4‐butanediamine (BD), 1,10‐decanediamine (DD), itaconic acid (IA), and sebacic acid (SA). Isothermal crystallization, melting behavior, and nonisothermal crystallization of BDIS polyamides were investigated by differential scanning calorimetry (DSC). The Avrami equation was used to describe the isothermal crystallization of BDIS polyamides. The modified Avrami equation, the Ozawa equation, the modified Ozawa equation, and an equation combining the Avrami and Ozawa equations were used to describe the nonisothermal crystallization. The equilibrium melting point temperature of BDIS polyamide was determined to be 163.0°C. The Avrami exponent n was found to be in the range of 2.21–2.79 for isothermal crystallization and 4.10–5.52 for nonisothermal crystallization. POLYM. ENG. SCI., 56:829–836, 2016. © 2016 Society of Plastics Engineers     

Nonisothermal crystallization kinetics of poly(butylene terephthalate)/montmorillonite nanocomposites

The melt intercalation method was employed to prepare poly(butylene terephthalate) (PBT)/montmorillonite (MMT) nanocomposites, and the microstructures were characterized with X‐ray diffraction and transmission electron microscopy. Then, the nonisothermal crystallization behavior of the nanocomposites was studied with differential scanning calorimetry (DSC). The DSC results showed that the exothermic peaks for the nanocomposites distinctly shifted to lower temperatures at various cooling rates in comparison with that for pure PBT, and with increasing MMT content, the peak crystallization temperature of the PBT/MMT hybrids declined gradually. The nonisothermal crystallization kinetics were analyzed by the Avrami, Jeziorny, Ozawa, and Mo methods on the basis of the DSC data. The results revealed that very small amounts of clay (1 wt %) could accelerate the crystallization process, whereas higher clay loadings reduced the rate of crystallization. In addition, the activation energy for the transport of the macromolecular segments to the growing surface was determined by the Kissinger method. The results clearly indicated that the hybrids with small amounts of clay presented lower activation energy than PBT, whereas those with higher clay loadings showed higher activation energy. The MMT content and the crystallization conditions as well as the nature of the matrix itself affected the crystallization behavior of the hybrids. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3257–3265, 2006     

Cold‐crystallization kinetics of syndiotactic polystyrene

The kinetics of the isothermal and nonisothermal cold crystallization of syndiotactic polystyrene (s‐PS) were characterized with differential scanning calorimetry. A Johnson–Mehl–Avrami analysis of the isothermal experiments indicated that the cold crystallization of s‐PS at a constant temperature followed a diffusion‐controlled growth mode with a decreasing nucleation rate. Furthermore, the slow nucleation rate was the controlling step of the entire kinetic process. For nonisothermal cold‐crystallization kinetics, we used a simple model based on a combination of the well‐known Avrami and Ozawa models. The analysis revealed that, unlike for melt crystallization, the Avrami and Ozawa exponents were not equal. The activation energies for the isothermal and nonisothermal cold crystallizations of s‐PS were 792.0 and 148.62 kJ mol^?1, respectively, indicating that the smaller motion units in cold crystallization had a weaker temperature dependence than those in melt crystallization. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3464–3470, 2003     

Nonisothermal crystallization behavior of biodegradable poly(butylene terephthalate‐co‐butylene adipate‐co‐ethylene terephthalate‐co‐ethylene adipate) copolyester

A series of biodegradable aliphatic‐aromatic copolyester, poly(butylene terephthalate‐co‐butylene adipate‐co‐ethylene terephthalate‐co‐ethylene adipate) (PBATE), were synthesized from terephthalic acid (PTA), adipic acid (AA), 1,4‐butanediol (BG) and ethylene glycol (EG) by direct esterification and polycondensation. The nonisothermal crystallization behavior of PBATE copolyesters was studied by the means of differential scanning calorimeter, and the nonisothermal crystallization kinetics were analyzed via the Avrami equation modified by Jeziorny, Ozawa analysis and Z.S. Mo method, respectively. The results show that the crystallization peak temperature of PBATE copolyesters shifted to lower temperature at higher cooling rate. The modified Avrami equation could describe the primary stage of nonisothermal crystallization of PBATE copolyesters. The value of the crystallization half‐time (t_1/2) and the crystallization parameter (Z_c) indicates that the crystallization rate of PBATE copolyesters with more PTA content was higher than that with less PTA at a given cooling rate. Ozawa analysis was not suitable to study the nonisothermal crystallization process of PBATE copolyesters, but Z.S. Mo method was successful in treatingthis process. POLYM. ENG. SCI., 2011. © 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.     

Isothermal and nonisothermal crystallization kinetics of nylon 10 12

This article studied the crystallization behaviors of a newly industrialized polyamide, Nylon 10 12, under isothermal and nonisothermal conditions from the melt. A differential scanning calorimeter (DSC) was used to monitor the energetics of the crystallization process. During isothermal crystallization, relative crystallinity develops in accordance with the time dependence described by the Avrami equation with the exponent n=2.0. For nonisothermal studies, several different analysis methods were used to describe the crystallization process. The experimental results show that the Ozawa approach cannot adequately describe the nonisothermal crystallization kinetics. However, Avrami treatment for nonisothermal crystallization is able to describe the system very well. The calculated activation energy is 264.4 KJ/mol for isothermal crystallization by Arrhenius form and 235.5 KJ/mol for nonisothermal crystallization by Kissinger method.     

Effect of photofunctional organo anion-intercalated layered double hydroxide nanoparticles on poly(ethylene terephthalate) nonisothermal crystallization kinetics

Very recently, we report a facile preparation and strong UV-shielding function of poly(ethylene terephthalate) (PET) nanocomposites using 4,4′-diaminostilbene-2,2′-disulfonic acid anion-intercalated layered double hydroxide (LDH_DDA). Herein, the effect of the photofunctional organo anion-intercalated LDH nanoparticles on nonisothermal crystallization kinetics of PET is reported by differential scanning calorimetry technique. First, the nonisothermal crystallization behaviour is discussed by several basic parameters including crystallization peak temperature, relative degree of crystallinity with temperature or time, and half-time of crystallization. Then, Avrami and Jeziorny method, as well as Mo model were applied for the PET/LDH_DDA nanocomposites. Finally, the crystallization activation energy was investigated by Kissinger method and Flynn conversion. The results reveal that the incorporation of LDH_DDA nanoparticles acted as nucleating agent and significantly accelerated the PET nonisothermal crystallization process, whereas had little effect on the three-dimensional growth pattern of spherulites.     

Nonisothermal and isothermal crystallization kinetics of nylon‐12

The isothermal and nonisothermal crystallization behavior of Nylon 12 was investigated using differential scanning calorimetry (DSC). An Avrami analysis was used to study the isothermal crystallization kinetics of Nylon 12, the Avrami exponent (n) determined and its relevance to crystal growth discussed and an activation energy for the process evaluated using an Arrhenius type expression. The Lauritzen and Hoffman analysis was used to examine the spherulitic growth process of the primary crystallization stage of Nylon 12. The surface‐free energy and work of chain folding were calculated using a procedure reported by Hoffmann and the work of chain folding per molecular fold (σ) and chain stiffness of Nylon 12 (q) was calculated and compared to values reported for Nylons 6,6 and 11. The Jeziorny modification of the Avrami analysis, Cazé and Chuah average Avrami parameter methods and Ozawa equation were used in an attempt to model the nonisothermal crystallization kinetics of Nylon 12. A combined Avrami and Ozawa treatment, described by Liu, was used to more accurately model the nonisothermal crystallization kinetics of Nylon 12. The activation energy for nonisothermal crystallization processes was determined using the Kissinger method for Nylon 12 and compared with values reported previously for Nylon 6,6 and Nylon 11. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008