Crystallization behavior of biodegradable poly(L‐lactic acid) filled with a powerful nucleating agent: N,N′‐bis(benzoyl) suberic acid dihydrazide

N,N′‐Bis(benzoyl) suberic acid dihydrazide (NA) as nucleating agent for poly(L ‐lactic acid) (PLLA) was synthesized from benzoyl hydrazine and suberoyl chloride, which was deprived from suberic acid via acylation. PLLA/NA samples were prepared by melt blending and a hot‐press forming process. The nonisothermal and isothermal crystallization, spherulite morphology, and melting behavior of PLLA/NA with different contents of NA were investigated with differential scanning calorimetry, depolarized‐light intensity measurement, scanning electron microscopy, polarized optical microscopy, and wide‐angle X‐ray diffraction. With the incorporation of NA, the crystallization peak became sharper and shifted to a higher temperature as the degree of supercooling decreased at a cooling rate of 1°C/min from the melt. Nonisothermal crystallization indicated that the presence of NA accelerated the overall PLLA crystallization. In isothermal crystallization from the melt, the presence of NA affected the isothermal crystalline behaviors of PLLA remarkably. The addition of NA led to a shorter crystallization time and a faster overall crystallization rate; this meant that there was a heterogeneous nucleation effect of NA on the crystallization of PLLA. With the addition of 0.8% NA, the crystallization half‐time of PLLA/NA decreased from 26.5 to 1.4 min at 115°C. The Avrami theory was used to describe the kinetics of isothermal crystallization of the PLLA/NA samples. Also, with the presence of NA, the spherulite number of PLLA increased, and the spherulite size decreased significantly. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Crystallization behavior and crystallite morphology control of poly(L‐lactic acid) through N,N′‐bis(benzoyl)sebacic acid dihydrazide

Adding a nucleating agent is one of the best ways to accelerate the crystallization rate of poly(L ‐lactic acid) (PLLA) so as to obtain a high degree of crystallinity during the process, which will improve the heat distortion temperature of final products. In the work reported, N, N′‐bis(benzoyl)sebacic acid dihydrazide (BSAD) was synthesized and used as a nucleating agent for PLLA. Isothermal and non‐isothermal crystallization behaviors were investigated using differential scanning calorimetry (DSC). The addition of BSAD successfully enhances the crystallization rate of PLLA. A unique phase separation behavior of PLLA/BSAD blends is found from DSC as well as from polarized optical microscopy, which explains the difference of optimal BSAD concentration between isothermal and non‐isothermal crystallization. This is the first recording of a phase separation peak in PLLA/nucleating agent blends using DSC. In thermogravimetric analysis, the enhanced thermal stability indicates that there are strong hydrogen bonds between BSAD and PLLA matrix. BSAD can dissolve in PLLA melt below its melting point through intermolecular hydrogen bonding with PLLA and self‐assemble upon cooling, leading to the surface being capable of nucleating PLLA. Different phase separation temperatures can be used to control the morphology of BSAD, which finally determines the crystallite morphology of PLLA. © 2012 Society of Chemical Industry     

Synergistic effects of N,N′‐bis (benzoyl) sebacic acid dihydrazide and talc on the physical and mechanical behaviors of poly(l‐latic acid)

The important practical problem of poor heat stability of poly(l ‐lactic acid) (PLLA) is addressed by the addition of N, N′‐bis (benzoyl) sebacic acid dihydrazide (BSAD) and talc as a nucleating agent system. The idea of incorporating talc into the PLLA/BSAD composites is that talc can provide supplementary nucleation effect with very small amount of BSAD (0.2 wt %) and therefore can improve the heat deflection resistance of PLLA materials. Effects of BSAD/talc on morphology, crystallization behavior, heat resistance, and mechanical properties of PLLA/BSAD/talc were investigated after annealing processes. The results indicated that the BSAD/talc system increased the crystallinity from 6.0% of pure PLLA to a maximum 42.9% by the synergistic effects of BSAD and talc increasing the growth of spherulites and nucleation density, respectively. After annealing at different temperatures, the heat deflection temperature (HDT) of PLLA was improved dramatically due to synergistic effects of BSAD/talc between restricted chain movement and acceleration of crystallization. At high temperature (above T_g), the thermo‐mechanical properties of PLLA is mainly determined by the crystallinity and the reinforcement effect of talc acted as a filler. Moreover, effects of BSAD/talc on mechanical properties were discussed. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41454.     

Enhanced nonisothermal and isothermal cold crystallization kinetics of biodegradable poly(l‐lactide) by trisilanolisobutyl‐polyhedral oligomeric silsesquioxanes in their nanocomposites

In this work, the nonisothermal and isothermal cold crystallization behaviors of poly(l ‐lactide) (PLLA)/trisilanolisobutyl‐polyhedral oligomeric silsesquioxanes (tsib‐POSS) nanocomposites with low tsib‐POSS contents were fully investigated. For all the samples, the variations of heating rate and the tsib‐POSS loading may influence the nonisothermal cold crystallization of PLLA. During the nonisothermal crystallization kinetics study, the Ozawa equation failed to fit the nonisothermal crystallization process of PLLA, while the Tobin equation could fit it well. For the isothermal crystallization kinetics study, the crystallization rates of all the samples increased with increasing crystallization temperature. The cold crystallization activation energy of PLLA was increased with 1 wt % tsib‐POSS. Moreover, the addition of tsib‐POSS and the increment of tsib‐POSS loading could increase the crystallization rate of PLLA, indicating the nucleating agent effect of tsib‐POSS. However, the crystallization mechanism and crystal structure of PLLA remained unchanged in the nanocomposites. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43896.     

Crystallization and melting behavior of partially miscible six‐armed poly(l‐lactic acid)/poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) blends

The crystallization kinetics and spherulitic morphology of six‐armed poly(L‐lactic acid) (6a‐PLLA)/poly(3‐hydroxybutyrate‐co?3‐hydroxyvalerate) (PHBV) crystalline/crystalline partially miscible blends were investigated with differential scanning calorimetry and polarized optical microscopy in this study. Avrami analysis was used to describe the isothermal crystallization process of the neat polymers and their blends. The results suggest that blending had a complex influence on the crystallization rate of the two components during the isothermal crystallization process. Also, the crystallization mechanism of these blends was different from that of the neat polymers. The melting behavior of these blends was also studied after crystallization at various crystallization temperatures. The crystallization of PHBV at 125°C was difficult, so no melting peaks were found. However, it was interesting to find a weak melting peak, which arose from the PHBV component for the 20/80 6a‐PLLA/PHBV blend after crystallization at 125°C, and it is discussed in detail. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42548.     

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     

Crystallization kinetics of poly (L‐lactic acid)/montmorillonite nanocomposites under isothermal crystallization condition

Poly(L ‐lactic acid)/o‐MMT nanocomposites, incorporating various amounts of organically modified montmorillonite (o‐MMT; 0–10 wt %), were prepared by solution intercalation. The montmorillonite (MMT) was organically modified with dilauryl dimethyl ammonium bromide (DDAB) by ion exchange. Transmission electron microscopy (TEM) and X‐ray diffraction (XRD) reveal that the o‐MMT was exfoliated in a poly(L ‐lactic acid), (PLLA) matrix. A series of the test specimens were prepared and subjected to isothermal crystallization at various temperatures (T₁–T₅). The DSC plots revealed that the PLLA/o‐MMT nanocomposites that were prepared under nonisothermal conditions exhibited an obvious crystallization peak and recrystallization, but neat PLLA exhibited neither. The PLLA/o‐MMT nanocomposites (2–10 wt %) yielded two endothermic peaks only under isothermal conditions at low temperature (T₁), and the intensity of Tm₂ (the higher melting point) was proportional to the o‐MMT content (at around 171°C). The melting point of the test samples increased with the isothermal crystallization temperature. In the Avrami equation, the constant of the crystallization rate (k) was inversely proportional to the isothermal crystallization temperature and increased with the o‐MMT content, especially at low temperature (T₁). The Avrami exponent (n) of the PLLA/o‐MMT nanocomposites (4–10 wt %) was 2.61–3.56 higher than that of neat PLLA, 2.10–2.56, revealing that crystallization occurred in three dimensions. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Thermal,crystalline, and mechanical properties of octa(3‐chloropropylsilsesquioxane)/ poly(L‐lactic acid) hybrid films

A series of organic‐inorganic hybrid films were prepared based on octa(3‐chloropropylsilsesquioxane) (OCPS) and poly(L‐lactic acid) (PLLA) via simply solution blending method. The thermal, crystalline and mechanical properties of OCPS/PLLA hybrid films were characterized by Fourier transform infrared, scanning electron microscopy, energy dispersive spectrometer, differential scanning calorimetry (DSC), X‐ray diffraction, polarized optical microscopy, thermogravimetric analysis (TGA), and tensile tests. The results showed that OCPS could be dispersed well at molecular level when its content was less than 3 wt % and began to crystallize in PLLA matrix when the content increased to 5 wt %. DSC study revealed that OCPS acted as a plasticizer to decrease both T_g and T_m of the PLLA matrix at various heating rates. The addition of OCPS did not change the crystal form of PLLA, while had an great influence on the cold crystallization and melting behaviors of PLLA in the second heating cycles. Moreover, the initial crystallinity of OCPS/PLLA was higher than that of pure PLLA. The results suggested that OCPS could be an effective heterogeneous nucleating reagent to promote the crystallization of PLLA. TGA showed that the PLLA thermal degradation mechanism remained unchanged, whereas the weight loss temperatures and residual weights were improved. Tensile tests indicated that the incorporation of OCPS into PLLA matrix changed the tensile behavior of the hybrid films from brittle to ductile, and the strain at break was improved remarkably as a result of the plasticizer effect of OCPS. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Influence of clay content on the melting behavior and crystal structure of nonisothermal crystallized poly(L‐lactic acid)/nanocomposites

To study the effect of organophilic clay concentration on nonisothermal crystallization, poly(L ‐lactic acid) (PLLA)/montmorillonite (MMT) nanocomposites were prepared by mixing various amounts of commercial MMT (Cloisite^® 30B) and PLLA. The effect of MMT content on melting behavior and crystal structure of nonisothermal crystallized PLLA/MMT nanocomposites was investigated by differential scanning calorimetry (DSC), small‐angle X‐ray scattering, and wide‐angle X‐ray diffraction (XRD) analyses. The study was focused on the effect of the filler concentration on thermal and structural properties of the nonisothermally crystallized nanocomposite PLLA/MMT. The results obtained have shown that at filler loadings higher than 3 wt %, intercalation of the clay is observed. At lower clay concentrations (1–3 wt %), exfoliation predominates. DSC and XRD analysis data show that the crystallinity of PLLA/MMT composites increases drastically at high clay loadings (5–9 wt %). In these nanocomposites, PLLA crystallizes nonisothermally in an orthorhombic crystal structure, assigned to the α form of PLLA. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect of nucleating agents on the crystallization of poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate)

The effect of nucleating agents on the crystallization behavior of poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV) was studied. A differential scanning calorimeter was used to monitor the energy of the crystallization process from the melt and melting behavior. During the crystallization process from the melt, nucleating agent led to an increase in crystallization temperature (T_c) of PHBV compared with that for plain PHBV (without nucleating agent). The melting temperature of PHBV changed little with addition of nucleating agent. However, the areas of two melting peaks changed considerably with added nucleating agent. During isothermal crystallization, dependence of the relative degree of crystallization on time was described by the Avrami equation. The addition of nucleating agent caused an increase in the overall crystallization rate of PHBV, but did not influence the mechanism of nucleation and growth of the PHB crystals. The equilibrium melting temperature of PHBV was determined as 187°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. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2145–2152, 2002     

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     

Rapid crystallization of poly(l-lactic acid) induced by a nanoscaled zinc citrate complex as nucleating agent

A nanoscaled zinc citrate complex (ZnCC) was synthesized by the reaction of zinc acetate and citric acid using solution method. As a new eco-friendly nucleating agent, ZnCC was introduced into poly(l-lactic acid) (PLLA) via melt blending. The nonisothermal and isothermal crystallization, melting behavior, crystalline morphology and mechanical properties of the PLLA/ZnCC blends were investigated. It is found that ZnCC exhibits much more prominent nucleation activity on the crystallization of PLLA than conventional nucleating agent talc and commercial zinc citrate (ZnCit). By loading 0.05 wt% ZnCC, PLLA can complete crystallization upon cooling at 10 °C/min, and the crystallization peak shifts to a higher temperature with increasing ZnCC content. In the case of isothermal crystallization from the melt, the addition of ZnCC leads to a shorter crystallization time and a faster overall crystallization rate. Besides, the nucleation density of PLLA increases and the spherulite size decreases significantly in the presence of ZnCC. Epitaxy is the possible mechanism to elucidate the nucleation phenomenon of PLLA/ZnCC system. The tensile results show that ZnCC has a plasticization effect on the amorphous PLLA. Through a short-time annealing procedure, the mechanical properties such as tensile modulus and storage modulus of PLLA are improved by the addition of ZnCC.     

Crystallization kinetics of bacterial poly(3‐hydroxylbutyrate) copolyesters with cyanuric acid as a nucleating agent

Effects of cyanuric acid (CA) on nonisothermal and isothermal crystallization, melting behavior, and spherulitic morphology of bacterial copolyesters of poly(3‐hydroxybutyrate), i.e., poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV) and poly(3‐hydroxybutyrate‐co‐3‐hydroxyhexanoate) (PHBH), have been investigated. CA has excellent acceleration effectiveness on the melt crystallization of bacterial PHB, PHBV, and PHBH, better than the nucleating agents reported in the literatures, such as boron nitride, uracil, and orotic acid. PHBV and PHBH do not crystallize upon cooling from the melt at 10°C/min, while they are able to complete crystallization under the same conditions with an addition of 1% CA, with a presence of sharp crystallization exotherm at 75–95°C. Isothermal crystallization kinetics of neat and CA‐containing PHBV and PHBH were analyzed by Avrami model. Crystallization half‐times (t_1/2) of PHBV and PHBH decrease dramatically with an addition of CA. The melting behavior of isothermally melt‐crystallized PHBV and PHBH is almost not influenced by CA. Spherulitic numbers of PHBV and PHBH increase and the spherulite sizes reduce with an incorporation of CA. Nucleation densities of PHBV and PHBH increase by 3–4 orders of magnitude with a presence of 1% CA. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Effect of nucleating agents on the crystallization behavior and heat resistance of poly(l‐lactide)

Poly (l ‐lactide) (PLLA) blends with various nucleators were prepared by melt processing. The effect of different nucleators on the crystallization behavior and heat resistance as well as thermomechanical properties of PLLA was studied systematically by differential scanning calorimetry, X‐ray diffraction, heat deflection temperature tester, and dynamic mechanical analysis. It was found that poly(d ‐lactide), talcum powder (Talc), a multiamide compound (TMC‐328, abbreviated as TMC) can significantly improve the crystallization rate and crystallinity of PLLA, thus improving thermal–resistant property. The heat deflection temperature of nucleated PLLA can be as high as 150°C. The storage modulus of nucleated PLLA is higher than that of PLLA at the temperature above T_g of PLLA. Compared with other nucleating agents, TMC was much more efficient at enhancing the crystallization of PLLA and the PLLA containing TMC showed the best heat resistance. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42999.     

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     

Thermophysical properties of bacterial poly(3‐hydroxybutyrate): Characterized by TMA,DSC, and TMDSC

The melting, isothermal and nonisothermal crystallization behaviors of poly(3‐hydroxybutyrate) (PHB) have been studied by means of temperature modulated differential scanning calorimetry (TMDSC) and conventional DSC. Various experimental conditions including isothermal/annealing temperatures (80, 90, 100, 105, 110, 120, 130, and 140°C), cooling rates (2, 5, 10, 20, and 50°C/min) and heating rates (5, 10, 20, 30, 40, and 50°C/min) have been investigated. The lower endothermic peak (T_m1) representing the original crystals prior to DSC scan, while the higher one (T_m2) is attributed to the melting of the crystals formed by recrystallization. Thermomechanical analysis (TMA) was used to evaluate the original melting temperature (T_melt) and glass transition temperature (T_g) as comparison to DSC analysis. The multiple melting phenomenon was ascribed to the melting‐recrystallization‐remelting mechanism of the crystallites with lower thermal stability showing at T_m1. Different models (Avrami, Jeziorny‐modified‐Avrami, Liu and Mo, and Ozawa model) were utilized to describe the crystallization kinetics. It was found that Liu and Mo's analysis and Jeziorny‐modified‐Avrami model were successful to explain the nonisothermal crystallization kinetic of PHB. The activation energies were estimated in both isothermal and nonisothermal crystallization process, which were 102 and 116 kJ/mol in respective condition. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42412.     

Crystallization behavior and nucleation analysis of poly(l‐lactic acid) with a multiamide nucleating agent

To accelerate the crystallization of poly(L ‐lactic acid) (PLLA) and enhance its crystallization ability, a multiamide nucleator (TMC) was introduced into the PLLA matrix. The thermal characteristics, isothermal and nonisothermal crystallization behavior of pure PLLA and TMC‐nucleated PLLA were investigated by differential scanning calorimetry. The determination of thermal characteristics shows that the addition of TMC can significantly decrease the onset temperature of cold crystallization and meanwhile elevate the total crystallinity of PLLA. For the isothermal crystallization process, it is found that the overall crystallization rate is much faster in TMC‐nucleated PLLA than in pure PLLA and increases as the TMC content is increased, however, the crystal growth form and crystalline structure are not influenced much despite the presence of TMC. In the case of nonisothermal crystallization, the nucleation efficiency and nucleation activity were estimated and the results indicate that excellent nucleation‐promoting effect could be achieved when the weight percentage of TMC is chosen between 0.25% and 0.5%. Polarized optical microscopy observation reveals that the nuclei number of PLLA increases and the spherulite size reduces greatly with the addition of TMC. POLYM. ENG. SCI., 2012. © 2011 Society of Plastics Engineers     

Thermal and crystallization characteristics of poly(ethylene terephthalate) with poly(oxybenzoate‐p‐trimethylene terephthalate) copolymer

Poly(ethylene terephthalate) (PET) was blended with two different poly(oxybenzoate‐p‐trimethylene terephthalate) copolymers, designated T28 and T64, with the level of copolymer varying from 1 to 15 wt %. All samples were prepared by solution blending in a 60/40 (by weight) phenol/tetrachloroethane solvent at 50°C. The crystallization behavior of the samples was studied by DSC. The results indicate that both T28 and T64 accelerated the crystallization rate of PET in a manner similar to that of a nucleating agent. The acceleration of PET crystallization rate was most pronounced in the PET/T64 blends with a maximum level at 5 wt % of T64. The melting temperatures for the blends are comparable to that of pure PET. The observed changes in crystallization behavior are explained by the effect of the physical state of the copolyester during PET crystallization as well as the amount of copolymer in the blends. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1599–1606, 2002     

Crystallization behavior of poly(L‐lactic acid)‐based ecocomposites prepared with kenaf fiber and rice straw

Several composites of poly(L ‐lactic acid) (PLLA) with natural fibers (kenaf and rice straw) and pigments have been prepared and analyzed. The study of the thermal behavior has shown a rather important nucleation ability of these fillers for the crystallization of the PLLA component in the composites. Thus, the cooling from the melt of pure PLLA at 10°C/min leads to an almost completely amorphous sample, while a high crystallinity (around 60%) is exhibited by the sample PLLA and rice straw (PLLA‐RS)‐yellow under those conditions. The analysis of the isothermal crystallization from the melt indicates that a maximum rate of crystallization is obtained for all the samples at around 105°C, although the rate is three times faster for samples PLLA and kenaf fiber (PLLA‐KF), PLLA‐KF‐red, and PLLA‐RS, in comparison with pure PLLA. The rate is increased by another factor of three for sample PLLA‐RS‐yellow. The analysis of the melting temperatures and crystallinities as a function of the crystallization temperature shows that there is a break at around 115°C, which seems to be related to the formation of ordered crystals at higher temperatures and disordered ones at lower temperatures. Besides, the natural fibers are environmentally friendly and nonexpensive materials, and the higher crystallization rates of the composites will result in shorter production cycles of end‐use articles. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

Crystallization behavior and morphology of polylactic acid (PLA) with aromatic sulfonate derivative

This article provides a detailed investigation of crystallization behavior and morphology of polylactic acid (PLA) in the presence of a nucleating agent: potassium salt of 5‐dimethyl sulfoisothalate, an aromatic sulfonate derivative (Lak‐301). Isothermal crystallization kinetics of PLA melt mixed with Lak at concentrations of 0.25–1 wt % was investigated at a range of crystallization temperature, 140–150 °C. To gain further insight on the effect of Lak, nonisothermal differential scanning calorimetry (DSC), wide angle X‐ray diffraction (WAXD), polarized optical microscope (POM), heat deflection temperature (HDT), and rheology were also performed. At 0.25 wt % Lak, crystallinity of PLA increased from 10% to 45%, and in 1 wt % Lak, maximum crystallinity of 50% was achieved. With 1 wt % Lak, crystallization half time reduced to 1.8 min from 61 min for neat PLA at 140 °C. The isothermal crystallization kinetics was analyzed using Avrami model. Values of the Avrami exponent for PLA with Lak were mainly in the range of 3 indicating a three dimensional crystal growth is favored. Crystallization rate was found to increase with increase in Lak content. Observation from POM confirmed that the presence of Lak in the PLA matrix significantly increased the nucleation density. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43673.