Cold‐crystallization behavior of poly(L‐lactide)/ACR blend films investigated by in situ FTIR spectroscopy

The cold crystallization behavior of poly (L ‐lactide) (PLLA) blend films modified by small amount of acrylic rubber particles (ACR) have been investigated by in situ Fourier‐transform infrared (FTIR) spectroscopy. During the isothermal cold crystallization, the crystallization rate of PLLA is greatly improved with addition of only 1 wt % ACR. However, for PLLA with 8 wt % ACR, the crystallization rate is slower than that of neat PLLA. The relative crystallinity of PLLA with the addition of 1–5 wt % ACR is obviously higher than that of the neat PLLA. For the PLLA blend film with 3 % ACR, the relative crystallinity reaches a maximum. It was found that the addition of ACR particles below 5% accelerated the cold crystallization nucleation process and made the cold‐crystallization rate of PLLA/ACR be quicker than that of neat PLLA. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Crystallization behavior and isothermal crystallization kinetics of PLLA blended with ionic liquid, 1‐butyl‐3‐methylimidazolium dibutylphosphate

The crystallization behavior and isothermal crystallization kinetics of neat poly(l ‐lactic acid) (PLLA) and PLLA blended with ionic liquid (IL), 1‐butyl‐3‐methylimidazolium dibutylphosphate, were researched by differential scanning calorimetry (DSC), polarizing optical microscopy (POM), and wide angle X‐ray diffraction (WXRD). Similar to the non‐isothermal crystallization behavior of neat PLLA, when PLLA melt was cooled from 200 to 20°C at a cooling rate of 10°C min^?1, no crystallization peak was detected yet with the incorporation of IL. However, the glass transition temperature and cold crystallization temperature of PLLA gradually decreased with the increase of IL content. It can be attributed to the significant plasticizing effect of IL, which improved the chain mobility and cold crystallization ability of PLLA. Isothermal crystallization kinetics was also analyzed by DSC and described by Avrami equation. For neat PLLA and IL/PLLA blends, the Avrami exponent n was almost in the range of 2.5–3.0. It is found that t_1/2 reduced largely, and the crystallization rate constant k increased exponentially with the incorporation of IL. These results show that the IL could accelerate the overall crystallization rate of PLLA due to its plasticizing effect. In addition, the dependences of crystallization rate on crystallization temperature and IL content were discussed in detail according to the results obtained by DSC and POM measurements. It was verified by WXRD that the addition of IL could not change the crystal structure of PLLA matrix. All samples isothermally crystallized at 100°C formed the α‐form crystal. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41308.     

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     

Morphology,crystallization and enzymatic hydrolysis of poly(L‐lactide) nucleated using layered metal phosphonates

Poly(L ‐lactide) (PLLA) was prepared via melt blending and nucleated using three layered metal phosphonates, i.e. zinc phenylphosphonate (PPZn), calcium phenylphosphonate (PPCa) and barium phenylphosphonate (PPBa). The morphology, crystallization and enzymatic hydrolysis of PLLA nucleated using PPZn, PPCa and PPBa were investigated. The results of both wide‐angle X‐ray diffraction and transmission electron microscopy observations show that the layers of PPZn, PPCa or PPBa are barely exfoliated or intercalated by PLLA chains in the melt‐blending process. PPZn, PPCa and PPBa serve as effective nucleating agents, accelerating both non‐isothermal and isothermal crystallization and enzymatic hydrolysis of PLLA. An interesting aspect is that the nucleating ability of PLLA incorporating PPZn, PPCa and PPBa decreases in the order PPZn > PPCa > PPBa, whereas the enzymatic hydrolysis of PLLA incorporating PPZn, PPCa and PPBa decreases in the reverse order, which is due to the different dispersion and interfacial interactions of PPZn, PPCa and PPBa throughout the PLLA matrix. Copyright © 2010 Society of Chemical Industry     

Effect of interface and confinement size on the crystallization behavior of PLLA confined in coaxial electrospun fibers

Poly(l ‐lactide)/polyacrylonitrile (PLLA/PAN) core‐sheath composite fibers were fabricated by coaxial electrospinning. The crystallization behavior of PLLA within the coaxial electrospun fibers was studied by differential scanning calorimetry (DSC). The PLLA/PAN coaxial electrospun fiber with a PLLA diameter of ～32 nm (C1) exhibits a crystallization temperature (T_c) of 22.5 °C higher but a cold‐crystallization temperature (T_cc) of 10 °C lower than bulk PLLA. The crystallinity of C1 fiber is also higher than bulk PLLA. In both isothermal melt‐ and cold‐crystallization, PLLA in C1 fiber crystallizes faster than the bulk PLLA, as revealed by the smaller half crystallization times (t_1/2). The enhanced crystallizability of PLLA in the C1 fiber may be attributed to the increased nuclei number and crystal growth rate induced by the PAN surface, i.e., surface‐induction effect. However, PLLA also suffers a nano‐confinement effect exerted by PAN sheath in the coaxial electrospun fiber, which can suppress PLLA crystallization. When the diameter of PLLA is too small (< 32 nm), the nano‐confinement effect may prevail over the surface‐induction effect, leading to a slower crystallization rate and smaller crystallinity. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45980.     

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     

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 behavior,heat resistance,and mechanical performances of PLLA/myo‐inositol blends

In this work, use of myo‐inositol as a biobased nucleating agent (NA) for PLLA was researched. Effects of myo‐inositol on non‐isothermal and isothermal crystallization behaviors of PLLA at temperatures ranged from 85 °C to 130 °C were studied by using DSC, POM and WAXD. Isothermal crystallization kinetics results showed that the incorporation of myo‐inositol enhanced significantly the crystallization rate of the PLLA samples. It was confirmed that the optimum isothermal crystallization temperature range was 100 to 110 °C. The above results were instructive to confirm proper heat treatment time and temperature for compression or injection molding to fabricate highly crystallized PLLA articles. The relations among heat treatment time, crystallinity, heat resistance, and mechanical performances of the neat PLLA and PLLA/1% myo‐inositol specimens prepared by compression molding were investigated. Compared with the PLLA specimens, the PLLA/1% myo‐inositol specimens showed a shorter heat treatment time to reach the maximum crystallinity. Vicat softening temperature, as well as tensile strength, modulus, and toughness of the PLLA/1% myo‐inositol specimens was improved when crystallinity increased from 5.4% to 38.1%. Considering the nontoxicity and biocompatibility of myo‐inositol, PLLA/myo‐inositol blends would be potential to prepare some products, which are required higher health standard and can be used in elevated temperature environments. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44732.     

Stereocomplex formation between poly(L‐lactic acid) and poly(D‐lactic acid) with disproportionately low and high molecular weights from the melt

Poly(L ‐lactic acid) (PLLA) and poly(D ‐lactic acid) (PDLA) with very different weight‐average molecular weights (M_w) of 4.0 × 10³ and 7.0 × 10⁵ g mol^?1 (M_w(PDLA)/M_w(PLLA) = 175) were blended at different PDLA weight ratios (X_D = PDLA weight/blend weight) and their crystallization from the melt was investigated. The presence of low molecular weight PLLA facilitated the stereocomplexation and thereby lowered the cold crystallization temperature (T_cc) for non‐isothermal crystallization during heating and elevated the radial growth rate of spherulites (G) for isothermal crystallization, irrespective of X_D. The orientation of lamellae in the spherulites was higher for the neat PLLA, PDLA and an equimolar blend than for the non‐equimolar blends. It was found that the orientation of lamellae in the blends was maintained by the stereocomplex (SC) crystallites. Although the G values are expected to decrease with an increase in X_D or the content of high‐molecular‐weight PDLA with lower chain mobility compared with that of low‐molecular‐weight PLLA, G was highest at X_D = 0.5 where the maximum amount of SC crystallites was formed and the G values were very similar for X_D = 0.4 and X_D = 0.6 with the same enantiomeric excess. This means that the effect of SC crystallites overwhelmed that of chain mobility. The nucleating mechanisms of SC crystallites were identical for X_D = 0.1–0.5 in the T_c range 130–180 °C. Copyright © 2011 Society of Chemical Industry     

Deterioration of metal–organic framework crystal structure during fabrication of poly(l‐lactic acid) mixed‐matrix membranes

Poly(l ‐lactic acid) (PLLA) and metal–organic framework (MOF) mixed‐matrix membranes were prepared by melt extrusion of PLLA with 5% (w/w) of either activated or water‐saturated Cu₃(BTC)₂ (Cu₃(C₉H₃O₆)₂(H₂O)₃·xH₂O, HKUST‐1). The morphology and the stability of injection‐molded samples were evaluated using thermogravimetric analysis, differential scanning calorimetry, gel permeation chromatography, X‐ray diffraction (XRD) and scanning electron microscopy (SEM). The presence of activated and saturated MOF crystals increased the cold crystallization onset temperature as compared to neat PLLA. This can be attributed to the MOF crystals incorporated in the PLLA matrix, which decreased the mobility of PLLA and thus impeded the crystallization process. According to the XRD results, the activated MOF crystals were successfully incorporated into the PLLA matrix without altering the crystal structure of the MOF. Moreover, the findings from permeability and tensile tests as well as SEM imaging indicated good interfacial interactions between PLLA and activated MOF. However, during melt extrusion of PLLA with saturated MOF, water molecules from the saturated MOF altered the MOF crystal structure and contributed to the degradation of the PLLA polymer by reducing its molecular weight by around 21%. © 2013 Society of Chemical Industry     

The effect of poly(ethylene glycol) mixed with poly(l‐lactic acid) on the crystallization characteristics and properties of their blends

The non‐isothermal and isothermal crystallizations of extruded poly(l ‐lactic acid) (PLLA) blends with 10, 20 and 30 wt% poly(ethylene glycol) (PEG) were investigated with differential scanning calorimetry. The formation of α‐form crystals in the blend films was verified using X‐ray diffraction and an increase in crystallinity indexes using Fourier transformation infrared spectroscopy. Crystallization and melting temperatures and crystallinity of PLLA increased with decreasing cooling rate (CR) and showed higher values for the blends. Although PLLA crystallized during both cooling and heating, after incorporation of PEG and with CR = 2 °C min^?1 its crystallization was completed during cooling. Increasingly distinct with CR, a small peak appeared on the lower temperature flank of the PLLA melting curve in the blends. A three‐dimensional nucleation process with increasing contribution from nuclei growth at higher CR was verified from Avrami analysis, whereas Kissinger's method showed that the diluent effect of 10 and 20 wt% PEG in PLLA decreased the effective energy barrier. During isothermal crystallization, crystallization half‐time increased with temperature (T_ic) for the blends, decreased with PEG content and was lower than that of pure PLLA. In addition, the Avrami rate constants were significantly higher than those of pure PLLA, at the lower T_ic. Different crystal morphologies in the PLLA phase were formed, melting in a broader and slightly higher T_m range than pure PLLA. The crystallization activation energy of PLLA decreased by 56% after the addition of 10 wt% PEG, increasing though with PEG content. Finally, PEG/PLLA blends presented improved flexibility and hydrophilicity. © 2019 Society of Chemical Industry     

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 of poly(3‐hydroxybutyrate) with stereocomplexed polylactide as biodegradable nucleation agent

Crystallization kinetics behavior and morphology of poly(3‐hydroxybutyrate) (PHB) blended with of 2–10 wt% loadings of poly(L ‐ and D ‐lactic acid) (PLLA and PDLA) stereocomplex crystallites, as biodegradable nucleating agents, were studied using differential scanning calorimetry, polarizing‐light optical microscopy (POM), and wide‐angle X‐ray diffraction (WAXD). Blending PLLA with PDLA at 1:1 weight ratio led to formation of stereocomplexed PLA (sc‐PLA), which was incorporated as small crystalline nuclei into PHB for investigating melt‐crystallization kinetics. The Avrami equation was used to analyze the isothermal crystallization of PHB. The stereocomplexed crystallites acted as nucleation sites in blends and accelerated the crystallization rates of PHB by increasing the crystallization rate constant k and decreasing the half‐time (t_1/2). The PHB crystallization was nucleated most effectively with 10 wt% stereocomplexed crystallites, as evidenced byPOM results. The sc‐PLA complexes (nucleated PHB crystals) exhibit much small spherulite sizes but possess the same crystal cell morphology as that of neat PHB based on the WAXD result. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Cold Crystallization of PLLA Studied by Simultaneous SAXS and WAXS

Summary: The cold crystallization process of initially amorphous poly(L ‐lactic acid), PLLA, with two different molecular weights, during a heating at 2 °C/min, was investigated by DSC and time‐resolved simultaneous SAXS and WAXS, using synchrotron radiation. Equatorial scans of the isotropic 2D‐SAXS patterns showed that the average Bragg long period (L_B) of PLLA samples was approximately constant with the development of cold crystallization up to a temperature that corresponded to a melt/re‐crystallization process that took place before the nominal melting peak seen by DSC. L_B values were found to be higher for the high molecular weight material. This was in accordance with the higher melting temperature observed in the high molecular weight PLLA that implied the existence of thicker lamellae. WAXS results showed that the molecular weight did not apparently affect the crystal form and the final degree of crystallinity of PLLA. The Avrami parameters from WAXS and DSC were consistent, showing that the non‐isothermal cold crystallization of the two PLLA samples corresponded mainly to a three‐dimensional growth, although an imperfect crystallization process was involved at early times. The crystallization rate of PLLA, observed both by WAXS and DSC, decreased with increasing molecular weight.

SAXS profiles of PLLA2 as a function of temperature. The inset shows the 2D‐SAXS pattern obtained at 180 °C.     

Thermal transitions and stability of melt mixed TiO2/Poly(L‐lactic acid) nanocomposites

Poly(L‐lactic acid) (PLLA) nanocomposites containing 5, 10, and 20 wt% titanium dioxide (TiO₂), were prepared by mixing in a co‐rotating twin‐screw extruder. By X‐ray diffraction, a transformation of less ordered (α’‐form) to better organized crystalline (α‐form) structure of PLLA was observed with increasing TiO₂ content. Differential scanning calorimetry (DSC) tests revealed that cold crystallization was facilitated, as shown by the decrease of cold crystallization temperature (T_cc). The main melting peak of PLLA phase in nanocomposites, shifted towards higher temperatures and a shoulder appeared in the lower temperature flank of the curve, revealing a second peak for 20/80 w/w TiO₂/PLLA nanocomposites. The effect of TiO₂ on the isothermal crystallization of PLLA, in the temperature range T_ic: 100–120°C, was also investigated by DSC. At lower temperatures (T_ic: 100 and 110°C), the effect of TiO₂ nanoparticles is an increase of the crystallization rate, leading to lower time for the completion of crystallization, in comparison with that of pure PLLA. The inverse effect was observed at higher crystallization temperatures (T_ic: 115 and 120°C). The kinetic analysis of the crystallization behavior of the examined nanocomposites fits the Avrami equation quite well and gives values for exponent (n) varying between 2 and 3, suggesting a spherulitic crystalline morphology. POLYM. ENG. SCI., 59:704–713, 2019. © 2018 Society of Plastics Engineers     

Largely improved crystallization behavior and thermal stability of poly(L‐lactide) via the synergistic effects of graphene oxide and carbon nanotubes

Graphene oxide (GO) and carbon nanotubes (CNTs) and their compound were introduced into semicrystalline poly(l ‐lactide) (PLLA) to prepare the corresponding binary and/or ternary nanocomposites, respectively. The dispersion states of nanofillers in different nanocomposites were investigated using UV‐Vis spectroscopy, scanning electron microscopy (SEM) and rheological measurement. The results showed that when GO and CNTs were simultaneously present in the PLLA matrix, good dispersion states of both GO and CNTs could be achieved and the ternary nanocomposites exhibited percolated network structure. The effects of different nanofillers on the crystallization behavior of PLLA matrix were comparatively investigated under the different crystallization conditions including melt crystallization process (nonisothermal and isothermal crystallization from the melt) and cold crystallization (crystallization occurring from an amorphous state during the annealing process). The results showed that GO and CNTs exhibited apparent synergistic effects in improving crystallization ability and enhancing crystallinity of PLLA matrix. Study on the thermal stability of nanocomposites showed that the presence of nanofillers greatly improved the thermal stability of PLLA matrix. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40143.     

苯基磷酸锌对聚乳酸结晶行为影响的研究

采用DSC,POM研究了成核剂苯基磷酸锌（PPZn）对聚乳酸结晶行为的影响。结果表明：PPZn可以作为聚乳酸的高效成核剂,PPZn的加入显著提高了聚乳酸的结晶速率和结晶度。当PPZn的质量分数为5％0时TCs（起始结晶温度）降低了约24℃,TCe（终止结晶温度）降低了约29℃。PPZn的加入使聚乳酸的半结晶时间大大缩短。当PPZn的质量分数为2％时,结晶速率常数增大约5个数量级。     

Influence of dispersed organophilic montmorillonite at nanometer‐scale on crystallization of poly(L‐lactide)

We investigated the effects of surface‐treated organophilic clay on the crystallization of poly(L ‐lactide) (PLLA) in their hybrids. The natural nano‐clay in PLLA/clay hybrids acts as a heterogeneous nucleating agent to facilitate crystallization. On the contrary, extensive distributions of induction periods for nucleation are observed in the individual spherulites of neat PLLA and PLLA/organophilic clay hybrids. Therefore, it is suggested that nucleation type of neat PLLA and PLLA/organophilic clay hybrids implies nearly growth geometry as a homogeneous one. Further, under the presence of nano‐clay in their composites, PLLA matrix form the orthorhombic lattice structure corresponded to the α‐form crystal. Since this experimental fact implies little effect of the clay particles on polymorphism of PLLA crystal, the nucleating effect of the organophilic clay seems weaker than the natural clay itself. However, an increase in clay content enhances the growth rates of spherulite for hybrids. Consequently, most of hybrids exhibit an increase in overall crystallization rates at any crystallization temperature in spite of relatively lower nucleation rate of PLLA crystallites itself. In addition, the Avrami exponents (n) obtained by relatively low crystallization temperature ranged from 4 to 6, implying that the growth geometry was dominated sheaf‐like structure in early stage of isothermal crystallization. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Study of thermomechanical,structural and antibacterial properties of poly(lactic acid) reinforced with graphene oxide nanoparticles via melt mixing

Addition of graphene oxide (GO) to poly(l ‐lactic acid) (PLLA) offers an alternative approach for tuning its crystallinity, improving its mechanical properties and transfusing an antibacterial behavior. GO/PLLA nanocomposites were prepared by melt extrusion, thus avoiding the potentially toxic, for biomedical applications, residue of organic solvents. Fourier transform infrared spectroscopy verified the formation of intermolecular hydrogen bonds. Using differential scanning calorimetry experiments concerning the isothermal crystallization of PLLA and PLLA containing 0.4 wt% GO, a two‐dimensional disc‐like geometry of crystal growth was determined, whereas at 125 and 130 °C the nanocomposite developed three‐dimensional spherulitic growth. Higher crystallization rate constant values suggest that the incorporation of 0.4 wt% GO accelerated the crystallization of PLLA. The lowest crystallization half‐time for PLLA was observed at 115 °C, while at 110 °C GO caused its highest decrease, accompanied by the highest increase in melting enthalpy (ΔH_m), as compared to that of PLLA, after completion of isothermal crystallization. Their ΔH_m values increased with T_ic, whereas multiple melting peaks transited to a single one with increasing T_ic. GO improved the PLLA thermal stability, tensile strength and Young's modulus. Incorporation of 0.8 wt% GO endowed PLLA with another potential application as a biomaterial since the derived composite presented good thermomechanical properties and effective prohibition of Escherichia coli bacteria attachment and proliferation. This effect was more prominent under simulated sunlight exposure than in the dark. The preparation method did not compromise the intrinsic properties of GO. © 2020 Society of Chemical Industry     

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.