Microstructure and properties of poly(ethylene terephthalate)/organoclay nanocomposites prepared by water‐assisted extrusion: Effect of organoclay concentration

Poly(ethylene terephthalate) (PET)/Cloisite 30B (C30B) nanocomposites containing different concentrations of the organoclay were prepared using two different twin‐screw extrusion processes: conventional melt mixing and water‐assisted melt mixing. The reduction of the molecular weight of the PET matrix, caused by hydrolysis during the water‐assisted extrusion, was compensated by subsequent solid‐state polymerization (SSP). X‐ray diffraction, scanning electron microscopy, and transmission electron microscopy analyses showed intercalated/exfoliated morphology in all PET/C30B nanocomposites, with a higher degree of intercalation and delamination for the water‐assisted process. Rheological, thermal, mechanical, and gas barrier properties of the PET nanocomposites were also studied. Enhanced mechanical and barrier properties were obtained in PET‐C30B nanocomposites compared to the neat PET. The nanocomposites exhibited higher tensile modulus and lower oxygen permeability after SSP. The elongation at break was significantly higher for SSP nanocomposites than for nanocomposites processed by conventional melt mixing. POLYM. ENG. SCI., 54:1879–1892, 2014. © 2013 Society of Plastics Engineers     

Molecular characterization and rheological properties of modified poly(ethylene terephthalate) obtained by reactive extrusion

The use of a tetrafunctional epoxy‐based additive to modify the molecular structure of poly(ethylene terephthalate) (PET) was investigated with the aim of producing PET foams by an extrusion process. The molecular structure analysis and shear and elongation rheological characterization showed that branched PET is obtained for 0.2, 0.3 and 0.4 wt% of a tetrafunctional epoxy additive. Gel permeation chromatography (GPC) analysis led to the conclusion that a randomly branched structure is obtained, the structure being independent of the modifier concentration. The evolution of shear and extensional behavior as a function of molecular weight (M_w), degree of branching, and molecular weight distribution (MWD) were studied, and it is shown that an increase in the degree of branching and M_w and the broadening of the MWD induce an increase in Newtonian viscosity, relaxation time, flow activation energy and transient extensional viscosity, while the shear thinning onset and the Hencky strain at the fiber break decrease markedly.     

Effect of water‐assisted extrusion and solid‐state polymerization on the microstructure of PET/Clay nanocomposites

An melt‐mixing process has been used to prepare Poly(ethylene terephthalate) (PET)/clay nanocomposites with high degree of clay delamination. In this method, steam was fed into a twin‐screw extruder (TSE) to reduce the PET molecular weight and to facilitate their diffusion into the gallery spacing of organoclays. Subsequently, the molecular weight (M_W) reduction of the PET matrix due to hydrolysis by water was compensated by solid‐state polymerization (SSP). The effect of the thermodynamic compatibility of PET and organoclays on the exfoliated microstructure of the nanocomposites was also examined by using three different nanoclays. The dispersion of Cloisite 30B (C30B) in PET was found to be better than that of Nanomer I.28E (I28E) and Cloisite Na⁺. The effect of feeding rate and consequently residence time on the properties of PET nanocomposites was also investigated. The results reveal more delamination of organoclay platelets in PET‐C30B nanocomposites processed at low feeding rate compared to those processed at high feeding rate. Enhanced mechanical and barrier properties were observed in PET nanocomposites after SSP compared to the nanocomposites prepared by conventional melt‐mixing. POLYM. ENG. SCI., 54:1723–1736, 2014. © 2013 Society of Plastics Engineers     

In‐Situ Fiberized Poly(ethylene terephthalate) as a Reinforcement to Poly(propylene) Matrix

The reinforced poly(propylene) (PP)/poly(ethylene terephthalate) (PET) in‐situ fiberized composites were prepared by extrusion‐drawing‐injection molding. The influences of PET weight fraction (f_w) on the PET fiberization, phase morphology, and mechanical properties of the composites, together with their functional mechanisms were studied by contrast to the normal‐blended materials without drawing. The results show that as the f_w rises from 0 to 20%, the number of PET fibers increases, whereas their diameter and dispersity decrease till f_w = 15% and then increase, and the number of remained PET particles tends to rise. These changes of PET fiberization and phase morphology with f_w were attributed to the consequence of the combined actions of breakup, coalescence, and deformation of the PET dispersed phase in the PP matrix during the extrusion drawing. Correspondingly, the tensile strength (σ_t) and Young's modulus (E) of the in‐situ composites increase till f_w = 15% and then decrease, with maximum gains of σ_t and E of about 20 and 70% relative to the neat PP, respectively. This σ_t/f_w relation was ascribed to the counterbalanced result between the reinforcing effect of the dispersed phase on matrix and the interfacial flaw effect of two immiscible phases, while the E/f_w relation was considered as a representation of the rigidizing effect of the fibers on the matrix being controlled by both their number and diameter.

In‐situ PET fibres (PET/PP = 85/15) in an as‐drawn filament.     

High molecular weight poly (L‐lactic acid) clay nanocomposites via solid‐state polymerization

We propose here, a novel technique to synthesize high molecular weight (MW) poly (L ‐lactic acid)‐clay nanocomposite (PLACN), via solid state polymerization (SSP). We synthesize prepolymer of PLACN (pre‐PLACN) from both, L ‐lactic acid and L ‐lactide, as starting materials. Synthesis of pre‐PLACN from L ‐lactic acid is carried out via in situ melt polycondensation (MP) of L ‐lactic acid oligomer, followed by SSP, to achieve high MW PLACN (M_w ∼ 138,000 Da). In case of L ‐lactide as the starting material, we prepare L ‐lactide–clay intercalated mixture which yields moderate MW pre‐PLACN during subsequent ring opening polymerization (ROP). Interestingly, ROP is performed by using hydroxyl functionalized ternary catalyst system (L ‐lactide–Sn(II) octoate–oligo (L‐lactic acid) complex), which provides the terminal hydroxyl end‐groups, required for step‐growth SSP. Pre‐PLACN MW is now increased to M_w ∼ 127,000 Da, by the subsequent SSP process. ¹H NMR analyses confirm that these end‐groups, are indeed consumed during SSP. During SSP, the PLACN also achieves up to 90% crystallinity, which may be due to the synchronization of the slow step‐growth SSP of poly(L ‐lactic acid) (PLA) with the crystallization kinetics. Optical purity of PLACNs is similar to that of neat PLA, whereas the thermal stability of PLACNs is significantly superior. As evidenced by wide‐angle X‐ray scattering/small‐angle X‐ray scattering analyses and in line with the literature, both, intercalated and exfoliated PLACN morphologies, have been synthesized, by suitable selection of clays. We also verify the correlation between the PLA semicrystalline morphology and the PLACN morphology, which is consistent with those of PLACN synthesized by other techniques. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

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     

Dispersion of nanoclays with poly(ethylene terephthalate) by melt blending and solid state polymerization

Melt intercalation of clay with poly(ethylene terephthalate; PET) was investigated in terms of PET chain mobilities, natures of clay modifiers, their affinities with PET, and nanocomposite solid state polymerization (SSP). Twin screw extrusion was used to melt blend PET resins with intrinsic viscosities of 0.48, 0.63, and 0.74 dL/g with organically modified Cloisite 10A, 15A, and 30B montmorillonite clays. Clay addition caused significant molecular weight reductions in the extruded PET nanocomposites. Rates of SSP decreased and crystallization rates increased in the presence of clay particles. Cloisite 15A blends showed no basal spacing changes, whereas the basal spacings of Cloisite 10A and Cloisite 30B nanocomposites increased after melt extrusion, indicating the presence of intercalated nanostructures. After SSP these nanocomposites also exhibited new lower angle X‐ray diffraction peaks, indicating further expansion of their basal spacings. Greatest changes were seen for nanocomposites prepared from the lowest molecular weight PET and Cloisite 30B, indicating its greater affinity with PET and that shorter more mobile PET chains were better able to enter its galleries and increase basal spacing. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Crystallization behavior and UV‐protection property of PET‐ZnO nanocomposites prepared by in situ polymerization

The aim of this study was to investigate the crystallization behavior and UV‐protection property of polyethylene terephthalate (PET)‐ZnO nanocomposits. PET‐ZnO nanocomposites containing 0.5–3.0 wt % of ZnO were successfully synthesized by in situ polymerization. The Fourier transformed infrared (FTIR) spectroscopy indicated the silane coupling agent was anchored onto the surface of ZnO. Scanning electron microscope (SEM) images showed ZnO particles were dispersed homogeneously in PET matrix with amount of 0.5–1.0 wt %. Differential scanning calorimetry (DSC) results exhibited that the incorporation of ZnO into PET resulted in increase of the melting transition temperature (T_m) and crystallization temperature (T_c) of PET‐ZnO nanocomposites. The crystallization behavior of PET and PET‐ZnO nanocomposites was strongly affected by cooling rate. ZnO nanoparticles can act as an efficient nucleating agent to facilitate PET crystallization. UV–vis spectrophotometry showed that UV‐ray transmittance of PET‐ZnO nanocomposites decreased remarkably and reached the minimum value of 14.3% with 1.5 wt % of ZnO, compared with pure PET whose UV‐ray transmittance was 84.5%. PET‐ZnO nanocomposites exhibited better UV‐protection property than pure PET, especially in the range of UVA. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Calorimetric study of nanocomposites of multiwalled carbon nanotubes and isotactic polypropylene polymer

Modulated differential scanning calorimetry (MDSC) was used to measure the complex specific heat of the crystallization and melting transitions of nanocomposites of isotactic polypropylene (iPP) and carbon nanotubes (CNT) as function of CNT weight percent and temperature scan rate. In the last few years, great attention has been paid to the preparation of iPP/CNT nanocomposites due to their unique thermal and structural properties and potential applications. As the CNT content increases from 0 to 1 wt %, heterogeneous crystal nucleation scales with the CNT surface area. Above 1 wt %, nucleation appears to saturate with the crystallization temperature, reaching ～8 K above that of the neat polymer. Heating scans reveal a complex, two‐step, melting process with a small specific heat peak, first observed ～8 K below a much larger peak for the neat iPP. For iPP/CNT samples, these two features rapidly shift to higher temperatures with increasing ?_w and then plateau at ～3 K above that in neat iPP for ?_w ≥ 1 wt %. Scan rates affect dramatically differently the neat iPP and its nanocomposites. Transition temperatures shift nonlinearly, while the total transition enthalpy diverges between cooling and heating cycles with decreasing scan rates. These results are interpreted as the CNTs acting as nucleation sites for iPP crystal formation, randomly pinning a crystal structure different than in the neat iPP and indicating complex transition dynamics. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Films made from poly(vinyl alcohol‐co‐ethylene) and soluble biopolymers isolated from postharvest tomato plant

Blended films were obtained from polyvinyl alcohol‐co‐ethylene (EVOH) with 52 kDa weight average molecular weight (M_w) and three water soluble biopolymers isolated from exhausted tomato plants hydrolysates. Two biopolymers contained mainly polysaccharides and had 27 and 79 kDa M_w, respectively. The third contained mainly lignin‐like C moieties and had 392 kDa M_W. The films were fabricated with a biopolymer/EVOH w/w ratio ranging from 0.1 to 0.9. All blends had molecular weight and solubility which were substantially different from the starting materials. They were characterized for the chemical nature, and the thermal, rheological, and mechanical properties. Evidence of a chemical reaction between the biopolymers and EVOH was found. Generally, the films exhibited higher mechanical strength but lower strain at break then the neat EVOH. The best performing blended film was fabricated from the 27 kDa M_w polysaccharide. This contained less than 10% biopolymer. It exhibited 1043 MPa Young's modulus and 70% strain at break against 351 MPa modulus and 86% strain for neat EVOH. The results offer scope for investigating biopolymers sourced from other biowastes to understand more the reasons of the observed effects and exploit their full potential to modify or to replace synthetic polymers. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41935.     

Molecular weight and chain conformation of amylopectin from rice starch

By using laser light scattering (LS) and size exclusion chromatography combined LS, we have investigated the molecular weight and chain conformation of amylopectin from rice of India (II‐b), japonica (IJ‐b), and glutinous (IG‐b) in dimethyl sulfoxide (DMSO) solution. The weight‐average molecular weight (M_w) and radius of gyration (〈S²〉^½) of amylopectin were determined to be 4.06 × 10⁷ and 128.5 nm for India rice, 7.41 × 10⁷ and 169.6 nm for japonica rice, 2.72 × 10⁸ and 252.3 nm for glutinous rice, respectively. The 〈S²〉^½ values were much lower than that of normal polymers, indicating a small molecular volume of amylopectin, as a result of highly branched structure. Ignoring the difference of degree of branching, approximated dependences of 〈S²〉^½ and intrinsic viscosity ([η]) on M_w for amylopectin in DMSO at 25°C were estimated to be 〈S²〉^½ = 0.30M_w^0.35 (nm) and [η] = 0.331M_w^0.41 (mL g^?1) in the M_w range studied. Moreover, from the 〈S²〉^½ values of numberless fractions obtained from many experimental points in the SEC chromatogram detected with LS, the dependence of 〈S²〉^½ on M_w for the II‐b sample was estimated also to be 〈S²〉^½ = 0.34 M_w^0.347, coinciding with the above results. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Isothermal cold crystallization and melting behaviors of poly(L‐lactic acid)s prepared by melt polycondensation

The isothermal cold crystallization and melting behaviors of poly(L ‐lactic acid)s (PLLAs, weight average molecular weight, M_w, 6000–80,000) prepared via melt polycondensation were studied with differential scanning calorimeter in this work. It is found that the crystallization rate increased with decreasing M_w, reached a maximum at M_w of ca. 21,000 and then decreased again. The crystallinity of PLLA can be controlled in the range 30–50% by crystallization temperature (T_c) and time to fulfill the requirement of subsequent solid state polycondensation. The melting behavior strongly depends on T_c. The samples crystallized at high T_c melted with a single peak but those crystallized at low T_c melted with double peaks. The higher melting point (T_mH) kept almost constant and the lower melting point (T_mL) increased clearly with T_c. But the T_mL changed in jumps and a triple melting peak appeared at the vicinity of a characteristic crystallization temperature T_b, possibly because of a change of crystal structure. The equilibrium melting temperature of PLLA with M_w of 21,300 was extrapolated to be 222°C with nonlinear Hoffman‐Weeks method. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

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     

Nitroxide‐mediated synthesis of styrenic‐based segmented and tapered block copolymers using poly(lactide)‐functionalized TEMPO macromediators

Poly(styrene)‐poly(lactide) (PS‐PLA), poly (tert‐butyl styrene)‐poly(lactide) (PtBuS‐PLA) diblocks, and poly(tert‐butyl styrene)‐poly(styrene)‐poly(lactide) (PtBuS‐PS‐PLA) segmented and tapered triblocks of controlled segment lengths were synthesized using nitroxide‐mediated controlled radical polymerization. Well‐defined PLA‐functionalized macromediators derived from hydroxyl terminated TEMPO (PLA_T) of various molecular weights mediated polymerizations of the styrenic monomers in bulk and in dimethylformamide (DMF) solution at 120–130°C. PS‐PLA and PtBuS‐PLA diblocks were characterized by narrow molecular weight distributions (polydispersity index (M_w/M_n) < 1.3) when using the PLA_T mediator with the lowest number average molecular weight M_n= 6.1 kg/mol while broader molecular weight distributions were exhibited (M_w/M_n = 1.47‐1.65) when using higher molecular weight mediators (M_n = 7.4 kg/mol and 11.3 kg/mol). Segmented PtBuS‐PS‐PLA triblocks were initiated cleanly from PtBuS‐PLA diblocks although polymerizations were very rapid with PS segments ～ 5–10 kg/mol added within 3–10 min of polymerization at 130°C in 50 wt % DMF solution. Tapering from the PtBuS to the PS segment in semibatch mode at a lower temperature of 120°C and in 50 wt % DMF solution was effective in incorporating a short random segment of PtBuS‐ran‐PS while maintaining a relatively narrow monomodal molecular weight distribution (M_w/M_n ≈ 1.5). © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Thermal properties of poly(ethylene terephthalate) recovered from municipal solid waste by steam autoclaving

The steam autoclaving of municipal solid waste followed by size separation was shown to be a way to recover virtually 100% of recyclable poly(ethylene terephthalate) (PET); this is a yield not attainable by a typical material recovery facility. The polymer properties of the recovered PET, which had undergone various degrees of thermal processing, were evaluated by thermogravimetric analysis, differential scanning calorimetry, gel permeation chromatography, viscometry, and solid‐state NMR to assess the commercial viability of polymer reuse. The weight‐average molecular weight (M_w) decreased as a result of autoclaving from 61,700 g/mol for postconsumer poly(ethylene terephthalate) (pcPET) to 59,700 g/mol for autoclaved postconsumer poly(ethylene terephthalate) [(apcPET)]. M_w for the reclaimed poly(ethylene terephthalate) (rPET) was slightly lower, at 57,400 g/mol. The melting temperature increased with two heat cycles from 236°C for the heat‐crystallized virgin poly(ethylene terephthalate) (vPET) pellets to 248°C for apcPET and up to 253°C for rPET. Correspondingly, the cold crystallization temperature decreased with increased processing from 134°C for vPET to 120°C for apcPET. The intrinsic viscosity varied from 0.773 dL/g for the vPET to 0.709 dL/g for rPET. Extruded samples were created to assess the potential commercial applications of the recovered rPET samples. The M_w values of the extruded apcPET and rPET samples dropped to 37,000 and 34,000 g/mol, respectively, after extrusion (three heat cycles); this indicated that exposure to heat dictated that these materials would be better suited for downcycled products, such as fibers and injected‐molded products. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2012     

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 crystallization kinetics of linear metallocene polyethylenes

The effect of weight‐average molecular weight (M_w) on the nonisothermal crystallization kinetics of linear metallocene polyethylene (m‐PE) was studied with modulated differential scanning calorimetry. Six linear m‐PEs of molecular weights in the range 122–934 kg/mol were prepared by gas‐phase polymerization. The cooling rate (R) was varied in the range 2–20°C/min, and it significantly affected the crystallization behavior. M_w had a weak influence on both the peak crystallization temperature and the crystallization onset temperature. All m‐PEs showed primary and secondary crystallizations. At both low and high R's, the crystallinity showed a significant drop (～ 30%) when M_w was increased from 122 to 934 kg/mol. At low R's (< 10°C/min), the rate parameters in the modified Avrami method [primary rate constant (k_R)] and Mo method [F(T)] of analyses agreed in suggesting that an increased M_w slowed the rate of crystallization. The M_w dependency of k_R followed the Arrhenius type (k_R = k_Roe²⁸¹/M_w, where k_Ro is a rate‐dependent constant). However, at higher R's, k_R approached a constant value. The order parameters obtained by the different methods of analysis (n and α) were independent of M_w, which suggests that the crystal type remained the same. Hoffman–Lauritzen theory was used for data analysis, and activation energy per segment showed a significant decrease, from 225.0 to 11.8 kJ/mol, when M_w was increased from 152 to 934 kg/mol. Finally, all methods of analysis suggested a significant effect of M_w on slowing the overall crystallization process. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effect of sepiolite on the crystallization behavior of biodegradable poly(lactic acid) as an efficient nucleating agent

To enhance the crystallization kinetics of poly(lactic acid) (PLA), fibrous sepiolite was explored for nucleating the crystallization of PLA. PLA/sepiolite nanocomposites were prepared via the melt‐extrusion method. The effect of sepiolite on the crystallization behavior, spherulite growth and crystal structure of PLA were investigated by means of differential scanning calorimetry (DSC), polarized optical microscope (POM), wide angle X‐ray diffraction (WAXD), Fourier transform infrared (FTIR), and scanning election microscope (SEM). On the basis of DSC and POM results, the overall crystallization kinetics of PLA/sepiolite nanocomposites were significantly enhanced leading to higher crystallinity and nucleation density, faster spherulite growth rate (G) and lower crystallization half‐time (t_1/2) compared with the neat PLA. Under non‐isothermal conditions, the PLA blend comprising 1.0 wt% of sepiolite still revealed two crystallization peaks upon cooling at a rate of 35°C/min. Above phenomena strongly suggested that sepiolite was an effective nucleating agent for PLA. FTIR and WAXD analyses confirmed that the crystal structure of PLA matrix was the most common α‐form. SEM micrographics illustrated the fine three‐dimensional spherulite structures with the lath‐shape lamellae regularly arranged in radial directions. POLYM. ENG. SCI., 55:1104–1112, 2015. © 2014 Society of Plastics Engineers     

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

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

Nonisothermal crystallization kinetics of poly(ethylene terephthalate) and poly(methyl methacrylate) blends

The nonisothermal crystallization kinetics of poly(ethylene terephthalate) (PET) and poly(methyl methacrylate) (PMMA) blends were studied. Four compositions of the blends [PET 25/PMMA 75, PET 50/PMMA 50, PET 75/PMMA 25, and PET 90/PMMA 10 (w/w)] were melt‐blended for 1 h in a batch reactor at 275°C. Crystallization peaks of virgin PET and the four blends were obtained at cooling rates of 1°C, 2.5°C, 5°C, 10°C, 20°C, and 30°C/min, using a differential scanning calorimeter (DSC). A modified Avrami equation was used to analyze the nonisothermal data obtained. The Avrami parameters n, which denotes the nature of the crystal growth, and Z_t, which represents the rate of crystallization, were evaluated for the four blends. The crystallization half‐life (t_½) and maximum crystallization (t_max) times also were evaluated. The four blends and virgin polymers were characterized using a thermogravimetric analyzer (TGA), a wide‐angle X‐ray diffraction unit (WAXD), and a scanning electron microscope (SEM). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3565–3571, 2006