Analysis of the complex thermal behavior of poly(L‐lactic acid) film. I. Samples crystallized from the glassy state

The melting behavior of poly(L ‐lactic acid) film crystallized from the glassy state, either isothermally or nonisothermally, was studied by wide angle X‐ray diffraction (WAXD), small angle X‐ray scattering (SAXS), differential scanning calorimetry (DSC), and temperature‐modulated differential scanning calorimetry (TMDSC). Up to three crystallization and two melting peaks were observed. It was concluded that these effects could largely be accounted for on the basis of a “melt‐recrystallization” mechanism. When molecular weight is low, two melting endotherms are readily observed. But, without TMDSC, the double melting phenomena of high molecular weight PLLA is often masked by an exotherm just prior to the final melting, as metastable crystals undergo melt‐recrystallization during heating in the DSC. The appearance of a double cold‐crystallization peak during the DSC heating scan of amorphous PLLA film is the net effect of cold crystallization and melt‐recrystallization of metastable crystals formed during the initial cold crystallization. Samples cold‐crystallized at 80 and 90 °C did not exhibit a long period, although substantial crystallinity developed. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3200–3214, 2006     

Reversible and irreversible heat capacity of poly(trimethylene terephthalate) analyzed by temperature‐modulated differential scanning calorimetry

The heat capacity of poly(trimethylene terephthalate) (PTT) has been analyzed using temperature‐modulated differential scanning calorimetry (TMDSC) and compared with results obtained earlier from adiabatic calorimetry and standard differential scanning calorimetry (DSC). Using quasi‐isothermal TMDSC, the apparent reversing and nonreversing heat capacities were determined from 220 to 540 K, including glass and melting transitions. Truly reversible and time‐dependent irreversible heat effects were separated. The extrapolated vibrational heat capacity of the solid and the total heat capacity of the liquid served as baselines for the analysis. As one approaches the melting region from lower temperature, semicrystalline PTT shows a reversing heat capacity, which is larger than that of the liquid, an observation that is common also for other polymers. This higher heat capacity is interpreted as a reversible surface or bulk melting and crystallization, which does not need to undergo molecular nucleation. Additional time‐dependent, reversing contributions, dominating at temperatures even closer to the melting peak, are linked to reorganization and recrystallization (annealing), while the major melting is fully irreversible (nonreversing contribution). © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 622–631, 2000     

Temperature‐modulated differential scanning calorimetry studies on the origin of double melting peaks in isothermally melt‐crystallized poly(L‐lactic acid)

In this work, the melting behaviors of nonisothermally and isothermally melt‐crystallized poly(L ‐lactic acid) (PLLA) from the melt were investigated with differential scanning calorimetry (DSC) and temperature‐modulated differential scanning calorimetry (TMDSC). The isothermal melt crystallizations of PLLA at a temperature in the range of 100–110 °C for 120 min or at 110 °C for a time in the range of 10–180 min appeared to exhibit double melting peaks in the DSC heating curves of 10 °C/min. TMDSC analysis revealed that the melting–recrystallization mechanism dominated the formation of the double melting peaks in PLLA samples following melt crystallizations at 110 °C for a shorter time (≤30 min) or at a lower temperature (100, 103, or 105 °C) for 120 min, whereas the double lamellar thickness model dominated the formation of the double melting peaks in those PLLA samples crystallized at a higher temperature (108 or 110 °C) for 120 min or at 110 °C for a longer time (≥45 min). © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 466–474, 2007     

Polymer crystalline structure and morphology changes in nylon‐6/ZnO nanocomposites

The influence of ZnO nanoparticles on the crystalline structures of nylon‐6 under different crystallization conditions (annealing at different temperatures from the amorphous solid, isothermal crystallization from the melt at different temperatures, and crystallization from the solution) has been examined with differential scanning calorimetry (DSC), wide‐angle X‐ray diffraction, field emission scanning electron microscopy, and Fourier transform infrared. ZnO nanoparticles can induce the γ‐crystalline form in nylon‐6 when it is cooled from the melted state and annealed from the amorphous solid. This effect of ZnO nanoparticles increases with decreasing particle size and changes under different crystallization conditions. The effects of ZnO nanoparticles on the crystallization kinetics of nylon‐6 have also been studied with DSC. The results show that ZnO nanoparticles have two competing effects on the crystallization of nylon‐6: inducing the nucleation but retarding the mobility of polymer chains. Finally, the melting behavior of the composites has been investigated with DSC, and the multiple melting peaks of composites containing ZnO nanoparticles and pure nylon‐6 are ascribed to the reorganization of imperfect crystals. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1033–1050, 2003     

Control of thermal cross‐linking reactions and the degree of crystallinity of syndiotactic 1,2‐polybutadiene

Thermal stability, crystallization, morphological development, subsequently melting, and crystallinity control of a syndiotactic 1,2‐polybutadiene sample were carefully carried out by thermogravimetry (TGA), polarized optical microscopy (POM), differential scanning calorimetry (DSC), temperature‐modulated differential scanning calorimetry (TMDSC), and wide‐angle X‐ray diffraction (WAXD), respectively. The experiments indicate that thermal cross‐linking reaction rates under nitrogen protection and in air are different for this polymer at temperature above 155 °C. Under nitrogen protection, the thermal cross‐linking reaction rate is delayed and the mechanism of melt crystallization obtained from the DSC results is in good accordance with that from POM observation. TMDSC results indicate that melting–recrystallization–melting model is more proper to explain the double melting events of this sample. At the same time, the evolution of the degree of crystallinity as the function of the time was investigated by WAXD profiles for the samples firstly crystallized at 145 °C for 1 h and then kept at 163 °C mediated between the temperatures of the double peaks. It shows that as prolonging the annealing time at 163 °C thermal cross‐linking reactions possibly occur, leading to gradual reduction of the apparent crystallite sizes, evaluated by Scherrer equation and the degree of crystallinity. The changing sequence of the relative intensity of the stronger four diffraction peaks with time due to thermal cross‐linking reactions is (111)/(201) > (210) > (010) > (200)/(110). © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2885–2897, 2005     

Differential scanning calorimetry,small‐angle X‐ray scattering,and wide‐angle X‐ray scattering on homogeneous and heterogeneous ethylene‐α‐copolymers

The objective of this work was to use both X‐ray and differential scanning calorimetry techniques in a comparative study of the lamellar and crystalline structures of heterogeneous and homogeneous ethylene‐α‐copolymers. The samples differed in the comonomer type (1‐butene, 1‐hexene, 1‐octene, and hexadecene), comonomer content, and catalyst used in the polymerizations. Step crystallizations were performed with differential scanning calorimetry, and the crystallinity and lamellar thicknesses of the different crystal populations were determined. Wide‐angle X‐ray scattering was used to determine crystallinities, average sizes of the crystallites, and dimensions of the orthorhombic unit cell. The average thickness, separation of the lamellae, and volume fractions of the crystalline phase were determined by small‐angle X‐ray scattering (SAXS). The results revealed that at densities below 900 kg/m³, polymers were organized as poorly organized crystal bundles. The lamellar distances were smaller and the lamellar thickness distributions were narrower for the homogeneous ethylene copolymers than for the heterogeneous ones. Step‐crystallization experiments by SAXS demonstrated that the long period increased after annealing. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 1860–1875, 2001     

Melting and crystallization of poly(butylene terephthalate) by temperature‐modulated and superfast calorimetry

Quantitative temperature‐modulated differential scanning calorimetry (TMDSC) and superfast thin‐film chip calorimetry (SFCC) are applied to poly(butylene terephthalate)s (PBT) of different thermal histories. The data are compared with those of earlier measured heat capacities of semicrystalline PBT by adiabatic calorimetry and standard DSC. The solid and liquid heat capacities, which were linked to the vibrational and conformational molecular motion, serve as references for the quantitative analyses. Using TMDSC, the thermodynamic and kinetic responses are separated between glass and melting temperature. The changes in crystallinity are evaluated, along with the mobile–amorphous and rigid–amorphous fractions with glass transitions centered at 314 and 375 K. The SFCC showed a surprising bimodal change in crystallization rates with temperature, which stretches down to 300 K. The earlier reported thermal activity at about 248 K was followed by SFCC and TMDSC and could be shown to be an irreversible endotherm and is not caused by a glass transition and rigid–amorphous fraction, as assumed earlier. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1364–1377, 2006     

Matching Cure Characteristics of Automotive Rubber Compound and Polyurethane Coating

The present investigation focuses on matching cure characteristics of EPDM rubber compound and polyurethane (PU) coating using temperature modulated and pressure differential scanning calorimetry (TMDSC, PDSC). TMDSC provides a detailed and better understanding of the curing process of model rubber system as well as complex automotive rubber compounds. The low level of unsaturation present in EPDM, results in the small heat of vulcanization (2–5 J g^–1), which is difficult to accurately measure using conventional differential scanning calorimetry (DSC). Thus, curing of highly filled EPDM compound was investigated using TMDSC. The kinetics of PU curing was monitored using pressure DSC (PDSC), and heat of curing was determined as 4.2 J g^–1 at 10°C min^–1 heating rate. It is found that complex automotive compounds and the PU coating are curing simultaneously. This revised version was published online in July 2006 with corrections to the Cover Date.     

Calorimetric study of the conformational relaxation times in polystyrene

The temperature dependence of the relaxation times of the structural relaxation process of polystyrene is determined by temperature-modulated differential scanning calorimetry (TMDSC) and by conventional differential scanning calorimetry (DSC) in the latter by modelling the experimental heat capacity curves measured in heating scans after different thermal histories. The good agreement between both measuring techniques in the temperature interval just above the glass-transition temperature is a guide for the interpretation of the results of the TMDSC technique in the glass-transition region. In addition, the same model applied to DSC scans is used to simulate the TMDSC experiment and the calculated response is compared with the measured scans. Received: 22 February 1999 Accepted in revised form: 11 June 1999     

Polydispersity of ethylene sequence length in metallocene ethylene/α‐olefin copolymers. II. Influence on crystallization and melting behavior

In this work, crystallization and melting behavior of metallocene ethylene/α‐olefin copolymers were investigated by differential scanning calorimetry (DSC) and atomic force microscopy (AFM). The results indicated that the crystallization and melting temperatures for all the samples were directly related to the long ethylene sequences instead of the average sequence length (ASL), whereas the crystallization enthalpy and crystallinity were directly related to ASL, that is, both parameters decreased with a decreasing ASL. Multiple melting peaks were analyzed by thermal analysis. Three phenomena contributed to the multiple melting behaviors after isothermal crystallization, that is, the melting of crystals formed during quenching, the melting‐recrystallization process, and the coexistence of different crystal morphologies. Two types of crystal morphologies could coexist in samples having a high comonomer content after isothermal crystallization. They were the chain‐folded lamellae formed by long ethylene sequences and the bundlelike crystals formed by short ethylene sequences. The coexistence phenomenon was further proved by the AFM morphological observation. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 822–830, 2002     

Thermal transitions of benzene in copolymers and interpenetrating polymer networks based on hydrophilic and hydrophobic components: Experimental evidence of hydrophobic interaction

Thermal transitions of benzene in a hydrophobic polymer network have been explained by us in terms of the phase diagram of the polymer‐solvent system. In this work, we executed a similar study on copolymers and interpenetrating polymer networks (IPNs) with controllable hydrophilic/hydrophobic ratios. Copolymers and IPNs were swollen with different amounts of benzene and subjected to cooling and heating scans with differential scanning calorimetry (DSC). Synthesis of the IPNs was carried out in such a way that phase separation appeared, and three qualitatively different types of DSC thermograms were identified depending on the benzene content of IPN. Thermal transitions of benzene in the hydrophilic/hydrophobic copolymers can also be explained as a consequence of the phase diagram of the system, but an increase in the glass‐transition temperature of the system can be correlated with the interactions among the hydrophilic groups of the copolymer. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1713–1721, 2003     

Thermal properties and influence of orientation on crystalline morphologies in stereoblock polypropylene and related elastomers

Atomic force microscopy (AFM), small angle X‐ray scattering (SAXS), temperature modulated differential scanning calorimetry (TMDSC), variable heating rate DSC, an independent rapid heating rate method for melting points, and cyclic mechanical testing were used to study semicrystalline thermoplastic elastomeric polypropylenes (ELPPs) and related semicrystalline polyolefins including ethylene copolymers. Low crystallinity (ca., 9 and 15%) ELPP samples were studied by AFM in the nonoriented and melt‐oriented states. AFM images taken as a function of time after quenching of a melt‐drawn and highly nucleated film resolved details of secondary crystallization involving lateral growth on the ordered row‐nucleated structures. For nonoriented films, isothermal melt crystallization at high temperatures (110 °C) led to similar features for the two ELPPs. The dominant crystalline morphology studied by AFM consisted of small (several nm in width) granular crystallites organized into immature but large spherulites spanning tens of microns. A striking cross‐hatch morphology was detected in regions of the surface in 110 °C crystallized samples, which is contrasted with melt‐drawn films where row nucleated structures dominated the morphology in the film under no external stress. AFM was also used to monitor the morphological changes that occurred as the films were stretched at 25 °C. Break‐down of lamellae was observed, resulting in oriented narrow fibrils. Cyclic stress‐strain curves showed the expected result where lower crystallinity ELPPs had higher recoverable levels of set after both 100 and 500% elongation. TMDSC was used to resolve the broad melting and recrystallization regions in these low to medium crystallinity ELPP systems, and to contrast the results with ethylene copolymers. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

The phase behavior of a polymer‐fullerene bulk heterojunction system that contains bimolecular crystals

Polymer:fullerene blends have been widely studied as an inexpensive alternative to traditional silicon solar cells. Some polymer:fullerene blends, such as blends of poly(2,5‐bis(3‐tetradecylthiophen‐2‐yl)thieno[3,2‐b]thiophene (pBTTT) with phenyl‐c71‐butyric acid methyl ester (PC₇₁BM), form bimolecular crystals due to fullerene intercalation between the polymer side chains. Here we present the determination of the eutectic pBTTT:PC₇₁BM phase diagram using differential scanning calorimetry (DSC) and two‐dimensional grazing incidence X‐ray scattering (2D GIXS) with in‐situ thermal annealing. The phase diagram explains why the most efficient pBTTT:PC₇₁BM solar cells have 75–80 wt % PC₇₁BM since these blends lie in the center of the only room‐temperature phase region containing both electron‐conducting (PC₇₁BM) and hole‐conducting (bimolecular crystal) phases. We show that intercalation can be suppressed in 50:50 pBTTT:PC₇₁BM blends by using rapid thermal annealing to heat the blends above the eutectic temperature, which forces PC₇₁BM out of the bimolecular crystal, followed by quick cooling to kinetically trap the pure PC₇₁BM phase. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Effect of the γ‐form crystal on the thermal fractionation of poly(propylene‐co‐ethylene)

The effect of the γ‐form crystal on the thermal fractionation of a commercial poly(propylene‐co‐ethylene) (PPE) has been studied by differential scanning calorimetry (DSC) and wide‐angle X‐ray diffraction (WAXD) techniques. Two thermal fractionation techniques, stepwise isothermal crystallization (SIC) and successive self‐nucleation and annealing (SSA), have been used to characterize the molecular heterogeneity of the PPE. The results indicate that the SSA technique possesses a stronger fractionation ability than that of the SIC technique. The heating scan of the SSA fractionated sample exhibits 12 endothermic peaks, whereas the scan of the SIC fractionated sample only shows eight melting peaks. The WAXD observations of the fractionated PPE samples prove that the content of the γ‐form crystals formed during the thermal treatment of the SIC technique is much higher than that of the SSA treatment. The former is 57.4%, whereas the later is 12.6%. The effect of theγ‐form crystals on thermal fractionation ability is discussed. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4320–4325, 2004     

Probing multiple melting behaviors in poly(ethylene naphthalene 2,6‐dicarboxylate) with different thermal histories by simultaneous wide‐angle and small‐angle X‐ray scattering

A simultaneous wide‐angle and small‐angle X‐ray scattering study of two poly(ethylene naphthalene 2,6‐dicarboxylate) samples crystallized from the glassy state at different annealing temperatures for different annealing times was carried out with synchrotron radiation. Either single or dual melting was induced in the samples, as confirmed by differential scanning calorimetry (DSC). The correlation function and interface distribution function were calculated to evaluate microstructural parameters such as the long spacing, the thickness of the amorphous and crystalline phases, and the width of the size distributions. The sample with dual melting behavior exhibited an abrupt increase of all microstructural parameters at temperatures above the melting of the lowest endotherm, whereas the sample revealing a single melting endotherm did not show such a sudden change. This finding agrees with the concept that the appearance of two melting peaks in DSC traces can be explained by the dual lamellar stacking model. © 2001 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 881–894, 2001     

Intercalated poly(vinylidene fluoride)/clay nanocomposites: Structure and properties

The preparation and characterization of melt‐intercalated poly(vinylidene fluoride) (PVDF)/clay nanocomposites are reported. Organophilic clay (clay treated with dimethyl dihydrogenated tallow quaternary ammonium chloride) was used for the nanocomposite preparation. The composites were characterized with X‐ray diffraction (XRD), differential scanning calorimetry (DSC), and dynamic mechanical analysis (DMA). XRD results indicated the intercalation of the polymer in the interlayer spacing. The incorporation of clay in PVDF resulted in the β form of PVDF. DSC nonisothermal curves showed an increase in the melting and crystallization temperatures along with a decrease in crystallinity. Isothermal crystallization studies show an enhanced rate of crystallization with the addition of clay. DMA indicated significant improvements in the storage modulus over a temperature range of ?100 to 150 °C. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 31–38, 2003     

Correlation study among oxygen permeability,molecular mobility,and amorphous structure change of poly(ethylene‐vinylalcohol copolymers) by moisture

Oxygen permeability and the free‐volume hole size (cavity size) of ethylene‐vinylalcohol copolymers (EVOH) indicate abnormal humidity dependence, that is, they have minimum values in the range of around 20–40% RH, not showing a monotonic increase with humidity. To clarify this abnormal phenomenon, we investigated its molecular mobility and amorphous structure change by means of solid‐state NMR and temperature‐modulated differential scanning calorimetry (TMDSC). The glass transition temperature (T_g) decreased with humidity. Specimens stored at 15–60% RH showed large enthalpy relaxation, and it was found that the amorphous structure became more compact and the molecular conformation became more stable by ageing within this range of humidity. Under these conditions, solid‐state NMR measurement showed a component with intermediate relaxation time in the amorphous region. The results obtained by TMDSC and solid‐state NMR showed a reduction in molecular mobility by densifying in the amorphous region under the condition of 15–60% RH. The fact that the oxygen permeability and the cavity size of EVOH indicate minimum values at low humidity are attributed to the reduction in molecular mobility by enthalpy relaxation. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1181–1191, 2009     

Characterization and properties of chemically modified Corchorus capsularis jute fiber via pulping and grafting: Infrared,thermogravimetric analysis,differential scanning calorimetry,scanning electron microscopy,X‐ray diffraction,biodegradation, and superabsorbency

Jute fiber (Corchorus capsularis, JRC‐321 variety), an environmentally and ecologically friendly product, was chemically modified by the cooking alkaline sulfite process to unbleached and bleached pulps, which were further modified via graft copolymerization with acrylamide monomer with a complex initiating system: CuSO₄/glycine/KHSO₅. The above samples were characterized and morphologically analyzed by IR, thermogravimetric analysis, differential scanning calorimetry, scanning electron microscopy, and X‐ray diffraction. The biodegradability and superabsorbency of the samples were also evaluated for their novel commercial importance as jute‐based superabsorbents. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2696–2703, 2003     

Phase behavior of blends of PCBM with amorphous polymers with different aromaticity

The phase behavior of [6,6]‐phenyl C₆₁‐butyric acid methyl ester (PCBM) blends with amorphous polymers with different degrees of aromaticity has been investigated by differential scanning calorimetry (DSC) and small‐angle neutron scattering (SANS). The polymers investigated are the homologous series of polystyrene (PS), poly(2‐vinyl‐naphthalene) (P2VN), and poly(9‐vinyl‐phenanthrene) (P9VPh). The DSC results show that the miscibility of PCBM in these polymers increases nonlinearly from 16.5 wt % in PS, 57.0 wt % in P2VN, and 74.9 wt % in P9VPh. The SANS results show that at all concentrations of PCBM, the blends are composed of two mixed phases. Analysis shows that the phase dimensions remain largely independent of PCBM content, but there is a strong dependence of the PCBM concentration difference in the two phases with increasing PCBM content. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 994–1001