Stereochemical heterogeneity of biodegradable poly(L‐lactide) homopolymer as revealed by temperature rising elution fractionation and successive self‐nucleation/annealing thermal fractionation

Commercial poly(L ‐lactide) is typically heterogeneous in chain structure due to the existence of a small amount of D ‐lactyl units that are produced by the racemization reactions during the synthesis. In this article, the stereochemical heterogeneity of two commercial poly(L ‐lactide) was investigated with temperature rising elution fractionation (TREF) and successive self‐nucleation/annealing (SSA) thermal fractionation. For both samples, three fractions were collected and characterized with rotatory power analysis and DSC. The fractions show distinct optical purity and DSC results, which reflect the structure differences among them directly. After SSA treatment, the observation of multiple endotherms for each physically separated fraction confirms the fractionated sample contains a heterogeneous intermolecular and intramolecular distribution of defects. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Nucleation and crystallization kinetics of polyamide 12 investigated by fast scanning calorimetry

Nucleation and crystallization of polyamide 12 (PA 12) have been systematically investigated by fast scanning calorimetry at non-isothermal and isothermal conditions. The critical cooling rates of crystallization and crystal nucleation were determined as 300 and 10,000 K/s, respectively. Moreover, the half-times of nucleation (t_1/2,nucl) and overall crystallization (t_1/2,cry) show monomodal and bimodal dependencies on the crystallization temperature. t_1/2,nucl has an approximate minimum value of about 0.0005 s at 333 K, which is about 10–20 K above the glass transition temperature, and t_1/2,cry has two minima of about 0.05 and 0.8 s at about 333 and 383 K, respectively. Comparing the crystallization behavior of PA 12 with other polyamides, the activation energy for crystallization increases and the energy barrier of short-range diffusion decreases with the increase of the amide-group density in the chains.     

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     

Investigation on nonisothermal crystallization kinetics of the high‐flow nylon 6 by differential scanning calorimetry

The crystallization kinetics of the high‐flow nylon 6 containing polyamidoamine (PAMAM) dendrimers units in nylon 6 matrix was investigated by differential scanning calorimetry. The Ozawa and Mo equations were used to describe the crystallization kinetics under nonisothermal condition. The values of Avrami exponent m and the cooling crystallization function F(T) were determined from the Ozawa plots, which showed bad linearity, and were divided into three sections depending on different cooling rates. The plots of the m and log F(T) values versus crystallization temperatures were obtained, which indicated that the actual crystallization mechanisms might change with the crystallization temperatures. The high‐flow nylon 6 has higher values of m and log F(T) than those of pure nylon 6, which implied that the high‐flow nylon 6 had more complicated crystallization mechanisms and slower crystallization rate than those of pure nylon 6. The good linearity of the Mo plots verified the success of this combined approach. The activation energies of the high‐flow nylon 6 ranged from 157 to 174 kJ/mol, which were determined by the Kissinger method. The ΔE values were lower than those of pure nylon 6, and the ΔE values were affected by both the generation and the content of PAMAM units in the nylon 6 matrix. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2201–2211, 2008     

Nonisothermal crystallization and melting behavior of a luminescent conjugated polymer,poly(9,9‐dihexylfluorene‐alt‐co‐2,5‐didecyloxy‐1,4‐phenylene)

The nonisothermal crystallization kinetics of a luminescent conjugated polymer, poly(9,9‐dihexylfluorene‐alt‐co‐2,5‐didecyloxy‐1,4‐phenylene) (PF6OC10) with three different molecular weights was investigated by differential scanning calorimetry under different cooling rates from the melt. With increasing molecular weight of PF6OC10, the temperature range of crystallization peak steadily became narrower and shifted to higher temperature region and the crystallization rate increased. It was found that the Ozawa method failed to describe the nonisothermal crystallization behavior of PF6OC10. Although the Avrami method did not effectively describe the nonisothermal crystallization kinetics of PF6OC10 for overall process, it was valid for describing the early stage of crystallization with an Avrami exponent n of about 3. The combined method proposed in our previous report was able to satisfactorily describe the nonisothermal crystallization behavior of PF6OC10. The crystallization activation energies determined by Kissinger, Takhor, and Augis‐Bennett models were comparable. The melting temperature of PF6OC10 increased with increasing molecular weight. For low‐molecular‐weight sample, PF6OC10 showed the characteristic of double melting phenomenon. The interval between the two melting peaks decreased with increasing molecular weight, and only one melting peak was observed for the high‐molecular‐weight sample. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 976–987, 2007     

Crystallinity of poly(3‐hexylthiophene) in thin films determined by fast scanning calorimetry

Using fast scanning calorimetry, we determined the crystallinity of thin films of poly(3‐hexylthiophene) crystallized from the melt from measurements of the specific melting enthalpy. A broad range of film thicknesses from 10 µm down to 26 nm was covered. The sample mass was determined from measurements of the specific heat capacity in the molten state allowing a quantitative analysis of the heat flow data. Films with a thickness 400 nm slowly cooled from the melt showed the same crystallinity as bulk samples measured with conventional DSC. Below 350 nm the melting enthalpy decreased strongly. We assign this strongly reduced crystallinity to the restricted crystallization kinetics originating from hindered spherulitic growth under thin film confinement. A higher crystallinity could be partially regained by extended isothermal crystallization at elevated temperatures. Much faster cooling, with rates above about 100 Ks^?1 led to a partial suppression of crystallization even for thick films. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1791–1801     

Enthalpy of fusion of poly(3‐hexylthiophene) by differential scanning calorimetry

The enthalpy of fusion for a perfect, infinite poly(3‐hexylthiophene) (P3HT) crystal () must be known to evaluate the absolute crystallinity of P3HT. This value, however, is still ambiguous as different values have been reported using various experimental techniques. Here, we extrapolate the enthalpy of fusion for extended chain crystals of oligomeric P3HT to infinite molecular weight and obtain a value of 42.9 ± 2 J/g employing differential scanning calorimetry with a correction based on grazing incidence small angle X‐ray scattering data. Also, we define the onset of chain folding within P3HT crystallites at a chain length of 5 Kuhn segments. Knowledge of allows calculation of P3HT percent crystallinity in thin films for applications such as organic field effect transistors and solar cells. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 1469–1475     

Interaction parameters of crystalline/crystalline polypropylene/poly(butene‐1) blends: Effect of molecular fractionation

Compatibility of crystalline/crystalline polypropylene (PP)/poly(butene‐1) (PB‐1) blends was investigated via the method of equilibrium melting temperature depression followed by determining the polymer–polymer interaction parameter (χ) using the Nishi–Wang equation. The composition variation of the equilibrium melting temperatures of blends (T) was determined with the Hoffman–Weeks plot. The T and its variation with the blend composition depended on the crystallization temperature range. The morphological effect of the blend composition was not a contribution factor for the T depressions of PP and PB‐1 in the blends. The interplay of the dilution effect and molecular fractionation effect of the amorphous component on crystallization of the crystalline component in the blends governed the relation of T with the blend composition. The calculated χ values were negative depending on the blend composition. The negative χ values suggested that PP and PB‐1 in the amorphous region were compatible. The composition variation of the χ values was attributed to the molecular fractionation effect during crystallization. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 638–648, 2002; DOI 10.1002/polb.10125     

Polydispersity of ethylene sequence length in metallocene ethylene/α‐olefin copolymers. I. Characterized by thermal‐fractionation technique

In this article, the polydispersity of the ethylene sequence length (ESL) in ethylene/α‐olefin copolymers was studied by atomic force microscopy (AFM) and the thermal‐fractionation technique. The crystal morphology observation by AFM showed that morphology changed gradually with decreasing average ESL from complete lamellae over shorter and more curved lamellae to a granular‐like morphology, and the mixed morphology was observed after stepwise crystallization from phase‐separated melt. This result indicated that the ethylene sequence with different lengths crystallized into a crystalline phase with a different size and stability at the copolymer systems. The thermal‐fractionation technique was used to characterize the polydispersity of ESL. Three of the following statistical terms were introduced to describe the distribution of ESL and the lamellar thickness: the arithmetic mean L?_n, the weight mean L?_w, and the broadness index I = L?_w/L?_n. It was concluded that the polydispersity of ESL could be quantitatively characterized by the thermal‐fractionation technique. The effects of temperature range, temperature‐dependent specific heat capacity C_p of copolymer, and the molecular weight on the results of thermal fractionation were discussed. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 813–821, 2002     

Novel characterization of the crystalline segment distribution and its effect on the crystallization of branched polyethylene by differential scanning calorimetry

Based on a thermal segregation treatment, a novel semiquantitative method for the characterization of the crystalline segment distribution in branched polyethylene copolymers was established by the results of differential scanning calorimetry being treated with the Gibbs–Thomson equation. The method was used to describe the segment distribution of Ziegler–Natta‐catalyzed linear low‐density polyethylene (Z–N LLDPE), metallocene‐catalyzed linear low‐density polyethylene (m‐LLDPE), and a commercial linear low‐density polyethylene with a wide molecular weight distribution. The isothermal crystallization kinetics of Z–N LLDPE and m‐LLDPE were studied to assess the effect of different segment distributions. According to their molecular characteristics, the crystallization behaviors were analyzed. They indicated that the different segment distributions of the two polymers resulted in different crystallization processes, including the nucleation and growth of crystals under various crystallization conditions. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2107–2118, 2002     

Long‐term X‐ray stimulated crystallization of poly(N‐methyldodecano‐12‐lactam) in blend with poly(styrene‐stat‐acrylic acid)

The effect of X‐ray irradiation on crystallization of the blend of poly(N‐methyldodecano‐12‐lactam) (PMDL) with 29.5% of statistical copolymer poly(styrene‐stat‐acrylic acid) (PSAA) was studied using DSC, WAXD, and solid‐state ¹³C NMR methods. Significant acceleration of crystallization was found in the as‐prepared X‐ray irradiated (XI), that is, WAXD‐measured, samples compared with the nonirradiated (NI) ones. In the XI blend, the incubation period was shortened and crystallization proceeded at significantly higher rate. In the asymptote, after 100–120 days, both NI and XI samples reached the same final crystallinity of about 18%. The second DSC runs indicated that the stimulating effect of X‐ray irradiation was eliminated by heating the sample during the first run. The ¹³C NMR studies have shown that PMDL chains crystallize exclusively in cis conformation on the C? N bond. Both in neat PMDL and in the blend with PSAA, the XI samples contained a significantly higher proportion of cis conformers in amorphous phase than the NI samples. It is suggested that energy absorbed by the sample during the standard WAXD measurement helps overcome the barrier of the trans/cis transition in the PMDL molecules. This opens the way to the formation of a higher number of critical equilibrium nuclei and, finally, results in accelerated crystallization of the XI samples. No irreversible changes were found in the XI samples. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 311–321, 2008     

Scaling of the molecular weight‐dependent thermal volume transition of poly(N‐isopropylacrylamide)

A series of narrowly distributed poly(N‐isopropylacrylamide) (PNIPAM) with molecular weight ranging from 8 × 10⁴ to 2.3 × 10⁷ g/mol were prepared by a combination of free radical polymerization and fractional precipitation. An ultrasensitive differential scanning calorimetry was used to study the effect of molecular weight on the thermal volume transition of these PNIPAM samples. The specific heat peak of the transition temperature (T_p,0) was obtained by extrapolation to zero heating rate (HR) because of the linear dependence of the transition temperature (T_p) on the HR. The relation between T_p,0 and the degree of polymerization (N) was investigated. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1388–1393, 2010     

Thermal properties of single walled carbon nanotube‐silicone nanocomposites

The effect of single walled carbon nanotube (SWCNT) fillers on the low temperature thermal properties and curing behavior of SWCNT‐silicone nanocomposite are reported for the first time. The SWCNT‐silicone composites were prepared by different mixing procedures and characterized by differential scanning calorimetry (DSC). Solution mix, with the aid of sonication and soaking achieved better dispersion of SWCNTs in the silicone. The adding of SWCNTs in polymer seriously hindered the curing of silicone elastomer. The hindrance increased with increasing concentration of SWCNT and the quality of dispersion. The glass transition temperatures (T_g) of the nanocomposites were found to be independent of the SWCNT addition, although, the steps in the heat capacity (Δc_p) of the glass transition were smaller with increasing SWCNTs concentration. The melt crystallization behavior was strongly dependent on the concentration and dispersion of SWCNT in the polymer. The cooling scan showed that the higher concentration and the better dispersion of SWCNTs in the silicone resulted in higher percentage of melt crystallization of this nanocomposite. The correlation of the change of thermal properties to the dispersion of CNT in polymer may be used to determine the quality of SWCNT dispersion in silicone polymer. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1845–1852, 2008     

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     

Carboxylic acid‐containing benzoxazines as efficient catalysts in the thermal polymerization of benzoxazines

The autocatalytic thermal polymerization behavior of three benzoxazine monomers containing carboxylic acid functionalities is reported. Several mixtures of these carboxylic monomers and 3‐phenyl‐3,4‐dihydro‐2H‐1,3‐benzoxazine were prepared and their thermal polymerization behavior was analyzed by differential scanning calorimetry. The acid character of these reactive monomers increases the concentration of oxonium species, thus catalyzing the benzoxazine ring opening reaction. In this way the polymerization temperature decreased by as much as 100 °C in some cases. The existence of decarboxylation processes at high temperatures has been established by FTIR‐ATR and related to the increase in thermal stability observed by TGA in some cases. A relationship between the presence of carboxylic groups in the resulting materials and their flame retardancy behavior has also been established. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6091–6101, 2008     

Temperature memory effect and its stability revealed via differential scanning calorimetry in ethylene‐vinyl acetate within glass transition range

In this article, we reveal the temperature memory effect (TME) in a commercial thermoplastic polymer, namely ethylene‐vinyl acetate (EVA), within its glass transition range via a series of differential scanning calorimeter (DSC) tests. In addition, we investigate the influence of heating holding time and also compare the observed TME in current study with that of shape memory alloys (SMAs). It is concluded that the TME via DSC (without any macroscopic shape change) is achievable within the glass transition range of a polymer. Conversely, although the observed TME shares the many similar features as those in SMAs, due to the nature of micro‐Brownian motion in the glass transition of polymers, the resulted TME is strongly affected by the heating holding time. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1731–1737     

Crystallization and melting of narrow composition distribution polyethylenes: Investigation and implications of crystal thickening

The crystal structure produced during the isothermal crystallization of polyethylene (PE) copolymers with a broad range of comonomer concentrations was determined by the measurement of the melting endotherms directly after crystallization. PE copolymers with higher concentrations of short‐chain branches (≥10 branches per 1000 total carbon atoms) exhibited strong resistance to crystal thickening during isothermal crystallization. Negligible thickening, estimated to be only about 0.1 nm in 10 min of isothermal crystallization, was observed. The side‐chain branches apparently acted as limiting points of chain incorporation into the crystals, which exhibited great resistance to the modification of their position, that is, crystal thickening. Even with long periods (up to 8 h) of isothermal storage, crystal thickening was very small or negligible, about 0.3 nm. The crystal thickness was calculated from differential scanning calorimetry data. The behavior of copolymers with lower branching concentrations and the unbranched PE homopolymer was quite different from that of the copolymers with higher branching. Polymers with low or no branching exhibited the initial crystallization of a thinner crystal population, which thickened substantially with increasing time. The thickening observed for these lower or unbranched polymers was an order of magnitude larger, that is, 1.6–2.0 nm in 10 min of isothermal crystallization. Copolymers with higher concentrations of branching had relatively short sequence lengths of ethylene units between branch points, and this resulted in strong control over the crystal thickness by the branch points and great resistance to crystal thickening, even with long times of isothermal crystallization. Copolymers with low concentrations of branching had relatively long sequence lengths of ethylene units between branch points, and this resulted in little control over the crystal thickness by the branch points and rapid crystal thickening upon isothermal crystallization. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 235–246, 2003     

Effect of annealing time on the self‐nucleation behavior of semicrystalline polymers

It is widely known that when a polymer is heated just above its melting point and is kept at a given temperature (denoted T_s) for a short time, when it is cooled down its nucleation density increases and its peak crystallization temperature shifts to higher temperatures, as detected for instance by differential scanning calorimetry (DSC). The T_s temperature range where the described process occurs has been named Domain II self‐nucleation (SN) because the selected T_s temperatures are high enough to melt the polymer without causing detectable annealing of any remnant crystals by DSC. Experimental results obtained by DSC, polarized light optical microscopy (PLOM), and rheology indicate that these techniques are unable to detect any remaining crystal fragments in Domain II. Our kinetic results demonstrate that Domain II SN is a transient phenomenon that can even disappear if enough time at T_s is allowed. Results of the study of the time dependence of the SN effect indicates two possibilities: (a) if crystal fragments are present (even if undetected by the employed techniques) their final melting is a very slow process (in the order of hours); (b) if all crystallites have melted in Domain II, then it may be more plausible to reinterpret self‐nuclei as arising from “precursors” whose detail nature has not been the subject of this investigation but that can be regarded as either a residual segmental orientation in the melt (i.e., a melt memory effect) or a mesophase in a preordered state. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1738–1750, 2006     

Nonisothermal crystallization kinetics of in situ nylon 6/graphene composites by differential scanning calorimetry

The nonisothermal crystallization kinetics was investigated by differential scanning calorimetry for the nylon 6/graphene composites prepared by in situ polymerization. The Avrami theory modified by Jeziorny, Ozawa equation, and Mo equation was used to describe the nonisothermal crystallization kinetics. The analysis based on the Avrami theory modified by Jeziorny shows that, at lower cooling rates (at 5, 10, and 20 K/min), the nylon 6/graphene composites have lower crystallization rate than pure nylon 6. However, at higher cooling rates (at 40 K/min), the nylon 6/graphene composites have higher crystallization rate than pure nylon 6. The values of Avrami exponent m and the cooling crystallization function F(T) from Ozawa plots indicate that the mode of the nucleation and growth at initial stage of the nonisothermal crystallization may be as follows: two‐dimensional (2D), then one‐dimensional (1D) for all samples at 5–10 °C/min; three‐dimensional (3D) or complicated than 3D, then 2D and 1D at 10–20 and 20–40 °C/min. The good linearity of the Mo plots indicated that the combined approach could successfully describe the crystallization processes of the nylon 6 and nylon 6/graphene composites. The activation energies (ΔE) of the nylon 6/graphene composites, determined by Kissinger method, were lower than those of pure nylon 6. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 49: 1381–1388, 2011