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Thermally stimulated depolarization current is applied to study the dielectric relaxations coexisting from 80 to 380 K in the PLLA/starch, immiscible biodegradable blend system. The relaxation parameters are determined for chain mobilities at different ranges, whether in the amorphous or cold-crystallized state for PLLA, and totally amorphous one for starch as demonstrated by wide-angle X-ray scattering experiments. The PLLA crystallization is favored by the presence of starch, in both the crystallinity degree reached and the crystallization time. The effect of moisture is followed for both the local modes and the segmental mobilities, where a bimodal relaxation for starch sweeps the temperature range, thus evidencing the heterogeneities existing in the starch disordered phase. The moisture plasticization effect is estimated and shows differences in the water absorption in starch either neat or as a minority component. The onset of the segmental mobility in PLLA is independent of composition or crystallinity, but the large intensity decrease observed when PLLA cold-crystallizes evidences the simultaneous formation of a rigid amorphous fraction and the crystallites. The normal relaxation mode is recorded in amorphous PLLA whether neat or blended, which again demonstrates the absence of interactions among the blend components. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016, 54, 680–691

Poly(e-caprolactone-ran-e-caprolactam) random copolymers, P(CLo-ran-CLa), were studied in a wide composition range (0 ≤ PCLo ≤ 55 wt %) and in the wet and dry states. Both crystalline and amorphous phases of the poly(ester amide)s were characterized, the first by wide-angle X-ray scattering and the latter by the thermally stimulated depolarization current technique. Only PCLa presented 3D order, i.e., γ* and α structures, in addition to increasing lamellar thicknesses as PCLo amount rises. The amorphous phase of wet PCLa shows additionally to moisture plasticization a loss of rigidity due to the presence of PCLo units, which affects both segmental and local mobilities. Two cooperative modes are caused by the intercalated water with two different bounds (loosely, tightly), and their behavior during the drying process is the result of two competing effects, i.e., the loss of moisture and the coexistence of the PCLo segments. In the dry state the miscible amorphous phase presents a single drastic composition...

The early stages of the cold crystallization process and the formation of a rigid amorphous phase as seen by the dielectric response of polylactide, PLA, and composites polylactide/carbon nanotubes, PLA/CNT, are studied here by broadband dielectric spectroscopy for CNT concentrations below percolation. The presence of precursors during the nucleation and crystallization process is demonstrated by the existence of a time shift between the decline in the number of mobile segments and the growth of a 3D ordered phase as seen by variable temperature wide angle X-ray scattering measurements. Also, the loss of the mobile amorphous phase is not justified by the slow lamellar growth in identical conditions. The variation of the molecular dynamics, either for short range reorientations or cooperative motions, is followed in both amorphous and semicrystalline states. The changes observed in the composites PLA/CNT show a moderate heterogeneous nucleating effect of the nanofiller and a sensitivity of the three subglass transitions to the chain ordering. The relaxation parameters of the segmental relaxation are not very sensitive to the presence either of lamellae or of the nanofiller.

Nanocomposites based on polycarbonate (PC) and different amounts of untreated graphene nanoplatelets (GnP) (from 1 to 7 wt %) were prepared by melt blending. The nanocomposites were thoroughly characterized employing the following techniques: broad band dielectric spectroscopy, thermally stimulated depolarization currents, differential scanning calorimetry, tensile testing, dynamic mechanical thermal analysis, and water vapor, carbon dioxide and oxygen permeability measurements. The presence of a MWS relaxation mode indicated the accumulation of electrical charges trapped at the interfaces of the polycarbonate with graphene 2D platelets. The addition of GnP produced nanocomposite materials with enhanced mechanical and barrier properties. The melt mixed PC/graphene nanocomposites prepared here exhibit well-balanced properties, even though unmodified graphene nanoplatelets were used. In addition, the nanocomposites were obtained by a single extrusion process, which is easily scalable for industrial applications. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 134, 44654.

After DC and AC conductivity measurements, percolation parameters, universality, and time-temperature-concentration superposition are evaluated in biocomposites based on poly(lactide) loaded with multiwalled carbon nanotubes either carboxylic, PLA/c-CNT, or pure but with a larger aspect ratio, PLA/LAR-CNT, in weight concentrations up to 7%. The polymer matrix is either 100% amorphous or cold-crystallized. Wide angle X-ray scattering is used to extract the crystallinity at each temperature. The nucleating effect for the cold crystallization of the PLA is greater for the LAR-CNT than for the carboxylic ones. DC and AC conductivities are measured in broad frequency and temperature ranges, from 1 mHz to 1 MHz and from 133 to 378 K, respectively. The critical percolation value increases for c-CNTs (from 1.8 to 2.4 vol%) upon cold crystallization of the PLA matrix as the formation of a conductive path is hindered by the existence of a crystalline phase, which is dominant over the reduction of the amorphous regions. No significant changes upon crystallization were found in the critical concentration value (0.6 vol%) for the LAR composites, where the conductive path is 2D. The universal scaling found here for different concentrations is lost when temperature varies. However, time-temperature superposition is present for each concentration of LAR or carboxylic CNTs. POLYM. COMPOS., 2013. © 2012 Society of Plastics Engineers

The effect of adding corn oil (CO) and corn germ (CG) on the thermal and mechanical properties of corn semolina (CS) was investigated. The lipids concentration employed were 2% and 3% of CO or CG. The thermal transitions were studied in a moisture content range of 3–27% (d.b.), by means of dynamic mechanical thermal analysis (DMTA) and differential scanning calorimetry (DSC) techniques. Wide angle X-ray scattering (WAXS) experiments showed that type-V amylose–lipid complexes were formed with the native lipids within the corn semolina during thermo-moulding and that re-crystallization to a type-A structure, favored by the added lipids, occurred upon storage in high relative humidity (RH) environments. Two thermal events were observed during the first DSC scan and tan δ DMTA curves. The first one appearing at around 55–60 °C was attributed to a possible phase separation or ageing phenomenon taking place during storage of the samples, while the second was ascribed to the glass transition temperature of CS. It was found that addition of both, CO and CG, reduced the moisture content required for these transitions to appear. The expected decrease in the glass transition temperatures with moisture content was well described by the Gordon–Taylor equation. The addition of CO and CG also causes plasticization of CS. Hence, corn germ meal can be used as a lipid source that is more convenient to handle than liquid fats. However, the CS Tg values were independent of the lipids content. Tensile properties of CS and CS-lipid systems were found to be influenced by the moisture content, the physical state of the samples, and their composition.

Two series of copolymers of styrene with di-n-alkyl itaconates or methyl n-alkyl itaconates with n-alkyl side chains of 12, 14, 16, 18, and 22, using different compositions in the feed have been prepared in bulk via radical at 60 °C with AIBN as initiator. In most of the cases the copolymers were obtained in goods yields, their composition being close to the feed composition and their physical states depending on the composition and the itaconate structure. The copolymers were characterized by FTIR and NMR spectroscopy. The 1H NMR studies indicate that the copolymers have a mainly random distribution of the monomeric units. The thermal degradation process occurs in one step with decomposition temperatures intermediate between those of polyitaconate and polystyrene. Finally, the alkyl side chains of the itaconate moieties are able to crystallize in a paraffinic phase where the melting temperature and enthalpy increase as the itaconate content and the side chain length rise.

Biodegradable poly(butylene succinate)/polylactide (PBS/PLA) blends with various blending ratios were prepared by melt mixing for morphological and rheological studies. Dynamic rheological measurements were performed on the blend systems and the viscoelastic responses were analyzed with several emulsion models. The results show that the PBS/PLA is an immiscible blend system with very narrow cocontinuous region and high percolation threshold. The phase inversion point could be precisely predicted by the small-amplitude oscillatory shear (SAOS) response. The Palierne model gave a better description of the viscoelastic response of PBS/PLA blends than that of the Gramespacher and Meissner (G-M) model. In addition, the interfacial tension between the two polymers was measured by several techniques, such as surface property characterizations, deformed drop retraction, and rheological approaches. The differences observed by these various methodologies were then further explored. Moreover, the melting and crystal...

Dc and ac conductivities in a broad angular frequency, 2π × 10−3 s−1 < ω < 2π × 107 s−1, and temperature range, 133 K < T < 323 K, were measured in poly(e-caprolactone)/multiwalled carbon nanotube nanocomposites as a function of weight concentration (0 wt % ≤ p ≤ 3 wt %) . The universal dynamic response was observed at low p values, and the parameters were adjusted by working in several domains. Scaling laws predicted by the variation of dc conductivity as a function of p or characteristic frequency in percolation theory were followed and showed the formation of a 3D percolative cluster at concentration values as low as 0.3 wt %. The existence of tunneling conduction was proved, and its independence on temperature indicates that we are in the presence of a conventional tunnel effect among nanoparticles not yet in physical contact, through energy barriers made by the polymer chains. All these combined facts allowed construction of a master curve evidencing the time−temperature−composition superposition exi...

Starch complexes were obtained from activated and pregelatinized cassava starch (AS) or carboxymethyl starch (CMS) by using quaternary ammonium salts (QAS). The synthesis of the CMS was carried out by a single or double step carboxymethylation reaction with monochloroacetic acid. Different parameters were assayed to prepare the ionic complexes: CMS or AS as starting materials, anhydroglucose unit/QAS ratio, and length of the alkyl chain of the alkyltrimethylammonium bromide (C n TAB) salt. The products were characterized by FTIR, 1 H and 13 C NMR, and the Kjeldhal method. The results indicated a much more favorable complex formation when using CMS, obtaining the highest degree of substitution or complexation (0.72) and reaction efficiency (0.96) when C 18 TAB was employed. DSC and WAXS experiments evidenced the crystallization of the octadecyl chain introduced in the starch, exhibiting a dependence on sample water content. TGA and TVA analysis showed the stability of the complexes up to ∼150 °C and that degradation takes place in at least two stages with the release of the surfactant moiety in a first stage and the degradation of the starch skeleton in a second stage.

Gamma irradiation effect over the properties of slow cooled and fast cooled HDPE/LDPE 10/90 blend was studied. The blend and the neat polyethylenes were irradiated at room temperature in the presence of air using the following doses (4.8 kGy/h): 0, 50, 150, 400 and 1000 kGy. Differential scanning calorimetry (DSC) experiments were carried out using the following heating rates: 5, 10 and 20 °C/min. DSC results for the slow and fast cooled blend showed traces with three melting peaks and with increasing irradiation dose two melting peaks were obtained, i.e. the high melting peak shifts toward lower temperatures to merge with the intermediate melting peak into one endotherm. No changes in crystal structure by X-ray diffraction were found as a result of samples irradiation. Radiation crosslinking prevents crystal rearrangements during heating in the DSC. Gel content and melt flow index (MFI) measurements showed that radiation induced a high degree of crosslinking for all samples; gel content values were above 50% and a drop of more than 90% in the MFI was found. Irradiation of slow cooled samples resulted in larger values of gel content and lower MFI values than for fast cooled samples, mainly because of the higher degree of crosslinking for the former.

DC and AC electrical conductivity of bionanocomposites based on the immiscible polymer blend poly(epsilon-caprolactone)/polylactide (PCL/PLA, w/w 70/30), loaded with multiwall carbon nanotubes (CNT), were studied in a wide frequency range, 10(-3)or = for = 10(7) Hz from 143 to 313 K. The nanofiller concentration ranged from 0 to 4 wt % and it was shown to be selectively located in the PCL phase. The PCL crystallinity degree was not affected by the presence of CNT. The variation of the DC conductivity allowed the determination of the percolation threshold, p(c) = 0.98 wt %, and the critical exponent t = 2.2 of the scaling law. The linear dependence of log (sigma(DC)) versus p(-1/3) showed the existence of tunneling conduction among CNT not yet in physical contact. The temperature independent results indicated a conventional tunnel effect. The AC conductivity of the nanocomposites followed the predictions of the universal dynamic response and the s exponents were determined at low concentrations. Master curves are presented showing the length and temperature-time superpositions.

Copolymers of racemic β-butyrolactone ((R,S)-BL) and e-caprolactone (CL), were synthesized by ring-opening polymerization initiated by sodium hydride (NaH). The initiator exhibited a satisfactory catalytic activity, producing copolymers whose yields are greatly influenced by the feed monomer ratio, CL/BL. All polymers obtained were characterized by nuclear magnetic resonance (NMR), gel permeation chromatography (GPC), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and wide angle X-rays scattering, WAXS. The molar composition of copolyesters determined by 1H-NMR spectra, showed that the incorporation of CL is favoured over the incorporation of (R,S)-BL. Gel permeation chromatography and 13C-NMR spectra indicated that CL/BL copolymers had block sequence distribution. The TGA analysis of copolymers showed that these copolymers are stable up to temperatures near 200°C, followed by a decomposition process in two steps; the first one is attributed to the (R,S)-BL block degradation and the second to the remaining PCL block. The crystallization process of these copolymers was studied by DSC and WAXS showing that the amorphous (R,S)-BL segments chains did not affect the crystallinity of the PCL blocks.

The thermally stimulated depolarization current technique, TSDC, has been used to study the dielectric relaxations in cassava starch on semi-crystalline and amorphous samples. The A-type structure was observed by WAXS experiments and the variation of the crystallinity as a function of the moisture content, h, was followed on native starch. Retrogradation of the amorphous sample occurred at room temperature after 4 weeks in a closed vessel with a water activity 97.3%. In these conditions the humidity content reached a value of 28.5 wt% dry base and the crystallinity degree was comparable to that of the native starch. Three secondary relaxation modes were detected and attributed to short range orientations of polar groups and to main chain restricted motion. The influence of the moisture plasticization effect on the relaxation parameters of the local modes, was determined by decomposing the global TSDC curve in elementary Debye peaks with Arrhenius relaxation times. The main relaxation, α, which is proposed to be the dielectric manifestation of the dynamic glass transition, sweeps a wide temperature interval around room temperature as the sample dries, shifting to higher temperatures as a result of the plasticization of the polysaccharide by water molecules. The α peak deconvolution lead to the 2D relaxation time distribution and Vogel–Tammann–Fulcher parameters were obtained confirming the cooperative character of this mode. The transformed sample showed a bimodal distribution of segmental relaxation times that is interpreted as the existence of a heterogeneous amorphous phase: the mobile one which is similar to the original disordered phase present in semi-crystalline native starch and a more restricted one originated by the disruption of the crystalline lamellae during the pre-gelatinization process.

A series of comb like poly(p-n-alkylstyrene)s with linear alkyl groups, containing even numbers of carbon atoms from 12 up to 22 were synthesized by radical polymerization and characterized by FTIR, 1H NMR, TGA, TVA DSC, and WAXS. All polymers were obtained in good yields and were soluble in organic solvents as chloroform, dichloromethane or tetrahydrofuran and insoluble in methanol; they are stable up to temperatures near 300 °C. On the other hand, the alkylic side chains of all series are able to crystallize in a paraffinic phase in which the melting temperature and enthalpy increase with the methylene number of the n-alkyl chain.

The effect of water content on the glass transition temperatures of cassava starch was determined by differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA). Samples were transformed to the amorphous state by compression molding at high temperature (as demonstrated by wide angle X-ray diffraction, WAXS), and then the samples were moisture conditioned. Both DSC and DMTA showed that water anti-plasticized cassava starch at lower moisture contents, and plasticized it at higher water contents. Samples with higher moisture contents stored at room temperature, 45 °C and 80 °C underwent retrogradation as indicated by WAXS. Sorption isotherms of cassava starch showed that for a w values lower than around 0.85, the sorption capacity decreased with increasing temperature; while the opposite behavior was observed at a w > 0.85. This inversion point ( a w = 0.85) was attributed to the fact that more active sites were exposed to the adsorption processes, due to the enhanced molecular mobility promoted in the amorphous regions by starch crystallization.

The complex dielectric modulus, M ∗ ( ω , T ), for poly( e -caprolactone) has been obtained by inverting the complex dielectric permittivity data, e ∗ ( ω , T ) recorded in a wide temperature and frequency range. The analysis of the dielectric loss modulus spectra M ″( ω , T ) have been performed by using a simulated annealing Monte Carlo procedure in order to extract the relaxation parameters for each relaxation mode. Besides the local modes γ and β, the segmental α mode associated to the glass transition, the conductivity and the interfacial polarization peaks could be analyzed with a better precision than by using the conventional non-linear least squares method in e ″ domain. The merging of the α and β modes at high temperatures is much better defined due to the less significant contribution of the ionic conductivity in M ∗ formalism.

Poly(α- n -alkyl β- l -aspartate)s, P n AALAs, are comb-like polymers with rod-like helical conformations which present crystallinity for long alkyl side chains ( n > 10). Dielectric spectroscopy experiments for P n AALAs (10 ⩽ n ⩽ 18) show the existence at low temperatures of two secondary modes corresponding to localized motions of the carbonyl group. At higher temperatures two cooperative mobilities coexist. The first corresponds to the segmental mobility of the amorphous side chains and has the characteristic of a polyethylene-like dynamic glass transition common to various series of nanophase segregated side chain polymers with different morphologies. A second segmental mode is attributed to the restricted rotational motion of the rigid rods which is hindered when the spacing between rods decreases. An extension to the results found for other polymer series with shorter lateral chains is presented, showing the tendency to approximate amorphous polyethylene dynamics in these confined nanodomains of increasing sizes.

The morphology, nucleation, and crystallization of polyethylene/carbon nanotubes nanocomposites were studied. The nanocomposites were prepared by in-situ polymerization of ethylene on carbon nanotubes (CNT) whose surface had been previously treated with a metallocene catalytic system. The effects of composition (5−22% CNT) and structure of the nanotube (single, double, or multiwall, i.e., SWNT, DWNT, and MWNT) were evaluated, and an excellent nucleating effect on polyethylene matrix was found regardless of the CNT type in comparison to neat high-density polyethylene (HDPE) prepared under identical conditions. The CNT were found to be more efficient in nucleating the HDPE than its own crystal fragments, a result obtained by self-nucleation studies. Differential scanning calorimetry (DSC) and transmission electron microscopy (TEM) results showed that under both isothermal and dynamic crystallization conditions the crystals produced within the nanocomposite HDPE matrix were more stable than those produced in...

Thermally stimulated depolarization currents, TSDC, wide-angle X-ray scattering, WAXS, differential scanning calorimetry, DSC, and polarized light optical microscopy, PLOM, have been used to examine poly(L-lactide)-b -poly( $ \upvarepsilon$ -caprolactone) diblock copolymers in a wide composition range. Both components are crystallizable and the miscibility in the amorphous phase has been determined from the behavior of the primary relaxations which are the dielectric manifestation of the glass transition, and also from the superstructural morphology revealed by PLOM and the compositional dependence of the melting points as determined by DSC. Distinct segmental mobilities in the amorphous phase which can be well resolved by TSDC are present; the $ \upalpha$ mode of the slower component shifts to lower temperatures as the PCL content increases while the glass transition of neat PCL is present for all compositions. A relaxation times bimodal distribution is apparent for PCL-rich copolymers. The composition dependence of the multiple glass transitions detected in these weakly segregated copolymers are predicted by the self-concentration model for a miscible blend made of components with a large Tg contrast.

A series of complexes from poly(itaconic acid) and poly(mono methyl itaconate) and alkyltrimethylammonium bromide surfactants with linear alkyl groups, containing even number of carbon atoms from 12 up to 22 were synthesized. The complexes were obtained in good yields and were soluble in organic solvents and stable up to temperatures near 150 °C. On the other hand, the paraffinic side chains are able to crystallize depending on the methylene number of the surfactant n-alkyl chain.

The effect of blending poly(styrene-co-maleic anhydride) with 14 mol% MA (PSMA14) with poly(ɛ-caprolactone) (PCL) is studied by calorimetry, X-ray diffraction, dielectric techniques, and microscopy. Variations in PCL crystallization, melting temperatures and crystallinity degree were observed. Additionally, the presence of a wide and asymmetric enthalpic step, whose position follows Fox predictions, demonstrates miscibility between the blend components. This is in agreement with the interlamellar location of PSMA14. Thermally stimulated depolarization techniques evidenced two segmental dynamics, with distinct compositional variations due to the local differences in composition perceived by each component as a consequence of chain connectivity. The two effective glass transition temperatures vary with composition, in agreement with the self-concentration model predictions when using the Kuhn's segment length for each component. From isothermal crystallizations a marked depression of the PCL equilibrium melting point ( T m o ) is observed in the blends together with an increase in the half-crystallization times, τ1/2, as the content of PSMA14 grows. PCL-rich blends exhibited ring-banded spherulites, with a ring periodicity that increased with crystallization temperature and with PSMA14 content. Preliminary results of the phase separation process are given from samples that were thermally treated under different conditions.

A first attempt was made to produce novel ABC triblock terpolymers with three potentially crystallisable blocks: polyethylene (PE), poly(ethylene oxide) (PEO), and poly(e-caprolactone) (PCL). Polybutadiene-b-poly(ethylene oxide) diblock copolymers were synthesized by living anionic polymerization. Then, a non-catalyzed thermal polymerization of e-caprolactone from the hydroxyl end group of the PB-b-PEO diblock precursors was performed. Finally, hydrogenation by Wilkinson catalyst produced PE-b-PEO-b-PCL triblock terpolymers. Side reactions were detected that lead to the formation of undesired PCL-b-PEO diblock copolymers, however, these impurities were successfully removed by purification. A range of triblock terpolymers with PCL and PEO minor components were prepared. Topological restrictions on the PEO middle block prevented this block from crystallizing while the complex crystallization behavior of the PE and PCL blocks was documented by DSC and WAXS measurements.

Polycarbonate/poly(e-caprolactone) (PC/PCL) blends are found to be miscible when extruded samples are studied without any further thermal treatment. PCL crystallizes in blends containing 60% or les...

In this work, the behavior of the crystallizable blocks within polystyrene- b -poly(ethylene oxide)- b -poly(e-caprolactone) linear triblock copolymers is studied. The apparent crystallization and melting temperatures of PEO and PCL can be coincident as a result of their close values, their dependence on the molecular weight of the blocks and on the relative amount of each component within the copolymers. When the content of both PEO and PCL is low, typically 20% or less, both blocks crystallized coincidentally upon cooling from the melt at very large supercoolings ( T c =−40 °C), suggesting that homogeneous nucleation has taken place. A S 63 EO 16 C 20 copolymer (where subscripts denote the weight fraction of the components) exhibited a small angle X-ray scattering (SAXS) pattern at room temperature that suggests a cylindrical morphology for the minor components, where the crystallization of PEO and PCL blocks can take place subsequently near −40 °C in a hard confinement fashion within the vitreous PS matrix. We have employed differential scanning calorimetry (DSC) to study the self-nucleation process and the results indicate that the difficulty in generating enough self-seeds to nucleate every isolated microdomain causes the disappearance of Domain II (or exclusive self-nucleation Domain ) and therefore a direct transition from complete melting ( Domain I ) to self-nucleation and annealing ( Domain III ) is observed. When the content of both PEO and PCL blocks is larger than 35%, a coincident crystallization can be observed as well as coincident melting. For a S 15 EO 37 C 48 triblock copolymer, PS is a minor phase and mixed spherulites composed of both PCL and PEO blocks were observed by Polarized Optical Microscope (POM) at appropriate supercoolings. In this case, the self-nucleation behavior is standard, and through its use the crystallization and melting process of both blocks can be separated. Wide angle X-ray scattering (WAXS) at different temperatures was used to corroborate the sequential melting of both semicrystalline blocks deduced by self-nucleation. Isothermal crystallizations were also followed by WAXS as a function of time and the results showed that depending on the crystallization temperature ( T c ), only the PCL block crystallizes (at high T c ), or the PCL block crystallizes first followed by the PEO at later times (at lower T c ).

New results of dielectric spectroscopy in semicrystalline nylon-6 samples with different moisture contents are presented by using a wide frequency (10-2−3 × 106 Hz) and temperature range (133−433 K). The dielectric absorption spectra in frequency domain are decomposed in Cole−Cole distributions corresponding to the local γ and β modes, two segmental α modes, and a high-intensity Maxwell−Wagner−Sillars relaxation. The presence of two segmental relaxations in the isothermal runs, attributed to the plasticized and the unplasticized α mode, is interpreted as the manifestation of two different length and time scales of cooperative motions. A quantitative comparison between the results obtained for the wet and dry samples, such as relaxation times variation, activation energies, Vogel−Tammann−Fulcher parameters, dielectric increments, and distribution widths, is presented for each mode and shows how the progressive drying of the sample during the experiment affects all these quantities.

A series of poly(mono n-alkyl itaconate)s, poly(methyl n-alkyl itaconate)s and poly(di n-alkyl itaconate)s with n ¼ 12; 14, 16, 18 and 22 have been prepared by radical polymerization. NMR studies point out that poly(methyl n-alkyl itaconate)s and poly(di n-alkyl itaconate)s are mainly syndiotactic polymers whereas poly(mono n-alkyl itaconate)s are obtained as almost atactic polymers. The characterization performed by DSC, solid state 13 C CP/MAS NMR and X-ray diffraction, indicates that the side chains of poly(mono n-alkyl itaconate)s and poly(methyl n-alkyl itaconate)s derivatives with more than 12 carbon atoms are able to crystallize in hexagonal lattices. In the case of poly(di n-alkyl itaconate)s, when the side chains contain 12 or more carbon atoms, they are able to crystallize also in hexagonal lattices. q 2003 Elsevier Science Ltd. All rights reserved.

Chain mobility in multiphase polymeric materials is studied by thermally stimulated depolarization currents and dielectric spectroscopy in poly(styrene)-b-poly(butadiene)-b-poly(c-caprolactone) triblock copolymers and poly(carbonate)/poly(c-caprolactone) blends. The variation in the relaxation time distribution of the dielectrically active components and in the number of orientable dipoles in the amorphous phases of these materials is interpreted as the result of the existence of a rigid amorphous phase constrained by the crystalline regions or in the case of the blends by a phase segregation which takes place when the crystallization process of the blend components advances. The mean relaxation times for the secondary and segmental motions are not affected when the phases are segregated.

Dielectric relaxations of polycarbonate (PC) and poly(e-caprolactone) (PCL) blends that were thought to be completely homogeneous in the amorphous phase from many previous calorimetric studies are performed by using the thermally stimulated depolarization currents technique. Samples kept for 18 months at room temperature were compression-molded and then either quenched or slowly cooled. Quenched samples evidenced a phase separation for the 20/80 PC/PCL composition and the existence of continuous concentration fluctuations for other blend compositions. The slowly cooled samples from the melt exhibited an increase of the crystallinity degree for both blend components, together with a segregation of a predominantly rich PCL phase and the appearance of high-temperature relaxations attributed to interfacial polarization. These findings are confirmed by new calorimetric results on the same blends and by transmission electron microscopy. The spherulitic growth rate also points to the coexistence of two phases wh...

Poly(ɛ-caprolactone)/starch biocomposites in a wide composition range were studied by thermally stimulated depolarization currents, TSDC, during the drying process following the effect on the dielectric relaxations of moisture loss and blend composition. PCL's cooperative chain mobility is unaffected by the presence of water which is mainly located in the starch inclusions as its segmental relaxation is fixed at 207K. The heterogeneities found in the amorphous phase of neat starch are also observed here as a bimodal α relaxation which shifts to higher temperatures as it dries. The blend plasticization by water molecules also affects the blend secondary relaxations showing how the local motions are hindered by the loss of water which is lower in the blend than in pure starch. The interfacial peak which is intermediate between the α relaxations of the two components is affected by the inclusions change from liquid to glassy state as the blend dries.

Thermal sampling peaks recorded after windowing polarization are studied for the segmental mode in poly(e-caprolactone). Also, numerical decompositions of the global thermally stimulated depolarization current peak into pure Debye contributions are performed with direct signal analysis (DSA) and simulated annealing direct signal analysis procedures for Arrhenius and Vogel–Tammann–Fulcher (VTF) temperature dependences, respectively. It is found that the results between the experimental and the numerical procedures agree very well and the approximations made in the analysis of the experimental curves are thus validated, despite the unphysical values for the relaxation parameters found by both methods when using Arrhenius relaxation times. On the contrary, when VTF relaxation times are used for the numerical decomposition, agreement is found with the results of isothermal dielectric absorption as a function of frequency, together with reasonable values for reorientation energies, pre-exponential factors and ...

The preparation of polystyrene-b-poly(ethylene oxide)-b-poly(-caprolactone) triblock co- polymers using three different strategies is described. Experimentally, a method we have called "thermal" is the simplest one of the three employed. However, it presents serious limitations for the preparation of high molecular weight triblock copolymers with low polydispersity. The titration method is a more elegant alternative to prepare the PS-b-PEO-b-PCL triblock copolymers. Nevertheless, the stoichiometric titration of the precursor terminal hydroxyl groups requires much expertise, and it becomes more difficult as the concentration of such terminal groups decreases when the precursor molecular weight increases. Finally, the sequential method may be regarded as the most convenient one. However, the experimental steps involved a solvent exchange during polymerization that must be performed under conditions of strict purity and high vacuum. Several triblock and pentablock copolymers of varying compositions and molecular weights were successfully prepared. The fact that these copolymers contain two crystallizable blocks, i.e., PEO and PCL, makes them very interesting from a structural point of view. The copolymers were found to be phase segregated according to evidence provided by DSC and WAXS. The crystallization and melting behavior of both PEO and PCL blocks is greatly affected by composition. Fractionated crystallization phenomena were detected when either one or both blocks constituted the minor components within the block copolymers.

In order to study the compatibility promoted in polyamide 6 (PA6) and ultra low-density polyethylene (ULDPE) blends by grafting polar groups into the ULDPE, several blend compositions were prepared in a twin screw extruder. The grafting agent was diethylmaleate (DEM), and the blend compositions prepared were 0, 20, 50, 80 and 100 wt.-% of PA6. The compatibility was evaluated by studying the rheological, thermal, morphological, and spectroscopic (infrared and dielectric) properties of the blends. The formation of a copolymer was observed by infrared spectroscopy after selective extraction of the components, presumably by the interaction of terminal NH 2 groups of PA6 and carbonyl groups of ULDPE(graft-DEM. Thermal properties showed changes due to compatibilization. For instance, fractionated crystallization of the PA6 component was observed when it formed the dispersed phase in reactive blends in view of the enhanced dispersion. Nucleation of the ULDPE component by the PA6 component was observed for reactive and non-reactive blends. The DSC melting results showed the presence of two crystalline forms of the PA6 in the blends. These were the less stable γ-form, predominant over the more stable α-form, in reactive blends, especially for the 20/80 and 50/50 wt.-% blend compositions. Dynamic rheological experiments provided data for fitting the Carreau viscosity model; the results revealed that longer characteristic times are obtained for compatibilized system. This was reinforced by the more elastic behavior that such systems presented in G'-G plots, as compared to the non-reactive ones. Dielectric spectroscopy revealed a noticeable shifting of the α-mode of the PA6 to lower temperatures for the 50/50-g, together with an enhancement of the β over the γ-mode which indicates the presence of tightly bound water. The T g depression could be due to the plasticization effect resulting from the substitution of intramolecular PA6 H-bonds by either water molecules or physical interactions across the interphases.

The high temperature dielectric relaxation process, observed above the glass transition temperature in poly(ϵ-caprolactone) is studied by Thermally Stimulated Depolarization Currents experiments. The characterization is made by using the windowing polarization technique, decomposing the complex high temperature relaxation into Debye-like peaks. The profile of each peak is then analyzed by using a general kinetic order model, and the origin of the complex relaxation is discussed through the analysis of the parameters obtained from the best fit to the model. The distribution of the trap depths is obtained and their activation energies is found to vary from 0.8 to 1.2 eV. The space charge accumulation is mainly responsible for this relaxation mode in poly(ϵ-caprolactone).

A family of four thermotropic polyesters starting with the poly(tetramethylene terephthaloyl bis-4-oxybenzoate), substituting either asymmetrically in the tetramethylene spacer or incorporating polar substituents onto the aromatic units of the mesogen, is studied by the Thermally Stimulated Depolarization Currents (TSDC) technique. The results are compared to the Dynamic-Mechanical Analysis at frequencies ranging from 0.1 to 1 Hz from 123 to 423 K. The unsubstituted polymer has a complex low-temperature TSDC spectrum corresponding to local reorientation modes due to the motion of the COO groups with different locations along the main chain. By comparing the effect of the Cl and CH3 substituents on the relative intensity and on the mean energies of the distribution of relaxation times determined by the DSA procedure, the lowest temperature mode is attributed to the COO peripheral groups and the modes located at higher temperatures, to the internal COO groups, which may be accompanied by adjacent segments. The mechanic and dielectric α-transitions are also very sensitive to the substituents, the addition of CH3 in the 1,4 flexible spacer shifting the glass transition temperature above room temperature. The existence of the three-dimensional order that is present in the materials with a linear spacer significantly broadens the α-relaxation. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 3038–3049, 1999

The existence of a distribution of relaxation times has been widely used to describe the relaxation function versus frequency in glass-forming liquids. Several empirical distributions have been proposed and the usual method is to fit the experimental data to a model that assumes one of these functions. Another alternative is to extract from the experimental data the discrete profile of the distribution function that best fits the experimental curve without any a priori assumption. To test this approach a Monte Carlo algorithm using the simulated annealing is used to best fit simulated dielectric loss data, ${\ensuremath{\varepsilon}}^{\ensuremath{''}}(\ensuremath{\omega}),$ generated with Cole-Cole, Cole-Davidson, Havriliak-Negami, and Kohlrausch-Williams-Watts (KWW) functions. The relaxation times distribution, $G(\mathrm{ln}(\ensuremath{\tau})),$ is obtained as an histogram that follows very closely the analytical expression for the distributions that are known in these cases. Also, the temporal decay functions, $\ensuremath{\varphi}(t),$ are evaluated and compared to a stretched exponential. The method is then applied to experimental data for $\ensuremath{\alpha}$-polyvinylidene fluoride over a temperature range $233 \mathrm{K}l~Tl~278 \mathrm{K}$ and frequencies varying from 3 MHz to 0.001 Hz. These data show the existence of two relaxation processes: the fast segmental ${\ensuremath{\alpha}}_{a}$ process associated with the glass transition and a ${\ensuremath{\alpha}}_{c}$ mode, which is slower and due to changes in conformation that can occur in the crystalline regions. The experimental curves are fitted by the simulated annealing direct signal analysis procedure, and the relaxation times distributions are calculated and found to vary with temperature. The decay function is also evaluated and it shows clearly its bimodal character and a good agreement with a KWW function with a temperature dependent $\ensuremath{\beta}$ for each mode. The relaxation plots are drawn for each mode and the Vogel-Tammann-Fulcher and Arrhenius parameters are found. The fragility parameter for polyvinylidene flouride (PVDF) is found to be 87, which characterizes this polymer as a relatively structurally strong material.

The analysis of Thermally Stimulated Depolarization Currents (TSDC) spectra in polymers requires the introduction of a distribution of relaxation times. Also, a decay of the induced polarization following a stretched exponential law can be used. Two different ways for introducing this effect in the TSDC equations are compared here together with the decomposition in elementary curves by a Simulated Annealing Monte Carlo procedure to find the distribution. It is found that the stretched exponential applied to computer generated curves corresponds in both cases to a nearly Debye process. Also the analysis of the α-peak of poly(e-caprolactone) with the three approaches are compared.

The effect of water sorption on the dielectric relaxation processes of nylon-6 samples with water concentrations ranging from the dry to the water-saturated polymer has been studied by thermally stimulated depolarization currents experiments in a broad temperature range, from 77 to 365 K. The strengths of the low-temperature modes, y- and β-peaks, are affected in opposite ways by the water concentration, h, as the first one shows a decrease in intensity and the second one grows as h increases. The precise determination of the relaxation parameters is made by the decomposition in elementary Debye processes and best fitting to the experimental profile of the complex peak. For h < 3%, the reorienting energies are almost independent of the water content, and the most significant intensity variations occur. The firmly bound water is held responsible for these effects. As for the higher temperature zone besides the α-peak, which is the dielectric manifestation of the glass transition, intermediate temperatures modes are observed at high h values and are originated by the loosely bound water, while the highest temperature peak is attributed to a Maxwell-Wagner interfacial polarization. The characteristic parameters of the α-mode are determined and related to the plasticization effect of water.

The αa-mode (associated to the dynamic glass transition) in PVDF-α has been studied by Thermally Stimulated Depolarization Currents (TSDC) and Dielectric Spectroscopy (DS) techniques. The distribution of relaxation parameters, reorientation energies, characteristic temperature, and preexponential factors of the Vogel–Tammann–Fulcher relaxation times have been precisely determined by using the Simulated Annealing Direct Signal Analysis applied to a partially discharged TSDC αa peak. This distribution has been used to predict the variation of the dielectric loss, e″(ω, T), in the temperature and frequency range where the DS measurements were made on the same material. The simulated e′(T, ω) for various ω, are compared to the experimental values. The width of the peak is always too low, due to the restricted distribution used for the generation of the curves. A relaxation map including the TSDC results is used to determine the relaxation time variation. In the limited frequency range where the AC DS experiments are performed (102 ≤ f ≤ 105 Hz) a master curve is drawn and the exponents of the frequency dependence are found at low and high frequency; also, a fitting to the Havriliak–Negami distribution is successfully performed. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 2483–2493, 1997

A series of tyrosine-derived polycarbonates with different lengths (2 ≤ n ≤ 8) for the alkyl ester pendent chain were studied by measuring thermally stimulated depolarization currents (TSDC). The observed spectra could be separated into three regions: the low-temperature zone with a broad, complex β band (80-240 K), the intermediate zone (250-300 K), and the high-temperature zone (300-400 K) with a sharp a peak. The application of direct signal analysis ( DSA) to decompose the complex peaks into elementary processes led to the determination of the relaxation time distribution and temperature dependence of each process. The variation of the relaxation parameters as a function of the pendent chain length facilitated the tentative identification of the relaxation mechanisms responsible for the observed current peaks. It is proposed that as the temperature increases one observes, first, the individual motion of each polar group, then the concerted motion of the entire pendent chain, and, last, the movement of the polymer backbone.

The present work describes the characterization and thermal properties of hydrophobic starch obtained by the esterification of cassava starch with acyl imidazoles, acid chlorides and methyl ester derivatives of fatty acids with n-alkyl chains with 12–22 carbon atoms, in order to compare the dependence of their properties as a function of the length of the side chain and the methodology used for their synthesis. The n-acyl starches presented degrees of substitution (DS) between 0.06 and 1.2. Most of the derivatives obtained with acyl imidazoles were found to be stable at temperatures up to 300 °C, whereas those synthesized with acid chlorides or methyl ester decomposed below. Finally, when the n-acyl starches were substituted with n-alkyl side chains of 16 or more carbon atoms, they were capable to crystallize in separate paraffinic phases independent of the starch backbone.

The relaxations occuring in poly(triethylene oxide terephthaloyl bis(4-oxybenzoate)), PTrETOB, were studied by thermally stimulated depolarization currents technique (TSDC), and dynamic mechanical analysis (d.m.a.), and the results compared with those obtained by differential scanning calorimetry, thermo-optical analysis and wide angle X-ray diffraction. The low temperature relaxation observed by TSDC and d.m.a. is a complex band and as the temperature increases there are three very sharp and intense peaks which are attributed, by comparing the results of the various techniques used here, to the primary glass transition of the amorphous zones of the material, to an additional crystallization process and to the crystal-liquid crystal transition. Our results show the existence of a phase transition from this smectic mesophase to a nematic one at 210°C and a transition to the isotropic melt at 250°C. The direct signal analysis was applied to the low temperature spectrum in order to decompose the complex band in elementary curves characterized by Arrhenius relaxation times. It was found that the low temperature band covers a wide energy range from 5.1 to 15.9 kcal mol −1 and that the pre-exponential factor is almost constant in this range. Similar results were obtained for the polyester with four oxymethylenic units in the spacer. These results can be understood if the mechanisms responsible for this low temperature relaxation are very localized motions of the COO groups of the mesogenic unit, whose parameters are not affected by changes in the length of the spacer.

New thermally stimulated depolarization currents (TSDC) results on LLD polyethylene functionalized with diethylmaleate polar groups are precisely computer fitted with the direct signal analysis technique. It is shown that the TSDC spectrum consists, with increasing temperatures, of a sub-γ peak, a sharp γ peak, and a β and an α relaxation. The first peak is analyzed in terms of Arrhenius relaxation times, whereas the γ and β transitions could only be fitted by using Vogel-Fulcher temperature dependence for the relaxation times. The best value for To obtained from both fittings is 69.7 K. This is a quantitative proof for the identification of the γ transition as one of the dielectric manifestations of the glass-rubber transition for polyethylenes, Tg = 136.5 K, which has been discussed extensively in the literature. The β relaxation, Tgβ = 237 K, has also the expected characteristic of a glass transition; the existence of two Tgs in polyethylene could explain our results. © 1996 John Wiley & Sons, Inc.

The Direct Signal Analysis is applied here to the decomposition of the whole TSDC peak in elementary curves with temperature dependencies for the relaxation times either Arrhenius or Vogel-Fulcher in crystalline (SrF 2 :Gd 3+ or La 3+ ) or amorphous materials (Bisphenol A Polycarbonate). The energy histogram obtained after fitting the complex peak gives the profile of the energy distributions ; Lorentzian distributions were found for the simple dipolar peaks and small clusters in crystalline materials, whereas for the β-band in PCBA, the distributions are Gaussian. The high temperature spectrum corresponds for both materials to very narrow distributions both for the Maxwell Wagner polarization originated high temperature peak in SrF 2 or for the glass rubber transition in PCBA. Vogel-Fulcher relaxation times had to be used in the latter case.

The relaxation behavior of poly(tetra ethylene oxide terephthaloyl-bis-4-oxybenzoate), PTETOB, was analyzed by thermally stimulated depolarization currents, TSDC, and dynamic mechanical techniques, DMTA, and the results compared with those obtained by differential scanning calcrimetry, thermo-optical analysis, and x-ray diffraction. In the low temperature region, −173–30°C, three main transitions were observed and assigned to the γ relaxation, the glass transition of the mesophase and the glass transition temperature of the amorphous material. The complex behavior observed in the range 110–160°C was as signed to a crystal-crystal transition which competed with the formation of a mesophase and afterward the formation of a smectic A mesophase. At higher temperatures, was observed the transition from the smectic A mesophase to a nematic one, prior to the isotropization temperature. In the TSDC experiments the formation of a permanent electret was detected and the charges trapped in the mesophase were canceled only at the isotropization temperature. © 1995 John Wiley & Sons, Inc.

A new method to evaluate the thermally stimulated depolarization current curves based on the direct signal analysis is first applied here to the fitting of computer-generated curves to test its validity and accuracy. The method consists in finding the N elementary curves that best fit the experimental spectrum. The adjustment of the τ0 values associated with each energy bin is also included in the fitting. The results are presented for a monoenergetic peak and a peak generated with a Gaussian broadened energy distribution both with a single τ0. Good agreement is also found when a random noise of width σ0 ≤ 0.01 Jmax is added to the data to simulate experimental errors. Experimental complex curves corresponding to the γ and β overlapping relaxations in DGEBA-EDA epoxy resin system are separated into their fine structure components. The complex band corresponding to water dipoles physisorbed in different sites of the microporosity of bituminous coal is analyzed and different processes are identified. The results are compared to those performed on cleaned peaks. Finally, the TSDC peak corresponding to the glass transition temperature in bisphenol-A polycarbonate is analyzed and could only be fitted by using a Vogel-Fulcher expression for the temperature dependence of the relaxation times. © 1994 John Wiley & Sons, Inc.

Ionic thermal currents (ITC) and electron paramagnetic resonance (EPR) experiments were performed to identify the different types of defects existing in Ca1−xGdxF2+x solid solutions, with x = 0.05% and 0.1%. The results show the presence of cubic and tetragonal centers together with cluster-associated relaxation peaks. Successive ITC runs were performed in order to duplicate recent results in which the ITC peaks were reported to change significantly in intensity, position and even in number after the application of an electric field. The results reported here show that there are no changes after successive ITC runs, neither in the ITC nor in the EPR spectra obtained from these crystals. Moreover, the absence of trigonal centers in these oxygen-free crystals is once more confirmed and the equilibration among the two dipolar types ascribed to the influence of the polarizing field is thus discarded in the CaF2:Gd3+ crystals.

Ionic thermal current (ITC) techniques were used to study the behaviour of water in two low-rank coals of

The combined results obtained on ${\mathrm{Ca}}_{1\mathrm{\ensuremath{-}}\mathit{x}}$${\mathrm{Gd}}_{\mathit{x}}$${\mathrm{F}}_{2+\mathit{x}}$ and ${\mathrm{Ca}}_{1\mathrm{\ensuremath{-}}\mathit{x}\mathrm{\ensuremath{-}}\mathit{y}}$${\mathrm{Lu}}_{\mathit{x}}$${\mathrm{Gd}}_{\mathit{y}}$${\mathrm{F}}_{2+\mathit{x}+\mathit{y}}$ solid solutions by ionic thermal currents and electron paramagnetic resonance techniques are presented for a wide range of x values. The ${\mathrm{Gd}}^{3+}$ ions are located in tetragonal and cubic sites, and in a variety of at least nine polarizable entities in the single-doped solid solutions whose range of existence and relaxation parameters have been precisely determined. In the double-doped crystals the ${\mathrm{Gd}}^{3+}$ probes are in constant concentration (y=0.0001) while the ${\mathrm{Lu}}^{3+}$ ions detected in the temperature range explored here constitute a very small fraction of the nominal concentration of the sample. The differences observed are accounted for by a scavenging of ${\mathrm{F}}_{\mathit{i}}^{\mathrm{\ensuremath{-}}}$ by clusters of increasing size in the single-doped matrix and by the existence of cubo-octahedra hexamers existing from very low doping levels in the double-doped crystals.