Temperature-modulated Differential Scanning Calorimetry Experiments Research Articles

Poly(lactic acid) phase transitions in the presence of nano calcium carbonate: Opposing effect of nanofiller on static and dynamic measurements

The effect of stearic acid-coated nano calcium carbonate (NCC) on transitions and chain mobility of poly(lactic acid) (PLA) was investigated. Dispersion state of NCC in polymeric matrix was explored using scanning electron microscopy and surface tension component measurements. Trends of PLA transitional phenomena were investigated using the results of dynamical mechanical analysis (DMA) and differential scanning calorimetry (DSC) in the nanocomposite systems based on PLA and NCC. In addition, two types of crystal structures and decreasing the glass transition temperature were distinguished using temperature-modulated DSC (TMDSC). Higher melting points of polymer crystals were found in TMDSC experiments due to low and dynamic heating rate compared to the conventional DSC. Dynamics of polymer chains, affected by NCC, were quantified using cooperativity length, ξ α, and the number of relaxing structural units, Nα, in the glass transition region. NCC particles hindered the cooperative motion of polymer chains at glass transitions and crystallization in TMDSC measurements, whereas the DMA results indicated that NCC particles may act as lubricant and simplified chain mobility.

Network-Forming Nanoclusters in Binary As\u2013S/Se Glasses: From Ab Initio Quantum Chemical Modeling to Experimental Evidences

Network-forming As2(S/Se)m nanoclusters are employed to recognize expected variations in a vicinity of some remarkable compositions in binary As–Se/S glassy systems accepted as signatures of optimally constrained intermediate topological phases in earlier temperature-modulated differential scanning calorimetry experiments. The ab initio quantum chemical calculations performed using the cation-interlinking network cluster approach show similar oscillating character in tendency to local chemical decomposition but obvious step-like behavior in preference to global phase separation on boundary chemical compounds (pure chalcogen and stoichiometric arsenic chalcogenides). The onsets of stability are defined for chalcogen-rich glasses, these being connected with As2Se5 (Z = 2.29) and As2S6 (Z = 2.25) nanoclusters for As–Se and As–S glasses, respectively. The physical aging effects result preferentially from global phase separation in As–S glass system due to high localization of covalent bonding and local demixing on neighboring As2Sem+1 and As2Sem−1 nanoclusters in As–Se system. These nanoclusters well explain the lower limits of reversibility windows in temperature-modulated differential scanning calorimetry, but they cannot be accepted as signatures of topological phase transitions in respect to the rigidity theory.

Structure of the Interfacial Region in Adsorbed Poly(vinyl acetate) on Silica

We performed a combined calorimetric and molecular modeling investigation of poly(vinyl acetate) (PVAc) on silica to characterize the intermolecular interactions and the behavior of the adsorbed polymer. From temperature-modulated differential scanning calorimetry experiments, different regions of thermal activity suggested a gradient of mobility in the adsorbed polymer. Polymer segments in more direct contact with silica (tightly bound) showed a significantly elevated and broadened glass transition relative to the bulk polymer, while polymer further away (loosely bound) showed only a slightly elevated transition relative to the bulk polymer. A thermal transition for PVAc at the air interface (more-mobile) was also observed and was at lower temperatures than the bulk polymer. Density profiles from molecular dynamics studies suggested a structure of the adsorbed polymer similar to that experimentally observed. These studies were consistent with the presence of a motional gradient in the polymer segments, a...

Conductivity Mechanism in Polymerized Imidazolium-Based Protic Ionic Liquid [HSO3–BVIm][OTf]: Dielectric Relaxation Studies

In this paper, we investigate the molecular dynamics and ions transport properties of polymerized imidazolium-based protic ionic liquid (HSO3−BVIm)(OTf)a new material with potential applications in energy storage and electrochemical devices. The results of dielectric measurements, analyzed in modulus M*(f) and conductivity σ*(f) formalisms, combined with temperature-modulated differential scanning calorimetry experiments, have revealed a fundamental difference between the conducting properties of the examined polymer membrane and its low-molecular weight counterpart. Our findings indicated a strong decoupling between conductivity relaxation times τσ (related to the ions migration through the polymer matrix) and segmental dynamics when the ionic transport is controlled by fast proton hopping through the dense hydrogen-bond network. Finally, we also discuss, for the first time, the effect of water content on the glass transition temperature value, relation between the charge and mass diffusion, reflected in the decoupling phenomenon, and the conductivity mechanism of examined poly(HSO3−BVIm)(OTf).

High Pressure as a Key Factor to Identify the Conductivity Mechanism in Protic Ionic Liquids

In this Letter we report the relation between ionic conductivity and structural relaxation in supercooled protic ionic liquids (PILs) under high pressure. The results of high-pressure dielectric and volumetric measurements, combined with rheological and temperature-modulated differential scanning calorimetry experiments, have revealed a fundamental difference between the conducting properties under isothermal and isobaric conditions for three PILs with different charge transport mechanisms (Grotthuss vs vehicle). Our findings indicate a breakdown of the fractional Stokes-Einstein relation and Walden rule when the ionic transport is controlled by fast proton hopping. Consequently, we demonstrate that the studied PILs exhibit significantly higher conductivity than one would expect taking into account that they are in fact a mixture of ionic and neutral species. Thus, the examined herein samples represent a new class of "superionic" materials desired for many advanced applications.

Plasticization of Adsorbed Poly(vinyl acetate) on Silica by Deuterium Solid-State NMR

Deuterium nuclear magnetic resonance spectroscopy and temperature modulated differential scanning calorimetry (TMDSC) were used to probe the segmental dynamics of methyl-labeled poly(vinyl acetate)-d3 (PVAc-d3) adsorbed on Cab-O-Sil silica in the presence and absence of a plasticizer, dipropyleneglycol dibenzoate. Unlike the effect of this plasticizer on the bulk polymer, where the reduction in the glass transition temperature (Tg), was proportional to the amount of plasticizer added, the effectiveness of the plasticizer on the adsorbed polymer depended on the amount of polymer adsorbed. For samples with very small amounts of adsorbed polymer (i.e., 0.81 mg/m2), there was little or no effect of plasticizer on the dynamics of the adsorbed polymer. For samples with more adsorbed polymer (i.e., 1.42 or 1.81 mg/m2), the efficiency of the plasticizer was easily measurable on a fraction of the adsorbed polymer that can be considered loosely bound. The 2H NMR line shape changes obtained from the adsorbed samples were fitted to a small jump model (based on the vertices of a “soccer-ball” shaped polyhedron) to obtain the distributions of jump rates contributing to the spectra. The same samples were also studied using TMDSC, and the results were consistent with the NMR results in terms of the effects of the plasticizer on the amount of polymer adsorbed. On the basis of the TMDSC experiments, the plasticizer tends to have a greater effect on the more loosely-bound polymer and lesser effect on a fraction that is more-tightly bound. Compared to the bulk polymer, where the glass transition range was on the order of 10 K, the range for the adsorbed polymer was more around 60 K.

Segmental dynamics of poly(methyl phenyl siloxane) confined to nanoporous glasses

The effect of a nanometer confinement on the molecular dynamics of poly (methyl phenyl siloxane) (PMPS) was studied by dielectric spectroscopy (DS), temperature modulated DSC (TMDSC) and neutron scattering (NS). Nanoporous glasses with pore sizes of 2.5-20 nm have been used. DS and TMDSC experiments show that for PMPS in 7.5 nm pores the molecular dynamics is faster than in the bulk which originates from an inherent length scale of the underlying molecular motions. For high temperatures the temperature dependence of the relaxation rates for confined PMPS crosses that of the bulk state. Besides finite states effects also the thermodynamic state of nano-confined PMPS is different from that of the bulk. At a pore size of 5 nm the temperature dependence of the relaxation times changes from a Vogel/Fulcher/Tammann like to an Arrhenius behavior where the activation energy depends on pore size. This is in agreement with the results obtained by NS. The increment of the specific heat capacity at the glass transition depends strongly on pore size and vanishes at a finite length scale between 3 and 5 nm which can be regarded as minimal length scale for glass transition to appear in PMPS.

Crystallization and melting behavior of biodegradable poly(butylene succinate‐co‐butylene carbonate)

AbstractAs a new biodegradable poly(ester carbonate), poly(butylene succinate‐co‐butylene carbonate) (PEC) is a random copolymer, which is composed of butylene succinate unit and butylene carbonate unit. The crystal structure, melting behavior, and morphology of PEC have been investigated by means of wide angle X‐ray diffraction (WAXD), differential scanning calorimetry (DSC), temperature modulated DSC (TMDSC), and optical microscopy (OM) in this manuscript. The crystal structure of PEC was found to be the same as that of poly(butylene succinate) (PBSU) through WAXD study, indicating that the butylene carbonate unit did not crystallize in the copolymer. Double melting behavior or one major melting endotherm with a shoulder was found on crystallizing PEC at various temperatures based on DSC study, which was explained by the melt‐recrystallization mechanism. The TMDSC experiment gave a direct proof for the melt‐recrystallization mechanism. The spherulitic growth of PEC was studied with OM at various crystallization temperatures. The spherulitic growth rates of PEC were analyzed by the Lauritzen‐Hoffman equation. The thermal parameters of PEC were compared with those of PBSU. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1556–1561, 2006

Effect of Static Magnetic Field Processing on Crystallization Behavior of Triacylglycerols

The influence of static magnetic field on crystallization of triacylglycerols (TAGs) was investigated. Melted TAGs were solidified under static magnetic field of 5 T with a superconductive magnet system. Polymorphic behavior of TAGs was examined by temperature modulated differential scanning calorimetry (TMDSC) and X-ray diffraction (XRD). In TMDSC experiment, saturated mono-acid TAGs (PPP and SSS) had no change in crystallization behavior under static magnetic field. Static magnetic field processing suppressed the crystallization of α form of SOS, PPO and POS. Furthermore, it suppressed the crystallization of sub-α form, α form, and β ′ form of POP. In case of SSO, the crystallization of α form and β ′ form was suppressed. On the other hand, in the XRD experiment the crystallization of α form in PPP and POP was suppressed by static magnetic field processing. PPO had no change in crystallization behavior under the static magnetic field. However, fluctuation in the ratio of the XRD peak area (wide angle region/small angle region) of α form was increased. This change suggested that the phase transition from α to β ′ form had occurred. From these results, the following can be considered as the influences of static magnetic field on crystallization of TAGs: (i) the effect of static magnetic field on crystallization of saturated mono-acid TAGs depended on the fatty acid chain length which constitutes TAG (PPP and SSS), (ii) the shorter the acyl chains of TAGs, the more sensitive to static magnetic field it was in saturated-unsaturated mixed-acid TAGs (PPO and SSO), and (iii) symmetrical type TAGs (POP and SOS) were more sensitive to static magnetic field rather than asymmetrical type of TAG (POS). It is speculated that the effect of a magnetic field on polymorphism of TAGs is due to the magnetic field gradient in a magnet and the molecular orientation caused by magnetic anisotropy of a TAG molecule. Much work is needed to clarify the mechanism of the polymorphic crystallization under static magnetic field.

Poly(methyl phenyl siloxane) in Random Nanoporous Glasses: Comparison of coated and uncoated confining surfaces

AbstractThe effect of a nanometer confinement on the molecular dynamics of poly(methyl phenyl siloxane) (PMPS) was studied by dielectric spectroscopy (DS) and temperature modulated DSC (TMDSC). As confining hosts random nanoporous glasses with nominal pore sizes of 2.5 nm – 20 nm have been used. Epically it is focused on the influence of a surface treatment on the dynamical behavior. DS and TMDSC experiments show that for PMPS in 7.5 nm pores the molecular dynamics is faster than in the bulk which originates from an inherent length scale of the underlying molecular motions. There is no influence of the surface treatment on the glassy dynamics for this pore size.At a pore size of 5 nm the temperature dependence of the relaxation times changes from a Vogel / Fulcher / Tammann like behavior to an Arrhenius one where the apparent activation energy depends on pore size. For silanized pores a higher value (102 kJ / mol) is found than for natives pores (73 kJ / mol). For a pore size of 2.5 nm the activation energy is independent of the surface treatment. The value of ca. 40 kJ / mol points to a real localized process.The increment of the specific heat capacity at the glass transition depends strongly on pore size and vanishes at a finite length scale which can be regarded as minimal length scale for glass transition to appear. The actual value depends on surface treatment. From this difference the thickness of an immobilized boundary layer of about 1 nm is estimated for uncoated pores.

DSC and TMDSC study of melting behaviour of poly(butylene succinate) and poly(ethylene succinate)

The subsequent melting behaviour of poly(butylene succinate) (PBSU) and poly(ethylene succinate) (PES) was investigated using DSC and temperature modulated DSC (TMDSC) after they finished nonisothermal crystallization from the melt. PBSU exhibited two melting endotherms in the DSC traces upon heating to the melt, which was ascribed to the melting and recrystallization mechanism. However, one melting endotherm with one shoulder and one crystallization exotherm just prior to the melting endotherm were found for PES. The crystallization exotherm was ascribed to the recrystallization of the melt of the crystallites with low thermal stability, and the shoulder was considered to be the melting endotherm of the crystallites with high thermal stability. The final melting endotherm was ascribed to the melting of the crystallites formed through the reorganization of the crystallites with high thermal stability during the DSC heating process. TMDSC experiments gave the direct evidences to support the proposed models to explain the melting behaviour of PBSU and PES crystallized nonisothermally from the melt.

Crystallization behaviour of biodegradable poly(ethylene succinate) from the amorphous state

Nonisothermal and isothermal crystallization kinetics of biodegradable poly(ethylene succinate) (PES) from the amorphous state were studied by differential scanning calorimetry (DSC). For the nonisothermal crystallization, there were two crystallization exotherms upon heating from the amorphous state. One major crystallization exotherm located at low temperature corresponded to the real cold crystallization of PES, while the other minor one located at high temperature may correspond to the melt-recrystallization of the unstable crystals formed during the nonisothermal crystallization earlier. Several methods, such as Avrami equation, Tobin equation and Ozawa equation, were applied to describe the nonisothermal crystallization process of PES. Meanwhile, Avrami equation was also employed to study the isothermal crystallization of PES from the amorphous state. Similar to the nonisothermal crystallization the minor crystallization exotherm was also found in the DSC trace upon heating to the melt after the isothermal cold crystallization finished completely, and was attributed to the melt-recrystallization of the unstable crystals formed during the isothermal cold crystallization. Temperature modulated differential scanning calorimetry (TMDSC) was used in this work to investigate the origin of the minor crystallization exotherm located at high temperature, and the TMDSC experiments gave a direct evidence that the origin of the minor crystallization exotherm was from the melt-recrystallization of the originally existed unstable crystals formed through previous crystallization.

Melting behaviour of poly(butylene succinate) in miscible blends with poly(ethylene oxide)

The melting behavior of poly(butylene succinate) (PBSU) in miscible blends with poly(ethylene oxide) (PEO), which is a newly found polymer blends of two crystalline polymers by our group, has been investigated by conventional differential scanning calorimetry (DSC). It was found that PBSU showed double melting behavior after isothermal crystallization from the melt under certain crystallization conditions, which was explained by the model of melting, recrystallization and remelting. The influence of the blend composition, crystallization temperature and scanning rate on the melting behavior of PBSU has been studied extensively. With increasing any of the PEO composition, crystallization temperature and scanning rate, the recrystallization of PBSU was inhibited. Furthermore, temperature modulated differential scanning calorimetry (TMDSC) was also employed in this work to investigate the melting behavior of PBSU in PBSU/PEO blends due to its advantage in the separation of exotherms (including crystallization and recrystallization) from reversible meltings (including the melting of the crystals originally existed prior to the DSC scan and the melting of the crystals formed through the recrystallization during the DSC scan). The TMDSC experiments gave a direct evidence of this melting, recrystallization and remelting model to explain the multiple melting behavior of PBSU in PBSU/PEO blends.

Annealing behavior of gel‐spun polyethylene fibers at temperatures lower than needed for significant shrinkage

AbstractThe annealing at 373 K of ultrastrong, gel‐spun polyethylene (PE) has been studied. At this temperature, the fibers show no significant shrinkage. Still, a significant decrease in the mechanical properties is observed. The fibers have been analyzed with differential scanning calorimetry (DSC), temperature‐modulated differential scanning calorimetry (TMDSC), atomic force microscopy (AFM), and small‐angle X‐ray scattering (SAXS). During the annealing, the glass transition of the intermediate phase is exceeded, as shown by DSC. When split for structure analysis by AFM, the annealed fibers undergo plastic deformation around the base fibrils instead of brittle fracture. The quasi‐isothermal TMDSC experiments are compared to the minor structural changes seen with SAXS and AFM. The loss of performance of the PE fibers at 373 K is suggested to be caused by the oriented intermediate phase, and not by major changes in the structure or morphology. The overall metastable, semicrystalline structure is shown by TMDSC to posses local regions that can melt reversibly. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 403–417, 2003

Poly(methyl phenyl siloxane) in Random Nanoporous Glasses: Molecular Dynamics and Structure

ABSTRACTThe effect of a nanometer confinement on the molecular dynamics of poly(methyl phenyl siloxane) (PMPS) was studied by dielectric spectroscopy (DS), temperature modulated DSC (TMDSC) and neutron scattering (NS). DS and TMDSC experiments show that for PMPS in 7.5 nm pores the molecular dynamics is faster than in the bulk which originates from an inherent length scale of the underlying molecular motions. At a pore size of 5 nm the temperature dependence of the relaxation times changes from a Vogel / Fulcher / Tammann like behavior to an Arrhenius one. At the same pore size Δcp vanishes. These results give strong evidence that the glass transition has to be characterized by an inherent length scale of the relevant molecular motions. Quasielastic neutron scattering experiments reveal a strong change even in the microscopic dynamic.

Dynamics of reversible melting revealed from frequency dependent heat capacity

Heat capacity of semi-crystalline polymers shows frequency dependence not only in the glass transition range. Also above glass transition and below melting temperature a frequency dependent heat capacity can be observed. The asymptotic value of heat capacity at high frequencies equals base-line heat capacity while the asymptotic value at low frequencies yield information about reversing melting. For polycarbonate (PC), poly(3-hydroxybutyrate) (PHB) and syndiotactic polypropylene (sPP) the asymptotic value at high frequencies can be measured by temperature-modulated DSC (TMDSC). For polycaprolactone (PCL) and sPP the frequency dependence of heat capacity can be studied in quasi-isothermal TMDSC experiments. The heat capacity spectra were obtained from single measurements applying multi-frequency perturbations (spikes in heating rate) like in StepScan™ DSC or rectangular temperature–time profiles. Actually, the dynamic range of commercial TMDSC apparatuses is limited and only a small part of the heat capacity spectrum can be measured by TMDSC. Nevertheless, comparison of measured base-line heat capacity with expected values from mixing rules for semi-crystalline polymers yield information about the formation (vitrification) and disappearance (devitrification) of the rigid amorphous fraction (RAF). For PC and PHB the RAF is established during isothermal crystallization while for sPP only a part of the RAF is vitrified during crystallization. Devitrification of the RAF seems to be related to the lowest endotherm.

Phase behavior of polymer–diluent systems characterized by temperature modulated differential scanning calorimetry

The thermodynamic phase behavior of a polymer–diluent system (atactic polystyrene–1-dodecanol) forms the fundamental basis of the description of thermally-induced demixing processes. In this paper, we demonstrate that temperature modulated differential scanning calorimetry (TMDSC) can accurately detect the liquid–liquid demixing transition. This transition can be clearly observed in the modulus of the complex heat capacity signal and in the phase angle. The phase angle shift is very small during liquid–liquid demixing so liquid–liquid demixing of a polymer–diluent system takes place at time scales instantaneously in comparison with the modulation period of TMDSC. In addition, the glass transition temperature of the polymer-rich phase and the crystallization temperature of the diluent can be determined as well within the same TMDSC experiment.

Glass transformation in vitreous As2Se3 studied by conventional and temperature-modulated differential scanning calorimetry

We have studied the glass transition behavior of vitreous As2Se3 by carrying out temperature-modulated differential scanning calorimetry (TMDSC) and conventional differential scanning calorimetry (DSC) experiments to measure the glass transition temperature Tg. In TMDSC experiments we have examined the reversing heat flow (RHF), that is the complex heat capacity CP in the glass transition region as the glass is cooled from a temperature above the glass transition temperature (from a liquidlike state) and also as the glass is heated starting from room temperature (from a solidlike state). The RHF, or CP versus T, in TMDSC changes sigmoidally through the glass transition region without evincing an enthalpic peak which is one of its distinct advantages for studying the glass transformations. The Tg measurements by TMDSC were unaffected by the amplitude of the temperature modulation. We have determined apparent activation energies by using Tg-shift methods based on the Tg-shift with the frequency (ω) of temperature modulation in the TMDSC mode and Tg-shift with heating and cooling rates, r and q, respectively, in the DSC mode. It is shown that the apparent activation energies ∆h* obtained from ln ω versus 1/Tg and ln q versus 1/Tg plots are not the same, but nonetheless, they are approximately the same as the apparent activation energy ∆hn of the viscosity over the same temperature range where the empirical Vogel expression of Henderson and Ast, η = 12.9 exp[2940/(T - 335)], was used for the viscosity. The latter observation is in agreement with the assertion that the structural relaxation time Ʈ is proportional to the viscosity h. The apparent activation energy ∆hr obtained from the ln r versus 1/Tg plot during heating DSC scans is lower than ∆h* observed during cooling scans. The results are discussed in terms of a phenomenological Narayanaswamy type relaxation time. It was observed that Tg obtained from TMDSC cooling experiments did not depend on the underlying cooling rate for q ≤ 1 °C min-1; and for temperature amplitudes 0.5–5 °C. The transition due to the temperature modulation was well separated from the transition due to the underlying cooling rate. Further, the apparent activation energies obtained from ln ω versus 1/Tg during cooling and heating scans for q and r ≤ 1 °C min−1 are approximately the same as expected from Hutchison's calculations using a single relaxation time model of TMDSC experiments.

The structural origin of broken chemical order in GeSe2 glass

Abstract Raman scattering, 119Sn Mössbauer spectroscopy and temperature-modulated differential scanning calorimetry experiments have been performed on (Ge0.99 Sn0.01)x Se1−x glasses in the 0.30 < x < 0.36 range. Both Raman and Mössbauer spectroscopies show that Ge‒Ge signatures first appear near x = 0.31(1), and their concentration slowly increases with increasing x to acquire a value of 1.92(30)% at x = 1/3, corresponding to GeSe2 glass. Thereafter (1/3 < x < 0.36) the concentration of these bonds increases precipitously with increasing x. Glass transition temperatures T g(x) reflect the connectivity of the network and are found to increase with increasing x; however, the rate dTg/dx of T g increase slows down markedly at (i) x ≥ 0.31(1), and the rate actually reverses sign (ii) at x ≥ 0.34. Feature (i) coincides with nucleation and (ii) with precipitous growth of Ge‒Ge signatures. These T g trends show that the presence of Ge‒Ge signatures decreases the global connectivity of the glasses. The results unequivocally demonstrate that the Ge‒Ge bonds constitute part of a marginally rigid Ge2(Se1/2)6-bearing nanophase that is formed separately from the Ge(Se1/2)4-tetrahedra-bearing backbone of the glasses.

Some elements in specific heat capacity measurement and numerical simulation of temperature modulated DSC (TMDSC) with R/ C network

One important application of temperature modulated DSC (TMDSC) is the measurement of specific heat of materials. In this paper, a thermal resistance/capacitance ( R/ C) numerical model is used to analyze the effects of experimental parameters and calibration on the measurement of specific heat in TMDSC under isothermal conditions. The actual TMDSC experiments were conducted with sapphire and pure copper samples, respectively. Both simulation and experiments showed that in TMDSC, the measured sample specific heat is a non-linear function of many factors such as sample mass, the heat transfer properties of the TMDSC instrument, temperature modulation period, the heat capacity difference between calibration material and the test material, but modulation amplitude has very little effect on the results. The typical behavior of a heat flux type TMDSC can be described as a low pass filter in terms of specific heat capacity measurement when the instrument heat transfer properties are taken into account. At least for metallic materials, where the temperature gradient inside the sample can normally be ignored, the sample should be chosen in such a way that its total heat capacity (mass times specific heat) is close to that of the calibration material in order to get a more accurate result. Also, a large modulation period is beneficial to improving the test accuracy.