Carlos Gracia-Fernández

Estimating the reversing and non‐reversing heat flow from standard DSC curves in the glass transition region

A mathematical model for the total heat flow obtained in differential scanning calorimetry (DSC) experiments from polymers with enthalpic relaxation is proposed. It is limited to the glass transition and enthalpic relaxation range of temperature and to the cases where the enthalpic relaxation is the only non‐reversing process taking place. The model consists of a mixture of functions representing the heat capacity heat flow of the glassy and non‐glassy fractions, the glass transition progress and the enthalpic relaxation heat flow.

New method for estimating shift factors in time–temperature superposition models

Prediction of polymer properties at short and long observation times is usually performed through time–temperature superposition (TTS) models, which make use of some calculated shift factors. Although TTS principle has been used for many decades, no firm rules have been developed for obtaining the master curves. In the absence of reliable long-term data, it has been a common practice to try to minimize the discrepancy between the individual shifted curves. It was reported that a TTS method is more reliable as that discrepancy is minimized. In this study, a new method for obtaining the shift factors is presented. The optimal shift factors were estimated by minimizing the distance between the single curve derivatives with respect to the derivative of the curve at the reference temperature. That shift factors were tested with some classical models. The data were analyzed by statistical methods, making use of bootstrap resampling and spline estimation. The shift factors obtained from the proposed method allow for obtaining smooth master curves. The accuracy of the estimations was evaluated.

Wood identification using pressure DSC data

This work addresses the problem of supervised classification of industrial wood species (seven different types in the present study) through their thermo‐oxidative stability. This is evaluated by pressure differential scanning calorimetry (PDSC) using the ASTM E2009. The maximization of the ratio of correct classification and the reduction of the costs of this activity are intended. This supervised classification problem was carried out using two different proposals: applying novel nonparametric functional data analysis techniques, based on kernel estimation, to the original PDSC curves, and using machine learning classification approaches applied to different multivariate data sets. The multivariate data sets were obtained, on the one hand, by estimating the fractal (Hausdorff) dimension of the PDSC curves by several methods, jointly with selecting the parameters from fitting a nonlinear model to the PDSC curves and, on the other hand, applying principal component analysis or partial linear squares to the thermograms. The results obtained show that the PDSC curves can be used to discriminate wood samples when these innovative and traditional statistical techniques are applied. In the best of the cases, a probability of correct classification that equals to 0.92 was obtained. PDSC represents a new alternative to the use of images, spectra, and other thermal signals as thermogravimetric analysis for classification purposes.Copyright

Study of gypsum by PDSC

Calcium sulfate dihydrate has been widely characterized by both differential scanning calorimetry and thermogravimetry (TG). Two dehydration processes were reported to be partially overlapping. High resolution TG and water vapor self generated atmosphere pin-hole lid strategies were used to increase the resolution of both dehydration processes. In this study, isobaric experiments were carried out in a pressure differential scanning calorimetry cell. The approach consisted in combining the pin-hole lid with different pressures with nitrogen atmosphere. Resolution was improved at moderately low pressures. At higher pressures other processes were observed.

Simultaneous application of electro and orthogonal superposition rheology on a starch/silicone oil suspension

Orthogonal superposition (OSP) rheology is successfully used in this work to study an electrorheological (ER) fluid composed of a starch/silicone oil suspension. Interactions between hydrodynamic and polarization forces and other ER effects, such as the typical two-step yield stress observed when ER fluids are subjected to variable shear rates with simultaneous application of an electrical field, were evaluated. In order to conveniently investigate these effects, a specially designed geometry was mounted on a strain controlled rheometer. The OSP tests basically consisted of a continuous rotation and a simultaneous oscillation along the rotation axis (orthogonal to the rotation plane). On the other hand, by combining electro and OSP it is possible to evaluate how the electric potential influences the typical two-step yield stress of ER fluids in continuous rotation while the viscoelastic properties are simultaneously studied by OSP. Obtaining reliable storage and loss moduli in the axial direction while ap...

Electrorheological behaviour of a starch-oil system

A simple system consisting of a suspension of 10 wt % of starch in silicone oil was subjected to electrorheological testing. The system exhibits a complex behaviour depending on the electrical field. On one hand, the application of an external electric field induced the formation of a linear structure, aligned with the electric field. The formation of that structure was studied by several rheological methods. The rate of modifying the electric field intensity resulted to be related to the electric field value at which percolation is observed. On the other hand, master curves for the structure formation and breakdown in squeeze experiments were obtained.

Characterization of MWCNT/TPU systems by large amplitude oscillation shear

Interest in polymeric materials with dispersed nanotubes has increased in recent years. There are several methods to characterize this kind of dispersions that may be based on evaluating the percolation concentration, the “goodness” of the dispersion, or the matrix-nanotube interphase. Among other techniques, rheology and conductivity are used to this aim. Commonly, the oscillatory rheology measurements are performed within the linear viscoelastic range, which is achieved by operating at small amplitude oscillation shear. Nevertheless, these measurements do not fully describe the behavior of the dispersion structure. In this work, we propose the use of medium amplitude oscillation shear and large amplitude oscillation shear to characterize the dispersion/structure of a thermoplastic polyurethane matrix filled with multiwalled carbon nanotubes. The Ewoldt framework mathematical approach is used to analyze the non-linear stress response. That approach allows obtaining physically grounded magnitudes from the experimental data. These magnitudes allow for a better understanding of the effects of the filler content.

Dynamic rheological comparison of silicones for podiatry applications

PURPOSE This work shows an effective methodology to evaluate the dynamic viscoelastic behavior of silicones for application in podiatry. The aim is to characterize, compare their viscoelastic properties according to the dynamic stresses they can be presumably subjected when used in podiatry orthotic applications. These results provide a deeper insight which extends the previous creep-recovery results to the world of dynamic stresses developed in physical activity. In this context, it shoulod be taken into account that an orthoses can subjected to a set of static and dynamic shear and compressive forces. METHODS Two different podiatric silicones, Blanda-blanda and Master, from Herbitas, are characterized by dynamic rheological methods. Three kinds of rheological tests are considered: shear stress sweep, compression frequency sweep and shear frequency sweep, all the three with simultaneous control of the static force at three different levels. The static force represents a static load like that produced by the weight of a human body on a shoe insole. In a practical sense, dynamic stresses are related to physical activity and are needed to evaluate the frequency effect on the viscoelastic behavior of the material. It is considered that the dynamic stresses can be applied in compression and shear since, in practice, the way the stresses are applied in real life depends on the orthoses geometry and its exact location with respect to the foot and shoe. The effects of static and dynamic loads are individualized and compared to each other through the relations between the elastic constants for isotropic materials. CONCLUSIONS The overall proposed experimental methodology can provide very insightful information for better selection of materials in podiatry applications. This study focuses on the rheological characterization to choose the right silicone for each podiatric application, taking into account the dynamic viscoelastic requirements associated to the physical activity of user. Accordingly, one soft and one hard silicones of common use in podiatry were tested. Each of the two silicones exhibit not only different moduli values, but also, a different kind of dependence of the dynamic moduli with respect to the static load. In the case of the soft sample a linear trend is observed but in the case of of the hard one the dependence is of the power law type. Moreover, these samples exhibit very different Poissons coefficient values for compression stresses lower than 20 kPa, and almost the same values for stresses above 40 kPa. That different dependence of the Poissons ratio on the static load should also be taken into account for material selection in customized podiatry applications, where static and dynamic loads are strongly dependent on the individual weight and activity.

Thermal characterization of poly- l -lactide by dielectric analysis and modulated DSC

Dielectric analysis (DEA) is a very sensitive technique, which allows for detection of small structural changes at the low scale. An advantage of DEA, with respect to other modulated techniques, is the possibility of using a wider frequency range. Molecular relaxations of the order of only a few nanometers are not observed by any other thermoanalytic method. Nevertheless, these small relaxations involve dipole changes that can be observed by DEA. Thus, this technique is used here, in combination with temperature-modulated differential scanning calorimetry (TMDSC) to obtain insightful information about the thermal transitions of poly-l-lactic acid (PLLA), one of the stereo-isomers of polylactide. Its complex thermal behavior is the subject of ongoing debate, with several overlapping crystallization and melting processes. The combined use of TMDSC and DEA provides a better insight of three important transitions of this polymer: the alpha relaxation, the enthalpic relaxation, and the cold crystallization. The dependences of the enthalpy relaxation on the dynamic glass transition relaxation and on the glass transition as a thermal event are evaluated. On the other hand, it will be shown how the cold crystallization can be identified by TMDSC, and DEA helps us understand the effect of crystallization on the dipole movements. The shape of the dielectric permittivity curve at low frequencies is compared to that of the reversing heat capacity to check whether both signals are sensitive or not to the same events. It is also verified how the experimental results of alpha relaxation of PLLA follow an Arrhenius or a Vogel trend.