Thermal degradation of lignin in nitrogen atmosphere is evaluated by linear heating and isothermal tests. While linear heating suggests that thermal decomposition in the 200–400 °C range mainly consists of a single step, a careful analysis of isothermal tests points to different lignin fractions having different stabilities. This is an important point for practical predictions, since kinetics obtained as if the degradations at different temperatures were the same would lack practical utility. Instead, stairway type tests are proposed to evaluate the degradation rates and sample quantities involved at the temperatures of interest.

Poly(lactic acid) (PLA) is an attractive candidate for replacing petrochemical polymers because it is fully biodegradable. This study investigated the potential of PLA as a sustainable and environmentally friendly alternative material that can be developed into commercially viable wearable mosquito repellent devices with desirable characteristics. PLA strands containing DEET and IR3535 were prepared by twin screw extrusion compounding and simultaneously functioned as plasticizers for the polymer. The plasticizing effect was investigated by thermal and rheological studies. DSC studies showed that the addition of DEET and IR3535 into PLA strands reduced the glass transition temperature consistent with predictions of the Fox equation, thus proving their efficiency as plasticizers. The rheology of molten samples of neat PLA and PLA/repellents blends, evaluated at 200 °C, was consistent with shear-thinning pseudoplastic behaviour. Raman studies revealed a nonlinear concentration gradient for DEET in the PLA strand, indicating non-Fickian Type II transport controlling the desorption process. Release data obtained at 50 °C showed initial rapid release followed by a slower, near constant rate at longer times. The release rate data were fitted to a novel modification of the Peppas-Sahlin desorption model.

In spite of the many studies performed, there is not yet a kinetic model to predict the thermal degradation of cellulose in isothermal and nonisothermal conditions for the full extent of conversion. A model proposed by the authors was tested on non-oxidising thermogravimetric data. The method consisted of initially fitting several isothermal and non-isothermal curves, then obtaining a critical temperature and an energy barrier from the set of fittings that resulted from different experimental conditions. While the critical temperature, approximately 226 °C, represented the minimum temperature for the degradation process, the degradation rate at a given temperature was related to both the critical temperature and the energy barrier. These results were compared with those observed in other materials. The quality of fittings obtained was superior to any other reported to date, and the results obtained from each single curve were in line with each other. The peak area. Represents the amount of sample involved in each transformation process, in linear heating conditions Fitting parameter, related to the peak shape in linear heating conditions. If =1, then is 4 times the maximum transformation rate per unit of sample mass KeywordsThe time elapsed from the beginning of the experiment to the instant where the maximum mass loss rate is observed, in linear heating experiments Fitting parameter related to the peak asymmetry ( =1 for a symmetric peak) yiso(t) Transformation rate, as a function of time, in isothermal conditionsThe peak area. Represents the amount of sample involved in each transformation process, in isothermal conditions

A model is proposed to fit differential scanning calorimetry (DSC) isothermal crystallization curves obtained from the molten state at different temperatures. A commercial 3D printing polylactic acid (PLA) sample is used to test the method. All DSC curves are fitted by a mixture of two simultaneous functions, one of them being a time derivative generalized logistic accounting for the exothermic effect and the other, a generalized logistic, accounting for the baseline. There is a rate parameter, which is allowed to vary across different temperatures. The rate parameter values obtained at different temperatures were jointly explained as a result of three crystallization processes, each one defined by a characteristic crystallization time, a characteristic temperature, and a dispersion or width factor. Apart from the very good fittings obtained at all temperatures, the results agree with the existence of a few crystal forms of PLA, which were demonstrated by other authors. Thus, the main significance of this work consists in providing a new approach in order to mathematically describe the isothermal crystallization kinetics of a polymer from the melt. Such a kinetic description is needed in order to predict the extent of a crystallization process as a function of time at any isothermal temperature. The approach used here allows to understand the overall crystallization of the PLA used in this work as the sum of three crystallization processes, each of them corresponding to a different crystal form. Each experimental crystallization exotherm, which may include more than one crystal form, can be reproduced by a generalized logistic function. The overall rate factor at a given temperature is the weighted sum of the rate factors of the different crystal structures at that temperature. The rate factor of each of these three processes is described by a Gaussian function whose parameters are a crystallization time, a characteristic temperature and a temperature dispersion factor. Therefore, the crystallization rate for each crystal form can be interpreted as a relative likelihood to crystallize at a given temperature. On the other hand, the characteristic crystallization time parameter refers to the time needed for a given crystal structure to be formed at the temperature at which the relative likelihood to crystallize of that form is highest.

A kinetic model is proposed to fit isothermal thermogravimetric data obtained from cellulose in an inert atmosphere at different temperatures. The method used here to evaluate the model involves two steps: (1) fitting of single time-derivative thermogravimetric curves (DTG) obtained at different temperatures versus time, and (2) fitting of the rate parameter values obtained at different temperatures versus temperature. The first step makes use of derivative of logistic functions. For the second step, the dependence of the rate factor on temperature is evaluated. That separation of the curve fitting from the analysis of the rate factor resulted to be very flexible since it proved to work for previous crystallization studies and now for thermal degradation of cellulose.

Waxes find use as processing aids in filled compounds and polyethylene‐based masterbatches. In such applications, the thermal and physical property changes they impart to the polymer matrix are important. Therefore, this study details results obtained for blends prepared by mixing a Fischer–Tropsch (F–T) wax with a high‐flow linear low‐density polyethylene (LLDPE). The melting and crystallization behavior are studied using hot‐stage polarized optical microscopy (POM) and differential scanning calorimetry (DSC). The calorimetry results are consistent with partial cocrystallization of the two components. The melting and crystallization exo‐ and endotherms for the wax‐ and LLDPE‐rich phases remained separate. However, they change in shape and shift toward higher‐ and lower temperature ranges, respectively. It is found that increasing the wax content delays the crystallization, decreases the overall crystallinity, and reduces the size of the crystallites of the polyethylene‐rich phase. Rotational viscosity is measured at 170 °C in the Newtonian shear‐rate range. The variation of the zero‐shear viscosity with blend composition is consistent with the assumption of a homogeneous melt in which the chains are in an entangled state. Therefore, it is concluded that the wax and LLDPE are, in effect, miscible in the melt and partially compatible in the solid state.

In some industrial sectors such as naval construction, the use of adhesives is still limited to some specific applications. However, shipbuilders, academia and classification societies are cooperating to expand the field of certificated applications of adhesive joints. As a part of a validation study, thermal and rheological studies of the curing process and of the cured adhesives should be included. While a neat glass transition and other relaxation processes can be normally identified by ramp temperature tests performed both on a differential scanning calorimeter or on a rheometer, there are some adhesive systems in which several glass transitions or melting or crystallization processes overlap. Applying a thermal treatment to delete the thermal history and conditioning are common practices to clarify what happens in complex systems. However, although that practices usually help, there are still some complexities due to overlapping processes that cannot be easily understood. An important point of this work is to show how differential scanning calorimetry (DSC) and rheology complement to each other in order to demonstrate several thermal relaxations and to obtain a better understanding of the cure process.The use of two different techniques along with a careful election of the setup parameter values allows to better interpret the thermal events. In addition, thermogravimetry (TG) helps to understand some rheological behaviors.In the end,this work shows how a good insight of the adhesive properties can be obtained by means of the combined use of DSC, rheology and TG.

This work proposes a green material for artificial reefs to be placed in Galicia (northwest Spain) taking into account the principles of circular economy and sustainability of the ecosystem. New concrete formulations for marine applications, based on cement and/or sand replacement by mussel shells, are analyzed in terms of resistance to abrasion. The interest lies in the importance of the canning industry of Galicia, which generates important quantities of shell residues with negative environmental consequences. Currently, the tests to determine the abrasion erosion resistance of concrete on hydraulic structures involve large and complex devices. According to this, an experimental test has been proposed to estimate and compare the wear resistance of these concretes and, consequently, to analyze the environmental performance of these structures. First, a numerical analysis validated with experimental data was conducted to design the test. Subsequently, experimental tests were performed using a slurry tank in which samples with conventional cement and sand were partially replaced by mussel shell. The abrasive erosion effect of concrete components was analyzed by monitoring the mass loss. It shows an asymptotic trend with respect to time that has been modeled by Generalized Additive Model (GAM) and nonlinear regression models. The results were compared to concrete containing only conventional cement and sand. Replacing sand and/or cement by different proportions of mussel shells has not significantly reduced the resistance of concrete against erosive degradation, except for the case where a high amount of sand (20 wt.%) is replaced. Its resistance against the erosive abrasion is increased, losing between 0.1072 and 0.0310 wt.% lower than common concrete. In all the remaining cases (replacements of the 5–10 wt.% of sand and cement), the effect of mussel replacement on erosive degradation is not significant. These results encourage the use of mussel shells in the composition of concrete, taking into account that we obtain the same degradation properties, even more so considering an important residue in the canning industry (and part of the seabed) that can be valorized.