Constant rate thermal analysis for thermal stability studies of polymers

This paper explores the relationship between the shapes of temperature-time curves obtained from experimental data recorded by means of constant rate thermal analysis (CRTA) and the kinetic model followed by the thermal degradation reaction. A detailed shape analysis of CRTA curves has been performed as a function of the most common kinetic models. The analysis has been validated with simulated data, and with experimental data recorded from the thermal degradation of polytetrafluoroethylene (PTFE), poly(1,4-butylene terephthalate) (PBT), polyethylene (PE) and poly(vinyl chloride) (PVC). The resulting temperature-time profiles indicate that the studied polymers decompose through phase boundary, random scission, diffusion and nucleation mechanisms respectively. The results here presented demonstrate that the strong dependence of the temperature-time profile on the reaction mechanism would allow the real kinetic model obeyed by a reaction to be discerned from a single CRTA curve.Junta de Andalucía TEP-03002Ministerio de Ciencia e Innovación MAT 2008-06619/MA

CO2 multicyclic capture of pretreated/doped CaO in the Ca-looping process. Theory and experiments

We study in this paper the conversion of CaO-based CO2 sorbents when subjected to repeated carbonation/calcination cycles with a focus on thermally pretreated/doped sorbents. Analytical equations are derived to describe the evolution of conversion with the cycle number from a unifying model based on the balance between surface area loss due to sintering in the loopingcalcination stage and surface area regeneration as a consequence of solid-state diffusion during the looping-carbonation stage. Multicyclic CaO conversion is governed by the evolution of surface area loss/regeneration that strongly depends on the initial state of the pore skeleton. In the case of thermally pretreated sorbents, the initial pore skeleton is highly sintered and regeneration is relevant whereas, for nonpretreated sorbents, the initial pore skeleton is soft and regeneration is negligible. Experimental results are obtained for sorbents subjected to a preheating controlled rate thermal analysis (CRTA) program. By applying this preheating program in a CO2 enriched atmosphere, CaO can be subjected to a rapid carbonation followed by a slow rate controlled decarbonation, which yields a highly sintered skeleton displaying a small conversion in the first cycle and self-reactivation in the next ones. Conversely, carbonation of the sorbent at a slow controlled rate enhances CO2 solid-state diffusion, which gives rise, after a quick decarbonation, to a highly porous skeleton. In this case, CaO conversion in the first cycle is very large but it decays abruptly in subsequent cycles. Data on CaO conversion retrieved from the literature and from further experimental measurements performed in our work are analyzed as influenced by a variety of experimental variables such as preheating temperature program, preheating exposition time, atmosphere composition, presence of additives, and carbonation/calcination conditions. Conversion data are well fitted by the proposed model equations, which are of help for a quantitative interpretation on the effect of experimental conditions on the multicyclic sorbent performance as a function of sintering/ regeneration parameters inferred from the fittings and allow foreseeing the critical conditions to promote reactivation. The peculiar behavior of some pretreated sorbents, showing a maximum of conversion at a small number of cycles, is explained in the light of the mode

Enhancement of fast CO2Capture by a Nano-SiO2/CaO composite atCa-Looping conditions

In this paper we show the performance of a new CO2sorbentconsisting of a dry physical mixture of a Ca-based sorbent and a SiO2nanostructuredpowder. Thermo-gravimetric analysis (TGA) performed at conditions close to the Ca-looping process demonstrate that the rate of CO2capture by the mixture is enhancedduring the fast carbonation stage of practical interest in applications. Moreover, theresidual capture capacity of the mixture is increased. SEM/EDX, physisorption, andXRD analyses indicate that there is a relevant interaction between the nanostructuredSiO2skeleton and CaO at high temperatures, which serves to improve the efficiency ofthe transfer of CO2to small reactive pores as well as the stability of the sorbent porestructur

Relevance of particle size distribution to kinetic analysis: the case of thermal dehydroxylation of kaolinite

Kinetic models used for the kinetic analysis of solid-state reactions assume ideal conditions that are very rarely fulfilled by real processes. One of the assumptions of these ideal models is that all sample particles have an identical size, while most real samples have an inherent particle size distribution (PSD). In this study, the influence of particle size distribution, including bimodal PSD, in kinetic analysis is investigated. Thus, it is observed that PSD can mislead the identification of the kinetic model followed by the reaction and even induce complex thermoanalytical curves that could be misinterpreted in terms of complex kinetics or intermediate species. For instance, in the case of a bimodal PSD, kinetics is affected up to the point that the process resembles a reaction driven by a multi-step mechanism. A procedure for considering the PSD in the kinetic analysis is presented and evaluated experimentally by studying the thermal dehydroxylation of kaolinite. This process, which does not fit any of the common ideal kinetic models proposed in the literature, was analyzed considering PSD influence. However, when PSD is taken into account, the process can be successfully described by a 3-D diffusion model (Jander’s equation). Therefore, it is concluded that the deviations from ideal models for this dehydroxylation process could be explained in terms of PSD.Ministerio de Economía y Competitividad CTQ2017-83602- C2-1-RJunta de Andalucía P18-FR-1087, US-1262507, DOC_0004

Nanoclay nucleation effect in the thermal stabilization of a polymer nanocomposite: A kinetic mechanism change

The enhanced thermal stability of polymer-clay nanocomposites over the original polymers is one of their most interesting features, and it has been profusely studied within the last decades. Here, a thorough kinetic analysis of polystyrene and a montmorillonite-polystyrene nanocomposite has been performed making use of state-of-the-art kinetic procedures. It has been found that the degradation mechanism changes from a chain scission process for the polymer to a complex two-step nucleation-driven reaction for the nanocomposite. This mechanism change can explain the delayed onset of degradation found in the nanocomposite. Moreover, observation by transmission electron microscopy (TEM) has shown that the clay platelets within the composite could act as nucleation centers for the decomposition.Junta de Andalucía TEP-03002Ministerio de Economía y Competitividad CTQ2011-2762

On the relevant role of solids residence time on their CO2 capture performance in the Calcium Looping technology

The multicycle CO capture performance of CaO derived from natural limestone and dolomite has been investigated by means of thermogravimetry under realistic Calcium-Looping conditions, which necessarily involve high CO concentration and high temperatures in the calcination stage and fast transitions between the carbonation and calcination stages. Natural dolomite allows reducing the calcination temperature as compared to limestone while high calcination efficiency is maintained. This could help reducing the energy penalty of the CaL process thus further enhancing the industrial competitiveness for the integration of this technology into fossil fuel power plants. Importantly, the CO capture capacity of the sorbents is critically affected by the solids residence time in the carbonation and calcination stages within the feasible range in practice. Thus, carbonation/calcination residence times play a critical role on the multicycle CO capture performance, which has been generally dismissed in previous studies. A main observation is the enhancement of carbonation in the solid-state diffusion controlled phase, which is against the commonly accepted conception that the only relevant phase in the carbonation stage is the fast reaction-controlled stage on the surface of the solids. Thus, the CO capture efficiency may be significantly enhanced by increasing the solids residence time in the carbonator.Ministerio de Economía y Competitividad CTQ2014-52763-C2-2-R, CTQ2014-52763-C2-1-RJunta de Andalucía FQM-5735, TEP-785

Limitations of model-fitting methods for kinetic analysis: Polystyrene thermal degradation

In this paper, some clarifications regarding the use of model-fitting methods of kinetic analysis are provided in response to the lack of plot linearity and dispersion in the activation energy values for the thermal degradation of polystyrene found in the literature and some results proposing an nth order model as the most suitable one. In the present work, two model-fitting methods based on the differential and integral forms of the general kinetic equation are evaluated using both simulated and experimental data, showing that the differential method is recommended due to its higher discrimination power. Moreover, the intrinsic limitations of model-fitting methods are highlighted: the use of a limited set of kinetic models to fit experimental data and the ideal nature of such models. Finally, it is concluded that a chain scission model is more appropriate than first order.Junta de Andalucía TEP‐03002Ministerio de Economía y Competitividad CTQ2011‐2762

Combined kinetic analysis of thermal degradation of polymeric materials under any thermal pathway

Combined kinetic analysis has been applied for the first time to the thermal degradation of polymeric materials. The combined kinetic analysis allows the determination of the kinetic parameter from the simultaneous analysis of a set of experimental curves recorded under any thermal schedule. Besides, the method does not make any assumption about the kinetic model or activation energy and allows the analysis even when the process does not follow one of the ideal kinetic models already proposed in literature. In the present paper the kinetics of the thermal degradation of both polytetrafluoroethylene (PTFE) and polyethylene (PE) have been performed. It has been concluded, without previous assumptions on the kinetic model, that the thermal degradation of PTFE obeys a first order kinetic law, while the thermal degradation of PE follows a diffusion-controlled kinetic model

Magnesium hydride for energy storage applications: The kinetics of dehydrogenation under different working conditions

A new approach to the kinetics of magnesium hydride dehydrogenation is considered. A model able to predict the dehydrogenation under different experimental conditions has been proposed. A new combined kinetic analysis method, which considers the thermodynamic of the process according to the microreversibility principle, has been used for performing the kinetic analysis of data obtained under different thermal schedules at hydrogen pressures ranging from high vacuum up to 20 bar. The kinetic analysis shows that the dehydrogenation mechanism of magnesium hydride depends on the experimental conditions. Thus, the reaction follows a first order kinetics, equivalent to an Avarmi-Erofeev kinetic model with an Avrami coefficient equal to 1, when carried out under high vacuum, while a mechanism of tridimensional growth of nuclei previously formed (A3) is followed under hydrogen pressure. An explanation of the change of mechanism is given. It has been shown that the activation energy is closed to the Mg-H bond breaking energy independently of the hydrogen pressure surrounding the sample, which suggests that the breaking of this bond would be the rate limiting step of the process. The reliability of the calculated kinetic parameters is tested by comparing simulated and experimental curves.Ministerio de Economía y Competitividad CTQ2014-52763-C2-1-RJunta de Andalucía TEP-7858, TEP-190

Pyrolysis kinetics of ethylene-propylene (EPM) and ethylene-propylene-diene (EPDM)

The thermal degradation kinetics of several ethylene-propylene copolymers (EPM) and ethylene-propylene-diene terpolymers (EPDM), with different chemical compositions, have been studied by means of the combined kinetic analysis. Until now, attempts to establish the kinetic model for the process have been unsuccessful and previous reports suggest that a model other than a conventional nth order might be responsible. Here, a random scission kinetic model, based on the breakage and evaporation of cleavaged fragments, is found to describe the degradation of all compositions studied. The suitability of the kinetic parameters resulting from the analysis has been asserted by successfully reconstructing the experimental curves. Additionally, it has been shown that the activation energy for the pyrolysis of the EPM copolymers decreases by increasing the propylene content. An explanation for this behavior is given. A low dependence of the EPDM chemical composition on the activation energy for the pyrolysis has been reported, although the thermal stability is influenced by the composition of the diene used.Ministerio de Economía y Competitividad CTQ2011-27626Junta de Andalucía TEP-785