Antonio Perejón

Kinetic Analysis of Complex Solid-State Reactions. A New Deconvolution Procedure

The kinetic analysis of complex solid-state reactions that involve simultaneous overlapping processes is challenging. A method that involves the deconvolution of the individual processes from the overall differential kinetic curves obtained under linear heating rate conditions, followed by the kinetic analysis of the discrete processes using combined kinetic analysis, is proposed. Different conventional mathematical fitting functions have been tested for deconvolution, paying special attention to the shape analysis of the kinetic curves. It has been shown that many conventional mathematical curves such as the Gaussian and Lorentzian ones fit kinetic curves inaccurately and the subsequent kinetic analysis yields incorrect kinetic parameters. Alternatively, other fitting functions such as the Fraser-Suzuki one properly fit the kinetic curves independently of the kinetic model followed by the reaction and their kinetic parameters, and moreover, the subsequent kinetic analysis yields the correct kinetic parameters. The method has been tested with the kinetic analysis of complex processes, both simulated and experimental.

Enhancement of Fast CO2 Capture by a Nano-SiO2/CaO Composite at Ca-Looping Conditions

In this paper we show the performance of a new CO(2) sorbent consisting of a dry physical mixture of a Ca-based sorbent and a SiO(2) nanostructured powder. Thermo-gravimetric analysis (TGA) performed at conditions close to the Ca-looping process demonstrate that the rate of CO(2) capture by the mixture is enhanced during the fast carbonation stage of practical interest in applications. Moreover, the residual capture capacity of the mixture is increased. SEM/EDX, physisorption, and XRD analyses indicate that there is a relevant interaction between the nanostructured SiO(2) skeleton and CaO at high temperatures, which serves to improve the efficiency of the transfer of CO(2) to small reactive pores as well as the stability of the sorbent pore structure.

Generalized kinetic master plots for the thermal degradation of polymers following a random scission mechanism.

In this paper, the f(alpha) conversion functions for random scission mechanisms have been proposed to allow for the construction of generalized master plots suitable for these kinds of mechanisms. The master plots have been validated by their application to simulated data and to the thermal degradation of poly(butylene terephthalate), polyethylene, and poly(tetrafluoroethylene).

Sedimentary patterns across the Lower–Middle Cambrian transition in the Esla nappe (Cantabrian Mountains, northern Spain)

In the carbonate platforms of the western Gondwana margin, the extinction recorded at the Lower–Middle Cambrian boundary is accompanied by a profound change in the style of carbonate deposition. The Lancara Formation of the Esla nappe (Cantabrian Mountains, northern Spain) contains a distinct sedimentary turnover due to a combination of tectonism, eustatic fluctuations, and immigration and colonization of new benthic communities, such as the youngest archaeocyathan assemblage of the entire Iberian Peninsula. During latest Early Cambrian times, a regressive trend is recorded in the Lancara Formation. This regression was recorded on a peritidal-dominant, homoclinal ramp that is topped by a tectonically induced discontinuity (D1). The latter surface marks the beginning of a last prograding, regressive tendency recorded on an intra-shelf ramp with ooidal/bioclastic shoals protecting archaeocyathan-microbial patch reefs. The overlying discontinuity (D2) corresponds to a major erosive unconformity, which coincides with the Lower–Middle Cambrian boundary in the Cantabrian Mountains. The subsequent, long-term, earliest Middle Cambrian rise in relative sea-level allowed deposition of low-relief, bioclastic shoals bearing a diverse and cosmopolitan assemblage of benthic fauna. Finally, the previous evolution is bounded by a third discontinuity (D3), which marks the beginning of a rhythmic sedimentation indicative of a major phase of tectonic breakdown and drowning of platforms recognised throughout southwestern Europe. Two associations of calcimicrobes occur in the latest Early Cambrian regressive trend of the Lancara Formation: (i) Proaulopora and Subtiflora are identified in peritidal, high-energy settings, lacking self-supported structures, whereas (ii) intergrowths of Epiphyton, Renalcis and Girvanella encrusted branching colonies and solitary archaeocyaths in protected (back-shoal) patch reefs. The latest Early Cambrian regression is correlated in southwestern Europe in both siliciclastic (Iberian Chains and Ossa–Morena) and carbonate-dominant platforms (Cantabrian Mountains, Montagne Noire and Sardinia). Its tops are recognised as diachronous unconformities ranging in age from early Bilbilian to the Bilbilian–Leonian or Lower–Middle Cambrian boundary.

Direct mechanosynthesis of pure BiFeO3 perovskite nanoparticles: reaction mechanism

In this work, a mechanochemical procedure is proposed as a simple and fast method to synthesize the pure BiFeO3 perovskite phase as a nanostructured material without the need for purification treatments, while the mechanochemical reaction mechanism has been investigated and correlated with that of the conventional solid-state reaction. Thus, different milling conditions have been used as a tool for tailoring the crystallite size of the resulting BiFeO3 nanoparticles. The materials prepared by the mechanochemical reaction could be annealed or sintered without the formation of undesirable phases. Both the ferroelectric and ferromagnetic transitions were observed by DSC. Finally, the dielectric constants of the prepared material at different frequencies as a function of the temperature have been measured, showing that the material is clearly an isolator below 200 °C, characteristic of a high quality BiFeO3 material.

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 looping-calcination 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 for 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 of 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 conversion in a small number of cycles, is explained in light of the model.

Quantitative characterization of multicomponent polymers by sample-controlled thermal analysis.

This paper explores the potential of sample-controlled thermal analysis (SCTA) in order to perform compositional analysis of multicomponent polymeric materials by means of thermogravimetric experiments. In SCTA experiments, the response of the sample to the temperature determines the evolution of the temperature by means of a feedback system; thus, what is controlled is not the temperature-time profile, as in conventional analysis, but rather the evolution of the reaction rate with time. The higher resolving power provided by the technique has been used for determining the composition of polymer blends composed of polyvinyl chloride (PVC) and different commercial plasticizers, a system where the individual components have very similar thermal stabilities, thereby rendering useless thermogravimetric experiments run under conventional conditions. Different SCTA procedures, such as constant rate thermal analysis (CRTA), which has received special attention, and high-resolution and stepwise isothermal analysis have been tested, and the results obtained have been compared with linear heating rate technique. It has been proven that CRTA can be used to effectively determine the exact composition of the blend.

Early Cambrian coelobiontic communities in tectonically unstable crevices developed in Neoproterozoic andesites, Ossa-Morena, southern Spain

A well-preserved biota of Lower Cambrian cavity-dwelling organisms is recorded within fissures in Neoproterozoic andesites in Ossa-Morena (southern Spain). The cavities are unique among described Lower Cambrian coelobiontic communities due to the igneous character of the host rock. Coelobiontic habitat was episodically enlarged by synsedimentary tectonic fracturing reflecting polyphase infill of recurrent facies. The pioneer coelobiontic biota was diverse, and consisted of encrusting stromatolites and thromboids (dominated by Epiphyton and Renalcis), attached to walls and ceilings of the cavities, associated with archaeocyaths. Sponge spicules and chancelloriid sclerites occur as dense clusters indicating in situ growth, death and decay of spiculate sponges and coeloscleritophorans. Other organisms, such as echinoderms, trilobites and brachiopods, are also found within the cavities as reworked skeletons, indicating that they were washed in from the overlying, open seafloor. The main feature of the coelobiontic biota is the dominance of a sessile, chemosynthetic and filter-feeding epibenthos, composed of microbial communities, archaeocyaths, spiculate sponges (demosponges and rarer hexactinellides) and coeloscleritophorans.

Clarifications regarding the use of model-fitting methods of kinetic analysis for determining the activation energy from a single non-isothermal curve

BackgroundThis paper provides some clarifications regarding the use of model-fitting methods of kinetic analysis for estimating the activation energy of a process, in response to some results recently published in Chemistry Central journal.FindingsThe model fitting methods of Arrhenius and Savata are used to determine the activation energy of a single simulated curve. It is shown that most kinetic models correctly fit the data, each providing a different value for the activation energy. Therefore it is not really possible to determine the correct activation energy from a single non-isothermal curve. On the other hand, when a set of curves are recorded under different heating schedules are used, the correct kinetic parameters can be clearly discerned.ConclusionsHere, it is shown that the activation energy and the kinetic model cannot be unambiguously determined from a single experimental curve recorded under non isothermal conditions. Thus, the use of a set of curves recorded under different heating schedules is mandatory if model-fitting methods are employed.

Combined TGA-MS kinetic analysis of multistep processes. Thermal decomposition and ceramification of polysilazane and polysiloxane preceramic polymers

The polymer-to-ceramic transformation kinetics of two widely employed ceramic precursors, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane (TTCS) and polyureamethylvinylsilazane (CERASET), have been investigated using coupled thermogravimetry and mass spectrometry (TG-MS), Raman, XRD and FTIR. The thermally induced decomposition of the pre-ceramic polymer is the critical step in the synthesis of polymer derived ceramics (PDCs) and accurate kinetic modeling is key to attaining a complete understanding of the underlying process and to attempt any behavior predictions. However, obtaining a precise kinetic description of processes of such complexity, consisting of several largely overlapping physico-chemical processes comprising the cleavage of the starting polymeric network and the release of organic moieties, is extremely difficult. Here, by using the evolved gases detected by MS as a guide it has been possible to determine the number of steps that compose the overall process, which was subsequently resolved using a semiempirical deconvolution method based on the Frasier-Suzuki function. Such a function is more appropriate that the more usual Gaussian or Lorentzian functions since it takes into account the intrinsic asymmetry of kinetic curves. Then, the kinetic parameters of each constituent step were independently determined using both model-free and model-fitting procedures, and it was found that the processes obey mostly diffusion models which can be attributed to the diffusion of the released gases through the solid matrix. The validity of the obtained kinetic parameters was tested not only by the successful reconstruction of the original experimental curves, but also by predicting the kinetic curves of the overall processes yielded by different thermal schedules and by a mixed TTCS-CERASET precursor.