Development of a novel pyrolysis-gas chromatography/mass spectrometry method for the analysis of poly(lactic acid) thermal degradation products

Thermal degradation of PLA is a complex process since it comprises many simultaneous reactions. The use of analytical techniques, such as differential scanning calorimetry (DSC) and thermogravimetry (TGA), yields useful information but a more sensitive analytical technique would be necessary to identify and quantify the PLA degradation products. In this work the thermal degradation of PLA at high temperatures was studied by using a pyrolyzer coupled to a gas chromatograph with mass spectrometry detection (Py-GC/MS). Pyrolysis conditions (temperature and time) were optimized in order to obtain an adequate chromatographic separation of the compounds formed during heating. The best resolution of chromatographic peaks was obtained by pyrolyzing the material from room temperature to 600 °C during 0.5 s. These conditions allowed identifying and quantifying the major compounds produced during the PLA thermal degradation in inert atmosphere. The strategy followed to select these operation parameters was by using sequential pyrolysis based on the adaptation of mathematical models. By application of this strategy it was demonstrated that PLA is degraded at high temperatures by following a non-linear behaviour. The application of logistic and Boltzmann models leads to good fittings to the experimental results, despite the Boltzmann model provided the best approach to calculate the time at which 50% of PLA was degraded. In conclusion, the Boltzmann method can be applied as a tool for simulating the PLA thermal degradation.

Mathematical approach for predicting non-negative tristimulus values using the CAT02 chromatic adaptation transform

It has been reported that for certain colour samples, the chromatic adaptation transform CAT02 imbedded in the CIECAM02 colour appearance model predicts corresponding colours with negative tristimulus values (TSVs), which can cause problems in certain applications. To overcome this problem, a mathematical approach is proposed for modifying CAT02. This approach combines a non-negativity constraint for the TSVs of corresponding colours with the minimization of the colour differences between those values for the corresponding colours obtained by visual observations and the TSVs of the corresponding colours predicted by the model, which is a constrained non-linear optimization problem. By solving the non-linear optimization problem, a new matrix is found. The performance of the CAT02 transform with various matrices including the original CAT02 matrix, and the new matrix are tested using visual datasets and the optimum colours. Test results show that the CAT02 with the new matrix predicted corresponding colours without negative TSVs for all optimum colours and the colour matching functions of the two CIE standard observers under the test illuminants considered. However, the accuracy with the new matrix for predicting the visual data is approximately 1 CIELAB colour difference unit worse compared with the original CAT02. This indicates that accuracy has to be sacrificed to achieve the non-negativity constraint for the TSVs of the corresponding colours.

Kinetic study of thermal 1,3-dipolar cycloaddition of azomethine ylides using differential scanning calorimetry as monitoring window

Kinetics of 1,3-dipolar cycloaddition involving azomethine ylides, generated from thermal [1,2]-prototropy of the corresponding imino ester, employing differential scanning calorimetry (DSC), is surveyed. Glycine and phenylalanine derived imino esters have different behavior. The first one prefers reacting with itself at 75 ºC, rather than with the dipolarophile. However, the α-substituted imino ester gives the cycloadduct at higher temperatures. The thermal dynamic analysis by 1H NMR of the neat reaction mixture of the glycine derivative reveals the presence of signals corresponding to the dipole in very small proportion. The non-isothermal and isothermal DSC curves of the cycloaddition of phenylalaninate and diisobutyl fumarate are obtained from freshly prepared samples. The application of known kinetic models and mathematical multiple non-linear regressions (NLR) allow to determine and to compare Ea, lnA, reaction orders, and reaction enthalpy. Finally a rate equation for each different temperature can be established for this particular thermal cycloaddition.

Price sensitivity to tourism activities: looking for determinant factors

The literature contains evidence that there is a marked heterogeneity in price responses to tourism products, leading to a great variety of tourist sensitivities to price. Thus the role price plays is complex, and a particularly challenging aspect of this complexity is that its effect is not unambiguous, thereby negating the idea that the demand for tourism products and tourist activities can always be regarded as demand for ordinary goods. This article identifies and explains, as a novelty for the tourism industry, price sensitivities to tourism activities individual by individual. The operative formalization uses a mixed logit model to estimate the individual sensitivities to price, and then a regression analysis is applied to detect their determinants. The empirical application finds that motivations, influenced by age, and length of stay with a non-linear effect, are explanatory factors of tourists’ price sensitivity to activities.

Revisiting the effect of foundation embedment on elastic settlement: A new approach

The effect of foundation embedment on settlement calculation is a widely researched topic in which there is no scientific consensus regarding the magnitude of settlement reduction. In this paper, a non-linear three dimensional Finite Element analysis has been performed with the aim of evaluating the aforementioned effect. For this purpose, 1800 models were run considering different variables, such as the depth and dimensions of the foundation and the Young’s modulus and Poisson’s ratio of the soil. The settlements from models with foundations at surface level and at depth were then compared and the relationship between them established. The statistical analysis of this data allowed two new expressions, with a mean maximum error of 1.80%, for the embedment influence factor of a foundation to be proposed and these to be compared with commonly used corrections. The proposed equations were validated by comparing the settlements calculated with the proposed influence factors and the true settlements measured in several real foundations. From the comprehensive study of all modelled cases, an improved approach, when compared to those proposed by other authors, for the calculation of the true elastic settlements of an embedded foundation is proposed.

Огляд наукових досліджень в галузі вивчення напружено-деформованого стану трубобетонних конструкцій

The paper presents an analytical review of the literature, which reflects the results of national and foreign scientific researches aimed to studying the features of the composition and dosage of components of self compacting concrete as one of the most promising aggregate for modern composite structures. In addition, the results of numerical and experimental researches of stress-strain state of composite structures (concrete-filled tubes) under the influence of various power factors, have been considered. The description and features of existing analytical methods for the determination of the bearing capacity of the considered structures under compression and bendings, have been given. The analysis of deformation model of confined concrete in a composition of the composite structure, as well as non-linear models of steel works with their distinctive features, has been carried out. The main approaches to the finite element modeling of composite structures have been determined.

Missing Rings in Pinus halepensis – The Missing Link to Relate the Tree-Ring Record to Extreme Climatic Events

Climate predictions for the Mediterranean Basin include increased temperatures, decreased precipitation, and increased frequency of extreme climatic events (ECE). These conditions are associated with decreased tree growth and increased vulnerability to pests and diseases. The anatomy of tree rings responds to these environmental conditions. Quantitatively, the width of a tree ring is largely determined by the rate and duration of cell division by the vascular cambium. In the Mediterranean climate, this division may occur throughout almost the entire year. Alternatively, cell division may cease during relatively cool and dry winters, only to resume in the same calendar year with milder temperatures and increased availability of water. Under particularly adverse conditions, no xylem may be produced in parts of the stem, resulting in a missing ring (MR). A dendrochronological network of Pinus halepensis was used to determine the relationship of MR to ECE. The network consisted of 113 sites, 1,509 trees, 2,593 cores, and 225,428 tree rings throughout the distribution range of the species. A total of 4,150 MR were identified. Binomial logistic regression analysis determined that MR frequency increased with increased cambial age. Spatial analysis indicated that the geographic areas of south-eastern Spain and northern Algeria contained the greatest frequency of MR. Dendroclimatic regression analysis indicated a non-linear relationship of MR to total monthly precipitation and mean temperature. MR are strongly associated with the combination of monthly mean temperature from previous October till current February and total precipitation from previous September till current May. They are likely to occur with total precipitation lower than 50 mm and temperatures higher than 5°C. This conclusion is global and can be applied to every site across the distribution area. Rather than simply being a complication for dendrochronology, MR formation is a fundamental response of trees to adverse environmental conditions. The demonstrated relationship of MR formation to ECE across this dendrochronological network in the Mediterranean basin shows the potential of MR analysis to reconstruct the history of past climatic extremes and to predict future forest dynamics in a changing climate.

The effects of economic crises on tourism success: an integrated model

This paper provides a theoretical model of the influence of economic crises on tourism destination performance. It discusses the temporary and permanent effects of economic crises on the global market shares of tourism destinations through a series of potential transmission mechanisms based on the main economic competitiveness determinants identified in the literature. The proposed model explains the non-neutrality of economic shocks in tourism competitiveness. The model is tested on Spain's tourism industry, which is among the leaders of the global tourism sector, for the period 1970–2013 using non-linear econometric techniques. The empirical analysis confirms that the proposed model is appropriate for explaining the changes in the market positions caused by the economic crises.

Cálculo del asiento elástico tridimensional de cimentaciones de rigidez variable en terrenos con una capa rígida inclinada

Las fórmulas basadas en la teoría de la elasticidad son ampliamente utilizadas para el cálculo de asientos de cimentaciones, ya que la totalidad de la normativa geotécnica recomienda su empleo. No obstante, estos métodos no cubren todas las situaciones geotécnicamente posibles ya que frecuentemente las condiciones geológicas son complejas. En este trabajo se analiza la influencia de la presencia de una capa rígida inclinada en los asientos elásticos de una cimentación superficial. Para ello se han resuelto 273 modelos tridimensionales no lineales de elementos finitos, variando los parámetros clave del problema: la inclinación y la profundidad de la capa rígida y la rigidez de la cimentación. Finalmente, se ha realizado un análisis estadístico de los resultados de los modelos y se ha propuesto una fórmula que puede ser utilizada en el cálculo de asientos por métodos elásticos, para tener en consideración la presencia de una capa rígida inclinada en profundidad.