Creep and damage models for the service behaviour of structural members

Deformability is often a crucial to the conception of many civil-engineering structural elements. Also, design is all the more burdensome if both long- and short-term deformability has to be considered. In this thesis, long- and short-term deformability has been studied from the material and the structural modelling point of view. Moreover, two materials have been handled: pultruded composites and concrete. A new finite element model for thin-walled beams has been introduced. As a main assumption, cross-sections rigid are considered rigid in their plane; this hypothesis replaces that of the classical beam theory of plane cross-sections in the deformed state. That also allows reducing the total number of degrees of freedom, and therefore making analysis faster compared with twodimensional finite elements. Longitudinal direction warping is left free, allowing describing phenomena such as the shear lag. The new finite-element model has been first applied to concrete thin-walled beams (such as roof high span girders or bridge girders) subject to instantaneous service loadings. Concrete in his cracked state has been considered through a smeared crack model for beams under bending. At a second stage, the FE-model has been extended to the viscoelastic field and applied to pultruded composite beams under sustained loadings. The generalized Maxwell model has been adopted. As far as materials are concerned, long-term creep tests have been carried out on pultruded specimens. Both tension and shear tests have been executed. Some specimen has been strengthened with carbon fibre plies to reduce short- and long- term deformability. Tests have been done in a climate room and specimens kept 2 years under constant load in time. As for concrete, a model for tertiary creep has been proposed. The basic idea is to couple the UMLV linear creep model with a damage model in order to describe nonlinearity. An effective strain tensor, weighting the total and the elasto-damaged strain tensors, controls damage evolution through the damage loading function. Creep strains are related to the effective stresses (defined by damage models) and so associated to the intact material.

Structural changes and dynamic behaviour of vanadium oxide-based catalysts for gas-phase selective oxidations

Selective oxidation is one of the simplest functionalization methods and essentially all monomers used in manufacturing artificial fibers and plastics are obtained by catalytic oxidation processes. Formally, oxidation is considered as an increase in the oxidation number of the carbon atoms, then reactions such as dehydrogenation, ammoxidation, cyclization or chlorination are all oxidation reactions. In this field, most of processes for the synthesis of important chemicals used vanadium oxide-based catalysts. These catalytic systems are used either in the form of multicomponent mixed oxides and oxysalts, e.g., in the oxidation of n-butane (V/P/O) and of benzene (supported V/Mo/O) to maleic anhydride, or in the form of supported metal oxide, e.g., in the manufacture of phthalic anhydride by o-xylene oxidation, of sulphuric acid by oxidation of SO2, in the reduction of NOx with ammonia and in the ammoxidation of alkyl aromatics. In addition, supported vanadia catalysts have also been investigated for the oxidative dehydrogenation of alkanes to olefins , oxidation of pentane to maleic anhydride and the selective oxidation of methanol to formaldehyde or methyl formate [1]. During my PhD I focused my work on two gas phase selective oxidation reactions. The work was done at the Department of Industrial Chemistry and Materials (University of Bologna) in collaboration with Polynt SpA. Polynt is a leader company in the development, production and marketing of catalysts for gas-phase oxidation. In particular, I studied the catalytic system for n-butane oxidation to maleic anhydride (fluid bed technology) and for o-xylene oxidation to phthalic anhydride. Both reactions are catalyzed by systems based on vanadium, but catalysts are completely different. Part A is dedicated to the study of V/P/O catalyst for n-butane selective oxidation, while in the Part B the results of an investigation on TiO2-supported V2O5, catalyst for o-xylene oxidation are showed. In Part A, a general introduction about the importance of maleic anhydride, its uses, the industrial processes and the catalytic system are reported. The reaction is the only industrial direct oxidation of paraffins to a chemical intermediate. It is produced by n-butane oxidation either using fixed bed and fluid bed technology; in both cases the catalyst is the vanadyl pyrophosphate (VPP). Notwithstanding the good performances, the yield value didn’t exceed 60% and the system is continuously studied to improve activity and selectivity. The main open problem is the understanding of the real active phase working under reaction conditions. Several articles deal with the role of different crystalline and/or amorphous vanadium/phosphorous (VPO) compounds. In all cases, bulk VPP is assumed to constitute the core of the active phase, while two different hypotheses have been formulated concerning the catalytic surface. In one case the development of surface amorphous layers that play a direct role in the reaction is described, in the second case specific planes of crystalline VPP are assumed to contribute to the reaction pattern, and the redox process occurs reversibly between VPP and VOPO4. Both hypotheses are supported also by in-situ characterization techniques, but the experiments were performed with different catalysts and probably under slightly different working conditions. Due to complexity of the system, these differences could be the cause of the contradictions present in literature. Supposing that a key role could be played by P/V ratio, I prepared, characterized and tested two samples with different P/V ratio. Transformation occurring on catalytic surfaces under different conditions of temperature and gas-phase composition were studied by means of in-situ Raman spectroscopy, trying to investigate the changes that VPP undergoes during reaction. The goal is to understand which kind of compound constituting the catalyst surface is the most active and selective for butane oxidation reaction, and also which features the catalyst should possess to ensure the development of this surface (e.g. catalyst composition). On the basis of results from this study, it could be possible to project a new catalyst more active and selective with respect to the present ones. In fact, the second topic investigated is the possibility to reproduce the surface active layer of VPP onto a support. In general, supportation is a way to improve mechanical features of the catalysts and to overcome problems such as possible development of local hot spot temperatures, which could cause a decrease of selectivity at high conversion, and high costs of catalyst. In literature it is possible to find different works dealing with the development of supported catalysts, but in general intrinsic characteristics of VPP are worsened due to the chemical interaction between active phase and support. Moreover all these works deal with the supportation of VPP; on the contrary, my work is an attempt to build-up a V/P/O active layer on the surface of a zirconia support by thermal treatment of a precursor obtained by impregnation of a V5+ salt and of H3PO4. In-situ Raman analysis during the thermal treatment, as well as reactivity tests are used to investigate the parameters that may influence the generation of the active phase. Part B is devoted to the study of o-xylene oxidation of phthalic anhydride; industrially, the reaction is carried out in gas-phase using as catalysts a supported system formed by V2O5 on TiO2. The V/Ti/O system is quite complex; different vanadium species could be present on the titania surface, as a function of the vanadium content and of the titania surface area: (i) V species which is chemically bound to the support via oxo bridges (isolated V in octahedral or tetrahedral coordination, depending on the hydration degree), (ii) a polymeric species spread over titania, and (iii) bulk vanadium oxide, either amorphous or crystalline. The different species could have different catalytic properties therefore changing the relative amount of V species can be a way to optimize the catalytic performances of the system. For this reason, samples containing increasing amount of vanadium were prepared and tested in the oxidation of o-xylene, with the aim of find a correlations between V/Ti/O catalytic activity and the amount of the different vanadium species. The second part deals with the role of a gas-phase promoter. Catalytic surface can change under working conditions; the high temperatures and a different gas-phase composition could have an effect also on the formation of different V species. Furthermore, in the industrial practice, the vanadium oxide-based catalysts need the addition of gas-phase promoters in the feed stream, that although do not have a direct role in the reaction stoichiometry, when present leads to considerable improvement of catalytic performance. Starting point of my investigation is the possibility that steam, a component always present in oxidation reactions environment, could cause changes in the nature of catalytic surface under reaction conditions. For this reason, the dynamic phenomena occurring at the surface of a 7wt% V2O5 on TiO2 catalyst in the presence of steam is investigated by means of Raman spectroscopy. Moreover a correlation between the amount of the different vanadium species and catalytic performances have been searched. Finally, the role of dopants has been studied. The industrial V/Ti/O system contains several dopants; the nature and the relative amount of promoters may vary depending on catalyst supplier and on the technology employed for the process, either a single-bed or a multi-layer catalytic fixed-bed. Promoters have a quite remarkable effect on both activity and selectivity to phthalic anhydride. Their role is crucial, and the proper control of the relative amount of each component is fundamental for the process performance. Furthermore, it can not be excluded that the same promoter may play different role depending on reaction conditions (T, composition of gas phase..). The reaction network of phthalic anhydride formation is very complex and includes several parallel and consecutive reactions; for this reason a proper understanding of the role of each dopant cannot be separated from the analysis of the reaction scheme. One of the most important promoters at industrial level, which is always present in the catalytic formulations is Cs. It is known that Cs plays an important role on selectivity to phthalic anhydride, but the reasons of this phenomenon are not really clear. Therefore the effect of Cs on the reaction scheme has been investigated at two different temperature with the aim of evidencing in which step of the reaction network this promoter plays its role.

The impact of structural conditions in communes on sports behaviour of adolescents and young adults in Switzerland

Young peoples’ sport activity in Switzerland differs considerably depending on the linguistic region (Lamprecht, Fischer, & Stamm, 2008). This appears to be based on cultural as well as on structural differences. The question then arises how differing structural conditions in communes (e.g. sport facilities, significance of the municipal promotion of sport) across different linguistic regions of Switzerland cause variation in sport behaviour. Based on the theory of social action (Coleman, 1990), it is assumed that individual behaviour is not only determined by individual but also by structural and socio-cultural factors in which a person is socially embedded. In two case studies, multilevel data was gathered analysing possible influences of structural factors on sports behaviour. Using an online survey, 15 to 25 year old inhabitants (N = 205) living in a German and French speaking commune were questioned about their sports participation in and outside of their commune, as well as their perception of sport-related structural characteristics in their commune. To collect information about communes’ sport facilities, the sport providers (N = 23) were interviewed. Sport-related characteristics of the communes were also collected through two interviews with representatives of the municipal administration. As expected, sport participation is significantly lower in the French speaking commune (Chi2 (1, N = 205) = 3.84, p < .05). Adolescents and young adults living in the French speaking commune are less satisfied with the sport infrastructure (F(1,135) = 9.65, p < .01) and evaluate the opportunities to be physically active in their commune significantly worse (F(1,144) = 15.33, p < .01) than their German-speaking counterparts. These first findings show the impact of structural conditions in communes on sport participation of adolescents and young people. However, it must be noted that this study is explorative and further communes would need to be examined in order to generalize the results. References Coleman, J. S. (1990). Foundations of social theory. Cambridge, MA: Belknap. Lamprecht, M., Fischer, A. & Stamm, H. (2008). Sport Schweiz 2008. Das Sportverhalten der Schweizer Bevölkerung. Magglingen: BASPO.

The impact of structural conditions in communes on physical activity and sports behaviour of adolescents and young adults in Switzerland

Introduction The physical activity of the Swiss population differs considerably depending on the linguistic region. German speakers are more often physically active than people living in the French- or Italian-speaking part of Switzerland (Stamm & Lamprecht, 2008). This study analyses how differing structural conditions in communes (e.g. sport facilities, significance of the municipal promotion of sport) across different linguistic regions of Switzerland correlate with physical activity and sports participation for adolescents and young adults. Methodological approach Based on the theory of social action (Coleman, 1990), it is assumed that individual behaviour is not only determined by individual but also by structural and socio-cultural factors in which a person is socially embedded. In two case studies, multilevel data was gathered analysing possible influences of structural factors on sports behaviour. Using an online survey, 15 to 25 year old inhabitants (N = 205) living in a German- and French-speaking commune were questioned about their sports participation in and outside of their commune, as well as their perception of sport-related structural characteristics in their commune. To collect information about communes’ sport facilities, the sport providers (N = 23) were interviewed. Sport-related characteristics of the communes were also collected through two interviews with representatives of the municipal administration. Results and discussion Physical activity is significantly higher (Chi2 (1, N = 183) = 4.78, p < .05) and sport participation is significantly lower in the French speaking commune (Chi2 (1, N = 205) = 3.84, p < .05). Adolescents and young adults in the French speaking commune (M = 3.15, SD = 1.23) are less satisfied with the opportunities to be physically active in the environment than their counterparts living in the German speaking commune (p < .001, Mann-Whitney U – test). These first findings show the impact of structural conditions in communes on physical activity and sport participation of adolescents and young people. However, it must be noted that this study is explorative and further communes would need to be examined in order to generalize the results. References Coleman J S (1990). Foundations of social theory. Belknap, Cambridge, MA. Stamm H, Lamprecht M (2008). EJSS, 8(1+2), 15-29.

The impact of structural conditions in communes on sports behaviour of adolescents and young adults in Switzerland

Young peoples’ sport activity differs considerably depending on the linguistic region in Switzerland (Lamprecht, Fischer, & Stamm, 2014). This appears to be based on cultural as well as on structural differences. The question then arises how differing structural conditions in communes (e.g. sport facilities, significance of the municipal promotion of sport) across different linguistic regions of Switzerland cause variation in sport behaviour. Based on the theory of social action (Coleman, 1990), it is assumed that individual behaviour is not only determined by individual but also by structural and socio - cultural factors in which a person is socially embedded . In 33 municipalities of the German and French speaking region of Switzerland, multilevel data was gathered analysing possible influences of structural factors on sports behaviour. Using an online survey, 15 to 30 year old inhabitants (N=3677) were questi oned about their sports participation, as well as their perception of sport - related structural characteristics in their commune. To collect information about communes’ sport facilities, sport providers as well as representatives of the municipal administra tion were interviewed and document analyses were conducted. Representatives of the municipal administration attach more importance to sport promotion in the German speaking than in French - speaking municipalities. Young people living in the French speaking commune are less satisfied with the sport facilities (F(1,3266)=31.31, p<.01) and they are less physically active than their German - speaking counterparts (Chi2(1,N=3537)=22.51, p<.05). These first findings show the impact of structural conditions in commun es on sport participation of adolescents and young people. However, further multilevel analyses will be conducted for a better understanding of correlations between structural conditions and different sports behaviour of young people. References Coleman, J. S. (1990). Foundations of social theory. Cambridge, MA: Belknap. Lamprecht, M., Fischer, A. & Stamm, H. (2014). Sport Schweiz 2014. Sportaktivität und Sportinteresse der Schweizer Bevölkerung. Magglingen: BASPO.

Behaviour of Concrete Structural Members Subjected to Air Blast Loading

Numerical analysis is a suitable tool in the design of complex reinforced concrete structures under extreme impulsive loadings such as impacts or explosions at close range. Such events may be the result of terrorist attacks. Reinforced concrete is commonly used for buildings and infrastructures. For this reason, the ability to accurately run numerical simulations of concrete elements subjected to blast loading is needed. In this context, reliable constitutive models for concrete are of capital importance. In this research numerical simulations using two different constitutive models for concrete (Continuous Surface Cap Model and Brittle Damage Model) have been carried out using LS-DYNA. Two experimental benchmark tests have been taken as reference. The results of the numerical simulations with the aforementioned constitutive models show different abilities to accurately represent the structural response of the reinforced concrete elements studied.

Modelling the input-output behaviour of piezoelectric structural health monitoring systems for composite plates

This paper investigates the input-output characteristics of structural health monitoring systems for composite plates based on permanently attached piezoelectric transmitter and sensor elements. Using dynamic piezoelectricity theory and a multiple integral transform method to describe the propagating and scattered flexural waves an electro-mechanical model for simulating the voltage input-output transfer function for circular piezoelectric transmitters and sensors adhesively attached to an orthotropic composite plate is developed. The method enables the characterization of all three physical processes, i.e. wave generation, wave propagation and wave reception. The influence of transducer, plate and attached electrical circuit characteristics on the voltage output behaviour of the system is examined through numerical calculations, both in frequency and the time domain. The results show that the input-output behaviour of the system is not properly predicted by the transducers' properties alone. Coupling effects between the transducers and the tested structure have to be taken into account, and adding backing materials to the piezoelectric elements can significantly improve the sensitivity of the system. It is shown that in order to achieve maximum sensitivity, particular piezoelectric transmitters and sensors need to be designed according to the structure to be monitored and the specific frequency regime of interest.

Iron(III) and iron(II) complexes of 1-thia-4,7-diazacyclononane ([9]aneN(2)S) and 1,4-dithia-7-azacyclononane ([9]aneNS(2)). X-Ray structural analyses, magnetic susceptibility, Mossbauer, EPR and electronic spectroscopy

The complexes [Fe([9]aneN(2)S)(2)][ClO4](2), [Fe([9]aneN(2)S)(2)][ClO4](3) and [Fe([9]aneNS(2))(2)][ClO4](2) ([9]aneN(2)S = 1-thia-4. 7-diazacyclononane and [9]aneNS(2) = 1,4-dithia-7-azacyclononane) have been prepared and the latter two characterised by X-ray crystallography. The Mossbauer spectra (isomer shift/mm s(-1), quadrupole splitting/mm s(-1), 4.2 K) for [Fe([9]aneN(2)S)(2)][ClO4](2) (0.52, 0.57), [Fe([9]aneN(2)S)(2)][ClO4](3) (0.25, 2.72) and [Fe([9]aneNS(2))(2)][ClO4](2) (0.43, 0.28) are typical for iron(II) and iron(III) complexes. Variable-temperature susceptibility measurements for [Fe([9]aneN(2)S)(2)][ClO4](2) (2-300 K) revealed temperature-dependent behaviour in both the solid state [2.95 mu(B) (300 K)-0.5 mu(B) (4.2 K)] and solution (Delta H degrees 20-22 kJ mol(-1), Delta S degrees 53-60 J mol(-1) K-1). For [Fe([9]aneN(2)S)(2)][ClO4](3) in the solid state [2.3 mu(B) (300 K)-1.9 mu(B) (4.2 K)] the magnetic data were fit to a simple model (H = -lambda L . S + mu L-z) to give the spin-orbit coupling constant (lambda) of -260 +/- 10 cm(-1). The solid-state X-band EPR spectrum of [Fe([9]aneN(2)S)(2)][ClO4](3) revealed axial symmetry (g(perpendicular to) = 2.607, g(parallel to) = 1.599). Resolution of g(perpendicular to) into two components at Q-band frequencies indicated a rhombic distortion. The low-temperature single-crystal absorption spectra of [Fe([9]aneN(2)S)(2)][ClO4](2) and [Fe([9]aneNS(2))(2)][ClO4](2) exhibited additional bands which resembled pseudotetragonal low-symmetry splitting of the parent octahedral (1)A(1g) --> T-1(2g) and (1)A(1g) ---> T-1(1g) transitions. However, the magnitude of these splittings was too large, requiring 10Dq for the thioether donors to be significantly larger than for the amine donors. Instead, these bands were tentatively assigned to weak, low-energy S --> Fe-II charge-transfer transitions. Above 200 K, thermal occupation of the high-spin T-5(2g) ground state resulted in observation of the T-5(2g) --> E-5(g) transition in the crystal spectrum of [Fe([9]aneN(2)S)(2)][ClO4](2). From a temperature-dependence study, the separation of the low-spin (1)A(1g) and high-spin T-5(2g) ground states was approximately 1700 cm(-1). The spectrum of the iron(III) complex [Fe([9]aneN(2)S)(2)][ClO4](3) is consistent with a low-spin d(5) configuration.

Simultaneous steady state and dynamic design of process systems using structural indicators

The simultaneous design of the steady-state and dynamic performance of a process has the ability to satisfy much more demanding dynamic performance criteria than the design of dynamics only by the connection of a control system. A method for designing process dynamics based on the use of a linearised systems' eigenvalues has been developed. The eigenvalues are associated with system states using the unit perturbation spectral resolution (UPSR), characterising the dynamics of each state. The design method uses a homotopy approach to determine a final design which satisfies both steady-state and dynamic performance criteria. A highly interacting single stage forced circulation evaporator system, including control loops, was designed by this method with the goal of reducing the time taken for the liquid composition to reach steady-state. Initially the system was successfully redesigned to speed up the eigenvalue associated with the liquid composition state, but this did not result in an improved startup performance. Further analysis showed that the integral action of the composition controller was the source of the limiting eigenvalue. Design changes made to speed up this eigenvalue did result in an improved startup performance. The proposed approach provides a structured way to address the design-control interface, giving significant insight into the dynamic behaviour of the system such that a systematic design or redesign of an existing system can be undertaken with confidence.

Hydromorphone-3-glucuronide - A more potent neuro-excitant than its structural analogue, morphine-3-glucuronide

In humans, hydromorphone (HMOR) is metabolised principally by conjugation with glucuronic acid to form hydromorphone-3-glucuronide (H3G), a close structural analogue of morphine-3-glucuronide (M3G), the major metabolite of morphine. In a previous study we described the biochemical synthesis of H3G together with a preliminary evaluation of its pharmacology which revealed that it is a neuro-excitant in rats in a manner analogous to M3G. Thus the aims of the current study were to quantify the neuro-excitatory behaviours evoked by intracerebroventricular (icv) H3G in the rat and to define its potency relative to M3G. Groups of adult male Sprague-Dawley rats received icy injections (1 muL) of H3G (1 - 3 mug), M3G (2 - 7 mug) or vehicle via a stainless steel guide cannula that had been implanted stereotaxically seven days prior to drug administration. Behavioural excitation was monitored by scoring fifteen different behaviours (myoclonic jerks, chewing, wet-dog-shakes, rearing, tonic-clonic-convulsions, explosive motor behaviour, grooming, exploring, general activity, eating, staring, ataxia, righting reflex, body posture, touch evoked agitation) immediately prior to icy injection and at the following post-dosing times: 5, 15, 25, 35, 50, 65 and 80 min. H3G produced dose-dependent behavioural excitation in a manner analogous to that reported previously for M3G by our laboratory and reproduced herein. H3G was found to be approximately 2.5-fold more potent than M3G, such that the mean (+/- S.D.) ED50 values were 2.3 (+/- 0.1) mug and 6.1 (+/- 0.6) mug respectively. Thus, our data clearly imply that if H3G crosses the BBB with equivalent efficiency to M3G, then the myoclonus, allodynia and seizures observed in some patients dosed chronically with large systemic doses of HMOR, are almost certainly due to the accumulation of sufficient H3G in the central nervous system, to evoke behavioural excitation. (C) 2001 Elsevier Science Inc. All rights reserved.

Structural refinement of systems specified in object-z and CSP

This paper is concerned with methods for refinement of specifications written using a combination of Object-Z and CSP. Such a combination has proved to be a suitable vehicle for specifying complex systems which involve state and behaviour, and several proposals exist for integrating these two languages. The basis of the integration in this paper is a semantics of Object-Z classes identical to CSP processes. This allows classes specified in Object-Z to be combined using CSP operators. It has been shown that this semantic model allows state-based refinement relations to be used on the Object-Z components in an integrated Object-Z/CSP specification. However, the current refinement methodology does not allow the structure of a specification to be changed in a refinement, whereas a full methodology would, for example, allow concurrency to be introduced during the development life-cycle. In this paper, we tackle these concerns and discuss refinements of specifications written using Object-Z and CSP where we change the structure of the specification when performing the refinement. In particular, we develop a set of structural simulation rules which allow single components to be refined to more complex specifications involving CSP operators. The soundness of these rules is verified against the common semantic model and they are illustrated via a number of examples.

Profiling consumer behaviour in cross-border tourism destinations

Tourism is a phenomenon that moves millions of people around the world, taking as a major driver of the global economy. Such relevance is reflected in the proliferation of studies in the overall area known as tourism, under various perspectives and backgrounds. In the light of such multitude of insights our study aims at gaining a deeper understanding of customer profiling and behavior in cross-border tourism destinations. Previous studies conducted in such contexts suggest that cross-border regions (CBRs) are an attractive and desirable idea, yet requiring further theoretical and empirical research. The new configuration of many CBRs calls for a debate on issues concerning its development, raising up important dimensions, such as, organization and planning of common tourism destinations. There is still a gap in the understanding of destination management in CBRs and the customer profile and motivations. Overall this research aims at attaining a deeper understanding of the profile and behavior of consumers in tourism settings, addressing the predisposition for the destination. The study addresses the following research question: “What factors influence customer behavior and attitudes in a CBRs tourism destination?” To address our question we will take an interdisciplinary perspective bringing together inputs from marketing, tourism and local economics. When addressing consumer behavior in tourism previous studies considered the following constructs: involvement, place attachment, satisfaction and destination loyalty. In order to establish the causal relationships in our theoretical model, we intend to develop a predominant quantitative design, yet we plan to conduct exploratory interviews. In the analysis and discussion of results, we intend to use Structural Equation Modeling. It will further allow understanding how the constructs in the research model relate to each other in the specified context. Results are also expected to have managerial implications. Consequently our results may assist decision makers in developing their local policies.