Fiber beam-columns models with flexure-shear interaction for nonlinear analysis of reinforced concrete structures

The aim of this study was to develop a model capable to capture the different contributions which characterize the nonlinear behaviour of reinforced concrete structures. In particular, especially for non slender structures, the contribution to the nonlinear deformation due to bending may be not sufficient to determine the structural response. Two different models characterized by a fibre beam-column element are here proposed. These models can reproduce the flexure-shear interaction in the nonlinear range, with the purpose to improve the analysis in shear-critical structures. The first element discussed is based on flexibility formulation which is associated with the Modified Compression Field Theory as material constitutive law. The other model described in this thesis is based on a three-field variational formulation which is associated with a 3D generalized plastic-damage model as constitutive relationship. The first model proposed in this thesis was developed trying to combine a fibre beamcolumn element based on the flexibility formulation with the MCFT theory as constitutive relationship. The flexibility formulation, in fact, seems to be particularly effective for analysis in the nonlinear field. Just the coupling between the fibre element to model the structure and the shear panel to model the individual fibres allows to describe the nonlinear response associated to flexure and shear, and especially their interaction in the nonlinear field. The model was implemented in an original matlab® computer code, for describing the response of generic structures. The simulations carried out allowed to verify the field of working of the model. Comparisons with available experimental results related to reinforced concrete shears wall were performed in order to validate the model. These results are characterized by the peculiarity of distinguishing the different contributions due to flexure and shear separately. The presented simulations were carried out, in particular, for monotonic loading. The model was tested also through numerical comparisons with other computer programs. Finally it was applied for performing a numerical study on the influence of the nonlinear shear response for non slender reinforced concrete (RC) members. Another approach to the problem has been studied during a period of research at the University of California Berkeley. The beam formulation follows the assumptions of the Timoshenko shear beam theory for the displacement field, and uses a three-field variational formulation in the derivation of the element response. A generalized plasticity model is implemented for structural steel and a 3D plastic-damage model is used for the simulation of concrete. The transverse normal stress is used to satisfy the transverse equilibrium equations of at each control section, this criterion is also used for the condensation of degrees of freedom from the 3D constitutive material to a beam element. In this thesis is presented the beam formulation and the constitutive relationships, different analysis and comparisons are still carrying out between the two model presented.

Semantic Enrichment of Scientific Documents with Semantic Lenses – Developing methodologies, tools and prototypes for their concrete use

Con questa dissertazione di tesi miro ad illustrare i risultati della mia ricerca nel campo del Semantic Publishing, consistenti nello sviluppo di un insieme di metodologie, strumenti e prototipi, uniti allo studio di un caso d‟uso concreto, finalizzati all‟applicazione ed alla focalizzazione di Lenti Semantiche (Semantic Lenses).

COBAMOS: Endnutzerprogrammierung auf Basis nachrichtenbasierter Komponentenvernetzung

Die Aufgabenstellung, welche dieser Dissertation zugrunde liegt, lässt sich kurz als die Untersuchung von komponentenbasierten Konzepten zum Einsatz in der Softwareentwicklung durch Endanwender beschreiben. In den letzten 20 bis 30 Jahren hat sich das technische Umfeld, in dem ein Großteil der Arbeitnehmer seine täglichen Aufgaben verrichtet, grundlegend verändert. Der Computer, früher in Form eines Großrechners ausschließlich die Domäne von Spezialisten, ist nun ein selbstverständlicher Bestandteil der täglichen Arbeit. Der Umgang mit Anwendungsprogrammen, die dem Nutzer erlauben in einem gewissen Rahmen neue, eigene Funktionalität zu definieren, ist in vielen Bereichen so selbstverständlich, dass viele dieser Tätigkeiten nicht bewusst als Programmieren wahrgenommen werden. Da diese Nutzer nicht notwendigerweise in der Entwicklung von Software ausgebildet sind, benötigen sie entsprechende Unterstützung bei diesen Tätigkeiten. Dies macht deutlich, welche praktische Relevanz die Untersuchungen in diesem Bereich haben. Zur Erstellung eines Programmiersystems für Endanwender wird zunächst ein flexibler Anwendungsrahmen entwickelt, welcher sich als Basis zur Erstellung solcher Systeme eignet. In Softwareprojekten sind sich ändernde Anforderungen und daraus resultierende Notwendigkeiten ein wichtiger Aspekt. Dies wird im Entwurf des Frameworks durch Konzepte zur Bereitstellung von wieder verwendbarer Funktionalität durch das Framework und Möglichkeiten zur Anpassung und Erweiterung der vorhandenen Funktionalität berücksichtigt. Hier ist zum einen der Einsatz einer serviceorientierten Architektur innerhalb der Anwendung und zum anderen eine komponentenorientierte Variante des Kommando-Musters zu nennen. Zum anderen wird ein Konzept zur Kapselung von Endnutzerprogrammiermodellen in Komponenten erarbeitet. Dieser Ansatz ermöglicht es, unterschiedliche Modelle als Grundlage der entworfenen Entwicklungsumgebung zu verwenden. Im weiteren Verlauf der Arbeit wird ein Programmiermodell entworfen und unter Verwendung des zuvor genannten Frameworks implementiert. Damit dieses zur Nutzung durch Endanwender geeignet ist, ist eine Anhebung der zur Beschreibung eines Softwaresystems verwendeten Abstraktionsebene notwendig. Dies wird durch die Verwendung von Komponenten und einem nachrichtenbasierten Kompositionsmechanismus erreicht. Die vorgenommene Realisierung ist dabei noch nicht auf konkrete Anwendungsfamilien bezogen, diese Anpassungen erfolgen in einem weiteren Schritt für zwei unterschiedliche Anwendungsbereiche.

Nondestructive evaluation of concrete compression strength by means of Artificial Neural Network (ANN)

The evaluation of structural performance of existing concrete buildings, built according to standards and materials quite different to those available today, requires procedures and methods able to cover lack of data about mechanical material properties and reinforcement detailing. To this end detailed inspections and test on materials are required. As a consequence tests on drilled cores are required; on the other end, it is stated that non-destructive testing (NDT) cannot be used as the only mean to get structural information, but can be used in conjunction with destructive testing (DT) by a representative correlation between DT and NDT. The aim of this study is to verify the accuracy of some formulas of correlation available in literature between measured parameters, i.e. rebound index, ultrasonic pulse velocity and compressive strength (SonReb Method). To this end a relevant number of DT and NDT tests has been performed on many school buildings located in Cesena (Italy). The above relationships have been assessed on site correlating NDT results to strength of core drilled in adjacent locations. Nevertheless, concrete compressive strength assessed by means of NDT methods and evaluated with correlation formulas has the advantage of being able to be implemented and used for future applications in a much more simple way than other methods, even if its accuracy is strictly limited to the analysis of concretes having the same characteristics as those used for their calibration. This limitation warranted a search for a different evaluation method for the non-destructive parameters obtained on site. To this aim, the methodology of neural identification of compressive strength is presented. Artificial Neural Network (ANN) suitable for the specific analysis were chosen taking into account the development presented in the literature in this field. The networks were trained and tested in order to detect a more reliable strength identification methodology.

Synthesis of hexa-peri-hexabenzocoronenes - from building blocks to functional materials

Discotic hexa-peri-hexabenzocoronene (HBC) derivatives have attracted intensive scientific interest due to their unique optoelectronic properties, which depends, to a large extend, upon the attached functional groups. The presented work covers the synthesis of novel HBC building blocks and new HBC derivatives as functional materials. The traditional preparation of HBC derivatives requires elaborate synthetic techniques and tremendous effort. Especially, more than 10 synthetic steps are usually necessary to approach HBCs with lower symmetries. In order to simplify the synthetic work and reduce the high costs, a novel synthetic strategy involving only four steps was developed based on 2,3,5,6-tetraphenyl-1,4-diiodobenzene intermediates and palladium catalyzed Suzuki cross coupling reactions. In order to introduce various functionalities and expand the diversity of multi-functionalizations, a novel C2v-symmetric dihalo HBC building block 2-47, which contains one iodine and one bromine in para positions, was prepared following the traditional intermolecular [4+2] Diels-Alder reaction route. The outstanding chemical selectivity between iodo and bromo groups in this compound consequently leads to lots of HBC derivatives bearing different functionalities. Directly attached heteroatoms will improve the material properties. According to the application of intramolecular Scholl reaction to a para-dimethoxy HPB, which leads to a meta-dimethoxy HBC, a phenomenon of phenyl group migration was discovered. Thereby, several interesting mechanistic details involving arenium cation intermediates were discussed. With a series of dipole functionalized HBCs, the molecular dynamics of this kind of materials was studied in different phases by DSC, 2D WAXD, solid state NMR and dielectric spectroscopies. High charge carrier mobility is an important parameter for a semiconductive material and depends on the degree of intramolecular order of the discotic molecules in thin films for HBC derivatives. Dipole – dipole interaction and hydrogen bonds were respectively introduced in order to achieve highly ordered supramolecular structure. The self-assembly behavior of these materials were investigated both in solution and solid state. Depending upon the different functionalities, these novel materials show either gelating or non-linear optical properties, which consequently broaden their applications as functional materials. In the field of conceivable electronic devices at a molecular level, HBCs hold high promise. Differently functionalized HBCs have been used as active component in the studies of single-molecular CFET and metal-SAMs-metal junctions. The outstanding properties shown in these materials promise their exciting potential applications in molecular devices.

Study of the mechanisms of shear transfer in fiber-reinforced concrete elements

matlab functions for the validation of push-off tests results

Development of glass-ceramics from combination of industrial wastes together with boron mining waste

The utilization of borate mineral wastes with glass-ceramic technology was first time studied and primarily not investigated combinations of wastes were incorporated into the research. These wastes consist of; soda lime silica glass, meat bone and meal ash and fly ash. In order to investigate possible and relevant application areas in ceramics, kaolin clay, an essential raw material for ceramic industry was also employed in some studied compositions. As a result, three different glass-ceramic articles obtained by using powder sintering method via individual sintering processes. Light weight micro porous glass-ceramic from borate mining waste, meat bone and meal ash and kaolin clay was developed. In some compositions in related study, soda lime silica glass waste was used as an additive providing lightweight structure with a density below 0.45 g/cm3 and a crushing strength of 1.8±0.1 MPa. In another study within the research, compositions respecting the B2O3–P2O5–SiO2 glass-ceramic ternary system were prepared from; borate wastes, meat bone and meal ash and soda lime silica glass waste and sintered up to 950ºC. Low porous, highly crystallized glass-ceramic structures with density ranging between 1.8 ± 0,7 to 2.0 ± 0,3 g/cm3 and tensile strength ranging between 8,0 ± 2 to 15,0 ± 0,5 MPa were achieved. Lastly, diopside - wollastonite (SiO2-Al2O3-CaO )glass-ceramics from borate wastes, fly ash and soda lime silica glass waste were successfully obtained with controlled rapid sintering between 950 and 1050ºC. The wollastonite and diopside crystal sizes were improved by adopting varied combinations of formulations and heating rates. The properties of the obtained materials show; the articles with a uniform pore structure could be useful for thermal and acoustic insulations and can be embedded in lightweight concrete where low porous glass-ceramics can be employed as building blocks or additive in cement and ceramic industries.

Dynamic resolution of alpha-substituted dihydrocinnamic aldehydes. A new asymmetric synthesis of pharmaceutically important amine building blocks.

Crystallization-induced diastereoisomer transformation (CIDT) was successfully employed in the enantioselective synthesis of 2-alkyl-3-aryl-propan-1-amines. These products are seen as potentially useful building blocks in the field of asymmetric organic chemistry, notably for pharmaceutically relevant compounds. The procedure was based on a recently reported protocol for deracemization of dihydrocinnamic aldehydes in which enantiomerically enriched 1-(amino(phenyl)methyl)naphthalen-2-ol (Betti base) is employed as a resolving agent. Additionally, fenpropimorph, a biologically active substance which contains the 2-alkyl-3-aryl-propan-1-amine moiety was synthetized, as an attempt to assess the usefulness of the enantiomerically enriched amines.

Analysis of an innovative slim floor composite beam conformed by a custom GFRP pultruded profile and reinforced concrete.

GFRP pultruded profiles have shown to be structural profiles with great stiffness, strenght and very low specific weight, making it a great candidate for the rehabilitation of damaged strucutres. To further enhance the strucutral mechanism of these type of beams, the Slimflor composite structural system has lead as basis for this analysis; by replacing the steel beam with a GFRP pultruded profile. To further increase its composite action, a continuous shear connector has been set as part of the beam cross section as well as its needed reinforcement and fire protection.

Hyperbranched polyether polyols as building blocks for complex macromolecular architectures

The present thesis deals with the development of new branched polymer architectures containing hyperbranched polyglycerol. Materials investigated include hyperbranched oligomers, hyperbranched polyglycerols containing functional initiator-cores at the focal point, well-defined linear-hyperbranched block copolymers and also negatively charged hyperbranched polyelectrolytes.rnHyperbranched oligoglycerols (DPn = 7 and 14) have been synthesized for the first time. The materials show narrow polydispersity (Mw/Mn ca. 1.45) and a very low content in cyclic homopolymers. 13C NMR evidences the dendritic structure of the oligomers and the DB could be calculated (44% and 52%). These new oligoglycerols were compared with the industrial products obtained by polycondensation which exhibit narrow polydispersity (Mw/Mn<1.3) butrnmultimodal distribution in SEC. Detailed 13C NMR and Maldi-ToF studies reveal the presence of branched units and cyclic compounds. In comparison, the hyperbranched oligoglycerols comprise a very low proportion of cyclic homopolymer which render them very interesting materials for biomedical applications for example.rnThe site isolation of the core moiety in dendritic structure offers intriguing potential with respect to peculiar electro-optical properties. Various initiator-cores (n-alkyl amines, UVabsorbing amines and benzophenone) for the ROMBP of glycidol have been tested. The bisglycidolized amine initiator-cores show the best control over the molecular weight and the molecular weight distribution. The photochemical analyses of the naphthalene containingrnhyperbranched polyglycerols show a slight red shift, a pronounced hypochromic effect (decrease of the intensity of the band) compared with the parent model compound and the formation of a relative compact structure. The benzophenone containing polymers adopt an open structure in polar solvents. The fluorescence measurements show a clear “dendritic effect” on the fluorescence intensities and the quantum yield of the encapsulated benzophenone.rnA convenient 3-step strategy has been developed for the preparation of well-defined amphiphilic, linear-hyperbranched block copolymers via hypergrafting. The procedure represents a combination of carbanionic polymerization with the alkoxide-based, controlled ring-opening multibranching polymerization of glycidol. Materials consisting of a polystyrene linear block and a hyperbranched polyglycerol block exhibit narrow polydispersity (1.01-1.02rnfor 5.4% to 27% wt. PG and 1.74 for 52% wt. PG) with a high grafting efficiency. The strategy was also extended to materials with a linear polyisoprene block.rnDetailed investigations of the solution properties of the block copolymers with linear polystyrene blocks show that block copolymer micelles are stabilized by the highly branched block. The morphology of the aggregates is depending on the solvent: in chloroform monodisperse spherical shape aggregates and in toluene ellipsoidal aggregates are formed. On graphite these aggregates show interesting features, giving promising potential applications with respect to the presence of a very dense, functional and stable hyperbranched block.rnThe bulk morphology of the linear-hyperbranched block copolymers has been investigated. The materials with a linear polyisoprene block only behave like complex liquids due to the low Tg and the disordered nature of both components. For the materials with polystyrene, only the sample with 27% wt. hyperbranched polyglycerol forms some domains showing lamellae.rnThe preparation of hyperbranched polyelectrolytes was achieved by post-modification of the hydroxyl groups via Michael addition of acrylonitrile, followed by hydrolysis. In aqueous solution materials form large aggregates with size depending on the pH value. After deposition on mica the structures observed by AFM show the coexistence of aggregates andrnunimers. For the low molecular weight sample (PG 520 g·mol-1) extended and highly ordered terrace structures were observed. Materials were also successfully employed for the fabrication of composite organic-inorganic multilayer thin films, using electrostatic layer-bylayer self-assembly coupled with chemical vapor deposition.

Hyperbranched polyglycerols as building blocks for complex amphiphilic structures: synthesis, characterization and applications

Among hyperbranched polymers, polyglycerol is one of the most promising and commonly used macromolecules due to its biocompatibility and versatility. However, the synthesis of high molecular weight polyglycerols still involves many intricacies and has only been understood to a limited extent. Furthermore, only few complex structures like star or block copolymers incorporating polyglycerol have been realized so far. Particularly biocompatible block copolymers are considered promising candidates for biomedical applications.rnThe scope of this thesis was the enhancement of the synthetic process leading to polyglycerol derivatives which implies improved molecular weight control for a broad molecular weight range as well as the assembly of more complex structures like amphiphilic block copolymers. Further insight into the relation between reaction solvent, degree of deprotonation during the ring-opening multibranching polymerization of glycidol and the characteristics of the obtained polymers were achieved within the scope of this work. Based on these results, a novel concept for the preparation of hyperbranched polyglycerols with molecular weights up to 20,000 g/mol was developed, applying a two step synthesis pathway. Starting from a partially deprotonated TMP core, low molecular weight hb-PGs were prepared using the known synthetic protocol that has been established since the late 1990ies. In a subsequent reaction sequence, these well defined polymers were used as hyperbranched macroinitiator cores in order to obtain high molecular weight hb-PGs with remarkably low polydispersity (Mw/Mn < 1.8). Molecular weight control was shown to be excellent and undesired low molecular weight side products were absent. Furthermore, the technique of continuous spin fractionation has been discovered as an efficient method for polyglycerol work-up to remove quantitatively residual monomer- and oligomer traces from hb-PG compositions to result in samples with significantly reduced polydispersities. Based on these results the synthesis of amphiphilic block copolymers containing hydrophilic hyperbranched polyglycerol blocks and linear, apolar poly(propylene oxide) blocks has been significantly improved and augmented to hb-PG-b-l-PPO-b-hb-PG ABA block copolymers. The influence of different polyglycerol-based amphiphiles on the fibril formation was studied by Thioflavin T Fluorescence showing remarkable increasing lag times which is promising in order to enhance the stability of this protein. In addition the first synthesis of poly(glyceryl glycerols) (PGG), introducing a new solketyl glycidyl ether monomer (IGG) was shown. It was furthermore demonstrated that core-functional carbosilane wedges allow application in block copolymer synthesis. Bisglycidolized amine functional polymers were successfully employed as macroinitiators for glycidol polymerization. This resulted in the first example of amphiphilic hyperbranched-hyperbranched polymer structures. Finally, it has been shown that the previously reported synthetic pathway to carboxylated hyperbranched polyglycerol polyelectrolytes can also be applied for the amphiphilic linear-hyperbranched block copolymers. These novel biocompatible and highly amphiphilic polyelectrolytes offer great potential for further investigations. rnrn

Life cycle assessment in construction field: A life cycle cost analysis of reinforcement concrete bridge

The present work is included in the context of the assessment of sustainability in the construction field and is aimed at estimating and analyzing life cycle cost of the existing reinforced concrete bridge “Viadotto delle Capre” during its entire life. This was accomplished by a comprehensive data collection and results evaluation. In detail, the economic analysis of the project is performed. The work has investigated possible design alternatives for maintenance/rehabilitation and end-of-life operations, when structural, functional, economic and also environmental requirements have to be fulfilled. In detail, the economic impact of different design options for the given reinforced concrete bridge have been assessed, whereupon the most economically, structurally and environmentally efficient scenario was chosen. The Integrated Life-Cycle Analysis procedure and Environmental Impact Assessment were also discussed in this work. The scope of this thesis is to illustrate that Life Cycle Cost analysis as part of Life Cycle Assessment approach could be effectively used to drive the design and management strategy of new and existing structures. The final objective of this contribution is to show how an economic analysis can influence decision-making in the definition of the most sustainable design alternatives. The designers can monitor the economic impact of different design strategies in order to identify the most appropriate option.

Novel porphyrin amino acids as building blocks for artificial photosynthetic reaction centers : photoinduced energy and electron transfer

This thesis reports on the synthesis and characterisation of trans-(M)AB2C meso-substituted porphyrin amino acid esters (PAr) (M = 2H or Zn) with tunable electron donating and electron withdrawing Ar substituents at B positions (Ar = 4-C6H4OnBu, 4-C6H4OMe, 2,4,6-C6H2Me3, 4-C6H4Me, C6H5, 4-C6H4F, 4-C6H4CF3, C6F5). These porphyrins were used as key building blocks for photosynthetic LHC (LHC = light-harvesting antenna complex) and RC (RC = reaction center) model compounds.rnBased on free-base or zinc(II) porphyrin amino acid esters and porphyrin acids several amide linked free-base bis(porphyrins) PAr1-PAr2 (Ar1 = 2,4,6-C6H2Me3, C6F5 and Ar2 = 2,4,6-C6H2Me3, 4-C6H4F, 4-C6H4CF3, C6F5), mono metallated bis(porphyrin) PAr1-(Zn)PAr2 (Ar1 = 2,4,6-C6H2Me3 and Ar2 =4-C6H4F) and its doubly zincated complexes (Zn)PAr1-(Zn)PAr2 were prepared. In the fluorescence spectra of free-base bis(porphyrins) the porphyrin with the strongest electron donating power of Ar substituents at B positions is the light emitting unity. The emission of mono metallated bis(porphyrin) occurs only from the free-base porphyrin building block. This phenomenon is caused by an efficient energy transfer likely via the Dexter through-bond mechanism.rnLinking of anthraquinone (Q) as electron acceptor (A) to the N-terminus of porphyrin amino acid esters ((M)PAr) and aminoferrocene (Fc) as electron donor (D) to the C-terminus of the porphyrin resulting in Q-(M)PAr-Fc triads (M = 2H or Zn, Ar = 4-C6H4OnBu, 4-C6H4OMe, 2,4,6-C6H2Me3, 4-C6H4Me, C6H5, 4-C6H4F, 4-C6H4CF3, C6F5) with tunable electron density at the porphyrin chromophore. In these triads initial oxidative PET (Q←(M)PAr) and reductive PET ((M)PAr→Fc) (PET = photoinduced electron transfer) are possible. Both processes leads to an emission quenching of (M)PAr. The efficiency of the PET pathways occurring in the Marcus normal region is controlled by the specific porphyrin electron density.rnAmide-linked conjugates PAr-Fc (Ar = 2,4,6-C6H2Me3, C6F5) and Fmoc-Fc-PAr1 (N-Fmoc-Fc = N-Fmoc protected 1,1’-ferrocene amino acid; Ar1 = C6H5, 4-C6H4F, 4-C6H4CF3, C6F5) as well as hinges PAr2-Fc-PAr1 (Ar1 = C6H5, 4-C6H4F and Ar2 = 2,4,6-C6H2Me3) were studied with respect to the reductive PET. The PET driving force (−GET) in dyads increases with the increasing electron withdrawing character of Ar substituents. Additionally, intramolecular energy transfer between porphyrins PAr1 and PAr2 is feasible in the hinges via the Förster mechanism.rn