Festkörper-NMR an polymeren Kompositmaterialien

In dieser Arbeit wurden polymere Kompositmaterialien mit Hilfe von Festkörper-NMR-Techniken untersucht, um den Einfluß von Polymer-Festkörper-Kontakten auf molekulare Materialeigenschaften zu betrachten. Dabei wurden sowohl Analysen am Polymer als auch am Füllmaterial durchgeführt.rnrnIm ersten Teil der Arbeit wurde die Dynamik von Poly(ethylmethacrylat) (PEMA) in sphärischen Bürstenpartikeln gemessen. Diese Bürsten bestanden aus einem Poly(silsesquioxan)-Kern und verpfropften PEMA-Ketten, die über ATRP (atom transfer radical polymerization) an verschiedenen Kettensequenzen mit 13C an der Carboxylgruppe markiert wurden. Statische 13C-NMR-Messungen konnten zeigen, dass die Dynamik dieser Sequenzen unabhängig vom Abstand zur Oberfläche verlangsamt ist, was auf eine eingeschränkte Reptation zurückgeführt wurde.rnrnDer zweite Teil der Arbeit beschäftigt sich mit den molekularen Unterschieden von Silika-Naturkautschuk-Kompositen, die über mechanisches Mischen bzw. über eine Sol-Gel-Reaktion hergestellt wurden. Durch kinetische 1H-NMR-Messungen wurde der Umsatz der Sol-Gel-Reaktion bestimmt. Mittels heteronuklearen 29Si{1H}-NMR-Korrelationsexperimenten wurde ein direkter räumlicher Kontakt zwischen dem Inneren der Partikel und dem Polymer nachgewiesen. Dies belegt experimentell, dass im Kompositmaterial die Polymerketten in den durch Sol-Gel-Reaktion hergestellten Silikapartikeln eingeschlossen sind.

Fully bio-based epoxy resins

Epoxy resins are mainly produced by reacting bisphenol A with epichlorohydrin. Growing concerns about the negative health effects of bisphenol A are urging researchers to find alternatives. In this work diphenolic acid is suggested, as it derives from levulinic acid, obtained from renewable resources. Nevertheless, it is also synthesized from phenol, from fossil resources, which, in the current paper has been substituted by plant-based phenols. Two interesting derivatives were identified: diphenolic acid from catechol and from resorcinol. Epichlorohydrin on the other hand, is highly carcinogenic and volatile, leading to a tremendous risk of exposure. Thus, two approaches have been investigated and compared with epichlorohydrin. The resulting resins have been characterized to find an appropriate application, as epoxy are commonly used for a wide range of products, ranging from composite materials for boats to films for food cans. Self-curing capacity was observed for the resin deriving from diphenolic acid from catechol. The glycidyl ether of the diphenolic acid from resorcinol, a fully renewable compound, was cured in isothermal and non-isothermal tests tracked by DSC. Two aliphatic amines were used, namely 1,4-butanediamine and 1,6-hexamethylendiamine, in order to determine the effect of chain length on the curing of an epoxy-amine system and determine the kinetic parameters. The latter are crucial to plan any industrial application. Both diamines demonstrated superior properties compared to traditional bisphenol A-amine systems.

Kontrolle der Grenzflächeneigenschaften anorganischer Nanopartikel mittels amphiphiler Polymere

Im Rahmen dieser Arbeit wurden amphiphile Co- und Terpolymere verwendet, um die Grenzflächeneigenschaften anorganischer Nanopartikel zu kontrollieren. Es wurde eine effiziente und vielseitige Methode entwickelt, mit der in-situ hydrophobierte, formanisotrope ZnO-, CdS- und Au-Nanopartikel sowie poröse TiO2-Nanopartikel hergestellt werden konnten. Diese Technik basierte auf der Fällung anorganischer Nanopartikel in einer inversen Emulsion mittels kombinierten Einsatzes zweier maßgeschneiderter amphiphiler Polymere. Ein Copolymer ermöglichte sowohl die Stabilisierung der Emulsion als auch die Hydrophobierung der Partikel, und ein weiteres Struktur-dirigierendes Agens (SDA) kontrollierte den Kristallisationsprozess. Infolge ihrer Form zeigten die Nanopartikel von sphärischen Teilchen abweichende Lagen der Oberflächenplasmonenresonanz und der Bandlücke. Aufgrund der hervorragenden Hydrophobierung dieser Kolloide mittels amphiphiler Copolymere konnten diese homogen in polymere Materialien eingearbeitet werden. Dies erlaubte es die speziellen Eigenschaften von nicht-sphärischen Kolloiden auf Nanokompositmaterialien zu übertragen. Darüber hinaus wurden amphipolare Copolymere genutzt, um superhydrophobe Oberflächen zu generieren. Hierzu wurden Filme bestehend aus rauen SiO2-Nanopartikeln mit fluorierten Emulgatoren beschichtet. In einem dritten Schwerpunkt dieser Arbeit wurden amphiphile Co- und Terpolymere verwendet, um anorganische Nanopartikel zu hydrophilieren. Durch Variation der Emulgatorzusammensetzung konnten die Ladung und Ladungsdichte auf der Partikeloberfläche gezielt gesteuert werden. Darüber hinaus konnte die Partikelhülle zusätzlich mit Farbstoffmolekülen funktionalisiert werden, was den erfolgreichen Einsatz der Kolloide in Zellaufnahmeexperimenten ermöglichte.

Modifizierungen des Enzyms Silicatein alpha zur direkten Immobilisierung auf verschiedenen Oberflächen : neuartige Herstellung von Kompositmaterialien unter physiologischen Bedingungen

Das Silicatein α ist ein 24 kDa großes Enzym, welches im Schwamm Suberites domuncula für die Synthese von Biosilikat verantwortlich ist. Vorhergehende Studien haben gezeigt, dass Silicatein auch die Synthese anderer Metalloxide wie Titandioxid, Galliumoxid und Zirkoniumdioxid katalysieren kann. Diese Fähigkeiten machen das Silicatein α für biomedizinische und biotechnologische Anwendungen interessant, da die Synthese unter nahezu physiologischen Bedingungen ablaufen kann, was die Herstellung neuartiger Kompositmaterialien mit einzigartigen Eigenschaften erleichtern würde. Zur Immobilisierung des Silicatein α auf verschiedenen Oberflächen wurde bislang ein Nickel-NTA-Kopolymer eingesetzt. Diese Art der Immobilisierung bietet eine Reihe von Möglichkeiten in der Nanobiotechnologie, stößt aber in der Biomedizin an ihre Grenzen, da sich nicht alle Oberflächen für ein solches Coating eignen. Zudem können die zur Aktivierung des Polymers nötigen Lösungsmittel und die über die Zeit freigesetzten Monomere aus dem Polymergerüst toxische oder mutagene Wirkung auf das umliegende Gewebe haben. Deshalb wurde das Silicatein α in dieser Arbeit mit zwei Affinitäts-Tags so modifiziert, dass es an verschiedene Oberflächen immobilisiert werden kann und dabei seine Aktivität beibehält. Zuerst wurde das Silicatein mit einem Glu-tag am N-terminalen Ende modifiziert. Dadurch gelang die direkte Immobilisierung an Hydroxyapatit und die folgende, enzymkatalysierte Synthese von Biosilikat-Beschichtungen auf diesem Träger. Die Eigenschaften eines solchen HA-Kompositmaterials können zum Beispiel zu einem verbesserten, schnelleren und stabileren Einwachsen von Knochenimplantaten führen, da Biosilikat die Reifung und Differenzierung von Osteoblasten beschleunigt. rnMit dem an Hydroxyapatit-Plättchen immobilisierten Glu-tag-Silicatein wurde ein modifizierter Pull-down Assay etabliert, wodurch bekannte, aber auch bis dahin noch unbekannte Protein-Interaktionspartner identifiziert werden konnten. rnUm zu zeigen, dass der entwickelte Glu-tag an präformierte, calciumhaltige Oberflächen binden kann, wurden die Nadeln des Kalkschwammes Paraleucilla magna als Modellorganismus verwendet. Die Nadeln konnten durch das immobilisierte Silicatein mit einer Titandioxid-Schicht überzogen werden und unter Verwendung des Interaktionspartners Silintaphin-1 konnte diese Beschichtung noch verstärkt werden. Solche CaCO3-Kompositmaterialien könnten sowohl in der Biomedizin als auch in der Biotechnologie zum Einsatz kommen. Neben den erwähnten calciumhaltigen Materialien finden auch andere Stoffe wie TiO2-Nanodrähte Verwendung in der Forschung. In weiterführenden Experimenten konnte gezeigt werden, dass der entwickelte Glu-tag auch Affinität zu Titandioxid-Oberflächen vermittelt. Auch hier konnte durch das oberflächenimmobilisierte Enzym eine Biosilikatbeschichtung synthetisiert werden. rnMit der zweiten Modifikation - einem Cys-tag - konnte Silicatein direkt auf Goldoberflächen immobilisiert werden. Durch die Verwendung eines Polydimethylsiloxan (PDMS)-Stempels wurde das Cys-getaggte Silicatein in einem linienförmigen Muster auf das Gold übertragen und die Synthese von Titandioxid dort nachgewiesen.rnDie Experimente und Ergebnisse dieser Arbeit haben gezeigt, dass Silicatein α durch einfache Modifikationen an verschiedene Oberflächen immobilisiert werden kann und dabei immer noch seine Aktivität behält. rnHierdurch ergibt sich die Möglichkeit, unter Normalbedingungen verschiedenste Kompositmaterialien herzustellen.rn

Heusler compounds for thermoelectric applications

The demands for energy is leading to social and political conflicts in the world. For example, the limited resources of fossil fuels causing a dependence on the oil conveying countries in the world, leading to political discords. One way to save energy is to increase the efficiency of a process. In the field of thermoelectricity waste heat is used to produce electricity, this leads to an improvement of the efficiency. Heusler compounds with C1b structure with the general formula XY Z (X, Y = transition metal, Z = main group element) are in focus of the present thermoelectric research. Their mechanical and thermal stability is exceptional in comparison to the commonly used thermoelectric materials. The possibility to substitute small amounts of elements from the parent compound without destructing the lattice structure allows tuning the electronic properties. This tunability also allows to avoid the use of toxic and expensive elements. The reported thermoelectric Heusler compounds exhibit high electrical conductivity and moderate values of the Seebeck coefficients, which lead to a high powerfactor. The disadvantage of Heusler compounds is their high thermal conductivity. Introducing mass disorder on the X-site lattice is one effective way to produce additional phonon scattering and with it to decrease the thermal conductivity. Another approach is to implement a nano or micro structure in the thermoelectric material. This can be achieved by phase separation, composite materials, pulverization with additional spark plasma sintering or by a complex lattice structure. In the first part of this work, the influence of element substitutions on the Zr0.5Hf0.5NiSn system was investigated, to obtain the knowledge on how to optimize the electronic properties of the Heusler compounds with C1b structure. In line with this, the change of the electronic structure was investigated and a possible mechanism is predicted. In the second part of this work, the phenomenon of phase separation was investigated. First, by applying a phase separation in the well-known system Co2MnSn and subsequently by systematic investiga- tions on the TixZryHfzNiSn. In the third part, the results from the previous parts before were used to produce and explain the best reported Heusler compound with C1b structure exhibiting a Figure of Merit of ZT= 1.2 at 830 K.

Experimental characterization of carbon-fiber-reinforced polymer laminates

The goal of this thesis is to make static tensile test on four Carbon Fiber Reinforced Polymer laminates, in such a way as to obtain the ultimate tensile strength of these laminates; in particular, the laminates analyzed were produced by Hand Lay-up technology. Testing these laminates we have a reference point on which to compare other laminates and in particular CFRP laminate produced by RTM technology.

Performance of vertebral cancellous bone augmented with compliant PMMA under dynamic loads

Increased fracture risk has been reported for the adjacent vertebral bodies after vertebroplasty. This increase has been partly attributed to the high Young's modulus of commonly used polymethylmethacrylate (PMMA). Therefore, a compliant bone cement of PMMA with a bulk modulus closer to the apparent modulus of cancellous bone has been produced. This compliant bone cement was achieved by introducing pores in the cement. Due to the reduced failure strength of that porous PMMA cement, cancellous bone augmented with such cement could deteriorate under dynamic loading. The aim of the present study was to assess the potential of acute failure, particle generation and mechanical properties of cancellous bone augmented with this compliant cement in comparison to regular cement. For this purpose, vertebral biopsies were augmented with porous- and regular PMMA bone cement, submitted to dynamic tests and compression to failure. Changes in Young's modulus and height due to dynamic loading were determined. Afterwards, yield strength and Young's modulus were determined by compressive tests to failure and compared to the individual composite materials. No failure occurred and no particle generation could be observed during dynamical testing for both groups. Height loss was significantly higher for the porous cement composite (0.53+/-0.21%) in comparison to the biopsies augmented with regular cement (0.16+/-0.1%). Young's modulus of biopsies augmented with porous PMMA was comparable to cancellous bone or porous cement alone (200-700 MPa). The yield strength of those biopsies (21.1+/-4.1 MPa) was around two times higher than for porous cement alone (11.6+/-3.3 MPa).

Characterization of thermal and mechanical properties of polypropylene-based composites for fuel cell bipolar plates and development of educational tools in hydrogen and fuel cell technologies

In this project we developed conductive thermoplastic resins by adding varying amounts of three different carbon fillers: carbon black (CB), synthetic graphite (SG) and multi-walled carbon nanotubes (CNT) to a polypropylene matrix for application as fuel cell bipolar plates. This component of fuel cells provides mechanical support to the stack, circulates the gases that participate in the electrochemical reaction within the fuel cell and allows for removal of the excess heat from the system. The materials fabricated in this work were tested to determine their mechanical and thermal properties. These materials were produced by adding varying amounts of single carbon fillers to a polypropylene matrix (2.5 to 15 wt.% Ketjenblack EC-600 JD carbon black, 10 to 80 wt.% Asbury Carbon's Thermocarb TC-300 synthetic graphite, and 2.5 to 15 wt.% of Hyperion Catalysis International's FIBRILTM multi-walled carbon nanotubes) In addition, composite materials containing combinations of these three fillers were produced. The thermal conductivity results showed an increase in both through-plane and in-plane thermal conductivities, with the largest increase observed for synthetic graphite. The Department of Energy (DOE) had previously set a thermal conductivity goal of 20 W/m·K, which was surpassed by formulations containing 75 wt.% and 80 wt.% SG, yielding in-plane thermal conductivity values of 24.4 W/m·K and 33.6 W/m·K, respectively. In addition, composites containing 2.5 wt.% CB, 65 wt.% SG, and 6 wt.% CNT in PP had an in–plane thermal conductivity of 37 W/m·K. Flexural and tensile tests were conducted. All composite formulations exceeded the flexural strength target of 25 MPa set by DOE. The tensile and flexural modulus of the composites increased with higher concentration of carbon fillers. Carbon black and synthetic graphite caused a decrease in the tensile and flexural strengths of the composites. However, carbon nanotubes increased the composite tensile and flexural strengths. Mathematical models were applied to estimate through-plane and in-plane thermal conductivities of single and multiple filler formulations, and tensile modulus of single-filler formulations. For thermal conductivity, Nielsen's model yielded accurate thermal conductivity values when compared to experimental results obtained through the Flash method. For prediction of tensile modulus Nielsen's model yielded the smallest error between the predicted and experimental values. The second part of this project consisted of the development of a curriculum in Fuel Cell and Hydrogen Technologies to address different educational barriers identified by the Department of Energy. By the creation of new courses and enterprise programs in the areas of fuel cells and the use of hydrogen as an energy carrier, we introduced engineering students to the new technologies, policies and challenges present with this alternative energy. Feedback provided by students participating in these courses and enterprise programs indicate positive acceptance of the different educational tools. Results obtained from a survey applied to students after participating in these courses showed an increase in the knowledge and awareness of energy fundamentals, which indicates the modules developed in this project are effective in introducing students to alternative energy sources.

Nanomechanics of cellulose crystals and cellulose-based polymer composites

Cellulose-polymer composites have potential applications in aerospace and transportation areas where lightweight materials with high mechanical properties are needed. In addition, these economical and biodegradable composites have been shown to be useful as polymer electrolytes, packaging structures, optoelectronic devices, and medical implants such as wound dressing and bone scaffolds. In spite of the above mentioned advantages and potential applications, due to the difficulties associated with synthesis and processing techniques, application of cellulose crystals (micro and nano sized) for preparation of new composite systems is limited. Cellulose is hydrophilic and polar as opposed to most of common thermoplastics, which are non-polar. This results in complications in addition of cellulose crystals to polymer matrices, and as a result in achieving sufficient dispersion levels, which directly affects the mechanical properties of the composites. As in other composite materials, the properties of cellulose-polymer composites depend on the volume fraction and the properties of individual phases (the reinforcement and the polymer matrix), the dispersion quality of the reinforcement through the matrix and the interaction between CNCs themselves and CNC and the matrix (interphase). In order to develop economical cellulose-polymer composites with superior qualities, the properties of individual cellulose crystals, as well as the effect of dispersion of reinforcements and the interphase on the properties of the final composites should be understood. In this research, the mechanical properties of CNC polymer composites were characterized at the macro and nano scales. A direct correlation was made between: Dispersion quality and macro-mechanical properties Nanomechanical properties at the surface and tensile properties CNC diameter and interphase thickness Lastly, individual CNCs from different sources were characterized and for the first time size-scale effect on their nanomechanical properties were reported. Then the effect of CNC surface modification on the mechanical properties was studied and correlated to the crystalline structure of these materials.

A study of acoustic emission technique for concrete damage detection

The Acoustic emission (AE) technique, as one of non-intrusive and nondestructive evaluation techniques, acquires and analyzes the signals emitting from deformation or fracture of materials/structures under service loading. The AE technique has been successfully applied in damage detection in various materials such as metal, alloy, concrete, polymers and other composite materials. In this study, the AE technique was used for detecting crack behavior within concrete specimens under mechanical and environmental frost loadings. The instrumentations of the AE system used in this study include a low-frequency AE sensor, a computer-based data acquisition device and a preamplifier linking the AE sensor and the data acquisition device. The AE system purchased from Mistras Group was used in this study. The AE technique was applied to detect damage with the following laboratory tests: the pencil lead test, the mechanical three-point single-edge notched beam bending (SEB) test, and the freeze-thaw damage test. Firstly, the pencil lead test was conducted to verify the attenuation phenomenon of AE signals through concrete materials. The value of attenuation was also quantified. Also, the obtained signals indicated that this AE system was properly setup to detect damage in concrete. Secondly, the SEB test with lab-prepared concrete beam was conducted by employing Mechanical Testing System (MTS) and AE system. The cumulative AE events and the measured loading curves, which both used the crack-tip open displacement (CTOD) as the horizontal coordinate, were plotted. It was found that the detected AE events were qualitatively correlated with the global force-displacement behavior of the specimen. The Weibull distribution was vii proposed to quantitatively describe the rupture probability density function. The linear regression analysis was conducted to calibrate the Weibull distribution parameters with detected AE signals and to predict the rupture probability as a function of CTOD for the specimen. Finally, the controlled concrete freeze-thaw cyclic tests were designed and the AE technique was planned to investigate the internal frost damage process of concrete specimens.

[Oral jewelry: a review]

Oral jewelry is popular. One of the most widely spread types are so-called tooth diamonds made of composite materials which are applied to the teeth with an adhesive. Note that parents are required to sign a release form for under-aged patients in Switzerland. Tooth cap grills and gold teeth are considered status symbols within the Hip-Hop fashion scene. However, tooth ornaments favour the accumulation of plaque and can diminish the ability to articulate. With respect to jewelry in oral soft tissue especially tongue and lip piercings are of significance to dentists. Besides the systemic complications, which are mostly caused by a lack of hygiene or the failure of noting medical contraindications by the piercer, local complications occur frequently. After surgery, pain, swelling, infections as well as hemorrhages or hematomas can be observed. Long-term effects can be problematic: gingival recession can be discernes mainly in the case of lip piercings the loss of hard tooth substance in the case of tongue piercings. Because of that, conservation therapies can become indespensable. Patients wearing dental jewelry have to be aware of risks of tooth damage, and they regularly have to undergo dental check-ups. Information campaigns--for dentists as well as patients--are necessary.

Posterior Vertical Bite Reconstructions of Erosively Worn Dentitions and the "Stamp Technique" - A Case Series with a Mean Observation Time of 40 Months

PURPOSE In the present case series, the authors report on seven cases of erosively worn dentitions (98 posterior teeth) which were treated with direct resin composite. MATERIALS AND METHODS In all cases, both arches were restored by using the so-called stamp technique. All patients were treated with standardized materials and protocols. Prior to treatment, a waxup was made on die-cast models to build up the loss of occlusion as well as ensure the optimal future anatomy and function of the eroded teeth to be restored. During treatment, teeth were restored by using templates of silicone (ie, two "stamps," one on the vestibular, one on the oral aspect of each tooth), which were filled with resin composite in order to transfer the planned, future restoration (ie, in the shape of the waxup) from the extra- to the intraoral situation. Baseline examinations were performed in all patients after treatment, and photographs as well as radiographs were taken. To evaluate the outcome, the modified United States Public Health Service criteria (USPHS) were used. RESULTS The patients were re-assessed after a mean observation time of 40 months (40.8 ± 7.2 months). The overall outcome of the restorations was good, and almost exclusively "Alpha" scores were given. Only the marginal integrity and the anatomical form received a "Charlie" score (10.2%) in two cases. CONCLUSION Direct resin composite restorations made with the stamp technique are a valuable treatment option for restoring erosively worn dentitions.

Mejora del comportamiento térmico de los morteros de cal aditivados y su empleo en la rehabilitación de inmuebles = Improvement of thermal behaviour of additived lime mortars and their use in rehabilitation of buildings

La envolvente de la edificación es la responsable de equilibrar el intercambio energético entre el interior y el exterior, por lo tanto cualquier actuación encaminada a la reducción del consumo energético ha de establecer, como uno de sus objetivos prioritarios, la mejora del comportamiento de la misma. Las edificaciones anteriores a 1940 constituyen la mayor parte de las existentes en áreas rurales y centros urbanos. En ellas, la repercusión de la fachada sobre las transmitancias globales pone de manifiesto la necesidad de intervención. Sin embargo, su elevada inercia térmica y los importantes saltos térmicos característicos de gran parte de España plantean la importancia de que aquélla se efectúe por el exterior. A tal respecto, la falta de disponibilidad de espesor suficiente para implantar sistemas tipo SATE deriva en que, frecuentemente, la única solución viable sea la de aislar por el interior perdiendo con ello la capacidad de acumulación térmica del muro y con el asociado riesgo de condensaciones. La amplia tradición en el empleo de revestimientos, especialmente en base de cal, permiten que éstos sean utilizados no sólo como elemento estético o de protección de la obra de fábrica antigua sino también para la mejora del comportamiento térmico del soporte, si se aprovecha el mecanismo de transmisión térmica por radiación. Éste es el objetivo de la presente Tesis Doctoral en la que se estudia la modificación de las propiedades radiantes de los morteros de revestimiento para la mejora de la eficiencia energética de las construcciones históricas, principalmente las constituidas por muros monolíticos, aunque podría ser de aplicación a otro tipo de construcciones compuestas por diversas capas. Como punto de partida, se estudió y revisó la documentación disponible sobre las investigaciones de las tres áreas científico-tecnológicas que convergen en la Tesis Doctoral: rehabilitación, material y comportamiento térmico, a partir de lo cual se comprobó la inexistencia de estudios similares al objeto de la presente Tesis Doctoral. Complementariamente, se analizaron los revestimientos en lo concerniente a los materiales que los constituyen, la composición de las mezclas y características de cada una de las capas así como al enfoque que, desde el punto de vista térmico, se estimaba más adecuado para la obtención de los objetivos propuestos. Basándonos en dichos análisis, se preseleccionaron ochenta materiales que fueron ensayados en términos de reflectancia y emisividad para elegir cuatro con los que se continuó la investigación. Éstos, junto con la cal elegida para la investigación y el árido marmóreo característico de la última capa de revestimiento, fueron caracterizados térmicamente, de forma pormenorizada, así como química y físicamente. Los fundamentos teóricos y los estudios preliminares desarrollados con distintos materiales, en estado fresco y endurecido, fueron empleados en la dosificación de componentes de las mezclas, en dos proporciones distintas, para el estudio del efecto del agregado. Éstas se ensayaron en estado fresco, para comprobar su adecuación de puesta en obra y prever su VI adherencia al soporte, así como en estado endurecido a 28 y 90 días de curado, para conocer las propiedades que permitieran prever su compatibilidad con aquél y estimar el alcance de la reducción de transferencias térmicas lograda. Además, se estudiaron las características generales de las mezclas que sirvieron para establecer correlaciones entre distintas propiedades y entender los resultados mecánicos, físicos (comportamiento frente al agua) y energéticos. Del estudio conjunto de las distintas propiedades analizadas se propusieron dos mezclas, una blanca y otra coloreada, cuyas características permiten garantizar la compatibilidad con la obra de fábrica antigua, desde el punto de vista físico y mecánico, y preservar la autenticidad de los revestimientos, en cuanto a la técnica de aplicación tradicional en sistemas multicapa. El comportamiento térmico de las mismas, sobre una obra de fábrica de 40 cm de espesor, se estimó, en estado estacionario y pseudo-transitorio, demostrándose reducciones del flujo térmico entre 16-48%, en condiciones de verano, y entre el 6-11%, en invierno, en función de la coloración y de la rugosidad de la superficie, en comparación con el empleo de la mezcla tradicional. Por lo que, se constata la viabilidad de los materiales compuestos propuestos y su adecuación al objetivo de la investigación. VII ABSTRACT The envelope is responsible for balancing the energy exchange between the inside and outside in buildings. For this reason, any action aimed at reducing energy consumption must establish, as one of its key priorities, its improvement. In rural areas and urban centers, most of the constructions were built before 1940. In them, the impact of the façade on the global transmittance highlights the need for intervention. However, its high thermal inertia and fluctuation of temperatures in the majority of Spain bring up that it should be placed outside the insulation. In this regard, the lack of availability of enough thickness to implement systems such as ETICS results in that often the only viable solution is to isolate the interior, losing thereby the wall’s heat storage capacity with the associated risk of condensation. The tradition in the use of renders, especially lime-based, allows us to use them not only as an aesthetic element or to protect the ancient masonry, but also for improved thermal performance of the support by taking advantage of the heat transfer mechanism by radiation. This is the aim of this Doctoral Thesis in which the modification of the radiative properties of lime mortars for renders to improve the energy efficiency of historic buildings, mainly composed of monolithic walls, is studied, although it could be applied to other structures composed of several layers. As a starting point, the available literature in the three scientific-technological areas that converge at the Doctoral Thesis: rehabilitation, material and thermal behaviour, was reviewed, and confirmed the absence of researches similar to this Doctoral Thesis. Additionally, the renders were studied with regard to the materials that constitute them, the composition of the mixtures and the characteristics of each layer, as well as to the approach which, from a thermal point of view, was deemed the most suitable for achieving the objectives sets. Based on thre aforementioned analysis, eighty materials tested in terms of reflectance and emissivity were pre-selected, to choose four with which the research was continued. Common marble sand, used in the last layer of the renders, together with the appointed materials and hydrated lime were characterized thermally, in detail, as well as chemically and physically. The theoretical bases and preliminary studies with different materials, in fresh and hardened state, were used in the dosage of the composition of the mixtures. In order to study their effect they were used in two different proportions, that is, ten mixtures in total. These were tested in their fresh state to evaluate their setting-up suitability and foresee their adhesion to the support, as well as in their hardened state, at 28 and 90 days of curing, to establish the properties which enabled us to anticipate their compatibility with the old masonry walls and estimate the scope of the reduction of heat transfers achieved. In addition, the general characteristics of the mixtures used to establish correlations and to understand the mechanical, physical and energy results were studied. Two mixtures, one white and one colored, were proposed as the result of the different properties analysed, whose characteristics allow the guarantee of mechanical and physical compatibility VIII with the old masonry and preserve the authenticity of the renders. The thermal behavior of both, applied on a masonry wall 40 cm thick, was estimated at a steady and pseudo-transient state, with heat flow reductions between 16-48% during summertime and 6-11% during wintertime, depending on the color and surface roughness, compared to the use of the traditional mixture. So, the viability of the proposed composite materials and their fitness to the aim of the research are established.

Estudio de la redistribución tensional en la interfase frp-hormigón

El uso de materiales compuestos para el refuerzo, reparación y rehabilitación de estructuras de hormigón se ha convertido en una técnica muy utilizada en la última década. Con independencia de la técnica del refuerzo, uno de los principales condicionantes del diseño es el fallo de la adherencia entre el hormigón y el material compuesto, atribuida generalmente a las tensiones en la interfaz de estos materiales. Las propiedades mecánicas del hormigón y de los materiales compuestos son muy distintas. Los materiales compuestos comúnmente utilizados en ingeniería civil poseen alta resistencia a tracción y tienen un comportamiento elástico y lineal hasta la rotura, lo cual, en contraste con el ampliamente conocido comportamiento del hormigón, genera una clara incompatibilidad para soportar esfuerzos de forma conjunta. Esta incompatibilidad conduce a fallos relacionados con el despegue del material compuesto del sustrato de hormigón. En vigas de hormigón reforzadas a flexión o a cortante, el despegue del material compuesto es un fenómeno que frecuentemente condiciona la capacidad portante del elemento. Existen dos zonas potenciales de iniciación del despegue: los extremos y la zona entre fisuras de flexión o de flexión-cortante. En el primer caso, la experiencia a través de los últimos años ha demostrado que se puede evitar prolongando el refuerzo hasta los apoyos o mediante el empleo de algún sistema de anclaje. Sin embargo, las recomendaciones para evitar el segundo caso de despegue aún se encuentran lejos de poder prever el fallo de forma eficiente. La necesidad de medir la adherencia experimentalmente de materiales FRP adheridos al hormigón ha dado lugar a desarrollar diversos métodos por la comunidad de investigadores. De estas campañas experimentales surgieron modelos para el pronóstico de la resistencia de adherencia, longitud efectiva y relación tensión-deslizamiento. En la presente tesis se propone un ensayo de beam-test, similar al utilizado para medir la adherencia de barras de acero, para determinar las características de adherencia del FRP al variar la resistencia del hormigón y el espesor del adhesivo. A la vista de los resultados, se considera que este ensayo puede ser utilizado para investigar diferentes tipos de adhesivos y otros métodos de aplicación, dado que representa con mayor realidad el comportamiento en vigas reforzadas. Los resultados experimentales se trasladan a la comprobación del fallo por despegue en la región de fisuras de flexión o flexión cortante en vigas de hormigón presentando buena concordancia. Los resultados condujeron a la propuesta de que la limitación de la deformación constituye una alternativa simple y eficiente para prever el citado modo de fallo. Con base en las vigas analizadas, se propone una nueva expresión para el cálculo de la limitación de la deformación del laminado y se lleva a cabo una comparación entre los modelos existentes mediante un análisis estadístico para evaluar su precisión. Abstract The use of composite materials for strengthening, repairing or rehabilitating concrete structures has become more and more popular in the last ten years. Irrespective of the type of strengthening used, design is conditioned, among others, by concrete-composite bond failure, normally attributed to stresses at the interface between these two materials. The mechanical properties of concrete and composite materials are very different. Composite materials commonly used in civil engineering possess high tensile strength (both static and long term) and they are linear elastic to failure, which, in contrast to the widely known behavior of concrete, there is a clear incompatibility which leads to bond-related failures. Bond failure in the composite material in bending- or shear-strengthened beams often controls bearing capacity of the strengthened member. Debonding failure of RC beams strengthened in bending by externally-bonded composite laminates takes place either, at the end (plate end debonding) or at flexure or flexure-shear cracks (intermediate crack debonding). In the first case, the experience over the past years has shown that this can be avoided by extending laminates up to the supports or by using an anchoring system. However, recommendations for the second case are still considered far from predicting failure efficiently. The need to experimentally measure FRP bonding to concrete has induced the scientific community to develop test methods for that purpose. Experimental campaigns, in turn, have given rise to models for predicting bond strength, effective length and the stress-slip relationship. The beam-type test proposed and used in this thesis to determine the bonding characteristics of FRP at varying concrete strengths and adhesive thicknesses was similar to the test used for measuring steel reinforcement to concrete bonding conditions. In light of the findings, this test was deemed to be usable to study different types of adhesives and application methods, since it reflects the behavior of FRP in strengthened beams more accurately than the procedures presently in place. Experimental results are transferred to the verification of peeling-off at flexure or flexure-shear cracks, presenting a good general agreement. Findings led to the conclusion that the strain limitation of laminate produces accurate predictions of intermediate crack debonding. A new model for strain limitation is proposed. Finally, a comprehensive evaluation based on a statistical analysis among existing models is carried out in order to assess their accuracy.

Análisis de elementos de madera reforzados con materiales compuestos

Gran parte del patrimonio construido cuenta con edificios cuya estructura está compuesta por elementos de madera. El volumen económico que supone el mantenimiento y renovación de dicho patrimonio es considerable, por ello, es de especial interés el estudio de las diferentes técnicas de refuerzo aplicables a este tipo de estructuras. Las estructuras de madera han sido tradicionalmente reforzadas con piezas del mismo material, aumentando la sección de los elementos dañados, o con acero. La aparición de los materiales compuestos de polímeros reforzados con fibras, y su progresiva aplicación en obras de construcción, hizo que a principios de la década de los noventa se comenzara a aplicar este material en refuerzos de estructuras de madera (Puente de Sins, 1992). La madera es un material natural con una excelente relación entre sus características mecánicas y su peso. Con el uso de materiales compuestos como refuerzo ésta característica se mantiene. En cuanto a su modelo constitutivo, se admite un comportamiento elástico lineal a tracción paralela a la fibra hasta la rotura, mientras que a compresión, se considera un comportamiento lineal elástico inicial, seguido de un tramo plástico. En vigas de madera aserrada sometidas a flexión predomina el modo de fallo por tracción localizándose la fractura frecuentemente en el canto inferior. Los FRP tienen un comportamiento elástico lineal a tracción hasta la rotura y cuentan con excelentes propiedades mecánicas en relación a su peso y volumen. Si se refuerza la viga por el canto inferior se aumentará su capacidad de absorber tracciones y por tanto, es previsible que se produzca un incremento en la capacidad de carga, así como un aumento de ductilidad. En este trabajo se analizan los beneficios que aportan distintos sistemas de refuerzos de materiales compuestos. El objetivo es contribuir al conocimiento de esta técnica para la recuperación o aumento de las propiedades resistentes de elementos de madera sometidos a flexión. Se ha llevado a cabo un estudio basado en datos obtenidos experimentalmente mediante el ensayo a flexión de vigas de madera de pino silvestre reforzadas con materiales compuestos. Las fibras que componen los tejidos utilizados para la ejecución de los refuerzos son de basalto y de carbono. En el caso de los compuestos de fibra de basalto se aplican en distintos gramajes, y los de carbono en tejido unidireccional y bidireccional. Se analiza el comportamiento de las vigas según las variables de refuerzo aplicadas y se comparan con los resultados de vigas ensayadas sin reforzar. Además se comprueba el ajuste del modelo de cálculo no lineal aplicado para predecir la carga de rotura de cada viga reforzada. Con este trabajo queda demostrado el buen funcionamiento del FRP de fibra de basalto aplicado en el refuerzo de vigas de madera y de los tejidos de carbono bidireccionales con respecto a los unidireccionales. ABSTRACT Many of the buildings of the built heritage include a structure composed by timber elements. The economic volume involved in the maintenance and renewal of this built heritage is considerable, therefore, the study of the different reinforcement techniques applicable to this type of structure is of special interest. The wooden structures have traditionally been reinforced either with steel or with pieces of the same material, increasing the section of the damaged parts. The emergence of polymer composites reinforced with fibers, and their progressive use in construction, started to be applied as reinforcement in timber structures at the beginning of the nineties decade in the 20th century (Sins Bridge, 1992). Wood is a natural material with an excellent ratio between its mechanic characteristics and its weight. This feature is maintained with the use of composites as reinforcement. In terms of its constitutive model, linear elastic behavior parallel to the fiber up to fracture is admitted when subjected to tensile stress, while under compression, an initial linear elastic behavior, followed by a section plasticizing, is considered. In sawn timber beams subjected to bending, the predominant failure is mainly due to tensile stress; and frequently the fracture is located at the beam lower face. The FRP have a linear elastic behavior until fracture occurs, and have excellent mechanical properties in relation to their weight and volume. If the beam is reinforced by its lower face, its capacity to absorb tensile stresses will increase, and therefore, an increase in its carrying capacity is likely to be produced, as well as an increase in ductility. This work analyzes the benefits different reinforcement systems of composite materials provide, with the aim of contributing to the knowledge of this technique for recovering or increasing the strength properties of timber elements subjected to bending loads. It is a study based on data obtained experimentally using bending tests of pine timber beams reinforced with composite materials. Fibers used for the execution of the reinforcement are basalt and carbon. Basalt fiber composites are applied in different grammages, whereas with carbon composites, unidirectional and bidirectional fabrics are used. The behavior of the beams was analyzed regarding the reinforcement variables applied, and the results are compared with those of the tested beams without reinforcement. Furthermore it has been proved adjunting the nonlinear calculation model applied to predict the failure load of each reinforced beam. This work proves the good behavior of fiber reinforce plastic (FRP) with basalt fiber when applied to timber beams, and that of bidirectional carbon fabrics as opposed to the unidirectional ones.