[ES] La investigación realizada forma parte del estudio, mucho más amplio, para la restauración de la Iglesia de los Santos Juanes de Valencia, que tiene por objeto establecer una metodología de reconstrucción para las pinturas murales de la grandioso bóveda que Antonio Palomino pintó entre 1699 y 1701, la cual fue incendiada durante la Guerra Civil. Al realizar un primer análisis sobre diferentes anclajes en la restauración, se han encontrado dos clases de técnicas de anclaje, las denominadas tradicionales y las modernas. Tras este análisis, se ha realizado un trabajo de investigación comparativa entre diversos espacios arquitectónicos, tanto de España como de Europa, concretamente de Italia, que ya habían sido restaurados, para poder identificar los materiales utilizados en sus realizaciones. Con todo este trabajo acabado, se contactó con el Profesor Vicente Amigó Borrás, investigador del laboratorio del Instituto de Tecnología de los Materiales, para estudiar otros materiales más novedosos que pudieran ayudar en nuestra labor. Para realizar el estudio, junto a él y muchos de sus compañeros, se desarrollaron un conjunto de probetas con el fin de elaborar diferentes tipos de laminados compuestos de fibra y matriz, los cuales han soportado los diferentes procesos y análisis para obtener los mejores resultados posibles. Estos análisis han permitido conocer muy a fondo cada material y la diversidad de sus propiedades, estableciendo estudios comparativos que han ayudado a escoger cuál de ellos resultará más apropiado para el trabajo de restauración y dar algunas conclusiones finales sobre ello en el proceso de intervención global en los Santos Juanes. Se puede afirmar que esta Tesis Doctoral demuestra la posible aplicación de materiales compuestos en diferentes bienes culturales, y en especial en la bóveda de la Iglesia de los Santos Juanes de Valencia. / [CA] La investigació realitzada forma part del estudi, molt més ample, realitzat per a la restauració de l'Església dels Sants Joans de València, que té per objectiu establir una metodologia de reconstrucció per a les pintures murals de la grandiosa volta que Antonio Palomino va pintar entre 1699 i 1701, la qual va ser incendiada durant la Guerra Civil. En realitzar una primera anàlisi sobre ancoratges en la restauració, ens hem trobat davant de dues classes de tècniques d'ancoratge, les denominades tradicionals i les modernes. Després d'aquesta anàlisi, s'ha realitzat un treball de recerca comparativa entre diversos espais arquitectònics, tant d'Espanya com d'Europa, concretament d'Italia, que ja havien sigut restaurats, per a poder identificar els materials utilitzats en les seues realitzacions. Amb tot aquest treball finalitzat, es va contactar amb el Profesor Vicente Amigó Borrás, investigador del laboratori de l'Institut de Tecnologia dels Materials, per a estudiar altres materials més nous que pogueren ajudar en la nostra labor. Per realitzar l'estudi, al costat d'ell i molts dels seus companys, es van desenvolupar un conjunt de provetes amb la finalitat d'elaborar diferents tipus de laminatges compostos de fibra i matriu, els quals han suportat els diferents processos i anàlisis per a obtenir els millors resultats possibles. Aquestes anàlisis han permés conéixer molt a fons cada material i la diversitat de les seues propietats, establint estudis comparatius que han ajudat a triar quin d'ells resultarà més apropiat per al treball de restauració i donar les conclusions finals sobre el procés d'intervenció. Es pot afirmar que aquesta Tesi Doctoral demostra la possible aplicació de materials compostos en diferents béns culturals, i especialment en la volta de l'Església dels Sants Joans de València. / [EN] The object of our study was to establish the methodology for the reconstruction of the painted murals of the great vault in the Santos Juanes church of Valencia which were painted by Antonio Palomino between 1699 and 1701 and which were burned during the Civil War. In conducting an initial study of the foundations we find two different types of technique, the traditional and modern. After this analysis a comparative investigation was carried out between the various architectural sites which have been restored, both in Spain and Europe, enabling a study of the materials which have been utilized. Having completed this work we were put in contact with Professor Vicente Amigo, Laboratory investigator of the Institute of Engineering of Technological Materials, to study alternative more modern materials, which could be put to use in our work. Finishing the study alongside him and his many colleagues, a series of tests have been carried out to develop different types of fibre and matrix laminate combinations, which have undergone a variety of analytical processes to obtain the best possible results. These analyses have enabled a closer and deeper understanding of each material and their individual properties, providing a comparative study to assist the selection of the most appropriate for our needs and giving final results closest to the procedure. It can be confirmed that this Doctorate Thesis demonstrates the possible usage of compounded materials in different cultural properties, especially in the vault of the Santos Juanes church of Valencia. / Peris Gisbert, S. (2021). Técnicas de refuerzo tradicionales y modernas aplicadas a la conservación y restauración de bienes culturales [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/180014 / TESIS

Gegenstand dieser Arbeit ist die Modifizierung von Oberflächen durch die Abscheidung alternierender Schichtsysteme auf Kohlenstofffasern und die Abscheidung von Aluminiumoxid auf organischen Membranen. Im ersten Kapitel wird das Vorgehen zur Abscheidung von organischen und anorganischen Schichten auf Kohlenstofffasern mittels der Atomlagenabscheidung und der oberflächeninitiierten Gasphasenabscheidung betrachtet. Dabei wird als Erstes auf die Abscheidung von Einzellagen und deren Optimierung eingegangen sowie im Anschluss auf die Übertragung dieser Parameter auf die Abscheidung von alternierenden Multilagensystemen. Mittels elektronenmikroskopischen-Untersuchungen, Rasterelektronenmikroskopie und energiedispersiver Röntgenspektroskopie, wird die Abscheidung der Materialien untersucht. Weiterhin können mit Hilfe von thermogravimetrischen Analysen die Oxidationsbeständigkeit der beschichteten Kohlenstofffasern sowie die einzelnen Schichtdicken bestimmt werden. Im zweiten Kapitel wird auf die Beschichtung von organischen Membranen eingegangen. Das Hauptaugenmerk liegt dabei auf der Beschichtung von nicht-hierarchisch und hierarchisch strukturierten Membranen mit Aluminiumoxid. Dafür werden die Atomlagenabscheidung und die Grenzflächenreaktion der Gasphase mit der im Feststoff gebundenen Flüssigphase angewendet. Unter Anwendung dieser beiden Verfahren ist es gelungen, dünne und gleichmäßige Schichten auf den Membranen abzuscheiden. Die Charakterisierung erfolgte mittels Rasterelektronenmikroskopie und energiedispersiver Röntgenspektroskopie. Zum Schluss wurden Filtrationsexperimente zum Vergleich der Stabilität und Durchflussraten der beschichteten mit den unbeschichteten Membranen durchgeführt.:Abkürzungsverzeichnis Symbolverzeichnis Abbildungsverzeichnis Tabellenverzeichnis 1. Einleitung und Zielsetzung 2 Oberflächenmodifizierung von Kohlenstofffasern 2.1 Einleitung 2.2 Stand der Wissenschaft 2.2.1 Kohlenstofffasern 2.2.2 Faserverstärkte Verbundwerkstoffe 2.2.3 Gasphasenabscheidung 2.2.3.1 Physikalische Gasphasenabscheidung 2.2.3.2 Chemische Gasphasenabscheidung 2.2.3.3 Atomlagenabscheidung 2.2.3.4 Oberflächeninitiierte Gasphasenabscheidung von Furfurylalkohol 2.3 Theoretische Grundlagen 2.3.1 Aufbau der Beschichtungsanlage 2.3.2 Versuchsplanung 2.3.3 Bestimmung der Schichtdicken 2.3.3.1 Bestimmung mittels Rasterkraftmikroskopie 2.3.3.2 Bestimmung mittels Rasterelektronenmikroskopie-Aufnahmen 2.3.3.3 Bestimmung mittels thermogravimetrischer Analyse 2.3.4 Untersuchungs- und Charakterisierungsmöglichkeiten von beschichteten Glas-, Kohlenstofffasern und planaren Substraten 2.4 Ergebnisse und Diskussion 2.4.1 Abscheidung von Aluminiumoxid 2.4.2 Abscheidung von Titanoxid 2.4.3 Abscheidung von Aluminiumphosphat 2.4.4 Abscheidung von Polyfurfurylalkohol 2.4.4.1 Beschichtung von Glasfasern Bestimmung der Versuchsparameter Verringerung der Furfurylalkohol-Zugabezeit Abscheidung von PFFA ohne Initiatorschicht 2.4.4.2 Pyrolyse von PFFA-Schichten zu kohlenstoffhaltigen Schichten 2.4.5 Herstellung von Multilagensystemen mit alternierender Abfolge verschiedener Schichten 2.4.5.1 Anorganische/organische Multilagensysteme auf planaren Substraten 2.4.5.2 Anorganische/organische Multilagensysteme auf Kohlenstofffasern 2.4.5.3 Anorganische/anorganische Multilagensysteme auf Kohlenstofffasern Abscheidung und Charakterisierung der Multilagensysteme Ermittlung der Schichtdicken 2.4.6 Bestimmung der Oxidationsstabilität der Multilagensysteme 2.4.6.1 Untersuchung der Oxidationsstabilität der Multilagensysteme mit TiO2 und PFFA (KP1 und KP2)100 2.4.6.2 Untersuchung der Oxidationsstabilität der Multilagensysteme mit TiO2 und PFFA (KP1-Apy und KP2-Apy und K1-py und K2-py) 2.4.6.3 Untersuchung der Oxidationsstabilität der anorganischen Multilagensysteme (K1 – K6) 2.4.6.4 Langzeitversuche zur Untersuchung der Oxidationsstabilität 3 Oberflächenmodifizierung von organischen Membranen 3.1 Einleitung 3.2 Stand der Wissenschaft 3.3 Ergebnisse und Diskussion 3.3.1 Abscheidung von Aluminiumoxid 3.3.2 Bestimmung der Permeabilitätskoeffizienten der einzelnen Mikrosiebe 4 Experimenteller Teil 4.1 Verwendete Geräte und Chemikalien 4.2 Durchführung der Abscheidungen 4.3 Untersuchung der Oxidationsstabilität 4.4 Parameter für die Festkörper-Kernspinresonanzspektroskopie Messungen 4.5 IR-Spektroskopie 4.6 XPS-Untersuchungen 4.7 PXRD-Untersuchungen 4.8 Untersuchung der Schichticken mittels Rasterkraftmikroskopie 4.9 Charakterisierung der Partikel und Mikrosiebe 5 Zusammenfassung und Ausblick 6 Literaturverzeichnis A Anhang Selbstständigkeitserklärung Lebenslauf Veröffentlichungen und Tagungsbeiträge Danksagung

Adhesive bonding which has been in use for long as a traditional joining method has gained ground in the last couple of decades due to the introduction of advanced composite materials into the aerospace industry. Bonded structures have advantages such as high corrosion and fatigue resistance, ability to join dissimilar materials, reduced stress concentration, uniform stress distribution, good damping characteristics etc. They also have certain limitations like environmental degradation, existence of defects like pores, voids and disbonds, difficulty in maintenance and repair etc. A serious drawback in the use of adhesively bonded structures has been that there are no established comprehensive non-destructive testing (NDT) techniques for their evaluation. Further, a reliable evaluation of the effect of the existing defects on strength and durability of adhesive joints is yet to be achieved. This has been a challenge for the research and development community over several decades and hence, been the motivation behind this piece of research work. Under the scope of the work carried out in the thesis, some of the primary factors such as the existence of defects, degradation of the adhesive, stress and strain distribution in the bonded region etc., have been considered to study the bond integrity in composite to composite lap shear joints. The problem becomes complex if all the parameters affecting the adhesive joint are varied simultaneously. Taking this into consideration, one of the key parameters affecting the bond quality, viz., the adhesive layer degradation was chosen to study its effect on the bonded joint. The epoxy layer was added with different, definite amount of Poly vinyl alcohol (PVA) to arrive at sets of bonded joint specimens with varied adhesive layer properties. A thorough review of different non destructive testing methods applied to this particular problem showed that ultrasonic wave based techniques could be the right choice. To start with, preliminary experimental investigations were carried on unidirectional glass fiber reinforced plastic (GFRP-epoxy) lap joints. The adhesive joints were subjected to non destructive evaluation (NDE) using ultrasonic through transmission and pulse echo techniques as also low energy digital X-ray techniques. The results obtained showed a variation in reflected and transmitted ultrasonic pulse amplitude with bond quality. Digital X-Ray radiography technique showed a variation in the intensity of transmitted x-rays due to variation in the density of adhesive. Standard mechanical tests revealed that the addition of PVA decreased the bond strength. A plot of coefficient of reflection from the first interface and the bond strength showed a linear correlation between them. After obtaining a cursory feel and understanding of the parameters involved with the preliminary experiments on GFRP adhesive joints which yielded interesting and encouraging results, further work was carried on specimens made out of autoclave cured carbon fiber reinforced plastic (CFRP)-epoxy bonded joints. Normal incidence ultrasound showed a similar trend. Analyses of the Acoustic Emission (AE) signals generated indicate early AE activity for degraded joints compared to healthy joints. Literary evidences suggest that the ultrasonic shear waves are more sensitive to interfacial degradation. An attempt was made to use oblique incidence ultrasonic interrogation using shear waves. The amplitude of reflected shear waves from the interface increased with an increase in degradation. Further, a signal analysis approach in the frequency domain revealed a shift in the frequency minimum towards lower range in degraded samples. This phenomenon was verified using analytical models. An inversion algorithm was used to determine the interfacial transverse stiffness which decreased significantly due to increase in degradation. Conventional ultrasonic evaluation methods are rendered ineffective when a direct access to the test region is not possible; a different approach with guided wave techniques can be explored in this scenario. Investigations on CFRP-epoxy adhesive joints using Lamb waves showed a decrease in the amplitude of ‘So’ mode in degraded samples. Theoretical dispersion curves exhibited a similar trend. Frequency domain studies on the received modes using Gabor wavelet transform showed a negative shift in frequency with increased degradation. It was also observed that the maximum transmission loss for the most degraded sample with 40 percent PVA occurred in the range of 650 – 800 kHz. Non linear ultrasonic (NLU) evaluation revealed that the nonlinearity parameter (β) increased with increased degradation. Kissing bonds are most commonly occurring type of defects in adhesive joints and are very difficult to characterize. A recent non-contact imaging technique called digital image correlation (DIC) was tried to evaluate composite adhesive joints with varied percentage of inserted kissing bond defects. The results obtained indicate that DIC can detect the kissing bonds even at 50 percent of the failure load. In addition, to different experimental approaches to evaluate the bonded joint discussed above, the effect of degradation on the stresses in the bond line region was studied using analytical and numerical approach. A linear adhesive beam model based on Euler beam theory and a nonlinear adhesive beam model based on Timoshenko beam theory were used to determine the adhesive peel and shear stress in the joint. Digital image correlation technique was used to experimentally obtain the bond line strains and corresponding stresses were computed assuming a plane strain condition. It was found that the experimental stresses followed a similar trend to that predicted by the two analytical models. A maximum peel stress failure criterion was used to predict failure loads. A failure mechanism was proposed based on the observations made during the experimental work. It was further shown that the critical strain energy release rate for crack initiation in a healthy joint is much higher compared to a degraded joint. The analytical models become cumbersome if a larger number of factors have to be taken into account. Numerical methods like finite element analysis are found to be promising in overcoming these hurdles. Numerical investigation using 3D finite element analysis was carried out on CFRP-epoxy adhesive joints. The adherend – adhesive interface was modeled using connector elements whose stiffness properties as well as the bulk adhesive properties for joints with different amounts of PVA were determined using ultrasonic inspection method. The peel and shear stress variation along the adhesive bond line showed a similar trend as observed with the experimental stress distribution (DIC) but with a lesser magnitude. A parametric study using finite element based Monte-Carlo simulation was carried out to assess the effect of variation in various joint parameters like adhesive modulus, bondline thickness, adherend geometrical and material properties on peel and shear stress in the joint. It was found that the adhesive modulus and bond line thickness had a significant influence on the magnitude of stresses developed in the bond line. Thus, to summarize, an attempt has been made to study the bond line integrity of a composite epoxy adhesive lap joint using experimental, analytical and numerical approaches. Advanced NDE tools like oblique incidence ultrasound, non linear ultrasound, Lamb wave inspection and digital image correlation have been used to extract parameters which can be used to evaluate composite bonded joints. The results obtained and reported in the thesis have been encouraging and indicate that in specific cases where the bond line thickness and other relevant parameters if can be maintained or presumed reasonably non variant, it is possible to effectively evaluate the integrity of a composite bonded joint.