Chapter 1 Dynamic Processes Occurring at the Cr^III_aq – Manganite (γ-MnOOH) Interface: Simultaneous Adsorption, Microprecipitation, Oxidation/Reduction and Dissolution The complex interaction between Cr^III_aq and manganite (γ-MnOOH) was systematically studied at room temperature over a pH range of 3 to 6, and within a concentration range of 10⁻⁴ to 10⁻² M CrOH²⁺_aq. Solution compositional changes during batch reactions were characterized by ICP and UVvis. The manganites were characterized before and after reaction with XPS, SEM, high-resolution FESEM, and EDS analysis. Fluid-cell AFM was used to follow these metal-mineral interactions in situ. The reactions are characterized by 1) sorption of Cr^III and the surface-catalyzed microprecipitation of Cr^III-hydroxy hydrate on manganite surfaces, 2) the acidic dissolution of the manganite, and 3) the simultaneous reductive dissolution of manganite coupled with the oxidation of Cr^III_aq to highly toxic Cr^VI_aq. Cr^III-hydroxy hydrate was shown to precipitate on the manganite surface while still undersaturated in bulk solution. The rate of manganite dissolution increased with decreasing pH due both to faster acid-promoted and Mn-reduction- promoted dissolution. Due to direct redox coupling with Mn reduction, Cr oxidation was most rapid in the lower pH range. Neither Mn^II nor Cr^VI were ever detected on manganite surfaces, even at the maximum rate of their generation. At the highest pHs of this study, Cr^III_aq was effectively removed from solution to form Cr^III-hydroxy hydrate on manganite surfaces and in the bulk solution, and manganite dissolution and Cr^VI_aq generation were minimized. All interface reactions described above were heterogeneous across the manganite surfaces. This heterogeneity is a direct result of the heterogeneous semiconducting nature of natural manganite crystals, and is also an expression of the proximity effect, whereby redox processes on semiconducting surfaces are not limited to next nearest neighbor sites. Chapter 2 Comparison of the Reactivity of Various Mn-Oxides with Cr^III_aq: Microscopic and Spectroscopic Observations of Dissolution, Cr-sorption and Cr and Mn Redox Interactions The interaction between Cr^III_aq and seven different Mn-oxides (6 monomineralic, 1 synthetic) have been observed in pH ~4.4 HNO₃ and pH ~4.4 ~10⁴ M Cr^III_aq solutions. For each mineral-solution interaction, the aqueous chemical concentrations (e.g. [Mn]_aq, [Cr]_aq, [Cr^VI_aq]) were measured with time. Reacted samples were examined by XPS to determine if, and to what extent, the surface chemical states of Cr, Mn and O had changed. Microscopic observations of the reacted surfaces were obtained using AFM and high-resolution, low-voltage FESEM. The solubility of the Mn-oxides in the acidic, non-Cr bearing solutions varied inversely with the average Mn valence, but did not show systematic behavior with respect to the mineral structure type (e.g. tunnel, layer, framework). This trend was interpreted as resulting from the relative ability of an adsorbed proton to polarize surface Mn-O bonds, with the polarizability being in the order Mn²⁺-O > Mn³⁺-O > Mn⁴⁺-O. For samples reacted with Cr^III_aq, the rate and extent of reductive dissolution was always greater than for acidic dissolution during the initial time period. The measured ratios of the [Mn]_aq : [Cr^VI]_aq were approximately in agreement with the values expected from the proposed stoichiometric reactions. Cr-uptake was observed to occur in undersaturated solutions as a result of adsorption, absorption and surface catalyzed precipitation. The chromium as detected by XPS was predominately Cr^III, however pyrolusite contained both Cr^III and Cr^VI. Previous studies have implicated a chromium surface precipitate to be responsible for the cessation of the Cr^III_aq oxidation reaction. Our surface sensitive FESEM and AFM observations tend to suggest that Cr-uptake is by isolated site binding, very small (<30 nm) surface clusters or monolayer scale films. Cr-uptake was followed by slow Cr-release on several of the solids (particularly the layered solids) after a substantial portion of the total aqueous Cr had been converted to Cr^VI_aq. The oxidizing ability of the different Mn-oxides for Cr^III_aq is evaluated with regards to the energy level of the redox couple (i.e. the redox potential) as compared with the Fermi energy level of the Mn-oxide. Although these energies were calculated rather than directly measured, the results indicate that electrons originating from adsorbed Cr^III ions may be transferred into the conduction band or more likely, into available surface states. The presence of an initial limited quantity of electron accepting surface states likely explains the observation of a rapid initial Cr^III-oxidation followed by much slower oxidation. The Mn-oxides that exhibited the greatest and longest lasting Cr^III-oxidizing power were the Mn-oxides containing Mn⁺, and in particular those containing Mn³⁺ and Mn⁺. It is believed that the combined presence of a reducible Mn ion (e.g. Mn³⁺) and a highly soluble Mn⁺ ion facilitates a sustained Cr^III-oxidation reaction because fresh surface is exposed during the reaction. / Ph. D.

[ES] Las piezas numismáticas constituyen un importante porcentaje de las colecciones de los museos y una de las evidencias que con mayor frecuencia se encuentra en las excavaciones, tratándose de vestigios arqueológicos e históricos fundamentales para el estudio de diferentes aspectos de las sociedades pasadas. Para la investigación y la caracterización de estos materiales es necesario el empleo de técnicas analíticas no invasivas o nanoinvasivas que no comprometan la integridad de las monedas. En este trabajo se presentan los resultados obtenidos en la exploración de las capacidades de dos técnicas instrumentales analíticas, VIMP y FIB-FESEM-EDX, ambas de carácter nanoinvasivo, en colecciones numismáticas fabricadas en aleaciones en base cobre, escasamente empleadas en el estudio de patrimonio metálico hasta la fecha. Además, y en cada caso de estudio abordado, se han diseñado estrategias multitécnica que incluye el uso de SEM-EDX, espectroscopia FTIR, M.O., colorimetría y espectroscopia Raman. En una primera parte de la investigación se han desarrollado metodologías analíticas para la identificación y discriminación de aleaciones, productos de corrosión e intervenciones previas en tres colecciones de distinta titularidad y procedentes de diferentes ambientes. La primera colección, procede de un ambiente aéreo o atmosférico y es de titularidad privada, la colección Doménech-Francés. La segunda colección, procede de un ambiente de enterramiento y pertenece al Museu de Prehistòria de València. La última colección estudiada con esta finalidad procede de un ambiente subacuático, y pertenece al Museo Nacional de Arqueología Subacuática. En la segunda parte, el trabajo se centra en el desarrollo de una metodología innovadora basada en la técnica de electroquímica en estado sólido VIMP, que permite la discriminación entre cecas y el conocimiento de las técnicas de acuñación empleadas. Esta nueva metodología se ha implementado sobre dos casos de estudio diferentes: el primero consiste en una serie de maravedís acuñados entre 1661 y 1664 por Felipe IV, y el segundo, en una colección de monedas íberas acuñadas en las cecas de Cástulo, Obulco e Iltirta entre los siglos II y I a.C., pertenecientes al Museu de Prehistòria de València. / [CA] Las peces numismàtiques constitueixen un important percentatge de les col·leccions dels museus i una de les evidències que amb major freqüència es troba en les excavacions, i es tracta de vestigis arqueològics i històrics fonamentals per a l'estudi de diferents aspectes de les societats passades. Per a la investigació i la caracterització d'aquests materials és necessari l'ús de tècniques analítiques no invasives o nanoinvasives, que no comprometen la integritat de les monedes. En aquest treball es presenten els resultats obtinguts en l'exploració de les capacitats de dues tècniques instrumentals analítiques, VIMP i FIB-FESEM-EDX, ambdues de caràcter nanoinvasiu, en col·leccions numismàtiques fabricades en aliatges amb base de coure, escassament emprades en l'estudi del patrimoni metàl·lic fins avui. A més, en cada cas d'estudi abordat, s'han dissenyat estratègies multitècnica que inclouen l'ús de SEM-EDX, espectroscòpia FTIR, M.O., colorimetria i espectroscòpia Raman. En una primera part de la investigació s'han desenvolupat metodologies analítiques per a la identificació i discriminació d'aliatges, productes de corrosió i intervencions prèvies en tres col·leccions de diferent titularitat i procedents de diferents ambients. La primera col·lecció, procedeix d'un ambient aeri o atmosfèric i és de titularitat privada, la col·lecció Doménech-Francés. La segona col·lecció procedeix d'un ambient d'enterrament i pertany al Museu de Prehistòria de València. La última col·lecció estudiada amb aquesta finalitat procedeix d'un ambient subaqüàtic i pertany al Museu Nacional d'Arqueologia Subaqüàtica. En la segona part, el treball se centra en el desenvolupament d'una metodologia innovadora basada en la tècnica d'electroquímica en estat sòlid VIMP, que permet la discriminació entre seques i el coneixement de les tècniques d'encunyació emprades. Aquesta nova metodologia s'ha implementat sobre dos casos d'estudi diferents: el primer consisteix en una sèrie de maravedís encunyats entre el 1661 i el 1664 per Felip IV; i el segon, en una col·lecció de monedes iberes encunyades a les seques de Cástulo, Obulco i Iltirta entre els segles II i I a. de C., pertanyents al Museu de Prehistòria de València. / [EN] The numismatic pieces constitute an important part of the collections of the museums and one of the evidences that more frequently found in the excavations, being archaeological and historical vestiges fundamental for the study of severe aspects of the past societies. The use of non-invasive or nanoinvasive analytical techniques that do not compromise the integrity of the coins is essential for the investigation and characterization of these materials. This PhD presents the results obtained in the exploration of the capabilities of two nanoinvasive analytical instrumental techniques, VIMP and FIB-FESEM-EDX, in numismatic collections made of copper-based alloys, scarcely used in the study of heritage metallic so far. In addition, and in each study case discussed, multi-technical strategies have been designed that include the use of SEM-EDX, FTIR spectroscopy, O.M., colorimetry and Raman spectroscopy. In the first part of the investigation, analytical methodologies for the identification and discrimination of alloys, corrosion products and previous interventions in three collections of different ownership and coming from different environments have been developed. The first collection, comes from an air or atmospheric environment, is privately owned, the Doménech-Francés collection, the second collection, comes from a burial environment and belongs to the Museum of Prehistory of Valencia, and the last collection studied for this purpose, comes from an underwater environment and belongs to the National Museum of Underwater Archaeology. In the second part, the work focuses on the development of an innovate methodology based on the technique of solid-state electrochemistry VIMP that allows the discrimination between mints and the knowledge of the coinage techniques used. This new methodology has been implemented on two different case studies: the first consists of a series of maravedís coined between 1661 and 1664 by Philip IV, and the second, in a collection of iberian coins minted in the mints of Cástulo, Obulco and Iltirta between the 2nd and 1st centuries BC, and belonging to the Museum of Prehistory of Valencia. / Agradecer todo el apoyo institucional que he tenido: al contrato FPI del Ministerio de Economía, Industria y Competitividad del que he podido disfrutar durante estos cuatro años (referencia de la ayuda BES-2015-072439) enmarcado dentro de los proyectos CTQ2014-53736- C3-1-P y CTQ2014-53736-C3-2-P, al proyecto CTQ2017-85317-C2-1-P, del Ministerio de Ciencia, Innovación y Universidades y cofinanciado por el Fondo Europeo de Desarrollo Regional (ERDF) y la Agencia Estatal de Investigación (AEI) / Álvarez Romero, C. (2020). DESARROLLO DE MÉTODOS DE CARACTERIZACIÓN Y CONTROL DE TRATAMIENTOS DE CONSERVACIÓN DE COLECCIONES NUMISMÁTICAS MEDIANTE TÉCNICAS DE MICROSCOPÍA ELECTRÓNICA Y NANOELECTROQUÍMICA [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/140316 / TESIS

Nowadays, electron microscopy is a widespread method used in many biological branches like medicine, physical science, mikrobiology or material technology. Scanning electron microscope is a type of an electron microscope that shows the sample surface by scanning it with a high-energy beam of electrons in a raster scan pattern. The signal of electrons reveals information about the sample such as morphology, chemical composition and structure and materials. Gold nanoparticles are widely used as a marker for immunolabeling in these days. The main point of this research was to find other nanoparticles, which can be used for multiple immunolabeling. The main task of this study is to conjugate these particles with atibodies, to use them for immunolocalisation on the convenient biological sample and to observe it in FESEM JEOL JSM-7401F.

Egg (the whole, the yolk or the white) is a natural product used since ancient times as tempera painting medium mainly in Europe and the Mediterranean Basin countries. In addition, egg is a complex multicomponent microstructured system susceptible of being influenced by the pigments that compose the paints, as well as a source of nutrient susceptible of biodeterioration. Modifying effect of artists' pigments on the binding medium as well as, the microbial biodeterioration are responsible for changes in the structure and composition of the binding medium and, consequently, on the physico-chemical properties of the paint. For this purpose, analytical techniques such as Fourier transform infrared spectroscopy - attenuated total reflection (FTIR-ATR) was used for the chemical characterization, Field emission scanning microscopy (FESEM) and Atomic force microscopy - nanoindentation (AFM-nanoindentation) were run for morphological and mechanical characterization of the deterioration processes resulted from the pigment-binder interactions involved in tempera painting. On the other hand, the current research report the application of the voltammetry of microparticles (VMP), complemented with FTIR-ATR, FESEM and AFM-nanoindentation techniques to monitor the deterioration of a series of tempera reconstructed model paint specimens under the action of different biological agents. This methodology would be of application for identifying the type of biological agent causing deterioration of painting, which is an important problem affecting cultural heritage. The analysis of biodeterioration processes is complicated by the fact that the action of microorganisms can affect both pigment and binding media. The deterioration of pictorial specimens by Acremonium chrysogenum, Aspergillus niger, Mucor rouxii, Penicillium chrysogenum and Trichoderma pseudokoningii fungi and Arthrobacter oxydans, Bacillus amyloliquefaciens and Streptomyces cellulofans bacteria was tested using sample-modified graphite electrodes immersed into aqueous electrolytes. Finally, the study carried out by means of FTIR-ATR, FESEM and AFM-nanoindentation confirms that egg proteins attached to the pigment grains changes their secondary structures. The results obtained also confirm that proteins and phospholipids are prevalently established linkages with the solid particles of pigment whereas triglycerides should be integrated in the complex binding network responsible for the cohesion of the paint film. Interactions between egg components with solid pigment particles are described and correlated with micromorphology and mechanical properties determined at micro- and nano-scale on the reconstructed model paint specimens. As a result of the crossing of VMP data with the results obtained by means of FTIR, FESEM and AFM-nanoindentation, the voltammetric signals obtained were associated to the electrochemical reduction of pigments and different complexes associated to the binding media. These results were particularly relevant in the study of biodeterioration, to allowing the electrochemical monitoring of biological attack. / El huevo (entero, yema o clara) es un producto natural utilizado desde la antigüedad como medio aglutinante en la pintura al temple, principalmente en Europa y los países de la cuenca mediterránea. Además, el huevo es un complejo sistema multicomponente microestructurado susceptible de ser alterado por los pigmentos que componen las pinturas, así como fuente de nutrientes susceptible de biodeterioro. El efecto de los pigmentos sobre el medio aglutinante, así como el biodeterioro microbiano son responsables de cambios en la estructura y composición del medio aglutinante y, por consiguiente, en las propiedades fisicoquímicas de la pintura. Es por esto que, se utilizaron técnicas analíticas como la Espectroscopía Infrarroja por Transformada de Fourier en modo Reflexión Total Atenuada (FTIR-ATR), para la caracterización química de los procesos de deterioro resultantes de las interacciones pigmento-aglutinante en la pintura al temple. Así mismo, se utilizó Microscopía Electrónica de Emisión de Barrido (FESEM) para el estudio morfológico de las muestras, y para el estudio de las propiedades mecánicas Microscopía de Fuerza Atómica en modo Nanoindentación (AFM-nanoindentación). Por otro lado, la presente investigación propone el uso de la Voltamperometría de Micropartículas (VMP), en conjunto con otras técnicas de análisis como FTIR-ATR, FESEM y AFM-nanoindentación para el estudio del biodeterioro producido por hongos y bacterias sobre una serie muestras pictóricas sometidas. El estudio de las alteraciones causadas por el biodeterioro es complicado por el hecho de que la acción de los microorganismos puede afectar tanto al pigmento como al medio aglutinante. Para esto, se prepararon una serie de muestras de pinturas al temple y emulsión que fueron inoculadas con los hongos Acremonium chrysogenum, Aspergillus niger, Mucor rouxii, Penicillium chrysogenum, y Trichoderma pseudokoningii, y las bacterias Arthrobacter oxydans, Bacillus amyloliquefaciens y Streptomyces cellulofans. El estudio voltamperometrico se realizó utilizando electrodos de grafito modificados con las muestras inmersos en un electrolito acuoso. Las conclusiones obtenidas de manera general, apuntan a que las proteínas presentes en el huevo cambian su estructura secundaria al adherirse a los granos de pigmento. La información química, morfológica y mecánica obtenida por las diferentes técnicas de análisis instrumental es consistente. Finalmente, como resultado del cruce de los datos VMP con los resultados obtenidos mediante FTIR, FESEM y AFM-nanoindentación, las señales voltamperometricas obtenidas se asociaron a la reducción electroquímica de los pigmentos y a los complejos formados con el medio aglutinante. Estos resultados fueron particularmente relevantes en el estudio del biodeterioro de las películas pictóricas inoculadas, para permitir la monitorización electroquímica del ataque microbiológico. / L'ou (sencer, rovell o clara) és un producte natural utilitzat des de l'antiguitat com a mitjà aglutinant en la pintura al tremp, principalment a Europa i els països de la conca mediterrània. A més, l'ou és un complex sistema multicomponent MICROESTRUCTURAT susceptible de ser alterat pels pigments que componen les pintures, així com a font de nutrients susceptible de biodeterioració. L'efecte dels pigments sobre el medi aglutinant, així com el BIODETERIORI microbià són responsables de canvis en l'estructura i composició del medi aglutinant i, per tant, en les propietats fisicoquímiques de la pintura. És per això que, es van utilitzar tècniques analítiques com l'Espectroscòpia Infraroja per Transformada de Fourier en mode Reflexió Total Atenuada (FTIR-ATR), per a la caracterització química dels processos de deteriorament resultants de les interaccions pigment-aglutinant en la pintura al tremp. Així mateix, es va utilitzar Microscòpia Electrònica d'emissió de Rastreig (FESEM) per a l'estudi morfològic de les mostres, i per a l'estudi de les propietats mecàniques Microscòpia de Força Atòmica en mode Nanoindentació (AFM-nanoindentació). D'altra banda, la present investigació proposa l'ús de la Voltamperometría de Micropartícules (VMP), en conjunt amb altres tècniques d'anàlisi, com FTIR-ATR, FESEM i AFM-nanoindentació per a l'estudi de l'biodeterioració produït per fongs i bacteris sobre una sèrie de mostres pictòriques sotmeses. L'estudi de les alteracions causades pel biodeteriori és complicat pel fet que l'acció dels microorganismes pot afectar tant el pigment com al medi aglutinant. Per això, es van preparar una sèrie de mostres de pintures al tremp i emulsió que van ser inoculades amb els fongs Acremonium chrysogenum, Aspergillus niger, Mucor rouxii, Penicillium chrysogenum, i Trichoderma pseudokoningii i els bacteris Arthrobacter oxydans, Bacillus amyloliquefaciens i Streptomyces cellulofans. L'estudi voltamperomètric es va realitzar utilitzant electrodes de grafit modificats amb les mostres immersos en un electròlit aquós. Les conclusions obtingudes de manera general, apunten que les proteïnes presents en l'ou canvien la seva estructura secundària al adherir-se als grans de pigment. La informació química, morfològica i mecànica obtinguda per les diferents tècniques d'anàlisi instrumental és consistent. Finalment, com a resultat de l'encreuament de les dades VMP amb els resultats obtinguts mitjançant FTIR, FESEM i AFM-nanoindentació, els senyals voltamperomètrics obtinguts es van associar a la reducció electroquímica dels pigments i als complexos formats amb el medi aglutinant. Aquests resultats van ser particularment rellevants en l'estudi del biodeteriori de les pel·lícules pictòriques inoculades, per tal de permetre la monitorització electroquímica de l'atac microbiològic. / Ortiz Miranda, A. (2017). Development of analytical methods for the characterization of tempera paintings at micro- and nano-scale and their deterioration and biodeterioration processes [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/90571 / TESIS

Soy flour (SF), a by-product of the soybean oil extraction processing, was investigated for its application in soy-polypropylene composites for interior automotive applications. The emphasis of this work was the understanding of this new type of filler material and the contribution of its major constituents to its thermal stability and impact properties. For this reason, reference materials were selected to represent the protein (soy protein isolate (SPI)) and carbohydrate (soy hulls (SH)) constituents of the soy flour. Additional materials were also investigated: the residue obtained after the protein removal from the soy flour which was called insoluble soy (IS), and the remaining liquid solution after acid precipitation of the proteins, containing mostly sugars and minerals, which was called soluble sugar extract (SSE). Two treatments, potassium permanganate and autoclave, were analyzed for their potential to modify the properties of the soy composite materials. An acid treatment with sulfuric acid conducted on soy flour was also considered. The soy materials were studied by thermogravimetric analysis (TGA) under isothermal (in air) and dynamic (in nitrogen) conditions. SPI had the highest thermal stability and SSE the lowest thermal stability for the early stage of the heating process. Those two materials had the highest amount of residual mass at the end of the dynamic TGA in nitrogen. The two treatments showed minimal effect on the isothermal thermal stability of the soy materials at 200 ??C. A minor improvement was observed for the autoclave treated soy materials. Fourier transformed infrared (FTIR) spectroscopy indicated that the chemical surface composition differed according to type of the soy materials but no difference could be observed for the treatments within one type of soy material. Contact angle analysis and surface energy estimation indicated differences of the surface hydrophobicity of the soy materials according to type of material and treatment. The initial water contact angle ranged from 57 ?? for SF to 85 ?? for SH. The rate of water absorption increased dramatically after the autoclave treatment for IS and SPI. Both materials showed the highest increase in the polar surface energy fraction. In general, the major change of the surface energy was associated with change of the polar fraction. After KMnO4 treatment, the polar surface energy of SF, IS and SPI decreased while SH showed a slight increase after KMnO4 treatment. A relationship between protein content and polar surface energy was observed and seen to be more pronounced when high protein containing soy materials were treated with KMnO4 and autoclave. Based on the polar surface energy results, the most suitable soy materials for polypropylene compounding are SPI (KMnO4), SH, and IS (KMnO4) because their polar surface energy are the lowest which should make them more compatible with non-polar polymers such as polypropylene. The soy materials were compounded as 30 wt-% material loading with an injection moulding grade polypropylene blend for different combinations of soy material treatment and coupling agents. Notched Izod impact and flexural strength as well as flexural modulus estimates indicated that the mechanical properties of the autoclaved SF decreased when compared to untreated soy flour while the potassium permanganate treated SF improved in impact and flexural properties. Combinations of the two treatments and two selected (maleic anhydride grafted polypropylene) coupling agents showed improved impact and flexural properties for the autoclaved soy flour but decreased properties for the potassium permanganate treated soy flour. Scanning electron microscopy of the fractured section, obtained after impact testing of the composite material, revealed different crack propagation mechanisms for the treated SF. Autoclaved SF had a poor interface with large gaps between the material and the polypropylene matrix. After the addition of a maleic anhydride coupling agent to the autoclaved SF and polypropylene formulation, the SF was fully embedded in the polymer matrix. Potassium permanganate treated SF showed partial bonding between the material and the polymer matrix but some of the material showed poor bonding to the matrix. The acid treated SF showed cracks through the dispersed phase and completely broken components that did not bind to the polypropylene matrix. In conclusion, the two most promising soy materials in terms of impact and flexural properties improvement of soy polypropylene composites were potassium permanganate treated SF and the autoclaved SF combined with maleic anhydride coupling agent formulation.