[pt] Neste trabalho estudamos filmes depositados por três organosilícios em forma líquida pelo método de deposição química na fase vapor assistido por plasma (PECVD) sobre chapas de aço inoxidável 316L e lâminas de silício cristalino <100>. Os líquidos empregados foram o Hexametidissilazano (HMDSN), Hexametidissiloxano (HMDSO) e Hexametildissilano (HMDS). Determinamos as propriedades estruturais, mecânicas e tribológicas dos filmes crescidos, e a viabilidade do seu uso como revestimento protetor. Foram depositados dois conjuntos de amostras para cada líquido, o primeiro a 200C e o segundo 300oC. Em cada um dos conjuntos, a tensão de autopolarização no crescimento foi variada indo de -150V até -450V. Tentou-se caracterizar filmes crescidos a temperatura ambiente, porém não obtivemos êxito, pois delaminavam. Os filmes foram caracterizados por técnicas de perfilometria, onde determinamos que os filmes crescidos com temperaturas de 200C tiveram a maior taxa de deposição. Estes filmes para todos os líquidos possuem uma tensão interna entre 1 e 2 GPa. Os filmes foram analisados também por espectroscopia de fotoelétrons induzidos por raios-x (XPS), espectroscopia de absorção no infravermelho e espectroscopia de emissão ótica (GDOES) onde identificamos as concentrações atômicas e as ligações químicas presentes nos filmes. Com a espectroscopia Raman observamos que os filmes têm presença de carbonos com hibridização sp2. Os filmes sintetizados têm um forte caráter polimérico, e para os crescidos com tensões de autopolarização maiores que -250V, observamos a presença das bandas D e G características de filmes de carbono amorfo. As análises feitas por nanoindentação determinou que os filmes tinham dureza entre 18 e 21 GPa. A microscopia de força atômica evidenciou que os filmes têm uma rugosidade rms em torno de 0,3nm. Medida de tribologia mostraram que os filmes têm um coeficiente de atrito de 0,25. Após as medidas de tribologia, foram feitas imagens de perfilometria para determinar o desgaste. Os filmes se mostraram resistentes, com a menor taxa de 7nm/min quando submetido a uma força de 0,3 Newtons e como contra corpo uma esfera de aço inoxidável (AISI302), e após as medidas os filmes não delaminaram. Com relação ao envelhecimento do filme, alguns foram sintetizados a mais de 4 anos, e continuam bem aderidos tanto sobre o substrato de aço, como o de silício. Verificamos também a viabilidade do uso do hexametildissílazano (HMDSN) como camada adesiva para a deposição de filmes de carbono amorfo hidrogenado sobre chapas de aço inoxidável com sucesso. Fizemos também a deposição de um filme depositado a partir do hexametildissiloxano (HMDSO) sobre um parafuso de aço inoxidável para verificar a viabilidade para deposições sobre materiais com geometrias diferentes, com sucesso, o filme bem aderido em sua superfície. / [en] In this work, we study films deposited by three organosilanes in liquid phase by the plasma deposition method (PECVD) on 316L stainless steel plates and crystalline silicon slides <100>. The liquids employed were Hexamethyldisilazane (HMDSN), Hexamethyldisiloxane (HMDSO) and Hexamethyldisilane (HMDS). We determined the structural, mechanical and tribological properties of grown films, and the feasibility of their use as a protective coating. Two sets of samples were deposited for each liquid, the first at 200C and the second at 300C. In each set, the bias at the growth was varied ranging from -150V to -450V. Attempts were made to characterize films grown at room temperature, but we did not succeed because they delaminated. The films were characterized by profilometry techniques, where we determined that the films grown with temperatures of 200oC had the highest deposition rate. The films were also analyzed by x-ray photoelectron spectroscopy (XPS), infrared absorption spectroscopy (FTIR) and glow discharge optical emission spectroscopy (GDOES), where we identified the atomic concentrations and the chemical bonds present in the films. With the Raman spectroscopy we observed that the films have presence of carbons with hybridization sp2. The films synthesized have a strong polymeric character, and for those grown with bias higher than -250V, we observed the presence of D- and G- bands that are characteristics of amorphous carbon films. Analysis by nanoindentation determined that the films had a hardness between 18 and 21 GPa. Atomic force microscopy showed that the films have a roughness RMS around 0.3nm. Measurement of tribology showed that the films have a coefficient of friction of 0.25. After the tribology measurements, profilometry images were made to determine the wear. The films were resistant, with the lowest rate of 7 nm/min when subjected to a force of 0.3 Newtons and as against a body of stainless steel (AISI302), and after the measurements the films did not delaminate. Regarding the aging of the film, some were synthesized for more than 4 years, and remain well adhered both on the steel substrate and silicon. We also verified the feasibility of using hexamethyldisilazane (HMDSN) as an adhesive layer for the deposition of hydrogenated amorphous carbon films on stainless steel substrate successfully. We also deposited a film from the hexamethyldisiloxane (HMDSO) on a stainless steel screw to verify the feasibility for deposition on materials with different geometries, successfully, the film was well adhered on its surface.

Στην εργασία αυτή μελετάμε μια σειρά από αντιπροσωπευτικά νανοφασικά συστήματα πυριτίου, στο πλαίσιο κοινών ιδιοτήτων και αρχών που θα βοηθήσουν σε μελλοντικές εφαρμογές σχεδιασμού μοριακών υλικών βασισμένων σε αυτά τα συστήματα. Οι κατηγορίες των συστημάτων με τα οποία ασχολούμαστε είναι (α) υδρογονωμένα και μη-υδρογονωμένα νανοσυσσωματώματα και νανοκρυσταλλικά συστήματα πυριτίου με ή χωρίς ενσωματωμένα μέταλλα μετάπτωσης, που αποτελούν χαρακτηριστικά μοντέλα ενδοεπιφάνειας μετάλλου−ημιαγωγού, (β) υπέρλεπτα υδρογονωμένα νανοσύρματα πυριτίου και (γ) οργανομεταλλικά πολλαπλών στρώσεων (multidecker-sandwiches) πυριτίου−άνθρακα. Εκτός από τη μελέτη των δομικών, ηλεκτρονικών, οπτικών, δονητικών και μαγνητικών ιδιοτήτων των συστημάτων, εστιάζουμε στην αναζήτηση μηχανισμών σταθεροποίησης και την εύρεση και καθορισμό κανόνων που μπορούν να λειτουργήσουν ως «εργαλεία μοριακού σχεδιασμού» με τη γενικότερη δυνατή ισχύ. Τα συσσωματώματα πυριτίου σταθεροποιούνται μέσου των μετάλλων μετάπτωσης σε δομές κλωβού και χαρακτηρίζονται συχνά από υψηλή συμμετρία και μεγάλα ενεργειακά χάσματα, ιδιότητες επιθυμητές για εφαρμογές στην οπτοηλεκτρονική και νανοηλεκτρονική. Στη μελέτη των νανοσυρμάτων πυριτίου συγκρίνουμε την σταθερότητα μεταξύ νανοσυρμάτων με διαφορετικές επιφανειακές δομές ενώ διατυπώνουμε κανόνα «μαγικότητας» νανοσυρμάτων με τον οποίο ερμηνεύουμε την σταθερότητά τους και την συνδέουμε με την ελαστικότητα και την κατανομή υδρογόνου στην επιφάνεια τους. Τέλος, βασιζόμενοι στην ισολοβική αρχή the boron connection, σχεδιάζουμε και μελετάμε μια νέα κατηγορία νανοδομών τύπου multidecker sandwiches οργανοπυριτίου. Στη διάρκεια εκπόνησης αυτής της διατριβής δημοσιεύτηκαν συνολικά 19 εργασίες σε διεθνή περιοδικά και σε πρακτικά συνεδρίων. / In this work we study a series of representative nanoscale systems based on silicon, in the context of common properties and principles which will assist in future applications in designing molecular materials based on these systems. The categories of the systems which we work on are (a) hydrogenated and non-hydrogenated silicon nanoclusters and nanocrystallic systems with or without embedded transition metals, which constitute models of metal−semiconductor interfaces, (b) ultrathin hydrogenated silicon nanowires and (c) organometallic silicon−carbon multidecker-sandwiches. In addition to the study of structural, electronic, optical, vibrational and magnetic properties of these systems, we focus on a search for stabilizing mechanisms and in finding and defining rules that can function as “molecular designing tools” with the broadest possible validity. The silicon nanoclusters are stabilized to cage-like structures by the insertion of transition metals and are characterized by high symmetry and large energy gaps, desirable properties for applications in optoelectronics and nanoelectronics. In the study of silicon nanowires we compare the stability between nanowires with different surface structures while we formulate “magicity” rules for nanowires with which we interpret their stability and associate it with their elasticity and the distribution of the surface hydrogen. Finally, based on the isolobal principle the boron connection, we design and study a new class of organometallic multidecker-sandwich type nanostructures. During the elaboration of this dissertation we published overall 19 papers in international scientific journals and conferences’ proceedings.

Magister Scientiae - MSc (Physics) / An increasing energy demand and growing environmental concerns regarding the use of fossil fuels in South Africa has led to the challenge to explore cheap, alternative sources of energy. The generation of electricity from Photovoltaic (PV) devices such as solar cells is currently seen as a viable alternative source of clean energy. As such, crystalline, amorphous and nanocrystalline silicon thin films are expected to play increasingly important roles as economically viable materials for PV development. Despite the growing interest shown in these materials, challenges such as the partial understanding of standardized measurement protocols, and the relationship between the structure and optoelectronic properties still need to be overcome.

Borate glasses and glass-nano/microcrystal composite fabrication and investigations into their physical properties, have been interesting from their multifunctionalities view point. Certain borate structural units possess high hyperpolarizabilities and give rise to high nonlinear optical effects. High refractive index materials are important for photonic applications. Heavy metal oxide (Bi2O3) containing compounds have high refractive indices. Glasses embedded with wide band-gap semiconducting oxide crystals such as TiO2 received much attention due to their easy processing, stability and promising physical properties. Though TiO2 is used as nucleating agent to fabricate glass-ceramics of various phases, crystallization of TiO2 in glass matrices is difficult and the data are scarce in the literature. Therefore it was worth attempting to find glass compositions in which one can obtain TiO2 crystallization in large volume fractions. Towards this TiO2 crystallization was accomplished in BaO-TiO2-B2O3 glass matrix over wide composition ranges by tuning the concentration of BaO-TiO2 content in B2O3 network. The physical properties of these glasses of various compositions and glass-nanocrystal composites of TiO2 phase (anatase) were investigated. Interestingly BaO-TiO2-B2O3 glasses found to be hydrophobic in nature. The results obtained in the present research work are classified into five chapters apart from the Introduction, Materials and Methods chapters. Chapter 1 constitutes preface to oxide glasses, principles of glass formation and structural criteria followed by crystallization kinetics. In addition, principles of dielectric, optical and mechanical phenomena in glasses are discussed, since the present thesis focuses on the aforesaid physical properties. This chapter concludes with scope of the present thesis. Chapter 2 includes the detailed description concerning the fabrication techniques of materials under study and various characterization methods that have been employed at various stages of the present research work. The principles and experimental tools adopted for the structural and microstructural studies of materials were illustrated. Measurement techniques and experimental setup used to study physical parameters such as dielectric, optical, mechanical etc. were elaborated. Chapter 3 comprises structural, dielectric, electrical transport characteristics and optical studies of mixed alkali borate glasses in the 0.5Li2O-0.5M2O-2B2O3 (M=Li, Na and K) system. Transparent glasses in the Li2O-2B2O3 (LBO), 0.5Li2O-0.5Na2O-2B2O3 (LNBO) and 0.5Li2O-0.5K2O-2B2O3 (LKBO) were fabricated via the conventional melt quenching technique. Amorphous and glassy nature of the samples was confirmed via the X-ray powder diffraction and the differential scanning calorimetry, respectively. LKBO glass was found to have high thermal stability than that of LBO and LNBO. The frequency and temperature dependent characteristics of the dielectric relaxation and the electrical conductivity were investigated in the 100 Hz - 10 MHz frequency range. The relaxation and conductivity were rationalized using impedance and modulus formalism. Imaginary part of the electric modulus spectra was modelled using an approximate solution of Kohlrausch-Williams-Watts relation. The stretching exponent, β, was found to be temperature independent for LNBO glasses. Activation energies for conduction and relaxation process were calculated using the Arrhenius relation. The activation energy was found to be higher (1.25eV) for LKBO glasses than that of the other glass systems under study. This is attributed to the mixed cation effect. It has wide optical transmission window and optical band gap. Urbach energies were calculated for all these glasses. LBO, LNBO and LKBO glass compositions were found to crystallize in Li2B4O7, LiNaB4O7 and LiKB4O7 phases respectively upon heat treatment at appropriate temperatures. Transparent glass-micro crystal composites of LiKB4O7 were fabricated from LKBO glasses and found to be SHG active. BaO-TiO2-B2O3 Chapter 4 delineates the evolution of nanocrystalline TiO2 phase (Anatase) in BaO-TiO2-B2O3 (BTBO) glasses. Transparent colourless glasses in the ternary system were fabricated via conventional melt-quenching technique. The glasses with certain molar concentrations of BaO and TiO2 upon heat treatment at appropriate temperatures yielded nanocrystalline phase of TiO2 associated with the crystallite size in the 5-15 nm range. Nanocrystallized glasses exhibited high refractive index (no=2.15) at λ=543nm. These glasses were found to be hydrophobic in nature associated with the contact angle of 90o. These high index glass nanocrystal composites would be of potential interest for optical device applications. Crystallization kinetics of anatase phase in BTBO glasses were studied using non-isothermal Differential Scanning Calorimetry (DSC) at three different heating rates (10, 20 & 30 K/min). Scanning Electron Microscopy (SEM) carried out on heat treated (at 920 K) glasses confirmed bulk nucleation and three-dimensional growth. Johnson-Mehl-Avrami model could not be applied for this system suggesting considerable overlap of the nucleation and growth involving complex transformation process. However, modified Kissinger and Ozawa models were used to calculate the effective activation energy associated with anatase crystallization. The kinetic exponent n was found to be temperature dependent indicating the change in the crystallization mechanism. This is attributed to the high entropy fusion of anatase phase, fast crystallization rate and nano dimension of the anatase phase. Chapter 5 illustrates structural changes that occur in the x(BaO-TiO2)-B2O3 (x=0.25, 0.5, 0.75 &1 mol.) system on increasing the x apart from the details concerning some physical property correlations. Thermal stability and glass forming ability as determined by Differential Thermal Analysis (DTA) were found to increase with increasing BaO-TiO2 (BT) content. However, there was no noticeable change in the glass transition temperature (Tg). This was attributed to the active participation of TiO2 in the network formation especially at higher BT contents via the conversion of the TiO6 structural units into TiO4 units which increased the connectivity and resulted in an increase in crystallization temperature. Dielectric and optical properties at room temperature were studied for all the glasses under investigation. Interestingly, these glasses were found to be hydrophobic. The results obtained were correlated with different structural units present in the glass and their connectivity. These glasses exhibited low loss (tan δ≈0.002), frequency (10 kHz- 10 MHz) and temperature independent (or very weak temperature response) flat-dielectric response. Crossover temperature was encountered between flat response and Jonscher’s universal response. The cross-over temperature and cross-over energy barrier from flat dielectric response to Jonscher’s response was deduced for all the glasses in the present investigation. Electric modulus formalism was invoked to rationalize the relaxation phenomena. The observed dielectric response and conduction process in these glasses were attributed to the local vibration and switching of non-bridging oxygen ions in their potential cage and hopping over distributed energy barriers above the crossover temperature. Chapter 6 depicts the dielectric and mechanical properties of glasses embedded with TiO2 nanocrystals. BaO-TiO2-B2O3 glasses on subjecting to appropriate heat treatment temperature yielded TiO2 nano crystalline anatase phase. NMR studies carried out on the as-quenched glasses facilitated the estimation of fraction of tetrahedral and trigonal borate units. Poisson’s ratio and Young’s modulus were evaluated through theoretical expressions proposed by Makishima and Mackenzie. Nano-indentation and micro-indentation studies were carried out on the as-quenched glasses and glass-nanocrystal composites to examine mechanical characteristics. Estimated and indentation Young’s modulus of glasses were found to be in reasonable agreement. Hardness and Young’s modulus increased with increasing fraction of nano crystallites whereas fracture toughness was found to depend strongly on surface conditions. The results were corroborated by the structural units and particulates present in these glasses. Dielectric constant increased with increasing volume fraction of the nanocrystals which was rationalized via mixture rule. Chapter 7 describes the dielectric properties, electrical conduction and electric relaxation phenomena in 2Bi2O3-B2O3 (BBO) glasses followed by thier linear and nonlinear optical characteristics. Glasses in BBO system were obtained via melt-quenching technique. X-ray diffraction and differential scanning calorimetry were used to study the structural characteristics. Dielectric studies carried out on these glasses revealed near constant loss (NCL) response in the 1 kHz to 1 MHz frequency range at moderately high temperatures (300-450 K) accompanied by relatively low loss (tan δ=0.006, at 1 kHz & 300 K) and high dielectric constant (ε' =37, at 1 kHz & 300 K). The variation in AC conductivity with temperature at different frequencies showed a cross over from NCL response characterized by local ion vibration within the potential well to universal Jonscher’s power law dependence triggered by ion hopping between potential wells or cages. Thermal activation energy for single potential well was found to be 0.48±0.05 eV from cross over points. Ionic conduction and relaxation processes were rationalized by modulus formalism. The promising dielectric properties (relatively high ε' and low tan δ) of the BBO glasses were attributed to high density (93 % of its crystalline counterpart), high polarizability and low mobility associated with heavy metal cations, Bi3+. Optical band gap obtained for BBO glasses was found to be 2.6 eV. The refractive index measured for these glasses was 2.25±0.05 at λ=543 nm. Nonlinear refraction and absorption studies were carried out on BBO glasses using z-scan technique at λ=532 nm of 10 ns pulse width. The nonlinear refractive index obtained was n2=12.1x10-14 cm2/W and two-photon absorption coefficient was β=15.2 cm/GW. The n2 and β values of the BBO glasses were higher than that reported for high index bismuth based oxide glass systems in the literature. These were attributed to the high density, high linear refractive index, low band gap and two-photon absorption associated with these glasses. The electronic origin of large nonlinearities was discussed based on bond-orbital theory. Thesis ends with summary and conclusions followed by prospective views, though each chapter comprises conclusions associated with complete list of references. Patent, publications and conference proceedings that are listed below are largely based on the studies conducted as a part of the research work reported in the present thesis.

The guanosine monophosphate synthetase (GMPS) is a class I glutamine amidotransferase, involved in the de-novo purine nucleotide biosynthesis. The enzyme catalyzes the biochemical transformation of xantosine (XMP) into guanosine monophosphate (GMP) in presence of ATP, Mg2+ and glutamine. All GMPSs consist of two catalytic sites 1) for GATase activity 2) for the ATPPase activity. The two catalytic sites may be housed in the same polypeptide (two-domain-type) or in separate polypeptides (two-subunit-type). Most of the studies have been performed on two-domain-type GMPSs, while only one study has been reported from two-subunit-type GMPS (Maruoka et al. 2009). The two-subunit-type GMPS presents an example where the component reactions of a single enzymatic reaction are carried out by two distinct subunits. In order to get better understanding of structural aspects and mechanistic principle that governs the GMPS activity in two-subunit-type GMPSs, we initiated the study by taking GMPS of Methanocaldococcus jannaschii as a model system. The GMPS of M. jannaschii (Mj) is a two-subunit-type protein. The GATase subunit catalyzes the hydrolysis of glutamine to produce glutamate and ammonia. The ATPPase subunit catalyses the amination of XMP to produce GMP using the ammonia generated in GATase subunit. Since the two component reactions are catalysed by two separate subunits and are coupled in the way that product of one reaction (ammonia) acts as a nucleophile in the second reaction. The cross-talk between these two subunits in order to maximise the efficiency of overall GMPS warrants investigation. The GATase activity is tightly regulated by the interaction with ATPPase domain/subunit, in all GMPS except in the case of P. falciparum. This interaction is facilitated by substrate binding to the ATPPase domain/subunit. Though, the conditions for the interaction between two subunits is known in a two-subunit-type GMP synthetase from P. horikoshii, the structural basis of substrate dependent interaction is not known. As a first step to understand the structural basis of interaction between the Mj GATase and Mj ATPPase subunits, we have determined the structure of Mj GATase (21 kDa) subunit using high resolution, multinuclear, multidimensional NMR spectroscopy. Sequence specific resonance assignments were obtained through analysis of various 2D and 3D hetero-nuclear multidimensional NMR experiments. NMR based distance restraints were obtained from assignment of correlations observed in NOE based experiments. Data were acquired on isotopically enriched samples of Mj GATase. The structure of Mj GATase (2lxn) was solved by using cyana-3.0 using NMR based restraints as input for the structure calculation. The ensemble of 20 lowest-energy structures showed root-mean-square deviations of 0.35±0.06 Å for backbone atoms and 0.8±0.06 Å for all heavy atoms. Attempts were also made to obtain assignments for the 69.6 kDa dimeric ATPPase subunit. Partial assignments have been obtained for this subunit. The GATase subunit is catalytically inactive. So far, there has been only one published report on a two-subunit-type GMPS from P. horikashii. The study has shown that the catalytic activity of GATase is regulated by the GATase-ATPPase interaction which is facilitated by the substrate binding to the ATPPase subunit. For the first time, we have provided the structural basis of interaction between GATase-ATPPase (112 kDa) in a two-subunit-type GMPS. Observed line width changes were used to identify residues in GATase residues that are involved in the Mj GATase-ATPPase interaction. Our data provides a possible explanation for conformational changes observed in the Mj GATase subunit upon GATase-ATPPase interaction that lead to GATase activation. Ammonia is generated in GATase subunit and is very reactive and labile. Thus, the faithful transportation of ammonia from GATase to ATPPase subunit is very crucial for optimal GMPS activity. Till date, a PDB query for GMPS retrieves only one structure which belongs to two-subunit-type GMPS, where authors have determined the structures of GATase and ATPPase subunits separately. However, the structure of holo-GMPS is not determined yet. Using interface information from experimental data and HADDOCK, we have constructed a model for the holo-GMPS from M. jannaschii. A possible ammonia channel has been deduced using the programs MOLE 2.0 and CAVER 2.0. This ammonia channel has a length of 46 Å, which is well within the range of the lengths calculated for similar channels in other glutamine amidotransferase. It had been suggested earlier that in addition to the magnesium required for charge stabilization of ATP, additional binding sites were present on GMPS. The effect of excess Mg2+ requirement on the GMPS activity has been studied in two-domain-type GMPS. However, the interaction between GATase and Mg2+ has been not investigated in any GMPS. This prompted us to investigate the effect of MgCl2 on Mj GATase subunit. For the first time, using chemical shift perturbation, we have established interaction between Mj GATase and Mg2+. The dissociation constant (Kd) of the Mj GATase-Mg2+ interaction was determined. The Kd value was found to be 1 mM, which indicates a very weak interaction. The substrate of the GATase subunit is glutamine. The condition of the hydrolysis of the glutamine is known in GMPS. However, the binding of the glutamine and associated conformational changes in GATase have been not studied in GMPS. Furthermore, till date there is no structure available for the glutamine bound GMPS/GATase. Using isotope edited one dimensional and two-dimensional NMR spectroscopy; we have shown that the Mj GATase catalytic residues are not in a compatible conformation to bind with glutamine. Thus, a conformational change in Mj GATase subunit is a pre-requisite condition for the binding of glutamine. These conformational changes are brought by the Mj GATase-ATPPase interaction.

This thesis is an attempt to understand ways to improve thermo-mechanical and structural properties of nano-structured materials. A detailed study on computational design and analysis of metallic nanowires is carried out. Molecular dynamic simulation method is applied. In particular, FCC metallic nanowires, NiAl, and CuZr nanowires are studied. Various bottom-up approaches are suggested with improved structural and thermo¬mechanical properties. In the first part of the thesis, Cu nanowires are considered. Existence of a novel and stable pentagonal multi-shell nanobridge structure of Cu under high strain rate tensile loading is reported. Such a structure shows enhanced mechanical properties. A three-fold pseudo-elastic-plastic shape recovery mechanism in such nanowires is established. This study also shows that the length of the pentagonal nanobridge structures can be characterized by its inelastic strain. It is also reported that an initial FCC structure is transformed into a new HCP structure. The evidence of HCP structure is confirmed with the help of experimental data published in the literature. Subsequent to the above study, a novel mechanism involving coupled temperature-stress dependent reorientation in FCC nanowires is investigated. A detailed map is generated for size dependent stress-temperature induced solid-solid reorientation in Cu nanowires. In the second part of the thesis, deformation mechanisms in NiAl based intermetallic nanowires are studied. A novel mechanism of temperature and cross-section dependent pseudo-elastic/pseudo-plastic shape and strain recovery by an initial B2 phase of NiAl nanowire is reported. Such a recoverable strain, which is as high as ~ 30%, can potentially be utilized to realize various types of shape memory and strain sensing phenomena in nano-scale devices. An asymmetry in tensile and compressive yield strength behavior is also observed, which is due to the softening and hardening of the nanowires under tensile and compressive loadings, respectively. Two different deformation mechanisms dominated by twinning under tension and slip under compression are found. Most interestingly, a superplastic behavior with a failure strain of up to 700% in the intermetallic NiAl nanowires is found to exist at a temperature of 0.36Tm. Such superplastic behavior is attributed to the transformation of the nanowire from a crystalline phase to an amorphous phase after yielding of the nanowire. In the last part the work, another type of nanowires having Cu-Zr system is considered. A novel stress induced martensitic phase transformation from an initial B2 phase to BCT phase in a CuZr nanowire under tensile loading is reported. It is further shown that such a stress induced martenistic phase transformation can be achieved under both tensile as well as compressive loadings. Tensile-compressive asymmetry in the stress-strain behavior is observed due to two different phase transformation mechanisms having maximum transformation strains of ~ 5% under compressive loading and ~ 20% under tensile loading. A size and temperature dependent tensile phase transformation in the nanowire is also observed. Small nanowires show a single step tensile phase transformation whereas the nanowires with larger size show a two step deformation mechanism via an intermediate R-phase hardening followed by R-phase yielding. A study of energetic behavior of these nanowires reveals uniform distribution of stress over the nanowire cross-section and such stress distribution can lead to a significant improvement in its thermo-mechanical properties. Similar improvement is demonstrated by designing the nanowires via manipulating the surface configuration of B2-CuZr system. It is found that the CuZr nanowires with Zr atoms at the surface sites are energetically more stable and also give a uniform distribution of stresses across the cross-section. This leads to the improvement in yield strength as well as failure strain. An approach to design energetically stable nano-structured materials via manipulating the surface configurations with improved thermo-mechanical properties is demonstrated which can help in fundamental understanding and development of similar structures with more stability and enhanced structural properties. Further ab-initio and experimental studies on the confirmation of the stability of the nanowires via manipulating the surface site is an open area of research and related future scopes are highlighted in the closure.

<div>The interactions of femtosecond lasers with gold targets were investigated with a numerical method combining molecular dynamics (MD) and the two-temperature model (TTM). Previous works using MD-TTM method did not consider all the thermodynamic parameters and the interatomic potential dependent of the electron temperature simultaneously. Therefore, we developed a LAMMPS function to achieve this. To accurately capture the physics behind the interactions, we also included the electron blast force from free electron pressure and the modified Fourier law with steep electron temperature gradient in our model. For bulk materials, a stress non-reflecting and heat conducting boundary is added between the atomistic and the continuum parts. The modified boundary force in our study greatly reduces the reflectivity of the atomistic-continuum boundary compared with its original form. Our model is the first to consider all these factors simultaneously and manage to predict four femtosecond laser ablation phenomena observed in the experiments. </div><div><br></div><div>In this dissertation, the thermodynamic parameters in the two-temperature model were extensively explored. We considered three different approaches to calculate these parameters: namely interpolation, <i>ab initio</i> calculation, and analytical expression. We found that simple interpolation between solid state and plasma state could lead to high level of inaccuracy, especially for electron thermal conductivity. Therefore, <i>ab initio</i> calculation and analytical expression were used for the calculation of the thermodynamic parameters in more advanced studies. The effects of electron thermal conductivity and electron-phonon coupling factor on electron and lattice temperatures were analyzed.</div><div><br></div><div>Our studies considered electron temperature dependent (ETD) and electron temperature independent (ETI) interatomic potentials. The ETI interatomic potential is easier to implement and therefore it is used in our phase change study to investigate the effects of target thickness on melting. Homogeneous melting occurred for thin films, while melting can be observed through the movement of the solid-liquid interface in thick or bulk materials. However, the ETI potential overestimated the bond strength at high temperatures. Therefore, ablation process was studied with the ETD potential. Three ablation mechanisms were found in our simulations at different laser fluences. Short nonthermal ablation was only observed at the ablation threshold. With increasing laser fluence, spallation was then seen. In high laser fluence regime, phase explosion occurred on the surface and coexisted with spallation.</div><div><br></div><div>Lastly, we researched on the effects of the delay time between two femtosecond laser pulses. Various delay times did not have much influence on melting depth. In low laser fluence regime, with increasing delay time, the target went through nonthermal ablation, to spallation and to no ablation. In high laser fluence regime, longer delay time encouraged phase explosion while suppressed spallation.</div>

<p>In the thesis are introduced and investigated spaces of Burling and of Roumieu type tempered ultradistributions, which are natural generalization of the space of Schwartz&rsquo;s tempered distributions in Denjoy-Carleman-Komatsu&rsquo;s theory of ultradistributions.&nbsp; It has been proved that the introduced spaces preserve all of the good properties Schwartz space has, among others, a remarkable one, that the Fourier transform maps continuposly the spaces into themselves.<br />In the first chapter the necessary notation and notions are given.<br />In the second chapter, the spaces of ultrarapidly decreasing ultradifferentiable functions and their duals, the spaces of Beurling and of Roumieu tempered ultradistributions, are introduced; their topological properties and relations with the known distribution and ultradistribution spaces and structural properties are investigated;&nbsp; characterization of&nbsp; the Hermite expansions&nbsp; and boundary value representation of the elements of the spaces are given.<br />The spaces of multipliers of the spaces of Beurling and of Roumieu type tempered ultradistributions are determined explicitly in the third chapter.<br />The fourth chapter is devoted to the investigation of&nbsp; Fourier, Wigner, Bargmann and Hilbert transforms on the spaces of Beurling and of Roumieu type tempered ultradistributions and their test spaces.<br />In the fifth chapter the equivalence of classical definitions of the convolution of Beurling type ultradistributions is proved, and the equivalence of, newly introduced definitions, of ultratempered convolutions of Beurling type ultradistributions is proved.<br />In the last chapter is given a necessary and sufficient condition for a convolutor of a space of tempered ultradistributions to be hypoelliptic in a space of integrable ultradistribution, is given, and hypoelliptic convolution equations are studied in the spaces.<br />Bibliograpy has 70 items.</p> / <p>U ovoj tezi su proučavani prostori temperiranih ultradistribucija Beurlingovog&nbsp; i Roumieovog tipa, koji su prirodna uop&scaron;tenja prostora Schwarzovih temperiranih distribucija u Denjoy-Carleman-Komatsuovoj teoriji ultradistribucija. Dokazano je ovi prostori imaju sva dobra svojstva, koja ima i Schwarzov prostor, izmedju ostalog, značajno svojstvo da Furijeova transformacija preslikava te prostore neprekidno na same sebe.<br />U prvom poglavlju su uvedene neophodne oznake i pojmovi.<br />U drugom poglavlju su uvedeni prostori ultrabrzo opadajucih ultradiferencijabilnih funkcija i njihovi duali, prostori Beurlingovih i Rumieuovih temperiranih ultradistribucija; proučavana su njihova topolo&scaron;ka svojstva i veze sa poznatim prostorima distribucija i ultradistribucija, kao i strukturne osobine; date su i karakterizacije Ermitskih ekspanzija i graničnih reprezentacija elemenata tih prostora.<br />Prostori multiplikatora Beurlingovih i Roumieuovih temperiranih ultradistribucija su okarakterisani u trećem poglavlju.<br />Četvrto poglavlje je posvećeno proučavanju Fourierove, Wignerove, Bargmanove i Hilbertove transformacije na prostorima Beurlingovih i Rouimieovih temperiranih ultradistribucija i njihovim test prostorima.<br />U petoj glavi je dokazana ekvivalentnost klasičnih definicija konvolucije na Beurlingovim prostorima ultradistribucija, kao i ekvivalentnost novouvedenih definicija ultratemperirane konvolucije ultradistribucija Beurlingovog tipa.<br />U poslednjoj glavi je dat potreban i dovoljan uslov da konvolutor prostora temperiranih ultradistribucija bude hipoeliptičan u prostoru integrabilnih ultradistribucija i razmatrane su neke konvolucione jednačine u tom prostoru.<br />Bibliografija ima 70 bibliografskih jedinica.</p>

[FR] Ce travail rapporte une investigation sur l’élaboration et la caractérisation de quelques oxydes transparents conducteurs, en occurrence l’oxyde de zinc (ZnO), l’oxyde de titane (TiO2) et l’oxyde de nickel (NiO). En revanche, une étude d’hétérojonction d’une couche de pérovskite déposée sur une couche de ZnO a été faite. Le spin coating et le spray pyrolyse qui sont des techniques simples et à faible coût ont été utilisées pour réaliser les différents dépôts. Les films obtenus ont été caractérisés par la Diffraction des Rayons X (DRX), la spectroscopie UV- Visible et la Microscopie Electronique à Balayage (MEB). En vue d’améliorer les propriétés de des oxydes élaborés, plusieurs dépôts ont été effectués. Le premier dépôt a permis de comparer leurs différentes propriétés. L’oxyde de zinc a présenté les meilleures propriétés par rapport aux autres. Il a fait preuve d’une bonne transmittance supérieure à 80%, une bande interdite de plus de 3,25 eV et une bonne cristallinité. Un dépôt a été effectué pour étudier l’influence de la concentration de la solution de ZnO sur ses différentes propriétés. Il est ressorti de cette étude que 0,5 M a donné les meilleurs résultats avec une transmittance de plus de 80% dans le visible et une bande interdite de 3,25 eV. Pour le dépôt de l’étude de l’effet du nombre de couches sur les différentes propriétés, quatre échantillons ont été produits (1 couche, 2 couches, 3 couches et 4 couches). L’échantillon à 4 couches a présenté les plus bons résultats. En plus d’avoir une transparence dans le visible de plus 70% et une bande interdite de 3,25 eV, il possède le plus de grains. Les résultats du dopage de l’oxyde de zinc par l’alumine ont montré que ses propriétés s’améliorent avec le dopage. Ainsi, l’échantillon dopé à 10% a donné de bons résultats comparés aux autres. Sa transmittance est plus de 90% et sa bande interdite est de 3,41 eV. Pour tous les dépôts, les résultats de la diffraction des rayons X ont révélé que l’oxyde de zinc présente deux principaux pics caractéristiques correspondant aux plans cristallographiques (002) et (101). Tous les films de ZnO produits sont polycristallins. Les résultats de l’UV-Visible ont montré que les oxydes élaborés ont une transmittance autour de 80% et une large bande interdite qui varie entre 3,20 eV et 3,41 eV. La perception des grains sur les images MEB a confirmé la cristallinité des films. Les pics identifiés du film de TiO2 correspondent aux plans (101) et (004), tous correspondant à la phase anatase tétragonale du TiO2. L'orientation préférentielle des grains est la direction (101). L’analyse de la DRX de NiO a montré que le pic indexé (111) à 37,636° correspond à la structure cubique des nanoparticules de NiO. Les dépôts de pérovskite sur la couche de ZnO en hétérojonction a révélé une bonne adhésion entre les deux couches. Ces dépôts ont permis d’étudier leurs stabilités et d’initier la fabrication d’une cellule solaire. / [ES] En este trabajo se informa de una investigación sobre el desarrollo y la caracterización de una serie de óxidos conductores transparentes, a saber, óxido de zinc (ZnO), óxido de titanio (TiO2) y óxido de níquel (NiO). Por otra parte, se llevó a cabo un estudio de heterounión de una capa de perovskita depositada sobre una capa de ZnO. Para producir los distintos depósitos se utilizaron técnicas sencillas y de bajo coste, como el recubrimiento por centrifugación y el pirólisis por pulverización. Las películas obtenidas se caracterizaron por difracción de rayos X (DRX), espectroscopia UV-Visible y microscopía electrónica de barrido (SEM). Para mejorar las propiedades de los óxidos producidos, se realizaron varios depósitos. El primer depósito se utilizó para comparar sus diferentes propiedades. El óxido de zinc mostró las mejores propiedades en comparación con los demás. Mostró una buena transmitancia de más del 80%, una brecha de banda de más de 3,25 eV y una buena cristalinidad. Se llevó a cabo una deposición para estudiar la influencia de la concentración de la solución de ZnO en sus distintas propiedades. El estudio demostró que 0,5 M daba los mejores resultados, con una transmitancia superior al 80% en el visible y una separación de banda de 3,25 eV. Se fabricaron cuatro muestras (1 capa, 2 capas, 3 capas y 4 capas) para estudiar el efecto del número de capas en las distintas propiedades. La muestra de 4 capas dio los mejores resultados. Además de tener una transparencia visible superior al 70% y un bandgap de 3,25 eV, presentaba la mayor cantidad de granos. Los resultados del dopaje del óxido de zinc con alúmina mostraron que sus propiedades mejoraban con el dopaje. La muestra dopada al 10% dio buenos resultados en comparación con las demás. Su transmitancia era superior al 90% y su brecha de banda era de 3,41 eV. Para todos los depósitos, los resultados de difracción de rayos X revelaron que el óxido de zinc tiene dos picos característicos principales correspondientes a los planos cristalográficos (002) y (101). Todas las películas de ZnO producidas son policristalinas. Los resultados de UV-Visible mostraron que los óxidos producidos tienen una transmitancia de alrededor del 80% y una amplia banda de separación que varía entre 3,20 eV y 3,41 eV. La percepción de los granos en las imágenes SEM confirmó la cristalinidad de las películas. Los picos identificados en la película de TiO2 corresponden a los planos (101) y (004), todos ellos correspondientes a la fase anatasa tetragonal del TiO2. La orientación de grano preferida es en la dirección (101). El análisis XRD del NiO mostró que el pico indexado (111) a 37,636° corresponde a la estructura cúbica de las nanopartículas de NiO. Los depósitos de perovskita sobre la capa de heterounión de ZnO revelaron una buena adherencia entre ambas capas. Estos depósitos permitieron estudiar su estabilidad e iniciar la fabricación de una célula solar. / [CA] Aquest treball informa d'una investigació sobre l'elaboració i caracterització d'alguns òxids conductors transparents, concretament l'òxid de zinc (ZnO), l'òxid de titani (TiO2) i l'òxid de níquel (NiO). D'altra banda, es va fer un estudi d'heterounió d'una capa de perovskita dipositada sobre una capa de ZnO. Per produir els diferents dipòsits es van utilitzar el recobriment per centrifugació i l'esprai de piròlisi, que són tècniques senzilles i de baix cost. Les pel·lícules obtingudes es van caracteritzar per difracció de raigs X (XRD), espectroscòpia UV-Vis i microscòpia electrònica d'escaneig (SEM). Pero tal de millorar les propietats dels òxids elaborats, s'han realitzat diversos dipòsits. El primer dipòsit va permetre comparar les seves diferents propietats. L'òxid de zinc va mostrar les millors propietats en comparació amb els altres. Va a demostrar una bona transmitància superior al 80%, un interval de banda superior a 3,25 eV i una bona cristalinitat. Es va fer un dipòsit per estudiar la influència de la concentració de la solució de ZnO en les seves diferents propietats. D'aquest estudi es va comprovar que 0,5 M va donar els millors resultats amb una transmitància de més del 80% en el visible i un interval de banda de 3,25 eV. Per a la presentació de l'estudi de l'efecte del nombre de capes sobre les diferents propietats, es van produir quatre mostres (1 capa, 2 capes, 3 capes i 4 capes). La mostra de 4 capes va mostrar els millors resultats. A més de tenir una transparència en el visible de més del 70% i un interval de banda de 3,25 eV, és el que té més grans. Els resultats del dopatge d'òxid de zinc amb alúmina van a demostrar que les seves propietats milloren amb el dopatge. Així, la mostra augmentada al 10% va a donar bons resultats en comparació amb les altres. La seva transmitància és superior al 90% i el seu interval de banda és de 3,41 eV. Per a tots els dipòsits, els resultats de la difracció de raigs X van revelar que l'òxid de zinc presenta dos pics característics principals corresponents als plans cristal·logràfics (002) i (101). Totes les pel·lícules de ZnO produïdes són policristalines. Els resultats UV-Vis van mostrar que els òxids elaborats tenen una transmitància al voltant del 80% i una àmplia banda prohibida que varia entre 3,20 eV i 3,41 eV. La percepció dels grans a les imatges SEM va confirmar la cristalinitat de les pel·lícules. Els pics identificats de la pel·lícula de TiO2 corresponen als plans (101) i (004), tots corresponents a la fase anatasa tetragonal de TiO2. L'orientació preferida del gra és la direcció (101). L'anàlisi XRD de NiO va a mostrar que el pic indexat (111) a 37,636 ° correspon a l'estructura cúbica de les nanopartícules de NiO. Els dipòsits de perovskita a la capa de ZnO d'heterounió van revelar una bona adhesió entre les dues capes. Aquests dipòsits van permetre estudiar la seva estabilitat i iniciar la fabricació d'una cèl·lula solar. / [EN] This work reports on an investigation into the elaboration and characterisation of some of transparent conducting oxides, namely zinc oxide (ZnO), titanium oxide (TiO2) and nickel oxide (NiO). On the other hand, a heterojunction study of a perovskite layer deposited on a ZnO layer was carried out. Spin coating and spray pyrolysis, which are simple, low-cost techniques, were used to produce the various deposits. The films obtained were characterised by X-ray Diffraction (XRD), UV-Visible spectroscopy and Scanning Electron Microscopy (SEM). In order to improve the properties of the oxides produced, several deposits were made. The first deposit was used to compare their different properties. Zinc oxide showed the best properties compared with the others. It showed good transmittance of over 80 %, a band gap of over 3.25 eV and good crystallinity. A deposition was carried out to study the influence of the concentration of the ZnO solution on its various properties. The study showed that 0.5 M gave the best results, with a transmittance of over 80 % in the visible and a band gap of 3.25 eV. Four samples were produced (1 layer, 2 layers, 3 layers and 4 layers) to study the effect of the number of layers on the different properties. The 4-layer sample gave the best results. As well as having a visible transparency of over 70 % and a band gap of 3.25 eV, it had the most grains. The results of doping zinc oxide with alumina showed that its properties improved with doping. The 10 % doped sample gave good results compared with the others. Its transmittance was over 90 % and its band gap was 3.41 eV. For all the deposits, the X-ray diffraction results revealed that the zinc oxide has two main characteristic peaks corresponding to the (002) and (101) crystallographic planes. All the ZnO films produced are polycrystalline. The UV-Visible results showed that the oxides produced have a transmittance of around 80 % and a wide band gap varying between 3.20 eV and 3.41 eV. The perception of the grains on the SEM images confirmed the crystallinity of the films. The peaks identified in the TiO2 film correspond to the (101) and (004) planes, all corresponding to the tetragonal anatase phase of TiO2. The preferred grain orientation is in the (101) direction. XRD analysis of NiO showed that the indexed peak (111) at 37.636° corresponds to the cubic structure of NiO nanoparticles. Deposits of perovskite on the heterojunction ZnO layer revealed good adhesion between the two layers. These deposits were used to study their stability and to initiate the manufacture of a solar cell. / Koné, KE. (2023). Élaboration et caractérisation des couches minces d'oxydes conducteurs transparents (TCO) pour les cellules solaires [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/201922

Tesis por compendio / [ES] El objetivo de esta tesis doctoral ha sido proporcionar conocimientos fundamentales y prácticos relacionados con la valorización de la biomasa de setas, para comprender la relación estructura-funcionalidad de extractos acuosos ricos en ß-glucanos, en términos de capacidad inmunorreguladora, antioxidante y antiviral, así como las propiedades tecnológicas (gelificantes y emulsionantes). El objetivo de esta tesis doctoral también ha sido explorar la viabilidad de dicha biomasa en el desarrollo de materiales compostables para el envasado de alimentos. Inicialmente, se aplicó un proceso de extracción secuencial, que implicaba varios tratamientos consecutivos tanto acuosos con y sin temperatura como alcalinos, aplicados a setas de gran consumo (P. ostreatus, L. edodes y G. frondosa), con la finalidad de comprender cómo las diferencias iniciales en la composición y la arquitectura de la pared celular afectaban a la extracción de ß-glucano. A partir de los resultados obtenidos, se analizó en profundidad la aplicación potencial de extractos acuosos, ricos en ß-glucanos, del género Pleurotus, explorando cómo la composición de los extractos y la complejidad estructural de ß-glucanos afectaban a su capacidad inmunorreguladora. Los resultados evidenciaron que tanto Pleurotus ostreatus como sus estipes mostraron los mejores resultados, con una actividad inmunoestimulante mucho mayor que las otras especies de Pleurotus exploradas. En la segunda parte de esta tesis, se evaluaron las propiedades funcionales (antivirales y antioxidantes) y tecnológicas (gelificantes y emulsionantes) de los extractos acuosos de ß-glucano, purificados y sin purificar, de Pleurotus ostreatus y sus estipes. El proceso de purificación, como era de esperar, incrementó el porcentaje en carbohidratos (con un mayor aumento en los estipes), lo que se tradujo en una mayor viscosidad y capacidad gelificante. Además, el extracto obtenido de los estipes mostró una fuerte actividad antiviral frente a norovirus murino, probablemente atribuida a la mayor complejidad estructural de sus ß-glucanos. Aunque la presencia de proteínas en los extractos acuosos de ß-glucanos potenció sus propiedades emulsionantes, esta propiedad fue dependiente de la accesibilidad de la proteína para adsorberse en la interfase O/W, lo que también afectó a la viscosidad de las emulsiones resultantes. La quitina y los ß-glucanos son dos de los principales carbohidratos de las setas, y tienen un gran potencial en la formación de materiales de envasado. En la última parte de esta tesis, se investigó la viabilidad de la biomasa de residuos de setas para desarrollar materiales de envasado de alimentos biodegradables y compostables. Los resultados mostraron que la composición de la biomasa de champiñón y las temperaturas de procesado tuvieron un impacto en las propiedades fisicoquímicas de los films desarrollados y, todas fueron biodesintegrables en condiciones de compostaje según la norma ISO 20200. Por lo tanto, esta tesis doctoral representa un importante avance en la valorización de la biomasa de setas (seta entera y estipes) y pone de relieve su idoneidad para desarrollar nuevos ingredientes funcionales y materiales de envasado para aplicaciones alimentarias y de envasado de alimentos. / [CA] L'objectiu d'aquesta tesi ha sigut proporcionar els coneixements fonamentals i pràctics relacionats amb la valorització de la biomassa de bolets, per a comprendre la relació estructura-funcionalitat d'extractes aquosos rics en ß-glucans, en termes de capacitat immunoreguladora, antioxidant i antiviral, així com de les propietats tecnològiques (gelificants i emulsionants). L'objectiu d'aquesta tesi ha estat també l'exploració de la viabilitat d'aquesta biomassa pel desenvolupament de materials compostables per a l'envasat d'aliments. Inicialment, es va aplicar un procés d'extracció seqüencial, que implicava diversos tractaments consecutius, tant aquosos amb temperatura i sense, com alcalins, aplicats a bolets de gran consum (P. ostreatus, L. edodes i G. frondosa), per tal de comprendre com les diferències inicials en la composició i l'arquitectura de la paret cel·lular afectaven l'extracció de ß-glucà. A partir dels resultats obtinguts, es va analitzar en profunditat la potencial aplicació d'extractes aquosos, rics en ß-glucans, del gènere Pleurotus, explorant així com la composició dels extractes i la complexitat structural dels ß-glucans afectaven a la seua capacitat immunoreguladora. Els resultats van evidenciar que tant Pleurotus ostreatus com les seues estipes mostraren els millors resultats, amb una activitat immunoestimulant molt més gran que la obtinguda per a les altres espècies de Pleurotus explorades. A la segona part d'aquesta tesi, es van avaluar les propietats funcionals (antivirals i antioxidants) i tecnològiques (gelificants i emulsionants) dels extractes aquosos de ß-glucà, purificats i sense purificar, de Pleurotus ostreatus i les seues estipes. El procés de purificació, com calia esperar, va incrementar el percentatge en carbohidrats (amb un major augment en els estipes), cosa que es va traduir en una major viscositat i capacitat gelificant. A més, l'extracte obtingut dels estipes va mostrar una forta activitat antiviral contra norovirus murí, probablement atribuïda a la complexitat estructural més gran dels seus ß-glucans. Tot i que la presència de proteïnes en els extractes aquosos de ß-glucans va potenciar les seues propietats emulsionants, aquesta propietat va ser dependent de l'accessibilitat de la proteïna per adsorbir-se a la interfase O/W, cosa que també va afectar la viscositat de les emulsions resultants. La quitina i els ß-glucans són dos dels principals carbohidrats dels bolets, i tenen un gran potencial en la formació de materials d'envasament. Així, a la darrera part d'aquesta tesi, es va investigar la viabilitat de la biomassa de residus de bolets per desenvolupar materials biodegradables i compostables d'envasat d'aliments. Els resultats van mostrar que la composició de la biomassa de bolets i les temperatures de processament van tenir un impacte en les propietats fisicoquímiques de les pel·lícules desenvolupades i, totes elles van ser biodesintegrables en condicions de compostatge segons la norma ISO 20200. Per tant, aquesta tesi doctoral representa un important pas endavant en la valorització de la biomassa de bolets (sencers i estipes) i posa en relleu la seua idoneïtat per desenvolupar nous ingredients funcionals i materials d'envasament per a aplicacions alimentàries i d'envasat d'aliments. / [EN] This doctoral thesis was aimed at providing fundamental and practical knowledge related to the valorisation of underexploited mushroom biomass, in order to understand the structure-function relationship of ß-glucan aqueous extracts in terms of immunoregulatory, antioxidant and antiviral capacity as well as technological (gelling and emulsifying) properties. It was also the aim of this PhD thesis to explore the feasibility of mushroom biomass to develop compostable food packaging materials. Initially, a sequential fractionation process, involving several consecutive cold or hot aqueous and alkaline treatments, was applied to widely consumed mushrooms (P. ostreatus, L. edodes and G. frondosa), in order to understand how the initial differences in composition and cell wall architecture affected ß-glucan extraction. Based on the results, the potential application of ¿-glucan aqueous extracts from Pleurotus genus was deeply analysed, thus exploring how the composition of the extracts and structural complexity of ¿-glucans affected their immunoregulatory capacity. The results evidenced that both Pleurotus ostreatus and its stipes showed the best results, with a much higher immunostimulant activity than the other explored Pleurotus species. In the second part of the thesis, functional (antiviral and antioxidant) and technological (gelling and emulsifying) properties of purified and unpurified¿¿-glucan aqueous extracts from Pleurotus ostreatus and its stipes were evaluated. The purification process, as expected, increased the carbohydrates content (greater in those obtained from the stipes), which resulted in a greater viscosity and gelling capacity. Furthermore, the extract obtained from the stipes showed a strong antiviral activity against murine norovirus, probably ascribed to the higher structural complexity of ß-glucans. Although the presence of proteins in the ¿-glucan aqueous extracts enhanced their emulsifying properties, it depended on the accessibility of the protein to adsorb at the O/W interphase, which also affected the viscosity of the resulting emulsions. Chitin and ß-glucans are two of the major carbohydrates of mushrooms, having a great potential in the formation of packaging materials. Thus, in the last part of this thesis, the feasibility of mushroom waste biomass to develop biodegradable and compostable food packaging materials was investigated. The results showed that the composition of mushroom biomass and the processing temperatures had an impact on the physicochemical properties of the developed films and, all of them were biodisintegrated under composting conditions according to ISO 20200. Therefore, this PhD thesis represents a significant step forward in the understanding of the discarded mushroom biomass (whole biomass and stipes) for valorisation purposes and highlights its suitability to develop new cost-efficient functional ingredients and packaging materials for food and food packaging applications. / This work was performed with the financial support of the CIEN project BIOPRO from “Centro para el Desarrollo Tecnológico Industrial” (CDTI), Ministry of Science and Innovation, Government of Spain. The Accreditation as Center of Excellence Severo Ochoa CEX2021-001189-S funded by MCIN/AEI/10.13039/501100011033 is also fully acknowledged. his study forms part of the AGROALNEXT programme and was supported by MCIN with funding from European Union NextGenerationEU (PRTR-C17. I1) and by Generalitat Valenciana. Synchrotron experiments were performed at NCD beamline at ALBA Synchrotron with the collaboration of ALBA staff (proposal 2,022,025,569). IF was supported by a postdoctoral contract grant for the requalification of the Spanish university system from the Ministry of Universities of the Government of Spain, financed by the European Union (NextGeneration EU) (MS21-006). / Pérez Bassart, Z. (2024). Fungal Biomass Valorization for Obtaining Functional Food-Related Materials [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/203841 / Compendio