Progress in x-ray spectroscopies for the study of advanced materials

This thesis work is focused on the use of selected core-level x-ray spectroscopies to study semiconductor materials of great technological interest and on the development of a new implementation of appearance potential spectroscopy. Core-level spectroscopies can be exploited to study these materials with a local approach since they are sensitive to the electronic structure localized on a chemical species present in the sample examined. This approach, in fact, provides important micro-structural information that is difficult to obtain with techniques sensitive to the average properties of materials. In this thesis work we present a novel approach to the study of semiconductors with core-level spectroscopies based on an original analysis procedure that leads to an insightful understanding of the correlation between the local micro-structure and the spectral features observed. In particular, we studied the micro-structure of Hydrogen induced defects in nitride semiconductors, since the analysed materials show substantial variations of optical and electronic properties as a consequence of H incorporation. Finally, we present a novel implementation of soft x-ray appearance potential spectroscopy, a core-level spectroscopy that uses electrons as a source of excitation and has the great advantage of being an in-house technique. The original set-up illustrated was designed to reach a high signal-to-noise ratio for the acquisition of good quality spectra that can then be analyzed in the framework of the real space full multiple scattering theory. This technique has never been coupled with this analysis approach and therefore our work unite a novel implementation with an original data analysis method, enlarging the field of application of this technique.

High Intensity Lasers Application to Advanced Materials Processing: Laser Peening and Related Processes

High Intensity Lasers Application to Advanced Materials Processing: Laser Peening and Related

Investigating polymer-peptide conjugates and electrospinning for the production of advanced materials

This thesis describes the production of advanced materials comprising a wide array of polymer-based building blocks. These materials include bio-hybrid polymer-peptide conjugates, based on phenylalanine and poly(ethylene oxide), and polymers with intrinsic microporosity (PIMs). Polymer-peptides conjugates were previously synthesised using click chemistry. Due to the inherent disadvantages of the reported synthesis, a new, simpler, inexpensive protocol was sought. Three synthetic methods based on amidation chemistry were investigated for both oligopeptide and polymerpeptide coupling. The resulting conjugates produced were then assessed by various analytical techniques, and the new synthesis was compared with the established protocol. An investigation was also carried out focussing on polymer-peptide coupling via ester chemistry, involving deprotection of the carboxyl terminus of the peptide. Polymer-peptide conjugates were also assessed for their propensity to self-assemble into thixotropic gels in an array of solvent mixtures. Determination of the rules governing this particular self-assembly (gelation) was required. Initial work suggested that at least four phenylalanine peptide units were necessary for self-assembly, due to favourable hydrogen bond interactions. Quantitative analysis was carried out using three analytical techniques (namely rheology, FTIR, and confocal microscopy) to probe the microstructure of the material and provided further information on the conditions for self-assembly. Several polymers were electrospun in order to produce nanofibres. These included novel materials such as PIMs and the aforementioned bio-hybrid conjugates. An investigation of the parameters governing successful fibre production was carried out for PIMs, polymer-peptide conjugates, and for nanoparticle cages coupled to a polymer scaffold. SEM analysis was carried out on all material produced during these electrospinning experiments.

Advanced mechanics of materials with microstructure

The study of advanced materials aimed at improving human life has been performed since time immemorial. Such studies have created everlasting and greatly revered monuments and have helped revolutionize transportation by ushering the age of lighter–than–air flying machines. Hence a study of the mechanical behavior of advanced materials can pave way for their use for mankind’s benefit. In this school of thought, the aim of this dissertation is to broadly perform two investigations. First, an efficient modeling approach is established to predict the elastic response of cellular materials with distributions of cell geometries. Cellular materials find important applications in structural engineering. The approach does not require complex and time-consuming computational techniques usually associated with modeling such materials. Unlike most current analytical techniques, the modeling approach directly accounts for the cellular material microstructure. The approach combines micropolar elasticity theory and elastic mixture theory to predict the elastic response of cellular materials. The modeling approach is applied to the two dimensional balsa wood material. Predicted properties are in good agreement with experimentally determined properties, which emphasizes the model’s potential to predict the elastic response of other cellular solids, such as open cell and closed cell foams. The second topic concerns intraneural ganglion cysts which are a set of medical conditions that result in denervation of the muscles innervated by the cystic nerve leading to pain and loss of function. Current treatment approaches only temporarily alleviate pain and denervation which, however, does not prevent cyst recurrence. Hence, a mechanistic understanding of the pathogenesis of intraneural ganglion cysts can help clinicians understand them better and therefore devise more effective treatment options. In this study, an analysis methodology using finite element analysis is established to investigate the pathogenesis of intraneural ganglion cysts. Using this methodology, the propagation of these cysts is analyzed in their most common site of occurrence in the human body i.e. the common peroneal nerve. Results obtained using finite element analysis show good correlation with clinical imaging patterns thereby validating the promise of the method to study cyst pathogenesis.

Sustainable mortars with incorporation of microencapsulated phase change materials

The construction industry is responsible for high energy and raw materials consumption. Thus, it is important to minimize the high energy consumption by taking advantage of renewable energy sources and reusing industrial waste, decreasing the extraction of natural materials. The mortars with incorporation of phase change materials (PCM) have the ability to regulate the temperature inside buildings, contributing to the thermal comfort and reduction of the use of heating and cooling equipment, using only the energy supplied by the sun. The simultaneous incorporation of PCM and fly ash (FA) can reduce the energy consumption and the amount of materials landfilled. However, the addition of these materials in mortars modifies its characteristics. The main purpose of this study was the production and characterization in the fresh and hardened state of mortars with incorporation of different contents of PCM and FA. The binders studied were aerial lime, hydraulic lime, gypsum and cement. The proportion of PCM studied was 0%, 20%, 40% and 60% of the mass of the sand. The content of fly ash added to the mortars was 0%, 20%, 40% and 60% of the mass of the binder. It was possible to observe that the incorporation of PCM and fly ash in mortars caused differences in properties such as workability, microstructure, water absorption, compressive strength, flexural strength and adhesion.

Tensile properties of polymer repair materials - effect of test parameters

In this research, five types of polymer repair materials were selected for investigation of the influence of sample shape, deformation rate and test temperature on the mechanical properties determined with an uniaxial tensile test. The results showed the clear effect of measurement conditions on tensile strength, elongation and modulus of elasticity. The highest tensile strength and modulus of elasticity were exhibited by epoxy resin for the filling of concrete cracks, which achieved 1% elongation. The lowest coefficient of dispersion characterized the results of tensile test carried out using dumbbell samples at a deformation rate of 50 mm/min. The effect of temperature varied with the material type.

Materials developed by mechanical alloying and melt spinning

Materials science is a multidisciplinary research topic related to the development of physics and technology. Mechanical alloying of ribbon flakes is a two steps route to develop advanced materials. In this work, a Fe based alloy was obtained using three pathways: mechanical alloying, melt-spinning and mechanical alloying of previously melt-spun samples. Processing conditions allow us to obtain amorphous or nanocrystalline structures. Furthermore, a bibliographic revision of mechanical alloying is here presented

Biomimetic Materials for Biomedical Applications

Objects with complex shape and functions have always attracted attention and interest. The morphological diversity and complexity of naturally occurring forms and patterns have been a motivation for humans to copy and adopt ideas from Nature to achieve functional, aesthetic and social value. Biomimetics is addressed to the design and development of new synthetic materials using strategies adopted by living organisms to produce biological materials. In particular, biomineralized tissues are often sophisticate composite materials, in which the components and the interfaces between them have been defined and optimized, and that present unusual and optimal chemical-physical, morphological and mechanical properties. Moreover, biominerals are generally produced by easily traceable raw materials, in aqueous media and at room pressure and temperature, that is through cheap process and materials. Thus, it is not surprising that the idea to mimic those strategies proper of Nature has been employed in several areas of applied sciences, such as for the preparation of liquid crystals, ceramic thin films computer switches and many other advanced materials. On this basis, this PhD thesis is focused on the investigation of the interaction of biologically active ions and molecules with calcium phosphates with the aim to develop new materials for the substitution and repair of skeletal tissue, according to the following lines: I. Modified calcium phosphates. A relevant part of this PhD thesis has been addressed to study the interaction of Strontium with calcium phosphates. It was demonstrated that strontium ion can substitute for calcium into hydroxyapatite, causing appreciable structural and morphological modifications. The detailed structural analysis carried out on the nanocrystals at different strontium content provided new insight into its interaction with the structure of hydroxyapatite. At variance with the behaviour of Sr towards HA, it was found that this ion inhibits the synthesis of octacalcium phosphate. However, it can substitute for calcium in this structure up to 15 atom %, in agreement with the increase of the cell parameters observed on increasing ion concentration. A similar behaviour was found for Magnesium ion, whereas Manganese inhibits the synthesis of octacalcium phosphate and it promotes the precipitation of dicalcium phosphate dehydrate. It was also found that Strontium affects the kinetics of the reaction of hydrolysis of α-TCP. It inhibits the conversion from α-TCP to hydroxyapatite. However, the resulting apatitic phase contains significant amounts of Sr2+ suggesting that the addition of Sr2+ to the composition of α-TCP bone cements could be successfully exploited for its local delivery in bone defects. The hydrolysis of α-TCP has been investigated also in the presence of increasing amounts of gelatin: the results indicated that this biopolymer accelerates the hydrolysis reaction and promotes the conversion of α-TCP into OCP, suggesting that its addition in the composition of calcium phosphate cements can be employed to modulate the OCP/HA ratio, and as a consequence the solubility, of the set cement. II. Deposition of modified calcium phosphates on metallic substrates. Coating with a thin film of calcium phosphates is frequently applied on the surface of metallic implants in order to combine the high mechanical strength of the metal with the excellent bioactivity of the calcium phosphates surface layers. During this PhD thesis, thank to the collaboration with prof. I.N. Mihailescu, head of the Laser-Surface-Plasma Interactions Laboratory (National Institute for Lasers, Plasma and Radiation Physics – Laser Department, Bucharest) Pulsed Laser Deposition has been successfully applied to deposit thin films of Sr substituted HA on Titanium substrates. The synthesized coatings displayed a uniform Sr distribution, a granular surface and a good degree of crystallinity which slightly decreased on increasing Sr content. The results of in vitro tests carried out on osteoblast-like and osteoclast cells suggested that the presence of Sr in HA thin films can enhance the positive effect of HA coatings on osteointegration and bone regeneration, and prevent undesirable bone resorption. The possibility to introduce an active molecule in the implant site was explored using Matrix Assisted Pulsed Laser Evaporation to deposit hydroxyapatite nanocrystals at different content of alendronate, a bisphosphonate widely employed in the treatments of pathological diseases associated to bone loss. The coatings displayed a good degree of crystallinity, and the results of in vitro tests indicated that alendronate promotes proliferation and differentiation of osteoblasts even when incorporated into hydroxyapatite. III. Synthesis of drug carriers with a delayed release modulated by a calcium phosphate coating. A core-shell system for modulated drug delivery and release has been developed through optimization of the experimental conditions to cover gelatin microspheres with a uniform layer of calcium phosphate. The kinetics of the release from uncoated and coated microspheres was investigated using aspirin as a model drug. It was shown that the presence of the calcium phosphate shell delays the release of aspirin and allows to modulate its action.

Modeling mechanical response of heterogeneous materials

Heterogeneous materials are ubiquitous in nature and as synthetic materials. These materials provide unique combination of desirable mechanical properties emerging from its heterogeneities at different length scales. Future structural and technological applications will require the development of advanced light weight materials with superior strength and toughness. Cost effective design of the advanced high performance synthetic materials by tailoring their microstructure is the challenge facing the materials design community. Prior knowledge of structure-property relationships for these materials is imperative for optimal design. Thus, understanding such relationships for heterogeneous materials is of primary interest. Furthermore, computational burden is becoming critical concern in several areas of heterogeneous materials design. Therefore, computationally efficient and accurate predictive tools are highly essential. In the present study, we mainly focus on mechanical behavior of soft cellular materials and tough biological material such as mussel byssus thread. Cellular materials exhibit microstructural heterogeneity by interconnected network of same material phase. However, mussel byssus thread comprises of two distinct material phases. A robust numerical framework is developed to investigate the micromechanisms behind the macroscopic response of both of these materials. Using this framework, effect of microstuctural parameters has been addressed on the stress state of cellular specimens during split Hopkinson pressure bar test. A voronoi tessellation based algorithm has been developed to simulate the cellular microstructure. Micromechanisms (microinertia, microbuckling and microbending) governing macroscopic behavior of cellular solids are investigated thoroughly with respect to various microstructural and loading parameters. To understand the origin of high toughness of mussel byssus thread, a Genetic Algorithm (GA) based optimization framework has been developed. It is found that two different material phases (collagens) of mussel byssus thread are optimally distributed along the thread. These applications demonstrate that the presence of heterogeneity in the system demands high computational resources for simulation and modeling. Thus, Higher Dimensional Model Representation (HDMR) based surrogate modeling concept has been proposed to reduce computational complexity. The applicability of such methodology has been demonstrated in failure envelope construction and in multiscale finite element techniques. It is observed that surrogate based model can capture the behavior of complex material systems with sufficient accuracy. The computational algorithms presented in this thesis will further pave the way for accurate prediction of macroscopic deformation behavior of various class of advanced materials from their measurable microstructural features at a reasonable computational cost.

Effect of Thermal Treatments on the Mechanical Properties Enhancement of High Reliability Metallic Materials by Laser Shock Processing

Laser shock processing (LSP) is increasingly applied as an effective technology for the improvement of metallic materials mechanical properties in different types of components as a means of enhancement of their fatigue life behavior. As reported in previous contributions by the authors, a main effect resulting from the application of the LSP technique consists on the generation of relatively deep compression residual stresses fields into metallic components allowing an improved mechanical behaviour, explicitly the life improvement of the treated specimens against wear, crack growth and stress corrosion cracking. Additional results accomplished by the authors in the line of practical development of the LSP technique at an experimental level (aiming its integral assessment from an interrelated theoretical and experimental point of view) are presented in this paper. Concretely, experimental results on the residual stress profiles and associated mechanical properties modification successfully reached in typical materials under different LSP irradiation conditions are presented. In this case, the specific behavior of a widely used material in high reliability components (especially in nuclear and biomedical applications) as AISI 316L is analyzed, the effect of possible “in-service” thermal conditions on the relaxation of the LSP effects being specifically characterized. I.

Opportunities and challenges in the use of inorganic fullerene-like nanoparticles to produce advanced polymer nanocomposites

Polymer/inorganic nanoparticle nanocomposites have garnered considerable academic and industrial interest over recent decades in the development of advanced materials for a wide range of applications. In this respect, the dispersion of so-called inorganic fullerene-like (IF) nanoparticles, e.g., tungsten disulfide (IF-WS2) or molybdenum disulfide (IF-MoS2), into polymeric matrices is emerging as a new strategy. The surprising properties of these layered metal dichalcogenides such as high impact resistance and superior tribological behavior, attributed to their nanoscale size and hollow quasi-spherical shape, open up a wide variety of opportunities for applications of these inorganic compounds. The present work presents a detailed overview on research in the area of IF-based polymer nanocomposites, with special emphasis on the use of IF-WS2 nanoparticles as environmentally friendly reinforcing fillers. The incorporation of IF particles has been shown to be efficient for improving thermal, mechanical and tribological properties of various thermoplastic polymers, such as polypropylene, nylon-6, poly(phenylene sulfide), poly(ether ether ketone), where nanocomposites were fabricated by simple melt-processing routes without the need for modifiers or surfactants. This new family of nanocomposites exhibits similar or enhanced performance when compared with nanocomposites that incorporate carbon nanotubes, carbon nanofibers or nanoclays, but are substantially more cost-effective, efficient and environmentally satisfactory. Most recently, innovative approaches have been described that exploit synergistic effects to produce new materials with enhanced properties, including the combined use of micro- and nanoparticles such as IF-WS2/nucleating agent or IF-WS2/carbon fiber, as well as dual nanoparticle systems such as SWCNT/IF-WS2 where each nanoparticle has different characteristics. The structure–property relationships of these nanocomposites are discussed and potential applications proposed ranging from medicine to the aerospace, automotive and electronics industries.

International Materials Science Seminars: A Bridge between Two Continents

International Materials Science Seminars aim at combining the expertise of several advanced research groups and creating an unique opportunity for foreign and Spanish students in terms of cutting-edge research.

Primary Raw Materials (1986-89) Volume 1 (Summary Reports of the R&D Programme). EUR 13647/I EN, 1992

"This document contains the Summary Reports of cost sharing Research and Development contracts funded under the "Primary Raw Materials" subprogramme of the Commission of the European Communities. This programme was part of the research and development programme on "Raw Materials and Advanced Materials" (1986 - 1989). The main objectives of the "Primary Raw Materials" subprogramme were to enhance the competitiveness of the European Community mining and metallurgical Industries and to reduce European Community vulnerability for minerals, particularly those of critical or strategic interest." Three research areas: Research and development exploration; Mining technology; Mineral processing.