Thesis (M.S.)--University of Nevada, Reno, 2005. / "May, 2005." Includes bibliographical references (leaves100-103). Online version available on the World Wide Web.

Thesis (Ph. D. in Chemistry)--Vanderbilt University, Dec. 2007. / Title from title screen. Includes bibliographical references.

Thesis (Ph. D.)--Ohio State University, 2006. / Full text release at OhioLINK's ETD Center delayed at author's request

Thesis (Ph. D.)--Washington State University, May 2007. / Includes bibliographical references.

Thesis (Ph. D.)--Ohio State University, 2006. / Title from first page of PDF file. Includes bibliographical references (p. 243-263).

Thesis (M. Phil.)--University of Hong Kong, 2006. / Title proper from title frame. Also available in printed format.

Thesis (M.Phil.)--City University of Hong Kong, 2006. / "Submitted to Department of Physics and Materials Science in partial fulfillment of the requirements for the degree of Master of Philosophy" Includes bibliographical references.

The search for cellulosic based products as a viable alternative for petroleum-based products was the impetus for covalently crosslinking lignocellulosic fibers and nanocellulose whiskers with poly(methyl vinyl ether) co maleic acid (PMVEMA) - polyethylene glycol (PEG). The lignocellulosics used were ECF bleached softwood (pine) and ECF bleached birch kraft pulp. This thesis also tests the hypothesis that water absorption and retention can be improved by grafting PMVEMA-PEG to the surface of ECF bleached kraft pulp hardwood and softwood fibers via microwave initiated crosslinking. The crosslinking of the PMVEMA to hardwood and softwood kraft ECF bleached pulp fibers resulted in enhanced water absorbing pulp fibers where the PMVEMA is grafted onto the surface of the fibers. The crosslinking was initiated both thermally and via microwave irradiation and the water absorption and water retention was measured as the percent of grafted PMVEMA. This was the first application of microwave crosslinking of pulp fibers with the goal of creating water absorbing pulp fibers. Ultimately, the water absorption values ranged from 28.70 g water per g dry crosslinked pulp fiber (g/g) to 230.10 g/g and the water retention values ranged from 26% to 71% of the water retained that was absorbed by the crosslinked pulp fibers. The microwave initiated crosslinked fibers had comparable results to the thermally crosslinked fibers with a decreased reaction time, from 6.50 min (thermal) to 1 min 45 sec (microwave). Cellulose nanowhiskers, crystalline rods of cellulose, have been investigated due to their unique properties, such as nanoscale dimensions, low density, high surface area, mechanical strength, and surface morphology and available surface chemistry. Prior to this study, the crosslinking of cellulose whiskers with the matrix via solution casting of liquid suspensions of whiskers and matrix had not been explored. The hypothesis to be investigated was that incorporating cellulosic whiskers with the PMVEMA-PEG matrix and crosslinking the whiskers with the matrix would yield films that demonstrate unique properties when compared to prior work of crosslinking of PMVEMA-PEG to macroscopic ECF bleached kraft pulp fibers. Solution cast composites of cellulose nanowhiskers-PMVEMA-PEG were crosslinked at 135 °C for 6.5 min and analyzed for crosslinking, thermal stability, strength and mechanical properties, whisker dispersion, and water absorption and uptake rates. The whisker-composites demonstrated unique properties upon crosslinking the whiskers with PMVEMA-PEG, especially the elongation at break and tensile strength upon conditioning of the final materials at various relative humidities. In addition, the whiskers improved the thermal stability of the PMVEMA-PEG matrix. This is significant as methods of improving processing thermal stability are key to developing new materials that utilize cellulose whiskers, PMVEMA, and PEG. This thesis addresses the hypothesis that cellulose nanowhiskers that are crosslinked with a matrix can create new whisker-matrix composites that behave differently after crosslinking.

L’aparició de noves propietats químiques i físiques dins l’escala nanomètrica és un dels motius principals que fa necessari l’estudi de nanopartícules de diferents metalls, del seus òxids i dels seus aliatges, pel disseny de les seves futures aplicabilitats. Aquesta tesi estudia dos blocs temàtics: i) la síntesi i ii) l’autoensamblatge de nanopartícules metàl·liques. En el primer bloc, s’estudien els aspectes més rellevants de la preparació de nanopartícules metàl·liques (constituïdes per un o dos metalls diferents) de mida i forma controlada. Es desenvolupa les síntesis de diferents partícules magnètiques, i s’obtenen dispersions col·loïdals de nanopartícules de cobalt (Co) i alguns del seus òxids, així com d’ or (Au), platí (Pt) i alguns dels seus aliatges. Les nanopartícules de Co estan rebent un interès creixent degut a les propietats magnètiques que presenta el material, la qual cosa les fa molt interessants per a un nombre elevat d’aplicacions tecnològiques. Però la sensibilitat del material en front l’oxidació (la qual produeix canvis en les seves propietats magnètiques) requereix que es faci un estudi profund d’aquests processos. En aquest treball, s’han sintetitzat nanopartícules de Co de diferents mides i s’han estudiat els paràmetres que afecten les seves propietats magnètiques. A més, s’han estudiat els processos d’oxidació de les nanopartícules de Co, que han generat tant nanopartícules core/shell (nucli/recobriment) Co/CoO com nanopartícules “hollow” (buides) d’òxid de Co. Les nanopartícules de Pt també són de gran interès degut a que presenten propietats òptiques i catalítiques úniques. Les seves propietats catalítiques depenen fortament dels seus àtoms superficials i, per tant, de la mida i de la forma de les nanopartícules. En aquesta tesi s’ha dut a terme la síntesi de nanopartícules de Pt de diferent mida i forma mitjançant el control de diferents paràmetres durant el procés sintètic (com la temperatura, els lligands i els temps de reacció). En particular, s’ha determinat la incorporació de traces metàl·liques durant la síntesis i el seu efecte en el control de la forma final de la nanopartícula. Finalment, l’or es un dels materials més estudiats en l’escala nanomètrica degut a les seves propietats òptiques i el seu caràcter inert, que fa que sigui un dels materials més utilitzats en aplicacions biològiques. Les propietats òptiques són especialment importants en materials amb “aspect ratios” (relació longitud/amplada). En aquesta tesi s’han sintetitzat Au “rods” (barres) de gran llargada utilitzant nanopartícules de Pt com a catalitzador de la reacció, i se n’ha explorat la llargada que poden aconseguir, relacionades amb les seves possibles aplicacions. En el segon bloc, s’estudia l’ús de les nanopartícules en la preparació de materials nanoestructurats mitjançant autoensamblatge. S’ha observat com depenent de la naturalesa i la forma de les nanopartícules, es creen diferents patrons. En particular, aquesta part es centra principalment en la utilització de nanopartícules de Co com a unitats de construcció de estructures autoensamblades, degut a les seves propietats magnètiques. S’ha estudiat l’autoensamblatge de nanopartícules de Co a sobre de diferents substrats d’interès tecnològic i les forces que intervenen en el procés. En particular, en destaquem: l’estudi de l’autoensamblatge de les partícules de Co sobre grafit i sobre substrats de silici. Finalment, s’ha estudiat la influència de les propietats en el procés d’autoensamblatge de nanopartícules de Co, així com l’estructura magnètica dels assemblats, mitjançant holografia electrònica i microscopia Lorentz. S’ha estudiat la variació de l’estructura magnètica dels diferents assemblats en funció de la seva mida total, i també en funció de la temperatura. L’estudi de les propietats individuals de les nanopartícules de Co dins l’assemblat és possible mitjançant les dues tècniques mencionades prèviament, i s’han observat els efectes col·lectius entre totes les partícules integrants de les estructures. Els resultats obtinguts indiquen que l’ordenació ferromagnètica dipolar és molt persistent en les estructures, fins i tot amb un elevat grau de desordre a la xarxa de partícules. / The emergence of new chemical and physical properties at the nanoscale is one of the main reasons that make necessary the study of nanoparticles of different metals, their oxides and alloys for different applications. In this thesis, two thematic blocks are studied: i) the synthesis and ii) the self- assembly of metallic nanoparticles. In the first block, the more relevant aspects in the preparation of metallic and bimetallic nanoparticles of controlled size and shape are studied. The syntheses of different metal nanoparticles are developed, and monodisperse colloidal suspensions of Co metal particles and some of their oxides, as well as Au, Pt and some alloy nanoparticles are obtained. Co particles are receiving much interest due to their magnetic properties of the material, which turn them interesting for a number of technological applications. On the other hand, the sensitivity of the material to oxidation (with a consequent change in its properties) makes necessary a deeper study of these processes. In this work, Co magnetic nanoparticles of different sizes have been synthesized and the parameters that affect the variation of their magnetic properties have been studied. Moreover, the oxidation processes of the Co nanoparticles have been also studied, generating both Co/CoO core/shell and CoO hollow nanoparticles. Pt nanoparticles are also a subject of interest due to their unique optical and catalytic properties. Their catalytic properties strongly depends on their surface atoms and, therefore, on the size and shape of the particles. During this thesis, different size and shape Pt nanoparticles have been synthesized by controlling different parameters during the synthetic process (i.e. temperature, surfactants, and reaction times). In particular, the incorporation of metal “traces” during the synthesis process, and their effect on the control of the shape are determined. Finally, Au is one of the most studied materials at the nanometer scale due to its optical properties and its inertness, making it one of the most used materials in biological applications. The optical properties are particularly important in materials with aspect ratios (length/width). In this thesis, the synthesis of extra long Au rods (bars) using Pt nanoparticles as the reaction catalyst have been synthesized, and the length that they can reach have been also explored for its potential applications (e.g. as connections between electrodes). In the second block, the use of nanoparticles for the preparation of nanostructured materials via self-assembly processes is studied. It is observed how, depending of both the nature and the shape of the nanoparticle, different patterns are created. In particular, this part focuses mainly on the use of Co nanoparticles as building block units for construction of self-assembled structures, due to their magnetic properties. The self-assembly of Co nanoparticles onto different substrates with technological interest and the forces involved in the process have been studied. Particularly, the works to be highlighted are the study of the self-assembly of Co on graphite and on silicon substrates due to dipolar interactions. Finally, the influence of the magnetic properties in the self-assembly process of Co nanoparticles, and the magnetic structure of the formed assemblies, are studied by electron holography and Lorentz microscopy. The variation of the magnetic structure of the different self-assembled structures has been studied as a function of both the assembly total size and the temperature. The study of the individual and collective behavior of the Co nanoparticles on the assembly is possible with these techniques, and collective effects among the whole NPs forming the structures have been observed. The obtained results showed that dipolar ferromagnetism order is extremely persistent even under a high degree of lattice disorder.

The Microelectronics industry has continuously pushed the limit of critical dimensions to sub-20 nm. One of the challenges is pattern collapse, caused by unbalanced capillary forces during the final rinse and drying process. The use of surfactants offers a convenient method to reduce capillary forces but causes another deformation issue. This thesis work focuses on alternative approaches that are compatible with lithographic processes to mitigate pattern collapse. First, an e-beam lithography pattern with a series of varying line and space widths has been specifically designed in order to quantitatively study pattern collapse behavior. This pattern generates increasing stress in the pairs of resist lines as one moves across the pattern array and eventually a sufficiently small space value (critical space, S1c) is reached in each array such that the stress applied to the resist exceeds the critical stress (σc) required for pattern bending and subsequently feature deformation and collapse occurrs. The patterns we designed allow us to qualitatively and quantitatively study pattern collapse and obtain consistent, reproducible results. In the first part of the thesis work, a quick surface crosslink (called a reactive rinse) that involves the strengthening of the resist using crosslinking via carbodiimide chemistry while the resist structures are still in their wet state, has been developed and demonstrated. This technique provides efficient and significant improvement on the pattern collapse issue. In the second part of the thesis work, a triethoxysilane compound, vinyl ether silane (VE), has been successfully synthesized. It can be used to modify the silicon or silicon nitride substrates and form a covalent bond with the resist film instead of manipulating the surface energies using common HMDS. Compared to traditional Hexamethyldisilazane (HMDS) vapor primed surfaces, the implementation of the VE adhesion promoter resulted in a significant improvement in the adhesion and resistance to adhesion based pattern collapse failure in small sub-60 nm resist features. In the third part of the thesis work, the effect of drying rates and drying methods has been systematically studied. SEM analysis and critical stress results showed that fast drying appear to reduce the resist collapse. The line pair orientations in each pattern array with respect to the wafer radius reveal an apparent effect of fluid flow and centrifugal forces on collapse. Finally, a comprehensive pattern collapse model that incorporates adhesion based pattern failure and elastoplastic deformation-based failure, and dimensionally dependent resist modulus properties has been developed. This model provides such an excellent prediction of the experimental data and supports the idea that this level of combined adhesion-failure and elastoplastic-failure based pattern collapse modeling, where one explicitly considers the dimensionally dependent mechanical properties of the resist can be quantitatively predictive and useful for understanding the pattern collapse behavior of polymeric nanostructures.