<p dir="ltr">This thesis delves into the dynamics and driving factors of thermal transport via natural convection, the onset and severity of quiescent cavitation and its impact of auto-injector device performance, and the controlled release of rapidly swelling pharmaceutical tablets. In each of these instances showcases how variations in external conditions or the introduction of new variables can disrupt the equilibrium of fluid systems, leading to complex behaviors. Vertical thermal convection illustrates how temperature gradients induce fluid movement and patterns; cavitation inception focuses on the formation of vapor cavities due to pressure drops within a fluid; and rapid tablet swelling explores the interaction between solid materials and liquids, leading to significant changes in concentration and mass transfer. These studies collectively enhance our understanding of transport dynamics, highlighting pathways to achieve optimal transport and delivery conditions for various industrial and pharmaceutical processes.</p>

L'Electrogravimetria AC empra una microbalança de quars electroquímica (EQCM) en règim dinàmic. En l'EQCM un dels elèctrodes d'or depositats sobre el cristall és recobert amb una fina pelolícula d'un polímer electroactiv i és emprat com a elèctrode de treball (WE) dins d'una celola electroquímica. Les variacions de la freqüència de ressonància de la microbalança de quars (QCM) permeten obtindre la resposta massa associada amb la transferència de càrrega que es dóna en la interfície polímer-electròlit. L'Electrogravimetria AC va ser proposta a fi de caracteritzar i separadament identificar el moviment dels ions i el solvent en la interfície polímer-electròlit. En esta tècnica s'analitza en el domine de la freqüència la resposta de massa davant de xicotetes pertorbacions de voltatge gràcies a l'ocupació de la microbalança de quars en règim dinàmic. Per a este propòsit s'aplica una xicoteta pertorbació sinusoidal superposada a una tensió contínua, entre l'elèctrode de referència i l'elèctrode de treball de la celola. Posteriorment, es pot dibuixar la funció de transferència electrogravimètrica (EGTF), definida esta com la raó (?m/?E) entre l'amplitud dels canvis de massa induïts (?m) i l'amplitud de la pertorbació sinusoïdal aplicada (?E). Esta funció de transferència se dibuixa en un pla complex per a cada una de les freqüències de la senyal de pertorbació. Les distintes espècies iònicas involucrades són identificades en el pla complex per mitjà de bucles característics sempre que els bucles no se superposen. Per mitjà d'esta tesi doctoral es proposa un nou sistema de conversió de freqüència-tensió basat en un doble ajust de freqüència implementat amb un PLL mesclant elements analògics i digitals (AD PLL). Els resultats trobats tant en la caracterització electrònica del dispositiu com en la fase experimental proven la fiabilitat del sistema per als mesuraments realitzats en la tècnica d'Electrogravimetria AC. / Torres Villa, RA. (2007). Instrumental techniques for improving the measurements based on Quartz Crystal Microbalances (Técnicas instrumentales para mejorar las mediciones con microbalanzas de cuarzo) [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/17323

No / Results of a study on the influence of process parameters such as impeller speed, granulation time and binder viscosity on granule strength and properties are reported. A high shear granulator (Cyclomix manufactured by Hosokawa Micron B.V., The Netherlands) has been used to produce granules. Calcium carbonate (Durcal) was used as feed powder and aqueous polyethylene glycol (PEG) as the binder. The dried granules have been analysed for their strength, density and size distribution. The results show that increasing the granulation time has a great affect on granules strength, until an optimum time has been reached. The underlying cause is an increase in granule density. Granules are consolidated more at higher impeller speeds. Moreover, the granule size distribution seems not to be affected significantly by an increase in impeller speed. Granules produced with high binder viscosity have a considerably lower strength, wide strength distribution due to poor dispersion of binder on the powder bed. Binder addition methods have showed no considerable effect on granule strength or on granule size distribution.

No / A novel method for manufacturing granules with a large particle at their core, referred to as seeded granules, is presented. As an example, calcium carbonate powders (Durcal) of different grades are used as primary particles and polyethylene glycol (PEG) as liquid binder in high shear granulators of different scales (Cyclomix, manufactured by Hosokawa Micron B.V., The Netherlands). The conditions giving rise to seeded granulations are specified in the form of an operational regime map. It is found that the seeded structure is strongly dependent on the impeller speed and the primary particles size distribution. It is shown that a Stokes number of around 0.1 represents the optimal dynamic conditions in the given example for producing seeded granules, regardless of the scale of the granulator.

Yes / Thermoplastic polyurethane (TPU)/multi-walled carbon nanotubes (CNT) nanocomposites were prepared by twin-screw extrusion and micro injection molding. The electrical conductivity of micro injection molded polymer nanocomposites exhibits a low value and uneven distribution in the micromolded samples. Real-time tracing of electrical conductivity was conducted to investigate the post thermal treatment on the electrical conductivity of microinjection molded composites. The results show that postmolding thermal treatment leads to a significant increase in the electrical conductivity by over three orders of magnitude for 5 wt % CNT-filled TPU composites. In-situ Transmission electron microscopy confirms the conductive CNT network does not change at the micron/sub-micron scale during thermal treatment. TEM image analysis by a statistical method was used to determine the spatial distribution of CNT in the sample and showed that the average distance between adjacent CNT reduced slightly at the nanometer scale after postmolding thermal treatment. A new conductive mechanism is proposed to explain the enhancement of electrical conductivity after thermal treatment, i.e. micro-contact reconstruction of adjacent CNT in the polymer matrix through annealing-induced relaxation of interfacial residual stress and strain. Raman spectra and small angle X-ray scattering curve of annealed samples provide supporting evidence for the proposed new conductive mechanism. The electron tunneling model was used to understand the effect of inter-particle distance on the conductivity of polymer composites. / Chinese Ministry of Education. Grant Number: 313036; National Natural Science Foundation of China. Grant Number: 51433006

<p dir="ltr">This thesis focuses on the study of wave propagation in architected material systems. Specifically of interest is wave propagation in topologically interlocking material (TIM) systems made of tetrahedra and bio-inspired blocks. TIM systems are assemblies of composed of blocks in which the block geometry constrains blocks in place. Individual blocks can only be removed by disassembling the system. This interlocking of block geometry allows these systems to bear loads without the need for adhesives. Overall, load bearing is affected by block geometry, contact interaction, and assembly architecture. Wavefronts and wave velocities are computed using an explicit finite element code. Wave propagation is investigated first in a row of interlocking tetrahedra, then in 3D planar TIM systems of tetrahedra and bio-inspired scutoid blocks.</p><p dir="ltr">The propagation of linear traveling waves through a row of interlocking tetrahedra is demonstrated by the use of finite element simulations. The wave velocity was found to be independent of wave amplitude for ideal contact conditions but dependent on impact velocity for an exponential pressure-overclosure relationship between surfaces. For a frictionless, constant contact stiffness model, the effective wave velocity is about 50% of the 1D material wave speed. In the presence of friction, the wave velocity increases to about 80% of the 1D material wave speed. The wave velocity is attributed to wave-guiding set by the geometry of the tetrahedra. The wave velocity is further modulated by the rocking motion of the tetrahedra about an axis perpendicular to the wave propagation direction. The rocking motion is affected by friction and is reduced as friction is increased. Experimental results on wave propagation in a row of 3D-printed triangular prisms demonstrate pulse-like voltage versus time wave responses. With rough and tacky surfaces, the velocity of the linear traveling waves is measured as approximately 20% the 1D material wave speed. For smooth and low friction surface conditions, significantly higher wave velocities are measured. Similarly, reducing the number of contact surfaces by fusing pairs of building blocks also results in higher measured wave velocities. Experiments on rectangular prisms lack the wave-guiding geometry and provide a reference configuration. Finite element models are used to gain detailed insight into the wave propagation process. Wave-guide models are defined to predict wave speeds based on the effective path of wave propagation. The proposed models closely predict measured and computed wave speeds for the tetrahedra and triangular prisms.</p><p dir="ltr">Scutoids are prism-like shapes containing lateral vertices between two parallel polygonal surfaces. With the lateral vertices at the midplane, scutoid blocks can be periodically and densely packed. Scutoid-based planar arrays are demonstrated to behave mechanically as TIM systems. Under quasi-static transverse loads, assembly properties (stiffness, strength, toughness) match or exceed those of the corresponding tetrahedra-based TIM systems. The scutoid-based TIM systems have unique chiral characteristics. Chirality is attributed to the combination of building block and assembly symmetry. Chirality leads to asymmetric internal load transfer patterns resulting in unbalanced in-plane reaction forces and reaction moments. Experiments confirm the computational findings. Under transverse indentation, these systems have nonlinear force-displacement responses and measurable torque responses.</p><p dir="ltr">Wave propagation following transverse impact on planar arrays of interlocking tetrahedra and scutoids is investigated. Unique wave speed and wavefront development are demonstrated to occur in these systems. The 1D material wave speed emerges as the limiting wave speed of the TIM systems, rather than the dilatational wave speed. In tetrahedra assemblies, waves propagate with a velocity of approximately 25% of the 1D material wave speed. The wave velocity is attributed to wave-guiding from the interlocking tetrahedra geometry. Tetrahedra are not perfectly space-filling and block-to-block interactions are not limited to one direction. In the scutoid assemblies, waves propagate at velocities between 80% and 90% of the 1D material wave speed. These velocities are along directions associated with dominant load paths. The wave velocities in the scutoid-based TIM systems approach the 1D material wave speed as the contact surfaces are substantially orthogonal to the assembly surface. In comparison to monolithic plates, wavefronts develop with significant spatial non-uniformity. Wave patterns exhibit the symmetry or asymmetry also observed in the quasi-static response. Overall, contact surface orientation, block geometry, and assembly architecture affect wave velocity and wavefront development.</p>

<p dir="ltr">Ultrafast optics is an important field of study for chemistry and physics, providing new information on the dynamics of matter and electrons. In this thesis I describe my work on ultrafast laser systems. The two main systems discussed are a high harmonic generated extreme ultraviolet system and a terahertz spectroscopy system. The first half describes the importance and background of both as well as how these systems are set up. The second half describes my work in designing and implanting these systems, and my work in constructing components for the operation of both.</p>

<div>Despite the abundant current applications for ionic hydrogels, much about the stimuli-responsive behavior of these materials remains poorly understood. Due to the soft nature of these materials, the number of traditional characterization methods which can be applied to these systems is limited. Many studies have been conducted to characterize bulk property responses of these materials, and experimental studies have been produced examining the distribution of free ions around single polyelectrolyte chains. However, little experimental work has been published in which molecular-scale interactions are elucidated in confined polyelectrolyte networks. Furthermore, the way in which responsive properties, other than bulk swelling capacity, scale with ionic fraction in mixed polyelectrolyte-non-polyelectrolyte hydrogel systems has not been thoroughly investigated.</div><div>The distribution and strength of polymer-counter-ion bonds has a remarkable effect on hydrogel properties such as absorption capacity, mechanical strength, and size and chemical selectivity. In order to tailor these properties for targeted applications in ionic environments, it is imperative that we thoroughly understand the character of these polymer-ion interactions and their arrangement within the bulk hydrogel. In order to do so, however, non-traditional methods of analysis must be employed.</div><div>This dissertation focuses on a model part-ionic hydrogel system, poly(sodium acrylate-co-acrylamide), in order to assess not only the polymer-counter-ion interactions but also the impact of gel ionic fraction on these interactions and the responses which they induce in gel performance properties. A model alkali (NaCl), alkaline earth (CaCl2), and transition (CuSO4) metal salt are employed to investigate changes in polymer properties from the macroscale to the nanoscale. The aim of this dissertation is to lay the foundation for the development of fundamental structure-property relationships by which we may fully understand the ionically-induced performance properties of polyelectrolyte networks.</div>

Ces travaux de thèse portent sur l’étude et l’optimisation des propriétés interfaciales verre/PA 6-6 pour la conception de matériaux composites de structure. Une méthode visant à nettoyer et réactiver la surface du verre a dans un premier temps été développée. Elle permet de travailler avec des substrats de type fibres ou substrats modèles (plaques de verre) et d’obtenir des surfaces « contrôlées » avant l’application de nouveaux revêtements. La maîtrise de l’interface entre renfort et matrice nécessite l’optimisation de l’ensimage, dont les principaux constituants sont des agents filmogènes et des agents de couplage. Au cours de ce travail, nous avons donc étudié les propriétés thermiques, mécaniques et de surface des nouveaux revêtements appliqués sur les substrats de verre. Différents agents filmogènes, sélectionnés pour être compatibles avec les conditions de mise en oeuvre du PA 6-6, ainsi que deux agents de couplages usuels ont été étudiés. Par le choix d’une large gamme de familles d’agents filmogènes, nous avons montré que l’utilisation d’un agent filmogène de composition chimique proche de celle de la matrice permet d’atteindre de meilleures propriétés interfaciales. L’augmentation de la rugosité de surface du revêtement contribue également à cette amélioration. Le greffage des agents de couplage sur le verre s’est révélé bien plus efficace avec un traitement thermique à 150°C qu’à 110°C et un effet de synergie a pu être observé lors de leur association avec un agent filmogène. L’utilisation d’agents filmogènes à haute résistance thermique a permis d’obtenir des propriétés interfaciales très intéressantes, renforcées pour certains systèmes par l’ajout de nanoparticules. Enfin, afin d’accéder à une estimation de la ténacité de l’interface, un test de DCB en mode I a été adapté à notre problématique. Les résultats obtenus ont été complémentaires à ceux obtenus par les tests du plot et de la microgoutte / This work is devoted to the study and optimisation of glass/PA 6-6 interfacial properties for the conception of structural composite materials. A method to clean and reactivate glass surface was first developed. It allowed us to work with glass fibres and model substrates (glass plates), aiming to get controlled surfaces before the application of new coatings. Controlling the interface between the reinforcement and the matrix requires the optimisation of the sizing, which is mainly composed of film formers and coupling agents. This study consisted in the characterisation of thermal, mechanical and surface properties of the new coatings applied to the glass substrates. Different film former bases, selected for their compatibility with the processing conditions of PA 6-6, and two usual coupling agents were studied. This work allowed to identify different parameters that play a role in the improvement of interfacial properties. By working with a wide range of film formers, we could show that the use of a film former with close chemical composition from the matrix allows to reach better interfacial properties. Increasing the surface roughness of coatings also participates in this improvement. The grafting of coupling agents was more efficient after 150°C thermal treatment than 110°C, and a synergistic effect was obtained by their association to a film former. The use of film formers with high thermal resistance provided very interesting interfacial properties, also improved, for some, by the addition of silica nanoparticles. Finally, DCB mode I mechanical test was adapted to our system, allowing to estimate the fracture toughness of the glass/PA 6-6 interface which is a complementary result to the estimation of the adhesion force measured by pull-off and pull-out tests

The pharmaceutical process of dry granulation using roller-compaction (DG/RC) is effectively a non-batch based procedure orientated to deliver a continuous stream of material free of a pre-defined batch-size with reduced plant equipment/scale-up R&D resources and an enhanced work-throughput, particularly suitable for moisture sensitive formulation. The desirable accreditations of DG/RC are many; yet by the nature of a more flexible approach than (i.e. wet-granulation), it must be highly monitored and controlled to accomplish higher-throughput rates and reduced ‘static’ material testing stages. To monitor rapidly and in-line with production, pre-granulated ribbons of RC (which highly correlates to the post milled granulates), terahertz time-domain spectroscopy (TDS) is used to elucidate the key physical attributes of post-compression density and thickness uniformity, key to end-product consistency. Invariably a great number of conditions apply to DG/RC (viz: System design, material characteristics, environmental and unit configuration), although widely regarded as the key processing parameters (PP’s) are roll-pressure and roll-gap [1-4]. The target of the study is to derive a strategy to position TDS as PAT to DG/RC. Two terahertz time-domain TD methods of a conventional transmission setup and reflection (TPI) THz analysis are used on standards of glass slides for verifying the interpretational foundations of the TD methods. Achieving RI/thickness error-discrepancies +2.2 to -0.4% c.f. literature ([150]) values provides foundations to test the solid-fraction ratios of pharma tablets with regard to RI’s being surrogate values to SF/path-length (R2 = 1). Combining transmission principles to the portion of reflected EMR removes the pre-requisite for RI or path-length knowledge, giving +1.5 to +2.4% RI agreement (vs. frequency-domain attained results) thus enabling thickness estimations to be above 95% against physical micrometre judgement in all models. Augmentation of the TD methods, refined in Experimental chapter 2 ,then chiefly focuses on TPI as the principle THz-TD method (as the most ideal tool for PAT) for adopting the RI measures for ribbon uniformity analysis in Experimental chapter 4 in an off-line environment again resulting in RI and thicknesses < 5 % error of known parameters of thickness and further use of RI as a proxy porosity equivalent to gas pycnometry. Elucidated in the work are the limitations encountered with tablets and RC’s, data interpretation of industrial considerations. Experimental chapter 3 diverges from RI to differentiate thickness in-order to assess the FD transmission for non-destructive mechanical assessment. This demonstrates a clear relationship between compaction force and the surrogate value for density, following a linear trend below a certain threshold of force. The ‘threshold’ value is observed for less massive tablets, and concluded is that the mechanistic interplay and permanent (plastic) consolidation is greater in instances where compaction-force increases proportionally with target-fill weights, and thus the various behaviour of MCC to stress.