It is the goal of this body of work to research an assortment of different photoacid generators (PAGs) and quantify their ability to perform the decomposition of poly(propylene carbonate) (PPC). Adding PAGs to PPC allows for a decreased polymer decomposition temperature, which can in turn be used as a sacrificial polymer for the fabrication of various microelectromechanical and microfluidic devices. A focus will be placed on relating the properties of the PAG such as acid strength, acid volatility, and PAG activation to processing issues like percentage of total film decomposition, amount and composition of film residue, decomposition rate, decomposition temperature, and environmental dependencies. This research discovered that the use of superacid triflic and nonaflic based PAGs were not adequate for the decomposition of PPC due to the high vapor pressure of the acid. Furthermore, the non-fluorinated sulfonic acid based PAGs do not posses the super-acid level acidity needed to sufficiently decompose PPC. Conversely, a perfluorinated methide and a tetrakis(pentafluoropheyl)borate based PAG both demonstrated the capability for high level PPC decomposition. Building on the knowledge gained through experimentation with these individual PAGs, the creation of a novel Combination PAG was accomplished. The Combination PAG uses acid groups with different physical properties collectively working to achieve what neither could complete individually.

Improvements for Chip-Chip Interconnects and MEMS Packaging Through Materials and Processing Research Erdal Uzunlar 129 Pages Directed by Dr. Paul A. Kohl The work presented in this dissertation focuses on improvements for ever-evolving modern microelectronic technology. Specifically, three topics were investigated in this work: electroless copper deposition on printed wiring boards (PWBs), polymer-based air-gap microelectromechanical systems (MEMS) packaging technology, and thermal stability enhancement in sacrificial polymers, such as poly(propylene carbonate) (PPC). In the electroless copper deposition study, Ag-based catalysts were identified as a low-cost and equally active alternative to expensive Pd-based catalysts. Hot H2SO4 treatment of PWBs was found as a non-roughening surface treatment method to minimize electrical losses. In MEMS packaging study, a sacrificial polymer-based air-gap packaging technique was improved in terms of identification and simplification of air-gap formation process options, optimization of thermal treatment steps, assessing air-gap formation performance, and analyzing the chemical composition of residue. It was found that non-photosensitive PPC leaves less residue, and creates more reliable air-gaps. The mechanical strength of air-gaps was found to come from residual stress in benzocyclobutene (BCB) caps. In thermal stability of PPC study, the mechanism of thermal stability increase on copper (Cu) surfaces was found as the complex formation between Cu(I) and iodonium of the photoacid generator (PAG), leading to hindrance of acid formation by PAG and restriction of acid-catalyzed decomposition of PPC.

The ultimate goal of this research was to gain a more fundamental understanding of the effects of “active"? alloying elements on the performance of low voltage, aluminum, sacrificial anodes. We have developed an overview of elemental trends and a comparison with literature, in support of a larger program on predicting anode behavior. The broader impact of this work was to enhance the ability to control corrosion and reduce the likelihood of hydrogen embrittlement induced by cathodic protection on ships and marine structures. As compared to high voltage anodes, low voltage, aluminum, sacrificial anodes reduce the likelihood of causing hydrogen embrittlement or stress corrosion cracking when used to protect high strength steels. In this study, open circuit potential, potentiostatic, galvanostatic and Tafel tests were performed on eleven high-purity aluminum-based binary and ternary alloys containing Bi, Ga, In and Zn in an effort to understand the individual effects of each element and the interactions between these elements. The microstructures of the as-cast alloys and the corrosion surfaces after testing were characterized using electron microscopy. Current capacities and current capacity efficiencies were calculated from potentiostatic and galvanostatic data. Galvanic coupling data from Druschitz et al was plotted with average values from potentiostatic and galvanostatic tests on Tafel curves for all alloys. [1] Variance of weight loss, average galvanostatic current, and average potentiostatic potential of the Al-0.57 wt% Zn-0.55 wt% Bi alloy was evaluated. Indium and gallium had the most significant effect on corrosion behavior (per wt% added), followed by zinc and bismuth. Bismuth had only a small effect on the weight loss, galvanostatic current and potentiostatic potential. However during potentiostatic testing Al-Bi alloys showed a steady increase in current with time, indicating that larger effects may be seen at longer periods of time. In Al-Zn alloys preferential dissolution of the zinc-rich interdendritic regions was observed. The Al-5.3 wt% Zn alloy showed high current values, but also exhibited high weight loss and more adherent corrosion products. Interdendritic corrosion also occurred with the Al-5.3 Zn-0.011 In alloy. Also, non-uniform dissolution of the remaining primary aluminum dendrites by the formation of small holes was observed, possibly due to indium precipitates. Grain boundary attack and severe intra-granular pitting was observed in Al-In alloys. Small holes were also evident on the surface of pits, similar to those seen on dendrites with the Al-5.3 Zn-0.011 In alloy. The addition of Indium greatly shifted voltages to more negative values (-0.802 to -0.858 VSCE at 9 A/m²) and significantly increased the observed currents (42-83 A/m² at -0.730 VSCE). High potentiostatic current capacities were exhibited by Al-In alloys, Al-0.1 wt% Ga, Al-5.3 wt% Zn-0.011 wt% In, and Al-0.57 wt% Zn-0.55 wt% Bi. However some calculated current capacity values were actually above the theoretical values, possibly due to corrosion products affecting the weight loss measurements. / Master of Science

Demands for using electrical resistivity techniques (surface and bulk resistivity) as an alternative to the rapid chloride penetrability test (RCPT) have been growing, for example by a number of transportation agencies in North America, to give an indication of the relative penetrability of concrete. While resistivity measurements may reflect the quality of pore structure in the cementitious matrix, their accuracy might be affected by a multitude of parameters including the concentration of ionic species in the pore solution, particularly when supplementary cementitious materials (SCMs) are incorporated in the binder. Hence, a systematic investigation on the resistivity of concrete and its corresponding physical penetrability is warranted. Zinc sacrificial anodes are considered an effective and economical method to prevent the electrochemical corrosion of steel bars by providing cathodic current to bars, which can provide corrosion protection at low galvanic current densities in the range of 0.2 to 2 mA/m2. Sacrificial anodes are commonly used in RC structures particularly in bridge decks to mitigate a critical phenomenon that occurs in the original concrete beside the repaired patches, which is known as the ‘halo effect’. One of the key factors affecting the efficacy of zinc anodes is the resistivity of concrete or cementitious repair material in which these anodes are embedded. There is a general notion that the higher the electrical resistivity of concrete or repair material, the less likely that zinc anodes produce the target galvanic current for optimum protection of steel bars. However, no systematic data are available on the maximum allowable electrical resistivity of repair materials/concretes beyond which zinc anodes cannot properly function to prevent corrosion. In the first part of this thesis, a tripartite relationship (nomogram) to correlate surface resistivity with penetrability (migration coefficient) and porosity of concrete using a wide range ii of concrete mixtures, taking into account the effect of key mixture design parameters (water-to-binder ratio, air-entrainment, SCMs and type of cement) was established. Relationships between surface and bulk resistivity as well as migration coefficient and porosity of concrete were also introduced. In addition, a penetrability classification of concrete based on the corresponding ranges of surface resistivity, migration coefficient and porosity has been proposed. The nomogram and penetrability classification provided reasonable assessment for the condition of field cores extracted from newly constructed and aging concrete pavement. In the second part of this thesis, the functionality of zinc anodes at mitigating patch accelerated corrosion (halo effect) in repaired concrete was explored. Concrete slabs were cast to simulate the patch repair configuration in the field, and the main parameters in this study were changing the resistivity of the repair section in the slabs (5,000, 15,000, 25,000, 50,000 and 100,000 Ω-cm), and anode spacing (25, 100, and 250 mm) inside the repair patch. Analysis of current and potential data shows a high level of effectiveness of the anodes at controlling corrosion in this slab configuration up to 52 weeks under a wetting-drying exposure. / February 2017

Sámi sacrificial sites were a central part of the Sámi pre-Christian belief. The Sámi saw the world from a holistic point of view where nature, humans and spirits were all connected. The interest for sacrificial sites have a long history and both older research and some more recent studies are available with new analysis methods. There are still unresolved questions regarding sacrificial sites such as those concerning how long the sacrificial sites have been used and what kind of continuity can be seen in the sacrificial practises. The aim of this paper is to analyse purpose, timespan and continuity of the sacrificial sites by combining a study of archaeological and historic material. The study concerns sacrificial sites that were separated from the living area and analyses the material from the two sacrificial sites, Unna Saiva and Viddjavárri. The study shows that the main purpose of the sacrifice was to gain wellbeing and good fortune in your everyday life as well as to maintain a good relationship with the nature and sprits. The overall timespan of the sacrificial practice was from the 6th and 8thcentury to 19thand 20thcentury with some traces to older and more recent dates. The continuity in the sacrificial practises can mainly be seen through the continuous purpose of the sacrifice and the continuity in selecting what parts of the animal to sacrifice.

To date, the reconstructive approach addressing chronic non-healing wounds, deep tissue damage, and severe wound defects relies upon avascular dermal grafts and autologous flap techniques. Such flaps are limited by donor site availability and morbidity, while current dermal grafts rely upon host cellular invasion for neovascularization and incorporation. These products fail to include an inherent vascular network and the supporting cells necessary to ensure adequate incorporation and graft survival beyond the most optimal wound beds. Herein, we fabricate a pre-vascularized full-thickness cellularized skin equivalent containing a three-dimensional vascularized network of interconnected macro and microchannels lined with vascular cells, within a collagen neodermis populated with fibroblasts, and an epidermis comprised of human keratinocytes capable of providing whole tissue perfusion. Previously, our lab has employed a sacrificial microfiber technique to develop tissue-engineered scaffolds with an inherent hierarchical network of microvessels, which recapitulates the organization of an arteriole, venule, and capillary bed. Utilizing a type-I collagen hydrogel matrix, vascular cells were seeded within pre-fabricated channels and allowed to proliferate to generate an endothelialized microvasculature. These collagen scaffolds were subsequently anastomosed into rat models to demonstrate the clinical feasibility of such approach. The present study aims to more closely recapitulate the in vivo structure of human skin via the incorporation of vital epidermal and dermal components of native skin into a biocompatible construct containing a complex hierarchical vasculature, which may be anastomosed using standard microsurgical techniques and immediately perfused. Pluronic F127 was used as the sacrificial material: 1.5 mm diameter “U” shaped macrofibers and 100-500 µm-interwoven microfibers were heat extruded and then embedded within type-I collagen into which Cyan Fluorescent Protein (CFP)-tagged human placental pericytes and human foreskin fibroblasts (HFF1) had been encapsulated. Following pluronic sacrifice, resultant channels were intraluminally seeded with Red Fluorescent Protein (RFP)-tagged human aortic smooth muscle cells, Green Fluorescent Protein (GFP)-tagged human umbilical vein endothelial cells, and topically seeded with human epidermal keratinocytes (HEK). Construct microstructure was analyzed using multiphoton microscopy (MPM) after 7, 14 and 28 days of culture. Additionally, after 14 and 28 days of culture, endothelial cells were extracted from the construct using collagenase digestion and Real Time (RT)-qPCR performed to analyze expression of markers of angiogenesis and maturation of the vascular network. MPM demonstrated a hierarchical vascular network containing macro and microvessels lined by endothelial and smooth muscle cells, supported by perivascular pericytes, all in appropriate microanatomic arrangement. Neodermal HFF1 proliferated throughout the observation period and the HEK neoepidermis developed into a stratified epidermis along the superior aspect of the construct. Angiogenic sprouting from the nascent vascular network into neovessel like structures was noted. RT- qPCR revealed relative expression of Jagged1, Dll4, Ve-Cadherin, and CD31. We have successfully fabricated a novel tissue-engineered pre-vascularized full thickness skin flap, which recapitulates the inherent hierarchical vasculature found within human skin and is suitable for in vivo perfusion. We provide the platform for an on- demand, geometrically tunable tissue engineered skin equivalent with an anastomosable vascular network. This tissue-engineered skin flap holds the potential to transform reconstructive surgical practice by eliminating the consequences of donor site morbidity, and enabling rationally designed, patient-specific flaps for each unique wound environment and anatomic location. / 2017-06-16T00:00:00Z

Recently, there are great demands for RF band pass filters with smaller size/volume, lighter weight, and higher performance for advanced mobile/wireless communication system. However, fabricated RF filters using traditional lumped element, dielectric resonators, or surface acoustic wave¡]SAW¡^filters have difficulties in on-chip integration, power handling capability, and temperature compensation. Alternatively, thin-film bulk acoustic wave resonator¡]FBAR¡^filters are very suitable devices for MMIC¡¦s since they can be fabricated on Si or GaAs substrates at a lower magnitude than lumped elements or dielectric resonators, plus they have a much lower insertion loss and higher power handling capabilities than surface acoustic wave devices and full integration with other CMOS RF IC circuitry for realizing a goal of system on chip¡]SOC¡^. In their simplest form, practical FBARs consist of a sputtered piezoelectric thin film sandwiched between top and bottom electrodes onto which an electric field is then applied. An FBAR must have two acoustically reflecting surfaces in order to trap energy and produce resonating characteristics. For this purpose, the thin film bulk acoustic resonator has to be isolated acoustically from the substrate. In view of this, in order to obtain a high Q factor and reduce spurious responses, this paper proposed the air gap type resonator using the sacrificial layer etching. The thickness of the AlN thin film used for piezoelectric thin film of Air-gap FBAR is 1um. Pt/Ti with 3000Å/300Å thickness is used as the top and bottom electrode. The device has a resonance frequency of 1.2GHz, and S11-paparameter of -25dB is also obtained.

Step and Flash Imprint Lithography (S-FIL) is a high resolution, next-generation lithography technique that uses an ambient temperature and low pressure process to replicate high resolution images in a UV-curable liquid material. Application of the S-FIL process in conjunction with multi-level imprint templates and new imprint materials enables one S-FIL step to reproduce the same structures that require two photolithography steps, thereby greatly reducing the number of patterning steps required for the copper, dual damascene process used to fabricate interconnect wirings in modern integrated circuits. Two approaches were explored for the implementation of S-FIL in the dual damascene process: sacrificial imprint materials and imprintable dielectric materials. Sacrificial imprint materials function as a pattern recording medium during S-FIL and a three-dimensional etch mask during the dielectric substrate etch, enabling the simultaneous patterning of both the via and metal structures in the dielectric substrate. Development of sacrificial imprint materials and the associated imprint and etch processes are described. Application of S-FIL and the sacrificial imprint material in a commercial copper dual damascene process successfully produced functional copper interconnect structures, demonstrating the feasibility of integrating multi-level S-FIL in the copper dual damascene process. Imprintable dielectric materials are designed to combine the multi-level patterning capability of S-FIL with novel dielectric precursor materials, enabling the simultaneous deposition and patterning of the interlayer dielectric material. Several candidate imprintable dielectric materials were evaluated: sol-gel, polyhedral oligomeric silsesquioxane (POSS) epoxide, POSS acrylate, POSS azide, and POSS thiol. POSS thiol shows the most promise as functional imprintable dielectric material, although additional work in the POSS thiol formulation and viscous dispense process are needed to produce functional interconnect structures. Integration of S-FIL with imprintable dielectric materials would enable further streamlining of the dual damascene fabrication process. The fabrication of electronic devices on flexible substrates represents an opportunity for the development of macroelectronics such as flexible displays and large area devices. Traditional optical lithography encounters alignment and overlay limitations when applied on flexible substrates. A thermally activated, dual-tone photoresist system and its associated etch process were developed to enable the simultaneous patterning of two device layers on a flexible substrate. / text

Afin de limiter les conséquences d’un hypothétique accident grave avec la fusion du coeur dans un réacteur à neutrons rapides de génération IV refroidi au sodium, la recriticité doit être évitée au sein du mélange de combustible oxyde et de structures fondus, appelé corium. Pour cela, des matériaux absorbants, tels que le carbure de bore B4C, seront utilisés dans ou près du coeur, et des matériaux diluants dans le récupérateur de corium. L’objectif de ce travail est de présélectionner des matériaux parmi ces deux types de familles et de comprendre leur comportement au contact avec le corium. Concernant le B4C, des calculs thermodynamiques et des expériences ont permis de conclure à la formation de deux phases immiscibles dans le système UO2 – B4C à haute température, une oxyde et une borure, ainsi qu’à la volatilisation d’une partie de l’élément absorbant bore. Cette séparation de phases pourra réduire l’efficacité de l’absorption neutronique au sein de la phase oxyde. Une solution à ce comportement serait d’augmenter la quantité de B4C ou d’utiliser un absorbant oxyde miscible avec le combustible. Eu2O3 ou HfO2 pourraient convenir car il a été montré qu’ils forment une solution solide avec UO2. Concernant le matériau diluant, les oxydes mixtes Al2O3 – HfO2 et Al2O3 – Eu2O3 ont été étudiés. L’interaction de ces systèmes avec UO2 étant inconnue à ce jour, les premiers points ont été recherchés sur les diagrammes ternaires correspondants. Contrairement au système Al2O3 – Eu2O3 – UO2, le mélange Al2O3 – HfO2 – UO2 présente un seul eutectique et donc un seul chemin de solidification ce qui permet de prévoir plus facilement la manière dont le corium solidifierait dans le récupérateur. / In order to limit the consequences of a hypothetical core meltdown accident in Generation IV Sodium Fast Reactors, absorber materials in or near the core, such as boron carbide B4C, and diluting materials in thecore catcher will be used to prevent recriticality within the mixture of molten oxide fuel and molten structures called corium. The aim of the PhD thesis was to select materials of both types and to understand their behaviour during their interaction with corium, from chemical and thermodynamic point of view. Concerning B4C, thermodynamic calculations and experiments agree with the formation of two immiscible phases at high temperature in the B4C – UO2 system: one oxide and one boride. This separation of phases can reduce the efficiency of the neutrons absorption inside the molten fuel contained in the oxide phase. Moreover, a volatilization of a part of the boron element can occur. According to these results, the necessary quantity of B4C to be introduced should be reconsidered for postulated severe accident sequence. Other solution could be the use of Eu2O3 or HfO2 as absorber material. These oxides form a solid solution with the oxide fuel. Concerning the diluting materials, mixed oxides Al2O3 – HfO2 and Al2O3 – Eu2O3 were preselected. These systems being completely unknown to date at high temperature in association with UO2, first points on the corresponding ternary phase diagrams were researched. Contrary to Al2O3 – Eu2O3 – UO2 system, the Al2O3 – HfO2 – UO2 mixture presents only one eutectic and thus only one solidification path which makes easier forecasting the behaviour of corium in the core catcher.

The scope of this study is to establish extensive material tests to determine the mechanical properties of cellular concrete and evaluate its potential as energy absorption material against air blast load. This study includes a literature review of existing studies on cellular concrete, proportioning, and its mechanical properties, together with studies on the properties and application of other foams such as aluminium and polymer foams. It is concluded that, unlike other foam materials, there is a lack of systematic studies on the mechanical properties of cellular concrete especially for densities less than 1000 kg/m3. The survey also reviewed the existence of materials being used as a sacrificial layer against air blast load, together with the analytical models proposed to determine the parameters required to design a cladding system. As a result it was found that cellular concrete can maintain most of the properties of the cladding materials and can be applied as a new sacrificial layer against the blast load. Extensive material tests are carried out to characterise the effect of ingredients and density on material properties of cellular concrete. Based on the experimental results, an empirical model is proposed which determines the plateau and densification regime of nominal stress-strain curve of the cellular concrete with different densities. The penetration resistance of cellular concrete with different densities under truncated, conical, flat and hemi-spherical solid indenters are studied experimental. By determining the deformation mechanism of cellular concrete under indentation with application of an X-Ray tomography image system, an analytical model is proposed to determine the resistance of cellular concrete under penetration of flat indenter. Experimental closed range blast tests are performed with 1kg and 3kg C4 explosive to determine the mitigation potential of cellular concrete against air blast load. Numerical modelling of the experimental blast test is carried out using Ansys LS-DYNA to evaluate the feasibility of the numerical modelling techniques to predict the response of cellular concrete against air blast load.