No description available.

In engineering, materials are often assumed to be homogeneous and isotropic; in actuality, material properties do change with sample direction and location. This variation is due to the anisotropy of the individual grains and their spatial distribution in the material. Currently there is a lack of communication between the design engineer, material scientist, and processor for solving multi-objective/constrained designs. If communication existed between these groups then materials could be designed for applications, instead of the reverse. Microstructure sensitive design introduces a common language, a spectral representation, where both design properties and microstructures are expressed. Using Hill bounds, effective elastic properties are expressed within the spectral representation. For the elastic properties, two FCC materials, copper and nickel, were chosen for computation and to demonstrate how symmetry enters into the methodology. This spectral representation renders properties as hyper-surfaces that translate through a multi-dimensional Fourier space depending on the property value of the hyper-surface. Property closures are generated by condensing the information contained within the multi-dimensional Fourier space into a 2-D representation. This compaction of information is beneficial for a quick determination of property limits for a particular alloy system. The design engineer can now dictate the critical design properties and receive sets of microstructures that satisfy the design objectives.

Texture evolution is a vital component of many computational tools that link structure, properties and processes of polycrystalline materials. By definition, this evolution process involves the manipulation, via rotation, of points in orientation space. The computational requirements of the current methods being used to rotate crystalline orientations are a significant limiting factor in the drive to merge the texture information of materials into the engineering design process. The goal of this research is to find and implement a practical rotation algorithm that can significantly decrease the computation time required to rotate macroscopic and microscopic crystallographic textures. Three possible algorithms are considered in an effort to improve the computational efficiency and speed of the rotation process. The first method, which will be referred to as the Gel'fand method, is based on a paper, [1], that suggests a practical application of some of Gel'fand's theories for rotations [2]. The second method, which will be known as the streamline method, is a variation on the Gel'fand method. The third method will be known as the principal orientation method. In this method, orientations in Fourier space are written as linear combinations of points on the convex surface of the microstructure hull to reduce the number of points that must be rotated during each step in the texture evolution process. This thesis will discuss each of these methods, their strengths and weaknesses, and the accuracy of the computational results obtained from their implementation.

This thesis has as its principal goal the development of sustainable pressure-sensitive adhesives (PSAs). To that end, we examined polymer reaction engineering practices and polymer formulations through the lens of the 12 Principles of Green Chemistry. To begin with, we employed emulsion polymerization as our polymer synthesis method because of its use of water instead of hazardous solvents. We also replaced various petroleum-based components with bio-based alternatives (e.g., starch, cellulose nanocrystals), thereby reducing synthesis hazards, increasing product safety and increasing the amount of sustainably sourced raw materials in the PSA. However, changing the synthetic method as well as key components in the formulation presented significant challenges to maintaining PSA performance. This thesis illustrates the challenging path taken towards developing a fully renewable PSA. PSAs should display a specific balance of adhesion and cohesion. Typically, petroleum-based additives (which are often hazardous/toxic) such as tackifiers, cross-linkers, chain transfer agents and rheology modifiers are added to tailor latex properties to fit the intended application. However, because of their inherently opposing effects, an additive used to increase adhesion will weaken the cohesive forces of the polymer, and vice versa. Cellulose nanocrystals (CNCs) are sustainable nanomaterials that have been shown to be effective to resolve the adhesion/cohesion conundrum. In the first part of this project, we developed a new technique to increase CNC loading in emulsion-based PSA formulations beyond the 1-2% limits previously encountered due to high latex viscosity, colloidal instability, and poor film properties. The higher CNC loadings were shown to continuously improve shear strength but resulted in eventual decreases to tack and peel strength. In the second part of this project, we replaced the sulfated CNCs with carboxylated CNCs (cCNCs), which are produced by a process using a “greener” catalyst (i.e., hydrogen peroxide instead of sulfuric acid). The cCNCs’ carboxylate surface groups interacted strongly with the polymer matrix, ultimately leading to catastrophic coagulation. The interactions between cCNCs and other standard latex components were studied and through the creative manipulation of the emulsion polymerization process, a reproducible method to incorporate the cCNCs in a seeded semi-batch reaction yielded stable, high-quality latexes. In the third part of this project, the effect of the cCNCs on the adhesive properties of the nanocomposite latex films was studied and compared to the effects of the sulfated CNCs. AFM imaging revealed that cCNCs interact with latex particles and each other; thus, omitting ultrasonication at the preparation stage was shown to preserve these interactions and lead to greater property enhancements. In the fourth part of this project, starch nanoparticles (SNPs) were used to displace some of the petroleum-based monomer in the production of core-shell (SNP cores, acrylic shell) latexes. SNPs are renewably sourced, inexpensive, and biodegradable. The challenge of locating the SNPs into the particle cores was overcome by crosslinking the SNPs using a food grade cross-linker (sodium trimetaphosphate) and functionalizing them using a sugar-based monomer (EcoMer™). To tune the PSA properties to rival a range of commercial tapes, a method to incorporate CNCs to the SNP-latexes in situ was developed. In addition, because monomers such as 2-octyl acrylate (2OA), styrene, and acrylic acid can be bio-sourced, they were selected as the acrylic shell monomers to encapsulate the SNPs in the nanocomposite latexes. Due to supply chain challenges, n-octyl acrylate was used as a model monomer for 2OA to produce latexes with ~80% bio-content that rivaled commercial Post-It™ notes, masking tapes, and duct tapes. After addressing the sustainability of the polymerization method and polymer components, we posed the question: what are the effects of using renewably sourced and bio-sourced materials on the end-of-life of the PSAs? Because the infrastructure for biodegradation studies at the lab scale via composting does not exist in Canada (to our knowledge), we designed an in-house aerobic composting set-up consisting of a series of bioreactors and sensors capable of measuring the aerobic biodegradability of our polymers in a simulated composting environment. Although not fully tested, the composting setup was designed, and its construction was begun. Steps to complete the construction and validate its operation are detailed. The path towards sustainability is often long and complex. In this four-year study, the re-design of an adhesive synthesis process using a more sustainable approach, emulsion polymerization, along with an 80% bio-sourced formulation required significant corrective measures. Overcoming the technical challenges required mustering all the polymer reaction engineering tools at our disposal. Despite the time and effort required, achieving a more sustainable process is indeed within our grasp.

In our fast-paced, hectic time, which is stamped by an ever-increasing degree of nervousness, unrest, and unsteadiness it has become customary for mankind to relax for a shorter or longer period of time from the habits of everyday life and recreation. To search for strength somewhere on earth that is away from the place of business, that invites you to rest from everyday worries and toils. So lures the Black Forest. With these words, the Sommerberg-Hotel was advertised already over 100 years ago. Nowadays stress has become a fashionable term in our modern and digital world. For many, it is almost a status symbol - because those who are stressed have a lot on their plate and are therefore important. This attitude is leading to increasing health issues and to a society that is not able to breathe anymore because they have to be in working order. After decades of being empty and unused, the Sommerberg-Hotel occupies a unique location on top of the mountain in the Black Forest. Following its rich past and responding to society's needs it becomes once more a refuge to escape the rush. In close dialogue with the existing, this project investigates a possible transformation and a repurposing of the old structures of the Sommerberg-Hotel. Making it to The Mental Wellbeing Place.

This thesis aims to improve the performance of latex-based pressure-sensitive adhesives (PSAs). PSA performance is usually evaluated by tack, peel strength and shear strength. Tack and peel strength characterize a PSA’s bonding strength to a substrate while shear strength reflects a PSA’s capability to resist shear deformation. In general, increasing shear strength leads to a decrease in tack and peel strength. While there are several commercial PSA synthesis methods, the two most important methods consist of either solvent-based or latex-based techniques. While latex-based PSAs are more environmentally compliant than solvent-based PSAs, they tend to have much lower shear strength, at similar tack and peel strength levels. Therefore, the goal in this thesis was to greatly improve the shear strength of latex-based PSAs at little to no sacrifice to tack and peel strength. In this study, controlling the polymer microstructure of latexes or their corresponding PSA films was used as the main method for improving the PSA performance. The research was sub-divided into four parts. First, the influence of chain transfer agent (CTA) and cross-linker on latex polymer microstructure was studied via seeded semi-batch emulsion polymerization of butyl acrylate (BA) and methyl methacrylate (MMA). Three techniques were used to produce the latexes: (1) adding CTA only, (2) adding cross-linker only, and (3) adding both CTA and cross-linker. It was found that using CTA and cross-linker simultaneously allows one to expand the range of latex microstructural possibilities. For example, latexes with similar gel contents but different Mc (molecular weight between cross-links) and Mw (molecular weight of sol polymers) could be produced if CTA and cross-linker concentration are both increased. However, for the corresponding PSAs with similar gel contents, the relationship between their polymer microstructure and performance was difficult to establish as almost all of the medium and high gel content PSAs showed very low tack and peel strength as well as extremely large shear strength readings. In the second part of this thesis, in order to improve the tack and peel strength of medium and high gel content PSAs, the monomer composition and emulsifier concentration were varied. It was found that changing the monomer mixture from BA/MMA to BA/acrylic acid (AA)/2-hydroxyethyl methacrylate (HEMA) while simultaneously decreasing emulsifier concentration dramatically improved the corresponding PSAs’ shear strength as well as tack and peel strength. The addition of polar groups to the PSA increased its cohesive strength due to the presence of strong hydrogen bonding; meanwhile, PSA films’ surface tension increased. In the third part, two series of BA/AA/HEMA latexes were generated by varying the amounts of CTA either in the absence or presence of cross-linker. The latexes produced in the absence of cross-linker exhibited significantly larger Mc and Mw compared to their counterparts with similar gel contents prepared with cross-linker. The PSAs with the larger Mc and Mw showed much larger shear strengths due to improved entanglements between the polymer chains. In the final part of the thesis, the performance of the BA/AA/HEMA PSAs was further improved by post-heating. Compared with original latex-based PSAs with similar gel contents, heat-treated PSAs showed not only significantly improved shear strengths, but also much larger tack and peel strengths. The different shear strengths were related to the PSAs’ gel structures, which were discrete in the original PSAs but continuous in the heat-treated PSAs. The improved tack and peel strengths were related to the PSA films’ surface smoothness. During the post-heating process, the PSA polymer flowed, resulting in much smoother surfaces than the original PSA films. In addition, the effect of post-heating was related to the polymer microstructure of the untreated PSAs. Decreasing the amount of very small or very big polymers or simultaneously increasing Mc and Mw could lead to post-treated PSAs with significantly better performance. Moreover, it was found that by optimizing the polymer microstructure of the original latex-based PSAs, it was possible to obtain a treated PSA with similar or even better performance than a solvent-based PSA with similar polymer microstructure. Our original objective was surpassed: in two cases, not only was shear strength greatly improved, but so were tack and peel strength due to the simultaneous modification of PSA bulk and surface properties.

Social network sites (SNS) were developed during the 90’s and got popularized in the mid 2010’s. SNSs are social platforms, where users can create a profile, add a network of contacts and communicate online. The LGBTQ+ community relies heavily on SNSs for information, exploration of identity, social support and community, but due to their marginalized status, they are more prone to victimization online. Whereas anonymity can protect users from bodily harm, it can’t protect against harassment and hatred, which is why it’s important to emphasize on user-centered design for marginalized communities within HCI. The objective with this study is to define design suggestions for future SNSs, based on the values of LGBTQ+ users. Two focus groups recruited from the local LGBTQ+ community in Berlin, consisting of seven participants in total, gathered in person. The focus groups discussed open ended questions around the topics of: safety, anonymity, accountability, social support and community online, seen from a queer perspective. The results of this study had correlations with prior research within HCI research and paints a picture of the differences between the “digital well- being” norm and the severity of the threats affecting the digital wellbeing of marginalized users. In conclusion, HCI and digital well-being research needs to be elaborated on, in regards to marginalized communities and their benefits and challenges of SNSs use and how that could be incorporated in a value sensitive design approach for future development.

No description available.

Multifunctional drug delivery systems incorporated with stimuli-sensitive drug release, magnetic nanoparticles and magnetic resonance (MR) T2 contrast agents is attracting increasing attention recently. In this thesis, works on polymer nanospheres response to temperature change, superparamagnetic iron oxide nanoparticles (SPION)/polymeric composite materials for MR imaging contrast agents are summarized. A “shell-in-shell” polymeric structure has been constructed through a “modified double-emulsion method”. Thermosensitive inner shell is comprised of poly(N-isopropylacrylamide) which undergoes phase transition at body temperature. Such a feature could facilitate drug release at an elevated temperature upon administration. Furthermore, the dual-shell structure is covered by a layer of gold nanoparticles. According to the cytotoxicity tests, the biocompatibility is shown to be enhanced due to the layer of gold. SPION have been prepared using a high temperature decomposition method. Particle growth of SPION is monitored by transmission electron microscope and synchrotron X-ray diffraction. Poly(L,L-lactide)@SPION (PLLA@SPION) composite particles have been prepared through surface-initiated ring-opening polymerization which has been developed in our lab. For biomedical applications, it is essential to transfer the particles to physiological solutions from organic solutions. Phase transfer of SPION has been carried out by utilizing small molecules. Stability at the neutral pH is of large concern for such transfer systems. A novel phase transfer agent, Pluronic F127 (PF127), a triblock copolymer has been applied and the stability of the aqueous PF127@oleic acid (OA)@SPION solution has been greatly enhanced over a broad pH range. Most interestingly, PF127@OA@SPION show remarkable efficacy as T2 contrast agents as indicated by relaxometric measurements compared with commercially available products. / QC 20101115

A positive physician-patient relationship is crucial for high quality and effective health care. Yet, cultural and language differences between providers and patients often challenge the establishment of effective physician-patient relationships. These challenges are especially evident in provider-refugee-patient interactions in which patients have experienced loss, torture, and trauma. Understanding of what constitutes a positive doctor-patient relationship is fundamental to diagnosis and treatment and is crucial for the delivery of quality care for diverse patient populations, including refugees. This qualitative, phenomenological case-study focuses on physician-reported experiences caring for refugees in order to identify what experiential factors contribute to effective therapeutic relationships.