Self-sealing of thermal fatigue and mechanical damage in fiber-reinforced composite materials

Fiber reinforced composite tanks provide a promising method of storage for liquid oxygen and hydrogen for aerospace applications. The inherent thermal fatigue of these vessels leads to the formation of microcracks, which allow gas phase leakage across the tank walls. In this dissertation, self-healing functionality is imparted to a structural composite to effectively seal microcracks induced by both mechanical and thermal loading cycles. Two different microencapsulated healing chemistries are investigated in woven glass fiber/epoxy and uni-weave carbon fiber/epoxy composites. Self-healing of mechanically induced damage was first studied in a room temperature cured plain weave E-glass/epoxy composite with encapsulated dicyclopentadiene (DCPD) monomer and wax protected Grubbs' catalyst healing components. A controlled amount of microcracking was introduced through cyclic indentation of opposing surfaces of the composite. The resulting damage zone was proportional to the indentation load. Healing was assessed through the use of a pressure cell apparatus to detect nitrogen flow through the thickness direction of the damaged composite. Successful healing resulted in a perfect seal, with no measurable gas flow. The effect of DCPD microcapsule size (51 um and 18 um) and concentration (0 - 12.2 wt%) on the self-sealing ability was investigated. Composite specimens with 6.5 wt% 51 um capsules sealed 67% of the time, compared to 13% for the control panels without healing components. A thermally stable, dual microcapsule healing chemistry comprised of silanol terminated poly(dimethyl siloxane) plus a crosslinking agent and a tin catalyst was employed to allow higher composite processing temperatures. The microcapsules were incorporated into a satin weave E-glass fiber/epoxy composite processed at 120C to yield a glass transition temperature of 127C. Self-sealing ability after mechanical damage was assessed for different microcapsule sizes (25 um and 42 um) and concentrations (0 - 11 vol%). Incorporating 9 vol% 42 um capsules or 11 vol% 25 um capsules into the composite matrix leads to 100% of the samples sealing. The effect of microcapsule concentration on the short beam strength, storage modulus, and glass transition temperature of the composite specimens was also investigated. The thermally stable tin catalyzed poly(dimethyl siloxane) healing chemistry was then integrated into a [0/90]s uniweave carbon fiber/epoxy composite. Thermal cycling (-196C to 35C) of these specimens lead to the formation of microcracks, over time, formed a percolating crack network from one side of the composite to the other, resulting in a gas permeable specimen. Crack damage accumulation and sample permeability was monitored with number of cycles for both self-healing and traditional non-healing composites. Crack accumulation occurred at a similar rate for all sample types tested. A 63% increase in lifetime extension was achieved for the self-healing specimens over traditional non-healing composites.

Reclaiming the Fall Zone: Mediating Physical and Cultural Exchange in Richmond, VA

This thesis will address cultural and physical place reclamation, at the ambiguous intersection of ‘city’ and nature.’ By creating a juxtaposed sequence of multi-scalar interventions, which challenge the conventional boundaries of architecture, and landscape architecture; in order to make commonplace a new dynamic threshold condition in Richmond, Virginia. At its core, this thesis is an attempt at place-making on a site which has become ‘no place.’ This concept will be manifest via a landscape park on Mayo Island in Richmond, anchored by a community retreat center, and architectural follies along a constructed path. The interventions will coincide with value of place in historical Richmond: an integrated, socially desegregated waterfront hinge; a social nexus of inherent change, at the point which the river itself changes at the fall line.

Modeling the impact of social discrimination on the physical and mental health of portuguese gay, lesbian and bisexual people

Background: Despite growing acceptance of same-sex sexuality in Portugal, identity development of lesbian, gay and bisexual (LGB) individuals is still restricted by negative societal attitudes, which maintain the experience of stigmatization and discrimination. The purpose of this study is to document the frequency of discriminatory events experienced by sexual minorities and their association with indicators of physical and mental health in Portugal. Methods: A total of 610 LGB participants completed an online survey (mean age = 34.48, SD = 11.54). Most participants were single and self-identified as gay (73.8%). The survey included five categories of survey items: demographic information, social support, physical health, mental health, and discrimination experiences. Results: Physical and mental health results revealed that bisexual people were more likely to report higher levels of psychological distress than gay men. Overall, between one-fifth and one-fourth of the participants in this sample frequently felt the need to hide their sexual orientation to prevent discrimination experiences across the different settings. Regarding actual discrimination experiences, close to 20% reported having suffered from verbal abuse, followed by close to 10% who suffered from written threats, harassment, and physical threats. A hierarchical multiple regression analysis was performed to assess the effects of anticipated and actual discrimination on mental health. Possible confounding variables were added in the first block – age, sexual orientation, being in a relationship, body mass index, and HIV status. Anticipated and actual discrimination experiences were added in the second block. The first block of the analysis explained 6% of the overall variance, while the second block – discrimination experiences – explained an additional 17%. Conclusion: Portuguese culture and stigma/discrimination create discriminatory experiences which impact LGB people’s health. Unless policies are changed to allow for the acceptance of LGB people, they will continue to experience violence and discrimination as a result of homophobia.

Changes in physical and chemical parameters of the traditional portuguese product água-mel during the production process

Changes in physical and chemical parameters (viscosity, total soluble solids and Hunter color parameters L*, a*, b*, chroma and hue angle) of água-mel were investigated throughout processing. Kinetic parameters for color change of heatprocessed água-mel were monitored. A zero-order kinetic model was applied to changes in L* and b*, while a* and C* were described using a first-order kinetic model. The heating process changed all three color parameters (L*, a*, b*), causing a shift toward the darker colors. Parameters L* decreased, while a*, b*, C* and hue angle (°h) increased during heating. Regarding changes in total soluble solids and in apparent viscosity, both fitted first-order kinetics. A direct relationship was found between the changes in these two parameters. The increase in both total soluble solids and viscosity affected a*, b* and C*. In addition, a flow diagram for the Portuguese água-mel production process has been established.

Hybrid materials based on polyethylene and MCM-41 microparticles functionalized with silanes: catalytic aspects of in situ polymerization, crystalline features and mechanical properties

New nanocomposites based on polyethylene have been prepared by in situ polymerization of ethylene in presence of mesoporous MCM-41. The polymerization reactions were performed using a zirconocene catalyst either under homogenous conditions or supported onto mesoporous MCM-41 particles, which are synthesized and decorated post-synthesis with two silanes before polymerization in order to promote an enhanced interfacial adhesion. The existence of polyethylene chains able to crystallize within the mesoporous channels in the resulting nanocomposites is figured out from the small endothermic process, located at around 80 C, on heating calorimetric experiments, in addition to the main melting endotherm. These results indicate that polyethylene macrochains can grow up during polymerization either outside or inside the MCM-41 channels, these keeping their regular hexagonal arrangements. Mechanical response is observed to be dependent on the content in mesoporous MCM-41 and on the crystalline features of polyethylene. Accordingly, stiffness increases and deformability decreases in the nanocomposites as much as MCM-41 content is enlarged and polyethylene amount within channels is raised. Ultimate mechanical performance improves with MCM-41 incorporation without varying the final processing temperature.

Structural and mechanical properties of La0.6Sr0.4M0.1Fe0.9O3-δ (M: Co, Ni and Cu) perovskites

La0.6Sr0.4M0.1Fe0.9O3-δ (M: Co, Ni and Cu) perovskite nanostructures were synthesized using low frequency ultrasound assisted synthesis technique and effect of substitution of Fe by Co, Ni and Cu on crystal structure and mechanical properties in La0.6Sr0.4FeO3-δ perovskite were studied. The HRTEM and Rietveld refinement analyses revealed the uniform equi-axial shape of the obtained nanostructures with the existence of La0.6Sr0.4M0.1Fe0.9O3−δ with mixed rhombohedral and orthorhombic structures. Substitution of Cu decreases the melting point of La0.6Sr0.4FeO3-δ. The results of mechanical characterizations show that La0.6Sr0.4Co0.1Fe0.9O3−δ and La0.6Sr0.4Ni0.1Fe0.9O3−δ have ferroelastic behavior and comparable elastic moduli, however, subtitution of Ni shows higher hardness and lower fracture toughness than Co in Bsite doping

Effect of rare earth dopants on structural and mechanical properties of nanoceria synthesized by combustion method

Structural characteristics of combustion synthesized, calcined and densified pure and doped nanoceria with tri-valent cations of Er, Y, Gd, Sm and Nd were analyzed by X-ray diffraction (XRD) and high resolution transmission electron microscopy (HRTEM). The results showed that the as-synthesized and calcined nanopowders were mesoporous and calculated lattice parameters were close to theoretical ion-packing model. The effect of dopants on elastic modulus, microhardness and fracture toughness of sintered pure and doped ceria were investigated. It was observed that tri-valent cation dopants increased the hardness of the ceria, whereas the fracture toughness and elastic modulus were decreased.

Estudo da adição de resíduo de scheelita em matriz cerâmica: formulação, propriedades físicas e microestrutura

Extractivism mineral is considered an activity highly degrading, due to the large volume of material that he moves in the form of ore and residues. The vast majority of mining companies do not show any technology or economically viable application that will allow the recycling of mineral residue, these being launched in areas receiving located the "open skies" degrade the environment. In Rio Grande do Norte to the production of ceramic red restricts their activities to the production of products such as: solid bricks, ceramic blocks, tiles, among others. Seeking to unite experiences and technical information that favor sustainable development, with important benefits to the construction sector and civil society in general, the present work studies the incorporation of the residue of scheelite in ceramic matrix kaolinitic, coming from the municipality of Boa Saúde - RN, in percentage of 5 %, 10 %, 20 %, 30% 40% and 50 %, by evaluating its microstructure, physical properties and formulation. The raw materials were characterized through the trials of X ray fluorescence, Diffraction of X rays, Differential Thermal Analysis and Termogravimetric Analysis. The samples were formed and fired at temperatures of 850o, 900o, 1000o, 1050o, 1100o, 1150o and 1200 oC, with isotherm of 1 hour and heating rate of 10 oC/min. Assays were performed technological of loss to fire, Water Absorption, Apparent Porosity, Apparent Density, Mass Loss in Fire and Bending Resistance; in addition to the Scanning Electron Microscopy, analyzing their physical and mechanical properties. The use of residue of scheelite in ceramic mass kaolinitic provided a final product with technological properties that meet the technical standards for the production of bricks and roofing tiles, with the percentage of 20% of waste that showed the best results

Physical and chemical properties of starch and flour from different common bean (Phaseolus vulgaris L.) cultivar.

The physical, chemical and pasting properties of the flour and isolated starches from six different bean cultivars (Phaseolus vulgaris L.) were investigated in order to obtain information for application in new products. The protein and total starch contents of the bean flours ranged from 17.72 to 20.27% and from 39.68 to 43.78%, respectively. The bean starches had low amounts of proteins, lipids and ash and showed an amylose content ranging between 45.32 and 51.11% and absolute density values between 1.55 and 1.78 g.cm?3. The bean starch granules were round to oval with a smooth surface. Results viscoamylographic profiles of the starches and flours showed the possibility of selecting cultivars for specific applications according to these characteristics.

Design, Fabrication, and Mechanical Property Analysis of 3D Nanoarchitected Materials

Recent developments in micro- and nanoscale 3D fabrication techniques have enabled the creation of materials with a controllable nanoarchitecture that can have structural features spanning 5 orders of magnitude from tens of nanometers to millimeters. These fabrication methods in conjunction with nanomaterial processing techniques permit a nearly unbounded design space through which new combinations of nanomaterials and architecture can be realized. In the course of this work, we designed, fabricated, and mechanically analyzed a wide range of nanoarchitected materials in the form of nanolattices made from polymer, composite, and hollow ceramic beams. Using a combination of two-photon lithography and atomic layer deposition, we fabricated samples with periodic and hierarchical architectures spanning densities over 4 orders of magnitude from ρ=0.3-300kg/m³ and with features as small as 5nm. Uniaxial compression and cyclic loading tests performed on different nanolattice topologies revealed a range of novel mechanical properties: the constituent nanoceramics used here have size-enhanced strengths that approach the theoretical limit of materials strength; hollow aluminum oxide (Al₂O₃) nanolattices exhibited ductile-like deformation and recovered nearly completely after compression to 50% strain when their wall thicknesses were reduced below 20nm due to the activation of shell buckling; hierarchical nanolattices exhibited enhanced recoverability and a near linear scaling of strength and stiffness with relative density, with E∝ρ^1.04 and σy∝ρ^1.17 for hollow Al₂O₃ samples; periodic rigid and non-rigid nanolattice topologies were tested and showed a nearly uniform scaling of strength and stiffness with relative density, marking a significant deviation from traditional theories on “bending” and “stretching” dominated cellular solids; and the mechanical behavior across all topologies was highly tunable and was observed to strongly correlate with the slenderness λ and the wall thickness-to-radius ratio t/a of the beams. These results demonstrate the potential of nanoarchitected materials to create new highly tunable mechanical metamaterials with previously unattainable properties.

Equal-channel angular pressing and annealing of a twinning-induced plasticity steel : microstructure, texture, and mechanical properties

In this work, a high-manganese Fe-23Mn-1.5Al-0.3C Twinning-Induced Plasticity (TWIP) steel was subjected to plastic shear deformation using Equal-Channel Angular Pressing (ECAP) at 300 °C following route BC and additional annealing. The microstructure evolution during both deformation by ECAP and subsequent annealing was investigated and correlated with the mechanical properties. The successive grain refinement during ECAP was promoted by two parallel mechanisms, namely dislocation driven grain fragmentation and twin fragmentation, and accounted for the ultra-high strength. In addition, due to the relatively low volume fraction of deformation twins after ECAP at 300 °C, further contribution of deformation twinning during room temperature deformation allowed additional work-hardening capacity and elongation. During subsequent recovery annealing the ultra-fine grains and deformation twins were thermally stable, which supported retainment of the high yield strength along with regained uniform elongation. For the first time, the texture evolution during ECAP and during the following heat treatment was analyzed. After 1, 2, and 4 ECAP passes a transition texture with the characteristic texture components of both high- and low-SFE materials developed. During the following heat treatment the texture evolution proceeded similar to that observed in the same material after cold rolling. Retaining of the ECAP texture components due to oriented nucleation at grain boundaries and triple junctions as well as annealing twinning accounted for the formation of a weak, retained ECAP texture after recrystallization.

Comparison of two measures of work functioning in a population of claimants with physical and psychological injuries

Research has focused on advancing our understanding of strategies to improve return to work outcomes following a physical injury. There has been limited research on the different types of supports needed for workers returning to work following a psychological injury. Developing a better understanding of work limitations when people are back at work is a key step in the development of strategies in this area. Unfortunately, measurement tools have been established separately by injury type, limiting research opportunities to compare differences in work limitations. In this article, we compare two measures of work functioning in a population of claimants that have returned to work following a musculoskeletal or psychological injury: a modified version of the Work Limitations Questionnaire (WLQ) developed for workers with physical injuries and the Lam Employed Absence Productivity Scale (LEAPS) developed for workers with mental health claims. A telephone questionnaire was administered to 214 claimants who returned to work following a claim for a psychological injury or a musculoskeletal injury. While the modified WLQ detected differences in work limitations by injury type, there were no significant differences in levels of work functioning detected by the LEAPS. The comparison demonstrated the value of including questions about work limitations that go beyond mental and interpersonal demands for claimants with psychological injuries; however, there is also a need to limit questions about physical constraints. A modified version of the WLQ is recommended to further our understandings of the similarities and differences in the experiences of workers with psychological versus physical injuries.