Among the alternative processes for the traditional distillation, adsorption and membrane separations are the two most promising candidates and metal-organic frameworks (MOFs) are the new material candidate as adsorbent or membrane due to their high surface area, various pore sizes, and highly tunable framework functionality. This dissertation presents an investigation of the formation process of MOF membrane, framework defects, and two-dimensional (2D) MOFs, aiming to explore the answers for three critical questions: (1) how to obtain a continuous MOF membrane, (2) how defects form in MOF framework, and (3) how to obtain isolated 2D MOFs. To solve the first problem, the accumulated protons in the MOF synthesis solution is proposed to be the key factor preventing the continuous growth among Universitetet I Oslo-(UiO)-66 crystals. The hypothesis is verified by the growth reactivation under the addition of deprotonating agent. As long as the protons were sufficiently coordinated by the deprotonating agent, the continuous growth of UiO-66 is guaranteed. Moreover, the modulation effect can impact the coordination equilibrium so that an oriented growth of UiO-66 film was achieved in membrane structures. To find the answer for the second problem, the defect formation mechanism in UiO-66 was investigated and the formation of missing-cluster (MC) defects is attributed to the partially-deprotonated ligands. Experimental results show the number of MC defects is sensitive to the addition of deprotonating agent, synthesis temperature, and reactant concentration. Pore size distribution allows an accurate and convenient characterization of the defects. Results show that these defects can cause significant deviations of its pore size distribution from the perfect crystal. The study of the third questions is based on the established bi-phase synthesis method, a facile synthesis method is adopted for the production of high quality 2D MOFs in large scale. Here, pyridine is used as capping reagent to prevent the interplanar hydrogen bond formation. Meanwhile, formic acid and triethylamine as modulator and deprotonating agent to balance the anisotropic growth, crystallinity, and yield in the 2D MOF synthesis. As a result, high quality 2D zinc-terephthalic acid (ZnBDC) and copper-terephthalic acid (CuBDC) with extraordinary aspect ratio samples were successfully synthesized.

A new type of electronics was envisioned, namely edible electronics. Edible electronics are made by Food and Drug Administration (FDA) certified edible materials which can be eaten and digested by human body. Different from implantable electronics, test or treatment using edible electronics doesn’t require operations and perioperative complications.

This dissertation bridges the food industry, material sciences, device fabrication, and biomedical engineering by demonstrating edible supercapacitors and electronic components and devices such as pH sensor.

Edible supercapacitors were fabricated using food materials from grocery store. 5 of them were connected in series to power a snake camera. Tests result showed that the current generated by supercapacitor have the ability to kill bacteria. Next more food, processed food and non-toxic level electronic materials were investigated. A “preferred food kit” was created for component fabrication based on the investigation. Some edible electronic components, such as wires, resistor, inductor, etc., were developed and characterized utilizing the preferred food kit. These components make it possible to fabricate edible electronic/device in the future work. Some edible electronic components were integrated into an edible electronic system/device. Then edible pH sensor was introduced and fabricated. This edible pH sensor can be swallowed and test pH of gastric fluid. PH can be read in a phone within seconds after the pH sensor was swallowed. As a side project, an edible double network gel electrolyte was synthesized for the edible supercapacitor.

In recent years, a new type of ionic salt based solid propellant, considered inert until the application of an electric current induces an electro-chemical reaction, has been under investigation due to its broad range of possible uses. However, while many electric propellant formulations and applications have been explored over the years, a fundamental understanding of the operational mechanisms of this propellant is necessary in order to move forward with development and implementation of this technology. It has been suggested that the metallic additive included in the formulation studied during this investigation may be playing an additional, currently unknown role in the operation and performance of the propellant. This study was designed to examine variations of an electric propellant formulation with the purpose of investigating propellant bulk volume electrical resistivity in order to attempt to determine information regarding the fundamental science behind the operation of this material. Within a set of fractional factorial experiments, variations of the propellant material made with tungsten, copper, carbon black, and no additive were manufactured using three different particle size ranges and three different volume percentage particle loadings. Each of these formulations (a total of 21 samples and 189 specimens) were tested for quantitative electrical resistivity values at three different pulse generator input voltage values. The data gathered from these experiments suggests that this electric propellant formulation’s resistivity value does change based upon the included additive. The resulting data has also revealed a parabolic response behavior noticeable in the 2D and 3D additive loading percentage versus additive particle size visualizations, the lowest point of which, occurring at an approximately 2.3% additive loading percentage value, could be indicative of the effects of the percolation phenomena on this material. Finally, the investigation results have been loosely correlated to power consumption testing results from previous work that may indicate that it is possible to relate propellant electrical resistivity and operating requirements. Throughout this study, however, it is obvious based on the data gathered that more information is required to be certain of these conclusions and in order to fully understand how this technology can be controlled for future use.

This study aims to determine the feasibility of producing mechanophore-incorporated epoxy that can be healed. This was accomplished by grafting a synthesized mechanophore into tris(2-aminoethyl)amine to create a new epoxy hardener. Then this branched hardener was combined with a second hardener, diethylenetriamine (DETA). A proper ratio of the branched hardener to the DETA will ensure that the created epoxy will retain the force responsive characteristics without a noticeable decline in both the physical and thermal properties. Furthermore, it was desired that the natural structure of the epoxy would be left in place, and there would only be enough branched hardener present to elicit a force response and provide the possibility for healing. The two hardeners would then be added to Diglycidyl Ether of Bisphenol F (DGEBPF), which is the epoxy resin. The mechanophore-incorporated epoxy was compared to a standard epoxy—just DETA and DGEBPF—and it was determined that the incorporation of the mechanophore led to an 8.2 degrees Celsius increase in glass transition temperature, and a 33.0% increase in cross link density. This justified the mechanophore-incorporated epoxy as a feasible alternative to the standard, as its primary thermal and physical properties were not only equal, but superior. Then samples of the mechanophore-incorporated epoxy were damaged with a 3% tensile strain. This would cause a cycloreversion in the central cyclobutane inside of the mechanophore. Then they were healed with UV light, which would redimerize the severed hardener moieties. The healed samples saw a 4.69% increase in cross-link density, demonstrating that healing was occurring.

This thesis investigates an interpenetrating network of polyacrylamide and poly acrylic acid for use in a dynamic tactile display, which presents traditionally two-dimensional electronic screens as three-dimensional topographical models that can be experienced through touch. This kind of display would allow for greater access to traditionally visual information for the visually impaired. This hydrogel demonstrates Upper Critical Solution Temperature (UCST) near room temperature which facilitates a swelling transition, characterized by a sharp increase in swelling as this temperature is surpassed. Through the utilization of light responsive additives, light can trigger this shift, as the additives harness visible light, convert it into heat to raise the gel’s temperature, and increase the volume of the gel. Light-responsive additives explored include chlorophyllin, gold nanoparticles, and carbon black. Each of these additives required unique synthesis planning and strategies in order to optimize the performance of the gels. Synthesized gels were characterized using thermal swelling tests, light response tests and compression tests to determine the material strength. The best performing additive was chlorophyllin and allowed for a 20.8%±4.5% percent weight increase upon exposure to light for 10 minutes. In addition to investigating light-responsive additives, modifications were pursued to alter the overall UCST behavior, such as the addition of sodium chloride. By adding sodium chloride into the hydrogel, the gel was found to have a wider transition. Overall, light-responsive behavior was developed, and further work can be done in improving the response time and degree of swelling in order to make this material more viable for use in a dynamic tactile display.

Nanomaterials (NMs), implemented into a plethora of consumer products, are a potential new class of pollutants with unknown hazards to the environment. Exposure assessment is necessary for hazard assessment, life cycle analysis, and environmental monitoring. Current nanomaterial detection techniques on complex matrices are expensive and time intensive, requiring weeks of sample preparation and detection by specialized equipment, limiting the feasibility of large-scale monitoring of NMs. A need exists to develop a rapid pre-screening technique to detect, within minutes, nanomaterials in complex matrices. The goal of this dissertation is to develop a tiered process to detect and characterize nanomaterials in consumer products and environmental samples. The approach is accomplished through a two tier rapid screening process to screen likely presence/absence of elements present in common nanomaterials at environmentally relevant concentrations followed by a more intensive three tier characterization process, if nanomaterials are likely to occur. The focus is on SiO2 and TiO2 nanomaterials with additional work performed on hydroxyapatite (Ca5(PO4)3(OH)). The five step tiered process is as follows: 1) screen for elements in the sample by laser induced breakdown spectroscopy (LIBS) and X-ray fluorescence (XRF), 2) extract nanomaterials from the sample and screen for extracted elements by LIBS and XRF, 3) confirm presence and elemental composition of nanomaterials by transmission electron microscopy paired with energy dispersive X-ray spectroscopy, 4) quantify the elemental composition of the sample by inductively coupled plasma – mass spectrometry, and 5) identify mineral phase of crystalline material by X-ray diffraction. This dissertation found LIBS to be an accurate method to detect Si and Ti in food matrices (tier one approach) with strong agreement with the product label, detecting Si and Ti in 93% and 89% of the samples labeled as containing each material, respectively. In addition XRF identified Ti, Si, and Ca in 100% of food samples TEM-confirmed to contain Ti, Si, and Ca respectively. As a tier two approach, LIBS on the 0.2 micrometer filter identified nano silicon in 42% of samples confirmed by TEM to contain nano Si and 67% of TEM-confirmed samples to contain Ti. XRF identified Si, Ti, and Ca loaded on to a 0.1 µm filter and Ti in the surfactant rich phase of CPE of water and water with NOM.

With the maturity of advanced composites as feasible structural materials for various applications there is a critical need to solve the challenge of designing these material systems for optimal performance. However, determining superior design methods requires a deep understanding of the material-structure properties at various length scales. Due to the length-scale dependent behavior of advanced composites, multiscale modeling techniques may be used to describe the dominant mechanisms of damage and failure in these material systems. With polymer matrix fiber composites and nanocomposites it becomes essential to include even the atomic length scale, where the resin-hardener-nanofiller molecules interact, in the multiscale modeling framework. Additionally, sources of variability are also critical to be included in these models due to the important role of uncertainty in advance composite behavior. Such a methodology should be able to describe length scale dependent mechanisms in a computationally efficient manner for the analysis of practical composite structures.

In the research presented in this dissertation, a comprehensive nano to macro multiscale framework is developed for the mechanical and multifunctional analysis of advanced composite materials and structures. An atomistically informed statistical multiscale model is developed for linear problems, to estimate and scale elastic properties of carbon fiber reinforced polymer composites (CFRPs) and carbon nanotube (CNT) enhanced CFRPs using information from molecular dynamics simulation of the resin-hardener-nanofiller nanoscale system. For modeling inelastic processes, an atomistically informed coupled damage-plasticity model is developed using the framework of continuum damage mechanics, where fundamental nanoscale covalent bond disassociation information is scaled up as a continuum scale damage identifying parameter. This damage model is coupled with a nanocomposite microstructure generation algorithm to study the sub-microscale damage mechanisms in CNT/CFRP microstructures. It is further integrated in a generalized method of cells (GMC) micromechanics model to create a low-fidelity computationally efficient nonlinear multiscale method with imperfect interfaces between the fiber and matrix, where the interface behavior is adopted from nanoscale MD simulations. This algorithm is used to understand damage mechanisms in adhesively bonded composite joints as a case study for the comprehensive nano to macroscale structural analysis of practical composites structures. At each length scale sources of variability are identified, characterized, and included in the multiscale modeling framework.

Materials with unprecedented properties are necessary to make dramatic changes in current and future aerospace platforms. Hybrid materials and composites are increasingly being used in aircraft and spacecraft frames; however, future platforms will require an optimal design of novel materials that enable operation in a variety of environments and produce known/predicted damage mechanisms. Nanocomposites and nanoengineered composites with CNTs have the potential to make significant improvements in strength, stiffness, fracture toughness, flame retardancy and resistance to corrosion. Therefore, these materials have generated tremendous scientific and technical interest over the past decade and various architectures are being explored for applications to light-weight airframe structures. However, the success of such materials with significantly improved performance metrics requires careful control of the parameters during synthesis and processing. Their implementation is also limited due to the lack of complete understanding of the effects the nanoparticles impart to the bulk properties of composites. It is common for computational methods to be applied to explain phenomena measured or observed experimentally. Frequently, a given phenomenon or material property is only considered to be fully understood when the associated physics has been identified through accompanying calculations or simulations.

The computationally and experimentally integrated research presented in this dissertation provides improved understanding of the mechanical behavior and response including damage and failure in CNT nanocomposites, enhancing confidence in their applications. The computations at the atomistic level helps to understand the underlying mechanochemistry and allow a systematic investigation of the complex CNT architectures and the material performance across a wide range of parameters. Simulation of the bond breakage phenomena and development of the interface to continuum scale damage captures the effects of applied loading and damage precursor and provides insight into the safety of nanoengineered composites under service loads. The validated modeling methodology is expected to be a step in the direction of computationally-assisted design and certification of novel materials, thus liberating the pace of their implementation in future applications.

The ability to sense applied damage and correlate it with a measurable signal is extremely desirable in any material application to prevent catastrophic failure and the possible loss of use of the material or human injury. Mechanochemistry, in which mechanical forces induce chemical changes, can allow for targeted damage detection by way of embedded mechanophore units, with certain mechanophore chemistries emitting a fluorescent signal in response an applied force. In this work, we successfully employed microparticles of the mechanophore dimeric 9-anthracene carboxylic acid (Di-AC) in a thermoset polyurethane matrix to study their application as universal stress-sensing fillers in network polymer matrix composites. Under a compressive force, there is bond breakage in the mechanically weak cyclooctane photodimers of Di-AC, such that there is reversion to the fluorescent anthracene-type monomers. This fluorescent emission was then correlated to the applied strain, and the precursors to damage were detected with a noticeable fluorescent signal change at an applied strain of only 2%. This early damage detection was additionally possible at very low particle loadings of 2.5 and 5 wt%, with the 5 wt% loading showing enhanced material properties compared to the 2.5 wt%, due to particle reinforcement in the composite. Overall, the synthesis of Di-AC as a stress-sensitive particle filler allows for facile addition of advanced functionality to these ubiquitous thermoset composites.

Statistical process control (SPC) is an important quality application that is used throughout industry and is composed of control charts. Most often, it is applied in the final stages of product manufacturing. However it would be beneficial to apply SPC throughout all stages of the manufacturing process such as the beginning stages. This report explores the fundamentals of SPC, applicable programs, important aspects of implementation, and specific examples of where SPC was beneficial. Important programs for SPC are general statistical software such as JMP and Minitab, and some programs are made specifically for SPC such as SPACE: statistical process and control environment. Advanced programs like SPACE are beneficial because they can easily assist with creating control charts and setting up rules, alarms and notifications, and reaction mechanisms. After the charts are set up it is important to apply rules to the charts to see when a system is running off target which indicates the need to troubleshoot and investigate. This makes the notification part an integral aspect as well because attention and awareness must be brought to out of control situations. The next important aspect is ensuring there is a reaction mechanism or plan on what to do in the event of an out of control situation and what to do to get the system running back on target. Setting up an SPC system takes time and practice and requires a lot of collaboration with experts who know more about the system or the quality side. Some of the more difficult parts of implementation is getting everyone on board and creating trainings and getting the appropriate personnel trained.