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Flocculation is not only an important part of sediment dynamics within coastal marine waters, but is also a factor of sediment transport within small freshwater streams in Blacksburg, Virginia. The goal of this project was to develop a relationship between floc sizes and stream characteristics (temperature, salinity, chlorophyll-a, organic content, TSS, pH) and to compare how that relationship varies seasonally and spatially across two streams in the same watershed with a similar drainage area but different land uses within these areas. Microscopic images of flocs and water samples were taken within two local streams every two to four weeks throughout the span of one year. The images were analyzed to obtain the floc sizes and the water samples were tested in a lab for various stream properties. The compiled data from the entire year were analyzed to determine if there was a seasonal relationship between floc sizes and the various properties of the water. The process was also repeated at multiple locations along the entire length of both of the streams once in the summer and once in the winter to see if there was a spatial relationship within a single stream. Our study found that significant rainfall events tend to have the greatest effect on floc size in the small headwater streams. However, many of the individual variables alone do not correlate strongly with floc size and a combination of variables may be the best way to analyze the floc size. / Master of Science / Flocculation is the process of single particles coming together to form larger aggregated particles called "flocs". This project focuses on flocculation of sediment within local streams and how the sizes of these flocs may vary throughout the year. The rate of flocculation and the size of these flocs can have a large effect on the movement of sediment within freshwater streams. Images of flocs and water properties such as water temperature, salinity, and pH, were analyzed every two to four weeks throughout the span of a year to determine if there was a relationship between floc size and any of the measured water properties. While a relationship between rainfall and floc size was noticed, it is apparent that multiple variables should be factored into the analysis to get the most accurate results.

Additive manufacturing (AM) is a growing section of the advanced manufacturing field and is being used to fabricate an increasing number of critical components, from aerospace components to medical implants. At the same time, cyber-physical attacks targeting manufacturing systems have continued to rise. For this reason, there is a need to research new techniques and methods to ensure the integrity of parts fabricated on AM systems. This work seeks to address this need by first performing a detailed analysis of vulnerabilities in the AM process chain and how these attack vectors could be used to execute malicious part sabotage attacks. This work demonstrated the ability of an internal void attack on the .STL file to reduce the yield load of a tensile specimen by 14% while escaping detection by operators. To mitigate these vulnerabilities, a new impedance-based approach for in situ monitoring of AM systems was created. Two techniques for implementing this approach were investigated, direct embedding of sensors in AM parts, and the use of an instrumented fixture as a build plate. The ability to detect changes in material as small as 1.38% of the printed volume (53.8 mm3) on a material jetting system was demonstrated. For metal laser powder bed fusion systems, a new method was created for representing side-channel meltpool emissions. This method reduces the quantity of data while remaining sensitive enough to detect changes to the toolpath and process parameters caused by malicious attacks. To enable the SCMS to validate part quality during fabrication required a way to receive baseline part quality information across an air-gap. To accomplish this a new process noise tolerant method of cyber-physical hashing for continuous data sets was presented. This method was coupled with new techniques for the storage, transmission, and reconstructing of the baseline quality data was implemented using stacks of "ghost" QR codes stored in the toolpath to transmit information through the laser position. A technique for storing and transmitting quality information in the toolpath files of parts using acoustic emissions was investigated. The ATTACH (additive toolpath transmission of acoustic cyber-physical hash) method used speed modulation of infill roads in a material extrusion system to generate acoustic tones containing quality information about the part. These modulations were able to be inserted without affecting the build time or requiring additional material and did not affect the quality of the part that contained them. Finally, a framework for the design and implementation of a SCMS for protecting AM systems against malicious cyber-physical part sabotage attacks was created. The IDEAS (Identify, Define, Establish, Aggregate, Secure) framework provides a detailed reference for engineers to use to secure AM systems by leveraging the previous work in vulnerability assessment, creation of new side-channel monitoring techniques, concisely representing quality data, and securely transmitting information to air-gapped systems through physical emissions. / Doctor of Philosophy / Additive manufacturing (AM), more widely known as 3D printing, is a growing field of manufacturing where parts are fabricated by building layers of material on top of each other. This layer-based approach allows the production of parts with complex shapes that cannot be made using more traditional approaches such as machining. This capability allows for great freedom in designing parts, but also means that defects can be created inside of parts during fabrication. This work investigates ways that an adversary might seek to sabotage AM parts through a cyber-physical attack. To prevent attacks seeking to sabotage AM parts several new approaches for security are presented. The first approach uses tiny vibrations to detect changes to part shape or material by attaching a small sensor either directly to the parts or to the surface that they are built on. Because an attack that sabotages an AM system (3D printer) could also affect the systems used to detect part defects these systems should be digitally separated from each other. By using a series of QR codes fabricated by the AM system along with the parts, information can be sent from the AM system to the monitoring system through its sensors. This prevents a cyber-attack from jumping from the AM system to the monitoring system. By temporarily turning off the laser power and tracking the movements of the guiding mirrors the QR code information can be sent to the monitoring system without having to actually print the QR code. The information stored in the QR code is compared to the emission generated when fabricating the parts and is used to detect if an attack has occurred since that would change the emissions from the part, but not from the QR code. Another approach for sending information from the AM system using physical emissions is by using sounds generated during part fabrication. Using a desktop scale 3D printer, the speed of certain movements was increased or decreased. The change in speed causes the sound emitted from the printer to change, while not affecting the actual quality of the print. By using a series of tones, similar to Morse code, information can be sent from the printer. Research was performed on the best settings to use to transmit the information as well as how to automatically receive and decode the information using a microphone. The final step in this work is a framework that serves as a guide for designing and implementing monitoring systems that can detect sabotage attacks on AM parts. The framework covers how to evaluate a system for potential vulnerabilities and how to use this information to choose sensors and data processing techniques to reduce the risk of cyber-physical attacks.

Shape memory ceramics (SMCs) are burgeoning functional materials based on zirconia with a reversible, stress-inducible martensitic phase transformation. Compared to metallic shape memory alloys, SMCs have broader operating temperatures, higher critical stresses, and larger mechanical hysteresis loops. These advantages make SMCs attractive for high-output actuation and sensing in extreme environments or energy dissipation applications; however, the key phase transformation generates large stresses and strains that accumulate at grain boundaries and result in fracture of monolithic SMCs. This means that material forms with decreased mechanical constraint are necessary. Transformation without fracture has been previously demonstrated with SMC micropillars and individual microparticles, but these material forms lack useful applications. By utilizing easily scalable granular packings of discrete free particles, the transformation can be triggered in bulk without fracture in much the same way. The granular packing material form introduces significant complexity as the internal stress distributions responsible for the phase transformation are highly heterogeneous on the macro-, meso-, and micro-scales. Moreover, the unconstrained phase transformation behaves differently than the constrained transformation, which is more studied in zirconia. The interactions of these various factors are explored from a fundamental perspective in this work, notably including (1) a unique 'continuous mode' of both forward and reverse transformation in granular packings, (2) the dependence of transformation behavior on macro-, meso-, and microstructure, and (3) the evolution of the granular packings' structure and energy dissipation capacity over 10,000 loading cycles. Diverse experimental techniques are employed, ranging from mechanical testing and calorimetry to in situ neutron diffraction, to support theory based on the martensitic phase transformation in zirconia, the shape memory and superelastic effects, and granular material physics. / Doctor of Philosophy / Shape memory materials are capable of remembering their original shape even when they are deformed, and can return to that shape when they are heated. This unique property stems from a phenomenon called martensitic phase transformation which bridges the gap between microscopic structural changes and macroscopic shape changes as a response to specific environmental changes. Most of the common shape memory materials are metallic, like nitinol (NiTi), which has uses in orthodontic wires and cardiological stents, but there are also ceramic materials that can display the shape memory effect. These shape memory ceramics are based on zirconia (ZrO2), and are distinct from metallic shape memory materials because of their brittle behavior and high temperature stability owing to their chemical structure. The work presented in this thesis concerns the behavior of shape memory ceramics in granular form (i.e., loose powders) over a range of external conditions. Diverse experimental techniques are employed to investigate differences between granular and non-granular shape memory ceramics. This work shows how the unique structure of a granular material, which is dominated by highly uneven force distributions and microscopic effects, interacts with the martensitic phase transformation in shape memory ceramics to produce a 'continuous' mode of transformation that differs from non-granular shape memory materials. This continuous mode is itself dependent on the granular material's macro-, meso-, and micro-structure, and on the shape memory material's composition and history. In the future, shape memory ceramics might leverage the insights gained from this work for applications including energy dissipation or on-demand shape changes (i.e., actuation).

Additive friction stir deposition (AFSD) is an emerging solid-state metal additive manufacturing technology that uses deformation bonding to create near-net shape 3D components. As a developing technology, a deeper understanding of the processing science is necessary to establish the process-structure relationships and enable improved control of the as-printed microstructure and material properties. AFSD provides a unique opportunity to explore the friction stir fundamentals via direct observation of the material during processing. This work explores the relationship between the processing parameters (e.g., tool rotation rate Ω, tool velocity V, and material feed rate F) and the thermomechanical history of the material by process monitoring of i) the temperature evolution, ii) the force evolution, and iii) the interfacial contact state between the tool and deposited material. Empirical trends are established for the peak temperature with respect to the processing conditions for Cu and Al-Mg-Si, but a key difference is noted in the form of the power law relationship: Ω/V for Cu and Ω2/V for Al-Mg-Si. Similarly, the normal force Fz for both materials correlates to V and inversely with Ω. For Cu both parameters show comparable influence on the normal force, whereas Ω is more impactful than V for Al-Mg-Si. On the other hand, the torque Mz trends for Al-Mg-Si are consistent with the normal force trends, however for Cu there is no direct correlation between the processing parameters and the torque. These distinct relationships and thermomechanical histories are directly linked to the contact states observed during deformation monitoring of the two material systems. In Cu, the interfacial contact between the material and tool head is characterized by a full slipping condition (δ=1). In this case, interfacial friction is the dominant heat generation mechanism and compression is the primary deformation mechanism. In Al-Mg-Si, the interfacial contact is characterized by a partial slipping/sticking condition (0<δ<1), so both interfacial friction and plastic energy dissipation are important mechanisms for heat generation and material deformation. Finally, an investigation into the contact evolution at different processing parameters shows that the fraction of sticking is critically dependent on the processing parameters which has many implications on the thermomechanical processing history. / Doctor of Philosophy / Additive manufacturing or three-dimensional (3D) printing technologies have been lauded for their ability to fabricate complex geometries and multi-material parts with reduced material waste. Of particular interest is the use of metal additive manufacturing for repair and fabrication of industrial and structural components. This work focuses on characterizing the thermomechanical processing history for a developing technology Additive Friction Stir Deposition (AFSD). AFSD is solid-state additive manufacturing technology that uses frictional heat and mechanical mixing to fabricate 3D metal components. From a fundamental materials science perspective, it is imperative to understand the processing history of a material to be able to predict the performance and properties of a manufactured part. Through the use of infrared imaging, thermocouples, force sensors, and video monitoring this work is able to establish quantitative relationships between the equipment processing parameters and the processing history for Cu and Al. This work shows that there is a fundamental difference in how these two materials are processed during AFSD. In the future, these quantitative relationships can be used to validate modeling efforts and improve manufacturing quality of parts produced via friction stir techniques.

Reactivity ratios for the homogeneous free radical initiated copolymerization of acrylonitrile and methyl acrylate were measured by NMR on isolated, low conversion copolymers and by real time in situ FTIR. The system utilized azobisisobutyronitrile (AIBN) initiator in dimethyl formamide (DMF) at 62°. The FTIR technique allowed rapid generation of extensive copolymer compositions, which permitted application of nonlinear least squares methodology for the first time to this copolymer system. Thus, reactivity ratios at the 95% confidence level were determined to be 1.29 ± 0.2 and 0.96 ± 0.2 for acrylonitrile and methyl acrylate, respectively. The results are useful for the development of acrylonitrile (<90%) melt processable copolymer fibers and films, which could include precursors for carbon fibers. / Master of Science

Gold gains many useful properties when it is formed into a nanoporous structure, but it also becomes macroscopically brittle due to flow localization and may therefore be unreliable for many applications. The goal of this work was to establish processing/structure/property relationships of nanoporous gold, discover controllable structure features, and understand the role of structure on flow localization. The nanoporous gold structure, consisting of a 3D network of nanoscale gold ligaments, was quantified with an automatic software developed for this work called AQUAMI, which uses computer vision techniques to make statistically reliable numbers of repeatable and unbiased measurements per image. AQUAMI increased the efficiency and accuracy of characterization in this work, allowed for the conduction of more experiments, and provided better confidence in morphology and size distribution of the complex NPG microstructural features. Nanoporous gold was synthesized while varying numerous processing factors such as dealloying time, annealing time, and mechanical agitation. Through the expanded scope of synthesis experiments and detailed analysis, it was discovered that the curvature of the ligaments and the distribution width of ligament diameters could be controlled through processing. In situ tensile experiments in SEM and TEM revealed that large ligaments arrested crack propagation while curved ligaments increase ductility by straightening in the tensile direction and forming geometrically required defects, which inhibit dislocation activity. Through synthesis and microstructure characterization, two new controllable structure features were discovered experimentally. In situ mechanical testing revealed the role these structures play on the deformation behavior and flow localization of nanoporous gold. / Doctor of Philosophy / Nanoporous gold contains a network of connected pores running through and between at network of solid gold ligaments or struts. It somewhat resembles the structure of coral. The nanoscale pores and ligaments give the material many useful properties. However, this structure also makes the material very fragile and unreliable in many potential application environments. The goal of this research is to investigate how the structure makes the material so fragile and look for ways the material might be made less fragile while still preserving its useful properties. The material properties are controlled through the material’s structure, which in turn is controlled by processing. To control the structure of nanoporous gold, the structure first had to be characterized. A software called AQUAMI was developed, which uses computer vision, to automatically calculate many features of the structure by looking at an image of it. This software was much faster and more accurate than making hundreds of hand measurements on each image. To find new ways to control the structure through processing, nanoporous gold was synthesized in many different conditions and then the structure was analyzed to determine the effect of each synthesis condition. It was discovered that a single specimen could be given a larger variety of ligament thicknesses by making it with a weaker acid or a smaller variety by heating the structure after forming it. Stirring during synthesis resulted in a structure with curvier ligaments. Mechanical tests were performed in electron microscopes to see how these features affected deformation. Large ligaments slowed crack propagation suggesting that a larger variety of ligament diameters could increase strength by having more large ligaments. Curved ligaments deformed more without breaking by straightening during deformation. Through this work, new ways of controlling the nanoporous gold structure were found and mechanical tests suggest that controlling these features may increase the material’s strength making it reliable in more environments