Advanced Adhesion Strength Testing Methods of Thin Film Multilayers in Electronic Packaging Systems

With the continued miniaturization and increasing performance of electronic devices, new technical challenges have arisen. One such issue is delamination occurring at critical interfaces inside the device. This major reliability issue can occur during the manufacturing process or during normal use of the device. Proper evaluation of the adhesion strength of critical interfaces early in the product development cycle can help reduce reliability issues and time-to-market of the product. However, conventional adhesion strength testing is inherently limited in the face of package miniaturization, which brings about further technical challenges to quantify design integrity and reliability. Although there are many different interfaces in today's advanced electronic packages, they can be generalized into two main categories: 1) rigid to rigid connections with a thin flexible polymeric layer in between, or 2) a thin film membrane on a rigid structure. Knowing that every technique has its own advantages and disadvantages, multiple testing methods must be enhanced and developed to be able to accommodate all the interfaces encountered for emerging electronic packaging technologies. For evaluating the adhesion strength of high adhesion strength interfaces in thin multilayer structures a novel adhesion test configuration called “single cantilever adhesion test (SCAT)” is proposed and implemented for an epoxy molding compound (EMC) and photo solder resist (PSR) interface. The test method is then shown to be capable of comparing and selecting the stronger of two potential EMC/PSR material sets. Additionally, a theoretical approach for establishing the applicable testing domain for a four-point bending test method was presented. For evaluating polymeric films on rigid substrates, major testing challenges are encountered for reducing testing scatter and for factoring in the potentially degrading effect of environmental conditioning on the material properties of the film. An advanced blister test with predefined area test method was developed that considers an elasto-plastic analytical solution and implemented for a conformal coating used to prevent tin whisker growth. The advanced blister testing with predefined area test method was then extended by employing a numerical method for evaluating the adhesion strength when the polymer’s film properties are unknown.

Strategic Alert Throttling for Intrusion Detection Systems

Network intrusion detection systems are themselves becoming targets of attackers. Alert flood attacks may be used to conceal malicious activity by hiding it among a deluge of false alerts sent by the attacker. Although these types of attacks are very hard to stop completely, our aim is to present techniques that improve alert throughput and capacity to such an extent that the resources required to successfully mount the attack become prohibitive. The key idea presented is to combine a token bucket filter with a realtime correlation algorithm. The proposed algorithm throttles alert output from the IDS when an attack is detected. The attack graph used in the correlation algorithm is used to make sure that alerts crucial to forming strategies are not discarded by throttling.

Microfluidic platforms for the characterization of in meso membrane protein crystallization

Membrane proteins, which reside in the membranes of cells, play a critical role in many important biological processes including cellular signaling, immune response, and material and energy transduction. Because of their key role in maintaining the environment within cells and facilitating intercellular interactions, understanding the function of these proteins is of tremendous medical and biochemical significance. Indeed, the malfunction of membrane proteins has been linked to numerous diseases including diabetes, cirrhosis of the liver, cystic fibrosis, cancer, Alzheimer's disease, hypertension, epilepsy, cataracts, tubulopathy, leukodystrophy, Leigh syndrome, anemia, sensorineural deafness, and hypertrophic cardiomyopathy.1-3 However, the structure of many of these proteins and the changes in their structure that lead to disease-related malfunctions are not well understood. Additionally, at least 60% of the pharmaceuticals currently available are thought to target membrane proteins, despite the fact that their exact mode of operation is not known.4-6 Developing a detailed understanding of the function of a protein is achieved by coupling biochemical experiments with knowledge of the structure of the protein. Currently the most common method for obtaining three-dimensional structure information is X-ray crystallography. However, no a priori methods are currently available to predict crystallization conditions for a given protein.7-14 This limitation is currently overcome by screening a large number of possible combinations of precipitants, buffer, salt, and pH conditions to identify conditions that are conducive to crystal nucleation and growth.7,9,11,15-24 Unfortunately, these screening efforts are often limited by difficulties associated with quantity and purity of available protein samples. While the two most significant bottlenecks for protein structure determination in general are the (i) obtaining sufficient quantities of high quality protein samples and (ii) growing high quality protein crystals that are suitable for X-ray structure determination,7,20,21,23,25-47 membrane proteins present additional challenges. For crystallization it is necessary to extract the membrane proteins from the cellular membrane. However, this process often leads to denaturation. In fact, membrane proteins have proven to be so difficult to crystallize that of the more than 66,000 structures deposited in the Protein Data Bank,48 less than 1% are for membrane proteins, with even fewer present at high resolution (< 2Å)4,6,49 and only a handful are human membrane proteins.49 A variety of strategies including detergent solubilization50-53 and the use of artificial membrane-like environments have been developed to circumvent this challenge.43,53-55 In recent years, the use of a lipidic mesophase as a medium for crystallizing membrane proteins has been demonstrated to increase success for a wide range of membrane proteins, including human receptor proteins.54,56-62 This in meso method for membrane protein crystallization, however, is still by no means routine due to challenges related to sample preparation at sub-microliter volumes and to crystal harvesting and X-ray data collection. This dissertation presents various aspects of the development of a microfluidic platform to enable high throughput in meso membrane protein crystallization at a level beyond the capabilities of current technologies. Microfluidic platforms for protein crystallization and other lab-on-a-chip applications have been well demonstrated.9,63-66 These integrated chips provide fine control over transport phenomena and the ability to perform high throughput analyses via highly integrated fluid networks. However, the development of microfluidic platforms for in meso protein crystallization required the development of strategies to cope with extremely viscous and non-Newtonian fluids. A theoretical treatment of highly viscous fluids in microfluidic devices is presented in Chapter 3, followed by the application of these strategies for the development of a microfluidic mixer capable of preparing a mesophase sample for in meso crystallization at a scale of less than 20 nL in Chapter 4. This approach was validated with the successful on chip in meso crystallization of the membrane protein bacteriorhodopsin. In summary, this is the first report of a microfluidic platform capable of performing in meso crystallization on-chip, representing a 1000x reduction in the scale at which mesophase trials can be prepared. Once protein crystals have formed, they are typically harvested from the droplet they were grown in and mounted for crystallographic analysis. Despite the high throughput automation present in nearly all other aspects of protein structure determination, the harvesting and mounting of crystals is still largely a manual process. Furthermore, during mounting the fragile protein crystals can potentially be damaged, both from physical and environmental shock. To circumvent these challenges an X-ray transparent microfluidic device architecture was developed to couple the benefits of scale, integration, and precise fluid control with the ability to perform in situ X-ray analysis (Chapter 5). This approach was validated successfully by crystallization and subsequent on-chip analysis of the soluble proteins lysozyme, thaumatin, and ribonuclease A and will be extended to microfluidic platforms for in meso membrane protein crystallization. The ability to perform in situ X-ray analysis was shown to provide extremely high quality diffraction data, in part as a result of not being affected by damage due to physical handling of the crystals. As part of the work described in this thesis, a variety of data collection strategies for in situ data analysis were also tested, including merging of small slices of data from a large number of crystals grown on a single chip, to allow for diffraction analysis at biologically relevant temperatures. While such strategies have been applied previously,57,59,61,67 they are potentially challenging when applied via traditional methods due to the need to grow and then mount a large number of crystals with minimal crystal-to-crystal variability. The integrated nature of microfluidic platforms easily enables the generation of a large number of reproducible crystallization trials. This, coupled with in situ analysis capabilities has the potential of being able to acquire high resolution structural data of proteins at biologically relevant conditions for which only small crystals, or crystals which are adversely affected by standard cryocooling techniques, could be obtained (Chapters 5 and 6). While the main focus of protein crystallography is to obtain three-dimensional protein structures, the results of typical experiments provide only a static picture of the protein. The use of polychromatic or Laue X-ray diffraction methods enables the collection of time resolved structural information. These experiments are very sensitive to crystal quality, however, and often suffer from severe radiation damage due to the intense polychromatic X-ray beams. Here, as before, the ability to perform in situ X-ray analysis on many small protein crystals within a microfluidic crystallization platform has the potential to overcome these challenges. An automated method for collecting a "single-shot" of data from a large number of crystals was developed in collaboration with the BioCARS team at the Advanced Photon Source at Argonne National Laboratory (Chapter 6). The work described in this thesis shows that, even more so than for traditional structure determination efforts, the ability to grow and analyze a large number of high quality crystals is critical to enable time resolved structural studies of novel proteins. In addition to enabling X-ray crystallography experiments, the development of X-ray transparent microfluidic platforms also has tremendous potential to answer other scientific questions, such as unraveling the mechanism of in meso crystallization. For instance, the lipidic mesophases utilized during in meso membrane protein crystallization can be characterized by small angle X-ray diffraction analysis. Coupling in situ analysis with microfluidic platforms capable of preparing these difficult mesophase samples at very small volumes has tremendous potential to enable the high throughput analysis of these systems on a scale that is not reasonably achievable using conventional sample preparation strategies (Chapter 7). In collaboration with the LS-CAT team at the Advanced Photon Source, an experimental station for small angle X-ray analysis coupled with the high quality visualization capabilities needed to target specific microfluidic samples on a highly integrated chip is under development. Characterizing the phase behavior of these mesophase systems and the effects of various additives present in crystallization trials is key for developing an understanding of how in meso crystallization occurs. A long term goal of these studies is to enable the rational design of in meso crystallization experiments so as to avoid or limit the need for high throughput screening efforts. In summary, this thesis describes the development of microfluidic platforms for protein crystallization with in situ analysis capabilities. Coupling the ability to perform in situ analysis with the small scale, fine control, and the high throughput nature of microfluidic platforms has tremendous potential to enable a new generation of crystallographic studies and facilitate the structure determination of important biological targets. The development of platforms for in meso membrane protein crystallization is particularly significant because they enable the preparation of highly viscous mixtures at a previously unachievable scale. Work in these areas is ongoing and has tremendous potential to improve not only current the methods of protein crystallization and crystallography, but also to enhance our knowledge of the structure and function of proteins which could have a significant scientific and medical impact on society as a whole. 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Strategic Alert Throttling for Intrusion Detection Systems

Network intrusion detection systems are themselves becoming targets of attackers. Alert flood attacks may be used to conceal malicious activity by hiding it among a deluge of false alerts sent by the attacker. Although these types of attacks are very hard to stop completely, our aim is to present techniques that improve alert throughput and capacity to such an extent that the resources required to successfully mount the attack become prohibitive. The key idea presented is to combine a token bucket filter with a realtime correlation algorithm. The proposed algorithm throttles alert output from the IDS when an attack is detected. The attack graph used in the correlation algorithm is used to make sure that alerts crucial to forming strategies are not discarded by throttling.

Performance Analysis of IP based WSNs in real time systems

Wireless sensor networks (WSNs) are the key enablers of the internet of things (IoT) paradigm. Traditionally, sensor network research has been to be unlike the internet, motivated by power and device constraints. The IETF 6LoWPAN draft standard changes this, defining how IPv6 packets can be efficiently transmitted over IEEE 802.15.4 radio links. Due to this 6LoWPAN technology, low power, low cost micro- controllers can be connected to the internet forming what is known as the wireless embedded internet. Another IETF recommendation, CoAP allows these devices to communicate interactively over the internet. The integration of such tiny, ubiquitous electronic devices to the internet enables interesting real-time applications. This thesis work attempts to evaluate the performance of a stack consisting of CoAP and 6LoWPAN over the IEEE 802.15.4 radio link using the Contiki OS and Cooja simulator, along with the CoAP framework Californium (Cf). Ultimately, the implementation of this stack on real hardware is carried out using a raspberry pi as a border router with T-mote sky sensors as slip radios and CoAP servers relaying temperature and humidity data. The reliability of the stack was also demonstrated during scalability analysis conducted on the physical deployment. The interoperability is ensured by connecting the WSN to the global internet using different hardware platforms supported by Contiki and without the use of specialized gateways commonly found in non IP based networks. This work therefore developed and demonstrated a heterogeneous wireless sensor network stack, which is IP based and conducted performance analysis of the stack, both in terms of simulations and real hardware.

Next generation membranes for membrane distillation and future prospects

This chapter presents the most recent advances in membrane materials technology and module configurations for membrane distillation (MD), as well as their novel applications. The impact of the material morphology, surface energy, and pore structure on MD performance is discussed. The differences between hollow fibres and flat sheet membrane materials are also examined and promising novel structures or module configurations reviewed. In addition, novel materials and module configuration strategies are also identified that may lead to superior MD systems. Also, this chapter identifies current gaps where further work may lead to ongoing improvements to MD.

Local deformation in roll forming

In a previous paper, a simple model was developed to extend the application of the traditional flower pattern diagram as a design tool for roll forming. The position of a point on the strip as it passes through each set of rolls can be identified as a series of points in the two-dimensional flower pattern diagram. In three dimensions, these points will lie on a non-circular cylindrical surface having its axis parallel to the machine axis. Assuming that these points are joined by a smooth curve, the forming path of a point on the strip as it passes through the roll forming process can be obtained as a plane curve on the plane development of this surface. It was shown in previous work that the longitudinal membrane strain and, in certain cases, local curvature of the sheet are functions of the slope of this plane curve. In this work, the strains on both surfaces at the edge of a strip in the forming of a simple V-channel are measured using strain gauges. It is shown that near the point of contact with the rolls, the strains differ by nearly an order of magnitude from those determined from the simple model which assumes that the trajectory is a smooth curve. A modification of the forming path is obtained from the measured bending strains. Although the changes in displacement are small, the peak values of strain near the point of roll contact are large and a consequence of highly localised changes in the forming path as the strip passes over each roll. Measurement of this perturbation in the forming path is difficult as the region is obscured by the forming rolls. The technique described here permits the reconstruction of this path and identifies a new area of investigation of longitudinal strains in roll forming. These are often associated with shape defects such as bow, warping and end flare.

WATER TRANSPORT THROUGH POROUS MEDIA AND IN FLOW CHANNELS OF PROTON EXCHANGE MEMBRANE FUEL CELL

Proton exchange membrane (PEM) fuel cell has been known as a promising power source for different applications such as automotive, residential and stationary. During the operation of a PEM fuel cell, hydrogen is oxidized in anode and oxygen is reduced in the cathode to produce the intended power. Water and heat are inevitable byproducts of these reactions. The water produced in the cathode should be properly removed from inside the cell. Otherwise, it may block the path of reactants passing through the gas channels and/or gas diffusion layer (GDL). This deteriorates the performance of the cell and eventually can cease the operation of the cell. Water transport in PEM fuel cell has been the subject of this PhD study. Water transport on the surface of the GDL, through the gas flow channels, and through GDL has been studied in details. For water transport on the surface of the GDL, droplet detachment has been measured for different GDL conditions and for anode and cathode gas flow channels. Water transport through gas flow channels has been investigated by measuring the two-phase flow pressure drop along the gas flow channels. As accumulated liquid water within gas flow channels resists the gas flow, the pressure drop increases along the flow channels. The two-phase flow pressure drop can reveal useful information about the amount of liquid water accumulated within gas flow channels. Liquid water transport though GDL has also been investigated by measuring the liquid water breakthrough pressure for the region between the capillary fingering and the stable displacement on the drainage phase diagram. The breakthrough pressure has been measured for different variables such as GDL thickness, PTFE/Nafion content within the GDL, GDL compression, the inclusion of a micro-porous layer (MPL), and different water flow rates through the GDL. Prior to all these studies, GDL microstructural properties have been studied. GDL microstructural properties such as mean pore diameter, pore diameter distribution, and pore roundness distribution have been investigated by analyzing SEM images of GDL samples.

IMPROVED SAMPLE INTRODUCTION SYSTEMS FOR INDUCTIVELY COUPLED PLASMA OPTICAL EMISSION SPECTROMETRY AND THEIR APPLICATION TO THE ANALYSIS OF SIMPLE AND COMPLEX MATRICES

The objective of this thesis is to explore new and improved methods for greater sample introduction efficiency and enhanced analytical performance with inductively coupled plasma optical emission spectrometry (ICP-OES). Three projects are discussed in which the capabilities and applications of ICP-OES are expanded: 1. In the first project, a conventional ultrasonic nebuliser was modified to replace the heater/condenser with an infrared heated pre-evaporation tube. In continuation from previous works with pre-evaporation, the current work investigated the effects of heating with infrared block and rope heaters on two different ICP-OES instruments. Comparisons were made between several methods and setups in which temperatures were varied. By monitoring changes to sensitivity, detection limit, precision, and robustness, and analyzing two certified reference materials, a method with improved sample introduction efficiency and comparable analytical performance to a previous method was established. 2. The second project involved improvements to a previous work in which a multimode sample introduction system (MSIS) was modified by inserting a pre-evaporation tube between the MSIS and torch. The new work focused on applying an infrared heated ceramic rope for pre-evaporation. This research was conducted in all three MSIS modes (nebulisation mode, hydride generation mode, and dual mode) and on two different ICP-OES instruments, and comparisons were made between conventional setups in terms of sensitivity, detection limit, precision, and robustness. By tracking both hydride-forming and non-hydride forming elements, the effects of heating in combination with hydride generation were probed. Finally, optimal methods were validated by analysis of two certified reference materials. 3. A final project was completed in collaboration with ZincNyx Energy Solutions. This project sought to develop a method for the overall analysis of a 12 M KOH zincate fuel, which is used in green energy backup systems. By employing various techniques including flow injection analysis and standard additions, a final procedure was formulated for the verification of K concentration, as well as the measurement of additives (Al, Fe, Mg, In, Si), corrosion products (such C from CO₃²¯), and Zn particles both in and filtered from solution. Furthermore, the effects of exposing the potassium zincate electrolyte fuel to air were assessed.

Alignment and characterisation of hexagonal lyotropic liquid crystalline nanostructure for membrane synthesis

Weiwei has been devoting to the alignment and characterisation of hexagonal lyotropic liquid crystalline nanostructure to uniform orientation by applying external fields. According to the Synchrotron small angle x-ray scattering results, it has produced distinct progress. This technique is aimed for improving the filtration efficiency of nanoporous membranes.

Investigating automated chemical evolution of oil-in-water droplets

One of the main unresolved questions in science is how non-living matter became alive in a process known as abiognesis, which aims to explain how from a primordial soup scenario containing simple molecules, by following a ``bottom up'' approach, complex biomolecules emerged forming the first living system, known as a protocell. A protocell is defined by the interplay of three sub-systems which are considered requirements for life: information molecules, metabolism, and compartmentalization. This thesis investigates the role of compartmentalization during the emergence of life, and how simple membrane aggregates could evolve into entities that were able to develop ``life-like'' behaviours, and in particular how such evolution could happen without the presence of information molecules. Our ultimate objective is to create an autonomous evolvable system, and in order tp do so we will try to engineer life following a ``top-down'' approach, where an initial platform capable of evolving chemistry will be constructed, but the chemistry being dependent on the robotic adjunct, and how then this platform can be de-constructed in iterative operations until it is fully disconnected from the evolvable system, the system then being inherently autonomous. The first project of this thesis describes how the initial platform was designed and built. The platform was based on the model of a standard liquid handling robot, with the main difference with respect to other similar robots being that we used a 3D-printer in order to prototype the robot and build its main equipment, like a liquid dispensing system, tool movement mechanism, and washing procedures. The robot was able to mix different components and create populations of droplets in a Petri dish filled with aqueous phase. The Petri dish was then observed by a camera, which analysed the behaviours described by the droplets and fed this information back to the robot. Using this loop, the robot was then able to implement an evolutionary algorithm, where populations of droplets were evolved towards defined life-like behaviours. The second project of this thesis aimed to remove as many mechanical parts as possible from the robot while keeping the evolvable chemistry intact. In order to do so, we encapsulated the functionalities of the previous liquid handling robot into a single monolithic 3D-printed device. This device was able to mix different components, generate populations of droplets in an aqueous phase, and was also equipped with a camera in order to analyse the experiments. Moreover, because the full fabrication process of the devices happened in a 3D-printer, we were also able to alter its experimental arena by adding different obstacles where to evolve the droplets, enabling us to study how environmental changes can shape evolution. By doing so, we were able to embody evolutionary characteristics into our device, removing constraints from the physical platform, and taking one step forward to a possible autonomous evolvable system.

On the zeros of the Abelian integrals for a class of Liénard systems

A planar polynomial differential system has a finite number of limit cycles. However, finding the upper bound of the number of limit cycles is an open problem for the general nonlinear dynamical systems. In this paper, we investigated a class of Liénard systems of the form x'=y, y'=f(x)+y g(x) with deg f=5 and deg g=4. We proved that the related elliptic integrals of the Liénard systems have at most three zeros including multiple zeros, which implies that the number of limit cycles bifurcated from the periodic orbits of the unperturbed system is less than or equal to 3.