Engineering topics
Marshall, Tim
Publications and source records attributed to Marshall, Tim.
Probing Heterogeneous Charge Distributions at the α-Al 2 O 3 (0001)/H 2 O Interface
Unlike metal or semiconductor electrodes, the surface charge resulting from the protonation or deprotonation of insulating mineral oxides is highly localized and heterogeneous in nature. In this work the Stark active C≡N stretch of potassium thiocyanate is used as a molecular probe of the heterogeneity of the interfacial electrostatic potential at the α-Al 2 O 3 (0001)/H 2 O interface. Vibrational sum frequency generation (vSFG) measurements performed in the OH stretching region suggest that thiocyanate species organize interfacial water similarly to halide ions. Changes in the electrostatic potential are then tracked via Stark shifts of the vibrational frequency of the thiocyanate stretch. Our vSFG measurements show that we can simultaneously measure the vSFG response of SCN – ions experiencing charged and neutral surface sites. We assign local potentials of +308 and -154 mV to positively and negatively charged aluminol groups that are present at pH = 4 and pH = 10, respectively. Thiocyanate anions at positively charged surface sites and negatively charged surface sites and those participating in contact ion pairing adopt similar orientations and are oppositely oriented relative to thiocyanate ions near neutral surface sites. All four species followed Langmuir adsorption isotherms. Density functional theory–molecular dynamics (DFT-MD) simulations of SCN – near the neutral α-Al 2 O 3 (0001)/H 2 O interface show that the vSFG response in the C≡N stretch region originates from a SCN–H–O–Al complex, suggesting the surface site specificity of these experiments. To our knowledge this is the first spectroscopic measurement of local potentials associated with a heterogeneously charged surface. The ability to probe the evolution of local charges in situ could provide vital insight into many industrial, electrochemical, and geochemically relevant interfaces.
Monovalent and Divalent Cations at the a-Al2O3(0001)/Water Interface: How Cation Identity Affects Interfacial Ordering and Vibrational Dynamics
Mineral oxide-water interfaces are important for a wide range of industrial, geochemical, and biological processes. The reactivity of these interfaces is strongly impacted by the presence of ions. Thus, it is critical to understand how ions alter the interfacial environment. This can be achieved by measuring the changes in the structure and vibrational dynamics of interfacial water induced by the presence of ions in close vicinity to the mineral surface. The a-Al2O3(0001) surface represents a flexible platform to study the effect of ions on interfacial aqueous environments at positive, neutral and negative surface charge. Using vibrational sum frequency generation (vSFG) in the frequency and time domain, we investigate how monovalent and divalent cations affect the hydrogen bonding environment of the first few layers of interfacial water next to a-Al2O3(0001). Our results indicate that monovalent cations, such as Li+, Na+, K+, and Cs+, appear to have lower binding affinities for the interface compared to Ca2+, Sr2+, and Ba2+. This leads to an interfacial region that is structured in a cation valence dependent manner. Addition of divalent cations at the negatively charged interface (pH 10) increases the spectral intensity in the 3400 cm-1 region compared to neat pH 10 H2O, in contrast to monovalent cations that only attenuate the vSFG signal. Time resolved vSFG measurements reveal that the O-H vibrational lifetime (T1) of interfacial species at pH 10 in the presence of NaCl and BaCl2 remains similar, but restructuring of the surface seen in steady state vSFG is manifested in the degree to which strongly hydrogen bonded species recover to their original populations post excitation. By tracking the accumulation of ions at the interface via the vSFG response, we can characterize the unique surface arrangements of interfacial water molecules induced by a range of monovalent and divalent cations at the a-Al2O3(0001)/water interface.
Exe-Guard Project
The exe-Guard Project is an alliance between Dominion Virginia Power (DVP), Sandia National Laboratories (SNL), Dartmouth University, and Schweitzer Engineering Laboratories (SEL). SEL is primary recipient on this project. The exe-Guard project was selected for award under DE-FOA-0000359 with CFDA number 81.122 to address Topic Area of Interest 4: Hardened platforms and Systems. The exe-Guard project developed an antivirus solution for control system embedded devices to prevent the execution of unauthorized code and maintain settings and configuration integrity. This project created a white list antivirus solution for control systems capable of running on embedded Linux® operating systems. White list antivirus methods allow only credible programs to run through the use of digital signatures and hash functions. Once a system’s secure state is baselined, white list antivirus software denies deviations from that state because of the installation of malicious code as this changes hash results. Black list antivirus software has been effective in traditional IT environments but has negative implications for control systems. Black list antivirus uses pattern matching and behavioral analysis to identify system threats while relying on regular updates to the signature file and recurrent system scanning. Black list antivirus is vulnerable to zero day exploits which have not yet been incorporated into a signature file update. System scans hamper the performance of high availability applications, as revealed in NIST special publication 1058 which summarizes the impact of blacklist antivirus on control systems: Manual or “on-demand” scanning has a major effect on control processes in that they take CPU time needed by the control process (Sometimes close to 100% of CPU time). Minimizing the antivirus software throttle setting will reduce but not eliminate this effect. Signature updates can also take up to 100% of CPU time, but for a much shorter period than a typical manual scanning process. Control systems are vulnerable to performance losses if off-the-shelf blacklist antivirus solutions aren’t implemented with care. This investment in configuration in addition to constant decommissioning to perform manual signature file updates is unprecedented and impractical. Additionally, control systems are often disconnected or islanded from the network making the delivery of signature updates difficult. Exe-Guard project developed a white list antivirus solution that mitigated the above drawbacks and allows control systems to cost-effectively apply malware protection while maintaining high reliability. The application of security patches can also be minimized since white listing maintains constant defense against unauthorized code execution. Security patches can instead be applied in less frequent intervals where system decommissioning can be scheduled and planned for. Since control systems are less dynamic than IT environments, the feasibility of maintaining a secure baselined state is more practical. Because upgrades are performed in infrequent, calculated intervals, it allows a new security baseline to be established before the system is returned to service. Exe-Guard built on the efforts of SNL under the Code Seal project. SNL demonstrated prototype Trust Anchors on the project which are independent monitoring and control devices that can be integrated into untrustworthy components. The exe-Guard team started with the lessons learned under this project then designed commercial solution for white list malware protection. Malware is a real threat, even on islanded or un-networked installations, since operators can unintentionally install infected files, plug in infected mass storage devices, or infect a piece of equipment on the islanded local area network that can then spread to other connected equipment. Protection at the device level is one of the last layers of defense in a security-in-depth defense model before an asset becomes compromised. This project provided non-destructive intrusion, isolation and automated response solution, achieving a goal of the Department of Energy (DOE) Roadmap to Secure Control Systems. It also addressed CIP-007-R4 which requires asset owners to employ malicious software prevention tools on assets within the electronic security perimeter. In addition, the CIP-007-R3 requirement for security patch management is minimized because white listing narrows the impact of vulnerabilities and patch releases. The exe-Guard Project completed all tasks identified in the statement of project objective and identified additional tasks within scope that were performed and completed within the original budget. The cost share was met and all deliverables were successfully completed and submitted on time. Most importantly the technology developed and commercialized under this project has been adopted by the Energy sector and thousands of devices with exe-Guard technology integrated in them have now been deployed and are protecting our power systems today