Estimation of the Structural and Geomechanical Anisotropy in Fault Gouges Using 3D Micro-Computed Tomography (µ-CT).

Fault gouges play an important role in the shear deformation of fault zones, by causing weakness and frictional instability in structures. Previous studies have investigated the evolution of shear deformation of fault zones by observing experiments using remolded and synthetic gouge specimens at a micro-scale. However, how the spatial configuration of the rock constituents accounts for the 3D anisotropy of intact structures of fault gouges, particularly at the core-scale, is not well understood. We obtained 3D µ-CT images of directionally cored gouge specimens and performed statistical analysis to quantify the major orientation of the internal structures. Direct shear tests were conducted to investigate the relationship between the distribution of the internal structures and geomechanical behavior. The results show that the undisturbed fault gouge has a clear anisotropy parallel to the fault plane even at the core-scale. Moreover, the direct shear test results show that the frictional resistance of a fault gouge has anisotropy related to the fault plane. The simple, yet robust method proposed in this study confirms that the core-scale structural anisotropy is correlated to the anisotropic shear resistance.

Influence of the capping material on pyridine-induced chemical interface damping in single gold nanorods.

Chemical interface damping (CID) is one of the plasmon decay processes that occur in gold nanoparticles. With the aim of exploring new functional groups that can induce CID as an alternative to thiol groups, we performed dark-field (DF) scattering studies of gold nanorods (AuNRs) using pyridine as adsorbate. We found that the adsorption of pyridine molecules on single AuNRs though nitrogen-gold interactions leads to an increase of the localized surface plasmon resonance (LSPR) linewidth. However, pyridine molecules were not adsorbed effectively on AuNR surfaces having a capping reagent. This study allows us to gain insight into the effect and role of the capping reagent in pyridine-induced CID. Furthermore, pyridine was revealed to induce a strong CID through the interaction of the nitrogen atom with the Au surface, provided the capping material was previously removed from the AuNRs by oxygen plasma treatment. Finally, we demonstrated that CID could be used to sense pyridine and its derivatives in real-time.

Single-particle correlation study: chemical interface damping induced by biotinylated proteins with sulfur in plasmonic gold nanorods.

Plasmonic gold nanoparticles can be an efficient source of hot electrons that can transfer to adsorbed molecules for photochemistry, followed by broadening of the homogeneous localized surface plasmon resonance (LSPR) linewidth. Although chemical interface damping (CID) is one of the main decay processes, it is the most poorly understood damping mechanism in gold nanoparticles. Herein, to better understand CID and to find new functional groups that can induce CID as an alternative to thiol groups (-SH, sulfhydryl groups), we carried out scanning electron microscopy (SEM) correlated dark-field (DF) scattering studies of gold nanorods (AuNRs) at the single-particle level. We found that biotin with sulfur can lead to strong plasmon damping in single AuNRs. We chose biotin in this study because it is widely used as a linker that can selectively bind to streptavidin in many biological sensing experiments. We further demonstrated the possibility of real-time detection of biological molecules, specifically biotinylated BSA proteins, by means of CID in single AuNRs. Therefore, this study allows us to gain a deeper insight into how adsorbate molecules with sulfur affect CID, which is an important step toward developing a CID-based LSPR biosensor to detect real biological molecules having sulfur or thiol groups without interference from the medium dielectric constant in single AuNRs.

Single particle study: size and chemical effects on plasmon damping at the interface between adsorbate and anisotropic gold nanorods.

Plasmon damping in gold nanorods (AuNRs) results in the broadening of the localized surface plasmon resonance (LSPR) linewidth. LSPR broadening of plasmonic nanoparticles is useful to maximize the fraction of light energy in light harvesting and energy conversion transferred to molecules attached on the surface. However, our understanding of plasmon decay channels in AuNRs is still limited, and chemical interface damping (CID) is the most poorly understood damping mechanism. Herein, to better understand plasmon damping including CID, we performed a single particle study of plasmonic anisotropic AuNRs using dark-field (DF) microscopy and spectroscopy. First, we examined the size-dependent broadening of the homogeneous LSPR linewidth of single AuNRs in water with three different aspect ratios (ARs) at a fixed diameter of 25 nm. The LSPR linewidth increased with a decrease in the AR of single AuNRs because of the reduced average distance of hot electrons to the surface. Second, we investigated the effect of refractive index variation of the surrounding medium on the LSPR linewidth in single AuNRs of three different sizes. The LSPR linewidth in single AuNRs remained almost constant regardless of their sizes while increasing the dielectric constant of the medium. Finally, we examined the effect of adsorbate thiol molecules on the homogeneous LSPR linewidth of single AuNRs in ethanol. The LSPR linewidth was broadened upon increasing the carbon chain length of 1-alkanethiol, and 4-nitrothiophenol with a strong electron withdrawing group induced a large broadening of the LSPR linewidth. Furthermore, single AuNRs with smaller ARs showed a larger broadening of the LSPR linewidth in the presence of adsorbate thiol molecules through CID. Therefore, this investigation provides a deeper insight into the size effect on plasmon damping including CID induced by the chemical interface effect in single AuNRs.

Effects of breccia and water contents on the mechanical properties of fault-core-zone materials.

Determining the mechanical properties of fault-core-zone materials is challenging because of the low strength of such materials, which affects field sampling, specimen preparation, and laboratory testing. We overcame this problem by preparing and testing mechanical properties of 132 artificial fault-core-zone specimens consisting of mixtures of breccia, sand, clay, and water. The unconfined compressive strength (UCS), elastic modulus (E), and penetration resistance value (PRV) of these fault-core-zone materials were measured, and the effects of breccia content and water content on mechanical properties were assessed. Results show that UCS is inversely proportional to breccia content and water content, and that E is inversely proportional to water content. Furthermore, the inverse relationship of UCS with water content varies with breccia content. UCS is proportional to both PRV and E, and the relationship for each varies with breccia content. High coefficients of determination (R2 = 0.62-0.88) between the parameters suggest that breccia content, water content, and PRV are potentially useful parameters for estimating the mechanical properties of fault core zones.