Photothermal Atomic Force Microscopy Coupled with Infrared Spectroscopy (AFM-IR) Analysis of High Extinction Coefficient Materials: A Case Study with Silica and Silicate Glasses.

Photothermal atomic force microscopy coupled with infrared spectroscopy (AFM-IR) brings significant value as a spatially resolved surface analysis technique for disordered oxide materials such as glasses, but additional development and fundamental understanding of governing principles is needed to interpret AFM-IR spectra, since the existing theory described for organic materials does not work for materials with high extinction coefficients for infrared (IR) absorption. This paper describes theoretical calculation of a transient temperature profile inside the IR-absorbing material considering IR refraction at the interface as well as IR adsorption and heat transfer inside the sample. This calculation explains the differences in peak positions and amplitudes of AFM-IR spectra from those of specular reflectance and extinction coefficient spectra. It also addresses the information depth of the AFM-IR characterization of bulk materials. AFM-IR applied to silica and silicate glass surfaces has demonstrated novel capability of characterizing subsurface structural changes and surface heterogeneity due to mechanical stresses from physical contacts, as well as chemical alterations manifested in surface layers through aqueous corrosion.

Estimating Internal Stress of an Alteration Layer Formed on Corroded Boroaluminosilicate Glass through Spectroscopic Ellipsometry Analysis.

Aqueous corrosion of glass may result in the formation of an alteration layer in the glass surface of which chemical composition and network structure are different from those of the bulk glass. Since corrosion occurs far below the glass-transition temperature, the alteration layer cannot fully relax to the new structure with the lowest possible energy. Molecular dynamics simulations suggested that such a network will contain highly strained chemical bonds, which can be manifested as a stress in the alteration layer. Common techniques to measure stress in thin films or surface layers were found inadequate for thick monolithic glass samples corroded in water. Here, we explored the use of spectroscopic ellipsometry to test the presence of internal stress in the alteration layer formed by aqueous corrosion of glass. A procedure for analyses of spectroscopic ellipsometry data to determine birefringence in the alteration layer was developed. Findings with the established fitting procedure suggested that a stress builds up in the corroded surface layer of a boroaluminosilicate glass if there is a change in relative humidity, pH, or electrolyte concentration of the environment to which the glass surface is exposed. A similar process may occur in other types of glass, and it may affect the surface properties of corroded glass objects.

Mechanical characterization of in vitro-formed short-term salivary pellicle.

Human saliva consists of approximately 98% water and a variety of electrolytes and proteins. Those proteins can be selectively adsorbed onto the enamel surface. The cuticular material formed on the enamel surface is termed acquired salivary pellicle (ASP), which is critical for the health of oral mucosa and teeth. The ASP is composed of a inner layer and a outer layer. The lubricating properties of ASP are closely associated with the inner layer. The aim of this research is to characterize the structural and mechanical properties of the inner layer of ASP. In this paper, enamel specimens were immersed for 1 min in human saliva. The ASP formed in vitro within 1 min was studied using a nanoindenter. The results show that the thickness of the inner layer of ASP is approximately 18 nm. Moreover, the inner layer is a heterogeneous pellicle with a gradient in density. From the surface of the inner layer to the enamel surface, the density and mechanical properties gradually increase. The research results may be helpful to extend the understanding of mechanical properties of salivary pellicle and to the oral hygiene industry for diagnose oral diseases.

Humidity Dependence of Tribochemical Wear of Monocrystalline Silicon.

The nanowear tests of monocrystalline silicon against a SiO2 microsphere were performed using an atomic force microscope in air as a function of relative humidity (RH=0%-90%) and in liquid water at a contact pressure of about 1.20 GPa. The experimental results indicated that RH played an important role in the nanowear of the Si/SiO2 interface. In dry air, a hillock-like wear scar with a height of ∼0.4 nm was formed on the silicon surface. However, with the increase of RH, the wear depth on the silicon surface first increased to a maximum value of ∼14 nm at 50% RH and then decreased below the detection limit at RH above 85% or in water. The transmission electron microscopy analysis showed that the serious wear on the silicon surface at low and medium RHs occurred without subsurface damage, indicating that the wear was due to tribochemical reactions between the Si substrate and the SiO2 counter surface, rather than mechanical damages. The RH dependence of the tribochemical wear could be explained with a model involving the formation of "Si-O-Si" chemical bonds (bridges) between two solid surfaces. The suppression of tribochemical wear at high RHs or in liquid water might be attributed to the fact that the thickness of the interfacial water layer is thick enough to prevent the solid surfaces from making chemical bridges. The results may help us understand the nanowear mechanism of silicon that is an important material for dynamic microelectromechanical systems.

Tribology of Si/SiO2 in humid air: transition from severe chemical wear to wearless behavior at nanoscale.

Wear at sliding interfaces of silicon is a main cause for material loss in nanomanufacturing and device failure in microelectromechanical system (MEMS) applications. However, a comprehensive understanding of the nanoscale wear mechanisms of silicon in ambient conditions is still lacking. Here, we report the chemical wear of single crystalline silicon, a material used for micro/nanoscale devices, in humid air under the contact pressure lower than the material hardness. A transmission electron microscopy (TEM) analysis of the wear track confirmed that the wear of silicon in humid conditions originates from surface reactions without significant subsurface damages such as plastic deformation or fracture. When rubbed with a SiO2 ball, the single crystalline silicon surface exhibited transitions from severe wear in intermediate humidity to nearly wearless states at two opposite extremes: (a) low humidity and high sliding speed conditions and (b) high humidity and low speed conditions. These transitions suggested that at the sliding interfaces of Si/SiO2 at least two different tribochemical reactions play important roles. One would be the formation of a strong "hydrogen bonding bridge" between hydroxyl groups of two sliding interfaces and the other the removal of hydroxyl groups from the SiO2 surface. The experimental data indicated that the dominance of each reaction varies with the ambient humidity and sliding speed.