Impact of pH, Dissolved Inorganic Carbon, and Polyphosphates for the Initial Stages of Water Corrosion of Copper Surfaces Investigated by AFM and NEXAFS

Abstract Nanoscale studies at the early stages of the exposure of copper surfaces after systematic treatments in synthesized water solutions can provide useful information about corrosion processes. The corrosion and passivation of copper surfaces as influenced by pH, dissolved inorganic carbon (DIC) and polyphosphate levels were investigated with nanoscale resolution, to gain insight about changes in surface morphology and the composition of adsorbates. Information regarding the surface morphology after chemical treatment was provided by atomic force microscopy (AFM) and the corresponding chemical composition of treated surfaces was obtained with near-edge X-ray absorption fine structure (NEXAFS). Changes in the surface topography of copper samples were readily detected within only 6 to 24 hours of exposure to water solutions. Topographic views of surface changes are presented to compare the growth of adsorbate layers that take place during the evolution of mineral deposits. Slight changes in the pH and concentrations of phosphates in the water samples have a substantial impact on the rate of growth and composition of surface deposits. These studies provide insight on the mechanisms and resulting chemical constituents that lead to surface passivation or corrosion of copper, simulating conditions that occur in water distribution systems

The interaction of hydrogen with simple and noble metals surfaces

The basic concepts of adsorption are illustrated by the investigation of a simple adsorbate (hydrogen) with the simplest metals (simple and noble metals). Theoretically tractable, these systems serve as an excellent test of our basic understanding of chemisorption. The interaction of atomic and molecular hydrogen with the surfaces of Mg(0001), Mg(1120), Li(110), K(110), Ag(110), and Ag(111) have been studied with a variety of experimental probes. In all cases, no evidence for H\sb2 associative or dissociative adsorption is observed at the substrate temperature investigated $(\geq$90 K). In the case of the simple metals below 150 K, atomic hydrogen is bound to the surfaces in a strongly chemisorbed state (hydride). For Mg and Li, the hydride is localized to the surface wherein the substrate electron density is lower than the bulk. Because of the low electron density, hydrogen is absorbed into the bulk of K at low temperatures and forms a bulk-hydride phase. However, these low-temperature phases are metastable. In the case of Mg, hydrogen moves into lower energy configuration bonding sites which are closer to or below the surface plane. However, the hydride characteristics are absent; the H atom is effectively screened because of the higher jellium density. In contrast, upon annealing, hydrogen is absorbed into the bulk of Li and K and phase separation occurs forming regions of clean metal and bulk hydride areas. The results are compared to theoretical studies; the propensity for absorption over adsorption is understood in terms of jellium-based models. In the case of silver, at 100 K, atomic hydrogen bonds in trigonal sites on both the (110) and (111) surfaces. As a function of H concentration, a sequence of lattice gas superstructures is observed; these phases are accompanied by small H-induced displacements of the substrate surface atoms. In the case of Ag(110), the low-temperature phase is metastable; upon annealing, hydrogen desorption from low energy states is accompanied by a surface reconstruction. Although silver is a noble metal, many of the H-induced properties are characteristic of similar H/transition systems

Optical excitations of metallic nanoclusters buried in TiO 2 for solar photochemistry

Ag deposited on TiO2(110) forms nanoclusters ∼5 nm across and 2 nm in height, shown by STM. These nanoclusters exhibit a plasmon loss at 3.8 eV as determined by EELS yet the substrate Fuchs-Kliewer phonon modes remain, indicating that the exposed TiO2 is not perturbed by the Ag clusters. Titania is grown on top of these clusters by evaporation of Ti and subsequent oxidation and both EELS and optical measurements show that new excitations are produced in the 1.5-2 eV range, a much better match to the solar spectrum than the 3.8 eV Ag plasmon. AFM measurements indicate that the Ag clusters retain their morphology upon titania coating. © 2009 SPIE

Pattern transfer by direct photo etching of poly(vinylidene fluoride) using X rays

A direct pattern transfer method has been developed by photo etching poly(vinylidene fluoride) (PVDF) using X rays (1-16 keV) from a synchrotron storage ring. The ability to pattern thin film of PVDF, a piezoelectric, pyroelectric and ferroelectric polymer, has potential applications in the areas of MEMS, nonlinear optics, and nonvolatile ferroelectric random access memory technology. Without the use of any reactive chemical gas, a maximum etched depth in excess of 9 μm is achieved. The etched depth for a given photon energy approaches saturation with respect to exposure time. An in situ mass spectrometry revealed the evolution of hydrogen, fluorine, and hydrogen fluoride species. The etched regions turned dark in color indicating a possible increase in the fraction of carbon atoms. The X-ray transmittance of photo etched PVDF approached that of a pure carbon as the exposure time is increased. Upon etching the root mean-square surface roughness of the etched portion increased by more than a factor of two. The rate of etching increased at elevated sample temperatures

Vibrational and Structural Studies of Environmentally Persistent Free Radicals Formed by Phenol-Dosed Metal Oxide Nanoparticles

Environmentally persistent free radicals (EPFRs) are formed by the adsorption of substituted aromatic precursors on the surface of metal oxides and are known to have significant health and environmental impact due to their unique stability. In this article, the formation of EPFRs is studied by adsorption of phenol on ZnO, CuO, Fe2O3, and TiO2 nanoparticles (â\u27¼10-50 nm) at high temperatures. Electron paramagnetic resonance indicates the formation of phenoxyl-type radicals. Fourier transform infrared spectroscopy provides further evidence of EPFR formation by the disappearance of-OH groups, indicating the chemisorption of the organic precursor on the metal oxide surface. These results are further confirmed by inelastic neutron scattering, which shows both ring out-of-plane bend and C-H in-plane bend motions characteristic of phenol adsorption on the studied systems. Also, the changes in the oxidation state of the metal cations are investigated by X-ray photoelectron spectroscopy, which shows that the direction of electron transfer (redox) during phenol chemisorption is strongly dependent on surface properties as well as surface defects of the metal oxide surface

Nanoscale surface characterization of aqueous copper corrosion: Effects of immersion interval and orthophosphate concentration

Morphology changes for copper surfaces exposed to different water parameters were investigated at the nanoscale with atomic force microscopy (AFM), as influenced by changes in pH and the levels of orthophosphate ions. Synthetic water samples were designed to mimic physiological chemistries for drinking water, both with and without addition of orthophosphate over a pH range 6.5-9. Copper surfaces treated with orthophosphate as a corrosion inhibitor after 6 and 24 h were evaluated. Tapping mode AFM images revealed dosing of the water with 6 mg/L of orthophosphate was beneficial in retarding the growth of copper by-products. The chemical composition and oxidation state of the surface deposits were characterized with X-ray diffraction (XRD), near edge X-ray absorption fine structure (NEXAFS) spectroscopy and Fourier transform infrared spectroscopy (FTIR). © 2013 Elsevier B.V. All rights reserved

Formation and stability of dense arrays of Au nanoclusters on hexagonal boron nitride/Rh(111)

We have studied the nucleation and growth of Au clusters at submonolayer and greater coverages on the h-BN nanomesh grown on Rh(111) by means of scanning tunneling microscopy (STM), x-ray photoelectron spectroscopy (XPS), and density functional theory (DFT). STM reveals that submonolayer Au deposited at 115 K nucleates within the nanomesh pores and remains confined to the pores even after warming to room temperature. Whereas there is a propensity of monoatomic high islands at low temperature, upon annealing, bi- and multilayer Au clusters emerge. Deposition of higher coverages of Au similarly results in Au clusters primarily confined to the nanomesh pores at room temperature. XPS analysis of core-level electronic states in the deposited Au shows strong final-state effects induced by restricted particle size dominating for low Au coverage, with indications that larger Au clusters are negatively charged by interaction through the h-BN monolayer. DFT calculations suggest that the structure of the Au clusters transitions from monolayer to bilayer at a size between 30 and 37 atoms per cluster, in line with our experiment. Bader charge analysis supports the negative charge state of deposited Au. © 2014 American Physical Society