Jessica Denayer

Electrochemical and spectroscopic study of the self-assembling mechanism of normal and chelating alkanethiols on copper.

The self-assembly of aliphatic thiol (RSH), dithiol (R(SH)(2)), and dithiocarboxylic acid (RS(2)H) onto mildly oxidized and highly oxidized copper was studied in real time by in situ electrochemical impedance spectroscopy (EIS). Ex situ characterization of the films was carried out using linear sweep voltammetry (LSV), polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS), and X-ray photoelectron spectroscopy (XPS). In situ EIS studies found a very fast adsorption of RSH, R(SH)(2), and RS(2)H (within 10-15 s). This fast adsorption step is followed by the long-term additional adsorption and consolidation of SAM. However, the self-assembly of RS(2)H passes through an intermediate step of molecule rearrangement for around 10 to 30 min after around 2 to 7 min of self-assembly. The binding of both sulfur moieties of R(SH)(2) with Cu happens simultaneous. The oxide reduction capacity of RSH, R(SH)(2), and RS(2)H was good. However, the XPS studies showed the decomposition of RS(2)H-based SAMs to Cu(2)S. Monolayers prepared on both mildly oxidized and heavily oxidized Cu with R(SH)(2) had the highest stability. Monolayers of RS(2)H showed the least stability on both mildly oxidized and heavily oxidized Cu. Although RSH-based SAMs had good organization on both mildly oxidized and highly oxidized Cu, R(SH)(2)-based SAMs did not show good organization in either case. The RS(2)H monolayer had good organization only on mildly oxidized Cu.

Bilayers Coating on Titanium Surface: The impact on the Hydroxyapatite Initiation

Most of the actual orthopaedic devices, widely made of titanium and its alloys, present different weaknesses like ions release and risks of loosening over a long period. To solve such problems, new developments in surface modification are crucial. This work is an extension of our recent effort on the development and improvement of a multifunctional inorganic/organic bilayers coating. A thin tantalum oxide layer is formed by sol-gel synthesis followed by the modification with organophosphonic acids of the tantalum oxide layer. We focus in particular on the effect of the bilayers coating on corrosion resistance and hydroxyapatite growth rate by immersion in a simulated body fluid solution. It is also highlighted that the structure of the organophosphonic acid is of major importance on the osteoinduction character of the material.