Interpretation of electrochemical measurements made during micro-scale abrasion-corrosion

This paper brings together and analyzes recent work based on the interpretation of the electrochemical measurements made on a modified micro-abrasion-corrosion tester used in several research programmes. These programmes investigated the role of abradant size, test solution pH in abrasion-corrosion of biomaterials, the abrasion-corrosion performance of sintered and thermally sprayed tungsten carbide surfaces under downhole drilling environments and the abrasion-corrosion of UNS S32205 duplex stainless steel. Various abrasion tests were conducted under two-body grooving, three-body rolling and mixed grooving-rolling abrasion conditions, with and without abrasives, on cast F75 cobalt-chromium-molybdenum (CoCrMo) alloy in simulated body fluids, 2205 in chloride containing solutions as well as sprayed and sintered tungsten carbide surfaces in simulated downhole fluids. Pre- and post-test inspections based on optical and scanning electron microscopy analysis are used to help interpret the electrochemical response and current noise measurements made in situ during micro-abrasion-corrosion tests. The complex wear and corrosion mechanisms and their dependence on the microstructure and surface composition as a function of the pH, abrasive concentration, size and type are detailed and linked to the electrochemical signals. The electrochemical versus mechanical processes are plotted for different test parameters and this new approach is used to interpret tribo-corrosion test data to give greater insights into different tribo-corrosion systems. Thus new approaches to interpreting in-situ electrochemical responses to surfaces under different abrasive wear rates, different abrasives and liquid environments (pH and NaCl levels) are made. This representation is directly related to the mechano-electrochemical processes on the surface and avoids quantification of numerous synergistic, antagonistic and additive terms associated with repeat experiments. (C) 2010 Elsevier Ltd. All rights reserved.

Micro- and Nano-scale Tribo-Corrosion of Cast CoCrMo

Previous studies have established that some of the wear damage seen on cast CoCrMo joint surface is caused by entrained third-body hard particles. In this study, wet-cell micro-indentation and nano-scratch tests have been carried out with the direct aim of simulating wear damage induced by single abrasive particles entrained between the surfaces of cast CoCrMo hip implants. In situ electrochemical current noise measurements were uniquely performed to detect and study the wear-induced corrosion as well as the repassivation kinetics under the micro-/nano-scale tribological process. A mathematical model has been explored for the CoCrMo repassivation kinetics after surface oxide film rupture. Greater insights into the nature of the CoCrMo micro-/nano-scale wear-corrosion mechanisms and deformation processes are determined, including the identification of slip band formation, matrix/carbide deformation, nanocrystalline structure formation and strain-induced phase transformation. The electrochemical current noise provides evidence of instantaneous transient corrosion activity at the wearing surface resulting from partial oxide rupturing and stripping, concurrent with the indent/scratch.

A '3-body' abrasion wear study of bioceramics for total hip joint replacements

The current study focuses on the effect of the material type and the lubricant on the abrasive wear behaviour of two important commercially available ceramic on ceramic prosthetic systems, namely, Biolox(R) forte and Bioloxl(R) delta (CeramTec AG, Germany). A standard microabrasion wear apparatus was used to produce '3-body' abrasive wear scars with three different lubricants: ultrapure water, 25 vol% new-born calf serum solution and 1 wt% carboxymethyl cellulose sodium salt (CMC-Na) solution. 1 mu m alumina particles were used as the abrasive. The morphology of the wear scar was examined in detail using Atomic Force Microscopy (AFM) and Scanning Electron Microscopy (SEM). Subsurface damage accumulation was investigated by Focused Ion Beam (FIB) cross-sectional milling and Transmission Electron Microscopy (TEM). The effect of the lubricant on the '3-body' abrasive wear mechanisms is discussed and the effect of material properties compared. (C) 2009 Elsevier B.V. All rights reserved.

Abrasive size and concentration effects on the tribo-corrosion of cast CoCrMo alloy in simulated body fluids

Some retrieved CoCrMo hip implants have shown that abrasive wear is one of the possible wear mechanisms invoked within such joints. To date, little work has focused on the third body abrasion of CoCrMo and therefore there is a general lack of understanding of the effect of abrasive size and volume concentration on the tribo-corrosion performance of the CoCrMo alloys. The present work assessed the tribo-corrosion behaviour of cast CoCrMo (F-75) under various abrasion-corrosion conditions by using a modified microabrasion tester incorporating a three-electrode electrochemical cell. The effects of reduced abrasive size/hardness and volume concentration, as well as the role of proteins on the tribo-corrosion performance of the cast CoCrMo alloy were addressed. The correlation between electrochemical and mechanical processes for different abrasion-corrosion test conditions has been discussed in detail. Results show that the reduction in abrasive size and volume concentration can significantly affect the abrasion-corrosion wear mechanisms and the wear-induced corrosion response of the material. The finding of this study implies that the smaller/softer third body particles generated in vivo could also result in significant wear-induced corrosion and therefore potential metal ion release, which could be potentially detrimental to both the patient health and the life span of the implants. © 2009 Elsevier Ltd. All rights reserved.

Micro-abrasion-corrosion of cast CoCrMo-Effects of micron and sub-micron sized abrasives

The abrasion damage on retrieved CoCrMo based hip joints is reported to be influenced by the entrainment of micron and sub-micron sized debris/hard particles. This paper represents the first attempt to look into the effects of relatively soft abrasives with micron and sub-micron dimensions on the abrasion mechanisms and the abrasion-corrosion performance of the cast CoCrMo in simulated hip joint environments. A modified micro-abrasion tester incorporating a liquid tank and a three-electrode electrochemical cell was used. Al O (300 nm and 1 μm) and sub-micron sized BaSO abrasives were chosen as being comparable in the size and hardness to the wear particles found in vivo. Results show that the specific wear rates of cast CoCrMo are dependent on the abrasive particle size, hardness and volume concentration. Larger particle size, higher hardness and greater abrasive volume fractions gave greater wear rates. The wear-induced corrosion current generally increases with increasing wear rates, and the presence of proteins seems to suppress the wear-induced corrosion current especially when abrasive volume fractions were high. This study shows that the nature of abrasives and the test solutions are both important in determining the wear mechanisms and the abrasion-corrosion response of cast CoCrMo. These findings provide new and important insights into the in vivo wear mechanisms of CoCrMo. © 2009 Elsevier B.V. All rights reserved.

Extracellular DNA impedes the transport of vancomycin in Staphylococcus epidermidis biofilms pre-exposed to sub-inhibitory concentrations of vancomycin

Staphylococcus epidermidis biofilm formation is responsible for the persistence of orthopedic implant infections. Previous studies have shown that exposure of S. epidermidis biofilms to sub-MICs of antibiotics induced an increased level of biofilm persistence. BODIPY FL-vancomycin (a fluorescent vancomycin conjugate) and confocal microscopy were used to show that the penetration of vancomycin through sub-MIC-vancomycin-treated S. epidermidis biofilms was impeded compared to that of control, untreated biofilms. Further experiments showed an increase in the extracellular DNA (eDNA) concentration in biofilms preexposed to sub-MIC vancomycin, suggesting a potential role for eDNA in the hindrance of vancomycin activity. Exogenously added, S. epidermidis DNA increased the planktonic vancomycin MIC and protected biofilm cells from lethal vancomycin concentrations. Finally, isothermal titration calorimetry (ITC) revealed that the binding constant of DNA and vancomycin was 100-fold higher than the previously reported binding constant of vancomycin and its intended cellular D-Ala-D-Ala peptide target. This study provides an explanation of the eDNA-based mechanism of antibiotic tolerance in sub-MIC-vancomycin-treated S. epidermidis biofilms, which might be an important factor for the persistence of biofilm infections.

Welland Canal Survey of Lands Philip Shaver 1829

Survey map and description of Philip Shaver's land created by The Welland Canal Company. Included is a written description of the land along with a drawing of the land. Noteable features include; locks no. 16, 17, 18, 19, 20, ravine, corner stone, St. Catharines ditch, waste weir, concession line, barn. Surveyor notes are seen in pencil on the map. The deed for the land is dated October 1st, 1829.

Welland Canal Survey of Lands Philip Carrol, 1830, 1846, n.d.

Survey map and description of Philip Carrol's land created by The Welland Canal Company. Included are three written descriptions of the lands along the Northern Reservoir, Southern Reservoir as well as the Canal and Reservoir with a drawing of the aforementioned lands. Noteable features for the Northern Reservoir include; line between Philip Carrol's land and Widow McAlpine's land. The land contains 9 acres, 2 roads and 24 perches of wood land. The survey is dated 1830. Noteable features for the Southern Reservoir include; Road to shorthills, side line North, and Watson's land. This survey is not dated. Noteable features for the Canal and Reservoir include; West line of lot, lot.213. The land contains 9 acres and 5 perches. The surveyor's updates for this survey are dated 1846. Surveyor notes are seen in pencil on the map.See also Pp 109-113

Province of Upper Canada Grant to Philip Chesneau Delatre

Province of Upper Canada Grant (vellum) to Philip Chesneau Delatre, late Lieutenant Colonel from the Township of Stamford. He is granted 633 acres in lot no.4 of the 4th Concession; lot no.2 in the 2nd Concession; lot no. 3 in the 3rd Concession and lot no.9 in the 5th Concession in Blandford in the County of Oxford. This was registered Nov. 3, 1836 – Folio no. 67, Oct. 31, 1836.

Province of Upper Canada Grant to Philip Chesneau Delatre

Province of Upper Canada Grant (vellum) to Philip Chesneau Delatre, late Lieutenant Colonel, of the Township of Stamford. He is granted 600 acres in the north and south halves of lot no. 2 in the 3rd Concession; south and north halves of lot no. 3 in the 2nd Concession; south and north halves of lot no. 2 in the 3rd Concession and south and north halves of lot no. 8 in the 11th Concession in the Township of Blandford in the County of Oxford. This was registered Nov. 13, 1837 – Folio no. 51, Oct. 25, 1837.

Province of Upper Canada Grant to Philip Chesneau Delatre

Province of Upper Canada Grant (vellum) to Philip Chesneau Delatre, late Lieutenant Colonel, of the Township of Stamford. He is granted 74 acres in the east and west halves of lot no. 36 in the 16th Concession and broken lot no. 11 in the 18th Concession in the Township of Zorra in the County of Oxford. This was registered Nov. 13, 1837 – Folio 50, Oct. 26, 1837.