High-voltage nanoimprint lithography of refractory metal films.

Local oxidation of metal, semiconductor, and polymer surfaces has provided a common basis from which to explore fundamental principles of nanolithography and prototype functional nanostructures for many years now. This article summarizes an investigation of local oxidation for iron and Group IV metal thin films using both scanning probe microscopy and high-voltage nanoimprinting methods. We illustrate how the underlying kinetics of metal oxidation in the presence of nitrogen, which is incorporated into the metal film during the growth process, is dramatically enhanced compared with that of single-crystal silicon. We then go on to demonstrate subsequent selective etching of latent features and a potential magnetic application.

Investigation of the characteristics of platinum group metal modified alumina nanofibers.

Alumina nanofibers containing either platinum or rhodium crystalline nanoparticles have been successfully fabricated by electrospinning a solution of polyvinylpyrrolidone mixed with platinum or rhodium chloride and subsequent calcination and hydrogen reduction. Transmission electron microscopy images indicate that the platinum and rhodium nanoparticles are well dispersed on the electrospun alumina nanofibers. X-ray diffraction results demonstrate that the platinum and rhodium nanoparticles are crystalline, while the alumina matrix is amorphous. Furthermore, X-ray photoelectron spectroscopy was used to investigate the chemical nature of these nanofibers containing noble metals before and after calcination and hydrogen processing.

Direct observation of chemical bond dynamics on surfaces.

The dynamics of chemisorbed species as they swing to-and-fro on their adsorption sites may be directly observed with electron-stimulated desorption. The observation of the thermal disorder in adsorbate chemical bond directions, through studies of the thermal excitation of librational modes, allows one to visualize the potential energy surfaces controlling the structure and dynamics of adsorbates on single crystal metal and semiconductor surfaces. This information may be useful in understanding surface diffusion as well as the spatial aspects of surface chemical reactions.

Differences in the surface composition of seemingly similar F75 cobalt-chromium micron-sized particulates can affect synovial fibroblast viability.

We present data and analyses concerning the cytotoxicity and bioreactivity associated with the surface composition of fine metal particulates that are similar to those commonly released in the body by prostheses used in total joint replacement surgery. Here we study the bulk and surface compositions of three separately procured cobalt-chromium-molybdenum (CoCrMo) micron-sized particulate powders, each identified by their corresponding vendor as being ASTM F75 grade material. We use energy dispersive spectroscopy (EDS) to verify the bulk metallic composition and X-ray photoelectron spectroscopy (XPS) to examine the surface metallic composition of each CoCrMo powder. Cultured synovial fibroblasts were then exposed to the particulate powders to see how the metallic surfaces might affect cellular viability. Results indicate that while the bulk metallic composition of each CoCrMo powder was similar, the surface metallic compositions were found to be dramatically different and yielded equally dramatic differences in terms of cytotoxicity and bioreactivity of synovial fibroblast in culture.

Microbial adhesion to zirconium alloys.

We present data and analyses concerning the adhesion of clinically relevant Staphylococcus aureus, Staphylococcus epidermidis, and Pseudomonas aeruginosa (bacteria) and Candida albicans (yeast) to Zircaloy-2 (Zry-2) and Zircadyne-705 (Zr705) surfaces. These zirconium-based materials are similar to those now being used in total hip and knee replacements. Here we study clinical strains of microbes under shaken and stationary exposure conditions, and their ability to adhere to Zr surfaces having different oxide thicknesses. We use X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), viable counts, endotoxin assays, and statistical analysis methods, and demonstrate a predictive model for microbial adhesion based on XPS data.

Measuring and modeling thermal fluctuations at nanometer length scales.

The size of mechanical, electrical, and optical devices continues to be reduced. As the length scales of such devices decrease, coupling to the external environment greatly increases. Thermal fluctuations due to momentum exchange between air molecules and micron scale devices under ambient conditions can effect the dynamics of a system. To illustrate this we use an atomic force microscope cantilever and detection system to measure background noise and thermal fluctuations of a micron size beam. The beam is modeled by a Langevin-type equation that is externally forced by a white-noise spectrum having an analytic as opposed to a statistical form. This model is compared with experimental data. It is found that at higher frequencies, a white-noise spectrum is not sufficient to model such a system. We modify the forcing spectrum so that it decays at higher frequencies and subsequently achieve closer agreement between the model and the experimental observations.

A comparison of the effects of prosthetic and commercially pure metals on retrieved human fibroblasts: the role of surface elemental composition.

The most common clinical cause of long-term failure in total joint replacement surgery is inflammatory aseptic osteolysis; a condition in which bone surrounding the prosthetic implant, and to which the implant is attached, is resorbed, rendering the artificial device loose and painful. Historically, the severity of this bone resorptive process has been thought to be predominately attributed to the size and shape of wear-debris particles, particularly the metallic particulates that interact biologically/immunologically with cells in the joint. Because the cytotoxic reactions are the result of interactions between the cells and the surfaces of the particulates, it is not clear in the realm of orthopedics to what extent different surface stoichiometric ratios contribute to instigating bioreactive or cytotoxic cellular responses that can lead to aseptic osteolysis. Using energy dispersive X-ray spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS), this study presents data and analyses concerning the respective bulk and surface stoichiometric ratios of two commercially pure metal micro-particulates (tantalum and titanium), two prosthetic F75 cobalt-chromium-molybdenum alloy micro-particulates, and prosthetic F136 titanium-aluminum-vanadium alloy micro-particulates, each containing elements common to total joint replacement surgery. Cell culture viability data from four volunteer donors are also presented, which suggest that micro-particulates containing large percentages of surface titanium and aluminum can cause moderate cellular toxicity, and micro-particulates containing large percentages of surface cobalt can result in extremely severe cellular toxicity. This work further suggests that surface analysis techniques, such as XPS, are essential to determine surface elemental characterization of metallic materials prior to interpreting cellular response results.

An introduction of various spectroscopic methods to identify in vivo metal wear in total knee arthroplasty.

While the industrial community already employs multiple surface analytical techniques to study compositional wearing of various metallic and nonmetallic materials, as yet, these methods have not been widely introduced into the biological community. We report on a novel approach, using the industrial spectroscopic techniques of X-ray photoelectron spectroscopy, micro-Raman spectroscopy, and scanning electron microscopy equipped with energy dispersive spectroscopy, to identify the fine wear particulates and other impurities deposited within the knee-joint following total knee arthroplasty. In this study, synovial fluid was extracted from knee-joints scheduled for revision of total knee arthroplasty. The small debris flake formed by centrifugation of the fluid was analyzed using the spectroscopic techniques mentioned above. These nondestructive techniques were successful in identifying numerous micron and submicron sized metallic particulates that appear to emanate from both the prosthetic bearing (articulating) surfaces and from backside (nonarticulating) surfaces, even when gross wearing of the prosthetic device was not detectable by direct visual inspection intraoperatively. Most interesting is that the ratio of the in vivo metallic debris is approximately the same ratio as that of the manufactured alloy, indicating prosthetic wearing as opposed to chemical dissolution. More importantly, using these spectroscopic techniques to probe both the surface and below the surface of the synovial deposits, we identify an inhomogeneous distribution of the wear debris. This indicates the need to use multiple techniques in order to adequately identify the elemental composition of the prosthetic wear material.

High-voltage SPM oxidation of ZrN: materials for multiscale applications.

Scanning probe microscope (SPM) oxidation was used to form zirconium oxide features on 200 nm thick ZrN films. The features exhibit rapid yet controlled growth kinetics, even in contact mode with 70 V dc applied between the probe tip and substrate. The features grown for times longer than 10 s are higher than 200 nm, and reach more than 1000 nm in height after 300 s. Long-time oxidation experiments and selective etching of the oxides and nitrides lead us to propose that as the oxidation reaches the silicon substrate, delamination occurs with the simultaneous formation of a thin layer of new material at the ZrN/Si interface. High-voltage oxide growth on ZrN is fast and sustainable, and the robust oxide features are promising candidates for multiscale (nanometre-to-micrometre) applications.