Tribological properties of mems materials measured on a small-scale device

Micro-electro-mechanical systems, MEMS, is a rapidly growing interdisciplinary technology within the general field of Micro-Systems Technology which deals with the design and manufacture of miniaturised machines with major dimensions at the scale of tens, to perhaps hundreds, of microns. Because they depend on the cube of a representative dimension, component masses and inertias rapidly become small as size decreases whereas surface and tribological effects, which often depend on area, become increasingly important. Although MEMS components and their areas of contact are small, tribological conditions, measured by contact pressures or acceptable wear rates, are demanding and technical and commercial success will require careful measurement and precise control of surface topography and properties. Fabrication of small numbers of MEMS devices designed to test potential material combinations can be prohibitively expensive and thus there is a need for small scale test facilities which mimic the contact conditions within a micro-machine without themselves requiring processing within a full semiconductor foundry. The talk will illustrate some initial experimental results from a small-scale experimental device which meets these requirements, examining in particular the performance of Diamond-Like-Carbon coatings on a silicon substrate. Copyright © 2005 by ASME.

Nanodiamond formation by hot-filament chemical vapor deposition on carbon ions bombarded Si

Nanocrystalline diamond films were grown by a two-step process on Si(1 0 0) substrate, which was first pretreated by pure carbon ions bombardment. The bombarded Si substrate was then transformed into a hot-filament chemical vapor deposition (HFCVD) system for further growth. Using the usual CH4/H-3 feed gas ratio for micro crystalline diamond growth, nanodiamond crystallites were obtained. The diamond nucleation density is comparable to that obtained by biasing the substrate. The uniformly distributed lattice damage is proposed to be responsible for the formation of the nanodiamond. (C) 2002 Elsevier Science B.V. All rights reserved.

Entangled metal-organic frameworks modulated by N-donor ligands of different conformations

Based on the aromatic dicarboxylic acid and N-donor ligands with different conformations, four Zn(II) metal-organic frameworks, namely [Zn(mfda)(L-1)](1), [Zn-2(mfda)(2)(L-2)]center dot DMF center dot H2O (2), [Zn-2(mfda)(2)(L-3)(H2O)]center dot DMF (3) and [Zn-2(mfda)(2)(L-4)] (4) have been synthesized (mfda = 9,9-dimethylfluorene-2,7-dicarboxylate anion, L-1 = 1,10-phenanthroline, L-2 = 4,4 '-bipyridine, L-3 = 2,5-bis(4-pyridyl)-1,3,4-ocadiazole and L-4 = 1,4-bis(imidazol-1-ylmethyl)benzene). Single-crystal X-ray diffraction has revealed that all compounds exhibit entangled structures. Compound 1 is composed of 1D zigzag chains that are entangled through the pi-pi stacking interactions to generate a three-fold interpenetrating diamond-like networks.

Direct electrochemistry and bioelectrocatalysis of horseradish peroxidase immobilized on active carbon

For the first time horseradish peroxidase (HRP) immobilized on the surface of active carbon powder modified at the surface of a glassy carbon electrode has been shown to undergo a direct quasi-reversible electrochemical reaction. Its formal potential, E-o/, is -0.363 V in phosphate buffer solution (pH 6.8) at a scan rate of 100 mV/s and is almost independent of the scan rate in the range of 50-700 mV/s. The dependence of E-o/ on the pH of the buffer solution indicated that the conversion of HRP-Fe(III)/HRP-Fe(II) is a one-electron-transfer reaction process coupled with one-proton-transfer. The experimental results also demonstrated that the immobilized HRP retained its bioelectrocatalytic activity to the reduction of H2O2. Furthermore, the HRP adsorbed oil the surface of the active carbon powder can be stored at 4 degreesC for several months without any loss of the enzyme activity. The method presented for immobilizing HRP can be easily extended to immobilize and obtain the direct electrochemistry of other enzymes.

Lipid membrane immobilized horseradish peroxidase biosensor for amperometric determination of hydrogen peroxide

Stable films of didodecyldimethylammonium bromide (DDAB, a synthetic lipid) and horseradish peroxidase (HRP) were made by casting the mixture of the aqueous vesicle of DDAB and HRP onto the glassy carbon (GC) electrode. The direct electron transfer between electrode and HRP immobilized in lipid film has been demonstrated. The lipid films were used to supply a biological environment resembling biomembrane on the surface of the electrode. A pair of redox peaks attributed to the direct redox reaction of HRP were observed in the phosphate buffer solution (pH 5.5). The cathodic peak current increased dramatically while anodic peak decreased by addition of small amount H2O2. The pH effect on amperometric response to H2O2 was studied. The biosensor also exhibited fast response (5 s), good stability and reproducibility.

Electrocatalytic oxidation of ascorbic acid by ferrocene in lipid film cast on a glassy carbon electrode

A ferrocene-dimyristoyl phosphatidylcholine (DMPC) film electrode was prepared by casting the solution of ferrocene and DMPC in chloroform onto a glassy carbon electrode surface. Ferrocene retained in the biological membrane gave a couple of irreversible peaks of cyclic voltammogram. The electrode exhibited good electrocatalytic activity for the oxidation of ascorbic acid (H(2)A) in phosphate buffer (pH 6.64) with an anodic peak potential of +340 mV (vs. Ag/AgCl). The anodic current was directly proportional to the square root of the scan rate below 150 mV s(-1). The influence of the pH value was investigated and it was observed that pH 6.64 was the suitable value to the anodic peak potential and current. The thickness of the film and the interference of uric acid were also studied. The electrode can be used to determine H(2)A in the presence of equimolar uric acid. The catalytic peak current increased linearly with the concentration of H(2)A in the range of 1 X 10(-4)-5 X 10(-3) mol L-1.

Mono-energetic ion beam acceleration in solitary waves during relativistic transparency using high-contrast circularly polarized short-pulse laser and nanoscale targets

In recent experiments at the Trident laser facility, quasi-monoenergetic ion beams have been obtained from the interaction of an ultraintense, circularly polarized laser with a diamond-like carbon target of nm-scale thickness under conditions of ultrahigh laser pulse contrast. Kinetic simulations of this experiment under realistic laser and plasma conditions show that relativistic transparency occurs before significant radiation pressure acceleration and that the main ion acceleration occurs after the onset of relativistic transparency. Associated with this transition are a period of intense ion acceleration and the generation of a new class of ion solitons that naturally give rise to quasi-monoenergetic ion beams. An analytic theory has been derived for the properties of these solitons that reproduces the behavior observed in kinetic simulations and the experiments. © 2011 American Institute of Physics.

Investigation of the solid-liquid phase transition of carbon at 150 GPa with spectrally resolved X-ray scattering

We have resolved the solid-liquid phase transition of carbon at pressures around 150GPa. High-pressure samples of different temperatures were created by laser-driven shock compression of graphite and varying the initial density from 1.30g/cm³ to 2.25g/cm³. In this way, temperatures from 5700K to 14,500K could be achieved for relatively constant pressure according to hydrodynamic simulations. From measuring the elastic X-ray scattering intensity of vanadium K-alpha radiation at 4.95keVat a scattering angle of 126°, which is very sensitive to the solid-liquid transition, we can determine whether the sample had transitioned to the fluid phase. We find that samples of initial density 1.3g/cm³ and 1.85g/cm³ are liquid in the compressed states, whereas samples close to the ideal graphite crystal density of 2.25g/cm³ remain solid, probably in a diamond-like state.

Collimated proton acceleration in light sail regime with a tailored pinhole target

A scheme for producing collimated protons from laser interactions with a diamond-like-carbon+pinhole target is proposed. The process is based on radiation pressure acceleration in the multi-species light-sail regime [B. Qiao et al., Phys. Rev. Lett. 105, 155002 (2010); T. P. Yu et al., Phys. Rev. Lett. 105, 065002 (2010)]. Particle-in-cell simulations demonstrate that transverse quasistatic electric field at TV/m level can be generated in the pinhole. The transverse electric field suppresses the transverse expansion of protons effectively, resulting in a higher density and more collimated proton beam compared with a single foil target. The dependence of the proton beam divergence on the parameters of the pinhole is also investigated. 

POCN-type Pincer Complexes of NiII and NiIII : synthesis, reactivities, catalytic activities and physical properties

Cette thèse décrit la synthèse, la caractérisation, les réactivités, et les propriétés physiques de complexes divalents et trivalents de Ni formés à partir de nouveaux ligands «pincer» de type POCN. Les ligands POCN de type amine sont préparés d’une façon simple et efficace via l’amination réductrice de 3-hydroxybenzaldéhyde avec NaBH4 et plusieurs amines, suivie par la phosphination de l’amino alcool résultant pour installer la fonction phosphinite (OPR2); le ligand POCN de type imine 1,3-(i-Pr)2PC6H4C(H)=N(CH2Ph) est préparé de façon similaire en faisant usage de PhCH2NH2 en l’absence de NaBH4. La réaction de ces ligands «pincer» de type POCN avec NiBr2(CH3CN)x en présence d’une base résulte en un bon rendement de la cyclométalation du lien C-H situé en ortho aux fonctions amine et phosphinite. Il fut découvert que la base est essentielle pour la propreté et le haut rendement de la formation des complexes «pincer» désirés. Nous avons préparé des complexes «pincer» plan- carrés de type POCN, (POCNRR΄)NiBr, possédant des fonctions amines secondaires et tertiaires qui démontrent des réactivités différentes selon les substituants R et R΄. Par exemple, les complexes possédant des fonctions amines tertiaires ArCH2NR2 (NR2= NMe2, NEt2, and morpholinyl) démontrent des propriétés rédox intéressantes et pourraient être convertis en leurs analogues trivalents (POCNR2)NiBr2 lorsque réagis avec Br2 ou N-bromosuccinimide (NBS). Les complexes trivalents paramagnétiques à 17 électrons adoptent une géométrie de type plan-carré déformée, les atomes de Br occupant les positions axiale et équatoriale. Les analyses «DSC» et «TGA» des ces composés ont démontré qu’ils sont thermiquement stables jusqu’à ~170 °C; tandis que la spectroscopie d’absorption en solution a démontré qu’ils se décomposent thermiquement à beaucoup plus basse température pour regénérer les complexes divalents ne possédant qu’un seul Br; l’encombrement stérique des substitutants amines accélère cette route de décomposition de façon significative. Les analogues NMe2 et N(morpholinyl) de ces espèces de NiIII sont actifs pour catalyser la réaction d’addition de Kharasch, de CX4 à des oléfines telles que le styrène, tandis qu’il fut découvert que l’analogue le moins thermiquement stable (POCNEt2)Ni est complètement inerte pour catalyser cette réaction. Les complexes (POCNRH)NiBr possédant des fonctions amines secondaires permettent l’accès à des fonctions amines substituées de façon non symétrique via leur réaction avec des halogénures d’alkyle. Un autre avantage important de ces complexes réside dans la possibilité de déprotonation pour préparer des complexes POCN de type amide. De telles tentatives pour déprotoner les fonctions NRH nous ont permis de préparer des espèces dimériques possédant des ligands amides pontants. La nature dimérique des ces complexes [P,C,N,N-(2,6-(i-Pr)2PC6H3CH2NR)Ni]2 (R= PhCH2 et Ph) fut établie par des études de diffraction des rayons-X qui ont démontré différentes géométries pour les cœurs Ni2N2 selon le substituant N : l’analogue (PhCH2)N possède une orientation syn des substitutants benzyles et un arrangement ressemblant à celui du cyclobutane du Ni et des atomes d’azote, tandis que l’analogue PhN adopte un arrangement de type diamant quasi-planaire des atomes du Ni et des atomes d’azote et une orientation anti des substituants phényles. Les espèces dimériques ne se dissocient pas en présence d’alcools, mais elles promouvoient l’alcoolyse catalytique de l’acrylonitrile. De façon intéressante, les rendements de ces réactions sont plus élevés avec les alcools possédant des fonctions O-H plus acides, avec un nombre de «turnover» catalytique pouvant atteindre 2000 dans le cas de m-cresol. Nous croyons que ces réactions d’alcoolyse procèdent par activation hétérolytique de l’alcool par l’espèce dimérique via des liaisons hydrogènes avec une ou deux des fonctions amides du dimère. Les espèces dimériques de Ni (II) s’oxydent facilement électrochimiquement et par reaction avec NBS ou Br2. De façon surprenante, l’oxydation chimique mène à l’isolation de nouveaux produits monomériques dans lesquels le centre métallique et le ligand sont oxydés. Le mécanisme d’oxydation fut aussi investigué par RMN, «UV-vis-NIR», «DFT» et spectroélectrochimie.