Bulk and surface modification of elastomers by electron beam irradation: Structure-property relationship

Bulk and surface modification of ethylene propylene diene monomer (EPDM) and fluoroelastomer by electron beam irradiation was investigated. The structure of the modified elastomers was analysed with the help of Infrared (IR) spectroscopy, Electron Spectroscopy for Chemical Analysis (ESCA) and gel content. Mechanical and dynamic mechanical properties of bulk modified fluoroelastomers and surface energy and frictional coefficient of the surface modified EPDMs were measured. The properties were correlated with the structure developed.     

Atomic force microscopy imaging of hair: correlations between surface potential and wetting at the nanometer scale

We report investigations of hair surface potential under wetting at the nanometric scale by atomic force microscopy (AFM). Surface potential imaging was used to characterize the electrostatic properties of the hair samples. We found that the surface potential noticeably increases along the edges of the cuticles. These results are correlated with wetting behavior of different liquids performed using AFM in noncontact mode.     

Image reversal for direct electron beam patterning of protein coated surfaces

Electron beam lithography (EBL) is used to create surfaces with protein patterns, which are characterized by immunofluorescence and atomic force microscopies. Both negative and positive image processes are realized by electron beam irradiation of proteins absorbed on a silicon surface, where image reversal is achieved by selectively binding a second species of protein to the electron beam exposed areas on the first protein layer. Biofunctionality at the cellular level was established by culturing cortical cells on patterned lines of fibronectin adsorbed on a bovine serum albumin background for 7 days in culture.     

Decomposition and decoloration of a direct dye by electron beam radiation

The wastewaters released by textile industries to the environment contain hazardous compounds like toxic refractory dye stuff at high concentration. In this study, electron beam irradiation-induced decoloration and decomposition of C.I. Direct Black 22 aqueous solutions were investigated. The influences of absorbed doses and initial dye concentration on the percent of decoloration, COD and pH of the solutions are described. The results show that the direct dye solutions can be effectively degraded by electron beam irradiation.     

Surface tailoring for controlled protein adsorption: effect of topography at the nanometer scale and chemistry

Protein adsorption behavior is at the heart of many of today's research fields including biotechnology and materials science. With understanding of protein-surface interactions, control over the conformation and orientation of immobilized species may ultimately allow tailor-made surfaces to be generated. In this contribution protein-surface interactions have been examined with particular focus on surface curvature with and without surface chemistry effects. Silica spheres with diameters in the range 15-165 nm with both hydrophilic and hydrophobic surface chemistries have been used as model substrates. Two proteins differing in size and shape, bovine serum albumin (BSA) and bovine fibrinogen (Fg), have been used in model studies of protein binding with detailed secondary structure analysis being performed using infrared spectroscopy (IR) on surface-bound proteins. Although trends in binding affinity and saturation values were similar for both proteins, albumin is increasingly less ordered on larger substrates, while fibrinogen, in contrast, loses secondary structure to a greater extent when adsorbing onto particles with high surface curvature. These effects are compounded by surface chemistry, with both proteins becoming more denatured on hydrophobic surfaces. Both surface chemistry and topography play key roles in determining the structure of the bound proteins. A model of the binding characteristics of these two proteins onto surfaces having differing curvature and chemistry is presented. We propose that properties of an adsorbed protein layer may be guided through careful consideration of surface structure, allowing the fabrication of materials/surface coatings with tailored bioactivity.     

Synthesis and hydrogen storage behavior of Mg-Co-H system at nanometer scale

There are few reports on the hydrogen storage behavior study of Mg-Co-H system in the literature, although Mg₂CoH₅ has a much higher hydrogen capacity than Mg₂NiH₄. This is due to the great difficulty in the synthesis of Mg₂CoH₅ and Mg₂Co in convenient conditions. Here we successfully synthesized the nanostructured Mg₂CoH₅ and Mg₂Co from Mg and Co nanoparticles prepared by hydrogen plasma-metal reaction method. The reaction mechanism of the synthesis of the Mg-Co-H system was studied. The morphology of the Mg-Co-H system in nanometer scale was observed. The hydrogen absorption curves and the pressure-composition isotherm (P-C-T) properties of the Mg-Co-H system were studied. The van’t Hoff equations and the formation enthalpies and entropies of the produced Mg₂CoH₅ and Mg₃CoH₅ were obtained. The results were discussed by comparing with the corresponding ones of Mg-Co-H system by other groups and the ones of nanostructured Mg-H and Mg-Ni-H systems by our group.     

Structural and physico-chemical studies on modification of polypropylene and its polyphenolic antioxidant by electron beam irradiation

As polypropylene (PP) is widely used in medical and pharmaceutical fields, the effect of sterilization on both the polymer and its additives must be taken into account. In this study, PP and its antioxidants Irganox 1010 and 1076 were electron beam irradiated in order to evaluate by Fourier transform infrared spectroscopy, differential scanning calorimetry and size exclusion chromatography, their structural and physico-chemical modifications. A good correlation between those analytical techniques has indicated the formation of oxidation products, chain scissions as well as crosslinking. The effect of the absorbed dose is underlined.     

PEW: Photopolymerization by evanescent waves. II. Revealing dramatic inhibiting effects of oxygen at submicrometer scale

A simplistic model of photopolymerization by evanescent waves (PEW) has been introduced in a previous paper. This model predicts a linear dependence of the polymerized thickness on the logarithm of exposure time. It provides the general trend of the experimental data. The present work shows that the properties of the material and the chemistry of the system also have to be taken into account to fit the experiments more precisely. Evidence was provided that dissolved oxygen has a marked effect on gel dose. In PEW the reaction is induced in very small solution volumes, so that marked competition seems to take place between reaction and diffusion. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2075–2085, 1999     

Monte Carlo model of the temperature rise at a GaAs surface under an electron beam

Scanning electron microscopy (SEM) has frequently been used to study semiconductor materials. It offers the possibility of obtaining reliable qualitative and quantitative information on relevant local material parameters. The temperature rise due to electron‐beam bombardment can influence some semiconductor parameters, which then will influence the SEM information. In this work we propose a model calculation based on the Monte Carlo (MC) method to calculate the temperature rise due to electron‐beam heating. The results show that the temperature rise increases with increasing numbers of electrons (electron‐beam current), and the inverse behavior is observed with respect to the electron energy (electron‐beam voltage). The decrease in temperature rise with depth is also obtained. Copyright © 2006 John Wiley & Sons, Ltd.     

Probing molecules adsorbed at the surface of nanometer colloidal particles by optical second-harmonic generation

It is observed that optical second-harmonic generation from molecules adsorbed at the surface of nanometer size colloidal particles occurs at angles as large as 90 degrees away from the fundamental beam direction. This phenomenon can be rigorously described by the nonlinear Rayleigh-Gans-Debye theory and used for probing molecules adsorbed on nanometer size colloidal particles.     

The direct resist-free deposition of a lithographic mask from vapor initiated by an electron beam

A dry resist-free process of electron-beam vapor deposition of an undecane precursor (C₁₁H₂₄) mask on SiO₂-on-silicon and copper-on-silicon substrates was studied. The band section was trapezoidal, and the band width at the base was much larger than the diameter of the electron beam and depended on the substrate (it was three or four times larger on copper than on SiO₂). In mask deposition on copper, the mask thickening rate v was found to depend strongly on the scan time τ_sc when scanning was performed along the band. When τ_sc changed from 20 ms to 13 s, v decreased by a factor of 7.4 (beam current 1.0 nA). This was probably caused by significant diffusion delay of precursor transport to the reaction zone during pixel time when τ_sc was 13 s. The ion-beam etching of the substrates through the deposited masks was performed (the SiO₂ substrate was etched with SF₆ ions, and the copper substrate, with Ar ions).     

Patterning of DNA nanostructures on silicon surface by electron beam lithography of self-assembled monolayer

Nanoscale patterns of modified oligonucleotides are produced on octadecyltrimethoxysilane self-assembled monolayers at a silicon surface by electron beam lithography. DNA structures with feature sizes of the order of 250 nm were detected by epi-fluorescence microscopy.     

Suppression of lithium deposition at sub-zero temperatures on graphite by surface modification

Lithium deposition on graphite anodes is considered as a main reason for failures and safety for lithium ion batteries (LIB). Different amounts of carbon coating on the surface of natural graphite are used in this work to suppress the amount of lithium deposited at − 10 °C. Pulse polarization experiments reveal relative polarization of graphite anodes at various temperatures and show that lithium deposition is accelerated at lowered temperatures. Electrochemical experiments, along with photographs, scanning electron microscopy (SEM) images and ex-situ X-ray diffraction (XRD) data suggest that carbon coating not only suppresses the lithium deposition but also enhances the formation of LiC₆ at − 10 °C. The homogeneous potential profile on the graphite surface attained by the carbon coating explains such an improved low temperature performance, as it allows efficient Solid Electrolyte Interface (SEI) film formation, which is a prerequisite for safety LIB.     

Comparison of rheological behavior of branched polypropylene prepared by chemical modification and electron beam irradiation under air and N2

Chemical and electron beam irradiation methods were used to introduce a branched structure into polypropylene and propylene–ethylene copolymer. The chemical method was carried out in an internal mixer using initiator and TMPTMA monomer. In irradiation method, the polymer was irradiated by electron beam under air and nitrogen atmosphere. The branched structure in the modified polymer was confirmed by rheological measurements. While degradation was significant in chemical method, branching occurred efficiently by irradiation under air. Small amount of ethylene in the propylene copolymer promoted branching over degradation.     

Rationalization of the behavior of solid-liquid surface free energy of water in Cassie and Wenzel wetting states on rugged solid surfaces at the nanometer scale

The present work aims to contribute to the understanding at a molecular level of the origin of the hydrophobic nature of surfaces exhibiting roughness at the nanometer scale. Graphite-based smooth and model surfaces whose roughness dimension stretches from a few angstroms to a few nanometers were used in order to generate Cassie and Wenzel wetting states of water. The corresponding solid-liquid surface free energies were computed by means of molecular dynamics simulations. The solid-liquid surface free energy of water-smooth graphite was found to be -12.7 ± 3.3 mJ/m(2), which is in reasonable agreement with a value estimated from experiments and fully consistent with the features of the employed model. All the rugged surfaces yielded higher surface free energy. In both Cassie and Wenzel states, the maximum variation of the surface free energy with respect to the smooth surface was observed to represent up to 50% of the water model surface tension. The solid-liquid surface free energy of Cassie states could be well predicted from the Cassie-Baxter equation where the surface free energies replace contact angles. The origin of the hydrophobic nature of surfaces yielding Cassie states was therefore found to be the reduction of the number of interactions between water and the solid surface where atomic defects were implemented. Wenzel's theory was found to fail to predict even qualitatively the variation of the solid-liquid surface free energy with respect to the roughness pattern. While graphite was found to be slightly hydrophilic, Wenzel states were found to be dominated by an unfavorable effect that overcame the favorable enthalpic effect induced by the implementation of roughness. From the quantitative point of view, the solid-liquid surface free energy of Wenzel states was found to vary linearly with the roughness contour length.     

Guided-ion beam and theoretical study of the potential energy surface for activation of methane by W+

A guided-ion beam tandem mass spectrometer is used to study the reactions, W(+) + CH(4) (CD(4)) and [W,C,2H](+) + H(2) (D(2)), to probe the [W,C,4H](+) potential energy surface. The reaction W(+) + CH(4) produces [W,C,2H](+) in the only low-energy process. The analogous reaction in the CD(4) system exhibits a cross section with strong differences at the lowest energies caused by zero-point energy differences, demonstrating that this reaction is slightly exothermic for CH(4) and slightly endothermic for CD(4). The [W,C,2H](+) product ion reacts further at thermal energies with CH(4) to produce W(CH(2))(x)(+) (x = 2-4). At higher energies, the W(+) + CH(4) reaction forms WH(+) as the dominant ionic product with smaller amounts of WCH(3)(+), WCH(+), and WC(+) also formed. The energy dependent cross sections for endothermic formation of the various products are analyzed and allow the determination of D(0)(W(+)-CH(3)) approximately 2.31 +/- 0.10 eV, D(0)(W(+)-CH(2)) = 4.74 +/- 0.03 eV, D(0)(W(+)-CH) = 6.01 +/- 0.28 eV, and D(0)(W(+)-C) = 4.96 +/- 0.22 eV. We also examine the reverse reaction, [W,C,2H](+) + H(2) (D(2)) --> W(+) + CH(4) (CH(2)D(2)). Combining the cross sections for the forward and reverse processes yields an equilibrium constant from which D(0)(W(+)-CH(2)) = 4.72 +/- 0.04 eV is derived. Theoretical calculations performed at the B3LYP/HW+/6-311++G(3df,3p) level yield thermochemistry in reasonable agreement with experiment. These calculations help identify the structures and electronic states of the species involved and characterize the potential energy surface for the [W,C,4H](+) system.     

Study of direct electron transfer and enzyme activity of glucose oxidase on graphene surface

In recent years, graphene has been widely used as a high performance two-dimensional material in the development of biosensors and biofuel cells for facilitating direct electron transfer (DET) of glucose oxidase (GOx). However, almost all of these reports perform experiments in the presence of oxygen (a natural mediator of oxidase) and whether the GOx with DET property retained their catalytic activity in the absence of mediators has not been studied in detail so far. In this paper, we investigated the DET property and enzyme activity of GOx on graphene surface without and with mediators. Experimental results showed that the biosensor had no response to glucose in mediator-free solutions, even though the DET of GOx was observed, indicating that the GOx with DET property lacked enzymatically catalytic activity. However, in the presence of mediators, the biosensor showed sensitive response to glucose, illustrating that the mediated enzymatic oxidation of glucose occurred, which can be attributed to the catalytically active GOx without DET capability. These results suggest that DET property and enzyme catalytic activity cannot occur on the same GOx simultaneously. Therefore, keeping enzyme activity and DET of GOx at the same time is still a major challenge for biosensor and biofuel cell researches.     

Crosslinking of recycled polyethylene by gamma and electron beam irradiation

Recycling of polymeric materials is usually accompanied by degradation and deleterious properties. Irradiation crosslinking of recycling low density polyethylene by electron beam and gamma rays could be the solution to improve their properties. This paper presents a comparison on the effects of gamma and electron irradiation on virgin and recycled polyethylene. Their mechanical, thermal and chemical properties were analyzed. VPE samples shown higher crosslinking percentages than RPE samples in all range of doses studied, unirradiated RPE samples had higher values on their tensile properties than VPE. Percentage crystallinity was similar in all range of doses studied.     

Selective surface activation of a functional monolayer for the fabrication of nanometer scale thiol patterns and directed self-assembly of gold nanoparticles

Application of a voltage bias between the tip of an atomic force microscope (AFM) and a silicon substrate causes the localized modification of a specially designed self-assembled monolayer (SAM), transforming a surface-bound thiocarbonate into a surface-bound thiol. The resulting surface-bound thiols are used to direct the patternwise self-assembly of gold nanoparticles (AuNPs). This methodology is applied to deposit individual AuNPs onto a surface with nanometer precision and to produce 10 nm lines of closely spaced AuNPs that are a single nanoparticle in width.     

Heterodimers of nanoparticles: formation at a liquid-liquid interface and particle-specific surface modification by functional molecules

On the basis of a fundamental property of nanoparticles, the self-assembling at a liquid-liquid interface to form "colloidosomes", a heterogeneous reaction takes place on the exposed surface of the nanoparticles to produce the heterodimers of two distinct nanospheres, which can be modified by two different functional molecules in a particle-specific manner.