Introduction to surface chemistry and catalysis

The mechanical properties of the surfaces used for exercising can affect sports performance and injury risk. However, the mechanical properties of treadmill surfaces remain largely unknown. The aim of this study was, therefore, to assess the shock absorption (SA), vertical deformation (VD) and energy restitution (ER) of different treadmill models and to compare them with those of other sport surfaces. A total of 77 treadmills, 30 artificial turf pitches and 30 athletics tracks were assessed using an advanced artificial athlete device. Differences in the mechanical properties between the surfaces and treadmill models were evaluated using a repeated-measures ANOVA. The treadmills were found to exhibit the highest SA of all the surfaces (64.2 ± 2; p < 0.01; effect size (ES) = 0.96), while their VD (7.6 ± 1.3; p < 0.01; ES = 0.87) and ER (45 ± 11; p < 0.01; ES = 0.51) were between the VDs of the artificial turf and track. The SA (p < 0.01; ES = 0.69), VD (p < 0.01; ES = 0.90) and ER (p < 0.01; ES = 0.89) were also shown to differ between treadmill models. The differences between the treadmills commonly used in fitness centers were much lower than differences between the treadmills and track surfaces, but they were sometimes larger than the differences with artificial turf. The treadmills used in clinical practice and research were shown to exhibit widely varying mechanical properties. The results of this study demonstrate that the mechanical properties (SA, VD and ER) of treadmill surfaces differ significantly from those of overground sport surfaces such as artificial turf and athletics track surfaces but also asphalt or concrete. These different mechanical properties of treadmills may affect treadmill running performance, injury risk and the generalizability of research performed on treadmills to overground locomotion.

The purpose of the study was to identify the effect of three different surfaces on energy consumption and the forces acting on the walking poles during ground contact in Nordic walking (NW). Thirteen female NW instructors (age = 26 +/- 4 yr, weight = 58.5 +/- 4.2 kg, height = 168.1 +/- 4.6 cm) volunteered in the study. The subjects walked a distance of 1200 m at a controlled, constant speed of 2.2 m x s(-1) on each of a concrete surface (C), an artificial athletics track (A), and a naturally grown soccer lawn (G). They used NW poles with inbuilt strain gauge force transducers to measure ground reaction forces acting along the long axes of the poles. Oxygen uptake, capillary blood lactate (La), HR, and RPE were measured before and after the tests. Impact forces, maximum forces, force rates during ground contact identified from the registered force time histories, displayed significant differences related to the surface conditions. However, force time integrals did not show surface-related differences. Relative oxygen consumption showed significant differences between NW on C and on G whereas no surface-related differences could be identified between the surface conditions for the parameters La, HR, and RPE. Our data indicate that the impulse that is generated by the poles on the subjects is identical between the varying surfaces. Because there are differences for the oxygen uptake between C and G, the main regulator for the propulsion must be the musculature of the lower extremities. The work of the upper extremities seems to be a luxury effort for Nordic walkers with a proper technique.

Surface materials: the frontier of solid state chemistry

Multiwalled-carbon-nanotube (MWNT)-reinforced polymer surfaces were prepared by infiltration and in situ polymerization of excess monomer into aligned MWNT arrays (see SEM image; scale bar=1 μm). The electrical and mechanical properties of the MWNT-reinforced surface were compared with those of the pure polymer surface. The reinforced polymer films show large enhancements in surface stiffness and electrical conductivity compared to the soft and insulating pure polymer.

Surface structure analysis by LEED and RHEED

Electrical and mechanical properties of surface layers deposited on copper by the novel IBAD method

Sum frequency generation (SFG) vibrational spectroscopy, atomic force microscopy (AFM), and other complementary surface-sensitive techniques have been used to study the surface molecular structure and surface mechanical behavior of biologically-relevant polymer systems. SFG and AFM have emerged as powerful analytical tools to deduce structure/property relationships, in situ, for polymers at air, liquid and solid interfaces. The experiments described in this dissertation have been performed to understand how polymer surface properties are linked to polymer bulk composition, substrate hydrophobicity, changes in the ambient environment (e.g., humidity and temperature), or the adsorption of macromolecules. The correlation of spectroscopic and mechanical data by SFG and AFM can become a powerful methodology to study and engineer materials with tailored surface properties. The overarching theme of this research is the interrogation of systems of increasing structural complexity, which allows us to extend conclusions made on simpler model systems. We begin by systematically describing the surface molecular composition and mechanical properties of polymers, copolymers, and blends having simple linear architectures. Subsequent chapters focus on networked hydrogel materials used as soft contact lenses and the adsorption of protein and surfactant at the polymer/liquid interface. The power of SFG is immediately demonstrated in experiments which identify the chemical parameters that influence the molecular composition and ordering of a polymer chain's side groups at the polymer/air and polymer/liquid interfaces. In general, side groups with increasingly greater hydrophobic character will be more surface active in air. Larger side groups impose steric restrictions, thus they will tend to be more randomly ordered than smaller hydrophobic groups. If exposed to a hydrophilic environment, such as water, the polymer chain will attempt to orient more of its hydrophilic groups to the surface in order to minimize the total surface energy. With an understanding of the structural and environmental parameters which govern polymer surface structure, SFG is then used to explore the effects of surface hydrophobicity and solvent polarity on the orientation and ordering of amphiphilic neutral polymers adsorbed at the solid/liquid interface. SFG spectra show that poly(propylene glycol) (PPG) and poly(ethylene glycol) (PEG) adsorb with their hydrophobic moieties preferentially oriented toward hydrophobic polystyrene surfaces. These same moieties, however, disorder when adsorbed onto a hydrophilic silica/water interface. Water is identified as a critical factor for mediating the orientation and ordering of hydrophobic moieties in polymers adsorbed at hydrophobic interfaces. The role of bulk water content and water vapor, as they influence hydrogel surface structure and mechanics, continues to be explored in the next series of experiments. A method was developed to probe the surface viscoelastic properties of hydroxylethyl methacrylate (HEMA) based contact lens materials by analyzing AFM force-distance curves. AFM analysis indicates that the interfacial region is dehydrated, relative to the bulk. Experiments performed on poly(HEMA+MA) (MA = methacrylic acid), a more hydrophilic copolymer with greater bulk water content, show even greater water depletion at the surface. SFG spectra, as well as surface energy arguments, suggest that the more hydrophilic polymer component (such as MA) is not favored at the air interface; this may explain anomalies in water retention at the hydrogel surface. Adsorption of lysozyme onto poly(HEMA+MA) was found to further reduce near-surface viscous behavior, suggesting lower surface water content. Lastly, protein adsorption is studied using a model polymer system of polystyrene covalently bound with a monolayer of bovine serum albumin. SFG results indicate that some amino acid residues in proteins adopt preferred orientations. SFG spectra also show that the phenyl rings of the bare polystyrene substrate in contact with air or liquid are ordered, with a dipole component directed along the surface normal, but slightly disorder after protein adsorption. Differences in AFM friction values suggest that protein interacts more strongly with the polystyrene substrate at the air/solid interface. The molecular orientation and ordering of surface phenyl groups are also shown to affect substrate hydrophobicity.

The electrical properties of surface- and buried-channel p-MOSFETs containing strained GeSi heterostructures synthesized by high-dose Ge implantation and solid phase epitaxial growth have been investigated. Compared with Si control devices on the same chips, GeSi transistors exhibited improved performance: the channel hole mobility and linear transconductance was up to 18% higher for surface-channel GeSi transistors, and up to 12% higher for buried-channel GeSi p-MOSFETs, than for equivalent Si devices. Ion-beam synthesis of GeSi strained layers therefore offers an attractive means for realising improved device performance in conventional Si device structures.

Porous silicon (PS) layers were formed on textured crystalline silicon by electrochemical etching in HF-based electrolyte. Optical and electrical properties of the TMAH textured surfaces with PS formation are studied. Moreover, the influences of the initial structures and the anodizing time on the optical and electrical properties of the surfaces after PS formation are investigated. The results show that the TMAH textured surfaces with PS formation present a dramatic decrease in reflectance. The longer the anodizing time is, the lower the reflectance. Moreover, an initial surface with bigger pyramids achieved lower reflectance in a short wavelength range. A minimum reflectance of 3.86% at 460 nm is achieved for a short anodizing time of 2 min. Furthermore, the reflectance spectrum of the sample, which was etched in 3 vol.% TMAH for 25 min and then anodized for 20 min, is extremely flat and lies between 3.67% and 6.15% in the wavelength range from 400 to 1040 nm. In addition, for a short anodizing time, a slight increase in the effective carrier lifetime is observed. Our results indicate that PS layers formed on a TMAH textured surface for a short anodization treatment can be used as both broadband antireflection coatings and passivation layers for the application in solar cells.

Scanning Force Microscopy (SFM) has been used to quantitatively measure the elastic modulus, friction and hardness of polymer surfaces with special emphasis on polyethylene and polypropylene. In the experiments, tips of different radii of curvature ranging from 20 nm to 1000 nm have been used and the high pressure applied by the SFM have been observed to affect the values obtained in the measurements. The contact of the SFM tip with the polymer surface is explained by fitting the experimental curves to theoretical predictions of contact mechanics. Sum Frequency Generation (SFG) Vibrational Spectroscopy has been used to measure vibrational spectra of polymer surfaces in the vibrational range of 2700 to 3100 cm-1. Strong correlations are established between surface chemistry and surface structure as probed by SFG and mechanical properties measured by SFM on the surfaces. In these studies segregation of low surface energy moieties, from the bulk of the polymer to the surface have been studied. It was found that surface segregation occurs in miscible polymer blends and a small concentration of surface active polymer can be used to totally modify the surface properties of the blend. A novel high vacuum SFM was built to do temperature dependent measurements of mechanical changes occurring at the surface of polypropylene during the glass transition of the polymer. Using this instrument the modulus and friction of polypropylene was measured in the range of room temperature to ˜-60°C. An increase in the ordering of the backbone of the polymer chains below the glass transition measured by SFG correlates well with the increase in modulus measured on the same surface with SFM. Friction measurements have been done on polyethylene with three different instruments by applying loads ranging from nN to sub newton i.e. over eight orders of magnitude. Pressure and contact area effects were observed to play a significant role in determining the frictional response of the polymer, with higher friction coefficients observed at high pressures and when contact areas are on the size of the crystalline lamellae.

Determining the geotechnical properties of planetary regolith using Low Velocity Penetrometers

Due to their ability to confer key functions of the native extracellular matrix (ECM) poly(ethylene glycol) (PEG)-based and PEG-modified materials have been extensively used as biocompatible and biofunctionalized substrate systems to study the influence of environmental parameters on cell adhesion in vitro. Given wide-ranging recent evidence that ECM compliance influences a variety of cell functions, the detailed determination and characterization of the specific PEG surface characteristics including topography, stiffness and chemistry is required. Here, we studied two frequently used bio-active interfaces - PEG-based and PEG-modified surfaces - to elucidate the differences between the physical surface properties, which cells can sense and respond to. For this purpose, two sets of surfaces were synthesized: the first set consisted of nanopatterned glass surfaces containing cRGD-functionalized gold nanoparticles surrounded by a passivated PEG-silane layer and the second set consisted of PEG-diacrylate (PEG-DA) hydrogels decorated with cRGD-functionalized gold nanoparticlesAlthough the two sets of nanostructured materials compared here were highly similar in terms of density and geometrical distribution of the presented bio-ligands as well as in terms of mechanical bulk properties, the topography and mechanical properties of the surfaces were found to be substantially different and are described in detail. In comparison to very stiff and ultrasmooth surface properties of the PEG-passivated glasses, the mechanical properties of PEG-DA surfaces in the biologically relevant stiffness range, together with the increased surface roughness at micro- and nanoscale levels have the potential to affect cell behavior. This potential was verified by studying the adhesive behavior of hematopoietic KG-1a and rat embryonic fibroblast (REF52) cells on both surfaces.

Molecular level studies of the structure and mechanical properties of polymer surfaces have been carried out by sum frequency generation (SFG) surface vibrational spectroscopy and atomic force microscopy (AFM). The surfaces of different grades of polyethylene and polypropylene have been characterized-including during the glass transition and when mechanically stretched. Copolymers that have hard and soft segments with different glass transition temperatures show phase separation, an effect of hydrogen bonding between the hard and soft segments, that influences their adhesive and friction properties. AFM and SFG show that low surface energy additives migrate to the surface and alter the surface mechanical properties. Polymers, where the chemical nature of the end groups is different from the backbone, show surface segregation of the hydrophobic part of the chain in air and the hydrophilic part in water. Likewise, in miscible polymer blends, surface segregation of the more hydrophobic component in air and the more hydrophilic component in water is observed. This area of surface science requires increased attention because of the predominance of polymers as structural materials and as biomaterials.

Nanoindentation and dynamic mechanical analysis were used to measure changes in the surface and bulk mechanical properties of Winsor & Newton Yellow Ochre oil paint films following exposure to deionized water, aliphatic mineral spirits (Shellsol D40™), and D5 silicone solvent (decamethylcyclopentasiloxane). Yellow ochre paint films were exposed to the selected solvents by 24-h immersion, and sponge-cleaning. 24-h immersion in deionised water and Shellsol D40 caused measurable changes to bulk and surface mechanical properties. However, there were no measurable changes to the bulk or surface mechanical properties following sponge cleaning.

Effect of IR-laser radiation on crosslinking and some physical and mechanical properties of a composition surface