Surface analysis of environmentally exposed painted composites manufactured from Quickstep and autoclave processes

The surface finishes of laminates produced by Quickstep™ and autoclave processes for use in automotive outer skin panels were compared. Automotive quality, painted carbon fibre samples, manufactured via both processes, were exposed to typical exposure environments including combinations of temperature (70, 120, 170°C), UV-B, humidity (95% RH) and immersion in water.

The microscopy and surface roughness results demonstrated that the surfaces produced by the Quickstep process were less susceptible to damage in the aging environments than the surfaces of the autoclaved samples. Quickstep samples displayed surface bubbling of only 5 μm, compared to the autoclaved surface bubbles which reached a diameter of 30 mm before bursting, with complete delamination occurring between the paint and the composite. The surface roughness measurements revealed the autoclave samples (Ra = 0.72 μm) were up to three times the roughness of the Quickstep samples (Ra = 0.23 μm).

Anaerobic degradation of organic materials - significance of the substrate surface area

In anaerobic degradation of substrates containing mainly particulate organic matter, solids hydrolysis is rate-limiting. In these investigations, the particle size of various substrates was reduced by comminution to support hydrolysis. Two positive effects of comminution were observed. For substrates with high fibre content, which are particularly resistant to biodegradation, a significant improvement of the degradation degree was observed as a result of comminution. Secondly, for all substrates tested, and particularly for those rich in fibres, the degradation rate of comminuted samples was significantly higher. The first reason for both effects is an increase of the sample surface area. Several methods for measuring the specific surface area of organic materials, including particle size analysis, Nitrogen-adsorption and enzyme adsorption, were used and compared for the purpose of this study, where the surface area accessible to microbial enzymes is critical. The significance of the surface area in anaerobic degradation of particulate substrates was investigated through a kinetic model where the hydrolysis rate was based on the sample surface area. Good agreements were obtained between model and experiments carried out with samples of various specific surface areas. These results reinforced the significance of the sample surface area in anaerobic degradation processes. However, other effects of comminution responsible for the increased degradation degree and degradation rate were identified and discussed. These include: the increase of dissolved compounds due to cell rupture, exposition of surface areas previously inaccessible for microbial degradation, and alteration of the sample structure such as the lignin-cellulose arrangements.

The voltammetric reduction, deprotonation and surface activity of ruthenium photovoltaic sensitizers in acetone

The reductive voltammetry of the photovoltaic sensitizer [(H2-dcbpy)2Ru(NCS)2] (H2-dcbpy=2,2′-bipyridine-4,4′-dicarboxylic acid) and [(H3-tctpy)Ru(NCS)3]− (H3-tctpy=2,2′:6′,2″-terpyridine-4,4′,4″-tricarboxylic acid) has been investigated in acetone. Significant surface interactions at both platinum and glassy carbon electrodes occur at 0.6 V prior to the reversible potential expected for ligand-based reduction process of the fully protonated acids. The origin of the surface interactions are attributed to the acid–base behaviour of the compounds, combined with overall deprotonation and reduction to hydrogen, since repetitive cycling of the potential reveals well-defined reversible reduction processes in the negative potential range, resulting from formation of doubly deprotonated [(H-dcbpy−)2Ru(NCS)2]2− and singly deprotonated [(H2-tctpy−)Ru(NCS)3]2−, respectively. The extent of the surface interactions has been estimated by electrochemical quartz crystal microbalance and chronocoulometric measurements. Under certain conditions, a thick conducting polymer consisting of several hundred monolayers is formed.

Finite element simulation of deformation processes of micro-components

The aim of this paper is to improve the understanding of deformation of micro medical needle and thread during assembly and then to develop an economical and flexible deformation method. Therefore, the swaging process is computationally simulated with the finite element method in this paper. A commercially available explicit nonlinear finite element analysis code, LS-Dyna, is used to model the 3-D deformation and contact problem. As the firmness of the assembly on the needle depends on the contact force and friction, the contact and the slide between the needle and thread are taken into account in the simulation. The general surface-to-surface contact algorithm (STS) is used to simulate the contact. The paper provides an insight into the deformation of the micro products.

Regional-scale models for relating land cover to basin surface-water quality using remotely sensed data in a GIS

Plant-based management systems implementing deep-rooted, perennial vegetation have been identified as important in mitigating the spread of secondary dryland salinity due to its capacity to influence water table depth. The Glenelg Hopkins catchment is a highly modified watershed in the southwest region of Victoria, where dryland salinity management has been identified as a priority. Empirical relationships between the proportion of native vegetation and in-stream salinity were examined in the Glenelg Hopkins catchment using a linear regression approach. Whilst investigations of these relationships are not unique, this is the first comprehensive attempt to establish a link between land use and in-stream salinity in the study area. The results indicate that higher percentage land cover with native vegetation was negatively correlated with elevated in-stream salinity. This inverse correlation was consistent across the 3 years examined (1980, 1995, and 2002). Recognising the potential for erroneously inferring causal relationships, the methodology outlined here was both a time and cost-effective tool to inform management strategies at a regional scale, particularly in areas where processes may be operating at scales not easily addressed with on-site studies.

Potentiostatic control of ionic liquid surface film formation on ZE41 magnesium alloy

The generation of potentially corrosion-resistant films on light metal alloys of magnesium have been investigated. Magnesium alloy, ZE41 [Mg−Zn−Rare Earth (RE)-Zr, nominal composition 4 wt % Zn, 1.7 wt % RE (Ce), 0.6 wt % Zr, remaining balance, Mg], was exposed under potentiostatic control to the ionic liquid trihexyl(tetradecyl)phosphonium diphenylphosphate, denoted [P_6,6,6,14][DPP]. During exposure to this IL, a bias potential, shifted from open circuit, was applied to the ZE41 surface. Electrochemical impedance spectroscopy (EIS) and chronoamperometry (CA) were used to monitor the evolution of film formation on the metal surface during exposure. The EIS data indicate that, of the four bias potentials examined, applying a potential of −200 mV versus OCP during the exposure period resulted in surface films of greatest resistance. Both EIS measurements and scanning electron microscopy (SEM) imaging indicate that these surfaces are substantially different to those formed without potential bias. Time of flight-secondary ion mass spectrometry (ToF-SIMS) elemental mapping of the films was utilized to ascertain the distribution of the ionic liquid cationic and anionic species relative to the microstructural surface features of ZE41 and indicated a more uniform distribution compared with the surface following exposure in the absence of a bias potential. Immersion of the treated ZE41 specimens in a chloride contaminated salt solution clearly indicated that the ionic liquid generated surface films offered significant protection against pitting corrosion, although the intermetallics were still insufficiently protected by the IL and hence favored intergranular corrosion processes.

Visualisation of chemical processes during corrosion of zinc using magnetic resonance imaging

Compositional and structural changes within an electrolyte solution above an electrochemically active metal surface have been visualised using magnetic resonance imaging (MRI) for the first time. In these proof-of-concept experiments, zinc metal was galvanically corroded in a saturated lithium chloride solution. Magnetic resonance relaxation maps were taken during the corrosion process and spatial variations in both T₁ and T₂ relaxation times were observed to change with time. These changes were attributed to changes in the speciation of zinc ions in the electrolyte.

Photochromic fabrics from hybrid silica surface coatings

In this study, hybrid silica prepared by a sol-gel technique and doped with a photochromic dye was used to produce photochromic coatings on fabric surfaces. The coated fabrics showed a strong photochromic effect with very fast optical response speed. Good coating adhesion was obtained on wool fabrics. The photostability of the photochromic fabrics was improved by three different processes: adding a photo stabilizer, adjusting the surface wettability and sealing off the dye-containing pores with additional silica coating. Four UV stabilizers were added separately to the photochromic silica coatings to investigate their influence on the photostability and photochromic behaviour. The addition of UV stabilizers retarded the photochromic response and reduced photochromic absorption, but increased photochromic lifetime. Among the four UV stabilizers studied, the quencher resulted in the best improvement to the photostability with minimal reduction in the photochromic absorption. Increasing the hydrophobicity of the coating, and sealing-off the dye-containing pores were also found to improve photostability.

Evaluating the stability of disulfide bridges in proteins: a torsional potential energy surface for diethyl disulfide

Disulfide bonds formed by the oxidation of cysteine residues in proteins are the major form of intra- and inter-molecular covalent linkages in the polypeptide chain. To better understand the conformational energetics of this linkage, we have used the MP2(full)/6-31G(d) method to generate a full potential energy surface (PES) for the torsion of the model compound diethyl disulfide (DEDS) around its three critical dihedral angles (χ2, χ3, χ2′). The use of ten degree increments for each of the parameters resulted in a continuous, fine-grained surface. This allowed us to accurately predict the relative stabilities of disulfide bonds in high resolution structures from the Protein Data Bank. The MP2(full) surface showed significant qualitative differences from the PES calculated using the Amber force field. In particular, a different ordering was seen for the relative energies of the local minima. Thus, Amber energies are not reliable for comparison of the relative stabilities of disulfide bonds. Surprisingly, the surface did not show a minimum associated with χ2 − 60°, χ390, χ2′ − 60°. This is due to steric interference between Hα atoms. Despite this, significant populations of disulfides were found to adopt this conformation. In most cases this conformation is associated with an unusual secondary structure motif, the cross-strand disulfide. The relative instability of cross-strand disulfides is of great interest, as they have the potential to act as functional switches in redox processes.

Attractive forces between surfaces : what can and cannot be learned from a jump-in study with the surface forces apparatus?

We study theoretically the dynamics of film thinning under the action of an attractive surface force near the point of a jump instability. Our approach is illustrated by modeling van der Waals and hydrophobic attractive forces. The main result is that with the hydrophobic force law reported previously it is often impossible to establish the jump separation with any certainty. The surfaces instead approach slowly from a distance which is much larger than the point where an actual jump is expected. We conclude that an attractive force measured by the static jump technique is overestimated, and we formulate principles of a new dynamic jump method. The use of this new technique would permit direct measurements of attractive forces at separations below the static jump distance down to contact of the surfaces.

Wire beam electrode : a new tool for studying localised corrosion and other heterogeneous electrochemical processes

Heterogeneous electrochemical processes are very common in industry and are important, but difficult topics in electrochemical and corrosion science studies. Traditional electrochemical techniques which employ a conventional one-piece electrode have major limitations in studying heterogeneous electrochemical processes since the one-piece electrode has major difficulties in measuring electrochemical parameters from local areas of the electrode surface. In order to overcome this problem, a multi-piece electrode, namely the wire beam electrode, has been developed. This new electrode enables the measurement of electrochemical parameters from local areas over a working electrode surface and thus it can be used to study heterogeneous electrochemical processes. This paper describes how this new electrode was applied in studying several typical heterogeneous electrochemical processes including water-drop corrosion, corrosion under non-uniform organic films and cathodic protection.

Controlled synthesis of TiO2 hierarchical nanofibre structures via electrospinning and solvothermal processes : photocatalytic activity for degradation of methylene blue

The present article describes a new titanium oxide‐based (TiO2) photocatalyst that shows promise for acceleration of dye degradation. A hierarchical TiO2 nanostructure comprising nanorods on‐nanofibres has been prepared using a sol–gel route and electrospinning. Calcination of electrospun nanobre mats was performed in air at 500 °C. The TiO2 nanofibre surface was then exploited as a ‘seeding ground’ to grow TiO2 nanorods by a solvothermal process in NaOH. The nanofibres had a diameter of approximately 100 nm while the nanorods were evenly distributed on the nanofibre surface with a mean diameter of around 50–80 nm. The hierarchical nanostructure showed enhanced photocatalytic activity when compared to pure TiO2 nanofibres. This improved efficiency in degrading methylene blue through the photocatalytic process was attributed to the larger specific surface area of the TiO2 nanostructures, as well as high surface‐to‐volume ratio and higher reactive surface resulting in enhanced surface adsorption and interfacial redox reaction.

Structure retention in cross-linked poly(ethylene glycol) diacrylate hydrogel templated from a hexagonal lyotropic liquid crystal by controlling the surface tension

Retaining hexagonal lyotropic liquid crystal (LLC) structures in polymers after surfactant removal and drying is particularly challenging, as the surface tension existing during the drying processes tends to change the morphology. In this study, cross-linked poly(ethylene glycol) diacrylate (PEGDA) hydrogels were prepared in LLC hexagonal phases formed from a dodecyltrimethylammonium bromide (DTAB)/water system. The retention of the hexagonal LLC structures was examined by controlling the surface tension. Polarized light microscopy, X-ray diffraction and small angle X-ray scattering results indicate that the hexagonal LLC structure was successfully formed before polymerization and well retained after polymerization and after surfactant removal when the surface tension forces remained neutral. Controlling the surface tension during the drying process can retain the nanostructures templated from lyotropic liquid crystals which will result in the formation of materials with desired nanostructures.

The electrochemical surface forces apparatus : the effect of surface roughness, electrostatic surface potentials, and anodic oxide growth on interaction forces, and friction between dissimilar surfaces in aqueous solutions

We present a newly designed electrochemical surface forces apparatus (EC-SFA) that allows control and measurement of surface potentials and interfacial electrochemical reactions with simultaneous measurement of normal interaction forces (with nN resolution), friction forces (with μN resolution), and distances (with Å resolution) between apposing surfaces. We describe three applications of the developed EC-SFA and discuss the wide-range of potential other applications. In particular, we describe measurements of (1) force–distance profiles between smooth and rough gold surfaces and apposing self-assembled monolayer-covered smooth mica surfaces; (2) the effective changing thickness of anodically growing oxide layers with Å-accuracy on rough and smooth surfaces; and (3) friction forces evolving at a metal–ceramic contact, all as a function of the applied electrochemical potential. Interaction forces between atomically smooth surfaces are well-described using DLVO theory and the Hogg–Healy–Fuerstenau approximation for electric double layer interactions between dissimilar surfaces, which unintuitively predicts the possibility of attractive double layer forces between dissimilar surfaces whose surface potentials have similar sign, and repulsive forces between surfaces whose surface potentials have opposite sign. Surface roughness of the gold electrodes leads to an additional exponentially repulsive force in the force–distance profiles that is qualitatively well described by an extended DLVO model that includes repulsive hydration and steric forces. Comparing the measured thickness of the anodic gold oxide layer and the charge consumed for generating this layer allowed the identification of its chemical structure as a hydrated Au(OH)3 phase formed at the gold surface at high positive potentials. The EC-SFA allows, for the first time, one to look at complex long-term transient effects of dynamic processes (e.g., relaxation times), which are also reflected in friction forces while tuning electrochemical surface potentials.

Water-soluble complexes of hydrophobically modified polymer and surface active imidazolium-based ionic liquids for enhancing oil recovery

The current study introduces the water-soluble complexes containing hydrophobically associating copolymer and a series of surface activity imidazolium-based ionic liquids (CnmimBr, n=6, 8, 10, 12, 14 and 16). The polymer, denoted as PAAD, was prepared with acrylamide (AM), acrylic acid (AA) and N,N-diallyl-2-dodecylbenzenesulfonamide (DBDAP). And the hydrophobic associative behavior of PAAD was studied by a combination of the pyrene fluorescence probe and viscosimetry. Incorporation of CnmimBr (n=10, 12, 14 and 16) in PAAD leaded to the white thick gel, while the pellucid solutions were obtained in complexes of PAAD and CnmimBr (n=6 and 8); addition of C6mimBr around critical micelle concentration resulted in a large decrease in viscosity of solution. Therefore, we particularly investigated the performance of PAAD/C8mimBr complex. The interfacial tension of PAAD/C8mimBr complex solution and crude oil under different conditions was examined. Moreover, PAAD/C8mimBr complex exhibited superior temperature resistance and shear reversible performance for enhancing oil recovery (EOR) by rheological test. The promising EOR of 21.65% can be obtained by PAAD/C8mimBr complex showing high potential to utilize this kind of new complex in EOR processes.