Tailoring the surface chemistry of carbon fiber and E-glass composites for improved adhesion

The main challenges in the manufacture of composite materials are low surface energy and the presence of silicon-containing contaminants, both of which greatly reduce surface adhesive strength. In this study, carbon fiber (CF) and E-glass epoxy resin composites were surface treated with the Accelerated Thermo-molecular adhesion Process (ATmaP). ATmaP is a multiaction surface treatment process where tailored nitrogen and oxygen functionalities are generated on the surface of the sample through the vaporization and atomization of n-methylpyrrolidone solution, injected via specially designed flame-treatment equipment. The treated surfaces of the polymer composites were analyzed using XPS, time of flight secondary ion mass spectrometry (ToF-SIMS), contact angle (CA) analysis and direct adhesion measurements. ATmaP treatment increased the surface concentration of polar functional groups while reducing surface contamination, resulting in increased adhesion strength. XPS and ToF-SIMS showed a significant decrease in silicon-containing species on the surface after ATmaP treatment. E-glass composite showed higher adhesion strength than CF composite, correlating with higher surface energy, higher concentrations of nitrogen and CO functional groups (from XPS) and higher concentrations of oxygen and nitrogen-containing functional groups (particularly C₂H₃O⁺ and C₂H₅NO⁺ molecular ions, from ToF-SIMS).

Surface-sensitive method to determine calcium carbonate filler contents in cellulose matrices

This paper describes a method using attenuated total reflectance infra-red spectroscopy to determine the surface concentration of calcium carbonate in paper samples, by applying the linear relationship between the relative infra-red absorption integrals and the concentration. The method was able to detect micro-variations in the surface concentration and could also distinguish between different sheets as well as between the top and bottom side of one sheet. The samples were also split and the calcium carbonate concentration was determined within and compared to bulk calcium carbonate concentration determined from ash testing. The surface results were also compared with analysed scanning electron microscopy images generated from back-scattering electrons. The comparison shows that both sets of results are in excellent agreement. Depending on the sample, large errors (95% confidence) were observed. These, however, are caused by micro-variations of the surface concentration, rather than by inaccuracies of the technique, which is estimated to be less than 1%. Furthermore, measurements of various sample orientations suggest that anisotropic polarisation effects can be neglected. The method can be applied to paper and cellulose matrices having calcium carbonate filler contents of less than 50%. Due to spectral overlaps it is not suitable to determine kaolin filler contents.

The characterization and chemical reactivity of powdered wool

Wool powders with various particle sizes have been produced using different milling techniques. Scanning electron microscopy (SEM) showed gradual breakdown of the fibre as it was progressively converted into powder form. Chlorination enhanced the effectiveness of subsequent air-jet milling. X-ray photoelectron spectroscopy (XPS) revealed an increase in the surface concentrations of oxygen and nitrogen, and a decrease in carbon and sulphur on conversion of the fibres into powders, as the cortex became exposed on the powder surface. An increased surface concentration of cysteic acid was observed for the chlorinated powder. Rapid uptake of dye by wool powders was observed in situations where there was virtually no uptake by the original fibre. Hydrophobic dyes were more readily sorbed than were hydrophilic dyes. The chlorination treatment led to a decrease in the sorption of acid dyes. Confocal microscopy, used in conjunction with a fluorescent stain, showed that chemicals were able to penetrate wool particles, even at room temperature. The rate and extent of uptake of dye by the finer powders were comparable to that obtained with activated charcoal, even though the surface area of the charcoal was 100 times greater.

Influence of particle concentration on initial collection efficiency and surface coverage in porous media filtration

Four sizes (0.095, 0.53, 1.0 and 2.01 μm) of polystyrene latex particles were used to prepare monodispersed suspensions at three different ionic strengths (10−3, 10−2.5 and 10−2M KCl). Filtration experiments were conducted using those suspensions in a filter column with glass beads as porous medium. The filter bed depth and the filtration velocity were kept at 5 cm and 1 m/h, respectively. When suspensions with equal mass concentrations (0.2 mg/L) or equal surface area concentrations (0.12 cm2/mL) were filtered through the system, the largest particles exhibited higher initial single collector efficiency, η. The difference between the η of largest particles and the smaller particles was prominent for suspensions with equal surface area concentrations at higher ionic strengths. The collision efficiency, α of those particles exhibits higher values at higher ionic strengths. Both at equal mass concentration and equal surface area concentration, α is only slightly dependent on particle sizes when compared to its dependence on ionic strength. Further, it was found that the specific surface coverage was similar for 0.095 μm, 0.53 μm and 1.0 μm particles during the transient stage of filtration at any ionic strength when the surface area concentrations of those suspension were equal.

Surface analysis of aluminium by glow-discharge optical emission spectrometry

Surface engineering in solids has become an important field in materials science. Glow-discharge optical emission spectrometry (GD-OES) has proven to be a powerful tool for the rapid analysis of elements in the surface of solids. One may employ GD-OES to determine quantitatively the bulk concentration of elements in a sample, and elemental concentrations as a function of depth. Presented here is an overview of GD-OES analysis and an application to aluminium.

The influence of polymerization time and dopant concentration on the absorption of microwave radiation in conducting polypyrrole coated textiles

Temperature changes in conducting polypyrrole/para-toluene-2-sulphonic acid (PPy/pTSA) coated nylon textiles due to microwave absorption in the 8–9 GHz and 15–16 GHz frequency ranges were obtained by a thermography station during simultaneous irradiation of the samples. The temperature values are compared and related to the amounts of reflection, transmission and absorption obtained with a non-contact free space transmission technique, indicating a relationship between microwave absorption and temperature increase. Non-conductive samples showed no temperature increase upon irradiation irrespective of frequency range. The maximum temperature difference of around 4 °C in the conducting fabrics relative to ambient temperature was observed in samples having 48% absorption and 26.5 ± 4% reflection. Samples polymerized for 60 or 120 min with a dopant concentration of 0.018 mol/l or polymerized for 180 min with a dopant concentration of 0.009 mol/l yielded optimum absorption levels. As the surface resistivity decreased and the reflection levels increased, the temperature increase upon irradiation reduced.

Response surface optimisation of medium components for naringinase production from staphylococcus xylosus MAK 2

Response surface methodology was used to optimize the fermentation medium for enhancing naringinase production by Staphylococcus xylosus. The first step of this process involved the individual adjustment and optimization of various medium components at shake flask level. Sources of carbon (sucrose) and nitrogen (sodium nitrate), as well as an inducer (naringin) and pH levels were all found to be the important factors significantly affecting naringinase production. In the second step, a 22 full factorial central composite design was applied to determine the optimal levels of each of the significant variables. A second-order polynomial was derived by multiple regression analysis on the experimental data. Using this methodology, the optimum values for the critical components were obtained as follows: sucrose, 10.0%; sodium nitrate, 10.0%; pH 5.6; biomass concentration, 1.58%; and naringin, 0.50% (w/v), respectively. Under optimal conditions, the experimental naringinase production was 8.45 U/mL. The determination coefficients (R ²) were 0.9908 and 0.9950 for naringinase activity and biomass production, respectively, indicating an adequate degree of reliability in the model.

Integral approach and numerical improvement to calculate the carbon concentration profiles in carburising process

In the present work, the carbon diffusion in steel, where the carbon diffusivity varies with the carbon content, was solved with the integral methods under the third boundary condition. The variation of carbon diffusivity in steel with the carbon content was described with two different functions ie. linear dependence and exponential dependence. The integral approximation for both cases was improved with the numerical computation to more accurately predict the carbon profiles. The integral solution is more accurate than the formulation based on the assumption of a constant diffusivity or those based on the assumption of a constant diffusivity and/or constant carbon content at part surface. It is also more easily used in practice than the numerical method to describe the carburising process and predict the carbon content at steel surface and carbon profiles in treated layer.

Aggregation, ageing and transport properties of surface modified fumed silica dispersions

We have investigated the aggregation, ageing and transport properties of surface modified silica dispersions in DMSO by photon correlation spectroscopy and conductivity measurements. The surface modification introduces Li+-ions that dissociate in the dispersion creating a single Li+-ion conducting electrolyte. We show that the surface modification changes the aggregation and ageing properties of the material. There is a pronounced ageing observed for the modified silica dispersions. At high concentrations of fumed silica a gel state is found, which in the case of the surface modified silica is a very weak gel that can be rejuvenated by ultrasonic treatment. The key parameter controlling the aggregation in this system is hydrogen bonding and the surface modification results in a very low number of sites for hydrogen bonding. In addition there is a contribution from repulsive electrostatic interactions in the surface modified silica dispersions due to the highly charged surfaces of these particles. Furthermore, the Li+-ion diffusion, at low silica concentration, is three orders of magnitude faster than that of the silica particles and in the gel state the silica particles are immobile. We also find that the Li+-ion diffusion is virtually independent of the silica concentration in the dispersions.

Exploring molecular changes at the surface of polypropylene after accelerated thermomolecular adhesion treatments

A central composite rotatable design (CCRD) method was used to investigate the performance of the accelerated thermomolecular adhesion process (ATmaP), at different operating conditions. ATmaP is a modified flame-treatment process that features the injection of a coupling agent into the flame to impart a tailored molecular surface chemistry on the work piece. In this study, the surface properties of treated polypropylene were evaluated using X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). All samples showed a significant increase in the relative concentration of oxygen (up to 12.2%) and nitrogen (up to 2.4%) at the surface in comparison with the untreated sample (0.7% oxygen and no detectable nitrogen) as measured by XPS. ToF-SIMS and principal components analysis (PCA) showed that ATmaP induced multiple reactions at the polypropylene surface such as chain scission, oxidation, nitration, condensation, and molecular loss, as indicated by changes in the relative intensities of the hydrocarbon (C₃H₇⁺ , C₃H₅⁺ , C₄H₇⁺, and C₅H₉⁺), nitrogen and oxygen-containing secondary ions (C₂H₃O⁺, C₃H₈N⁺, C₂H₅NO⁺, C₃H₆NO⁺, and C₃H₇NO⁺). The increase in relative intensity of the nitrogen oxide ions (C₂H₅NO⁺ and C₃H₇NO⁺) correlates with the process of incorporating oxides of nitrogen into the surface as a result of the injection of the ATmaP coupling agent.

Surface-enhanced raman scattering spectroscopy of resveratrol

We report here, for the first time, the surface-enhanced Raman scattering (SERS) spectra of resveratrol using KNO₃-aggregated citrate-reduced silver (Ag) colloids. The technique provided a substantial spectral enhancement and therefore good quality spectra of resveratrol at parts per million (ppm) concentrations. The detection limit was found to be <1 μM, equivalent to <0.2 ppm. The SERS profile additionally closely resembled its normal solid-state Raman spectrum with some changes in relative intensity. These intensity changes, together with a precise band assignment aided by density functional theory calculations at the B3LYP/6–31G(d) level, allowed the determination of the structural orientation of the adsorbed resveratrol on the surface of the metal nanoparticles. In particular, the SERS spectra obtained at different resveratrol concentrations exhibited concentration-dependent features, suggesting an influence of surface coverage on the orientation of the adsorbed molecules. At a high concentration, an adoption of close-to-upright orientation of resveratrol adsorbed on the metal surface through the p-OH phenyl ring is favoured. The binding structure is, however, altered at lower surface coverage when the concentration decreases to a tilted orientation with the trans-olefin C=C bond aligning closer to parallel to the surface of the Ag nanoparticles.

Surface coverage of filter medium in deep bed filtration : mathematical modelling and experiments

This paper highlights the importance of surface coverage in modeling the removal of particles in deep bed filtration. A model that considers the saturation of sites on which particle deposition occurs is used. Experimental results obtained with monodispersed suspensions of 0.46 and 0.816 μm latex particles at different influent concentrations and ionic strengths were used to calculate the fraction of filter grain surface (β1) on which actual particle deposition occurs. This will be useful in evaluating the filter performance in terms of the utilization of available surface area of the filter medium. Further, the level of dendrite formation of particles on filter grains during filtration is expressed in terms of β1 and the specific surface coverage, θT (the fraction of a filter grain surface that is covered by particles at time T, assuming that the filter grain is covered by a monolayer of particles). This can be used to compare the contribution of deposited particles in the removal efficiency of deep bed filtration for suspensions with different physical and chemical characteristics.

Chemotoxicity of doxorubicin and surface expression of P-glycoprotein (MDR1) is regulated by the Pseudomonas aeruginosa toxin Cif

P-glycoprotein (Pgp), a member of the adenosine triphosphate-binding cassette (ABC) transporter superfamily, is a major drug efflux pump expressed in normal tissues, and is overexpressed in many human cancers. Overexpression of Pgp results in reduced intracellular drug concentration and cytotoxicity of chemotherapeutic drugs and is thought to contribute to multidrug resistance of cancer cells. The involvement of Pgp in clinical drug resistance has led to a search for molecules that block Pgp transporter activity to improve the efficacy and pharmacokinetics of therapeutic agents. We have recently identified and characterized a secreted toxin from Pseudomonas aeruginosa, designated cystic fibrosis transmembrane conductance regulator (CFTR) inhibitory factor (Cif). Cif reduces the apical membrane abundance of CFTR, also an ABC transporter, and inhibits the CFTR-mediated chloride ion secretion by human airway and kidney epithelial cells. We report presently that Cif also inhibits the apical membrane abundance of Pgp in kidney, airway, and intestinal epithelial cells but has no effect on plasma membrane abundance of multidrug resistance protein 1 or 2. Cif increased the drug sensitivity to doxorubicin in kidney cells expressing Pgp by 10-fold and increased the cellular accumulation of daunorubicin by 2-fold. Thus our studies show that Cif increases the sensitivity of Pgp-overexpressing cells to doxorubicin, consistent with the hypothesis that Cif affects Pgp functional expression. These results suggest that Cif may be useful to develop a new class of specific inhibitors of Pgp aimed at increasing the sensitivity of tumors to chemotherapeutic drugs, and at improving the bioavailability of Pgp transport substrates.

Measurement of surface forces between mica sheets immersed in aqueous quaternary ammonium ion solutions

Forces between mica surfaces immersed in Me4NBr, Pr4NBr, and Pe4NBr solutions over a wide concentration range are reported (Me = methyl, Pr = propyl, Pe = pentyl). In each case the cation adsorbs quite strongly onto the negatively charged mica surface and determines the double-layer potential. However, this strong adsorption does not cause complete neutralization of the negative lattice charge apparently because of packing constraints due to the large size of these ions. Adsorption of Me4N+ ions gives rise to a short-range (<2 nm) repulsive force similar to that previously observed between bilayers of CTAB and may be due to the residual hydration of these ions. The large rations also, unexpectedly, give rise to short-range repulsive forces but of a somewhat different nature. In this case, the repulsive forces can be explained by assuming that the large adsorbed ions shift the plane of charge a distance of one ion diameter from the mica surface. At all but very high concentrations these larger ions could be displaced from the mica surfaces on forcing them together. No evidence of any “hydrophobic attraction” was observed between surfaces containing these adsorbed ions. Previous studies on coagulation are discussed in the light of our results.