The widespread use of silver nanoparticles (Ag-NPs) in commercial products, especially textiles, will likely result in an unknown spread of Ag into the environment. The quantification and characterization of the Ag released from nano-Ag-products is an important parameter needed to predict the effect of Ag-NPs on the environment. The aim of this study was to determine the amount and the form of Ag released during washing from nine fabrics with different ways of silver incorporation into or onto the fibers. The effect of pH, surfactants, and oxidizing agents was evaluated. The results show that little dissolution of Ag-NPs occurs under conditions relevant to washing (pH 10) with dissolved concentrations 10 times lower than at pH 7. However, bleaching agents such as hydrogen peroxide or peracetic acid (formed by the perborate/TAED system) can greatly accelerate the dissolution of Ag. The amount and form of Ag released from the fabrics as ionic and particulate Ag depended on the type of Ag-incorporation into the textile. The percentage of the total silver emitted during one washing of the textiles varied considerably among products (from less than 1 to 45%). In the washing machine the majority of the Ag (at least 50% but mostly >75%) was released in the size fraction >450 nm, indicating the dominant role of mechanical stress. A conventional silver textile did not show any significant difference in the size distribution of the released silver compared to many of the textiles containing nano-Ag. These results have important implications for the risk assessment of Ag-textiles and also for environmental fate studies of nano-Ag, because they show that under conditions relevant to washing, primarily coarse Ag-containing particles are released.
We have measured the adsorption isotherms of water on a single surface of freshly cleaved mica with K+ on the surface, and on mica where the K+ has been exchanged for H+. Using a very sensitive interferometric technique, we have found a significant difference between the two isotherms at submonolayer coverage, for relative vapor pressures p/p0 < 0.5. The K+-mica isotherm shows a pronounced convexity, suggesting distinct adsorption sites, whereas the H+-mica isotherm is flatter. The two isotherms converge above monolayer coverage. The results give a graphic demonstration of the importance of nanoscale surface heterogeneities for vapor adsorption at submonolayer coverage.
This article describes details of the operation and performance of fast spectral correlation interferometry, which allows for considerably improved operation of the surface forces apparatus. Up to 150 interference fringes can be simultaneously tracked over a wide spectral range, leading to considerably more precise and simultaneous extraction of multiple optical quantities, over a greatly extended distance range. When used for surface-separation measurement, a precision of 25 pm is readily achievable over a distance ranging from 0 to >10 μm. Data acquisition rates are also considerably improved, allowing for dynamic measurements. Automated actuation of optical deflectors introduces a multidimensional scanning capability to the optical probe with a lateral resolution of 1 μm. The entire process is computer controlled and features unattended batch processing of complex measurements. This publication illustrates experimental setup, methodology, measurements, and detailed error calculation for a selection of practically relevant situations in the extended surface forces apparatus.
Knowing the behavior of a fluid in small volumes is essential for the understanding of a vast array of common problems in science, such as biological interactions, fracture propagation, and molecular tribology and adhesion, as well as pressure solvation and other geophysical processes. When a fluid is confined, its phase behavior is altered and excluded-volume effects become apparent. Pioneering measurements performed with the surface forces apparatus have revealed so-called structural or oscillatory solvation forces as well as the occurrence of a finite shear stress, which was interpreted as a solidification transition. Here, we report measurements obtained with an extended surface forces apparatus, which makes use of fast spectral correlation to gain insight into the behavior of a thin film of cyclohexane confined within attoliter volumes, with simultaneous measurement of film thickness and refractive index. With decreasing pore width, cyclohexane is found to undergo a drastic transition from a three-dimensional bulk fluid to a two-dimensional adsorbate with strikingly different properties. Long-range density fluctuations of unexpected magnitude are observed.
The molecular interactions on a protein-resistant surface coated with low-molecular-weight poly(ethylene glycol) (PEG) copolymer brushes are investigated using the extended surface forces apparatus. The observed interaction force is predominantly repulsive and nearly elastic. The chains are extended with respect to the Flory radius, which is in agreement with qualitative predictions of scaling theory. Comparison with theory allows the determination of relevant quantities such as brush length and adsorbed mass. Based on these results, we propose a molecular model for the adsorbed copolymer morphology. Surface-force isotherms measured at high resolution allow distinctive structural forces to be detected, suggesting the existence of a weak equilibrium network between poly(ethylene glycol) and water--a finding in accordance with the remarkable solution properties of PEG. The occurrence of a fine structure is interpreted as a water-induced restriction of the polymer's conformational space. This restriction is highly relevant for the phenomenon of PEG protein resistance. Protein adsorption requires conformational transitions, both in the protein as well as in the PEG layer, which are energetically and kinetically unfavorable.
Nano-TiO(2) has the highest production of all nanomaterials, and pigment-TiO(2) is a commodity used on the million tons/year scale. Information on the release of TiO(2) from consumer products is therefore an important part of analyzing the potential environmental exposure to TiO(2). For this study, we investigated the release of TiO(2) from six different functional textiles during washing. TiO(2) is used in textiles because of its UV-absorbing properties and as pigment. Analysis of fiber cross sections showed that the TiO(2) was contained in the fiber matrix. The sun-protection textiles had Ultraviolet Protection Factors that were between 58 and 6100 after washing and therefore above the labeled factor of 50+. Five of the textiles (sun-protection clothes) released low amounts of Ti (0.01 to 0.06 wt % of total Ti) in one wash cycle. One textile (with antimicrobial functionality) released much higher amounts of Ti (5 mg/L, corresponding to 3.4 wt % of total Ti in one wash cycle). Size fractionation showed that about equal amounts were released as particles below and above 0.45 μm. After 10 washings, only in two textiles significantly lower Ti contents were measured. Electron microscopy showed that the TiO(2) particles released into washing solution had a roundish appearance with primary particle sizes between 60 and 350 nm that formed small aggregates with up to 20 particles. The results indicate that functional textiles release some TiO(2) particles, but that the amounts are relatively low and mostly not in the nanoparticulate range.
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