Reverse osmosis (RO) is currently the most important desalination technology and it is experiencing significant growth. The objective of this paper is to review the historical and current development of RO membrane materials which are the key determinant of separation performance and water productivity, and to define the targets for those who are developing new RO membrane materials. The chemistry, synthesis mechanism(s) and desalination performance of various RO membranes are discussed from the point of view of membrane materials science. The review starts with the first generation of asymmetric polymeric membranes and finishes with current proposals for nano-structured membrane materials. The review provides an overview of RO performance in relation to membrane materials and methods of synthesis. To date polymeric membranes have dominated the RO desalination industry. From the late 1950s to the 1980s the research effort focussed on the search for optimum polymeric membrane materials. In subsequent decades the performance of RO membranes has been optimised via control of membrane formation reactions, and the use of poly-condensation catalysts and additives. The performance of the state-of-the-art RO membrane has been highlighted. Nevertheless, the advances in membrane permselectivity in the past decade has been relatively slow, and membrane fouling remains a severe problem. The emergence of nano-technology in membrane materials science could offer an attractive alternative to polymeric materials. Hence nano-structured membranes are discussed in this review including zeolite membranes, thin film nano-composite membranes, carbon nano-tube membranes, and biomimetic membranes. It is proposed that these novel materials represent the most likely opportunities for enhanced RO desalination performance in the future, but that a number of challenges remain with regard to their practical implementation.
This review deals with the static and dynamic behavior of liquids inside carbon nanotubes, a broad subject, which includes: the investigation of liquid entering inside the tubes, and the subsequent filling of them, the overall flow through tubes as well as the wetting of the nanotube walls. Although most of the numerical work has been done on small diameter nanotubes, due to computational limitations, a large wealth of experimental results have been obtained for larger diameter nanotubes, between 10 and 100 nm, or above. This review offers an overview of the major achievements in the field, with particular emphasis on the effect on liquid flow through them of the structure and chemistry of carbon nanotubes. The limit below which liquids confined in nanotubes will not obey classical fluid dynamics equations as well as the structure and state of liquids under confinement will also be reviewed. Finally, near-to commercialization and still-inthe-lab applications will be covered.
The use of carbon nanomaterials in various applications requires precise control of their surface and bulk properties. In this paper, we present a strategy for modifying the surface chemistry, wettability, and electrical conductivity of carbon tubes and films through annealing in a vacuum. Experiments were conducted with 60-300 nm nanotubes (nanopipes), produced by noncatalytic chemical vapor deposition (CVD) in a porous alumina template, and with thin films deposited by the same technique on a glassy carbon substrate having the same structure and chemistry of the CNTs. The surface of the as-produced CVD-carbon, treated with sodium hydroxide to remove the alumina template, is hydrophilic, and the bulk electrical conductivity is lower by a factor of 20 than that of fully graphitic multiwalled nanotubes (MWNT) or bulk graphite. The bulk electrical conductivity increases to the conductivity of graphite after annealing at 2000°C in a high vacuum. The analysis of CNTs by transmission electron microscopy (TEM) and Raman spectroscopy shows the ordering of carbon accompanied by an exponential increase of the in-plane crystallite size, L a , with increasing annealing temperature. Environmental scanning electron microscopy (ESEM) was used to study the interaction of CNT with water, and contact angle measurements performed using the sessile drop method on CVDcarbon films demonstrate that the contact angle increases nearly linearly with increasing annealing temperature.
All published reports on fluid flow enhancement and water slippage are associated with hydrophobic surfaces, such as carbon nanotubes. Here, we investigate water flow in hydrophilic alumina nanochannels with diameters ranging from 20 nm to 100 nm. For the smallest channels tested, the water permeability is more than double than the theoretical prediction using the Hagen-Poiseuille equation. Though such an enhancement is significantly smaller than what has been measured in carbon nanotubes, it clearly shows that flow enhancement and water slippage occurs on hydrophilic surfaces as well, contrary to existing theoretical models. To the authors' knowledge, it is the first experimental demonstration of water slippage on hydrophilic surfaces. The results show the dependence of the flow enhancement on the surface chemistry, diameter and length of the nanochannel.
Experimental and simulation measurements of water flow through carbon nanotubes have shown orders of magnitude higher flow rates than what was predicted using continuum fluid mechanics models. Different explanations have been offered, from slippage of water on the hydrophobic surface of the nanotubes to size confinement effects. In this work a model capable of explaining these observations, linking the enhanced flow rates observed to the solid-liquid molecular interactions at the nanotube wall is proposed. The model is capable of separating the effects on flow enhancement of the tube characteristic dimensions and the solid-liquid molecular interactions, accurately predicting the effect of each component for nanotubes of different sizes, wall surface chemistry and structure. Comparison with the experimental data available shows good agreement.
The high water flow rates observed in carbon nanotubes (CNTs) have previously been attributed to the unfavorable energetic interaction between the liquid and the graphitic walls of the CNTs. This paper reports molecular dynamics simulations of water flow in carbon, boron nitride, and silicon carbide nanotubes that show the effect of the solid-liquid interactions on the fluid flow. Alongside an analytical model, these results show that the flow enhancement depends on the tube's geometric characteristics and the solid-liquid interactions.
The handling, dispersion, manipulation, and functionalization of carbon nanotubes and nanopipes often require the use of solvents. Therefore, a good understanding of the wetting properties of the carbon nanotubes is needed. Such knowledge is also essential for the design of nanotube-based nanofluidic devices, which hold the promise of revolutionizing chemical analysis, separation, drug delivery, filtration, and sensing. In this work, we investigated the wetting behavior of individual nanopipes produced by the chemical vapor deposition (CVD) of carbon in porous alumina templates and of thin carbon films produced by the same technique. The carbon pipes and films have the same chemistry and structure as determined by Raman and infrared spectroscopies and, when similarly treated, demonstrate the same qualitative wetting behavior, as determined by optical microscopy. Thus, measurements conducted on the carbon film surface are relevant to the nanopipes. In the case of the nanopipes, filling with various liquids was monitored. Contact angle experiments with both polar (water, glycerol, ethylene glycol, ethanol, tetra-hydro furan, and 2-propanol alcohol) and nonpolar liquids (cyclohexane, hexadecane, poly(dimethylsiloxane), and a fluoro-silicone) were conducted on films using the sessile drop method. The contact angles on the CVD carbon films ranged from 0 to 79 degrees. The exposure of the carbon films to a NaOH solution, typically used to dissolve the alumina template, led to a significant decrease of the contact angle, especially in the case of polar liquids.
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