Micro- and Nanoscale Deviations from Bulk Properties in Water

In a number of branches of the nanoscience community, researchers have been working to answer the question of whether or not the properties of water differ from the macroscale when viewed on the micro- and nanoscale. Specific areas of disagreement include fluid flow, molecular properties, and interaction with the surrounding environment. Regarding these cases, certain studies have concluded that there are no deviations from the macroscale, while others have found changes in opposite directions. The following paper outlines a series of relevant studies, highlighting the results, the processes behind the results, and the validity of these processes. The conclusion found is that water demonstrates noticeably different properties when observed on the micro- and nanoscale. The most promising aspect of working within the micro- or nanoscale is that materials do not always retain the same properties that are observed in the macroscale. Two classic examples are that carbon atoms will bond with each other to form nanotubes and gold nanoparticles will appear red. However, the characterization of water at this scale is more difficult. Much research has issued claims of the changing properties of water as experiments are scaled down, but other work has refuted such ideas. The purpose of the current paper is to examine a set of relevant literature and come to a determination over whether or not water deviates from its macroscopic properties on the micro- and nanoscales. Key areas of interest include whether or not water flow exhibits a slip boundary, whether or not viscosity differs, how bond energy differs, and how the presence of electric fields and adjacent structures affect water flow.

Slip Boundary in the Micro- and Nanoscale Classic fluid dynamics teaches that fluid velocity reduces all the way to zero at the point where it is touching a fixed surface, a concept referred to as the no-slip boundary. The following equation describes the fluid velocity profile between fixed parallel plates and this phenomenon
[1]

where v is the velocity, h is the distance between plates, dP/dx is the pressure drop per unit length, is the viscosity, and y is the vertical distance from the midpoint between the plates. However, an alternative form of the equation governing the same set of circumstances states that
[2]

where is a term known as the slip length, and all other variables are the same as above. Based on this equation, for cases where the slip length is greater than zero, there will be velocity at the boundary. At the macroscale, this is known to be false. Thus, the only other possibility is that is quite small, in which case h would have to be quite small as well in order to see any meaningful effects on the fluid velocity. Tretheway and Meinhart (2002) proposed this to be the case, attempting to prove their hypothesis by examining water flow through microscale channels. Tretheway and Meinharts work involved creating channels 300 m in width, pumping water through these microchannels, and observing the flow patterns through a microscope. They tested for the no-slip boundary under two conditionswith hydrophilic channels and hydrophobic channelsand found contrasting results. In the hydrophilic case, there was no velocity at the interface of the channel wall, corresponding with the macroscale fluid dynamics. Yet in the hydrophobic case, the velocity at the same boundary was 10% of the maximum fluid velocity, meaning that the slip length was not zero and there was a noticeable slip boundary.[2] Other studies have corroborated these findings. Tas, et al. (2004) ran water through hydrophilic capillary tubes and found that the no-slip boundary condition prevailed.[3] Conlisk, et al. (2002) used electrical currents to run water through both micro- and nanochannels with hydrophilic surfaces, again observing the no-slip boundary condition.[4] Finally, Ortiz-Young, et al. (2013) implemented a cantilever and atomic force microscopy to deposit and view small quantities of water at a hydrophobic solid-liquid interface. Under this experimental setup, they observed a slip boundary.[5]

Viscosity in the Micro- and Nanoscale Closely related to the prevalence or lack of a no-slip boundary is the question of how the microand nanoscale affect viscosity. The viscosity of a fluid is the measure of its resistance to deformation from shear stress, and is a quantity that is characteristic of every fluid and generally constant in the bulk phase.[1] This property causes the velocity of fluids to reach zero as they approach the boundary because the shear stress is highest at said boundary. Thus, an examination into how viscosity changes at the micro- and nanoscale can either support or refute the arguments above. Ortiz-Young, et al. executed an extensive investigation into the viscosity of water and other fluids at the microscale. Through a series of calculations involving the shear stress, the change in velocity with respect to distance, the cross-sectional area, the surface to microscope tip length, and the slip length, they were able to calculate the viscosity of their experimental fluids under various conditions. Across all the trials, the group found that the viscosity noticeably increased from the macroscopic value under hydrophobic conditions and noticeably decreased from the macroscopic value under hydrophobic conditions, but did not disclose exact values. Furthermore, they postulated that the large decrease in viscosity under the hydrophobic conditions directly related to the slipping that occurs. Because the water was not interacting with the boundary as significantly as it does under no-slip conditions, a much lower viscosity was seen. They did not, however, comment on what increased the viscosity in the hydrophilic case.[5] As a result, the work of Tas, et al. adequately compliments the work of Ortiz-Young, et al. When running water through small hydrophilic capillaries, they observed increases in viscosity. They were able to make this claim by observing under a microscope the flow of water through the capillaries and applying the macroscale equation for capillary height. The equation states that
[3]

where x is the position of the meniscus, is the contact angle between the fluid and the channel walls, is the surface tension of the fluid, h is the channel height, t is the time, and is the viscosity. Because all variable were known besides , they were able to plot x vs t1/2 and solve for viscosity by examining the slope of the line. From their experimental data and the above equation, Tas, et al. found that viscosity increased at the nanoscale. For a 150nm capillary, they found the viscosity of water to be seven percent higher than the bulk viscosity, and for a 50nm capillary, they found the viscosity of water to be 23 percent higher than the bulk viscosity. Furthermore, they found that adding salt to the water negated these effects and brought the viscosity down to the macroscopic value. This observation led them to conclude that the viscosity increases on the nanoscale because of electroviscous effects.[3] This relationship is given by the equation
[6]

where 0 is the bulk viscosity, f is the viscoelectric coefficient, and E is the electric field. As the scale of a system is reduced, the effects of the small electric field surrounding any atom become magnified. On a macroscopic level, they are negligible and the viscosity is the bulk viscosity, but they become significant enough to cause a noticeable increase when examined on the nanoscale. Contrarily, Kalra, et. al (2003) refuted the findings of both Ortiz-Youngs group and Tas group by claiming that water viscosity at the nanoscale was very similar to the bulk viscosity. Their work employed powerful simulation software to examine osmotic flow of water through a carbon nanotube, achieved by placing nanotubes between compartments of pure water and concentrated salt solutions.[7] Nevertheless, it is unwise to use Kalras work as a grounds for discrediting the aforementioned studies. Though scientists routinely use simulations to draw various conclusions and results published via simulations are well regarded by the community, probing the fundamental limits of any science with software will always be difficult. Kalras work has been cited over 500 times, but it is impossible to know

if the simulation code is correct when no one can definitively say exactly what is happening. This fact especially applies to simulations at the nanoscale, where observations that were at one point thought to be impossible have become the norm.

Bond Energy in the Micro- and Nanoscale Another important question that the nanoscience community has yet to resolve is whether scale affects bond energy. On the molecular scale, water is a fairly unique substance in that exhibits strong hydrogen bonding, but there has been disagreement over whether this hydrogen bonding is exhibited within nanochannels. Hummer, et al. (2001) immersed hydrophobic carbon nanotubes in water and observed the flow of water through the nanotubes. They used calculations based on the excess potential energy at either end of the tube to determine the flow rate of molecules through the tube, and ultimately determined that an average of 17 water molecules passed through the nanotube each nanosecond. Furthermore, they were able to calculate that hydrogen bonds between molecules lasted for an average of 5.6 picoseconds and that only 0.02 percent of water molecules existed outside of unbound pairs. These values substantially exceed both the 1.0 picosecond length of an average hydrogen bond in bulk water and the 15 percent of water molecules existing outside of unbound pairs on the macroscale.[8] Contrasting this is the work of Gordillo and Marti (2000). From the Ewald sum, the Verlet integration algorithm, and a series of assumptions about the potential of carbon nanotubes and waterwater interactions, they were able to simulate water molecules passing through carbon nanotubes. Their simulation found that different types of carbon nanotubes were more or less conducive to hydrogen bonding within their channels, but all values proved less than the hydrogen bonding in bulk water.[9]

As was the case before, Gordillo and Marti used high powered software and have a highly respected paper that has been cited nearly 200 times. Yet the same arguments hold about the unreliability of using software to simulate environments where macroscopic principles do not necessarily hold true, especially because Gordillos simulation involved a series of assumptions about both the water molecules and the nanotubes. Intuitively, it makes sense that there might be less hydrogen bonding in the 1-D environment of a nanotube because the bonds would typically take place across all three dimensions; but it is also easy to argue that the lack of volume within the chamber would decrease the distance between molecules and facilitate increased bond frequency and strength. Thus, it is likely that Hummers interpretation is closer to what is truly taking place.

Adjacent Elements in the Micro- and Nanoscale Environment The final area of disagreement among the scientific community that this paper will address is whether or not elements adjacent to fluid flow will uniquely affect physics at the micro- and nanoscale. At the macroscale, it is possible to bend a stream of water with an electric field, but it is generally difficult to influence flow to a great degree. However, as has been seen across all discussed properties, what is true at the macroscale does not always continue to be the case as the scale shrinks. Specifically, it is possible to influence flow to a much larger degree with electric fields and it is possible to influence flow with adjacent structures. Li, et al. (2007) again passed water molecules through carbon nanotubes. While the water was flowing, they applied electric fields at various distances from the surfaces of the nanotubes and observed the water flow in each case. They found that when the electric field was applied directly at the surface of the nanotube, flow through the tube ceased. This is a far more significant effect than applied voltage would ever have on bulk water flow. Furthermore, as they moved the electric field further away, the flow steadily increased until a critical point was reached at a distanced equal to the size of a water

molecule.[10] Though they are not certain why the critical point occurred at this distance, they theorize that it related to the applied field occurring within the electric fields surrounding the atoms. Gong, et al. (2008) created another study that contrasted everything seen at the macroscale. They found that by adding nanostructures adjacent to water molecules flowing through a carbon nanotube, they were able to influence the flow. That scenario is akin to insulating a pipe or putting it through a wall and having the flow within be affected. They created a series of experimental setups, all of which involved passing a carbon nanotube through graphitic sheets. The first setup ran the nanotube through one graphitic sheet; the second setup ran the nanotube through two graphitic sheets; the third setup ran the nanotube through five graphitic sheets; the fourth setup ran the nanotube through two graphitic sheets with water molecules occupying the free area between the sheets. Within these setups, the greatest flow occurred when the nanotube had a graphitic sheet at either end, and the least flow occurred when water molecules were between the sheets. [11]

Conclusion From all the arguments presented above, it is clear that water exhibits different properties in the micro- and nanoscale than the macroscale, both at the fluid interface and within the fluid. These differences include exhibiting a slip boundary when interacting with a hydrophobic surface; exhibiting a higher viscosity when interacting with a hydrophilic surface and a lower viscosity when interacting with a hydrophobic surface; exhibiting a higher bonding strength and frequency; and exhibiting the ability to be influenced at all by surrounding surfaces and to a much greater degree by electric fields. Though some resisted the recognition of these scaled down property changes, enough research has supported the claim that it can no longer be questioned. Nevertheless, there is still much for the scientific community to learn and understand before society will realize the full potential of nanotechnology.

Works Cited [1] B. R. Munson, W. W. Huebsch and A. P. Rothmayer, Fundamentals of Fluid Mechanics, Wiley, John & Sons Inc., 2011. [2] D. C. Tretheway and C. D. Meinhart, Apparent fluid slip at hydrophobic microchannel walls, Physics of Fluids, vol. 14, no. 3, pp. L9 12, 2002. [3] Tas, N. R., J. Haneveld, H. V. Jansen, M. Elwenspoek, and A. Van Den Berg. Capillary Filling Speed of Water in Nanochannels. Applied Physics Letters 85.15 (2004): 3274. Print. [4] A. T. Conlisk, J. McFerran, Z. Zheng and D. Hansford, Mas Transfer and Flow in Electrically Charged Micro- and Nanochannels, Analytical Chemistry, vol. 74, no. 9, pp. 2139 50, 2002. [5] D. Ortiz-Young, H.-C. Chiu, S. Kim and E. Riedo, The interplay between apparent viscosity and wettability in nanoconfined water, Nature Communications, vol. 4, no. 2482, 2013. [6] R. J. Hunter and J. V. Leyendekkers, "Viscoelectric Coefficient of Water," Journal of the Chemical Society, Faraday Transactions 1, vol. 74, pp. 450 - 455, 1977. [7] A. Karla, S. Garde and G. Hummer, "Osmotic water transport through carbon nanotube membranes," Proceedings of the National Academy of Sciences of the United States of America, vol. 100, no. 18, pp. 10175 - 10180, 2003. [8] G. Hummer, J. C. Rasaiah and J. P. Noworyta, "Water conduction through the hydrophobic channel of a carbon nanotube," Letters to Nature, vol. 414, pp. 188 - 190, 2001. [9] M. C. Gordillo and J. Marti, "Hydrogen bond structure of liquid water confined in nanotubes," Chemical Physical Letters, vol. 329, no. 5 - 6, pp. 341 - 345, 2000. [10] J. Li, X. Gong, H. Lu, D. Li, H. Fang and R. Zhou, "Electrostatic gating of a nanometer water channel," Proceedings of the National Academy of Sciences, vol. 104, no. 10, pp. 3687 - 3692, 2007. [11] X. Gong, J. Li, H. Zhang, R. Wan, H. Lu, S. Wang and H. Fang, "Enhancement of Water Permeation across a Nanochannel by the Structure outside the Chanell," Physical Review Letters, vol. 101, pp. 257801-4, 2008.