Research Papers: Micro/Nanoscale Heat Transfer

A Molecular Dynamics Study on Heat Transfer Characteristics Over the Interface of Self-Assembled Monolayer and Water Solvent

[+] Author and Article Information
Gota Kikugawa

Institute of Fluid Science,
Tohoku University,
2-1-1 Katahira,
Aoba-ku, Sendai 980-8577, Japan
e-mail: kikugawa@microheat.ifs.tohoku.ac.jp

Taku Ohara

Institute of Fluid Science,
Tohoku University,
2-1-1 Katahira,
Aoba-ku, Sendai 980-8577, Japan

Tohru Kawaguchi

500-1 Minamiyama, Komenoki-cho,
Nisshin, Aichi 470-0111, Japan

Ikuya Kinefuchi, Yoichiro Matsumoto

Department of Mechanical Engineering,
The University of Tokyo,
7-3-1 Hongo,
Bunkyo-ku, Tokyo 113-8656, Japan

1Corresponding author.

Contributed by the Heat Transfer Division of ASME for publication in the JOURNAL OF HEAT TRANSFER. Manuscript received July 25, 2013; final manuscript received June 18, 2014; published online July 15, 2014. Assoc. Editor: Patrick E. Phelan.

J. Heat Transfer 136(10), 102401 (Jul 15, 2014) (5 pages) Paper No: HT-13-1369; doi: 10.1115/1.4027910 History: Received July 25, 2013; Revised June 18, 2014

We performed molecular dynamics (MD) simulations of the interface which is comprised of self-assembled monolayer (SAM) and water solvent to investigate heat transfer characteristics. In particular, local thermal boundary conductance (TBC), which is an inverse of so-called Kapitza resistance, at the SAM–solvent interface was evaluated by using the nonequilibrium MD (NEMD) technique in which the one-dimensional thermal energy flux was imposed across the interface. By using two kinds of SAM terminal with hydrophobic and hydrophilic properties, the local TBCs of these interfaces with water solvent were evaluated, and the result showed a critical difference due to an affinity between SAM and solvent. In order to elucidate the molecular-scale mechanism that makes this difference, microscopic components contributing to thermal energy flux across the interface of hydrophilic SAM and water were evaluated in detail, i.e., the total thermal energy flux is decomposed into the heat transfer modes such as the contribution of molecular transport and that of energy exchange by molecular interactions. These heat transfer modes were also compared with those in the bulk water.

Copyright © 2014 by ASME
Your Session has timed out. Please sign back in to continue.


Das, S. K., Choi, S. U. S., and Patel, H. E., 2006, “Heat Transfer in Nanofluids—A Review,” Heat Transfer Eng., 27, pp. 3–19. [CrossRef]
Keblinski, P., Phillpot, S. R., Choi, S. U. S., and Eastman, J. A., 2002, “Mechanisms of Heat Flow in Suspensions of Nano-Sized Particles (Nanofluids),” Int. J. Heat Mass Transfer, 45, pp. 855–864. [CrossRef]
Keblinski, P., Eastman, J. A., and Cahill, D. G., 2005, “Nanofluids for Thermal Transport,” Mater. Today, 8, pp. 36–44. [CrossRef]
O’Brien, P. J., Shenogin, S., Liu, J., Chow, P. K., Laurencin, D., Mutin, P. H., Masashi Yamaguchi, M., Keblinski, P., and Ramanath, G., 2012, “Bonding-Induced Thermal Conductance Enhancement at Inorganic Heterointerfaces Using Nanomolecular Monolayers,” Nature Mater., 12, pp. 118–122. [CrossRef]
Kaur, S., Raravikar, N., Helms, B. A., Prasher, R., and Ogletree, D. F., 2014, “Enhanced Thermal Transport at Covalently Functionalized Carbon Nanotube Array Interfaces,” Nat. Commun., 5. [CrossRef]
Ulman, A., 1996, “Formation and Structure of Self-Assembled Monolayers,” Chem. Rev., 96, pp. 1533–1554. [CrossRef] [PubMed]
Schreiber, F., 2000, “Structure and Growth of Self-Assembling Monolayers,” Prog. Surf. Sci., 65, pp. 151–256. [CrossRef]
Love, J. C., Estroff, L. A., Kriebel, J. K., Nuzzo, R. G., and Whitesides, G. M., 2005, “Self-Assembled Monolayers of Thiolates on Metals as a Form of Nanotechnology,” Chem. Rev., 105, pp. 1103–1169. [CrossRef] [PubMed]
Dubois, L. H., and Nuzzo, R. G., 1992, “Synthesis, Structure, and Properties of Model Organic Surfaces,” Annu. Rev. Phys. Chem., 43, pp. 437–463. [CrossRef]
Ge, Z., Cahill, D. G., and Braun, P. V., 2006, “Thermal Conductance of Hydrophilic and Hydrophobic Interfaces,” Phys. Rev. Lett., 96, p. 186101. [CrossRef] [PubMed]
Shenogina, N., Godawat, R., Keblinski, P., and Garde, S., 2009, “How Wetting and Adhesion Affect Thermal Conductance of a Range of Hydrophobic to Hydrophilic Aqueous Interfaces,” Phys. Rev. Lett., 102, p. 156101. [CrossRef] [PubMed]
Kikugawa, G., Ohara, T., Kawaguchi, T., Torigoe, E., Hagiwara, Y., and Matsumoto, Y., 2009, “A Molecular Dynamics Study on Heat Transfer Characteristics at the Interfaces of Alkanethiolate Self-Assembled Monolayer and Organic Solvent,” J. Chem. Phys., 130, p. 074706. [CrossRef] [PubMed]
Kuang, S., and Gezelter, J. D., 2011, “Simulating Interfacial Thermal Conductance at Metal-Solvent Interfaces: The Role of Chemical Capping Agents,” J. Phys. Chem. C, 115, pp. 22475–22483. [CrossRef]
Stocker, K. M., and Gezelter, J. D., 2013, “Simulations of Heat Conduction at Thiolate-Capped Gold Surfaces: The Role of Chain Length and Solvent Penetration,” J. Phys. Chem. C, 117, pp. 7605–7612. [CrossRef]
Harikrishna, H., Ducker, W. A., and Huxtable, S. T., 2013, “The Influence of Interface Bonding on Thermal Transport Through Solid–Liquid Interfaces,” Appl. Phys. Lett., 102, p. 251606. [CrossRef]
Schoen, P. A. E., Michel, B., Curioni, A., and Poulikakos, D., 2009, “Hydrogen-Bond Enhanced Thermal Energy Transport at Functionalized, Hydrophobic and Hydrophilic Silica–Water Interfaces,” Chem. Phys. Lett., 476, pp. 271–276. [CrossRef]
Lincoln, R. C., Koliwad, K. M., and Ghate, P. B., 1967, “Morse-Potential Evaluation of Second- and Third-Order Elastic Constants of Some Cubic Metals,” Phys. Rev., 157, pp. 463–466. [CrossRef]
Shevade, A. V., Zhou, J., Zin, M. T., and Jiang, S., 2001, “Phase Behavior of Mixed Self-Assembled Monolayers of Alkanethiols on Au(111): A Configurational-Bias Monte Carlo Simulation Study,” Langmuir, 17, pp. 7566–7572. [CrossRef]
Khare, R., Sum, A. K., Nath, S. K., and de Pablo, J. J., 2004, “Simulation of Vapor-Liquid Phase Equilibria of Primary Alcohols and Alcohol-Alkane Mixtures,” J. Phys. Chem. B, 108, pp. 10071–10076. [CrossRef]
Balasubramanian, S., Klein, M. L., and Siepmann, J. I., 1995, “Monte Carlo Investigations of Hexadecane Films on a Metal Substrate,” J. Chem. Phys., 103, pp. 3184–3195. [CrossRef]
Zhang, L., Goddard, W. A., III, and Jiang, S., 2002, “Molecular Simulation Study of the c(4 × 2) Superlattice Structure of Alkanethiol Self-Assembled Monolayers on Au(111),” J. Chem. Phys., 117, pp. 7342–7349. [CrossRef]
Berendsen, H. J. C., Grigera, J. R., and Straatsma, T. P., 1987, “The Missing Term in Effective Pair Potentials,” J. Phys. Chem., 91, pp. 6269–6271. [CrossRef]
Rappé, A. K., Casewit, C. J., Goddard, W. A., III, and Skiff, W. M., 1992, “UFF, a Full Periodic Table Force Field for Molecular Mechanics and Molecular Dynamics Simulations,” J. Am. Chem. Soc., 114, pp. 10024–10035. [CrossRef]
Essmann, U., Perera, L., Berkowitz, M. L., Darden, T., Lee, H., and Pedersen, L. G., 1995, “A Smooth Particle Mesh Ewald Method,” J. Chem. Phys., 103, pp. 8577–8593. [CrossRef]
Tuckerman, M., Berne, B. J., and Martyna, G. J., 1992, “Reversible Multiple Time Scale Molecular Dynamics,” J. Chem. Phys., 97, pp. 1990–2001. [CrossRef]
Jund, P., and Jullien, R., 1999, “Molecular-Dynamics Calculation of the Thermal Conductivity of Vitreous Silica,” Phys. Rev. B, 59, pp. 13707–13711. [CrossRef]
Torii, D., Nakano, T., and Ohara, T., 2008, “Contribution of Inter- and Intramolecular Energy Transfers to Heat Conduction in Liquids,” J. Chem. Phys., 128, p. 044504. [CrossRef] [PubMed]
Howell, C., Maul, R., Wenzel, W., and Koelsch, P., 2010, “Interactions of Hydrophobic and Hydrophilic Self-Assembled Monolayers With Water as Probed by Sum-Frequency-Generation Spectroscopy,” Chem. Phys. Lett., 494, pp. 193–197. [CrossRef]
Tasić, U., Day, B. S., Yan, T., Morris, J. R., and Hase, W. L., 2008, “Chemical Dynamics Study of Intrasurface Hydrogen-Bonding Effects in Gas-Surface Energy Exchange and Accommodation,” J. Phys. Chem. C, 112, pp. 476–490. [CrossRef]


Grahic Jump Location
Fig. 1

A snapshot of the computational system of the C11OH-SAM/water system. The wireframe around the molecular system indicates a boundary of the MD basic cell and 3D periodic boundary condition is applied to that.

Grahic Jump Location
Fig. 2

Number density profiles and temperature distribution in (a) the C12-SAM/water system and (b) the C11OH-SAM/water system. Thick marked lines denotes the temperature, and thin solid lines denote the number density of each constituent. For alkanethiol SAM phase, green, yellow, red, and gray lines indicate the number density of carbon, sulfur, oxygen, and hydrogen atom, respectively. Only half of the cell is depicted due to system symmetry.

Grahic Jump Location
Fig. 3

Probability distribution of tilt angle of SAM molecules from the surface normal in both systems. Each profiles are normalized by sin θ, where θ is tilt angle.

Grahic Jump Location
Fig. 4

Contributions to total thermal energy flux at the SAM–solvent interface region in the C11OH-SAM/water system

Grahic Jump Location
Fig. 5

Contributions to total thermal energy flux in the bulk-like region of water solvent in the C11OH-SAM/water system



Some tools below are only available to our subscribers or users with an online account.

Related Content

Customize your page view by dragging and repositioning the boxes below.

Related Journal Articles
Related eBook Content
Topic Collections

Sorry! You do not have access to this content. For assistance or to subscribe, please contact us:

  • TELEPHONE: 1-800-843-2763 (Toll-free in the USA)
  • EMAIL: asmedigitalcollection@asme.org
Sign In