Nanoparticle manipulation by thermal gradient
© Wei et al; licensee Springer. 2012
Received: 2 September 2011
Accepted: 26 February 2012
Published: 26 February 2012
A method was proposed to manipulate nanoparticles through a thermal gradient. The motion of a fullerene molecule enclosed inside a (10, 10) carbon nanotube with a thermal gradient was studied by molecular dynamics simulations. We created a one-dimensional potential valley by imposing a symmetrical thermal gradient inside the nanotube. When the temperature gradient was large enough, the fullerene sank into the valley and became trapped. The escaping velocities of the fullerene were evaluated based on the relationship between thermal gradient and thermophoretic force. We then introduced a new way to manipulate the position of nanoparticles by translating the position of thermostats with desirable thermal gradients. Compared to nanomanipulation using a scanning tunneling microscope or an atomic force microscope, our method for nanomanipulation has a great advantage by not requiring a direct contact between the probe and the object.
Keywordsmolecular dynamics simulation thermal gradient thermophoresis manipulation carbon nanotube mass transport
Manipulation of atoms using a scanning tunneling microscope (STM) or an atomic force microscope (AFM) reveals the new era of nanotechnology or nanodesign . Atoms can now be arranged on demand. However, these approaches require a direct contact between the probe of STM/AFM and the object, which is of strong instrumental dependence and thus greatly restrains the manipulation. It is therefore desirable to seek new methods to manipulate nanoparticles without contact. In this work, we demonstrated that the mechanism of thermophoresis, in which case, atoms move opposite to the thermal gradient, could be utilized for nanoparticle manipulation.
Thermophoresis was actually discovered in the nineteenth century  which was induced by thermodiffusion. It was originally used to provide driving forces for molecules to move in fluids or gases [3, 4]. Recently, thermophoresis has been used for the manipulation and stretching of DNA [4, 5]. Carbon nanotubes (CNTs) have been selected as ideal 'transfer belts' for transferring gases and liquids by thermophoresis due to their atomically smooth surfaces and solid walls [6–11]. It is not until very recently that thermophoresis is found applicable on large molecular clusters or nanostructures. Experimentally, driven by thermal gradients, short CNTs are found to move relative to coaxial, longer CNTs [12, 13]; they can act as shuttles or capped capsules inside the longer CNTs  or as cargos attached to the outer walls of the longer CNTs . These short CNTs move while confined and guided by the host CNTs, and the motions could be translational or helical depending on the chirality of the CNTs . These exciting experimental results have stimulated much theoretical research on thermophoretic transport. From the theoretical calculations, all nanoparticles enclosed in the CNTs, including short CNTs , fullerene , gold nanoparticles [16, 17], and water droplets [10, 11] are found to move opposite to the imposed thermal gradient, and the terminal velocities are linearly proportional to the gradient. In addition, Zambrano et al.  discovered that the magnitude of thermophoretic force was not only related to the temperature gradient, but also dependent on the velocities of the transported molecules. At the same temperature gradient, the faster the motion, the smaller the thermophoretic force. Furthermore, thermophoresis is becoming one of the main approaches for cargo transport at nanoscale . Nevertheless, in all these previous reports, thermophoretic force is basically used to provide driving forces for the transportation of molecular linear motors.
In this paper, we extend the study of thermophoresis on nanotechnology in the aspect that not only the motions, but also the physical positions of the nanoparticles can be manipulated. Based on the mechanism of thermophoresis, we propose a model in which a fullerene is placed inside a CNT and subjected to a eudipleural thermal gradient. The cold region is in the middle, and the hot regions are in both ends, with periodic conditions along the axial direction. The fullerene inside will then be pushed to the middle cold region by the thermophoretic forces. In this case, we create a potential valley based on the temperature gradient. When the potential barrier is high enough, the fullerene will be trapped inside the potential valley. More interestingly, the trapped fullerene can also move as the cold source is shifted. Our results indicate the feasibilities of manipulating nanoparticles utilizing thermophoretic forces. The application of thermophoresis can then be extended from the thermal driving of molecular linear motors to thermal restrain using potential valleys and to thermal nanomanipulation.
where T i (slab) is the temperature of the i th slab, N is the number of carbon atoms in this slab, kB is the Boltzmann constant, and p j is the momentum of atom j. The nonequilibrium molecular dynamics (NEMD) simulation is performed under NEV ensemble for 5 ns.
Results and discussions
where k T is 449,384.5 and b T is -6.68 (Figure 3d). It would have been desirable to find out the relationship between the capture time of C60 and the thermal gradient, but this is difficult to obtain because of the position dependence of the thermal gradient. Note that the thermal gradients created in our NEMD simulations are higher than those used in the experiments [12, 13], where the thermal gradient was created by Joule heating  and/or the electron beam of a transmission electron microscope , which was roughly in the range of 1 to 3 K/nm. In our NEMD simulations, it would be time-consuming to trap the molecule in such a low thermal gradient. Therefore, our simple power-law relationship as described above can be used to provide some theoretical predictions for experimental exploitation, e.g., with a low thermal gradient of 1 to 3 K/nm as used in the previous experiments [12, 13]; the capture time is estimated to be about 4.38 to 450.6 μs.
where k A is 1.02. Therefore, a narrower thermostat is preferable if we want to accurately control the nanoparticles by thermal gradient.
In summary, we propose a new approach to manipulate nanoparticles by imposing a thermal gradient on the system. We extend the study of thermophoresis in nanotechnology from the continuous linear motion of nanoparticles that has been actively studied to the position restraining of nanoparticles by designing a one-dimensional thermal potential barrier. Nanoparticles will be pushed to the cold region by thermophoretic force and be restrained in the cold region with a small vibration of ± 1.0 nm along the tube's axial direction. Moreover, we further extend the idea of nanoparticle restraining to nanomanipulation. When the nanoparticle is restrained by thermal gradient potential valley, nanomanipulation can be achieved by translating thermal sources, and the nanoparticle will move following the same trace of the cold source. A nanoparticle inside CNT can therefore be manipulated on demand by thermophoretic force without a contact with it. The study of thermophoresis by nanorestrain and nanomanipulation will lead to a much wider usage of thermophoresis in the nanosystem and reveal the great potential applications of thermophoresis in nanodesign, mass transport, drug delivery, etc. Experimental work is thus called for to realize the thermophoretic utilization of nanomanipulation and nanodesign in potential applications.
This work is supported by the Specialized Research Fund for the Doctoral Program of Higher Education (grant nos. 20090121120028 and 20100121120026), the Natural Science Foundation of Fujian Province, China (grant no. 2010J05138), and the Program for New Century Excellent Talents in University (NCET; grant no. NCET-09-0680)
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