Running Head: Thermodynamics on the Nanoscale

Thermodynamics on the Nanoscale

Seth Roberts
ENGR 1050-001: Introduction to Nanotechnology

Thermodynamics on the Nanoscale

Since the dawn of Human innovation, Humans have sought to refine methods of
execution and improve their ability to accomplish tasks. Innovative technologies have allowed
them to move great amounts of Earth, refine and sculpt metals, and even take to the skies. Recent
innovations have inundated Human culture with electronics that continue to get smaller, more
compact and run for longer and longer periods of time. Decreasing the size of electronics brings
the components in its circuitry closer and closer together until the smallest changes to the system
can diminish the integrity of the system, ceasing its functioning ability. When the size of a
system is between 1-100nm it is considered to be a nanoscale system. Technology on the
nanoscale is beneficial in a variety of ways such as: smaller more compact electronics, faster
processing speeds and higher energy efficiencies. These benefits have allowed for a variety of
innovations within the technology field that has come with great success but also comes with its
own set of issues to be worked around. The longer a circuit has a current flowing through it the
more time there is for heat to build up. When chemicals undergo increases in temperature they
may be released from their bonds and reorient themselves momentarily. This changes the
directionality of say a circuit and in turn causes it to stop functioning how it was designed to. It is
these kinds of changes that have partially inspired the field of study known as NanoThermodynamics.
Nano-Thermodynamics is the study of the thermal properties of materials and objects
with sizes of 1 to 100 nm. Objects on the bulk or macroscale have a high volume to surface ratio,
whereas particles on the nanoscale have high surface to volume ratios. This means that if a
sphere has a constant inner temperature the rate at which it dissipates this energy at its surface is
dependent on the surface area. If the sphere is continually shrunk down to the nanoscale it will
eventually have a higher surface area dissipation rate then if it were on the bulk scale. This

Thermodynamics on the Nanoscale

conceptual example shows that particles on the nanoscale radiate energy far more quickly than
their bulk counterparts; this is why nanoscale electronics are so efficient at energy transport.
While this efficiency is what current innovators seek it is also the cause of some reasonable
issues with the nanotech when heat is considered. A high exchange rate for heat means a lot of
free energy radiating within the system. High energy within the system provides it with the
needed energy for the components to reorient themselves and recrystallize. Depending on the
temperature and the components being considered this free energy may induce growth of
structure size, change in structure orientation or even cause chemicals to disassociate all together.
This becomes problematic for electronics as a change in the systems structure, changes it very
functioning ability. With technologies having increasing run times the study of NanoThermodynamics is becoming increasingly necessary in the creation of nanotech and the
effectiveness of models meant to predict the effects of temperature exchange on the nanoscale.
Measuring temperature on the nanoscale can be very difficult given that objects on the
nanoscale are around one billionth of a meter. When temperature is taken with a thermometer
energy is transferred from the object to the thermometer, this technically changes the objects
temperature, but on the bulk scale this change is so small it is often disregarded. On the
nanoscale this exchange of temperature is rather significant and may change the very
temperature of the nano object under study. This is why researchers at the University of Exeter
and the University College of London have devised a method for measuring the temperature of
nanoscale objects somewhat indirectly. By using light of wavelength 1,064 nm linked through
lenses from single-mode optical bers, the researchers created an optical trap. By trapping a nano
sized silica sphere in this dual-beam the researchers were able to monitor the changes in the
molecular motion of the air molecules that surrounded the silica sphere. This technique allowed

Thermodynamics on the Nanoscale

the researchers to observe the effects of the nanoparticles changing temperature on its
environment and in turn infer its temperature. They claim that this technique will also allow for
individual surface measurements which could have numerous benefits in the field of
nanotechnology as well as the field of meteorological study, considering that this method also
gives light on temperature exchange on the nanoscale which could be used for atmospheric
study. (Nature, 2014)
Monitoring the rate of temperature exchange on the nanoscale can be a bit tricky that is
why researchers Yihua Gao and Yoshio Bando from the Advanced Materials Laboratory and
Nanomaterials Laboratory at the National Institute for Materials Science have come up with an
idea for a nanoscale thermometer. By using carbon nano tubes with an inner diameter of 75nm
these researchers were able to fill the tubes with liquid gallium at a diameter of 75nm. The intent
of the research was to observe the expansion characteristics of nano-liquid gallium compared to
its macroscale counterpart. Gallium has been found to have a somewhat unique property with
respect to temperature in that the surface expansion rate as temperature increases is virtually
identical on both the nanoscale and macroscale. These researchers found that this property is
consistent in the ranges of 50-500C. Suggesting volumetric expansion coefficient can be
directly used for the calibration of a given nano thermometer with a diameter larger than 10 nm.
This showed that liquid Gallium within a carbon nanotube can be an effective measure of
temperature exchange on the nanoscale. (Gao, 2002) A key concept to be taken from their
research is that of surface tension being measured on the nanoscale, by confining an element or
molecule within a structure with known rates of energy transfer data can be obtained about the
element or molecule in question regarding their surface properties on the nanoscale. This data
can be extremely useful once compiled as it can aid in nanotechnology developmental methods.

Thermodynamics on the Nanoscale

Being able to accurately measure temperature exchange on the nanoscale would be very
beneficial. However, the problem with current nanotechnology has a lot to do with the instability
of a system as temperature increases. When two wires on the nanoscale heat up they begin to
reorient themselves and in some cases two wires can merge to form a single wire, this causes
there to be a larger wire that no longer exhibits the separate flows of two wires but a single flow
within one. If these two wires were initially designed to send energy to separate places the
molecular merger would cause the entire system to become faulty. This is why researchers at the
Institute of Problems of Chemical Physics, Russian Academy of Sciences, have been making
efforts to reduce these effects. The attempts by these researchers have been that of coating the
surface of nanostructures with metal alloys that are doped with certain chemicals. By coating the
surface of the nanostructures the researchers were able to change the surface chemistry and in
turn prevent some of this grain growth and grain reorientation. The highest degree of thermal
stability was achieved when annealing nanomaterials with an iron alloy that had a minor amount
of zirconium added. (R, A. A., 2014)
When materials undergo increases in temperature they also undergo increased rates of
oxidation. Oxidation is a process in which one chemical loses electrons to another chemical that
has bonded to it; this is known as rust when iron oxidizes. The researchers from the Russian
Academy of Sciences tackled this issue with the same approach as they did with the grain growth
problem. By annealing the surface of nanostructures with Fe, Cr, Ni alloys, with minor
zirconium additives, nanostructure of the alloys remained unchanged when undergoing
prolonged exposure times. The researchers then used secondary ion mass spectrometry to
observe the surface characteristics, finding that a Cr2 O3 layer formed at the surface creating a
protective layer that decreased the rate of oxidation. While observations of the nickel alloys

Thermodynamics on the Nanoscale

showed an increased rate of oxidation. This research is key in showing how doping alloys can in
some cases increase strength and durability while in others it can cause things to degrade faster.
This also aids in the prevention of grain growth as part of grain growth is linked to chemical
activity at the surface, such as in the case of oxidation. (R, A. A., 2014)
Being able to measure the temperature of nanoscale objects will provide a better
understanding of nanoscale temperatures. While being able to measure the rate of temperature
exchange on the nanoscale will allow us a better handle on how components should be placed in
a system or what they should consist of. Knowing the temperature and its exchange rate is vital
to the study of nanothermodynamics but knowing how to resist the effect that temperature has on
nanoscale systems is vital to the nanotechnology world.
Nanomaterials have a tendency to loose structural integrity under certain temperatures
from processes such as grain reorientation, grain growth, and chemical disassociation. The study
of nanothermodynamics will provide methods for extending the life expectancy of nanoscale
systems as well as increasing the efficiency of energy transfer. Currently there is much energy
lost at the nanoscale due to excessive free flowing energy that has yet to be controlled. The study
of nanothermodynamics will allow for us to not only increase the efficiency of nanoscale
systems but also increase the predictive/simulation models for analyzing the effects of
temperature across the electromagnetic spectrum. This will benefit society not only by improving
our handle on the nano world but by also providing a longer lifetime to the technologies used as
well as some key tools in the development and innovation of nanotechnology.

Thermodynamics on the Nanoscale

References
Gao, Y., & Bando, Y. (2002). Nanothermodynamic analysis of surface effect on expansion
characteristics of Ga in carbon nanotubes. Applied Physics Letters, 81(21), 3966.

Nature (2014). New method for measuring temperature of nanoscale objects discovered. Nature
Nanotechnology. Retrieved from http://phys.org/news/2014-05-method-temperaturenanoscale.html.

R, A. A. (2014). Thermal stability of consolidated metallic nanomaterials. Russian Chemical

Reviews, Volume 83(4). Retrieved from
http://iopscience.iop.org/article/10.1070/RC2014v083n04ABEH004405?
fromSearchPage=true.