Nanomaterials

Boxuan Gu and David McQuilling

What are they?
 Nano = 10-9 or one billionth in size
 Materials with dimensions and tolerances in
the range of 100 nm to 0.1 nm
 Metals, ceramics, polymeric materials, or
composite materials
 One nanometer spans 3-5 atoms lined up in a
row
 Human hair is five orders of magnitude larger
than nanomaterials
Nanomaterial Composition
 Comprised of many different elements
such as carbons and metals
 Combinations of elements can make up
nanomaterial grains such as titanium
carbide and zinc sulfide
 Allows construction of new materials
such as C60 (Bucky Balls or fullerenes)
and nanotubes
How they are made
 Clay/polymer nanocomposites can be made
by subjecting clay to ion exchange and then
mixing it with polymer melts
 Fullerenes can be made by vaporizing carbon
within a gas medium
 Current carbon fullerenes are in the gaseous
phase although samples of solid state
fullerenes have been found in nature
Bucky Ball properties
 Arranged in pentagons and hexagons
 A one atom thick seperation of two spaces; inside the
ball and outside
 Highest tensile strength of any known 2D structure or
element, including cross-section of diamonds which
have the highest tensile strength of all known 3D
structures (which is also a formation of carbon atoms)
 Also has the highest packing density of all known
structures (including diamonds)
 Impenetrable to all elements under normal
circumstances, even a helium atom with an energy of
5eV (electron Volt)
Bucky Ball properties cont.
 Even though each carbon atom is only bonded with
three other carbons (they are most happy with four
bonds) in a fullerene, dangling a single carbon atom
next to the structure will not affect the structure, i.e.
the bond made with the dangling carbon is not
strong enough to break the structure of the fullerene
 No other element has such wonderful properties as
carbon which allows costs to be relatively cheap;
after all it’s just carbon and carbon is everywhere
Buckminsterfullerene uses
 Due to their extremely resilient and sturdy nature bucky
balls are debated for use in combat armor
 Bucky balls have been shown to be impervious to lasers,
allowing for defenses from future warfare
 Bucky balls have also been shown to be useful at fighting
the HIV virus that leads to AIDS
 Researchers Kenyan and Wudl found that water soluble
derivates of C60 inhibit the HIV-1 protease, the enzyme
responsible for the development of the virus
 Elements can be bonded with the bucky ball to create
more diverse materials including superconductors and
insulators
 Can be used to fashion nanotubes
 Bucky Balls

Bucky Ball (C60) C240 colliding with C60 at

300 eV (Kinetic energy)
http://www.pa.msu.edu/cmp/csc/simindex.html
Nanotube properties
 Superior stiffness and strength to all other materials
 Extraordinary electric properties
 Reported to be thermally stable in a vacuum up to 2800
degrees Centigrade (and we fret over CPU temps over
50o C)
 Capacity to carry an electric current 1000 times better
than copper wires
 Twice the thermal conductivity of diamonds
 Pressing or stretching nanotubes can change their
electrical properties by changing the quantum states of
the electrons in the carbon bonds
 They are either conducting or semi-conducting
depending on the their structure
Nanotube uses
 Can be used for containers to hold various
materials on the nano-scale level
 Due to their exceptional electrical properties,
nanotubes have a potential for use in
everyday electronics such as televisions and
computers to more complex uses like
aerospace materials and circuits
 Nanotubes

Carbon based nanotubes Switching nanotube-based memory

http://www.pa.msu.edu/cmp/csc/simindex.html
Applications of
Nanotechnology
 Next-generation computer chips
 Ultra-high purity materials, enhanced thermal

conductivity and longer lasting nanocrystalline

materials
 Kinetic Energy penetrators (DoD weapon)
 Nanocrystalline tungsten heavy alloy to replace

radioactive depleted uranium

 Better insulation materials
 Create foam-like structures called ‘aerogels’ from

nanocrystalline materials
 Porous and extremely lightweight, can hold up to

100 times their weight

More applications…
 Improved HDTV and LCD monitors
 Nanocrystalline selenide, zinc sulfide, cadmium

sulfide, and lead telluride to replace current

phosphors
 Cheaper and more durable

 Harder and more durable cutting materials

 Tungsten carbide, tantalum carbide, and titanium

carbide
 Much more wear-resistant and corrosion-resistant

than conventional materials

 Reduces time needed to manufacture parts,

cheaper manufacturing
Even more applications…
 High power magnets
 Nanocrystalline yttrium-samarium-cobalt grains

possess unusually large surface area compared to

traditional magnet materials
 Allows for much higher magnetization values

 Possibility for quieter submarines, ultra-sensitive

analyzing devices, magnetic resonance imaging

(MRI) or automobile alternators to name a few
 Pollution clean up materials
 Engineered to be chemically reactive to carbon

monoxide and nitrous oxide

 More efficient pollution controls and cleanup
Still more applications…
 Greater fuel efficiency for cars
 Improved spark plug materials, ‘railplug’

 Stronger bio-based plastics

 Bio-based plastics made from plant oils lack

sufficient structural strength to be useful

 Merge nanomaterials such as clays, fibers and

tubes with bio-based plastics to enhance strength

and durability
 Allows for stronger, more environment friendly

materials to construct cars, space shuttles and a

myriad of other products
Applications wrapup
 Higher quality medical implants
 Current micro-scale implants aren’t porous enough for tissue
to penetrate and adapt to
 Nano-scale materials not only enhance durability and
strength of implants but also allow tissue cells to adapt more
readily
 Home pregnancy tests
 Current tests such as ‘First Response’ use gold nanoparticles
in conjunction with micro-meter sized latex particles
 Derived with antibodies to the human chorionic
gonadotrophin hormone that is released by pregnant women
 The antibodies react with the hormone in urine and clump
together and show up pink due to the nanoparticles’
plamson resonance absortion qualities
 Modeling and Simulation of
Nanostructured Materials and
Systems
 Preface
 Each distinct age in the development of
humankind has been associated with advances in
materials technology.
 Historians have linked key technological and

societal events with the materials technology

that was prevalent during the “stone age,” “bronze
age,” and so forth.
 Significant events In materials
 1665 - Robert Hooke …material microstructure
 1808 - John Dalton … atomic theory
 1824 - Portland cement
 1839 - Vulcanization
 1856 - Large-scale steel production
 1869 - Mendeleev and Meyer … Periodic Table
of the Chemical Elements
 1886 - Aluminum
 1900 - Max Planck …. quantum mechanics
 Cont.
 1909 - Bakelite
 1921 - A. A. Griffith …. fracture strength
 1928 - Staudinger… polymers (small molecules that
link to form chains)
 1955 - Synthetic diamond
 1970 - Optical fibers
 1985 - First university initiatives attempt
computational materials design
 1985 - Bucky balls (C60) discovered at Rice University
 1991 - Carbon nanotubes discovered by Sumio Iijima
 Why we need Computational
Materials?
Traditionally, research institutions have relied on a
discipline-oriented approach to material
development and design with new materials.
It is recognized, however, that within the scope of
materials and structures research, the breadth of length
and time scales may range more than 12 orders of
magnitude, and different scientific and engineering
disciplines are involved at each level.
To help address this wide-ranging interdisciplinary
research, Computational Materials has been
formulated with the specific goal of exploiting the
tremendous physical and mechanical properties of
new nano-materials by understanding materials at
atomic, molecular, and supramolecular levels.
Computational Materials at LaRC draws from
physics and chemistry, but focuses on
constitutive descriptions of materials that
are useful in formulating macroscopic
models of material performance.
 Benefit of Computational
materials
 First, it encourages a reduced reliance on costly trial and
error, or serendipity, of the “Edisonian” approach to
materials research.
 Second, it increases the confidence that new materials will
possess the desired properties when scaled up from the
laboratory level, so that lead-time for the introduction of new
technologies is reduced.
 Third, the Computational Materials approach lowers the
likelihood of conservative or compromised designs that
might have resulted from reliance on less-than-perfect
materials.
Schematic illustration of relationships between time and
length scales for the multi-scale simulation methodology.
Cont.

 The starting point is a quantum description

of materials; this is carried forward to an
atomistic scale for initial model
development.
Models at this scale are based on molecular
mechanics or molecular dynamics.
 Cont.
 At the next scale, the models can incorporate
micro-scale features and simplified constitutive
relationships.
 Further progress up, the scale leads to the meso
or in-between levels that rely on combinations of
micromechanics and wellestablished theories
such as elasticity.
 Cont.
 The last step towards engineering-level
performance is to move from mechanics of
materials to structural mechanics by using
methods that rely on empirical data,constitutive
models, and fundamental mechanics.
 Nanostructured Materials
 The origins of focused research into nanostructured
materials can be traced back to a seminal lecture given
by Richard Feynman in 1959[1].
 In this lecture, he proposed an approach to “the problem
of manipulating and controlling things on a small scale.”
The scale he referred to was not the microscopic scale
that was familiar to scientists of the day but the
unexplored atomistic scale.
 The nanostructured materials based on carbon
nanotubes and related carbon structures are of
current interest for much of the materials
community.
 More broadly then, nanotechnology presents the
vision of working at the molecular level, atom by
atom, to create large structures with
fundamentally new molecular organization.
Simluation methods
 Atomistic, Molecular Methods
 The approach taken by the Computational
Materials is formulation of a set of integrated
predictive models that bridge the time and length
scales associated with material behavior from the
nano through the meso scale.
 At the atomistic or molecular level, the reliance is on
molecular mechanics,
 molecular dynamics, and coarse-grained, Monte-Carlo
simulation.
 Molecular models encompassing thousands and
perhaps millions of atoms can be solved by these
methods and used to predict fundamental, molecular
level material behavior. The methods are both static
and dynamic.
 Molecular dynamics simulations generate
information at the nano-level, including atomic
positions and velocities.
 The conversion of this information to
macroscopic observables such as pressure,
energy, heat capacities, etc., requires statistical
mechanics.
 An experiment is usually made on a macroscopic
sample that contains an extremely large number of
atoms or molecules, representing an enormous
number of conformations.
 In statistical mechanics, averages corresponding to
experimental measurements are defined in terms of
ensemble averages.
 For example
M
V  1 / M * Vi
i 1

where M is the number of configurations in the molecular

dynamics trajectory and Vi is the potential energy of each
configuration.
 1 M
 mi
N

K
M
  vi vi 
j 1  i 1 2 j
where M is the number of configurations in the simulation, N is the
number of atoms in the system, mi is the mass of the particle i and vi
is the velocity of particle i.
To ensure a proper average, a molecular dynamics simulation must
account for a large number of representative conformations.
 By using Newton’s second law to calculate a
trajectory, one only needs the initial positions of the
atoms, an initial distribution of velocities and the
acceleration, which is determined by the gradient of
the potential energy function.
 The equations of motion are deterministic; i.e., the
positions and the velocities at time zero determine the
positions and velocities at all other times, t. In some
systems, the initial positions can be obtained from
experimentally determined structures.
 In a molecular dynamics simulation, the time dependent
behavior of the molecular system is obtained by
integrating Newton’s equations of motion.
 The result of the simulation is a time series of
conformations or the path followed by each atom.
 Most molecular dynamics simulations are performed
under conditions of constant number of atoms, volume,
and energy (N,V,E) or constant number of atoms,
temperature, and pressure (N,T,P) to better simulate
experimental conditions.
Basic steps in the MD simulation
 1. Establish initial coordinates.
 2. Minimize the structure.
 3. Assign initial velocities.
 4. Establish heating dynamics.
 5. Perform equilibration dynamics.
 6. Rescale the velocities and check if the
temperature is correct.
 7. Perform dynamic analysis of trajectories.
 Monte Carlo Simulation
 Although molecular dynamics methods provide
the kind of detail necessary to resolve molecular
structure and localized interactions, this fidelity
comes with a price. Namely, both the size and
time scales of the model are limited by numerical
and computational boundaries.
 To help overcome these limitations,coarse-grained
methods are available that represent molecular chains
as simpler, bead-spring models.
 Coarse-grain models are often linked to Monte Carlo
(MC) simulations to provide a timely solution.
 The MC method is used to simulate stochastic events
and provide statistical approaches to numerical
Integration.
There are three characteristic steps in the MC
simulation that are given as follows.
1. Translate the physical problem into an
analogous probabilistic or statistical model.
2. Solve the probabilistic model by a numerical
sampling experiment.
3. Analyze the resultant data by using statistical
methods.
 Continum Methods
 Despite the importance of understanding the
molecular structure and nature of materials, at
some level in the multi-scale analysis the
behaviour of collections of molecules and atoms
can be homogenized.
 At this level, the continuum level, the observed
macroscopic behaviour is explained by disregarding the
discrete atomistic and molecular structure and assuming
that the material is continuously distributed throughout
its volume.
The continuum material is assumed to have an average
density and can be subjected to body forces such as
gravity and surface forces such as the contact between
two bodies.
The continuum can be assumed to obey several
fundamental laws.
 The first, continuity, is derived from the conservation of

mass.
 The second, equilibrium, is derived from momentum

considerations and Newton’s second law.

 The third, the moment of momentum principle, is based

on the model that the time rate of change of angular

momentum with respect to an arbitrary point is equal to
the resultant moment.
•These laws provide the basis for the continuum model
and must be coupled with the appropriate constitutive
equations and equations of state to provide all the
equations necessary for solving a continuum problem.
•The state of the continuum system is described by
several thermodynamic and kinematic state variables.
•The equations of state provide the relationships
between the non-independent state variables.
 The continuum method relates the deformation of
a continuous medium to the external forces
acting on the medium and the resulting internal
stress and strain.
 Computational approaches range from simple
closed-form analytical expressions to
micromechanics to complex structural mechanics
calculations basedon beam and shell theory.
 The continuum-mechanics methods rely on
describing the geometry, (I.e.physical model),
and must have a constitutive relationship to
achieve a solution.
 For a displacement –based form of continuum
solution, the principle of virtual work is
assumed valid.
In general, this is given as:
W    ij ij dV
V

  Pju j dV   T ju j dS  F ju j

V S
where W is the virtual work which is the work done by imaginary
or virtual displacements, is the strain, is the stress, P is the body
force, u is the virtual displacement, T is the tractions and F is the
point forces. The symbol is the variational operator designating
the virtual quantity.
For a continuum system, a necessary and sufficient condition for
equilibrium is that the virtual work done by sum of the external
forces and internal forces vanish for any virtual displacement.
Software for Nanomaterials
BOSS-Biochemical and Organic
Simulation System

 The B O S S program performs (a)

Monte Carlo (MC) statistical mechanics
simulations for solutes in a periodic
solvent box, in a solvent cluster, or in a
dielectric continuum including the gas
phase, and (b) standard energy
minimizations, normal mode analysis,
and conformational searching.
XMakemol

 XMakemol is a mouse-based program,

written using the LessTif widget set, for
viewing and manipulating atomic and
other chemical systems. It reads XYZ
input and renders atoms, bonds and
hydrogen bonds.
Features
 Animating multiple frame files
 Interactive measurement of bond lengths,
bond angles and torsion angles
 Control over atom/bond sizes
 Exporting to XPM, Encapsulated PostScript
and Fig formats
 Toggling the visibility of groups of atoms
 Editing the positions of subsets of atoms
A water
molecule with
vectors along
the principal
axes
As above,
with
lighting
turned off
Candidate
structure for the
H2O(20) global
minimum
Buckminster
Fullerene
 Amsterdam Density Functional
(ADF) package
 The Amsterdam Density Functional (ADF)
package is software for first-principles
electronic structure calculations. ADF is
used by academic and industrial
researchers worldwide in such diverse fields
as pharmacochemistry and materials
science
It is currently particularly popular in the
research areas of:
 homogeneous and heterogeneous catalysis

 inorganic chemistry

 heavy element chemistry

 various types of spectroscopy

 biochemistry
 ARP/wARP 

ARP/wARP  is a package for automated protein

model building and structure refinement. It is
based on a unified approach to the structure
solution process by combining electron density
interpretation using the concept of the hybrid
model, pattern recognition in an electron density
map and maximum likelihood model parameter
refinement.
The ARP/wARP suite is under continuous
development. The present release, Version 6.0,
can be used in the following ways:
1. Automatic tracing of the density map and model
building. This includes the refinement of MR
solutions and the improvement of MAD and
M(S)IR(AS) phases via map interpretation
2. Free atoms density modification

3. Building of the solvent structure

 Chemsuite - A suite designed for
chemistry on Linux
Chemsuite is composed by several program:
 Chem2D: A 2D molecular drawer.

 Molcalc: A molecular weight calculator  

 ChemModel3D: Molecular 3D modeler

 ChemIR: An infrared spectra processor.

 It can read, process, export and print Perkin

Elmerspectra.
 ChemNMR: 1D NMR Processor

 ChemMC: Monte carlo Simulator and Integrator

 General Atomic and Molecular
Electronic Structure System
(GAMESS)
 GAMESS is a program for ab initio quantum
chemistry. Briefly, GAMESS can compute
SCF wavefunctions ranging from RHF,
ROHF, UHF, GVB, and MCSCF. Correlation
corrections to these SCF wavefunctions
include Configuration Interaction, second
order perturbation theory, and Coupled-
Cluster approaches, as well as the Density
Functional Theory approximation.
Useful site
http://www.linuxlinks.com/Software/Scien
tific/Chemistry/