MODULE 3

ENG 201

THE SOLID STATE &

MATERIALS CHEMISTRY
3.4. ENGINEERED NANOMATERIALS

DEPARTMENT OF CHEMICAL ENGINEERING

UNIVERSITY OF SANTO TOMAS
MANILA, PHILIPPINES
Intended Learning Outcomes
• Define Nanotechnology

• Identify discoveries and milestones

in nanotechnology.

• Describe two fundamental

approaches in the synthesis of
nanomaterials.

• Classify nanomaterials based on

their origin, dimension, and
composition.

• Identify applications of
nanomaterials in different fields.
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Magic?!?

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Real-life cloaking technologies

Mirage Effect
Bending of lights
Metamaterials
(Nanomaterials)
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Nano Language
Nanoscience: The science and study of matter at the
nanoscale that deals with understanding their size and
structure-dependent properties and compares the
emergence of individual atoms or molecules or bulk
material related differences.

Nanotechnology: Manipulation and control of matter

on the nanoscale dimension by using scientific
knowledge of various industrial and biomedical
applications.

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 Nanoscale dimension
Material with any internal or external structures on the
nanoscale dimension, i.e. 1 – 100 nm in atleast 1 dimension

How small is
nanoscale?

https://www.science.org.au/curious/technology-future/how-small-nanoscale-small

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Nanomaterials
Materials with 1 - 100 nm dimension in atleast 1 direction
AR < 1000 AR ≥ 1000

0D

nanoparticle nanorods nanowires nanoplates

1D
2D
3D

aerogel nanobelts nanotubes nanosheets

*AR – aspect ratio, i.e. length-to-width ratio

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 Classification of Nanomaterials
based on Dimension

all dimensions at the two dimensions at one dimension at the no dimensions at the
nanoscale the nanoscale nanoscale nanoscale
one dimension at two dimensions at all dimension at
macroscale macroscale macroscale

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Nanocomposites
Multiphase structure with at least one phase on the nanoscale dimension.
nanocomposite

polymer based non-polymer based

• polymer/ceramic • metal nanocomposite
• inorganic/organic polymer • ceramic nanocomposite
• inorganic/organic hybrid • ceramic-ceramic nanocomposite
• polymer/layered silicate

Luna, J. & Vilchez, A., Micro and Nano Technologies, Elsevier, Lee, W., et al, nanotoday, 2018, 23, 97-123
chapter 7, 2017, 119-147

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Nanostructured materials
Materials containing surface nanostructure

Roach, P. et al, Soft Matter, 2008, 4, 224-240

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Nanostructured materials

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Nanostructured materials

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Nanostructured materials
Biomimetics
an interdisciplinary field in which principles from
engineering, chemistry and biology are applied to the
synthesis of materials, synthetic systems or machines that
have functions that mimic biological processes

CA ≥ 150°

Chun, M., et al, J. Mater. Chem., 2009, 19, 9025-9029

Koch, K. et al, Soft Matter, 2009, 5, 1386-1393
Han, J., et al., RSC Andvances, 8(12), 6733-6744

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Nanostructured materials

Germany makes anti-urination walls that pee back.

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Classification of Nanomaterials
based on their Origin
(i) Natural nanomaterials
• Produced in nature either by biological species or through
anthropogenic activities.

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Classification of Nanomaterials
based on their Origin
(ii) incidental nanomaterials
• Produced incidentally as a byproduct of industrial processes
such as nanoparticles produced from vehicle engine exhaust,
welding fumes, combustion processes and even some natural
process such as forest fires.

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Classification of Nanomaterials
based on their Origin
(ii) Synthetic nanomaterials (e.g. Engineered
Nanomaterials)
• Produced by mechanical grinding, or are synthesized by
physical, chemical, biological or hybrid methods.

• Manufactured to have certain required properties for

desired applications.

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Nanotechnology Milestones
• Premodern Examples
• Early examples of nanostructured materials were based on
craftsmen’s empirical understanding and manipulation of
materials. Use of high heat was one common step in their
process to produce these materials with novel properties.

• Examples of discoveries and developments

enabling nanotechnology in modern era
• These are based on increasingly sophisticated scientific
understanding and instrumentation, as well as
experimentation

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Premodern Examples
4th Century – Roman glass workpiece is the most famous example
of ancient metallic nanoparticle usage
• Lycurgus cup, 4th century AD
(now at the British Museum,
London).

• Depicts King Lycurgus of

Thrace being dragged to the
underworld
• When illuminated from outside,
it appears green. However, when
illuminated from within the cup,
it glows red.
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Premodern Examples
Lycurgus cup: THE SECRET

Suspensions of spherical gold particles with various diameters (150, 100, 80,
60, 40, 20 nm from left to right) in water. The difference in colors is due to
different scattering and absorption behavior of small and large gold particles.

http://www.webexhibits.org/causesofcolor/9.html

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Premodern Examples
6th - 15th century – Gold nanoparticles and Silver nanoparticles of different sizes
used to produce different colors in stained glass windows in medieval churches

Detail of a medieval window

at Troyes Cathedral, France
(14th century)
Gold-plated Church Windows
Purify Air!
The South rose window of -Zhu Huai Yong
(Queensland University of Technology)
Notre Dame Cathedral, ca
1250 https://sciences.ucf.edu/chemistry/cnc/research-projects/
https://www.livescience.com/5067-gold-plated-church-windows-purify-air.html

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Premodern Examples
9th - 17th century – “Luster” ceramic glazes used in the Islamic world

Polychrome lustreware bowl,

9th C, Iraq, British Museum
(©Trinitat Pradell 2008)

• glowing and glittering

• contained silver or copper or
other metallic nanoparticles

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Premodern Examples
13th - 18th century – “Damascus” saber blades
• known for its strength, resilience,
ability to hold a keen edge, and a
visible moiré pattern in the steel
that give the blades their name.
• contained carbon nanotubes and
cementite nanowires

High-resolution transmission electron

microscopy image of carbon nanotube in
genuine Damascus saber after dissolution in
hydrochloric acid, showing remnants of
cementite nanowires encapsulated by carbon
nanotubes (scale bar, 5 nm) (M. Reibold, P.
Paufler, A. A. Levin, W. Kochmann, N. Pätzke &
D. C. Meyer, Nature, 444, 286, 2006)

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Nanotechnology Milestones
• Premodern Examples
• Early examples of nanostructured materials were based on
craftsmen’s empirical understanding and manipulation of
materials. Use of high heat was one common step in their
process to produce these materials with novel properties.

• Examples of discoveries and developments

enabling nanotechnology in modern era
• These are based on increasingly sophisticated scientific
understanding and instrumentation, as well as
experimentation

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Examples of discoveries and developments
enabling nanotechnology in modern era
Discovered in: 1857
Discovered by: Michael Faraday

COLLOIDAL “RUBY” GOLD

• Nanostructured gold under certain
lighting conditions produces
different colored solution
• The first scientific description to
report NP preparation and initiated
the history of nanomaterials in
scientific arena

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Examples of discoveries and developments
enabling nanotechnology in modern era
Invented in: 1936
Invented by: Erwin Müller
(Siemens Research Laboratory)

FIELD EMISSION MICROSCOPE (FEM)

• allowing near-atomic-resolution
images of materials
• characterization of surface
structures and electronic properties

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Examples of discoveries and developments
enabling nanotechnology in modern era
Invented in: 1951
Invented by: Erwin Müller

FIELD ION MICROSCOPE (FIM)

a means to imagine
the arrangement of
atoms at the surface
of a sharp metal tip;
he first imaged
tungsten atoms

B. Gault, et al., Atom Probe Microscopy, Springer Series in Materials Science 160, DOI
10.1007/978-1-4614-3436-8_2, # Springer Science+Business Media, LLC 2012

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 Examples of discoveries and developments
enabling nanotechnology in modern era
Introduced in: 1959
Introduced by: Dr. Richard P. Feynman
California Institute of Technology

“There is plenty of room at

the bottom”
•“Why cannot we write the entire 24 volumes
of the Encyclopedia Britannica on the head of a
pin?”
•Dr. Richard Feynman, one of America’s most
notable physicists, 1918-1988
•considered to be the first lecturer on
technology and engineering at the atomic
scale
•American Physical Society meeting at Caltech
Dr. Feynman, Continued
• “The problems of chemistry and
biology can be greatly helped if our
ability to see what we are doing, and
to do things on an atomic level, is
ultimately developed – a development
which I think cannot be avoided.”

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Examples of discoveries and developments
enabling nanotechnology in modern era
Introduced in: 1974
Introduced by: Norio Taniguchi
Tokyo Science University Professor

Coined the term

“NANOTECHNOLOGY”
to describe precision machining of materials to
within atomic-scale dimensional tolerances

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 Examples of discoveries and developments
enabling nanotechnology in modern era
Invented in: 1981
Invented by: Gerd Binnig and
Heinrich Rohrer
IBM Zurich lab

SCANNING TUNNELING
MICROSCOPE (STM)

• allowing scientists to "see" (create direct

spatial images of) individual atoms for the first
time.
•won the Nobel Prize for this discovery in 1986

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Examples of discoveries and developments
enabling nanotechnology in modern era
Invented in: 1981
Invented by: Alexei Ekimov

QUANTUM DOTS IN
GLASS MATRIX

• nanocrystalline and semiconducting

• Ekimov conducted pioneering
studies of their electronic and optical
properties.

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Examples of discoveries and developments
enabling nanotechnology in modern era
discovered in: 1985
discovered by: Harold Kroto,
Sean O’Brien,
Robert Curl, and
Richard Smalley
Rice University researchers

BUCKYBALL
Buckminsterfullerene (C60)
• a molecule resembling a soccerball • the diameter of a C60 molecule is
in shape and composed entirely of about 1 nm.
carbon, as are graphite and diamond. •Are detected in space and may be
responsible for the mystery interstellar
absorption
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Examples of discoveries and developments
enabling nanotechnology in modern era
Published in: 1986
Written by: Kim Eric Drexler

“Engines of Creation”
• First book on nanotechnology

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 Examples of discoveries and developments
enabling nanotechnology in modern era
Invented in: 1986
Invented by: Gerd Binning,
Calvin Quate
and Christoph Gerber

Atomic Force http://biophys.w3.kanazawa-u.ac.jp/

Microscope (AFM)
• the capability to view, measure,
and manipulate materials down to
fractions of a nanometer in size,
including measurement of various
forces intrinsic to nanomaterials
https://www.hitachi-hightech.com/global/science/technical/tech/microscopes/spm/descriptions/mechanical/ffm.html

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 Examples of discoveries and developments
enabling nanotechnology in modern era
Made in: 1989
Made by: Don Eigler and Erhard Schweizer
IBM's Almaden Research Center

IBM logo made with

individual atoms

• First in history to move and control individual atoms

https://www.reddit.com/r/explainlikeimfive/comments/7ulcoc/eli5_why_can_we_see_the
_xenon_atoms_in_the_ibm/

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Examples of discoveries and developments
enabling nanotechnology in modern era

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Examples of discoveries and developments
enabling nanotechnology in modern era
discovered in: 1991
discovered by: Sumio Iijima

Carbon Nanotubes (CNT)

•are entirely composed of carbon, but
in a tubular shape
• They exhibit extraordinary properties
in terms of strength, electrical and
thermal conductivity, among others

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Examples of discoveries and developments
enabling nanotechnology in modern era
Appeared in: 1999–early 2000’s:

CONSUMER PRODUCTS
• lightweight nanotechnology-enabled automobile
bumpers that resist denting and scratching
• golf balls that fly straighter
•tennis rackets that are stiffer (therefore, the ball
rebounds faster),
•baseball bats with better flex and "kick," nano-silver
antibacterial socks, clear sunscreens,
•wrinkle- and stain-resistant clothing, deep-penetrating
therapeutic cosmetics,
•scratch-resistant glass coatings,
• faster-recharging batteries for cordless electric tools,
•improved displays for televisions, cell phones, and
digital cameras..

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Examples of discoveries and developments
enabling nanotechnology in modern era
1999 – “Nanomedicine” – 1st nanomedicine book by R. Freitas

http://www.rfreitas.com/

2000 – President Clinton launched the “National Nanotechnology

Initiative” in the US
• To coordinate Federal R&D efforts and
promote U.S. competitiveness in
nanotechnology
• Congress funded the NNI for the first
time in FY2001

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 Examples of discoveries and developments
enabling nanotechnology in modern era
fabricated in: 2004 World’s Smallest Globe (Nano-Globe)
fabricated by: Kenji Yamazaki and
made using electron beam
Hideo Namatsu

Electron microscope images of the nano-globe. Illustration showing how

Unlabeled scale bars indicate 3 μm. a sample rotates.
http://www.brl.ntt.co.jp/E/activities/file/report03/E/report03.html Yamazaki, K., et al, Jpn J Appl Phys, 43 (2), 2004, 88

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Examples of discoveries and developments
enabling nanotechnology in modern era
fabricated in: 2010
fabricated by: IBM

Nanoscale 3D relief map of the world

A rendered image of a nanoscale silicon tip chiseling out
the smallest relief map of the world from a substrate of
organic molecular glass. Shown middle foreground is the
Mediterranean Sea and Europe. (Image courtesy of
Advanced Materials.)
https://www.nationalgeographic.org/photo/worlds-smallest-map/
• a silicon tip, measuring only a few
nanometers at its apex (similar to the tips
used in atomic force microscopes), were used
to chisel away material from a substrate
• 1,000 world maps could fit on a grain of salt
• 500,000 pixels, i.e. 20 nm2 each
• in 2 minutes and 23 seconds!
• generating nanoscale patterns and structures
as small as 15 nanometers on a polymer
substrate measuring 22 by 11 micrometers
• hold the Guinness World RecordsTM record
for smallest 3D map of the earth

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 Examples of discoveries and developments
enabling nanotechnology in modern era
Developed in: 2006
Developed by: James Tour and colleagues
Rice University
Nanoscale Car
• Made of oligo(phenylene ethynylene) with
alkynyl axles and four buckyballs (C60) wheels
• the nanocar moved about on a gold surface
as a result of the buckyball wheels turning in
response to increase in temperature
•>300°C, the nanocar moved too fast for the
chemist to keep track of it
• the nanocar measures 3-4 nm across, e.i.
slightly wider than a strand of DNA
• hold the Guinness World RecordsTM record
Tour, J., et al.,Chem. Soc. Rev., 2006, 35, 1043-1055
https://crnano.typepad.com/crnblog/2006/06/students_buildi.html
for smallest nanocar

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Examples of discoveries and developments
enabling nanotechnology in modern era

The Nanocar Race (2017)

The world's first international race for molecular cars.
Rapenne, G. and Joachim, C., Nat. Rev. Mater., 2, 2017, 17040
https://phys.org/news/2017-03-world-international-molecular-cars-nanocar.html

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Examples of discoveries and developments
enabling nanotechnology in modern era
Smallest movie: “A boy and his atom” (2013)
• hold the Guinness World RecordsTM record for World’s Smallest Stop-Motion Film

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Nanomaterial Synthesis
• There are two approaches for the synthesis of nanomaterials and fabrication of
nanostructures

• Top-Down approach refers to slicing • Bottom-up refers to the build up of a

or successive cutting of bulk material material from the bottom: atom by
to get nano sized particle atom, molecule by molecule

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Nanomaterial Synthesis

Top Down Approach Bottom Up Approach

ADVANTAGES ADVANTAGES
• Large scale production • Narrow size distribution is
• Chemical purification is not possible (1-20 nm)
required • Cheaper technique
DISADVANTAGES DISADVANTAGES
• Broad size distribution • Large scale production is
(1-1000 nm) difficult
• Varied particle shapes and • Chemical purification of
geometry nanoparticles is required
• Expensive technique
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Growth Mechanism Surface Energy
Surface energy is the sum of all the excess energy of the surface atoms

For liquid: surface energy = surface tension

Bulk atoms: surface atoms:

Zero net force a net attractive force

pointing toward the bulk

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Surface Energy (g) Lost CN
Consider the atoms in the
bulk and surface regions of
a crystal:

• Surface: atoms possess

higher energy since they
are less tightly bound.

• Bulk: atoms possess

lower energy since they
are much tightly bound.

The higher the lost CN of

CNloss = 2 CNloss = 1 the surface atoms the
higher g lower g higher the surface energy
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Growth Mechanism
c
a
ga < gc a ga > gc

NANOPLATES NANORODS NANOWIRES

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Growth Mechanism
Sn nanowires

DFT calculation of
surface energy:

Surface
Plane energy
(J/m2)
Side 0.39
basal 0.49
Qiao, R., et al, Adv. Mater. Interfaces,
2014, 1, 1300115−1300121

Wang, J., Gao, F., & Gu, Z., 2017 IEEE 67th Electronic Components and
Technology Conference (ECTC), 2017, 2175-2180.

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Does
size
matter
???

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How sizing down to nano affect material
properties?

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Classification of Nanomaterials based on their composition
1. Carbon-based nanomaterials
• NMs contain carbon, and are found in morphologies such as hallow tubes, ellipsoids
or spheres.

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Classification of Nanomaterials based on their composition
2. Inorganic-based nanomaterials
• These NMs include metal and metal oxide NPs.
• These NMs can be synthesized into metals such as Au or Ag NPs, metal oxides such as
TiO2 and ZnO NPs, and semiconductors such as silicon and ceramics

Loiseau, A., et al., Biosensors, 9 (2), 2019, 78

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Classification of Nanomaterials based on their composition
3. Organic-based nanomaterials
• These include NMs made mostly from organic matter, excluding carbon-based or
inorganic NMs.
• The utilization of noncovalent (weak) interactions for the self-assemble and design of
molecules helps to transform the inorganic NMs into desired structures such as
dendrimers, micelles, and liposomes.

Mishra, R. K., et al., Journal of Science: Advanced Materials and Devices, 3 (3), 2018, 263-288

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Applications of nanomaterials
Chemical Engineering
catalyst, sensor, coating, adsorption, drug delivery etc

catalyst sensors

https://www.x-mol.com/paper/939669 Karaduman, I, et al, J. Alloys Compd., 722, 2017, 569-578

Drug delivery

https://gifer.com/en/DhFf

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 Applications of nanomaterials
Civil Engineering
fire-resistant, self-healing, self-cleaning, anti-corrosion materials, etc.

Fire retardant

Thirsty concrete

https://safetybrief.creativesafetysupply.com/pervious-concrete-gulps-stormwater/
https://www.coating.co.nz/fire-retardant-paint/
Wang, J.Y., et al., Cem Concr Res, 56, 2014, 139-152
Self-healing concrete

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Applications of nanomaterials
Electrical Engineering
Improve conductivity (reduction of losses) and insulation (raising of electrical insulation,
mechanical stability, thermal load behaviour, chemical resistance), miniaturizing of design,
reduction of used material, higher reliability, improvement of electromagnetic
compatibility (EMV) , Long-term improvement of efficiency and elongation of life time
period

high electrical conductivity https://pioneertechsolutions.com/porcelain-glass-

insulators-pioneer-technology-solutions-why-
hydrophobic-coatings/

improve the performance of insulators,

reducing flashovers and power outages
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 Applications of nanomaterials
Electronics Engineering
Materials for chips, lighting/display, lasers, batteries, fuel cells, photovoltaic cells, etc.

Fiber optics
wearable electronics

flexible electronics
Transparent electronics
https://www.azonano.com/article.aspx?ArticleID=4994
http://www.koreaherald.com/view.php?ud=20200413000322
https://www.technologyvista.in/pin/new-electronic-skin-tracks-heart-rate-respiration/
https://www.nanowerk.com/nanotechnology-news/newsid=46942.php

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 Applications of nanomaterials
Mechanical Engineering
nanoscale manufacturing, micro- and nano-fluidics, biomolecular detection, nanoscale
thermal transport, computational modeling, nanomechanical materials, etc.

nanofluids
electric vehicle

https://www.bloomberg.com/news/articles/2017-11-21/tesla-is-blowing-through-8-000-every-minute-amid-model-3-woes
https://www.eqmagpro.com/consumers-energy-launches-new-electric-vehicle-charging-and-customer-rebate-program/

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 SAQ:
Application of
nanomaterials
in your chosen
field.

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END OF MODULE 3.4

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