ENGD3114

Emerging Materials and

Processes
Introduction of nanomaterials

Mater. Adv., 2021,2, 1821-1871

 ‘nano’ in Greek - means
dwarf

What are nanomaterials?

 Nanoscale materials are defined as materials where at least one dimension is less
than 100 nanometers or …are likely to have one or more dimensions (length, width,
height) in the nanometer scale.

Question: How many nanometers should have a object to be considered/qualified as a

nanomaterial?

 Is defined as any material that has unique or novel properties, due to the nanoscale
( nano metre- scale) structuring.

 The most important aspect of nanomaterials is that the physical and chemical
properties are size dependent

Not just “small”………..”small and different”

https://www.nanowerk.com/nanotechnology/ten_things_you_should_know_9.php
What are nanomaterials?
US National Nanotechnology initiative (NNI) 2004 Nanotechnology is the
understanding and control of matter at dimensions of roughly 1 to 100 nanometers,
where unique phenomena enable novel applications.

European Commision (EC), 2011; Nanomaterials are chemical substances or

materials with particle sizes between 1 to 100 nanometres in at least one
dimension. Due to an increased specific surface area by volume, nanomaterials may
have different characteristics compared to the same material without nanoscale features.
https://www.nanowerk.com/nanotechnology/ten_things_you_should_know_9.php
 Why are nanomaterials important? Why so much
interest in nanomaterials ?
The physical and chemical properties of nanomaterials are significantly different from
those of bulks materials (large scale of the same material). As materials are reduced to the
nanometer scale the properties of the material may change abruptly so that the material may
have some exceptional properties

Gold is a chemical element with the symbol Au (from Latin: aurum) It is

Bulk gold a bright,, dense, soft, malleable, and ductile metal in a pure form
slightly orange-yellow
Melting point 1337 K,
Chemically inert

Gold nanoparticles are soluble;

dispersed into transparent media (water)
generates intense colours
Melt at lower temperature as their size decrease below 50 nm example 600 K for
3nm diameter NPs.
Gold NPs are chemically active
Gold (suspension of gold nanoparticles in water ) have been used to colour glasses ;
ruby glass contains dispersed gold colloids

CdSe:
(a) Bulk CdSe single crystal (scale bar 1 cm)
(b) CdSe nanocrystals with diameter ranging from 2nm
(yellow) to 5 nm (red powder)
(c ) suspension of CdSe nanocrystals with diameter
ranging from 2nm (left) and 5 nm (right ) under ambient
light illumination
(d) suspension of CdSe nanocrystals with diameter
ranging from 2nm (left) and 5 nm (right ) under UV
excitation
 History of nanomaterials

Figure 1. Lycurgus cup;

one of the oldest nanomaterials nanoparticles
Dichroism (two colours)
Silver – gold alloy (Ag:Au 7:3) & 10% copper Medieval church windows.
disperse in the glass matrix 50 – 100 nm diameter The south rose window of
Notre Dame Cathedral in
Paris

Faraday demonstrated how gold

nanoparticles produce different-
colored solutions under certain
lighting conditions
http://dx.doi.org/10.3390/molecules25010112
https://www.smithsonianmag.com/history/this-1600-year-old-goblet-shows-that-the-romans-were-nanotechnology-pioneers-
787224/
 1959 - The first time the concept of nanotechnology was presented by
the famous professor of physics Dr. Richard Feynman – he imagined
the entered Encyclopedia Britannica written on the head of pin.
What I want to talk about is the problem of manipulating and
controlling things on a small scale.
Plenty of Room at the Bottom by Richard P. Feynman (Dated: Dec. 1959)
Lecture given to the American Physical Society
in Pasadena on December 1959

Rearranging the atoms Miniaturizing the computer

But I am not afraid to consider the final I don't know how to do this on
question as to whether, ultimately - in a small scale in a practical
the great future - we can arrange way, but I do know that
the atoms the way we want; the very computing machines are very
atoms, all the way down! What would
large; they fill rooms. Why
happen if we could arrange the atoms
one by one the way we want them
can't we make them very
(within reason, of course; you can't put small, make them of little
them so that they are chemically wires, little elements and by
unstable, for example). little, I mean little.
In July 1990, the first session of the International Symposium on Nanoscience and
Nanotechnology was held in Baltimore, US, and formally announced to the world the
science of nanomaterials as a novel branch of materials science.

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The origin of the size dependence of the properties of
nanomaterials - two key concepts of nanotechnology

1. Increase in the surface/volume ratio with

decreasing size
2. Quantum confinement or Spatial confinement effects
Increase in the surface/volume ratio with decreasing
size
As the NP size decrease the number of the atoms is gradually reduced and the fraction of the atoms
located at the surface increases (more atoms/molecules are exposed to the to the surroundings)

Surface effect

Surface forces are very

important, while bulk forces
are not as important.

The ratio increases

dramatically when
Spherical particle of the nanoparticle
100 nm diameter has aprox. 2% of its total atoms on surface diameter drops
10 nm diameter has aprox 20-25% on surface below about 100 nm
3 nm diameter has aprox. 45-60% of the atoms exposed to the surroundings
 2 cm

1cm 3 cm
Increase in the surface/volume ratio with decreasing
size
Extremely high Surface effect
surface
to volume ratio
Surface forces are very
huge fraction of important, while bulk
surface atoms forces are not as
in the total important.
amount of atoms.

Surface atoms have

Fewer neighbours and hence posses unsatisfied chemical bonds
Have free energy
High reactivity
Increase mobility
Melting and evaporation temperature decreases
Reactivity (more active chemically), elasticity and plasticity increases

Properties of materials are size-dependent 

Bulk materials properties are generated by the bulk properties (bulk
properties preserved)
Bulk materials have fixed properties and hence their applications
are limited

When the thickness is reduced, beyond certain limits the properties

show a drastic changes
Surfaces and/or interface effects have an influence on the internal
physical properties (Length > film thickness)
increasing surface to volume ratio by decreasing the
thickness

Strongly influenced by surface and interface

effects
 Quantum confinement effects

Spatial confinement effects is a results of the quantum mechanical nature of the materials

Spatial confinement effects starts to play a important role when the size/number of atoms
decrease below a certain critical limit.

The critical length scale:

1. Is not the same for different physical properties and different materials
2. Depends both under the property under consideration and the exact nature of the
chemical bonds in the material
3. The impact of the spatial confinement is not the same for different materials and /or
different properties.

Properties of materials are size-dependent 

de Mello Donegá, C. (2014). The Nanoscience Paradigm: “Size Matters!”. In: de Mello Donegá, C. (eds)
Nanoparticles. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-662-44823-6_1
 CdSe nanoparticles

http://pubs.rsc.org/en/content/articlelanding/2009/cc/b902195g#!divAbstract
http://www.renishaw.com/en/photoluminescence-explained--25809
Physical properties

1. Large fraction of surface atoms.

2. Large surface energy - High reactivity
3. Lower melting point.
4. Lower phase transition temperature.
5. Reduced lattice constants due to a huge fraction of surface atoms.
6. Spatial confinement.
7. Reduced imperfections.
Reduced Melting Point -- Nanomaterials may have a
significantly lower melting point and substantially reduced lattice
constants (spacing between atoms is reduced), due surface
effect
Changes of the Ag melting
Point
Tconv. = 6700C
Tnano < 100 0C

Ultra Hard -- Mechanical properties of nanomaterials may

reach the theoretical strength.
For metals, there is an obvious trend for the hardness to
be 3–10 times higher for the smallest nanoparticles than
for those larger than 100 nm.
Ceramic materials are usually very brittle, and a ceramic
pot can be easily broken
nanoceramic material can have the same good tenacity as
a spring. The enhancement in mechanical strength is
simply due to the reduced probability of defects.
Classification of nanomaterials

•DOI: 
•10.1002/9781119418900.ch4
Classification of nanomaterials (dimensionality)
2 – dimensional
Zero –dimensional
(2-D)
(0-D)
 Nano thin films
 Nano-coatings
 Nanoparticles
 Nanocapsules
 Fullerene
 Dendrimers
 Quantum dots
 Nanopores

1Dimensional
(1 – D)
 Nanofibers
 Nanowires
 Nanotubes
 Nanorods

https://doi.org/10.1186/s12989-018-0282-0
 ttps://doi.org/10.1016/B978-0-12-813341-5.00001-2

•DOI:  10.5296/emsd.v6i2.12047
 What is a "thin film" ?
A thin film is a layer of material ranging from few nanometers to
several micrometers in thickness

thin = less than about one micron thickness film

DISTINCTION “THIN” BY “THICK” FILM
A thin film - one of its dimension is very small in comparison with the
other two dimensions
Thin film has a larger surface to volume ratio

bulk
properties
dominated

surface and
interface effects
Dendrimers are highly
ordered, branched
polymeric molecules

A nanocomposite comb
ines two or more
materials – of which at
least one is a
nanomaterial – with
different physical and
chemical properties.
 Summary

Nanotechnology
has the potential
to engineer the Nanotechnolo
various gy has high
properties such potential to
as resistivity, revolutionary
refractive index, development
thermal of new novel
coefficient, materials and
surface devices
roughness,
porosity)

https://doi.org/10.3390/molecules25010112
 Applications of nanomaterials
Nanomaterials possess attractive properties
and therefore can have versatile
applications.

The thin film science and technology plays

an important role in the development of
devices in the future ….
 Thin film coatings
“Coating” means a substance applied to other materials to change the
surface properties, such as color, gloss, resistance to wear or chemical
attack, permeability, without changing the bulk properties.

http://geomatec sputtering.com/reason/what.html
http://rareoxide.en.ec21.com/offer_detail/Sell_oxide_sputtering_targets_and--9654627.html
http://www.photonicsonline.com/doc/precision-thin-film-coating-0001
https://en.wikipedia.org/wiki/Thin-film_optics
http://blog.gkboptical.com/tag/eyewear-online/
 Thin film coatings
Application Material  
Optical coatings Dielectric oxides SiO2; Ta2O5; Nb2O5
Metal carbides GeC
Micromechanical devices Ferroelectric oxides Fe
Metallization metals W,
Erosion protection Metals  
Adhesion layer Metals Ti
Corrosion resistant coatings Metal carbides Ti, Ta
V carbide
Corrosion protection Metals Cr, Ti
Metal carbides Cr7C3; Cr3C2
Wear resistant coatings Metals/metal nitrides Mo, TiN
Metal carbides Cr7C3; Cr3C2
Friction reduction coatings metal nitrides TiN
Decorative coatings metal nitrides TiN
Hard coatings for machine tools / tool coatings metal nitrides ZrH, HfN
Metal carbides WC, W2C; W3C
Hard coatings for cuttings and milling Metal carbides TiC
Oxidation resistant coating for composites; Metal carbides HfC
coatings for superalloys
Protective coatings Metal carbides Ta and Nb carbide
 Thin film coatings
Coating Technologies

There are several deposition technologies commonly used to apply thin film coatings
including thermal evaporation, sputtering, spin coating and s.a.
No single coating technology is the ideal choice for every application, as each technology
has unique strengths that make it optimal for some specific and overlapping use cases. 
 Thin film coatings – Automotive industry

https://www.researchgate.net/publication/
344488130_Nanotechnology_Applications_In_Automobiles_Comprehensive_Review_
Of_Existing_Data?enrichId=
 Hydrophobic coating using nano TiO2 (repelling the water)
The solutions for coatings were prepared by dispersing TiO2
hydrophobic powder of 5wt.% by weight in 95 wt.% by weight of an
acetone.
Table 1. Physico-chemical data Water contact angle
of Hydrophobic on TiO2 coated paint lid.
titanium dioxide nano-powder

Lotus effect – self-cleaning 

 Thin film coatings – Sport
Roger Federer at
Wimbledon 2009
with a Wilson K
Factor racquet
containing silica
nanoparticles

Oscar Pereiro Sio at Tour de

Romandie 2007 riding a Pinarello  Speedo (the
bicycle containing carbon nanotubes. company which
designed the suit)
used
nanotechnology

highly lightweight, flexible and

quick-drying swimsuit
that provides the wearer with
a more efficient performance.
https://www.nanowerk.com/spotlight/spotid=30661.php
https://www.azonano.com/article.aspx?ArticleID=4859
 Applications of thin film in
http://phome.postech.ac.kr/user/
indexSub.action?
codyMenuSeq=69391&siteId=lamp&
menuUIType=top

electronics
Miniaturization is one of the trends in
electronics, optoelectronics and other
industry sectors (e.g., life sciences,
energy, sensors)

http://www.mobilephonehistory.co.uk/ericsson/ericsson.php
http://www.shellypalmer.com/2013/04/how-to-re-use-your-clunky-old-laptop/
http://www.anyit.com/new-used-computer-servers/
http://gajitz.com/ultra-flexible-smartphone-idea-with-multiple-personalities/
https://imc401.wordpress.com/2013/11/26/how-to-buy-a-good-monitor-2/
https://forums.creativecow.net/thread/8/1215734

https://cleantechnica.com/2011/11/09/europes-largest-solar-power-park-to-ope The number of transistors per square

n-this-year
/
inch on integrated circuits had doubled
http://www.vgloryenergy.com/sell-1492957-no-1-usa-flexible-solar-panel-80w-
with-high-efficiency-cell-for-golf-car-etc.html
every year (now 18 months) since their
http://www.digitaltrends.com/cool-tech/moth-eye-graphene
https://en.wikipedia.org/wiki/Incandescent_light_bulb
invention – Gordon Moore, 1965
Applications of thin film in
electronics

https://cleantechnica.com/2011/11/09/europes-largest-solar-power-park-to-open-this-year/
http://www.vgloryenergy.com/sell-1492957-no-1-usa-flexible-solar-panel-80w-with-high-efficiency
-cell-for-golf-car-etc.html
http://phome.postech.ac.kr/user/indexSub.action?
http://www.digitaltrends.com/cool-tech/moth-eye-graphene
codyMenuSeq=69391&siteId=lamp&menuUIType=top
https://en.wikipedia.org/wiki/Incandescent_light_bulb
Applications of thin film in electronics
Computer electronics/memory
Hard disk

https://www.sec.gov/Archives/edgar/data/1104657/000095012310055203/
l39902exv99w1.htm
Applications of thin film
Future – skin electronics
The electronic skin fitted with 'disco lights': Sticky film could lead to
wearable screens that track your health and even show FILMS

http://goodereader.com/blog/e-paper/plastic-logic-debuts-flexible-screen-
technology-for-wearables

http://www.popsci.com/technology/article/2012-08/electronic-smart-fingertips-
could-give-robots-and-doctors-virtual-touch
http://futuristicnews.com/tag/flexible/
Applications of
nanomaterials
in

medicine