Polymer Nano Composites

Dr. AMIR HABIB

References:
1.Ash B.J. Polymer Nanocomposites with Particle and Carbon Nanotube Fillers,
Dekker Encyclopedia of Nanoscience and Nanotechnology.
2.Springer Handbook of Nanotechnology Editor Bhushan
3.Synthesis of Inorganic Materials by Ulrich Schubert
4. Caruso, F. Nanoengineering of particle surfaces.Adv. Mater. 2001, 13, 11–22.
 Introduction

• Polymer nano composites (PNCs) are

composites with polymer matrix and a filler with
at least one dimensions less than 100nm
• Fillers may be plate like clays, high aspect ratio
NTs and lower aspect ratio or equiaxed
nanoparticles.
Examples from Nature and Old Use
• Carbon black and fumed
silica filled polymers have
been used over a century.
• Diatoms, like radiolaria
represent the incredible
control Nature exerts over
the assembly of organic-
inorganic materials.
 Recent increased interest
• Our ability to synthesis and manipulate alot of
nanofillers.
• Nanoparticle and NT filled composites´
uniqueness over traditional composites.
• Large changes in material properties require
small nanofiller loadings.
 Outline

• Uniqueness of Nanofiller to micronfilled

composites.

• Surface modification of nanofillers.

• Examples of mechanical, electrical and optical

properties in nanoparticle/nanotube filled
polymers.
 What makes Nanocomposites
Unique
• Small Size
• Small mechanical, optical and electrical
defects.
• No decrease in ductility of the polymer.
• Do not scatter light below 50nm.
• Nanofillers do not concentrate electro-
magnetic fields.
Nanomaterial;Different from their bulk

• Decrease in melting point of Au nano particle

• CdSe colloidal suspension

• Magnetization and Charge storing capacity;e.g.,

BaTiO3 nano particles.
 Interfacial Area and Interparticle
Spacing

• Small size leads to large

interfacial area.

• Interparticle spacing
(~100A°) decrease at
even small volume
fractions of filler.
 Interaction Zone
• Interaction zone(IZ (~
2-9nm thick) is the
region where
structure and
properties of the filler
are changed.

• IZ; a region of altered

chemistry, polymer
conformation, chain
mobility, degree of
cure, or crystallinity.
Challanges in processing nanofillers
• Dispersion of nano particles and
nanotubes.

• Controlling the size and the agglomeration

of nanofillers.

• Large radius of curvature and increase in

surface energy.
Methods of Surface Modification of
Nanoparticles
• Silanes and organotitanates are used to link the
surrounding matrix and to lower the surface
energy of nanoparticels.

• Radiation grafting.

• Chemical Vapour Depositon.

• Polymerize polymer chains off of initiating

agents coupled to the surface.
 Surface Modification of CNTs
• MWNT are easily
separated by sonication.
• SWNT exfoliation is
more difficult i.e.,without
shortening and
introducing defects.
• Dispersing them
uniformly in poymer
matrix and preventing
agglomeration is
achieved by attaching
functional groups.
SWNTs
 Chemical Methods of Modification

• Noncovalent surface modification of

nanoparticles and CNTs

• Covalent attachment of chemical groups to nano

particles and walls of nanotubes
Noncovalent surface modification of
CNTs
• Noncovalent surface modification of CNT include
all treatments that cause a change in the
functional groups that face the solvent (or the
polymer), without modifying chemical nature of
NT.
• Advantage of noncovalent modification is; the
basic structure and hence the mechanical and
eletrical properties are not changed.
• Noncovalent attachement is possible if there is a
secondary bonding between these groups and
the surface of NT.
 Covalent attachment of chemical groups to
walls of Nanotubes
• Attack of defect sites
by nitric acid, forming
carboxylic acid gropus.

• The resultant carboxy-

lated NTs can further
covalently modified by
reactions based on the
carboxylic acid groups.
Other types of Covalent surface modifications.
 Mechanical Properties
• Improvement in yield stress 30% and Young
modulus 170% in nano filled polypropylene
compared to micron filled polypropylene
• Nylon 6 filled with 50nm silica NPs showed
increase in tensile strength 15%, strain to failure
150%, Youngs modulus 23%, and impact
strength 78% with only 5 wt.% NPs.
• The load transfer to MWNTs dispersed in an
epoxy resin was much higher in compression
than in tension.
 Thermal properties
• Important from mechanical stability and
processing perspective.
• Tg changes as function of filler content;
increase/decrease in Tg reported is linked to
immobilization of the matrix within IZ.
• Industrial epoxy loaded with 1wt% SWNTs
showed an increase in thermal conductivity of
70% and 125% at 40K and at room temperature,
respectively.
 Optical properties
• Clarity for visible wavelengths,adding nano
particles/tubes can as well introduce additional
functionality in form of UV absorption &
alteration of refractive index of polymer.
• TiO2 NPs to polymers
• NCs of leadsulfide & polyethylene oxide increases refractive
index to 3.9
• Gold NPs in gelatin reduce ref. Ind. to 1
• In these NCs interaction with polarized light vary
with direction and intensity of light.
 Electrical properties
• NCs have enhanced properties like conductive
polymers, superpara magnetism in magnetic
material.
• Percolation threshold has been shown to lower
in NCs than traditional Cs.
• The dielectric breakdown strength of NCs can be
enhanced over compositions with micron-scale
fillers.
• Organic-inorganic NCs as etch resists showed
improved rigidity and higher Tg which enhaces
resist performance for nm pattern fabrication.
 Conclusion
• PNCs are a novel class of composites.

• Choice is between SWNTs and MWNTs in case

of NTs.

• Tailoring the nanoparticle/tube-matrix interface is

a challenge and a topic of current interest for
scientists.
Thanks