Rheology of Polymer/Layered

Silicate Nano-composites

Submitted by-

7th Nov. 2014

Ajay Kumar(110020060)
Puja Agarwala (133020017)
Shikha Rajouria(133020018)
Aayush Raj

Introduction
Composite: material made of more than one
component
Composite material categories: Polymeric,
metallic, and ceramic
Nanocomposite: The nanoscale composite
Polymer nanocomposites: nanocomposite
made with polymer and nano- scale filler

Types of fillers

Layered silicates
Metal oxide nanoparticles
Inorganic nanotubes
Expandable graphite
Layered titanate
Cellulose nanowhiskers
Carbon nanotubes

Structure and Properties of Layered Silicates

Layered Silicates crystal structure consists of layers made up of
two tetrahedrally coordinated silicon atoms fused to an edgeshared octahedral sheet of either aluminium or magnesium
hydroxide.
The layer thickness is around 1 nm, and the lateral dimensions of
these layers may vary from 30 nm to several microns or larger,
depending on the particular layered silicate
Isomorphic substitution within the layers (for example, Al+3
replaced by Mg+2or Fe+2, or Mg+2replaced by Li+1) generates
negative charges that are counterbalanced by alkali and alkaline
earth cations situated inside the galleries.

Structure of Layered silicates

Types of Silicate layered composites

On the basis of the strength of the polymer/layered silicate
interfacial interaction, three structurally different types of
composites are achievable
Phase- separated composite: when polymer matrix has no
interaction with layered silicate
Intercalated nanocomposites: where insertion of polymer
chains into the silicate structure occurs in a crystallographically
regular fashion, regardless of the polymer-to-layered silicate
ratio, and a repeat distance of few nanometers
Exfoliated nanocomposites: in which the individual silicate
layers are separated in the polymer matrix by average distances
that totally depend on the layered silicate loading.

Layered silicates

Enhancement in properties

High moduli,
Increased strength
Heat resistance,
Decreased gas permeability
Flammability,
Increased degradability of biodegradable polymers
Improved properties in nanocomposites is due to
interfacial interaction between the polymer and
layered silicate, as opposed to conventional
composites.

Properties variation due to Silicate

layered matrix in PCL:
From, graph, we can observe that slope changes as percentage amount of
silicate layer nano-filler increases. This is due to high amount network
formation with in molten state of polymer structure.

Values of 2 and 1 are expected for non- crosslinked polymer melts

Rheological Behaviour

Moduli increase with increasing silicate loading at all frequencies

At high frequencies, the qualitative behaviour of the storage and loss moduli are
essentially unaffected.
At low frequencies the frequency dependence of the moduli gradually changes from
liquidlike to solidlike for nanocomposites
This behaviour is due to the presence of stacks of intercalated silicate layers and
those are randomly oriented in the polymer matrix, forming three dimension
network structure.
At large frequency due to rapid compression and expansion these 3D network
breaks down

Complex viscosity vs frequency analysis

Complex viscosity vs frequency analysis

Difference in deviation in HMW,MMW and LMW is due to
interaction strength (increases with high molecular mass)
that would affect the mesoscopic structure and the
rheological properties of these nanocomposites
Due to the network formation in polymer layered Silica
nanoparticles viscosity increases at low frequencies but at
high frequencies, these network breaks down due to high
oscillatory shear

Viscosity vs shear rate

For fixed shear rate, with increase in silicate particle loading, viscosity increases
monotonically
In the low-shear rate region neat polymer showed Newtonian behavior, whereas
intercalated nanocomposites showed shear thinning behaviour and its more
prominent with higher silicate loading.
At high shear rate both neat polymer and nanocomposites displayed strong shear
thinning behaviour.

Elongation flow rheology

Time dependence of elongation viscosity curve for PP/clay (4)

(polypropylene based nanocomposite ) shows that viscosity first increases
gradually and after a certain time t, it increases rapidly.
The time dependent thickening behaviour is known as rheopexy.
Pure polymer does not exhibit any strain-induced hardening.

Conclusion
Linear rheological material functions showed that the nanocomposites
are characterized by a solid-like behavior as revealed by the
presence of a low-frequency plateau on storage modulus
The magnitude of such plateau or pseudo-plateau is found to strongly
depend on the level of interactions between the polymer matrix and the
modified layered silicate. Such specific interactions favour the state of
dispersion-distribution of the layered silicate within the polymeric
matrix that lead to the formation of a long range or short range
percolating network. However, such a network does not seem very
stable
In fact steady shear flow destroys such connectivity and imparts the
material with a rather Newtonian behavior in the high-shear rate region.
For the moment it is not clear whether or not such percolating network
can be maintained when the nanocomposites are reprocessed in
machines such as extruders and injection moldings

References :
J. Ind. Eng. Chem., Vol. 12, No. 6, (2006) 811-842
Journal of materials science, 39(2004)1919 1925
Appl. Organometal. Chem. 12, 675+680 (1998)

Thank You