Polymer/Clay

Nanocomposites
Properties

Intercalation vs.
Exfoliation

Intercalation vs.
Exfoliation
TEM micrographs of
poly(styrene)-based
nanocomposites: (a) intercalated
nanocomposite and (b) exfoliated
nanocomposite.

Intercalation vs.
Exfoliation
XRD patterns of: (a)
phase separated
microcomposite; (b)
intercalated
nanocomposite and (c)
exfoliated
nanocomposite.

2d sin

Mechanical Properties
Tensile Modulus

Effect of clay preparation

Sample
preparation

Filler
Content
(wt %)

MW (X103)

Youngs modulus
(GPa)

Commercial
nylon-6

13.0

1.11

NCC

13.0

1.06

NCH

4.7

16.3

1.87

L-NCH

5.3

19.7

2.04

22.6
2.25
NCC:One-pot-NCH
montmorillonite-based 4.1
nylon microcomposite.
NCH: nanocomposite obtained by in situ intercalative polymerization
of e-caprolactam in protonated aminododecanoic modified
montmorillonite.
L-NCH: nanocomposite obtained by in situ intercalative polymerization
of e-caprolactam in protonated e-caprolactam modified
montmorillonite.

Effect of aspect ratio

Nonlinear behavior

Exfoliation
Aspect
ratio

Effect of layer charge

density

Mechanical Properties
Tensile Strength

Effect of clay-matrix
interface
Matrix

Matrix tensile
strength

Nanofiller
content (wt.
%)

Nanocomposit
e type

Nanocomposit
e tensile
strength (MPa)

Nylon-6

68.6

4.7

NCH

97.2

68.6

5.3

L-NCH

97.3

68.6

4.1

One-pot-NCH

102

53.9

12.6

Intercalated

62.0

53.9

20.7

Intercalated

62.0

31.4

5.0

Intercalated

29.5

32.6

4.8

Intercalated?

31.7

28.7

11.3

Intercalated

21.7

28.7

17.2

Intercalated

23.4

28.7

24.6

Intercalated

16.6

28.7

34.1

Intercalated

16.0

PMMA

PP

PS

Effect of Epoxy Tg

In high Tg epoxy thermoset, neither intercalated

nor exfoliated nano-silicates lead to an
improvement of the tensile stress at break, they
rather make the materials more brittle.
This effect appears to be generally more
pronounced for intercalated structures than for
exfoliated ones.
In contrast, nanocomposites based on both epoxy
and polyurethanes elastomeric matrices exhibit a
sizeable increase in tensile stress at break upon
the addition of small quantities of nanofillers.

Mechanical Properties
Elongation at break

Effect of matrix

Intercalated PMMA and PS or

intercalated & exfoliated PP: the
elongation at break is reduced.
Such a loss in ultimate elongation
does not occur in elastomeric
epoxy or polyol polyurethane
matrices.

Effect of preparation

Effect of Exfoliation

Mechanical Properties
Impact

Effect of clay content

Clay/Naylon-6 Timing belt

Good resistance to impact

a high Young's modulus

good flexural modulus

Higher heat distortion temperature (from 65 oC for pure

nylon-6 to more than 150oC for nanocomposites)

Replace glass fiber reinforced nylon or poly(propylene) in

the production of timing belt covers of automotive engines

The belt cover, obtained by injection-molding, shows good

rigidity, excellent thermal stability and no wrap. It
moreover saves weight up to 25% due to the very small
content of inorganic material in the final composition.

Mechanical Properties
DMA

Dynamic mechanical
analysis

DMA: measures the response of a given

material to a cyclic deformation (usually
tension or three-point flexion type
deformation) as a function of the temperature.
DMA results:

the storage modulus (E), corresponding to the

elastic response to the deformation;
the loss modulus (E), corresponding to the plastic
response to the deformation
tan , that is the (E/E) ratio, useful for determining
the occurrence of molecular mobility transitions such
as the glass transition temperature.

Temperature dependence of E and

tan

Effect of matrix
Trend of the

Nanocomposites

storage modulus E
at 25oC for SBSbased nano- and
micro-composite.

Microcomposites

Effect of matrix

PPCC: microcomposite

Effect of clay preparation

DMA Summary

The storage elastic modulus appears to be

substantially enhanced at temperatures
above Tg for exfoliated nanocomposites filled
with layered silicates of high aspect ratio.
A possible explanation for such an
improvement could be the creation of a threedimensional network of interconnected long
silicate layers, strengthening the material
through mechanical percolation.

Other Properties
Thermal Stability

Approach

The thermal stability of a material is usually

assessed by thermo-gravimetric analysis
(TGA) where the sample mass loss due to
volatilization of degraded by-products is
monitored as a function of temperature
ramp.
When the heating is operated under an inert
gas flow (nitrogen, helium, . . .), a nonoxidative degradation occurs while the use
of air or oxygen allows to follow the
oxidative degradation of the sample.

Thermal stability

TGA traces for PDMS

Effect of Clay
loading/preparation

PS-based nanocomposites
with different clay
modifications

Other Properties
Flame Retardancy

Approach

Cone calorimetry: the sample is exposed

to a given heat flux (often taken as 35
kW/m2) and the heat release rate (HRR)
as well as the mass loss rate are
recorded as a function of time.
It is worth noting that reduction of the
peak HRR is the most clear-cut evidence
for the efficiency of a flame retardant.
Moreover, gas and soot production are
also measured.

Effect of clay filling

Other Properties
Gas barrier

CO2 permeability of polyimide

clay
Pc and Pp:
composite
and the
unfilled
polymer
permeability

Effect of exfoliation
As the length of the clay
increases, the relative
permeability decreases
drastically.
The best gas barrier properties
will be obtained by fully
exfoliated rather long layered
silicates.