The Effect of Hybrid Nanoparticle Additives On Epoxy-Nanocomposite Behavior and Morphology
The Effect of Hybrid Nanoparticle Additives On Epoxy-Nanocomposite Behavior and Morphology
The Effect of Hybrid Nanoparticle Additives On Epoxy-Nanocomposite Behavior and Morphology
INTRODUCTION
Nanocomposites of epoxy resin materials are a popular material choice for the engineering industry due
to their unique organic-inorganic characteristics and
enhanced physical properties such as improved thermal stability, dielectric breakdown strength, tensile
strength, hardness, and many other attributes.16
Montmorillonite (MMT) clay is a popular nano-additive because it is readily available, environmentally
friendly and low cost, but its efficacy as a nanocomposite constituent is dependant on the dispersion of
the clay in the epoxy matrix. Poor dispersion can
result in agglomeration and worse rather than
improved properties. MMT clays consist of stacked
6
silicate layers with a typical thickness of 10 A
which unmodified are hydrophilic and tend to form
self-assembled multilayer intercalated structures
which have a tendency to agglomerate.4 To create a
well-dispersed exfoliated structure, the MMT clay
needs to be treated to reduce its polarity and make
it compatible with most polymer matrices. Surface
treatment can be used to open up the interlayer
space allowing more movement of polymer in
between the layers and improve the miscibility of
the clay and the epoxy matrix.7 Organic ammonium
has been used to create a cation exchange effect on
EXPERIMENTAL
Materials
Clay nanopacticles Cloisite 15A, were obtained from
Southern Clay Products and the Hunstman CY219
DGEBA based epoxy resin and HY5160 curing agent
were used as the matrix. The hybrid organic/inorganic POSS-NH2 nanoparticles (hereafter described
as POSS) were produced our laboratories via a process described previously.13
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TABLE I
A Summary of the Thermal Properties
Ref epoxy
3% Clay
3% Clay 1% POSS
3 % Clay 3% POSS
3% Clay 10% POSS
10% POSS
Tg
( C)a
Td 5%
( C)b
Td 50%
( C)c
Char
yield %d
49
46
28
43
40
51
313
307
338
277
259
220
400
402
408
403
426
412
5.4
10.2
12.7
11.3
18.9
13.2
RESULTS
Nanocomposite preparation
The commercial epoxy and curing agent were used
in the recommended formula and any included
amine containing POSS was in addition to those in
the original system. To mix the components, the
hardener was heated to 40 C and POSS and clay
were added separately, and the mixture was stirred
mechanically for 30 min. The epoxy resin was then
added, and the stirring was continued for 15 min.
The composite mix was cast into a mould. Samples
were heat treated at room temperature for 12 h and
held at 60 C post curing for 24 h to enable the removal of residual solvents.
Microscopy
Scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) analysis were carried out
using a JEOL JSM-5900LV scanning electron microscope equipped with a OXFORD Isis spectrometer
with germanium detector. The fracture surface of the
cured resin nanocomposite was investigated with
SEM for morphological characterization. EDS mapping of silicon, carbon, and oxygen was carried out
over the same area as imaged.
Microscopy
SEM and EDS mapping were carried out on the fracture surface of each sample to inspect the fracture
mechanisms and determine if any agglomeration
was evident. The EDS inspection mapped the distribution of silicon, which is present in low amounts in
the epoxy and is a major constituent of the POSS
and clay nanoparticles.
The neat epoxy exhibits a smooth fracture surface
indicative of brittle fracture behavior typical of an
unfilled epoxy. The sample containing 10% POSS
without additional clay also exhibits the same
smooth fracture surface indicating that the POSS
was evenly distributed in the epoxy matrix.
The fracture surface (Fig. 2) of the samples containing clay has considerably different fractographic
features, it can be observed from the surface roughness that the crack propagation was deflected and
perturbed because of the presence of clay nanoparticle agglomerates. These agglomerates can be
observed in the EDS map of Si. Such crack deflection
would indicate an increase in fracture toughness of
a material. In some places, microvoids can be seen.
The clay agglomerates are likely to act as stress concentrator sites which could lead to de-bonding of the
Thermal analysis
Small samples were cut from the cast composites for
thermal analysis. Thermogravametric analysis (TGA)
was carried out on a Perkin Elmer TGA 7 instrument
under a nitrogen atmosphere at a heating rate of
20 C/min from 49 to 850 C. Sample mass was
between 12 and 17 mg. Selected samples were also
run at 10 C/min and showed no evidence of thermal
lag. Differential scanning calorimetry (DSC) was carried out using a Perkin Elmer Pyris 1 to verify that
there was no residual unreacted matter and determine the glass transition temperature (Tg). Samples
of 45 mg were used in standard aluminium pans.
Heating from 20 to 200 C, followed by holding isothermally for 2 min and cooling from 200 to 20 C,
3214
JAHREN ET AL.
In the sample containing clay and no POSS a reflection peak at 5.1 2y which is assigned to the (001)
basal plane indicating that the clay particles are
aligned in a layered intercalated structure within the
epoxy matrix. This is symptomatic of the agglomerates observed in the SEM. With the addition of
POSS to the epoxy nanoclay system, the reflection
peak reduces in intensity, indicating that the nanoclay is becoming increasingly dispersed in the matrix forming a more exfoliated structure (as shown
schematically in Fig. 4). The results show that the
addition of 3% POSS reduces the degree of intercalation, but the addition of 1% has a greater effect and
10% effectively creates an almost entirely exfoliated
structure. It can be noted that the peak position does
not significantly alter with addition of POSS indicating the d-spacing, and therefore the distance
between the platelets is largely unaffected. This
implies that the POSS functions improve the miscibility of the MMT clay layers rather than increasing
the interlayer distance.
DSC
DSC was used to measure the glass transition temperature of the samples after curing. The results
(shown in Fig. 5 and Table 1) show that the reference sample has a Tg around 49 C. Other articles14
have reported that the addition of clay restricts the
chain movement increasing the Tg, however in this
case the addition of 3% clay slightly reduced the Tg
of 46 C due to the poor distribution of the clay and
the resulting agglomerates acting in a small extant
as a plasticizer.15 The effect is even more pronounced with the addition of 1% POSS decreasing
the Tg to 28 C.
With addition of POSS to the system, we have
introduced an increased number of crosslinking sites
Figure 2 SEM images and energy dispersive spectroscopy mapping of facture surfaces of (a) neat epoxy, (b) epoxy 10% POSS (c) epoxy 3% MMT clay, (d) epoxy, 3%
MMT clay, 1% POSS, (e) epoxy, 3% MMT clay, 3% POSS,
(f) epoxy, 3% MMT clay, 10% POSS. All images are shown
at 200 magnification.
epoxy matrixclay interface or break up or delaminate the clay agglomerates, both of which would
lead to the formation of microvoids.
XRD
Figure 3 represents the XRD patterns of the samples
containing nanoclay and varying amounts of POSS.
Journal of Applied Polymer Science DOI 10.1002/app
3215
Figure 4 Schematic illustration of the mechanism of dispersion. (a) Untreated nanoclay platelets form intercalcated
stacks, (b) surface treatment with POSS NH2 reduces the surface polarity, (c) the treated surface is more organophilic
and allows permeation of the epoxy matrix.
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JAHREN ET AL.
Thanks are due to Jest Beylich, Kjell Windsland for contributions to the experimental work.
Reference
1. Liu, T. X.; Tjiu, W. C.; Tong, Y. J.; He, C. B.; Goh, S. S.; Chung,
T. S. J Appl Polym Sci 2004, 94, 1236.
2. Kornmann, X.; Lindberg, H.; Berglund, L. A. Polymer 2001,
42, 4493.
3. Singha, S.; Thomas, M. J. IEEE Trans Dielectr Electr Insul
2008, 15, 12.
4. Tarrio-Saaavedra, J.; Lopez-Beceiro, J.; Naya, S.; Artiaga, R.
Polym Degrad Stab 2008, 93, 2133.
5. Tjong, S. C. Mater Sci Eng R Rep 2006, 53, 73.
6. Zhao, J. Q.; Fu, Y.; Liu, S. M. Polym Polym Compos 2008, 16, 483.
7. Park, J. H.; Jana, S. C. Macromolecules 2003, 36, 2758.
8. Yei, D. R.; Kuo, S. W.; Su, Y. C.; Chang, F. C. Polymer 2004,
45, 2633.
9. Ramirez, C.; Rico, M.; Barral, L.; Diez, J.; Garcia-Garabal, S.;
Montero, B. Calorimetry and Thermal Analysis Conference,
Santiage de Compostela, Spain, July 912, 2006, p 69.
10. Lee, A.; Lichtenhan, J. D. J Appl Polym Sci 1999, 73, 1993.
11. Lee, A.; Lichtenhan, J. D. J Appl Polym Sci 1999, 73, 1993.
12. Fu, B. X.; Namani, M.; Lee, A. Polymer 2003, 44, 7739.
13. Pilz, M.; Mannle, F.; Smon, C.; Trevor, S. L.; Bu, H.; Tanen, B.
S. Solid State Phenom 2009, 151, 10.
14. Zhang, Z. P.; Liang, G. Z.; Wang, J. L.; Ren, P. G. Polym Compos 2007, 28, 175.
15. Park, J.; Jana, S. C. Macromolecules 2003, 36, 8391.
16. DellErba, I. E.; Williams, R. J. J. 35th Annual Conference of
the North-American-Thermal-Analysis-Society, E Lansing, MI,
August 2629, 2007, p 95.
17. Montero, B.; Ramirez, C.; Rico, M.; Torres, A.; Cano, J.; Lopez,
J. 46th Microsymposium on Macromolecules - Nanostructured
Polymers and Polymer Nanocomposites, Prague, Czech
Republic, July 8August 12, 2007, p 74.
18. Baney, R. H.; Itoh, M.; Sakakibara, A.; Suzuki, T. Chem Rev
1995, 95, 1409.
19. Zhang, Z.; Liang, G.; Ren, P.; Wang, J. Polym Compos 2007,
28, 755.
20. Zhang, Z. P.; Liang, G. Z.; Wang, X. L. Polym Bull 2007, 58, 1013.