Applied Surface Science 256 (2010) 2759–2763

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Applied Surface Science

journal homepage: www.elsevier.com/locate/apsusc

Surface-coated fly ash used as filler in biodegradable poly(vinyl alcohol) composite

films: Part 1—The modification process
D.C.D. Nath a, S. Bandyopadhyay a,*, S. Gupta a, A. Yu a, D. Blackburn b, C. White b
a
School of Materials Science and Engineering, The University of New South Wales, Sydney, NSW, Australia
b
Research and Ash Development, Cement Australia, Brisbane, Queensland, Australia

A R T I C L E I N F O A B S T R A C T

Article history: The surfaces of fly ash (FA) particles were modified by surfactant, sodium lauryl sulphate (SLS) and used
Received 7 August 2009 in fabrication of composite films with polyvinyl alcohol (PVA). Both unmodified fly ash (FA) and modified
Received in revised form 3 October 2009 fly ash (SLS–FA) samples were examined using a range of analytical tools including X-ray fluorescence
Accepted 9 November 2009
spectroscopy (XRF), scanning electron microscopy (SEM), transmission electron microscopy (TEM),
Available online 13 November 2009
Fourier transform infrared (FTIR) and X-ray photoelectron spectroscopy (XPS). The distribution patterns
of SLS–FA particles were shifted to the higher regions compared to FA by adding 1.2–4.2 mm in the
Keywords:
ranges between 2 and 25 mm, whereas the modification process reduced the size of the particles over
Fly ash
25 mm due to grinding during the activation process. The increased 1.2–4.2 mm in average can be
Polyvinyl alcohol (PVA)
Composite film considered the thickness of the surfactant on the SLS–FA surface. On the oxides based chemical analysis
Surfactant by XRF, the compositions were almost unchanged. SEM and TEM were visualised the irregular sizes
Interface morphology mostly spherical of the particles, although it is impossible to capture the images of exactly
same particles in modified and unmodified forms. The composite films reinforced with SLS–FA showed
33% higher strength than those of FA filled films. The enhancement of tensile strength attributed from
the level of physical bonding between SLS–FA and PVA surfaces.
ß 2009 Elsevier B.V. All rights reserved.

1. Introduction Due to convenient choice of suitable functional group, polymers

Fly ash (FA) is an industrial by-product in coal fired power
station. Only a small amount of namely 30% of FA is used by cement
industry, while a large proportion often goes to landfill and ash
ponds. This poses great environmental risk due to possible long
term adverse effect of transition metal oxides dependent on
processing condition [1,2]. Therefore, it is a great challenge to find
alternative sound environmental solutions to dispose FA.
A range of alternatives are being pursued to utilise FA.
Recently, there is growing interest to use as a filler material for
making high performance composites. Often, the properties of the
polymer composites such as mechanical properties, heat resis-
tance and anti-flammability are better to those made from either
matrix or filler [3]. Mechanical properties of composites are
influenced by the physical and chemical nature of fillers such as
size distribution, aspect ratio, volume fraction and the intrinsic
adhesion with the polymer surfaces [4]. High aspect ratio of filler
particles e.g. fibre shape increases the yield strength due to
capability of attaining high local stress transferred from the
polymer matrix [5].
* Corresponding author. Tel.: +61 2 9385 4509; fax: +61 2 9385 5956.
E-mail address: S.Bandyopadhayay@unsw.edu.au (S. Bandyopadhyay).
are the preferred material for the fabrication of high performance
materials. The formation and development of stronger interfacial
interaction offers to categorize the composites into rigid materials.
PVA is one of the popular precursor polymer matrixes for the
fabrication of environmentally friendly, biodegradable and water-
soluble biopolymers. PVA based composites find applications in a
wide range of industries including textiles, chemical and food for
coating, adhesives, emulsifiers, colloidal stabilizers, film packag-
ing, etc. [6].
Different types of fillers such as sugar cane [7], starch [8], clay
[9], carbon nanotube [10], wood dust [11], cement [12], organo-
ceramic [13] and TiO2 [14] have been tested to establish suitable
filler material for PVA based composites. In most of the cases, the
mechanical strengths were decreased with filler proportion [7,8].
However, due to some unique properties of FA, there has been
growing interest for recycling FA as filler for developing eco-
friendly composite materials with advanced mechanical properties
in metal matrix [15] as well as polymer matrix e.g. polyester [16],
epoxy [17], polypropylene (PP) [18,19]. The polymer composites
showed lower strength compared to neat matrixes. The improve-
ment of mechanical strength of composite with FA is an interesting
issue in research. The modification of surface properties of single-
wall-carbon nanotube (SWCN) after coating with ‘‘dodecyl
sulphate’’ of sodium [10,20–22] and of lithium in aqua solution

0169-4332/$ – see front matter ß 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.apsusc.2009.11.024
2760 D.C.D. Nath et al. / Applied Surface Science 256 (2010) 2759–2763

[23], has been reported to significantly improve the mechanical time per step 0.5 s. Qualitative phase analysis of FA/SLS–FA was
and magnetic properties of PVA composite, and was attributed to performed using the search/match software program.
increase the degree of homogeneous orientation of SWCNs [23]. (d) Hitachi 4500-II scanning electron microscope was used to
The aim of the study is to characterize the surfactant coating examine the morphology of all samples. The electrically non-
layer on the FA surface and investigate the effect of coating on conductive surfaces of samples were coated in a chromium
improvement of mechanical strength of the composite films with sputter unit by chromium. Two coating cycles were applied to
unmodified filled FA. improve the conductivity of the film surfaces for a better
picture.
2. Experimental procedure (e) Philips CM200 TEM (transmission electron microscopy) was
used with a field emission gun (FEG), which provides very high
2.1. Materials resolution but requires more care than a normal TEM filament.
It is very important that a high vacuum is maintained in the gun
FA sample was obtained from Swanbank Coal Fire Plant, Cement chamber at all times. The FA/SLS–FA particles were dispersed in
Australia, Queensland. Polyvinly alcohol (PVA) (Mw: 125,000 and ethanol with sonication and a drop of diluted suspension was
degree of hydrolysis approx. 89%) from Fine-Chemical Ltd., Cross- poured onto cupper grid, which is directly injected in sample
linking agent, glutaraldehyde (GLA) (25% contents in water) from injection holder.
Laboratory Unilab Reagent and sodium lauryl sulphate (SLS) from (f) XPS (X-ray photoelectron spectroscopy) experiment was
Ajax Chemicals were purchased and used as received. undertaken for determination of hydroxyl concentration on
FA/SLS–FA surfaces in a vacuum generator instrument model
2.2. Activation process of FA surfaces Escalb 220-IXL with resolution of 0.8 eV at 240 W (Al Ka,
12 kV).
FA particles were immersed in 0.5 wt.% aqua solution of (g) FA and SLS–FA were characterized by FTIR spectroscope
surfactant SLS at 50 8C under vigorous stirring. After 10 h, the (NEXUS-870, Thermo Nicolet Corporation) running with Omnic
suspension was filtered and washed by distilled water several software. The condition for the measurement of FTIR: detector,
times to remove non-adsorbed SLS followed by drying under MCT/A; base splitter, KBr; window, diamond; velocity, 0.6329;
vacuum for 2 days at 50 8C as reported elsewhere [10,20–23]. aperture, 100; resolution, 2 cm 1 and scan, 64.
(h) The mechanical properties of composite films were determined
2.3. Preparation of composite films from stress–strain relationship tests using an Instron 1185
with crosshead movement 50 mm/min. The specimens were
The composite films were fabricated by casting aqueous prepared as ASTM D882-95a (length 22 mm, width 5 mm and
solution of PVA combined with FA or SLS–FA. The neat PVA was thickness 0.05 mm) [9,11]. Five samples were tested in each
dissolved in distilled water at 80 8C to prepare 1.2 wt.% solutions. A category and the results are considered the average values.
range of FA or SLS–FA concentrations from 5 to 25 wt.% were
dispersed and sonicated for 5 min. The distilled water solution of 3. Results and discussion
1N HCl (50 mml) and 1 wt.% GLA (0.50 ml) was sequentially added
to FA or SLS–FA containing PVA solution. The resulting solution 3.1. Effect of coating on fly ash properties
was poured in glass petri-dishes (diameter: 10 cm) and the
bubbles were completely removed by careful shaking. The petri- The chemical analysis of fly ash samples was measured by XRF
dishes were kept at room temperature until dried. The casted films and expressed the data based on oxides in Table 1. The percentages
were peeled out and dried in oven at 60 8C in vacuum for 6 h. The of elemental oxides did not change significantly. Fig. 1 compares
thickness of the films was 0.05–0.07 mm. The thickness of the films the XRD spectra of two fly ash samples. This shows that hexagonal
was controlled by using the same amount of materials and same quartz (SiO2) and orthorhombic mullite (3Al2O3
2SiO2) were the
sized glass petri-dish [10,11]. main crystalline phases while small amounts of hematite (Fe2O3)
and magnetite (Fe3O4) were also present. No apparent change in
2.4. Testing and analytical instruments for characterization of mineral phases was observed as a consequence of coating. Both
samples elemental and mineral of fly ash samples clearly show that due to
surface coating, no change in chemical composition of bulk fly ash
(a) Malvern Light Scattering Particle Size Analyser (MLSPSA) was samples occurred.
used to determine the particle size and distribution pattern of
FA and SLS–FA the experiments run for 60 s in water as fluid. Table 1
Chemical composition of fly ashes analysed by XRF.
(b) The chemical composition of FA and SLS–FA was obtained using
X-ray fluorescence spectroscopy (XRF, PanAlytical PW 2400 Compounds FA SLS–FA
with Rh end-window tube) method. The samples were SiO2 73.55 73.35
prepared as 40 mm glass beads using lithium meta-borate as Al2O3 19.25 19.39
a fluxing agent. The XRF is calibrated for a wide range of Fe2O3 0.97 0.71
elements using certified reference materials prepared as glass CaO 0.99 0.77
MgO 0.60 0.59
beads for major element oxides, using optimum machine
TiO2 1.31 1.33
parameters, and correcting for spectral overlapping lines. BaO 0.08 0.08
Software used was ‘‘Super Q’’ and all majors are expressed as Cr2O3 0.15 0.15
oxides. K2O 0.29 0.29
MnO 0.01 0.01
(c) Wide angle X-ray diffraction (WAXRD) was carried out to
Na2O 1.48 1.23
investigate the structure of FA, SLS–FA. This was conducted in a P2O5 0.05 0.05
multipurpose diffraction (MPD-Scherrer) with diffracted beam SrO 0.02 0.02
graphite monochromators using Ni filtered Cu Ka radiation. LOI 0.31 1.65
Diffractometer conditions for data collection were 40 kV and
100 100
20 mA, 2u scanning range from 58 to 908 with step size 0.02,
 D.C.D. Nath et al. / Applied Surface Science 256 (2010) 2759–2763
Fig. 1. XRD spectra of SLS–FA and FA.
3.2. Fly ash particle size distribution patterns
Fig. 2 compares the size distribution of fly ash particles before
and after coating. The size distribution profiles show relatively
narrow sharp peaks between the ranges of 0–25 mm. The
treatment of FA particles with SLS solution gives higher particle
size and the ranges vary from 1.2 to 4.2 mm in the lower size of
particle between 2 and 25 mm. The modification process reduced
considerable level of the size of the particles over 25 mm due to
stirring during activation process. The increased 1.2–4.2 mm in
average can be considered the thickness of SLS on the FA surface.
3.3. Fly ash morphology
Fig. 3 illustrates the SEM surface images of fly ash particles
before and after coating. The unmodified FA particles look like a
scattered spherical and non-spherical shape, whereas the modified
one becomes multiple stacked layers with mostly irregular shape.
The multiple stacked layers seem to be characterized by high
aspect ratios and help together only weak inter-particle forces [24].
The surfactant coats on the surface of FA particles and gives
contribution to the superior light reflecting quality of the particles.
The thin layers reduce the attraction forces of particle–particle and
help to disperse in aqua/or matrix media. The orderly distributed
Fig. 2. Particle size distributions of SLS–FA and FA determined by Malvern light
scattering size analyser.
2761
Fig. 3. SEM morphology images of fly ashes: (a) FA and (b) SLS–FA.
filler in polymer composite attributes the higher mechanical
strength compared to neat polymer matrix.
3.4. Fly ash surface topography
The TEM images of modified and unmodified FA particles along
with the measurement of size were shown in Fig. 4(a and b). The
size analysis of TEM micrographs of particles will show some
empirical result because it is not exactly the same particles before
or after modification. The existing interfacial interactions between
the unmodified particles are disappeared in the modified particles
and the phenomena will play a significant role in reduction of
agglomeration of particles in fabrication of composite films.
Under atmospheric condition, metal and metal oxide surfaces
are well known to be absorbed/adsorbed with functional hydroxyl
(–OH) group or ions, which plays a critical role in establishing
physical bonding with other substrates. The –OH group has also
been seen in fully hydroxylated silica powder [25,26]. Quartz,
mullite and glassy alumina-silicates are the major phases of fly ash
samples. Therefore, it is important to identify the presence of
(–OH) group associated with these phases. The XPS spectra of FA
and SLS–FA are shown in Fig. 5 in the range of binding energy 95–
110 eV. Clearly combined peaks of –OH and –O– attached to a-
quartz SiO2 and mullite are present at the binding energy 103.7 eV.
The binding energy of modified and unmodified FA in the ranges of
95–110 eV was unchanged. The –OH group present on the surface
of fly ash has been attributed to improve interfacial interactions
with PVA chain by physical and/or chemical bonding.
2762 D.C.D. Nath et al. / Applied Surface Science 256 (2010) 2759–2763

Fig. 6. FTIR spectra of FA and SLS–FA.

3.5. Structural configuration of fly ash

Fig. 6 compares the FTIR spectra of two types of fly ash samples

while selected band positions were given in Table 2. The stretching
vibrations of Si–O–Al bonds were mainly appeared in the ranges of
1200–600 cm 1. All the dominant bands are centred at 1065, 796,
779 and 698 cm 1 for the vibrations of Si–O and Al–O bonds in FA. A
bit shifting to higher position of the parent peaks were observed in
the modified FA system. The shifting may come from the results of
physical bonding between the Al–O/Si–O/other oxides in FA with
highly active polar group in SLS. The actions of physical bonding in
the groups between –OH group in PVA and Al–O/Si–O/other oxides
on FA surface molecules shifted the band of related bonds to lower
frequency with reduction of sharpness of peaks [27].

3.6. Effect of coating on mechanical properties of composite films

The relationship of tensile strength and strain of the composite

films reinforced with 20 wt.% FA and SLS–FA was shown in Fig. 7.
The addition of FA/SLS–FA to neat PVA enhances the tensile
strength irrespective quality of fly ash particles. The modified SLS–
FA particles increased the strength of the composite films up to
74.8% and 33% higher than those of neat PVA and film with
Fig. 4. TEM images of fly ashes: (a) FA and (b) SLS–FA.
unmodified FA, respectively. The strain at break shows the reverse
order of tensile strength with addition of FA/SLS–FA.
The strains at failures in Fig. 7 decreased with addition of fly ash
irrespective of modification or non-modification due to the
formation of interfacial interaction. The interfacial interaction
restricts the mobility of molecular chain of PVA [4]. The spherical
particle fly ash decreased the tensile strength in the composite of
PP at room temperature investigation [18,19]. The non-polar PP
has less possible chance to form an interfacial interaction zone to
fly ash surface physically and/or chemically. The formation of
interracial interaction between the two small different molecules
in polymer composite play a significant role in improvement of
mechanical strength compared to neat polymer [4].
PVA is high potential matrix in the formation of intra- and inter-
molecular hydrogen bonding between the –OH and –COOCH3

Table 2
The selected FTIR absorption peaks of fly ashes.
1
Samples Peak positions of structural groups in (cm )

Si–O/Al–O Al–O Al–O Al–O

FA 1065 796 779 698

SLS–FA 1070 806 781 698
Fig. 5. XPS spectra of FA and SLS–FA.
 D.C.D. Nath et al. / Applied Surface Science 256 (2010) 2759–2763
Fig. 7. Relationship of tensile stress and strain of the composite films reinforced
with SLS–FA and FA.
groups [6]. In the presence of modified SLS–FA, the existence of –
OH groups on the particle surface may take part in the formation of
hydrogen bonding between PVA and SLS–FA, and chemically cross-
linking with GLA molecules. The degree of bonding refers the
strength of the composites. The insolubilization of PVA by cross-
linking acetalization reactions of intra- and inter-molecular chains
have been reported with acid-catalysed glyoxal, glutaraldehyde
and terephthalaldehyde [28].
The spherical particles generally decrease the mechanical
strength of the composites. The decreasing of mechanical strength
comes from the weak and/or absence of interfacial interaction
between the polymer and filler. The mechanical strength can be
designed and controlled by consideration of formation of interfacial
interaction. The agglomeration of spherical particles in composites is
considered a hazard effect for decreasing the mechanical strength.
The reduction of agglomeration of particles will come from the
reduction of the interaction force of particle–particle. The Van der
Waals forces between the particle–particle can be depleted by
coating adsorbed amphiphilic molecules [20–23].
The nature and concentration of surfactant are considerable
parameters to play a role in phase behaviour and the isolated
phases are not being an effect system for enhancement of
interfacial interaction. Poulin et al. [21] conducted a series of
reactions in fabrication of PVA fibre with different concentrations
of SDS on coated SWCN. At the higher concentration of SDS, the
black textures were observed which reflected the clusters of
surfactant. The clusters became larger and denser with increasing
the SDS concentration and appeared as surfactant aggregation,
micelle. The micelles easily separated the phase of the composites.
The optimum concentration therefore, is set 0.3–1.5% SDS and used
in their rest of works. Besides, the 1% SDS is also used in other
research groups to achieve improved mechanical strength of PVA
and SWCN composite films [10,20–23].
4. Conclusions
In conclusion, the key points of the study were summarized
here in modification of FA and its application in PVA composite
films.
1. The increasing size of the modified particles reflects an effective
coating on the surface of FA. The thickness of the layer was
calculated to be 1.2–4.2 mm.
2. The modification changed the morphology of FA particles from
irregular platelets to multiple stacked layers. The stacked layers
2763
gave the high aspect ratio which is controlling parameter in
designing the mechanical strength of composite.
3. The surfactant-activated FA particles enhanced the tensile
strength of the composite up to 33% and 75% higher compared
to those of the composite with unmodified FA and neat PVA,
respectively. The intimate contact may come from the physical/
chemical bonding in two surfaces and makes a network, which
can easily transfer the load without creating local stress.
4. The study demonstrated that fly ash can be successfully recycled
to design high performance biodegradable composite films.
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