Effect of Different Surface Modification on Properties of Fly Ash/Epoxy

Composites

(Kesan Rawatan Permukaan Abu Terbang Ke Atas Sifat-Sifat Komposit Abu Terbang/Epoksi)

NEE KAH POHa,b,, NOR YULIANA BINTI YUHANAa,b

a
Department of Chemical and Process Engineering,
b
Faculty of Engineering and Built Environment, Universiti Kebangsaan Malaysia, Bangi, Malaysia

ABSTRACT

The application of fly ash as mineral filler in polymers is greatly restricted by incompatibility between the
hydrophilic surface of fly ash and hydrophobic surface of polymer. In order to promote the interaction between the
surfaces, surface treatment is necessarily performed on fly ash to modify the hydrophilic properties of the fly ash.
Surface treatment of fly ash can include mechanical, chemical and thermal treatment. In this study, coal fly ash
collected from coal power plant was treated with sodium lauryl sulphate (SLS) and palmitic acid (PA). The
properties of PA-treated products were compared with untreated samples and SLS-treated samples to study the
effect of surface modification of fly ash on the properties of composites formed. Besides, 1g, 2g, 3g and 5g of fly ash
were used to study the effect of amount of fly ash on the properties of composites. The properties of different
composites were compared by means of Fourier-transform infrared spectroscopy (FTIR), X-ray fluorescence (XRF)
and X-ray powder diffraction (XRD) spectroscopy, differential scanning calorimetry (DSC), scanning electron
microscopy (SEM), Rockwell hardness test, water absorption test, density test and particle size analysis. From FTIR
analysis, formation of new functional group, -OH group was observed at the PA-treated fly ash. XRF and XRD
results showed that the chemical composition of fly ash was not altered significantly after treatment. From Rockwell
hardness test, water absorption test and density test, the increment in performance in mechanical and water
absorption properties was observes after surface modification of fly ash, especially PA-treated fly ash. Particle size
analysis showed a slight increase in fly ash particle after treatment due to absorption of pre-treatment solution by
the particles.

Keywords: fly ash; epoxy resin; sodium lauryl sulfate (SLS); palmitic acid; surface treatment

ABSTRAK

Penggunaan abu terbang sebagai pengisi disekat oleh ketidakserasian antara permukaan abu terbang yang bersifat
hidrofilik dan permukaan polimer yang bersifat hidrofobik. Bagi meningkatkan interaksi di antara permukaan,
rawatan permukaan abu terbang diperlukan untuk mengubahsuaikan sifat hidrofilik permukaan abu terbang.
Rawatan permukaan termasuk rawatan mekanikal, kimia, dan termal. Dalam kajian ini, abu terbang yang diperoleh
daripada loji kuasa arang batu dirawat dengan natrium lauril sulfat (SLS) dan asid palmitik (PA). Sifat komposit
yang mengandungi abu terbang rawatan PA dibandingkan dengan komposit mengandungi abu terbang tanpa
rawatan dan rawatan SLS dengan menjalankan analisis spektroskopi inframerah transformasi Fourier (FTIR),
analisis spektroskopi pendarfluor sinar-X (XRF), analisis spektroskopi difraksi sinar-X (XRD), analisis kalorimetri
pembiasan kebedaan (DSC), ujian mikroskopi elektron imbasan (SEM), ujian kekerasan Rockwell, ujian penyerapan
air, ujian ketumpatan dan analisis saiz zarah. Berdasarkan analisis FTIR, kumpulan berfungsi yang baru, -OH
terbentuk selepas rawatan PA dijalankan. Analisis XRF dan XRD menunjukkan bahawa perbezaan komposisi yang
terkandung dalam abu terbang tidak ketara. Ujian kekerasan Rockwell, penyerapan air dan ujian ketumpatan
menunjukkan peningkatan dalam prestasi seperti sifat mekanikal dan penyerapan air selepas rawatan permukaan
dijalankan, terutamanya abu terbang rawatan PA. Daripada analisis saiz zarah, saiz abu terbang bertambah
selepas rawatan disebabkan oleh penyerapan larutan pra-rawatan oleh zarah abu terbang.

Kata kunci: abu terbang; resin epoksi; natrium lauril sulfat; asid palmitik; rawatan permukaan
 INTRODUCTION
Nowadays, the consumption of fossil fuels to produce
energy kept on increasing from one year to another.
Coal as one of the most important fossil fuel is widely
used in industry especially to generate steam that will be
used to generate electricity (Nath et al. 2010; Ondova et
al. 2012; Nyale et al. 2013). In the burning process of
coal, the carbon content and some of the volatile
components in the coal are burned off, and the
remaining minerals like clay and some remaining carbon
that was not completely burned are carried out from the
combustion chamber together with the exhaust gas
(Ondova et al. 2012). The remaining minerals solidified
into particulate called fly ash and is trapped by the
electrostatic precipitator (Rackley 2010; Miller 2011;
Anwar et al. 2014).
Fly ash is an amorphous material which made
up of fine spherical particles. Its color ranged from
white, grey to black, depending on the unburned carbon
that remained in the fly ash (Ahmaruzzaman 2010; Yao
et al. 2014). Most fly ash has irregular and hydrophilic
surface with porous structure (Ahmaruzzaman & Gupta
2012). Fly ash has a pozzolanic property. A pozzolan is
defined as siliceous or combination of siliceous and
aluminous material that itself possess little or no
cementitious property, but it the presence of moisture, it
will chemically reacts with calcium hydroxide, Ca(OH)2
to form compounds having cementitious property. This
characteristic makes fly ash a suitable material to
produce cement, construction material and concrete
(Ahmaruzzaman 2010; Ondova et al. 2013; Yao et al.
2015; Abbas et al. 2017; Hemalatha & Ramaswamy
2017).
Fly ash is a complex structure as more than
188 types of mineral groups identified in the structure
of fly ash. Chemical properties of fly ash depend on
the properties and types of coal burned. All fly ash
has same content of basic element, but in different
proportion. The main elements in a fly ash structure
are silicon, aluminium, iron, and calcium (Nath et al.
2010; Zhang et al. 2017), with a small amount of
sulphur, magnesium and others. The most common
mineral groups found in fly ash include oxides of
silica, alumina and iron. The existence of these oxides
compounds make fly ash to become a valuable
material in the manufacturing of clay, concrete or
cement (Holanda 2015). According to ASTM C618-
15 Standard (ASTM 2015), fly ash can be classified
into 2 major categories: Class F and Class C fly ash.
The main difference of these two classes is the
mineral groups content. Class F consists of an amount
of SiO2 + Al2O3 + Fe2O3>70% whereas Class C
consists of an amount of SiO2 + Al2O3 + Fe2O3< 70%.
Because of the hydrophilic properties of the
fly ash surface, the incompatible between fly ash and
hydrophobic epoxy become the largest constraint that
restricts the use of fly ash as filler. Hence, surface
treatment of fly ash is necessary in order to increase
the compatibility. Previous research focused on the
modification of fly ash surface using acid or alkali
(Shawabkeh et al. 2011; Sharma et al. 2012; Anwar et
al. 2014; Gao et al. 2017) and surfactant such as
sodium lauryl sulfate (SLS) (Nath et al. 2010;
Mathebula 2013; van der Merwe et al. 2014) or silane
coupling agent (Goh et al. 2016).

TABLE 1. Content of different types of fly ash

Fly Ash (wt%)

Component
Europe fly USA fly ash Brazil fly ash China fly Malaysian
ash ash fly ash
SiO2 28.50-59.60 35.00-52.00 58.80-71.00 56.58 56.58
Al2O3 17.60-35.60 15.00-32.00 19.00-26.30 27.83 27.83
Fe2O3 2.60-16.00 8.00-25.00 2.34-8.00 4.05 4.00
CaO 0.50-27.30 0.70-8.00 0.20-3.78 4.31 4.30
MgO 0.60-3.80 0.30-1.50 0.20-1.80 1.49 1.40
Na2O 0.10-1.80 - 0.10-0.70 - -
K2O 0.40-4.50 - 0.40-1.76 - -
P2O5 0.10-1.70 - 0.04-0.06 - -
TiO2 0.50-2.60 - 1.18-1.21 - -
MnO 0.02-0.10 - 0.02-0.04 - -
SO3 0.10-8.60 0.10-2.80 0.10-0.70 - -
LOI 1.10-8.10 1.30-13.00 0.20-2.71 2.82 2.53
 The purpose of this paper is to investigate the
probability of using palmitic acid as treating agent for
fly ash in order to improve the overall performance of
the fly ash/epoxy composites produced. Palmitic acid
can be counted as a green chemical as it is extracted
from the plants and does not bring any negative impact
on human health. As there was no previous research on
surface treatment of fly ash using palmitic acid, the
results of this paper is unpredictable. Hence, the results
obtained by palmitic acid treated fly ash is compared
with sodium lauryl sulfate (SLS) treated fly ash.
Various analytical methods used to study the
physical, mechanical, and chemical properties of
palmitic acid and SLS treated fly ash epoxy composites,
including Fourier transform infrared spectroscopy
(FTIR), X-ray fluorescence spectroscopy (XRF), X-ray
diffraction spectroscopy (XRD), differential scanning
calorimetry (DSC), scanning electron microscopy
(SEM), Rockwell hardness test, water absorption test,
density test and particle size analysis. Based on the
observation obtained from these analyses made, the
suitability of palmitic acid as treating agent for fly ash is
further discussed.
METHODOLOGY
Fly Ash Preparation
1 g of fly ash was weighed and dried using hot plate
operating at temperature of 100°C to remove the
moisture. The drying process continued for 15 minutes
to ensure all moisture has been removed from fly ash. If
moisture is not removed from the fly ash, formation of
air bubbles will be occurred during mixing of fly ash
with epoxy resin.
Preparation of 0.5wt% SLS and Palmitic Acid Solution
0.5g SLS powder was placed into a stainless steel cup.
99.5g of distilled water was mixed and stirred by using a
glass rod. The steps are repeated to prepare palmitic acid
solution by replacing SLS powder to palmitic acid. The
acid solution was heated to 100°C to reduce the
viscosity of the solution.
Surface Treatment of Fly Ash
The surface treatment of fly ash was performed by
sodium lauryl sulfate (SLS) and palmitic acid. 1g of
dried fly ash was put into a stainless steel cup. 100ml of
0.5wt% SLS solution was mixed with the fly ash in the
cup and the mixture was heated by using magnetic hot
plate stirrer of 100°C for 1 hour. The fly ash was taken
out from the beaker and rinsed with distilled water to
wash off the SLS or palmitic acid remained on the
surface of fly ash. The fly ash was then dried in oven
type OF-22 at 60°C for 24 hours. The procedures
were repeated for palmitic acid and repeated for 2g,
3g and 5g of fly ash used.
Preparation of Fly Ash/Epoxy Composites
100g epoxy resin type diglycidyl ether of bisphenol-A
(DGEBA) was prepared in a stainless steel cup.
Treated or untreated fly ash was mixed and the
mixture was heated and stirred at 50°C for 1 hour and
50 minutes. Then, 30g hardener Boxxodur EC301 was
mixed and stirring process continued for 10 minutes.
The mixture was poured into a Teflon mold with
dimension of 100mm x 100mm x 3mm. The mixture
was allowed to harden for 24 hours to form
composites before analysis on the composites were
carried out.
Fourier Transform Infrared Spectroscopy (FTIR)
The chemical structure characterization of treated and
untreated fly ash was carried out by means of FTIR
analysis using a Nicolet 6700 spectrometer from
Thermo ElectronTM. This technique measured the
amount of infrared radiation being adsorbed against at
different wavelength. Components and organic
molecular structure can be determined using FTIR
analysis, where every functional group and molecular
bonding has its own wavelength between the ranges
of infrared.
A sample of 1-2mg of fly ash and 1.0g of
dried KBr powder were mixed thoroughly. The
mixture was hydraulically pressed to 10 tons /m2 to
obtain a thin circular transparent disc. The thin disc
was placed in an oven at 100°C for 2h to remove the
water vapour. FTIR spectra were taken in the range of
600-4000cm-1 at room temperature. The spectral
resolution of FTIR was set at 4cm-1 (Anwar et al.
2014).
X-ray Fluorescence Spectroscopy (XRF)
XRF analysis is a qualitative and quantitative
technique to determine the elemental composition in
fly ash/epoxy composites. The peak height of every
element shows its elemental concentration in the fly
ash structure.
The samples were grinded into powder form.
1g of sample powder was prepared and 6g of folic
acid was mixed and the mixture was compressed at 20
tonnes to form pellet sample. The pellet was analysed
using XRF spectrometer type Bruker S8 Tiger.
 X-ray Diffraction Spectroscopy (XRD)
XRD analysis is a technique used to determine
mineralogy composition of fly ash/epoxy composites.
The XRD patterns were collected from 5° to 80° with
spectrometer XRD type Bruker D8 Advance.
Differential Scanning Calorimetry (DSC)
DSC analysis was carried out to determine the glass
transition temperature of fly ash/epoxy composites. This
analysis measured the amount of heat required to
increase the temperature of the sample.
Approximately 13mg sample was used for DSC
analysis. The temperature was increased from 25°C to
170°C with heating rate of 10°C/min and kept constant
at 170°C for 2 minutes. Then the sample was cooled
from 170°C to -20°C with cooling rate of 20°C/min and
heated back to 170°C with heating rate of 10°C/min.
Scanning Electron Microscopy (SEM)
SEM is an analysis carried out to observe the structure
and morphology at the surface of the sample. The
sample was cut into appropriate dimension and coated
with iridium to make the surface of the sample became
conductive. The sample was analysed on scanning
electron microscope type Merlin Gemini 2.
Rockwell Hardness Test
Rockwell hardness test was carried out to test the
hardness of composites sample. Rockwell hardness test
machine model DXT-1 with a steel indenter of diameter
of 6.35mm was used in this test. HRL scale was used.
Water absorption test
The ability of composites to absorb water was tested
using water absorption test where the change in mass of
the sample was recorded at 24 hours instant. From the
change in mass, the percentage of water absorption can
be calculated. Sample was cut into a dimension of
80mm x 30mm x 3mm and dried in oven at 60°C for 24
hours to remove the moisture. The initial mass of the
sample was recorded and it was immersed into distilled
water at 24°C for 24 hours. The wet sample was dried
using the cloth and the mass of the sample was recorded.
The procedures were repeated for a period of 7 days
until the mass of sample was nearly constant. The
percentage of water absorption was then calculated and
the results were recorded.
Density test
Density of fly ash/epoxy composites was measured by
using density meter type Sartorius BSA224S-CW.
The sample was prepared in a dimension of 30mm x
30mm x 3mm. The mass of sample in the air and the
mass of sample in the water was recorded. The
density of the sample was then calculated.
Particle size analysis
Particle size analysis was carried out to determine size
of fly ash particle. Approximately 5g fly ash was sent
for analysis by using Zeta Sizer type Melvern.
Atomic Force Microscopy (AFM)
AFM is an analysis to study the surface topography
and determine the mechanical properties of the
sample such as roughness and stiffness of the sample.
In this study, AFM machine model TS-150 has been
used to determine the surface characteristics of the
composites.
RESULTS AND DISCUSSION
Fourier transform infrared spectroscopy (FTIR)
The presence of new functional group in SLS and PA
treated fly ash was determined by FTIR analysis.
Figure 1 showed the FTIR spectra for fly ash treated
with different surfactant. The untreated fly ash had 6
major peaks at 3676, 2917, 1473, 1026, 731 and
467cm-1. These peaks are related to O-H, C-H, C=C,
C-O, C-H and C-Cl bonds respectively. For SLS and
PA treated fly ash, O-H and C-H stretching vibrations
were disappeared, meaning surface treatment of fly
ash able to break the bonds in the structure to form
new bonds between fly ash particles. Figure 2 showed
the FTIR spectra for epoxy composites containing, 3g
fly ash respectively. The spectra did not show a
significant change in the functional group. Epoxy
composites containing 2g untreated fly ash showed
peak at 3372cm-1 which indicated the presence of N-H
stretching vibration for secondary amine. N-H group
has lone pairs which can react with H2O molecules to
form hydrogen bond which is a strong intermolecular
force between particles. Treatment using SLS will
remove N-H group whereas treatment using PA can
maintain the N-H group in the structure, indicated that
treatment using PA had more advantages compared
with SLS treatment. From Figure 2, epoxy composites
containing 3g SLS-treated fly ash showed peaks at
2000 and 2100 cm-1 due to presence of N=C=S ash surface and surface of epoxy matrix. PA treatment
stretching vibration for isocyanate. N=C=S is polar and can remove N=C=S from the sample structure.
not beneficial in promoting the interaction between fly

100

95

% transmittance
90
Untreated
85
SLS
80 treated
PA treated
75

70
4000 3500 3000 2500 2000 1500 1000 500 0
Wavenumbers (cm-1)

FIGURE 1. FTIR spectra of fly ash

100

90

80

% Transmittance
70 Epoxy
U3gFA
60 SLS3gFA
PA3gFA
50

40

30
4000 3500 3000 2500 2000 1500 1000 500 0
Wavenumber (cm-1)

FIGURE 2. FTIR spectra of epoxy composites containing 3g fly ash

left on the stirrer or stainless steel cup. After fly ash

X-ray fluorescence spectroscopy (XRF) has been added to the epoxy, the content of inorganic
compound s increased significantly, especially Fe2O3,
SiO2, Al2O3 and CaO. The increase in inorganic
Table 2 showed the comparison between chemical
compound content enhanced the interaction between
compounds present in epoxy composites without fly ash
fly ash surface and surface of epoxy matrix. XRF
and composites containing 3g fly ash with different
results proven that organic compounds such as Fe2O3,
treatment. Theoretically, epoxy without fly ash should
CaO, SiO2, Al2O3, Cl, SO3, K2O, Na2O and MgO.
only contained organic elements such as carbon, oxygen
(Assi et al. 2018; Huber et al. 2018; Tian et al. 2018).
and hydrogen. Inorganic elements such as aluminium,
Epoxy composites containing 3g fly ash treated with
iron, and potassium were not supposed to present in the
PA showed the highest amount of inorganic
epoxy. Traces of inorganic matters present may be due
compounds compared with others.
to residue or impurities
 TABLE 2. Chemical compounds present in epoxy composites

Formula Content (%)

Without fly ash U3gFA SLS3gFA PA3gFA
Fe2O3 0.41 3.85 2.91 4.72
SiO2 0.36 1.09 0.64 0.84
CaO 0.06 1.01 0.87 1.43
Cl 0.52 0.55 0.51 0.51
Al2O3 0.06 0.36 0.29 0.29
CuO 0.31 0.25 0.08 0.08
TiO2 - 0.12 0.12 0.17
K2O - 0.13 0.11 0.16
MgO 0.12 0.06 0.07
ZnO 0.12 0.14 0.07 0.05
Cr2O3 0.03 0.09 0.03 -
PbO - 0.08 - 0.10

X-ray diffraction spectroscopy (XRD) The cystallinity of epoxy composites containing 3g

Mineralogical composition and degree of crystallinity of
the fly ash/epoxy composites can be determined by
XRD analysis. The results of XRD showed almost the
same results with XRF analysis, which claimed that the
chemical composition present in fly ash contained iron
(III) oxide, silicon oxide, chlorine oxide, copper oxide,
zinc oxide, aluminium oxide and magnesium oxide.
Addition of fly ash formed new compounds such as
titanium oxide and sulphur oxide.
fly ash with different treatment was shown in Table 3.
According to Cardinal et al. (2016), increase in
degree of crystallinity increased the hardness but
decrease in toughness. From Table 3, the SLS-treated
composites showed more amorphous properties while
PA-treated composites had highest degree of
crystallinity compared with untreated and SLS-treated
composites. Study carried out by Song et al. (2016)
showed that the degree of crystallinity not only affect
the mechanical properties but also the thermal
performance. This is because crystal had higher
resistance against heat.

TABLE 3. Degree of crystallinity of different epoxy composites

Sample Crystallinity (%) Amorphous (%)

3g untreated fly ash composites (U3gFA) 34.8 65.2
3g SLS-treated fly ash composites SLS (SLS3gFA) 26.0 74.0
3g PA-treated fly ash composites (PA3gFA) 39.6 60.4

Differential scanning calorimetry (DSC)
DSC analysis is a technique used to determine the
amount of heat required to raise the temperature of the
sample. Through analysis DSC, the glass transition
temperature of epoxy composites can be determined.
Table 4 showed the glass transition temperature (Tg) of
epoxy composites containing 1g, 2g, 3g and 5g of fly
ash with different treatment.
Overall, the glass transition temperature of
epoxy composites ranged between 75-85°C. However,
there are some uncommon results obtained for 2g SLS-
treated fly ash and 5g untreated fly ash which showed
the glass transition temperature of 46.42°C and 51.36°C
respectively. This may be caused by improper way to
prepare the samples or error occurred during heating or
cooling process of the samples.
Based on Table 4, almost all samples showed
decrease in Tg after fly ash has been added to the
composites compared with Tg of composites without
fly ash of 84.28°C. The results can be related to the
crystallinity of the samples. Studies showed that fly
ash is more likely to have amorphous properties.
(Ahmaruzzaman 2010; Goh et al. 2016; Hemalatha &
Ramaswamy 2017). Addition of fly ash into epoxy
composites will decrease the degree of crystallinity.
Studies had been conducted to study the effect of
crystallinity on the glass transition temperature. The
studies proven that the higher the degree of
crystallinity, the higher the glass transition
temperature.
 TABLE 4. Glass transition temperature of different epoxy composites
Type of sample 1g fly ash 2g fly ash
Without treatment 79.62
SLS-treated 78.66
PA-treated 76.97
Scanning Electron Microscopy (SEM)
The structural and morphology of the surface of epoxy
composites was observed by SEM analysis. Energy
dispersive X-ray spectroscopy (EDX) analysis was also
carried out to determine the element present in the
structure of the samples.
Figure 3(a) showed the SEM micrograph of
epoxy without fly ash under magnification of 5000X.
The surface of the composite was smooth and flat with
some propagated cracks on the surface. There were also
a lot of pores and voids observed. Formation of pores
was not favoured as the pores can cause decrease in
mechanical performance of the composites. EDX
analysis showed that epoxy without fly ash contained
only carbon, oxygen and phosphorus with weight
percentages of 79.6%, 19.3% and 1.1% respectively.
(a)
(c)
FIGURE 3. SEM micrograph of composite (a) without FA, (b) untreated FA, (c) SLS-treated FA, (d) PA-treated FA
Glass transition temperature (°C)
3g fly ash 5g fly ash
84.79 81.88 51.36
46.42 78.43 82.40
84.41 92.97 84.48
Figure 3(b) showed the SEM micrograph of
composite containing 3g untreated fly ash. Particles
with irregular shape which attached together to form
agglomerates can be observed (Yu et al. 2012). The
major component observed at the surface is C-H
(Jafer et al. 2018). Needle like ettringites were
observed at the space between the matrix surface and
the fly ash particle. Formation of ettringites may be
due to formation of calcium bicarbonate and sodium
lignosulfonate which turned the small crystals into
needle-shaped ettringites.
Figure 3(c) and (d) showed the SEM
micrograph of composites containing 3g SLS and PA-
treated fly ash. Study of Jafer et al. (2018) showed
that C-H will turn into C-S-H gel after treatment due
to hydration reaction. The small pores at the surface
were filled by C-S-H gel which form a more stable
and dense structure.
(b)
(d)
 Rockwell Hardness Test
Rockwell hardness test is a quick and cost effective
technique to determine the mechanical properties of
epoxy composites samples. In this test, the readings
were taken 5 times and the average value was calculated
to ensure a more accurate result was obtained. Table 5
showed the Rockwell hardness of different epoxy
composites containing different weight of fly ash.
The Rockwell hardness of epoxy composites
without fly ash was the lowest, which was 76.4 HRL.
With the presence of filler, strength of the composites
was increased. Composites containing PA-treated fly
ash showed the higher values of hardness compared
with SLS-treated fly ash. Besides, composites
containing 3g fly ash showed highest hardness with
the sequence of increasing hardness of 1g < 5g < 2g <
3g.

TABLE 5. Rockwell hardness of different epoxy composites

Hardness (HRL)
Mass of fly ash Untreated SLS-treated PA-treated
1g 77.14±0.46 89.46±0.68 93.36±1.63
2g 87.94±1.07 91.36±0.79 97.12±2.46
3g 89.3±0.81 93.04±1.28 104.00±2.86
5g 81.64±4.12 85.94±2.52 87.8±2.61

Water absorption test Table 6 and Figure 4 showed the percentage

Moisture in epoxy composites can cause negative effect
on physical, thermal, electrical and mechanical
properties (Fan et al. 2009; Chaichanawong et al. 2016).
Hydrophilic fly ash had low resistance against water
molecules in water absorption (Goh et al. 2016).
Therefore, chemical treatment such as treatment with
surfactant on fly ash was necessary to increase the
resistance of fly ash against water(Alamri & Low 2013).
Surfactant used to modify the surface of fly ash to
increase the hydrophobic properties of fly ash.
of water absorption of different epoxy composites
From Table 6 and Figure 4, epoxy composites
containing 3g PA-treated fly ash showed the lowest
percentage of water absorption. In other words, it has
the greatest resistance against water. Epoxy
composites treated with SLS and PA showed decrease
in water absorption percentage. Therefore the
chemical treatment of fly ash successfully modified
the surface of fly ash as it increased the hydrophobic
properties and this increase the resistance of
composites against water.

TABLE 6. Water absorption percentage of different epoxy composites

Cumulative Water absorption percentage (%)

Day 0 1 2 3 4 5 6 7
Epoxy 0.00 0.48 0.82 1.02 1.19 1.24 1.27 1.29
U1gFA 0.00 0.82 0.98 1.11 1.25 1.35 1.37 1.39
U2gFA 0.00 0.49 0.65 0.74 0.96 1.08 1.09 1.10
U3gFA 0.00 0.43 0.50 0.61 0.84 0.91 0.92 0.92
U5gFA 0.00 0.56 0.73 0.87 1.04 1.15 1.18 1.19
S1gFA 0.00 0.55 0.72 0.83 1.01 1.10 1.12 1.15
S2gFA 0.00 0.67 0.82 0.98 1.25 1.45 1.48 1.52
S3gFA 0.00 0.41 0.53 0.62 0.80 0.95 0.95 0.96
S5gFA 0.00 0.50 0.63 0.75 0.96 1.08 1.11 1.15
P1gFA 0.00 0.42 0.53 0.62 0.78 0.87 0.89 0.93
P2gfA 0.00 0.45 0.57 0.65 0.85 0.96 0.97 0.98
P3gfA 0.00 0.19 0.31 0.41 0.53 0.65 0.67 0.68
P5gfA 0.00 0.43 0.75 1.04 1.24 1.43 1.61 1.67
 1.8

1.6
Epoxy
1.4 U1gFA
Water absorption percentage (%)

U2gFA
1.2 U3gFA
U5gFA
1
SLS1gFA
0.8 SLS2gFA
SLS3gFA
0.6 SLS5gFA
PA1gFA
0.4
PA2gfA
0.2 PA3gfA
PA5gfA
0
0 1 2 3 4 5 6 7
Day

FIGURE 4. Water adsorption percentages of different epoxy composites

Density test Composites containing fly ash showed the

Increase in density of composites can reduce the empty
spaces between particles and this can increase the
resistance of composites against water. Increase in
density also can increase the mechanical strength of the
composites (Kumar et al. 2016; Yoon et al. 2016; Cravo
et al. 2017).
From Table 7 and Figure 5, composites added
with fly ash had higher density. After treatment of fly
ash, the density of epoxy composites will further
increased. Composites containing fly ash treated with
PA showed the highest density compared with untreated
and SLS-treated composites.
higher density because of the presence of inorganic
substances such as calcium and iron. Besides, the
surface treatment of fly ash promoted the interaction
between epoxy matrix and the fly ash surface. From
the results obtained from FTIR and SEM analysis, PA
treatment can cause the formation of hydrogen bond
and this bonding greatly increase the strength of the
structure and also the density of the composites.
The greater the mass of fly ash added, the
higher the density of the composites because fly ash
had a higher density of 1120-1500kg/m3 compared
with density of epoxy of 1160-1190kg/m3.

TABLE 7. Density of different epoxy composites

Weight of fly ash Density (kg/m3)

Untreated SLS-treated PA-treated
1g 1162.94 1160.44 1163.85
2g 1163.48 1165.44 1169.89
3g 1164.62 1166.84 1175.35
5g 1174.03 1172.07 1181.96
 1190

1180

1170
Density (kg/m3)

1160 Untreated
SLS-treated
1150 PA-treated
Epoxy
1140

1130

1120
Epoxy 1g 2g 3g 5g
Weight of fly ash

FIGURE 5. Density of different epoxy composites

Particle size analysis Atomic Force Microscopy (AFM)

Particle size is an important criterion that affects the
performance of the composites formed. Table 8 showed
the particle size of fly ash with different treatment. The
treated fly ash particles showed the greater size because
they absorbed the pre-treatment solution and cause the
swollen of the particle. However, PA-treated fly ash
showed less increment in size compared with SLS-
treated fly ash.
TABLE 8. Particle size of fly ash
Types of fly ash Particle size (nm)
Untreated 560.17±8.95
SLS-treated 626.87±55.73
PA-treated 596.83±78.34
treatment on the fly ash. Composites with fly ash treated
with PA showed the highest value of roughness.
Skewness is a parameter to indicate either most points
located at the peak or valley of the mean surfaces. The
positive value of skewness predominated the peak
whereas the negative value of skewness predominated
In AFM analysis, the topography of the composites
surfaces was observed. Figure 6 showed the 3-
dimensional AFM spectrograph of different
composites. From the topography, parameter such as
surface roughness, peak-to-valley height and
skewness of the surface can be determined. Table 9
showed the surface characteristics of the composites
produced. Roughness is a parameter which affects the
mechanical characteristics of the composites. The
increase in roughness can increase the contact area
and this increases the adhesion between two surfaces.
Hence, the bonding between two materials can be
increased (Hong et al. 2014; Qudoos et al. 2018).
From Table 9, the average and root mean square
roughness increased after fly ash has been added, and
the roughness continued to increase after the surface
the valley. In this study, all the samples showed
positive value in skewness, meaning the surfaces
contained more peak compared with valley. The
higher the value of skewness, the greater the
roughness. Besides, the maximum peak and valley
height of each composite was also determined.
 (a) (b)

(c) (d)

FIGURE 6. 3-dimensional AFM spectrograph of composite (a) without FA, (b) untreated FA, (c) SLS-treated FA,
(d) PA-treated FA
 TABLE 9. Surface characteristics of composites

Characteristics Types of samples

Epoxy U3gFA SLS3gFA PA3gfA
Average roughness, Sa (nm) 21.032 27.538 36.895 48.099
Root mean square roughness, Sq (nm) 24.977 39.912 47.159 70.274
Maximum peak-to-valley height, St (nm) 135.863 477.632 363.635 991.229
Maximum peak height, Sp (nm) 73.925 206.793 217.338 606.170
Maximum valley height, Sv (nm) 61.938 270.839 146.297 385.059
Skewness, Ssk 0.087 0.554 0.462 1.397

The characteristics of the pores on the composites amount of pores can be decreased after the fly ash has
surface such as amount of pores, area, size and length of been added to the composites as the fly ash is small in
pores can also be determined in AFM analysis. Table 10 size and can filled in the empty spaces or pores on the
showed the characteristics of the pores. Generally, the surface.

TABLE 10. Pores characteristics of composites

Sifat Jenis Sampel

Epoksi U3gFA SLS3gFA PA3gFA
Amount of pores detected 6782 82 2565 160
2
Area (μm ) 0.0011±0.0005 13.072±11.359 0.0087±0.0084 21.739±17.119
Size (μm) 0.0324±0.0075 3.350±1.359 0.0868±0.0342 4.336±1.714
Length (μm) 0.0507±0.0165 5.324±2.206 0.144±0.0797 7.036±2.727
Width (μm) 0.0214±0.0044 2.135±0.910 0.0541±0.0172 2.725±1.206

CONCLUSION surface of epoxy matrix to enhance the mechanical

properties of the epoxy. Rockwell hardness test, water
The uses of fly ash as mineral filler were greatly
absorption test and density test showed the increase in
restricted by incompatibility between fly ash and epoxy
performance after surface treatment of fly ash has
surfaces. Fly ash was treated with sodium lauryl
been carried out. For AFM analysis, the topography of
sulphate and palmitic acid to modify the surface of fly
the surfaces has been studied and from the
ash to promote the interaction between surfaces. The
topography, the surface roughness, height of peak and
effect of weight of fly ash used on the properties of the
valley and skewness of the surface can be determined.
composites produces was investigated using weight of
The addition of fly ash can increase the surface
1g, 2g, 3g and 5g of fly ash. The results showed that 3g
roughness and treatment on fly ash by SLS and PA
fly ash has the best performance over other weight of fly
can further increase the roughness which can increase
ash. To study the effect of surface treatment on the
the adhesion force of the composites produced.
properties of fly ash/epoxy composites, several analysis
were carried out, including FTIR, XRF, XRD, DSC,
SEM analysis, Rockwell hardness test, water adsorption ACKNOWLEDGEMENT
test, density test and particle size analysis. XRD and
XRF results proven that inorganic compounds such as The author would like to thank Universiti Kebangsaan
Fe2O3, Al2O3, CaO, TiO2 and K2O are present in fly ash Malaysia for their financial support.
and these compounds play important role in enhancing
the mechanical, physical and thermal properties of the
composites produced. SEM analysis showed that fly ash
which is small in size is able to fill into the pores on the
 REFERENCES
Abbas, S., M. A. Saleem, S. M. S. Kazmi & M. J. Munir
2017. Production of sustainable clay bricks
using waste fly ash: Mechanical and durability
properties. Journal of Building Engineering
14(Supplement C): 7-14.
Ahmaruzzaman, M. 2010. A review on the utilization of
fly ash. Progress in Energy and Combustion
Science 36(3): 327-363.
Ahmaruzzaman, M. & V. K. Gupta 2012. Application of
Coal Fly Ash in Air Quality Management.
Industrial & Engineering Chemistry Research
51(47): 15299-15314.
Alamri, H. & I. M. Low 2013. Effect of water
absorption on the mechanical properties of
nanoclay filled recycled cellulose fibre
reinforced epoxy hybrid nanocomposites.
Composites Part A: Applied Science and
Manufacturing 44: 23-31.
Anwar, P. M., H. I. Al-Abdul Wahhab, R. A.
Shawabkeh & I. A. Hussein 2014. Asphalt
modification using acid treated waste oil fly
ash. Construction and Building Materials
70(Supplement C): 201-209.
Assi, L. N., E. Eddie Deaver & P. Ziehl 2018. Effect of
source and particle size distribution on the
mechanical and microstructural properties of
fly Ash-Based geopolymer concrete.
Construction and Building Materials 167: 372-
380.
ASTM 2015. Standard Specification for Coal Fly Ash
and Raw or Calcinated Natural Pozzolan for
Use in Concrete. West Conshohocken, PA,
ASTM International. C618-15.
Cardinal, S., J. M. Pelletier, M. Eisenbart & U. E. Klotz
2016. Influence of crystallinity on thermo-
process ability and mechanical properties in a
Au-based bulk metallic glass. Materials
Science and Engineering: A 660: 158-165.
Chaichanawong, J., C. Thongchuea & S. Areerat 2016.
Effect of moisture on the mechanical properties
of glass fiber reinforced polyamide composites.
Advanced Powder Technology 27(3): 898-902.
Cravo, J. C. M., D. de Lucca Sartori, G. Mármol, G. M.
Schmidt, J. C. de Carvalho Balieiro & J.
Fiorelli 2017. Effect of density and resin on the
mechanical, physical and thermal performance
of particleboards based on cement packaging.
Construction and Building Materials 151: 414-
421.
Fan, X. J., S. W. R. Lee & Q. Han 2009. Experimental
investigations and model study of moisture
behaviors in polymeric materials.
Microelectronics Reliability 49(8): 861-871.
Gao, L., H. Wen, Q. Tian, Y. Wang & G. Li 2017.
Influence of surface modification by sulfuric
acid on coking coal's adsorption of coking
wastewater. Water Sci Technol 76(3-4): 555-
566.
Goh, C. K., S. E. Valavan, T. K. Low & L. H. Tang
2016. Effects of different surface
modification and contents on municipal solid
waste incineration fly ash/epoxy composites.
Waste Manag 58: 309-315.
Hemalatha, T. & A. Ramaswamy 2017. A review on
fly ash characteristics – Towards promoting
high volume utilization in developing
sustainable concrete. Journal of Cleaner
Production 147(Supplement C): 546-559.
Holanda, J. N. F. 2015. The properties and durability
of clay fly ash-based fired masonry bricks.
Dlm. (pnyt.). Ed. Eco-Efficient Masonry
Bricks and Blocks pp. 85-101. Oxford:
Woodhead Publishing.
Hong, L., X. Gu & F. Lin 2014. Influence of
aggregate surface roughness on mechanical
properties of interface and concrete.
Construction and Building Materials 65:
338-349.
Huber, F., H. Herzel, C. Adam, O. Mallow, D.
Blasenbauer & J. Fellner 2018. Combined
disc pelletisation and thermal treatment of
MSWI fly ash. Waste Management 73: 381-
391.
Jafer, H., W. Atherton, M. Sadique, F. Ruddock & E.
Loffill 2018. Stabilisation of soft soil using
binary blending of high calcium fly ash and
palm oil fuel ash. Applied Clay Science 152:
323-332.
Kumar, A., T. Vlach, L. Laiblova, M. Hrouda, B.
Kasal, J. Tywoniak & P. Hajek 2016.
Engineered bamboo scrimber: Influence of
density on the mechanical and water
absorption properties. Construction and
Building Materials 127: 815-827.
Mathebula, C. L. 2013. Surface modification of coal
fly ash by sodium lauryl sulphate.Tesis
University of Pretoria,
Miller, B. 2011. Anatomy of a Coal-Fired Power
Plant. Dlm. (pnyt.). Ed. Clean Coal
Engineering Technology pp. 248-249.
Nath, D. C. D., S. Bandyopadhyay, J. Campbell, A.
Yu, D. Blackburn & C. White 2010. Surface-
coated fly ash reinforced biodegradable
poly(vinyl alcohol) composite films: part 2-
analysis and characterization. Applied
Surface Science 257(4): 1216-1221.
Nath, D. C. D., S. Bandyopadhyay, S. Gupta, A. Yu,
D. Blackburn & C. White 2010. Surface-
coated fly ash used as filler in biodegradable
 poly(vinyl alcohol) composite films: Part 1—
The modification process. Applied Surface
Science 256(9): 2759-2763.
Nyale, S. M., O. O. Babajide, G. D. Birch, N. Böke & L.
F. Petrik 2013. Synthesis and Characterization
of Coal Fly Ash-based Foamed Geopolymer.
Procedia Environmental Sciences
18(Supplement C): 722-730.
Ondova, M., N. Stevulova & A. Estokova 2012. The
Study of the Properties of Fly Ash Based
Concrete Composites with Various Chemical
Admixtures. Procedia Engineering
42(Supplement C): 1863-1872.
Ondova, M., N. Stevulova & L. Meciarova 2013. The
Potential of Higher Share of Fly Ash as Cement
Replacement in the Concrete Pavement.
Procedia Engineering 65(Supplement C): 45-
50.
Qudoos, A., R. Atta ur, H. G. Kim & J.-S. Ryou 2018.
Influence of the surface roughness of crushed
natural aggregates on the microhardness of the
interfacial transition zone of concrete with
mineral admixtures and polymer latex.
Construction and Building Materials 168: 946-
957.
Rackley, S. A. 2010. Power Generation Fundamental.
Dlm. (pnyt.). Ed. Carbon Capture and Storage
pp. 52. Elsevier.
Sharma, A., K. Srivastava, V. Devra & A. Rani 2012.
Modification in Properties of Fly Ash through
Mechanical and Chemical Activation.
American Chemical Science Journal 2(4): 177-
187.
Shawabkeh, R., M. J. Khan, A. A. Al-Juhani, H. I. Al-
Abdul Wahhab & I. A. Hussein 2011.
Enhancement of surface properties of oil fly
ash by chemical treatment. Applied Surface
Science 258(5): 1643-1650.
Song, F., Q. Wang & T. Wang 2016. The effects of
*Nee Kah Poh
Department of Chemical and Process Engineering,
Faculty of Engineering and Built Environment,
Universiti Kebangsaan Malaysia,
43600 Bangi,
Selangor D.E.
Malaysia.
* Corresponding author; email:
neekahpoh@gmail.com
Received date: 23rd April 2018
Accepted date: XX
In Press date: XX
Published date: XX
crystallinity on the mechanical properties
and the limiting PV (pressure×velocity)
value of PTFE. Tribology International 93:
1-10.
Tian, S., Y. Zhu, B. Meng, J. Guan, Z. Nie, Q. Die,
W. Xu, M. Yu & Q. Huang 2018. Chemical
speciation of lead in secondary fly ash using
X-ray absorption spectroscopy.
Chemosphere 197: 362-366.
van der Merwe, E. M., C. L. Mathebula & L. C.
Prinsloo 2014. Characterization of the
surface and physical properties of South
African coal fly ash modified by sodium
lauryl sulphate (SLS) for applications in
PVC composites. Powder Technology
266(Supplement C): 70-78.
Yao, Z., M. S. Xia, P. Sarker & T. Chen. 2014. A
review of the alumina recovery from coal fly
ash, with a focus in China Ed. 120.
Yao, Z. T., X. S. Ji, P. K. Sarker, J. H. Tang, L. Q.
Ge, M. S. Xia & Y. Q. Xi 2015. A
comprehensive review on the applications of
coal fly ash. Earth-Science Reviews
141(Supplement C): 105-121.
Yoon, S., S. Kang, Y. Choi, H. Choi & S.-J. Lee
2016. Effect of relative density on
microstructure and mechanical properties of
Fe-12Mn-0.2C alloy fabricated by powder
metallurgy. Powder Technology 298: 106-
111.
Yu, J., X. Li, D. Fleming, Z. Meng, D. Wang & A.
Tahmasebi 2012. Analysis on Characteristics
of Fly Ash from Coal Fired Power Stations.
Energy Procedia 17(Part A): 3-9.
Zhang, Y., Z. Zhang, Z. Liu, P. Norris & W.-p. Pan
2017. Study on the mercury captured by
mechanochemical and bromide surface
modification of coal fly ash. Fuel
200(Supplement C): 427-434.
Nor Yuliana binti Yuhana
Department of Chemical and Process Engineering,
Faculty of Engineering and Built Environment,
Universiti Kebangsaan Malaysia,
43600 Bangi,
Selangor D.E.
Malaysia.