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Effect of chemical treatment and maleic anhydride grafted polypropylene

coupling agent on rice husk and rice husk reinforced composite

Article  in  Materials Express · April 2017

DOI: 10.1166/mex.2017.1359

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Materials Express
2158-5849/2017/7/001/011
Copyright © 2017 by American Scientific Publishers
All rights reserved. doi:10.1166/mex.2017.1359
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Effect of chemical treatment and maleic anhydride

grafted polypropylene coupling agent on rice
husk and rice husk reinforced composite
Umit Huner
Trakya University, Faculty of Engineering, Department of Mechanical Engineering, Edirne 22030, Turkey

ABSTRACT
The aim of this paper is to investigate the effect of chemical treatment and the maleic anhydride grafted
polypropylene (MAPP) coupling agent on rice husk and rice husk reinforced composites. Rice husk treatments

Article
were performed by using sodium hydroxide (NaOH) and propyl-trimethoxy-silane. Surface energy and adhesion
values were estimated by using AFM. The NaOH treatment showed the most compatible adhesion force and
work value (45 nN and 238 mJ/m2 ) to obtain a good interface with the polypropylene matrix. AFM and FTIR
investigations revealed that NaOH mostly has a dissolving effect and silane has a coating effect on rice husk
surface treatment. Water absorption value of composites was improved by chemical treatment and MAPP
coupling agent. While MAPP provided an improvement in tensile and flexural properties, chemically treated
husks caused a slight change in mechanical properties according to neat PP.
Keywords: Chemical Treatment, Atomic Force Microscopy (AFM), FTIR, Rice Husk, Polypropylene.

1. INTRODUCTION interaction is weak, physical and chemical modification

In recent years, the natural filler has a potential usage in
composite production. Cellulosic fibers like wheat straw,
rice husk and flax, as well as, many wastes cellulosic
products such as husk, shell flour and wood fiber have
been used as filler to reinforce the different plastic resins.
Cellulosic material reinforced plastics are low cost, light-
weighted, nonhazardous and have enhanced mechanical
properties.1–4
Interface and the interphase, which is the volumetric
part influenced by the interaction of the interface is the
most important term in that it can fulfill its composite
structural task.5 6 The interface, which is bridge between
the matrix and the reinforcement against the applied load,
reflects the physical and chemical interaction of both com-
ponents. The more successful the interaction, the more
successful the interface will be in performing the func-
tion of the composite structure. Therefore, at points where
Email: umithuner@trakya.edu.tr
needs arise.6 7 Despite their advantages, natural fillers
have the hydrophilic character in their nature and this
causes incompatibility between filler and matrix. There-
fore, adhesion of fiber/matrix and composite interface
should be improved by chemically or using coupling agent.
Chemical treatment is used to modify the surface char-
acteristics of filler by removing impurities or to coat the
surface.2 3 6 8 A coupling agent like MAPP also provides
to enhance the bonding properties of matrix and filler.9
Recently publications give informations about using
of natural fillers as reinforcement of composite applica-
tions. Besides, many researchers have investigated chem-
ical treatment of natural fillers to improve the surface
characteristics. Chemically treated rice husk reinforced
post-consumer polyethylene was studied by Favaro et al.4
FTIR and CNMR (Carbon-13 nuclear magnetic resonance)
spectrograph were used to characterization analysis of
chemically treated rice husks. In addition, mechanical per-
formance of composites was determined to evaluate the

Mater. Express, Vol. 7, No. 2, 2017 1

 Materials Express
effect of chemical treatment for a macro level. In view of
the surface treatment of lignocellulosic fillers highly cor-
related the type of chemical or agent. In chemical treat-
ment, the different mechanisms of chemical reaction and
interaction, such as bonding, dissolution and coating, are
also effective on surface characterization. Therefore, dif-
ferent chemical have been used to treat surface of fillers.
Tran et al.10 investigated the chemical treatment of wheat
and rice husk by using NaOH and two different organosi-
lanes (amino propyl triethoxysilane (APS) and glycidoxy
propyl trmethoxysilane (GPS). They aimed to change the
polarity of the surface and increase the surface energy of
husks. Therewithal, MAPP was used to improve interac-
tion between rice husk and polypropylene by Razavi-Nouri
et al.11
Although the literature has provided many investiga-
tions, much detailed information about surface change of
rice husk has been rarely reported. Moreover comparison
of coupling agent and chemical treatment doesn’t match
in a study at the same time. Besides, in Turkey, rice husk
production is not much but has potential. After harvesting
rice husk has no special usage as filler or something like
that. Low cost, low density, high modulus, etc. are some
of the properties that bring about to choose these fillers.
Article
Therefore, it may not be used as waste so it should be
estimated valuable technical filler.
This research reports effect of chemical treatment of
rice husk and the coupling agent effects on rice husk rein-
forced composite. Alkali and silane treatment were used
to change the surface properties of rice husk. Spectro-
scopic properties and AFM analyses were chosen to deter-
mine surface changes of rice husk after treatment. The
MAPP was used as coupling agent on natural fiber rein-
forced polypropylene to enhance the fiber-matrix inter-
face bonding. This study also aims to determine physical
and mechanical properties of reinforced PP composites.
Therefore, tensile, bending tests and water absorption were
carried out. The mechanical properties of the composite
material were compared with neat polypropylene.
2. EXPERIMENTAL DETAILS
2.1. Materials
In this study, S.R.L. was the base resin that is a polypropy-
lene homopolymer by ROM Petrol Petrochemicals with
density of 0.90 g/cm2 and has melt flow index of 9.36 g
Table I. Typical composition of some of natural fillers.1 9 22 23
Natural fillers Density (g/cm3  Cellulose %
Flax 1.51 65–85
Hemp 1.47 77.5
Kenaf 1.52 45–57
Sisal 1.45 50–64
Rice husk 0.34–0.40 31–34
(bulk density) 0.10–0.16
2 Mater. Express, Vol. 7, 2017
Effect of chemical treatment and MAPP coupling agent on rice husk
Huner
per 10 min (200  C per 2.16 kg load cell). Poly-propylene-
grafted Maleic Anhydride (PP-g-MA (Sigma Aldrich),
MA content = 1% wt).
Rice husk is the outer covering of paddy and accounts
for 20% of its weight. Moreover, it may be considered as
biodegradable filler due to having a high amount of cel-
lulose. The lignocellulosic material rice husk (RH) which
was used as reinforcement in the composite was col-
lected from Thrace region in Turkey at 2015 harvest time.
Particle size distribution of rice husks like that 82.8%
(wt) ≥ 2.0 mm, 14.6% (wt) ≥ 1.0–2.0 mm, 2.6% (wt) ≥
1.0–0.5 mm. It has moisture content (unseasoned) of
5.88% according to AACC Method No: 44-15A. (Anony-
mous, 2000 Approved Methods of American Association
of Cereal Chemists.10th ed. Minnesota, USA. Table I
presents the rice husk’s chemical content (cellulose, hemi-
celluloses, lignin, waxes, and water-soluble substances).
2.2. Chemical Treatments
The rice husks were soaked in a NaOH solution at 10%
(w/w) for 4 h at room temperature. Then, the rice husks
were cleaned with distilled water and neutralized with
acetic acid solution (10 drops in 1 L water).4 Finally,
the fillers were again washed with fresh distilled water in
many times until the sodium hydroxide was cleaned totally
and dried in an oven maintained at 80  C for 5 h. The
dried fibers were stored in a vacuumed plastic bag.
The rice husks were soaked in a methyl alcohol solu-
tion (alcohol:water = 60:40) containing 5% by weight of
propyltrimethoxysilane (C3 H7 -Si(OCH3 3  (XIAMETER
OFS-6264, Dow Corning Corp). The pH of the solution
was adjusted to 4.5 with acetic acid and then, the solution
was placed in an ultrasonic bath for five minutes to have
a homogeneous solution.10 The rice husks were immersed
in silane solution for 4 h at room temperature.
Finally, they were kept in the oven at 80  C for 5 h to
complete condensation of silanol groups of the surface and
to remove methanol and water. The condensation reaction
of silanol groups of the surface are shown in Figure 1.
The dried fibers were stored in a vacuumed plastic bag.
2.3. Composite Preparation
The moisture causes lower adhesion between filler and
matrix. Therefore, it should be removed from the compos-
ite structure by drying process. Rice husks were dried in a
Hemicelluloses % Lignin % Mineral ash % Water soluble M. %
18–20 1–4 5 1.5
10 3.7–13 0.8 1.8
21.5–23 15–19 2–5 1.9
10–24 7–11 0.6–1 1.7
22–26 22–23 11–14 7–9
Effect of chemical treatment and MAPP coupling agent on rice husk
Huner
Materials Express
NaOH-t RH-r PP NaOH-treated rice husk reinforced
polypropylene
Silane-t RH-r PP Silane-treated rice husk reinforced
polypropylene.

2.4. Water Absorption Study

Fig. 1. Hypothetical Reaction of Rice Husk Surface (RHS) and
Silane.
vacuum oven Ecocell 55 at 103 ± 2  C for 24 h to adjust
the moisture content of 1–3% and then stored over desic-
cant before compounding. For this study, moisture content
decreased from 5.88% to 1.58%. Figure 2 shows the struc-
ture of untreated and treated rice husks.
PP pellets, untreated and treated rice husks were dried
under vacuum at 50  C for 24 h before processing. The
reinforced plastic granules were produced by laboratory
scale single screw extruder (L/D = 28). The extruder has
four zones with controlled temperature. The temperature
setting for these zones was: Z1 = 120  C, Z2 = 155  C,
Water absorption tests were carried out according to
the ASTM D 570-98 method. Composite samples were
immersed in distilled water in Memmert WBN 22 model
water bath at 90  C. The samples were removed from the
distilled water, dried with blotting paper and weight val-
ues were determined. The dried specimens were weighed
with the precision of 0.0001 g by Sartorius ED224S preci-
sion balance. The water absorption percent was calculated
using the following formula,
M% = Mt − Mo /Mo × 100 (1)
Where, Mo and Mt denote the oven-dry weight and weight
after time t, respectively.
2.5. Structural Characterizations
AFM (atomic force microscopy) was used in contact mode
and tapping mode to obtain surface images and to estimate
the adhesion force (Nano Magnetics Instruments). In con-

Article
Z3 = 185  C and Z4 = 185  C. The screw velocity was
tact mode, while the AFM tip held to set up as clamped
40 rpm. The treated and untreated rice husk particles were
and sample moved over X and Y direction and scanning
incorporated into PP at 50% wt. Sheets of dimensions
process maintained in the Z direction. AFM was used for
180 × 180 × 4 mm3 were prepared by using a hydraulic
the rice husk roughness measurement. Peak force-tapping
press under a pressure of 150 kg cm2 .
mode was used in AFM, to generate nano mechanical
Hereafter, the following nomenclature is used in the
maps of sample surfaces. In this mode, at each pixel, the
description: AFM probe generates a small indentation on the sample
PP Polypropylene surface and a force-separation curve is collected. To ensure
PE Polyethylene a good reproducibility in the fiber preparation and in the
MA Maleic anhydride AFM observation, the roughness analysis was performed,
MAPP Maleic anhydride Polypropylene for each fiber, on at least four replicas, and for each
Unt RH Untreated Rice Husk replica, on a minimum of five different zones.
NaOH-t RH NaOH-treated rice husk F = −kZ (2)
Silane-t RH Silane-treated rice husk
RH-r PP Rice Husk reinforced polypropylene where k represents the cantilever spring constant.

Fig. 2. Rice husk treatment process (a) inner structure of rice husk (b) untreated, NaOH- and silane-treated husks.

Mater. Express, Vol. 7, 2017 3

 Materials Express Effect of chemical treatment and MAPP coupling agent on rice husk
Huner

Fig. 3. Gardner impact test set-up and standard test sample dimensions.

AFM tip has 30 nm diameters and cantilever spring con- results were reported. Gardner impact test was carried out
stant is 30 N/m. These parameters were used to determine according to Bruceton Staircase Method13 by 20 samples
adhesion force according to DMT12 (Derjaguin–Muller– of each calculated value. Figure 3 gives standard samples
Toropov) model. dimensions and Gardner test setup.
SEM was used for detecting morphology of interface
of composite materials. SEM micrographs of the surfaces
Article

of impact fractured specimens were taken using a ZEISS 3. RESULTS AND DISCUSSION
Evo® LS 10 scanning electron microscope and FEI F50 3.1. FTIR Analysis
SEM. The samples were first sputter-coated with a fine FT-IR gives information about internal structure of com-
layer of gold under vacuum for 60 secs. posite and fillers. These curves present both PP and filler’s
Fourier transform infrared (FT-IR) spectroscopy was characteristic chemical bands. Figure 4 depicts that the
used to detect the presence of the functional group that
exists on rice husk and rice husk reinforced polypropylene.
The IR spectrometer (Perkin-Elmer spectrum BX, Perkin-
Elmer Canada) was used to detect spectra of samples. FT-
IR spectra of the samples were collected in the range of
4000–400 cm−1 with a resolution of 4 cm−1 .

2.6. Mechanical Properties

Tensile, flexural and impact are used for determin-
ing mechanical properties of reinforced plastics. In this
study, both, tensile and flexural tests were performed
using an Instron Universal Testing Machine Model 8501,
equipped with a 500 kg load cell, strain-gauge extensome-
ter (Instron, model 2620) after conditioning at 23 ± 2  C
according to ISO 527 standard and ASTM D790, respec-
tively. The cross-head speed used for the type IA tensile
specimens was 5 mm/min. For the Flexural test (three-
point bending) a specimen with nominal dimensions of
80 × 10 × 4 mm3 , a span of 32 mm and a cross-head of
1 mm/min were used.16 Gardner impact test was carried
out using a Devostrans Drop Impact Test Machine accord-
ing to ASTM standard D5420. For the test a specimen
with nominal dimensions of 60 × 60 × 32 mm3 , striker
diameter 1270 ± 010 mm and support plate inside diam-
eter 1626 ± 0025 mm. Three specimens of each sample
were tested for tensile and flexural tests, and the average Fig. 4. Chemically-treated husk FTIR spectropy.

4 Mater. Express, Vol. 7, 2017

Effect of chemical treatment and MAPP coupling agent on rice husk
Huner
IR spectra of untreated and chemically treated of rice
husks. The peak at around 460 cm−1 corresponds to
O–Si–O bending vibration.18 The peaks at 1097 cm−1 and
797 cm−1 belong to O–Si–O stretching vibration. Bands at
3200 cm−1 to 3636 cm−1 are attributed to the chemisorbed
water and surface hydroxyl groups. The two peaks at about
1740–1750 cm−1 are due to the C O stretching from
aliphatic saturated compounds (cellulose and hemicellu-
loses). The peak 1650 cm−1 is attributed to the stretching
vibrations of the –OH.4 The peak 1240 cm−1 is ascribed
to C–O belongs to lignin.14 The large band of the range
1201–1150 cm−1 is attributed to vibration range of silica
bonds corresponding to silica present in rice husks used in
this study.
As compared to untreated one, the peak at 1240 cm−1
was clearly removed after NaOH treatment. This peak
belongs to C–O stretching from acetyl groups of lignin
which indicate the removal of lignin due to NaOH
treatment.14 The peak at 1373 cm−1 was due to the C–OH
stretching of the hydrogen bond intensity of crystalline
cellulose.20 These peaks remained unchanged for NaOH-t
RH and Silane-t RH. This suggests that the treatments
did not affect the cellulose structure of the husk. The
decreased carbonyl peak at 1650 cm−1 also indicates par-
tially removal of absorbed water (hemicelluloses) from the
NaOH-treated rice husk. In addition, the peaks at 1740–
1750 cm−1 were also removed due to the removal of
pectin and wax present in rice husk.4 The peak observed
at 2850 cm−1 which are attributed to C–H stretching of
hemicelluloses, was also disappeared due to NaOH treat-
ment. 1201–1150 cm−1 band decreased with NaOH treat-
ment. This result presented an evidence for higher lignin
and silica content of rice husks.
For the silane treatment, the major difference between
the different spectrums was the strong increase in the car-
bonyl stretching vibration (mC O) at 1740 cm−1 after
treatment.18 20 And also, the appearance of a new broad
peak at around 1560 cm−1 , which is attributed to the N–H
bending vibration of primary amine, resulted from silane
treatment. Similar peaks at 1350 cm−1 were represented by
Unt RH and Silane-t RH and this peak revealed that reac-
tion had taken place in the hemicellulose from the silane
treatment.
3.2. AFM Analysis
AFM results give information about surface topography.
In contact mode, the surface energy of samples can be
determined by using the interaction between silicon nitride
AFM tip and surface. In this study, AFM gave both qual-
itative and quantitative information on the surfaces of
treated and untreated RH. Figure 5 shows the topographic
image of untreated and treated rice husks at the nano level.
As shown in the images, the outer surface of rice husk
has a rougher surface than the inner husk surface. While
the cellulosic inner surface contains wax and fats, outer
Mater. Express, Vol. 7, 2017
Materials Express
surface contains the significant amount of silica.21 There-
fore, these impurities of surfaces affect the adhesion of rice
husk. Surface roughness is important because of debond-
ing and sliding properties which can significantly affect the
composite materials. Measured average surface roughness
and other surface topographic parameters are presented in
Table II.
In the outer surface of rice husk, the average surface
roughness was 97.03, 62.07 and 11.56 nm on untreated,
NaOH-treated and silane-treated samples, respectively. For
the inner surface of rice husk, average roughness value was
51.04, 31.08 and 5.06 nm on untreated, NaOH- and silane-
treated samples, respectively. These results indicated that
NaOH-removed impurities and other cement substance
from the husk surface. Image of NaOH-treated surface
exhibits a rougher surface with less level of roughness
height. Silane treatment provided the lowest level rough-
ness. This was attributed to the coupling effect of silane
treatment. Silane reacts with free hydroxyl groups of sur-
face and solution is absorbed by the surface. The texture
of surface seems like coated by low height roughness.
Morsi et al.15 studied ATRP (atom transfer radical poly-
merization) technique to graft the rice husk surface. They
used several chemical compositions for this process (acry-
Article
lonitrile (AN), Methyl methacrylate (MMA, 99%). They
measured the roughness of samples by using AFM both
in contact and tapping mode. Average roughness (Ra) was
measured as 7.92, 29.8 and 51.5 nm on RH-PMMA (poly-
methyl methacrylate), RH-PAN and RH-g-PMMA-b-PAN
surface, respectively.15 These results revealed that sur-
faces may not be uniformly covered with grafted polymer.
They suggested that there is a different interaction between
filler and grafting polymer due to adhesion. In this case,
silane achieved homogenous coating on husk surface and
acted as more efficient treatment agent according to graft-
ing polymer.
Force–distance measurements were performed on F –V
(force–volume) channel by using AFM. The outer sur-
face and the inner surface of husk were investigated sep-
arately. Derjaguin–Muller–Toporov12 (DMT) model was
used to determine adhesion forces. The empirical formula
for adhesion force F and the work of adhesion W a is
given by:
F = x ·  · R · Wa (3)
where the Constant x equals 2 for the DMT12 model
and R is the AFM tip radius (30 nm). Adhesion Force–
Distance curves were created by using software WSxM
5.0. WSxM 5.0 was also used to observe 2D-3D topo-
graphic images and to create F –V (Force–Volume) curves.
Figure 6 presents a graph sample which belongs to
the adhesion force of inner and outer surface of rice
husk. AFM tip is made from silicon nitride (Si3 N4 
which has hydrophilic structure. Therefore, the inter-
action between the AFM tip and the sample surface
5
 Materials Express Effect of chemical treatment and MAPP coupling agent on rice husk
Huner
Article

Fig. 5. Inner and outer surface of husk, force-volume channel 2D and 3D images (2 2 ).

reveals the hydrophilic–hydrophobic nature of compo- hemicellulose, lignin etc. at different rates for the outer
nents. When graph was examined, differences of adhe- and inner surface. Therefore, adhesion force was esti-
sion forces draw attention. This was may be attributed mated at both surfaces separately by using AFM. Results
to different topographic surface and presence of wax, revealed that outer surface showed higher adhesion force
than the inner surface of the husk. The highest average
Table II. Topographic parameters of husk surface.
adhesion force (63 nN) was obtained on the untreated
inner husk surface. The smallest average adhesion force
Coefficient (29 nN) was determined between NaOH treated fibers and
Sa Sq Ssk Sku the hydrophilic AFM tip. In contrast, it could provide an
Treatment/ (average) (root mean (surface (surface important adhesion with a hydrophobic material such as
material (nm) square) (nm) Skewness) Kurtosis)
the polypropylene resin.
Outer surface Surface skewness describes the profile of surface peaks,
Unt RH 97.03 ± 18 116.7 ± 21 1.147 ± 0.345 3.841 ± 0.41 scratches or valleys.16 Positive skewness value points
NaOH tRH 62.07 ± 7.1 70.2 ± 8 0.912 ± 0.362 1.992 ± 0.45
Silane tRH 11.56 ± 4.2 15.2 ± 5 0.251 ± 0.137 1.564 ± 0.28 out high peaks and large valley. This profile provides a
Inner surface wide wetting area to the matrix. Kurtosis is another sur-
Unt RH 51.04 ± 9 59.6 ± 5 0.771 ± 0.112 2.294 ± 0.32 face profile parameter which determines the sharpness of
NaOH tRH 31.08 ± 5 38.2 ± 8 0.541 ± 0.098 2.012 ± 0.14 peaks.16 Kurtosis > 3 value describes the sharp peaks and
Silane tRH 5.06 ± 0.31 8.1 ± 0.74 0.175 ± 0.061 1.784 ± 0.12
cracks which can cause notch effect on the husk surface.

6 Mater. Express, Vol. 7, 2017

Effect of chemical treatment and MAPP coupling agent on rice husk
Huner
Fig. 6. Inner and outer surface of husk adhesion force–distance graphs. Work of adhesion plays important role in this interaction.
Treated husks presented Kurtosis < 3 value and it has a
positive effect on integrity and strength of husk.
The reversible work of adhesion per unit contact area
can then be related to by the Dupré17 equation:
Wa = 13 + 23 − 12
where 12 is the solid (1)—solid (2) interfacial energy
(rice husk-Si3 N4 tip), 13 is the solid (1)—gas interfacial
energy (rice husk-air) and 23 is the solid (2)—gas inter-
facial energy (Si3 N4 tip-air). Table III presents work of
adhesion values of untreated and treated rice husks.
Morsi et al.15 presented the adhesion force maps of
untreated and treated rice husk by using AFM tapping
mode. They obtained adhesion force between AFM tip and
untreated rice husk as mean value 40 nN. Lower adhe-
sion value was observed as 16.7 nN on PMMA (poly
methyl methacrylate) grafted surface of rice husk accord-
ing to acrylonitrile grafted rice husk (23.5 nN). This was
attributed to the apolar structure of PMMA surface which
adheres less to polar AFM tip. In this study, the apolar
surface was provided by chemical treatment of rice husk.
NaOH removed the polar components of the lignocellu-
losic structure, so it provided to remain higher amount of
apolar components in the structure. In silane treatment,
silane reacts with free OH groups of surface and silanol
groups are occurred. These condensed or free silanol
Table III. Adhesion force and work of untreated and treated rice husks.
Treatement/ Mean adhesion Adhesion work
material force F (nN) Wa (DMT) (mJ/m2 )
Outer surface
Unt RH 63 ± 11
NaOH tRH 45 ± 9
Silane tRH 57 ± 13
Inner surface
49 ± 8
Unt RH
NaOH tRH 29 ± 4
Silane tRH 37 ± 6
Mater. Express, Vol. 7, 2017
Materials Express
groups are an available covalent reaction or physical inter-
action with other phases which is apolar polypropylene for
this study.
3.3. Water Absorption Analysis
(4)
Polypropylene is a non-polar polymer which has less
tend to bound with water. Generally, polypropylene hardly
Article
absorbs water due to its hydrophobic structure. In nor-
mal conditions, while the polypropylene may contain 0.1%
of water; at 90 degrees the water absorption value can
reach 0.25%. Higher temperature changes the free vol-
ume of polymer chains of polypropylene and possible
gaps in structure expand.17 Thus, more water diffuses
between the chains and into the gaps. The natural fillers
are hydrophilic, which restrict of their usage in polymer
matrix composite production.11 The hydrophilic charac-
ter of reinforcement of composites causes reduction of
mechanical properties. However, rice husk can absorb
water because of its hydrophilic character. Therefore,
fillers are required to undergo some operations before
incorporating into the matrix.
This study reports the effect of filler and chemical treat-
ment on the water absorption value of rice husk reinforced
composite. Figure 7 depicts that the water uptake depends
on the chemical treatment. Results revealed that the water
absorption decreased after the chemical treatment of rice
husks. In untreated rice husk reinforced PP, water absorp-
tion increases due to the presence of the free –OH groups
contained in cellulose.18 Therewith, PP matrix composite
acts as a hydrophilic structure.
10% NaOH concentration provided a decrease of water
334
absorption value on rice husk reinforced PP. This was
238 attributed to the modifying of crystallinity. The NaOH
302 treatment caused more apolar surface structure and this
provided more resistance to absorb water from rice husk
260
surface.10 Tran et al.10 presented similar results for
154
196 NaOH treated rice husk reinforced PLA (poly lactic acid)
composite. Their study revealed that the lower NaOH
7
 Materials Express Effect of chemical treatment and MAPP coupling agent on rice husk
Huner

Fig. 7. Water absorption values of untreated/treated rice husks reinforced and MAPP added PP composites.

concentration caused an increase in water absorption value
due to partial removing of lignin and waxes.
Silane treatment provided a decrease in water absorp-
tion of RH-r PP. This was mainly attributed reaction of
Article
for this is considered to be a change in the diffusion
mechanism of natural reinforcements. Water molecules
are transferred to micro-gaps in the polymer by diffu-
sion mechanism.18 In the fiber matrix interface, water

silane with free hydroxyl groups of cellulose. The water
absorption rate of silane-treated husk is lower than NaOH-
treated husk. This was explained by the reaction of silane
with free OH groups and it caused a decrease in the ability
of absorption of husk.10 But, silane has lower tendency
to react with free OH of husk surface than NaOH;7 so,
during the water absorption process, remaining OH groups
react with more attractive water molecules.
Use of MAPP ensures improvement in the interface
between the reinforcement and the matrix; this improve-
ment causes a decrease in water absorption. The reason
molecules are transferred by capillary action due to the
lack of wetting. And also, micro-cracks can occur during
the production process; this causes water transportation to
the gaps. Incorporation of MAPP decreases the micro gaps
due to enhanced bonding between filler and matrix. So,
water absorption value reduces by adding MAPP coupling
agent.
3.4. Mechanical Properties
Figure 8 shows the influence of coupling agent and dif-
ferent surface treatments on the mechanical properties of

Fig. 8. Tensile and flexural properties of MAPP-added and untreated/treated rice husk reinforced composites.

8 Mater. Express, Vol. 7, 2017

Effect of chemical treatment and MAPP coupling agent on rice husk
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rice husk reinforced polypropylene. Untreated rice husk
reinforced PP showed 13% decrease in tensile strength
and 29% increase in tensile modulus according to neat
PP. MAPP adding and chemical treatment of rice husk
enhanced the tensile strength. While the tensile strength
increased by 41.7% in MAPP added composite, NaOH
and silane treatments provided 12% and 6% increase,
respectively. Tensile modulus showed an increase of 13%
in MAPP, 15.4% in NaOH and 25% in silane treatment
according to neat polypropylene.
The highest improvement was observed in tensile
strength in MAPP added RH-r PP. This was mainly
attributed to good bridge effect of MAPP between filler
and matrix. Chemically, hydroxyl groups of husk react
with anhydride groups of MAPP through the esterification
reaction. This phenomenon acts as the effective factor of
improving interfacial adhesion between filler and matrix
as reported in the literature.9 NaOH and silane treatments
caused more hydrophobic structure on the rice husk sur-
face. This provided more attractive surface which bonded
with apolar polypropylene easily according to untreated
RH-r PP. A similar composition of PP composites was
investigated by other researchers19 20
Thuc et al.21 observed the highest tensile strength at
4% MAPP added 100% (phr) (55% wt.) RH-r PP compos-
ite. Their study revealed that the most effective incorpo-
ration rate of MAPP was 4% for tensile strength. It was
explained by the higher content of MAPP; the excess of
the compatibilizer amount may lead to the agglomera-
tion and the formation of a new MAPP phase. Favaro
et al.4 observed a decrease in tensile strength in 10% rice
husk reinforced polyethylene according to neat polyethy-
lene. They explained the decrease in tensile strength by
dewetting effect which causes stress concentration on rice
husk. And this leads to debonding at the interface region.
Therefore, this was may be attributed to the agglom-
eration of husk particles which cause weaker wetting
region. Tran et al.10 observed 6.5% decrease in tensile
strength of APS (aminopropyltriethoxysilane) treated rice
husk (20% wt.) reinforced PLA (polylactic acid). They
explained the decrease of strength by the surface energy
of filler rice husk and matrix PLA. They determined polar
and dispersive components of the surface energy of filler
and matrix. And their investigation revealed that surface
energy of APS treated rice husk has higher surface energy
than untreated rice husk. These results provided the more
attractive relation between filler and matrix.
Flexural strength and modulus of rice husk reinforced
composites were shown in Figure 8. Incorporation of rice
husk caused an increase in modulus and a decrease in
strength according to neat PP. While MAPP adding caused
an increase in flexural strength, modulus of composites
decreased according to untreated rice husk reinforced PP.
This was may be attributed to the incorporation of MAPP
provided an increase due to improvement in the boundary
region of filler and matrix.
Mater. Express, Vol. 7, 2017
Materials Express
Favaro et al.10 reported an increase in both flexural
strength and modulus in Unt RH/NaOH-t RH composites.
The slight decreases were observed in flexural modulus.
This was may be attributed to more brittle structure of
NaOH-t RH. Silane-t RH composites showed a decrease
in flexural strength and the negligible decrease in mod-
ulus. Tran et al. presented 50.7% reduction in flexural
strength and 5.7% increase in flexural modulus for NaOH-t
RH PLA (polylactic acid) composites. It was explained
by lower interfacial adhesion. They used 5% NaOH con-
centration and it may be not enough for improvement on
the surface. In this case, NaOH concentration provided
more efficient treatment for husks. APS treatment caused
a negligible change in flexural properties. Silane treatment
showed parallel results with Tran et al. This was may be
attributed to weak improvement effect of silane on husk
surface.
Impact failures are the result of rapid crack propagation
through the material. The crack growth rate is inversely
proportional to the impact resistance of the material. For
a polymer to be considered as having good impact resis-
tance, it should be able to absorb most of the impact
energy and slows the rate of crack propagation.
Gardner test is used for determining impact energy
Article
required for crack or failure on a flat surface. A striker is
used for impact by drop weight. The procedure determines
the energy (mass × gravity × height) that will cause 50%
of the specimens tested to fail.
Incorporation of rice husks provides for decrease of
impact strength according to neat PP. This is mainly
attributed to being lower energy absorbed capacity of
husks and it causes more fiber breakage and higher resid-
ual stress in the composite. MAPP adding makes the
composite structure more brittle and the free motion of
matrix chains is restricted by husks.21 During the loading,
matrix damps the force due to more matrix transport is
between husks. This causes an increase in impact strength
of the composite. Some others explained that is mainly
attributed to decrease in the crystallinity orientation factor
of MAPP.9
Chemical treatment of rice husks caused an increase of
the impact strength due to improved interfacial adhesion.
Table IV. Gardner impact test results.
Values expressed
as percent of the mean
Material Mean, J Vr r
Neat PP 5.89 2.81 795
Unt RHrPP 3.43 6.89 1949
MAPP added RHrPP 6.11 3.55 10,04
NaOH tRHrPP 8.44 5.11 14,46
Silane tRHrPP 7.78 2.23 6,31
Note: Vr = within-laboratory coefficient of variation of the mean r = 2.83 Vr
(Repeatability).
9
 Materials Express
Fig. 9. SEM images of untreated/treated rice husks and composites (a–c) untreated and treated rice husks, (d–e) untreated and treated rice husks
reinforced polypropylene composites, (g–h) MAPP added rice husk reinforced PP.
Therefore, the good bonding handles the energy of impact.
Article
Crack moves along the boundary region. Polymer matrix
blocks the crack propagation and this causes higher impact
strength. Chemical treatments increased the matrix wetted
regions and prevented crack propagation.
Table IV reveals that the Unt RH composite has lower
impact strength than MAPP added and chemical treated
husk reinforced composites. This may be attributed to
higher adhesion of husks that cause facilitating of stress
transfer to the matrix. Chemical treatment provided good
adhesion between husk and matrix; the meanwhile pro-
cess also decreased attraction of husk to each other. And
it restricted the agglomeration.
Figure 9 depicts untreated and treated rice husk and their
composites. Surface characteristics of untreated and treated
rice husks were presented in Figures 9(a)–(c). Remov-
ing of impurities from the husk surface by NaOH and
coating effect of silane was clearly seen in the figures.
Figures 9(d)–(h) shows the rice husk reinforced compos-
ites. The interface of filler and the matrix was presented
in the figures. SEM micrographs of composites revealed
that chemical treatment and MAPP adding enhanced the
boundary region between filler and matrix.
4. CONCLUSION
Effects of different surface treatments including NaOH,
silane agent (propyltrimethoxysilane) and coupling agent
(MAPP) on rice husk reinforced polypropylene were
investigated. MAPP coupling agent provided the highest
improvement on the mechanical properties of rice husk
reinforced polypropylene. Water absorption enhancement
10
Effect of chemical treatment and MAPP coupling agent on rice husk
Huner
remained under the chemically treated rice husks.
NaOH and silane treatments resulted lower water absorp-
tion value according to untreated and MAPP-added
composites.
Topography of husks revealed that alkaline treatment
provide rougher surface than untreated husk and silane
causes a minimum roughness due to coating effect.
According to estimated surface energy, NAOH-treated
husks showed higher compatibility more than untreated
and silane-treated husks. This study suggests that the prop-
erties of a rice husk reinforced composite significantly
improves by chemical treatment and incorporation of cou-
pling agent during composite production.
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