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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
Printed in the United States of America www.aspbs.com/mex

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

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

effect of chemical treatment for a macro level. In view of per 10 min (200  C per 2.16 kg load cell). Poly-propylene-
the surface treatment of lignocellulosic fillers highly cor- grafted Maleic Anhydride (PP-g-MA (Sigma Aldrich),
related the type of chemical or agent. In chemical treat- MA content = 1% wt).
ment, the different mechanisms of chemical reaction and Rice husk is the outer covering of paddy and accounts
interaction, such as bonding, dissolution and coating, are for 20% of its weight. Moreover, it may be considered as
also effective on surface characterization. Therefore, dif- biodegradable filler due to having a high amount of cel-
ferent chemical have been used to treat surface of fillers. lulose. The lignocellulosic material rice husk (RH) which
Tran et al.10 investigated the chemical treatment of wheat was used as reinforcement in the composite was col-
and rice husk by using NaOH and two different organosi- lected from Thrace region in Turkey at 2015 harvest time.
lanes (amino propyl triethoxysilane (APS) and glycidoxy Particle size distribution of rice husks like that 82.8%
propyl trmethoxysilane (GPS). They aimed to change the (wt) ≥ 2.0 mm, 14.6% (wt) ≥ 1.0–2.0 mm, 2.6% (wt) ≥
polarity of the surface and increase the surface energy of 1.0–0.5 mm. It has moisture content (unseasoned) of
husks. Therewithal, MAPP was used to improve interac- 5.88% according to AACC Method No: 44-15A. (Anony-
tion between rice husk and polypropylene by Razavi-Nouri mous, 2000 Approved Methods of American Association
et al.11 of Cereal Chemists.10th ed. Minnesota, USA. Table I
Although the literature has provided many investiga- presents the rice husk’s chemical content (cellulose, hemi-
tions, much detailed information about surface change of celluloses, lignin, waxes, and water-soluble substances).
rice husk has been rarely reported. Moreover comparison
of coupling agent and chemical treatment doesn’t match 2.2. Chemical Treatments
in a study at the same time. Besides, in Turkey, rice husk The rice husks were soaked in a NaOH solution at 10%
production is not much but has potential. After harvesting (w/w) for 4 h at room temperature. Then, the rice husks
rice husk has no special usage as filler or something like were cleaned with distilled water and neutralized with
that. Low cost, low density, high modulus, etc. are some acetic acid solution (10 drops in 1 L water).4 Finally,
of the properties that bring about to choose these fillers. the fillers were again washed with fresh distilled water in
Article

Therefore, it may not be used as waste so it should be many times until the sodium hydroxide was cleaned totally
estimated valuable technical filler. and dried in an oven maintained at 80  C for 5 h. The
This research reports effect of chemical treatment of dried fibers were stored in a vacuumed plastic bag.
rice husk and the coupling agent effects on rice husk rein- The rice husks were soaked in a methyl alcohol solu-
forced composite. Alkali and silane treatment were used tion (alcohol:water = 60:40) containing 5% by weight of
to change the surface properties of rice husk. Spectro- propyltrimethoxysilane (C3 H7 -Si(OCH3 3  (XIAMETER
scopic properties and AFM analyses were chosen to deter- OFS-6264, Dow Corning Corp). The pH of the solution
mine surface changes of rice husk after treatment. The was adjusted to 4.5 with acetic acid and then, the solution
MAPP was used as coupling agent on natural fiber rein-
was placed in an ultrasonic bath for five minutes to have
forced polypropylene to enhance the fiber-matrix inter-
a homogeneous solution.10 The rice husks were immersed
face bonding. This study also aims to determine physical
in silane solution for 4 h at room temperature.
and mechanical properties of reinforced PP composites.
Finally, they were kept in the oven at 80  C for 5 h to
Therefore, tensile, bending tests and water absorption were
complete condensation of silanol groups of the surface and
carried out. The mechanical properties of the composite
to remove methanol and water. The condensation reaction
material were compared with neat polypropylene.
of silanol groups of the surface are shown in Figure 1.
The dried fibers were stored in a vacuumed plastic bag.
2. EXPERIMENTAL DETAILS
2.1. Materials 2.3. Composite Preparation
In this study, S.R.L. was the base resin that is a polypropy- The moisture causes lower adhesion between filler and
lene homopolymer by ROM Petrol Petrochemicals with matrix. Therefore, it should be removed from the compos-
density of 0.90 g/cm2 and has melt flow index of 9.36 g ite structure by drying process. Rice husks were dried in a

Table I. Typical composition of some of natural fillers.1 9 22 23

Natural fillers Density (g/cm3  Cellulose % Hemicelluloses % Lignin % Mineral ash % Water soluble M. %

Flax 1.51 65–85 18–20 1–4 5 1.5

Hemp 1.47 77.5 10 3.7–13 0.8 1.8
Kenaf 1.52 45–57 21.5–23 15–19 2–5 1.9
Sisal 1.45 50–64 10–24 7–11 0.6–1 1.7
Rice husk 0.34–0.40 31–34 22–26 22–23 11–14 7–9
(bulk density) 0.10–0.16

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Effect of chemical treatment and MAPP coupling agent on rice husk
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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

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
Fig. 1. Hypothetical Reaction of Rice Husk Surface (RHS) and water bath at 90  C. The samples were removed from the
Silane. 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-
vacuum oven Ecocell 55 at 103 ± 2  C for 24 h to adjust sion balance. The water absorption percent was calculated
the moisture content of 1–3% and then stored over desic- using the following formula,
cant before compounding. For this study, moisture content
decreased from 5.88% to 1.58%. Figure 2 shows the struc- M% = Mt − Mo /Mo × 100 (1)
ture of untreated and treated rice husks.
Where, Mo and Mt denote the oven-dry weight and weight
PP pellets, untreated and treated rice husks were dried
after time t, respectively.
under vacuum at 50  C for 24 h before processing. The
reinforced plastic granules were produced by laboratory
2.5. Structural Characterizations
scale single screw extruder (L/D = 28). The extruder has
AFM (atomic force microscopy) was used in contact mode
four zones with controlled temperature. The temperature
and tapping mode to obtain surface images and to estimate
setting for these zones was: Z1 = 120  C, Z2 = 155  C,
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.

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 Materials Express Effect of chemical treatment and MAPP coupling agent on rice husk
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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
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Materials Express
IR spectra of untreated and chemically treated of rice surface contains the significant amount of silica.21 There-
husks. The peak at around 460 cm−1 corresponds to fore, these impurities of surfaces affect the adhesion of rice
O–Si–O bending vibration.18 The peaks at 1097 cm−1 and husk. Surface roughness is important because of debond-
797 cm−1 belong to O–Si–O stretching vibration. Bands at ing and sliding properties which can significantly affect the
3200 cm−1 to 3636 cm−1 are attributed to the chemisorbed composite materials. Measured average surface roughness
water and surface hydroxyl groups. The two peaks at about and other surface topographic parameters are presented in
1740–1750 cm−1 are due to the C O stretching from Table II.
aliphatic saturated compounds (cellulose and hemicellu- In the outer surface of rice husk, the average surface
loses). The peak 1650 cm−1 is attributed to the stretching roughness was 97.03, 62.07 and 11.56 nm on untreated,
vibrations of the –OH.4 The peak 1240 cm−1 is ascribed NaOH-treated and silane-treated samples, respectively. For
to C–O belongs to lignin.14 The large band of the range the inner surface of rice husk, average roughness value was
1201–1150 cm−1 is attributed to vibration range of silica 51.04, 31.08 and 5.06 nm on untreated, NaOH- and silane-
bonds corresponding to silica present in rice husks used in treated samples, respectively. These results indicated that
this study. NaOH-removed impurities and other cement substance
As compared to untreated one, the peak at 1240 cm−1 from the husk surface. Image of NaOH-treated surface
was clearly removed after NaOH treatment. This peak exhibits a rougher surface with less level of roughness
belongs to C–O stretching from acetyl groups of lignin height. Silane treatment provided the lowest level rough-
which indicate the removal of lignin due to NaOH ness. This was attributed to the coupling effect of silane
treatment.14 The peak at 1373 cm−1 was due to the C–OH treatment. Silane reacts with free hydroxyl groups of sur-
stretching of the hydrogen bond intensity of crystalline face and solution is absorbed by the surface. The texture
cellulose.20 These peaks remained unchanged for NaOH-t of surface seems like coated by low height roughness.
RH and Silane-t RH. This suggests that the treatments Morsi et al.15 studied ATRP (atom transfer radical poly-
did not affect the cellulose structure of the husk. The merization) technique to graft the rice husk surface. They
decreased carbonyl peak at 1650 cm−1 also indicates par- used several chemical compositions for this process (acry-

Article
tially removal of absorbed water (hemicelluloses) from the lonitrile (AN), Methyl methacrylate (MMA, 99%). They
NaOH-treated rice husk. In addition, the peaks at 1740– measured the roughness of samples by using AFM both
1750 cm−1 were also removed due to the removal of in contact and tapping mode. Average roughness (Ra) was
pectin and wax present in rice husk.4 The peak observed measured as 7.92, 29.8 and 51.5 nm on RH-PMMA (poly-
at 2850 cm−1 which are attributed to C–H stretching of methyl methacrylate), RH-PAN and RH-g-PMMA-b-PAN
hemicelluloses, was also disappeared due to NaOH treat- surface, respectively.15 These results revealed that sur-
ment. 1201–1150 cm−1 band decreased with NaOH treat- faces may not be uniformly covered with grafted polymer.
ment. This result presented an evidence for higher lignin They suggested that there is a different interaction between
and silica content of rice husks. filler and grafting polymer due to adhesion. In this case,
For the silane treatment, the major difference between silane achieved homogenous coating on husk surface and
the different spectrums was the strong increase in the car- acted as more efficient treatment agent according to graft-
bonyl stretching vibration (mC O) at 1740 cm−1 after ing polymer.
treatment.18 20 And also, the appearance of a new broad Force–distance measurements were performed on F –V
peak at around 1560 cm−1 , which is attributed to the N–H (force–volume) channel by using AFM. The outer sur-
bending vibration of primary amine, resulted from silane face and the inner surface of husk were investigated sep-
treatment. Similar peaks at 1350 cm−1 were represented by arately. Derjaguin–Muller–Toporov12 (DMT) model was
Unt RH and Silane-t RH and this peak revealed that reac- used to determine adhesion forces. The empirical formula
tion had taken place in the hemicellulose from the silane for adhesion force F and the work of adhesion W a is
treatment. given by:
F = x ·  · R · Wa (3)
3.2. AFM Analysis
AFM results give information about surface topography. where the Constant x equals 2 for the DMT12 model
In contact mode, the surface energy of samples can be and R is the AFM tip radius (30 nm). Adhesion Force–
determined by using the interaction between silicon nitride Distance curves were created by using software WSxM
AFM tip and surface. In this study, AFM gave both qual- 5.0. WSxM 5.0 was also used to observe 2D-3D topo-
itative and quantitative information on the surfaces of graphic images and to create F –V (Force–Volume) curves.
treated and untreated RH. Figure 5 shows the topographic Figure 6 presents a graph sample which belongs to
image of untreated and treated rice husks at the nano level. the adhesion force of inner and outer surface of rice
As shown in the images, the outer surface of rice husk husk. AFM tip is made from silicon nitride (Si3 N4 
has a rougher surface than the inner husk surface. While which has hydrophilic structure. Therefore, the inter-
the cellulosic inner surface contains wax and fats, outer action between the AFM tip and the sample surface

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

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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 groups are an available covalent reaction or physical inter-
positive effect on integrity and strength of husk. action with other phases which is apolar polypropylene for
The reversible work of adhesion per unit contact area this study.
can then be related to by the Dupré17 equation:
3.3. Water Absorption Analysis
Wa = 13 + 23 − 12 (4)
Polypropylene is a non-polar polymer which has less
where 12 is the solid (1)—solid (2) interfacial energy tend to bound with water. Generally, polypropylene hardly

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

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 Materials Express Effect of chemical treatment and MAPP coupling agent on rice husk
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Fig. 7. Water absorption values of untreated/treated rice husks reinforced and MAPP added PP composites.

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

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

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

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rice husk reinforced polypropylene. Untreated rice husk Favaro et al.10 reported an increase in both flexural
reinforced PP showed 13% decrease in tensile strength strength and modulus in Unt RH/NaOH-t RH composites.
and 29% increase in tensile modulus according to neat The slight decreases were observed in flexural modulus.
PP. MAPP adding and chemical treatment of rice husk This was may be attributed to more brittle structure of
enhanced the tensile strength. While the tensile strength NaOH-t RH. Silane-t RH composites showed a decrease
increased by 41.7% in MAPP added composite, NaOH in flexural strength and the negligible decrease in mod-
and silane treatments provided 12% and 6% increase, ulus. Tran et al. presented 50.7% reduction in flexural
respectively. Tensile modulus showed an increase of 13% strength and 5.7% increase in flexural modulus for NaOH-t
in MAPP, 15.4% in NaOH and 25% in silane treatment RH PLA (polylactic acid) composites. It was explained
according to neat polypropylene. by lower interfacial adhesion. They used 5% NaOH con-
The highest improvement was observed in tensile centration and it may be not enough for improvement on
strength in MAPP added RH-r PP. This was mainly the surface. In this case, NaOH concentration provided
attributed to good bridge effect of MAPP between filler more efficient treatment for husks. APS treatment caused
and matrix. Chemically, hydroxyl groups of husk react a negligible change in flexural properties. Silane treatment
with anhydride groups of MAPP through the esterification showed parallel results with Tran et al. This was may be
reaction. This phenomenon acts as the effective factor of attributed to weak improvement effect of silane on husk
improving interfacial adhesion between filler and matrix surface.
as reported in the literature.9 NaOH and silane treatments Impact failures are the result of rapid crack propagation
caused more hydrophobic structure on the rice husk sur- through the material. The crack growth rate is inversely
face. This provided more attractive surface which bonded proportional to the impact resistance of the material. For
with apolar polypropylene easily according to untreated a polymer to be considered as having good impact resis-
RH-r PP. A similar composition of PP composites was tance, it should be able to absorb most of the impact
investigated by other researchers19 20 energy and slows the rate of crack propagation.
Thuc et al.21 observed the highest tensile strength at Gardner test is used for determining impact energy
4% MAPP added 100% (phr) (55% wt.) RH-r PP compos-

Article
required for crack or failure on a flat surface. A striker is
ite. Their study revealed that the most effective incorpo- used for impact by drop weight. The procedure determines
ration rate of MAPP was 4% for tensile strength. It was the energy (mass × gravity × height) that will cause 50%
explained by the higher content of MAPP; the excess of of the specimens tested to fail.
the compatibilizer amount may lead to the agglomera- Incorporation of rice husks provides for decrease of
tion and the formation of a new MAPP phase. Favaro impact strength according to neat PP. This is mainly
et al.4 observed a decrease in tensile strength in 10% rice attributed to being lower energy absorbed capacity of
husk reinforced polyethylene according to neat polyethy- husks and it causes more fiber breakage and higher resid-
lene. They explained the decrease in tensile strength by ual stress in the composite. MAPP adding makes the
dewetting effect which causes stress concentration on rice composite structure more brittle and the free motion of
husk. And this leads to debonding at the interface region. matrix chains is restricted by husks.21 During the loading,
Therefore, this was may be attributed to the agglom- matrix damps the force due to more matrix transport is
eration of husk particles which cause weaker wetting
between husks. This causes an increase in impact strength
region. Tran et al.10 observed 6.5% decrease in tensile
of the composite. Some others explained that is mainly
strength of APS (aminopropyltriethoxysilane) treated rice
attributed to decrease in the crystallinity orientation factor
husk (20% wt.) reinforced PLA (polylactic acid). They
of MAPP.9
explained the decrease of strength by the surface energy
Chemical treatment of rice husks caused an increase of
of filler rice husk and matrix PLA. They determined polar
the impact strength due to improved interfacial adhesion.
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 Table IV. Gardner impact test results.
than untreated rice husk. These results provided the more Values expressed
attractive relation between filler and matrix. as percent of the mean
Flexural strength and modulus of rice husk reinforced
Material Mean, J Vr r
composites were shown in Figure 8. Incorporation of rice
husk caused an increase in modulus and a decrease in Neat PP 5.89 2.81 795
strength according to neat PP. While MAPP adding caused Unt RHrPP 3.43 6.89 1949
an increase in flexural strength, modulus of composites MAPP added RHrPP 6.11 3.55 10,04
NaOH tRHrPP 8.44 5.11 14,46
decreased according to untreated rice husk reinforced PP.
Silane tRHrPP 7.78 2.23 6,31
This was may be attributed to the incorporation of MAPP
provided an increase due to improvement in the boundary Note: Vr = within-laboratory coefficient of variation of the mean r = 2.83 Vr
(Repeatability).
region of filler and matrix.

Mater. Express, Vol. 7, 2017 9

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

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. remained under the chemically treated rice husks.
Article

Crack moves along the boundary region. Polymer matrix NaOH and silane treatments resulted lower water absorp-
blocks the crack propagation and this causes higher impact tion value according to untreated and MAPP-added
strength. Chemical treatments increased the matrix wetted composites.
regions and prevented crack propagation. Topography of husks revealed that alkaline treatment
Table IV reveals that the Unt RH composite has lower provide rougher surface than untreated husk and silane
impact strength than MAPP added and chemical treated causes a minimum roughness due to coating effect.
husk reinforced composites. This may be attributed to According to estimated surface energy, NAOH-treated
higher adhesion of husks that cause facilitating of stress husks showed higher compatibility more than untreated
transfer to the matrix. Chemical treatment provided good and silane-treated husks. This study suggests that the prop-
adhesion between husk and matrix; the meanwhile pro- erties of a rice husk reinforced composite significantly
cess also decreased attraction of husk to each other. And improves by chemical treatment and incorporation of cou-
it restricted the agglomeration. pling agent during composite production.
Figure 9 depicts untreated and treated rice husk and their
composites. Surface characteristics of untreated and treated
References and Notes
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Article
Received: 1 February 2017. Revised/Accepted: 19 April 2017.

Mater. Express, Vol. 7, 2017 11

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