Australian Journal of Basic and Applied Sciences, 8(15) Special 2014, Pages: 107-111

AENSI Journals

Australian Journal of Basic and Applied Sciences

ISSN:1991-8178

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Evaluation of process parameters for graft copolymerization of glycidyl methacrylate to

kenaf fiber using design of experiment method.
1,2

Nor Azillah Fatimah Othman, 2Tuan Amran Tuan Abdullah, 1Nor Azwin Shukri, 1Sarala Selambakkanu and 1Siti Fatahiyah Mohamad

Malaysian Nuclear Agency, Radiation Processing Technology, Bangi, 43000,Kajang, Selangor, Malaysia.
Universiti Teknologi Malayia, Institute of Hydrogen Economy, Faculty of Chemical Engineering, 81310, UTM Johor Bahru, Johor,
Malaysia.
2

ARTICLE INFO
Article history:
Received 15 September 2014
Accepted 5 October 2014
Available online 25 October 2014
Keywords:
Radiation induced grafting
Kenaf bast fiber
Glycidyl methacrylate
Evaluation of process parameters

ABSTRACT
Background: In this study, an evaluation of experimental parameter was carried out
using factorial design of experiment (DOE) method for graft co-polymerization of
glycidyl methacrylate (GMA) onto kenaf bast fiber (Hibiscus Cannabis L.) under postirradiation technique via electron beam. The kenaf fiber was treated with sodium
chlorite (NaClO2) before grafting. The effect of NaClO2 concentration, GMA
concentration, Tween-20 (Tw-20, surfactant) concentration, irradiation dose, reaction
time and reaction temperature were investigated by 26 fractional factorial DOE and
analyzed using Minitab 16. Objective: The effect of 6 reaction parameters in the
process of grafting GMA to kenaf fiber could be screened using 2-levels fractional
factorial design of experiment method. By using this method, most of the possible
variations of the reaction conditions and their interactions could be included in a
practical number of experiments. Results: Out of 6 parameters, it was found that
irradiation dose, GMA concentration, NaClO2 concentration and temperature have
influences on the percentage of grafting. The grafted fiber was confirmed using Fourier
Transformed Infra-Red Spectroscopy (FTIR) and Scanning Electron Microscopy
(SEM). Conclusion: These findings can be used to optimize the process parameters of
grafting kenaf-GMA copolymers and an essential knowledge for better understanding
of the interaction between each process parameters.

2014 AENSI Publisher All rights reserved.

ToCite ThisArticle: Nor Azillah Fatimah Othman, Tuan Amran Tuan Abdullah, Nor Azwin Shukri, Sarala Selambakkanu and 1Siti
Fatahiyah Mohamad., Evaluation of process parameters for graft copolymerization of glycidyl methacrylate to kenaf fiber using design of
experiment method. Aust. J. Basic & Appl. Sci., 8(15): 107-111, 2014

INTRODUCTION
Cellulose is one of the most abundant natural resources and easily available in low price. However, due to
its nature, cellulose-based materials requires modification either by carboxymethylization (Yan, Zhang et al.,
2011), grafting (OConnell, Birkinshaw et al., 2008) and crosslinking (Hong, Liu et al., 2009) to improve its
properties. Fast formation of free radical without any toxic chemical intermediates, like initiator or catalyst
offered by radiation-induced grafting make it favorable as an environmental-friendly modification method of
polymeric materials with high purity. Furthermore, polymeric material is prepared at low temperature, therefore
destruction of the polymer caused by heat can be avoid. Radiation induced grafting can be done simply based on
the irradiation of base polymer either in the presence of monomer (post-irradiation grafting) or without
monomer (pre-irradiation grafting) to create active sites(Ikel anl and Alkan Grsel, 2011). All of these
techniques can produce grafted copolymers with improved properties. Therefore, it is not possible to conclude
which of them is better. Through our work, we have proven that grafting via post-irradiation technique can
achieved reasonably good results with the experimental conditions used.
In this study, high and low values of selected parameters was determined based on our previous research
(Sharif, Mohamad et al., 2013). In the previous study, we successfully grafted GMA onto kenaf fiber using preirradiation method whereby 150% grafting yield was achieved using 50kGy irradiation dose and 3% monomer
concentration/1% surfactant concentration. However, this was not the optimum parameters for the grafting
process and a few other parameters that may influence the process are not included. Moreover, it is difficult to
observe the optimum value of one parameter and its interaction with other parameters while keeping all the
other parameters constant using classical approach of grafting as what we practice in the previous study.
Therefore, design of experiment method was performed in this study by practicing with different levels of all
Corresponding Author: Nor Azillah Fatimah Othman, Malaysian Nuclear Agency, Radiation Processing Technology,
Bangi, 43000,Kajang, Selangor, Malaysia.

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Australian Journal of Basic and Applied Sciences, 8(15) Special 2014, Pages: 107-111

probable parameters combinations. The results were analyzed using MINITAB 16 statistical software to
evaluate the effects as well as the statistical parameters and plots.
This study focuses mainly on the evaluation of process parameters for graft copolymerization of GMA onto
kenaf fiber treated with NaClO2 using design of experiment method. The graft copolymerization were done
using post-irradiation technique and the parameters selected for the study were NaClO2 concentration (for
treatment of kenaf fiber), GMA concentration (monomer), Tween-20 concentration (surfactant), irradiation
dose, reaction time and reaction temperature. The 26 fractional factorial design of experiment method was
applied to study most of the possible variation of reaction conditions and also to examine their interactions in a
practical number of experiments.
Methodology:
Water-retted kenaf bast fiber was supplied by Lembaga Kenaf dan Tembakau Negara (LKTN), Malaysia.
Reagent grade chemicals such as nitric acid (for pH adjustment) and NaClO 2 were obtained from Sigma Aldrich
(Malaysia) Sdn. Bhd. The monomer, glycidyl methacrylate and surfactant, polyoxyethylene sorbitan
monolaurate or Tween-20 was supplied by Sigma Aldrich and used as received.
2.2.1 Treatment of kenaf bast fiber:
Sodium chlorite (NaClO2) solution at predetermined concentration was prepared by dissolving sodium
chlorite in distilled water and adjusted to pH4 by adding nitric acid. NaClO 2 solution was placed on hot plate
stirrer and heated to 70C. Kenaf bast fiber was added to the solution and heated for 6 hours. Upon completion
the kenaf was removed from the solution and washed repeatedly with distilled water and dry in oven at 60C
until constant weight.
2.2.2 Radiation graft copolymerization:
About 0.2g of the dried fiber was weight accurately, purged with nitrogen and sealed in plastic zipper bag.
About 20mL GMA/Tw-20/Water solution was injected to the samples. The samples were placed on dry ice and
irradiated with electron beam at voltage of 2 MeV and current 10 mA at predetermined doses. The irradiated
fiber was left in temperature-controlled water bath for reaction at predetermined period of time. The grafted
kenaf was removed from the emulsion and washed repeatedly with methanol to remove excess monomer and
homopolymer. The weight of GMA grafted kenaf was measured after drying overnight in an oven at 40C.
Percentage of grafting (Pg) was determined gravimetrically and calculated according to the following
formula:
Pg (%) = ((W1 W0)/W0) x 100

(1)

Where, W0 is initial weight of kenaf and W1 is weight of kenaf after grafting.

2.2.3Design of experiment:
In order to complete study of all parameters and their interactions without increasing the number of
experimental runs beyond practical limitations, 2-levels fractional factorial design of experiment approach is
applied. The condition for each parameter is listed in Table 1. 26 fractional factorial design of experiment
method was applied and 66 run of experiments were conducted with duplicates. The interactions between
independent parameters were determined using the statistical software where the main effects were identified
based on the P value with >95% confidence level.
Table 1: Levels for each factors
Parameter
1. GMA conc.
2. Tween-20 conc.
3. Irradiation dose
4. Temperature
5. Reaction time
6. NaClO2 conc.

Notation
A
B
C
D
E
F

Units
%(wt/wt)
%(wt/wt)
kGy
C
min
%(wt/wt)

High
5
1
50
60
180
1.0

Low
3
0.5
10
40
60
0.1

The IR spectra of grafted fiber were obtained using Nicolet IS10 ATR-FTIR spectrometer (Thermo
Scientific) in transmittance mode at frequency in the range of 4000-400 cm-1. The grafted film morphology was
analyzed as a function of degree of grafting using SEM (FEI Quanta 400).
Results:

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Nor Azillah Fatimah Othman et al, 2014

Australian Journal of Basic and Applied Sciences, 8(15) Special 2014, Pages: 107-111

Normal Plot of the Standardized Effects

Pareto Chart of the Standardized Effects

(response is Pg[%], Alpha = 0.05)

(response is Pg[%], Alpha = 0.05)

99

2.01
F actor
A
B
C
D
E
F

C
A
AC
BD
D
ACD
BF

90

F actor
A
B
C
D
E
F

80

AD
ABCE
E

Effect Type
Not Significant
Significant

95

BD
F
D
ACD
BF
AD

70

Percent

Term

N ame
G M A C onc. [% ]
Tw -20 C onc. [% ]
Irradiation Dose [kG y ]
Temperature [C ]
Time [min]
N aC lO 2 C onc.[% ]

60
50
40
30

AC

N ame
G M A C onc. [% ]
Tw -20 C onc. [% ]
Irradiation Dose [kG y ]
Temperature [C ]
Time [min]
N aC lO 2 C onc.[% ]

20

AB

10

ABD
AF
B

AE

6
8
10
12
Standardized Effect

14

16

18

Fig. 1: Pareto chart of the standardized effects

-5

0.1%
0.3%
0.5%
0.7%
1.0%

Hold Values
Tw-20 Conc. [%]
Temperature [C]
Time [min]
NaClO2 Conc.[%]

30

0.5
40
60
0.1

10 kGy
20 kGy
30 kGy
40 kGy
50 kGy

100

80

80

60

60

Pg(%)

Pg[%]
<
0
100
200
300
400
> 400

Pg(%)

Ir r adiat ion Do se [kGy]

100

0
100
200
300

40

15

Fig. 2: Normal plot of the standardized effects

Co n to u r Plo t of Pg[% ] vs Irradiatio n Do se [kGy], GMA Con c . [% ]

50

5
10
Standardized Effect

40

40

20

20

20
0

0
0

10
3.0

3.5

4.0
GM A C o n c . [% ]

4.5

10

5.0

Fig. 3: Contour plot of percentage of grafting vs

irradiation dose and GMA concentration

20

30

40

Radiation Dose (kGy)

50

60

GMA conc. (%)

Fig. 4: Graph of irradiation dose and GMA

concentration vs percentage of grafting

A
B
Fig. 5: SEM of (A) Untreated fiber and (B) Treated and grafted fiber
A
B

Fig. 6: FTIR Spectra of (A) Untreated fiber and (B) Treated and grafted fiber
Discussion:
Figure 1 and Figure 2 shows that out of 6 parameters, only 4 parameters give significant effect to the
percentage of grafting. Irradiation dose, GMA concentration, NaClO 2 concentration and temperature were found
to be the most significant parameters and showed the largest effect on the result of the grafting reaction. The
highest percentage of grafting was 192.28% which is relatively high compared to other research on grafting
using post-irradiation technique. The best value to achieve this grafting yield was 5% monomer/1% surfactant

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Australian Journal of Basic and Applied Sciences, 8(15) Special 2014, Pages: 107-111

concentration with 50kGy irradiation dose and 60C temperature for 3 hours. Meanwhile the lowest percentage
of grafting was 5.5% with the parameters condition of 3% monomer/1% surfactant concentration, 10kGy
irradiation dose and 40C temperature for 3 hours. The condition for sodium chlorite treatment is 1.0% NaClO 2
concentration respectively. This treatment is important to remove phenolic compound especially lignin for the
enhancement of percentage of grafting (Mohamed, Tamada et al.,2013). This process also changes the
properties of kenaf from hydrophobic to hydrophilic which helps the monomer to penetrate easily for grafting
reaction.
The model equation related to the level of parameters and percentage of grafting obtained from the
experiment is shown in the equation below by substituting the regression coefficients. Please take note that the
other effects that are not significant are not included in the model equation. The interactions between parameters
give clear idea of the process. For example, it can predicted that although concentration of Tween-20 itself does
not contributes any main effects towards the process, but the interaction between Tween-20 concentration and
temperature is contributing significant effect to the percentage of grafting.
% = 45.975 + 13.318 + 38.113 + 7391 + 6.587 + 12.719 + 7.920 +
4.962 + 4.862 + 4.982[ ]

(2)

Contour plot of the two most significant parameters that contribute to the results shown in Figure 3 suggests
that the results are not optimized yet and need further improvement for optimization. A large number of work on
radiation-induced graft copolymerization (Chauhan, Guleria et al.,2005, Kang, Jeun et al.,2007, Seko, Ninh et
al.,2010, Wojnrovits, Fldvry et al.,2010, Nasef and Gven,2012, Madrid, Nuesca et al.,2013, Mohamed,
Tamada et al.,2013, Sharif, Mohamad et al.,2013) reported that percentage of grafting increase with the
increasing of irradiation dose as shown in Figure 4. This is mainly due to the formation of more free radicals at
higher irradiation doses which increasing the accessibility of monomer towards the active sites (Nasef and
Gven,2012). Madrid, Nuesca et al. (2013) also evidenced the same phenomena where the percentage of
grafting of GMA onto water hyacinth increase with the increase of irradiation dose(Madrid, Nuesca et al.,2013).
The scanning electron microscopy images of grafted material in Fig. 5(B) show a smooth surface and the
evidence of thick coating of GMA on the fiber. Raw kenaf in Fig. 5(A) is characterized with a rough, dirty
surface and glued together because it is coated with non-cellulose compound. Fig. 6 shows the FTIR spectra of
raw kenaf fiber, NaClO2 treated kenaf and GMA grafted kenaf. As shown in the spectrum of GMA grafted
kenaf fiber, the absorption bands at 1724 cm1 and 13001100cm1 region correspond to COO and COC
stretching of acrylate group. This is confirms that the agreement between this work and our previous work
(Sharif, Mohamad et al.,2013) is satisfactory.
Conclusion:
The effect of 6 process parameters in the grafting of GMA onto kenaf bast fiber could be evaluated by using
design of experiment 2-levels fractional factorial method. Irradiation dose, GMA concentration, NaClO2
concentration and temperature were found the most significant parameters and within the range of these
variations, the highest percentage of grafting achieved is 192%. Further investigations need to be conducted for
the optimization of the process parameter using response surface method (RSM).
ACKNOWLEGEMENT
The authors wish to thank to Malaysian Ministry of Science and Technology (MOSTI) for granting Science
Fund under the vote number of 03-03-01-SF0214.
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