Proceeding of MAMIP2012

Asian International Conference on Materials, Minerals and Polymer

rd th
23 – 24 March 2012, Vistana Hotel, Penang

PROCEEDING

PART 3

Asian International Conference on Materials, Minerals

and Polymer
(MAMIP 2012)

23rd – 24th March 2012, Vistana Hotel, Penang,

MALAYSIA

i
 Proceeding of MAMIP2012
Asian International Conference on Materials, Minerals and Polymer
rd th
23 – 24 March 2012, Vistana Hotel, Penang
MAMIP 2012

Table of Contents

No Title Page
75 Preliminary Study on Properties of Reinforced Polyethylene-Alpinia 606
galanga Natural Fiber Composites

Norhazwani C. D., M. Syahrizul C., Awang M., Rohani M., Aidil

M.A.A., and Nora’aini Ali
76 Study on the mechanical properties of recycled poly (ethylene 613
terephthalate) reinforced newspaper fiber composite

Sara Madadi Ardekani, Azman Hassan, Mat Uzir Wahit, Mariam A.

Al-Maadeed and Alireza Dehghani

77 Synthesis and Characterization of Various Colors of Silver 619

Nanopartilces by Chemical Reduction Method

W.G.I.U. Rathnayake, H.Ismail and A. Baharin

78 Synthesis & Characterization of Mesoporous Hydroxyapatite by 626
Co-Precipitation Method

Nur Farahiyah Mohammad, Fei-Yee YEOH, Neo Pei Ling and Radzali
Othman

79 The Photoelectrochemical Response of Various Surface Morphologies 634

of Titanium Anodic Oxide Films

Lai Chin Wei and Srimala Sreekantan

80 Study of structural properties of ZnO Sol-gel spin coated thin films for 643
front contact of thin film based solar cells
Ans Farooq, Anis-ur-Rehman, Nazar Abbas and Muhammad Kamran

81 Wear behavior of Al6061 reinforced with beryl under different loads 649

H.N.Reddappa, K.R.Suresh, H.B.Niranjan and K.G.Satyanarayana

82 Effects of Extrusion Conditions on the Dynamic Mechanical Properties 655

of Kenaf Fibre/HDPE Composites

Md. Salleh, F., Hassan, A. and Yahya, R

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 Proceeding of MAMIP2012
Asian International Conference on Materials, Minerals and Polymer
rd th
23 – 24 March 2012, Vistana Hotel, Penang
83 FLEXURAL STRENGTHENING OF REINFORCED CONCRETE 664
(RC) BEAMS USING NEAR SURFACE MOUNTED (NSM) GLASS
FIBER REINFORCED POLYMER (GFRP) BARS AND NSM STEEL
BARS

Marzuki N. A, Hamid H. A., Hasan D. and Albar A.

84 Friction and Wear study of Alumina-Epoxy Homogenous composites 672

and its functionally graded materials

Siddhartha, Amar Patnaik, Amba D. Bhatt

85 Characterization Studies and Gold Assaying Method In The 697

Assessment Of Low Grade Gold Ore

Norlia Baharun and Ong Pek Ling

86 ISOTHERMAL CRYSTALLIZATION OF 703

POLYPROPYLENE/POLYSTYRENE BLENDS

Nur Zalina Selamat, Ahmad Zuhdi Mohd On, Azman Hassan and Sani
Amril Samsudin
87 Synthesis of Nanocrystalline Cobalt Using Electrodeposition Method in 712
Different pH Values

Koay Mei Hyie, Nor Azrina Binti Resali and Wan Normimi Roslini
Binti Abdullah
88 The Effect of Co and Fe on Densification of W-Cu Composites 719
prepared by liquid infiltration

Hafed Ibrahim, Azizan Aziz and Azmi Rahmat

89 Crystal structure analysis and thermoelectric properties of p-type 726

Bi0.4Sb1.6Te3 alloys prepared by solid-state microwave synthesis

A. Kadhim, A. Hmood, and H. Abu Hassan

90 Effect of Process Variables on the Degree of Substitution of Cellulose 732

Acetate Synthesized from Oil Palm Empty Fruit Bunches

Fauzi Muhammad Djuned, Wan Rosli W.D and M.N. Mohamad

Ibrahim

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 Proceeding of MAMIP2012
Asian International Conference on Materials, Minerals and Polymer
rd th
23 – 24 March 2012, Vistana Hotel, Penang
6. Kim, D. H., Kim, C., Je, K., Ha, G. H., and Kim, H. (2011) .Fabrication and thermoelectric
properties of c-axis-aligned Bi0.5Sb1.5Te3 with a high magnetic field. Acta.Mater., 59, 4957–
4963.
7. Kwon, O., Park, J., Yim, J., Koo, H., Kim, J., You, H. (2011). The effect of microstructure on
the thermoelectric properties of Bi2Te3-PbTe alloy. Curr. Appl. Phys., 11, S242-S245.
8. Li, D., Sun, R.R., Qin, X.Y., (2011). Thermoelectric properties of p-type (Bi2Te3)x(Sb2Te3)1-x
prepared by spark plasma sintering. Intermetallics, 19, 2002-2005.

Effect of Process Variables on the Degree of Substitution of Cellulose

Acetate Synthesized from Oil Palm Empty Fruit Bunches
Fauzi Muhammad Djuned1,* Wan Rosli W.D1 and M.N. Mohamad Ibrahim2
1
Bioresource, Paper and Coating Technology Division, School of Industrial Technology,
Universiti Sains Malaysia, 11800 Minden, Penang, Malaysia
2
School of Chemistry, Universiti Sains Malaysia, 11800 Minden, Penang, Malaysia

*Corresponding author: fauziemdj@yahoo.com

Abstract: Cellulose acetate (CA) is one of the most important cellulose derivatives with a
wide application in the fields of membrane processes, coating, film and textile industries.
The typical cellulosic raw materials used in its synthesis are often wood-based. Nonetheless,
cellulose can also be extracted and is readily available in large quantities from non-wood
alternatives. One such viable source is empty fruit bunch fiber (OPEFB), a by-product of
the oil palm industry. OPEFB was first converted into dissolving pulp before synthesis
under heterogeneous conditions to obtain the cellulose acetate (CA). Various processing
variables can affect the degree of substitution (DS) of CA; in this study we focus on the
effects of acetylation time and ratio of acetic anhydride/cellulose. Results indicate that DS
had a logarithmic correlation with both variables.
Keywords: acetylation, cellulose acetate, OPEFB, degree of substitution.

1. INTRODUCTION
Cellulose acetate (CA) is one of the most commercially important cellulose
derivatives with a wide range of behavior and application. It may be fully acetylated that is
all three hydroxyl groups of monomeric unit of cellulose are substituted by acetyl groups or
only two or one hydroxyl in a regioselectively or statistically manner. Cellulose acetate can
be used for different applications, such as coating, film, textile, cigarette industries, and
membrane separation. The often used CAs includes diacetates having an average degree of
substitution (DS) from 2.2 to 2.7 and triacetates having an average DS above 2.8, films were
made from cellulose triacetate, and synthetic polymeric membranes from cellulose acetate
membrane with DS of 2–2.5[1,2].
Cellulose acetate is ussually prepared from high quality cellulose with an α-cellulose
content of more than 95%[2]. The main sources of cellulose for producing cellulose acetates
is cotton and wood pulp. This makes the raw materials expensive. In contrast, the low-cost
lignocellulosic biomass has become attractive as a renewable resource because it is available
in large quantities and routinely cultivated in the world. Among numerous biomass
resources, agricultural wastes, woody biomass and related resources form promising
feedstock for this purpose because they are underutilized cellulose resources. During the
past several years, much reasearch have been done to prepare cellulose materials and

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 Proceeding of MAMIP2012
Asian International Conference on Materials, Minerals and Polymer
rd th
23 – 24 March 2012, Vistana Hotel, Penang
cellulose derivatives from the agricultural by-products and other cellulose waste such as
sugarcane bagasse[3,4,5,6], wheat straw[7], cornhusk[8] and recycled newspaper[9]
Oil palm empty fruit bunches (OP-EFB) is a lignocellulosic biomass which is a
waste of palm oil mills. EFB was a potential source of biomass to produce cellulose due to
its abundance and year to year accumulation in line with the growth of palm oil industry. Oil
palm has now become a major economic crop, which triggered expansion of plantation area
in Malaysia and Indonesia. In 2008, Malaysia produced 17.7 million tonnes of palm oil and
Indonesia produced 17.37 million tonnes of crude palm oil. Palm oil industry generates large
amount of biomass such as palm frond, empty fruit bunch, palm kernel shell and fiber and
palm oil mill effluent. Empty fruit bunches (EFBs) was the most potential biomass from the
palm oil industry, with every ton of produced CPO giving 1.1 ton EFB as by product [10,11,12].
The main content of the EFB was α-cellulose (41-45%), hemicellulose (25-33%) and lignin
(27-32%). By removing hemicellulose and lignin, cellulose from EFB can be used as a row
material for producing cellulose acetate.
Various methods have been developed for producing cellulose acetates, in which
acetic anhydride and acetyl chloride are commonly used as acetylating reagents.
Industrially, cellulose acetates are often produced by reaction of cellulose with an excess of
acetic anhydride in the presence of sulfuric acid or perchloric acid as the catalysts. Due to
the heterogeneous nature of the reaction, it is impossible to synthesize partially substituted
cellulose acetates directly[8]. Cerqueira et al.[4] has investigated sugarcane bagasse as raw
material for producing cellulose acetate, and its membranes from this material. However,
membranes made of this material were difficult to work with due to their brittle character,
which was probably due to a low molecular weight of the produced material. An attempt to
improve the workability of these membranes was to produce blends with polystyrene, which
indeed resulted more resistant. In addition, cellulose acetate produced from sugarcane
bagasse cellulose had a low molecular weight, which was probably due to the acetylation
methodology. Shaikh et al.[6] also has published the utilization of sugarcane bagasse for
producing cellulose acetates. They used acetylation methodology that has been developed
by Kuo & Bogan[13] and Ozaki et al.[14], by using acetic acid as solvent, acetic anhydride as
acetylating agent, and sodium bisulfate and sulfuric acid as catalyst.
In most of the studies on cellulose acetate, emphasis was given on the
characterization of the CA prodeced, so far, the effect of process variables on the degree of
substitution (DS) of product has not been widely reported. Process variables sucs as
temperature, reaction time and reactants ratio will clearly affect the DS. Acetylation reaction
can take place from room temperature to 85oC[2], with most studies conducted at room
temperature. As for reaction time, it can vary from 1 to 48 hours depending on the sources
of cellulose as raw material. The ratio of acetic anhydride to cellulose was usually between
3.5-7 (v/w). DS generally increased with increasing reaction time and acetic anhydride to
cellulose ratio, but how exactly the correlation between DS and these process variables has
not been described in most literature[2,9,13,14].
This study focused on the effect of process variables (reaction time and acetic
anhydride to cellulose ratio) on the degree of substitution of cellulose acetate synthesized
from oil palm empty fruit bunches. The correlation between DS and both variables were
reported in this paper.

2. MATERIALS AND METHODS

2.1 Materials
The materials used in this study are cellulose extracted from oil palm empty fruit
bunches with an α-cellulose content of ~94%, acetic anhydride from Merck, acetic acid,

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 Proceeding of MAMIP2012
Asian International Conference on Materials, Minerals and Polymer
rd th
23 – 24 March 2012, Vistana Hotel, Penang
sodium hydroxide, sulfuric acid and hydrogen peroxide from QRëCTM and sodium bisulfate
from Bendosen.

2.2 Methods
Synthesis of cellulose acetate
The procedure for producing of cellulose acetate from OP-EFB was adopted from a
process described elsewhere by Shaikh et al.[6], Kuo & Bogan[13], and Ozaki et al.[14] with
some modification.
The first step of the process is activation of cellulose, were 5 g (dry weight) of EFB
pulp with moisture content about 65% was placed in a 500 ml beaker glass, and 200 ml of
glacial acetic acid was then added. After the addition of acetic acid the reaction mixture was
kept at room temperature with constant stirring for one hour, and then the cellulose was
filtered in a fritted funnel. Then, cellulose was collected and weighed to determined the
remaining water in sample and then placed in a 250 ml three neck round bottom flask fitted
with an overhead stirrer. The remaing water was converted to acetic acid by acetic
anhydride. An amount of glacial acetic acid was added into this flask to reached total liquid
volume of 90 ml. The reaction mixture was kept at room temperature with constant stirring
for one hour.
The next step is the acetylation reaction; the acetylating mixture (V ml acetic
anhydride + 0.1875 g sodium bisulfate + 0.125 ml sulfuric acid) was added to the activated
cellulose mixture. The ratio of acetic anhydride to cellulose was varied from 2-6 (v/w). The
reaction carried out between 1 to 4 hours (time variable) at room temperature. After
completion of the reaction time, a solution of 0.125 g sodium acetate in 10 ml aqueous
acetic acid was added to the reaction mixture and stirring continued for 15 min, so as to stop
the reaction and to remove any sulfate group substituent on the cellulose molecule. The
reaction mixture was then slowly poured into 1 L of distilled water with constant stirring to
precipitate the cellulose acetate, and filtered followed by washing with distilled water until
the product was free of acetic acid. Solution neutrality was ensured before subsequent
washing with ethanol 75% during filtration. The product was then oven dried at 60oC for 24
h.

Determination of degree of substitution (DS)

0.5 g oven dried cellulose acetate sample was added to 20 ml of 75% aqueous
ethanol and then heated for 30 min at 60oC. 20 ml of 0.5 N NaOH solution was then added
to the sample and reheated at 60oC for 15 min, after while the sample was left under
constant stirring for 48 hours at room temperature. The excess alkali in the CA sample was
titrated with HCl (0.5 N) using phenolphthalein as indicator. The disappearance of the pink
color indicated complete neutralization of the alkali. The small excess of acid was then back
titrated with sodium hydroxide to a phenolphthalein end-point. This procedure was repeated
in duplicate.
Eq. (1) was used in order to determined the percentage of acetyl groups and eq. (2)
was used to determined the degree of substitution.
(1)
(2)
Where %AG is percentage of acetyl groups; A is volume of NaOH added to sample; B is
volume of NaOH added to control; C is volume of HCl added to sample; D is volume of
HCl added to control; Na is HCl concentration; Nb is NaOH concentration; W is weight of
CA sample; and DS is degree of substitution.

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 Proceeding of MAMIP2012
Asian International Conference on Materials, Minerals and Polymer
rd th
23 – 24 March 2012, Vistana Hotel, Penang

3. RESULTS AND DISCUSSION

Synthesis of cellulose acetate from OP-EFB cellulose through acetylation process
was performed at room temperature with two process variables, i.e. reaction time and
reactants ratio. The effect of the degrees of substitution (DS) of cellulose acetate on the
variables is shown in Figure 1. Reaction time and reactants ratio were significantly affected
on DS, both variables correlated logarithmically on DS. Acetylation reaction increase
rapidly for two hours until the DS reaches 2.6 and then gradually slowed until DS reaches
2.9. For R5 and R6 samples acetylation process was almost complete after one hour of
reaction, however for the R2 sample the reaction was slow, where cellulose was not able to
be dissolve within one hour of reaction, and even up to four hours of reaction the value of
DS has not reached 2.0. Since actual value of DS for R2 sample at one hour reaction
couldn’t be determined, the DS value for this condition was predicted by extrapolation to
about 0.6. Maximum value of DS obtained was 2.937 for R6 sample after 4 hours reaction.

2.5
Degree of substitution

1.5 R2
R3
1
R4

0.5 R5
R6
0
0 1 2 3 4 5

Reaction time, hours

Fig. 1: Effect of reaction time and and acetic anhydride/cellulose ratio on degree of
substitution (DS) of CA produced from OP-EFB cellulose, R2 to R6 are ratio of acetic
anhydride to cellulose of 2-6 respectively.

The correlation between DS and process variables was derived from Figure 1 by
non-linear regression using Microsoft Excel® 2010. The correlation between DS and
reaction time for R2 to R6 obtained were written as Eq (3) to Eq. (7).
(3)
(4)
(5)
(6)
(7)
All the five equations were combined to obtained one equation expressing the correlation
between DS and both process variables.
(8)
Where Y is degree of substitution (DS); X1 is reaction time; and X2 is acetic
anhydride/cellulose ratio (v/w). The effect of time reaction and acetic anhydride/cellulose

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 Proceeding of MAMIP2012
Asian International Conference on Materials, Minerals and Polymer
rd th
23 – 24 March 2012, Vistana Hotel, Penang
ratio on the DS can also be described in a 2D contour graph base on Eq. (8) as shown in
Figure 2.

Fig. 2: Corroelation between DS with reaction time and acetic anhydride/cellulose ratio
displayed in 2D contour graph.

4. CONCLUSION
The degree of substitution (DS) of cellulose acetate synthesized from OP-EFB
cellulose is significantly influenced by reaction time and reactants ratio, where the DS
increase logarithmically with increasing of time reaction and acetic anhydride/cellulose
ratio. The correlation between the DS and both process variables can be formulated in a
mathematical model as below;

ACKNOWLEDGMENT
The authors acknowledge Universiti Sains Malaysia for financial support given through
research university post graduate research grant scheme (RUPGRS) and Aceh government
for scholarship given through Aceh Scholarships Committee.

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Asian International Conference on Materials, Minerals and Polymer
rd th
23 – 24 March 2012, Vistana Hotel, Penang
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