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International Journal of Biological Macromolecules 79 (2015) 144150

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International Journal of Biological Macromolecules


Preparation of food grade carboxymethyl cellulose from corn husk agrowaste

Md. Ibrahim H. Mondal , Mst. Sarmina Yeasmin, Md. Saifur Rahman
Polymer and Textile Research Lab., Department of Applied Chemistry and Chemical Engineering, Rajshahi University, Rajshahi 6205, Bangladesh

article info abstract

Article history: Alpha-cellulose extracted from corn husks was used as the raw material for the production of food-grade carboxymethyl
Received 9 February 2015 cellulose (CMC). Preparation of CMC from husk cellulose was carried out by an etherifica-tion process, using sodium
Received in revised form 17 April 2015 hydroxide and monochloroacetic acid (MCA), with ethanol as the supporting medium. Characterizations of CMC were
Accepted 23 April 2015 Available online 1
carried out by analyzing the spectra of FTIR, XRD patterns and SEM photomicrographs. Degree of substitution (DS) was
May 2015
determined with respect to particle size using chemical methods. Solubility, molecular weight and DS of CMC increased with
decreased cellulose particle sizes. Microbiological testing of the prepared CMC was done by the pour plate method.
Concentrations of heavy metals such as arsenic, lead, cadmium and mercury in the purified CMC were measured by Atomic
Absorption Spectroscopy technique and found to be within the WHO/FAO recommended value. A comparative study with
Carboxymethyl cellulose
Corn husk CMC available in the international market was conducted. The purity of the prepared CMC was higher, at 99.99% well above
Food grade the purity of 99.5% for standard CMC. High purity CMC showed a yield 2.4 g/g with DS 2.41, water holding capacity 5.11
Etherification g/g, oil holding capacity 1.59 g/g. The obtained product is well suited for pharmaceutical and food additives.

2015 Elsevier B.V. All rights reserved.

1. Introduction prepared by the reaction of monochloroacetic acid with alkali cel-lulose [4].

Cellulose is a common natural polymer. It can be found widely in plants There are several grades of CMC depending on their applica-tions such as
which are used as raw material for producing modified cellulose. Due to the technical, semi-purified and purified. Purified CMC is a white to cream
abundant supply of the polymer in nature, modified cellulose is now colored, tasteless, odorless, free-flowing powder
advancing in terms of production and innovation. The sources can range from [5] and used in a variety of industries including the food, deter-gents,
wood even to the agricul-tural waste. Corn or maize husk is an agricultural personal care, pharmaceutical etc. [6,7]. High purity grades are employed as
waste obtained from corn fields which is a rich source of cellulose. food additives [4] also known as cellulose gum
[8]. In the food industry, it can be used as suspending agent, water loss
Cellulose is a linear, high molecular weight, biodegradable polymeric reducer, thickener, emulsifying agent and stabilizer or dispers-ing agent. It is
material. However, due to its strong inter- and intra-molecular hydrogen used as a preservative for coating of fresh fruit and thickener for
bonds, cellulose neither melts nor dissolves readily in hot or cold water [1] pharmaceutical products [911].
and in most common organic solvents [2,3]. In order to utilize cellulose in the Some authors have reported the synthesis of CMC from various cellulosic
food indus-try, cellulose must be converted into its derivatives. One of the sources such as raw cellulose [7], paper sludge [12], wood residue [13], cotton
most common derivatives is carboxymethyl cellulose (CMC), also referred to linters [14,15], fibers [16] etc. There is consid-erable interest in finding
as Na-CMC which is currently finding an increasing number of applications. cheaper alternative methods to produce CMC. Recently cultivation of corn has
CMC is manmade modified cellulose, a linear, long-chain, water-soluble, tremendously increased in Bangladesh [17] and huge amounts of corn husks
anionic polysaccharide which is are either thrown away as waste or burnt. However, these are applications
with low added value, causing disposal as well as environment pollution

Corresponding author. Tel.: +880 1914254992; fax: +880 721750064.
The purpose of the present research is to investigate the
E-mail addresses:, suitabil-ity of the corn husk as a source to produce high purity
(Md.I.H. Mondal).
food-grade CMC. Every year in Bangladesh, large amounts of 0141-
CMC are being
8130/ 2015 Elsevier B.V. All rights reserved.
Md.I.H. Mondal et al. / International Journal of Biological Macromolecules 79 (2015) 144150 145

imported to meet domestic demand and the importance of CMC is increasing 2.3. Characterization
day-by-day [18]. Therefore, there is a need to produce CMC from locally
available cheap raw material, such as corn husk agricultural waste, 2.3.1. Measurement of CMC yield
economically on a large scale. The novelty of this study is the synthesis of CMC yield was measured based on a dry weight basis. The net weight of
CMC with higher DS as well as higher purity so that it can be used for food- dried CMC was divided by the weight of cellulose to get the yield value [21],
based products and pharmaceuticals. as follow:

yield (%) = Weight of prepared CMC

2. Materials and methods (g) 100 Weight of dried cellulose (g)

2.1. Materials
2.3.2. Determination of degree of substitution
Corn husks were collected from the Wheat Research Insti-tute, Rajshahi, To determine the degree of substitution, 0.5 g of dried sodium CMC was
Bangladesh. Chemicals used during the study were sodium hydroxide (Merck,
ashed gently between 450 and 550 C for 24 h, and then dissolved in 100 mL
India), monochloroacetic acid (BDH, England), standard CMC (BDH, of distilled water. 20 mL of this solution was titrated with 0.1 N sulphuric acid
England), ethanol (Merck, Germany), methanol (Merck, Germany), glacial using methyl red as an indicator. After the first end point, the solution was
acetic acid (BDH, England), silver nitrate (BDH, England), n-hexane (Merck, boiled and titrated to a sharp end point. The carboxymethyl content was
Germany), sodium chlorite (Merck, Germany), etc. All chemicals used were calculated from the degree of substitution [22], as follow:
of reagent grade and used without further purification.
0.162 B

Degree of Substitution (DS) = 1 0.08 B

2.2. Methods 0.1 b

2.2.1. Preparation of sample G

Locally collected corn husk samples were cut manually into small pieces where, b is the volume (in mL) of 0.1 N sulphuric acid and G is the mass of
and dried in the sun in order to remove moisture. The dried sample was pure CMC in grams.
ground into powder using a grinding disk mill (model: FFC-15). The
powdered sample was then sieved (sieve type: AFNOR X11-501), and 2.3.3. Determination of molecular weight
separated into different particle sizes, by passing the sample through sieves of CMC was dissolved in a 0.78 M NaOH solution and the molecu-lar weight
different mesh sizes (e.g. 10, 44, 100, 150 and 200 mesh) and stored in a was determined using an Ostwald viscometer. From the intrinsic viscosity, the
desiccator for com-positional and chemical analysis. molecular weight of the CMC was calculated by the MarkHouwink
Sakurada equation [23], as follow:
[ ]=KM
2.2.2. Isolation of -cellulose
A suitable amount of powdered husk sample was treated with 18% NaOH where K is the constant for solvent, a is the polymer shape factor, [ ] is the
solution for 2 h with occasional stirring in a solid to liquor ratio of 1:100 at intrinsic viscosity and M is the molecular weight of CMC.
room temperature. The cellulose residue was separated by filtration, washed
thoroughly with 2% acetic acid and then with hot distilled water. The
2.3.4. Water retention capacity and oil retention capacity
cellulose was stirred with n-hexane for 1 h at room temperature followed by
25 mL of distilled water or commercial olive oil were added to 1 g of dry
washing with 95% ethanol. After filtration, the cellulose thus obtained was

sample, stirred and incubated at 40 C for 1 h. After cen-trifugation, the
heated with 0.7% NaClO2 solution buffered at pH 4 in the solid to liquor ratio
residue was weighed, and water retention capacity (WRC) and oil retention

of 1:50 at 9095 C for 90 min. The -cellulose was separated by filtering and capacity (ORC) was calculated as gram water or oil per gram of dry sample,
washing with ethanol and distilled water. It was then treated with 0.2% respectively [24].
sodium meta bisulphite solution for 15 min, filtered, washed thoroughly with

distilled water, and finally dried at 60 C until reaching a constant weight 2.3.5. Moisture content and ash content
[19]. Moisture content in the CMC was measured by Moisture Ana-lyzer
(model: MAC 50/NH, Rad wag 26-600 Radom, Poland). Ash content was
determined using standard methods [25]. Approxi-mately 0.5 g of the vacuum
2.2.3. Synthesis of carboxymethyl cellulose dried sample was taken into the dried crucible and the sample was pre-ashed
Synthesis of CMC was carried out by two reactions: alkaliza-tion and in a fume hood. When the sample ceased giving off smoke, it was placed in a

etherification. The alkalization reaction was conducted at 30 C. First, a 30% preheated 600 C muffle furnace for 6 h. After completing the sample ashing,
(w/v) NaOH solution was infused into 5 g of pure cellulose. A cellulose-to- ash content was calculated using the equation below:
liquor ratio of 1:2.7 was created with mechanical stirring for an hour. 150 mL
ethanol was used as solvent in this step. Then, the etherification reaction wt. of ash 100
commenced. 120% (w/v) monochloroacetic acid (MCA) was added drop-by- content (%) = wt. of
drop, under constant stiring, for 30 min to create a celluloseliquor ratio of sample

1:1.2. This step was continued for 3.5 h at 55 C. The product thus obtained
was then filtered and suspended in 200 mL of methanol. The slurry was 2.4. Gel content
neutralized using glacial acetic acid. Then the sam-ple was washed, first in
70% ethanol solution four times and then with absolute ethanol, to remove Gel content of the CMC film was determined by Soxhlet extrac-tion using
undesired byproducts. Finally, the sample was filtered and dried in the oven hot toluene as solvent. Films (6 cm 4 cm) were weighed and placed in a
cellulose extraction thimble in the Soxhlet extrac-tor. The solvent extraction
(model: FC-610, Toyo, Japan) at 60 C temperature [20].
was carried out with 250 mL toluene for 6 h. After that, the sample was
vacuum dried and re-weighed until
146 Md.I.H. Mondal et al. / International Journal of Biological Macromolecules 79 (2015) 144150

it attained a constant weight. Gel content was calculated according to the Table 1
Preparation of CMC from corn husk cellulose in aqueous ethanolic medium with dif-ferent
following equation [26]:
particle sizes (30% NaOH in the celluloseliquor ratio, 1:2.7; 120% ClCH 2 COOH in the
Gel Content (%) = 100
celluloseliquor ratio, 1:1.2; temperature, 55 C; time, 3.5 h).
W0 Particle size Degree of Yield of CMC Solubility
( m) substitution (DS) (%)
where W0 is the weight before extraction and W1 is the weight after
1071 0.21 100.89 Insoluble in water
extraction. 340 0.38 115.75 Insoluble in water
149 1.52 195.51 Highly soluble in water
2.5. CMC content 100 2.21 210.87 Highly soluble in water
74 2.41 240.58 Highly soluble in water

Exactly 1.5 g of CMC was added to 100 mL of 80% aqueous methanol

solution. This mixture was stirred, kept for 10 min and filtered. The cake was count was used to detect all viable micro-organisms growing aer-obically, as
washed with 100 mL of fresh 80% aqueous methanol and dried to obtain pure reflecting the general hygiene condition of a sample. Nutrient agar media was
CMC [10]. The CMC content was calculated as follows: used for total plate count.

W 2.9. Atomic absorption spectroscopy

CMC content (%) = W0 100
The amount of arsenic (As), lead (Pb), cadmium (Cd) and mer-cury (Hg)
where W0 (g) is the weight of sample before washing and W (g) is the weight
in the prepared CMC was measured by Atomic Absorption Spectroscopy
of washed sample. (Model: AA-68000, Shimadzu, Japan) coupled with an auto-sampler (ASC-
6100, Japan) employing absorption of opti-cal radiation by free atoms in the
2.6. NaCl content in CMC gaseous state. Metal ions in the sample was quantitatively determined by
measuring the radiation absorbed by atoms of the sample solution with
2 g of CMC was added to 250 mL of 65% aqueous methanol and kept for compared to the amount absorbed by a known concentration.
5 h. 100 mL of this mixture in a liquid form was neutralized by diluted 0.1 N
HNO3 and titrated with 0.1 N AgNO3 solution [10]. The NaCl content was
calculated as follows: 2.10. FTIR spectroscopy
NaCl (%) = 1.461 V
M Infrared spectra of the prepared CMC samples were recorded with FTIR
(Model: FTIR-8900, Shimadju, Japan). Pellets were made from 0.2 mg CMC
where V (mL) is the amount of AgNO3 solution and M (g) is the weight of the
samples, which were ground with 2 mg KBr. Transmission was measured at
dried sample.
the wavenumber range of 4000400 cm .
2.7. Sodium glycolate content
2.11. X-ray diffractometry
0.5 g of CMC was moistened with 5 mL glacial acetic acid and 5 mL
water. 50 mL acetone and 1 g sodium chloride was added to the mixture and
stirring was continued for several minutes to ensure complete precipitation of Diffraction diagrams of samples were recorded between 10 and 50 using
CMC. The mixture was then fil-tered and clear supernatant was used to a Bruker D8 Advanced Germany X-Ray Diffractometer that generated CuK
prepare the test solution. A similar blank solution, using only reagents, was radiation. Powder samples were exposed to X-ray beam (40 kV, 30 mA) at

prepared. Acetone was removed from both the test solution and the blank 2 /min.
solution by heating both for 20 min in a boiling water bath. The solutions 2.12. Scanning electron microscopy
were cooled. Then 20 mL of 2,7-dihydroxynaphthalene was added to each
solution. Absorbance of the test solution, compared with that of blank A thin sample film was coated with gold using an ion sputter. The coated
solution, was measured at 540 nm wavelength using a UVvis samples were viewed and photographed with a scan-ning electron microscope
spectrophotometer (model: T 60, England). A calibration curve of pure (Model-S 3400 N, VP SEM, Hitachi, Japan) using 20 (kV) accelerating
standard glycolic acid was used to determine the unknown concentration of voltage.
sodium glycolate in the solution using the following formula [27]:
3. Results and discussion

a 1.29 Carboxymethyl cellulose was prepared from corn husks cellu-lose

Sodium glycolate, % =
b according to Scheme 1. The advantage of this process was the use of
recovered ethanol through distillation which was above 90%. The reaction
where 1.29 is a factor for converting glycolic acid into sodium gly-colate, a is was optimized with respect to DS by varying each of the parameters. The
mg of glycolic acid read from the calibration curve and b is the dry weight of yield of CMC at different cellulose particle sizes is shown in Table 1. It can be
sample in g. observed from Table 1 that % yield of CMC increased with decrease of
particle size and that the highest yield obtained was 240.58% with respect to
2.8. Microbiological test particle size 74 m. Decreased cellulose particle size provides a greater surface
area which increases the chance of collisions between reactants and cellulose
The presence of microorganisms such as yeasts and molds, Escherichia particles. Thus, the reaction rate increases as well as the production of CMC
coli, Coliform and Salmonella in the prepared CMC was determined using the
[29]. The solubility of the prepared CMC sam-ples with
following method described in the literature. Lactose broth was used for the
detection of Coliform, Salmonella and E. coli bacteria as per Standard different particle sizes as well as different DS was tested. It
Methods [28]. Potato dextrose agar media was used for yeast and mold was found that CMC, with DS 0.21 and 0.38, was insoluble in
detection. The test of total plate water but CMC, with DS 1.52 to 2.41, was highly soluble in
Md.I.H. Mondal et al. / International Journal of Biological Macromolecules 79 (2015) 144150 147

Scheme 1. Flow chart for the preparation of CMC from corn husk cellulose.

CMC, with DS less than 0.40, is insoluble in water. Above this value of DS, the fact that a greater number of carboxymethyl groups were sub-stituted for
CMC is fully soluble, with its hydro affinity increasing with increasing DS the hydroxyl groups of the cellulose molecules. These carboxymethyl groups
[30]. are hydrophilic. Therefore, an increase of DS increases the ability of CMC to
From Table 2, it can be seen that the DS, intrinsic viscosity and molecular immobilize water in a system [20].
weight of the prepared CMC increased gradually with the decrease of The results of moisture content, ash content, gel content, WRC and ORC
cellulose particle sizes. The highest DS obtained was 2.41 with respect to of standard CMC and that of prepared CMC are listed in Table 3. From Table
particle size 74 m. Smaller cellulose particle sizes have larger surface area, so 3, it can be seen that moisture content and ORC of standard CMC and
excess reactants can penetrate into the cellulose at the same time. prepared CMC are almost the same. However, ash content, gel content and
Etherification mainly depends upon the accessibility of reactants and the WRC of prepared CMC are higher than that of standard CMC. The high WRC
availability of the acti-vated hydroxyl groups [18]. When particle size implies that prepared CMC is highly hydrophilic. During etherification, more
decreases, surface area as well as the number of available free OH groups for hydroxyl groups were replaced by carboxymethyl groups, which are
substi-tution reaction increases, thus DS increases. Reduction in particle size hydrophilic [20]. The high gel content implies high reactivity [26]. The high
of cellulose could enhance the affinity between cellulose par-ticles and ash content implies high DS, perhaps because more hydroxyl groups are
reactants. Thus such smaller particle size increases the etherification rate as substituted by sodium salts of carboxymethyl groups during the etherification
well as the carboxymethyl substitution rate [31]. The molecular weight of the reaction.
prepared CMC increased with the increase of DS. Such molecular weight also
increased with the decrease of particle size. As the DS increased the number
of OH groups were replaced by heavier carboxymethyl groups. As a result the 3.5
molecular weight of the final product CMC increased [18].


Viscosity of a polymer solution depends mainly on the concen-tration and
size (i.e., molecular weight) of the dissolved polymer. Thus more the intrinsic 1.5
viscosity, larger the polymer size as well as the higher the molecular weight. 1
There is a direct relationship between intrinsic viscosity and DS of the
prepared CMC. Intrinsic viscosity increases with the increase of DS as
0.21 0.38 1.52 2.21 2.41
presented in Fig. 1. The effect of DS on viscosity was due to
Degree of Substitution

Fig. 1. Relationship between degree of substitution and intrinsic viscosity of pre-pared CMC.
Table 2
Determination of DS and molecular weight of prepared CMC
as a function of particle Table 3
a where, value of
sizes (molecular weight was calculated from equation [ ] = KM Determination of water holding capacity (WHC), oil holding capacity (OHC), mois-ture, ash
k = 37 10 dL/g and a = 0.61 at 35 C). and gel contents of synthesized CMC (DS = 2.41) and standard CMC (DS = 0.8).
Particle size Degree of Intrinsic Molecular
( m) substitution (DS) viscosity ( ) weight (Da) Samples name Moisture Ash WHC OHC Gel content
1071 0.21 0.36 79,163 content (%) content (%) (g/g) (g/g) (%)
340 0.38 0.54 153,886 Standard CMC 2.22 14.23 4.12 1.58 99.06
149 1.52 2.21 1,550,516 Prepared CMC 2.21 18.05 5.11 1.59 99.96
100 2.21 2.64 2,075,165
74 2.41 3.00 2,558,967
148 Md.I.H. Mondal et al. / International Journal of Biological Macromolecules 79 (2015) 144150

Table 4 Table 6
Physicochemical characteristics of corn husk CMC. CMC grades and typical applications (6).

Tests CMC Quality of CMC Examples of Content of Content of

application areas CMC, % salts, %
Organoleptic Odorless, white and tasteless with free flowing
powder Technical Detergents, mining <75 >25
Solubility Forms highly viscous solution with water but flotation
insoluble in ethanol Semi-purified Oil and gas drilling 7585 1525
Foam No layer of foam appears by shaking 0.1% muds
solution Purified Paper coating, >98 <2
pH in 1% solution 6.8 textile sizing and
Starch and dextrins No blue or reddish brown color with iodine printing, ceramic
solution glazing, oil drilling
Organic impurities No red color with acidified phlorogucinol muds
Film formability Able to form film Extra purified Food, toothpaste, >99.5 <0.5
(cellulose gum) pharmaceuticals

The physicochemical test results of prepared CMC obtained from corn

The culture responses of tested organisms in the prepared CMC are given
husk are listed in Table 4. Tested results in Table 4 show that produced CMC in Table 8. The total plate count is intended to indicate the number of
is white in color, fine powdered, odorless, taste-less, freely soluble in water microorganisms in a product. No colonies were observed in a sample
and insoluble in ethanol. The pH of 1% CMC solution was 6.80. No layer of
containing cultured media after 48 2 h incubation at 35 1 C. Where no
foam appeared after shaking a 0.1% solution of the CMC sample. This test
colonies are visible, the result is expressed as less than 100 cfu/g [28].
distinguishes CMC from other cellulose ethers and from alginates & natural
gums [32]. No blue or reddish brown color of CMC developed in an iodine
Yeasts grow as creamy-to-white colonies and molds grow as fil-amentous
solution or red color with acidified phlorogucinol. These tests confirm the colonies of various colors on Potato Dextrose Agar (PDA) media. When a 1 g
absence of starch, dextrin and organic impurities in the prepared CMC. The sample aliquot was poured on to a plate con-taining PDA, no colonies were
Joint FAO/WHO Expert Committee on Food Additives [33] has established
visible after 5 days incubation at 2025 C. This confirms the absence of
some standard for the identification and purity of CMC. The prepared CMC
yeasts and molds in the sample.
in this study meets these requirements.
E. coli grows as dark blue to violet colonies, Coliform as salmon to red
Heavy metals are potential environmental contaminants, with the
colonies and Salmonella as a colorless colony. Results in Table 8 also shows
capability to cause human health problems, due to their toxic effects, even at that Coliform, Salmonella and E. coli either failed to grow or produced
very low concentrations [34]. Toxic metal content in the prepared CMC was
negative results, after 24 2 h incubation at 35 1 C, in a plate containing a
determined and compared with the rec-ommended values shown in Table 5.
1 g sample in 99 mL lactose broth.
From the results in Table 5, it can be observed that the concentrations of Pb,
Cd, Hg and As are 0.0001, 0.0005, 0.001 and 0.0002 ppm, respectively. These
3.1. FTIR analysis
val-ues are within the World Health Organizations (WHO) permissible limits
for food additives and emulsifier.
Characterization of extracted cellulose was done by FTIR spec-troscopy.
The differences in result between the raw corn husk powder and the extracted
The purity of the CMC was measured after washing the prod-uct several
cellulose powder are shown in the FTIR spectra presented in Fig. 2. The main
times with 70% ethanol and absolute ethanol. Washing removed the reaction 1
by-products such as sodium chloride and sodium glycolate. Where the CMC differences were found in the region from 1800 to 1000 cm . The absorption
product is intended for human consumption, CMC must be purified to a level bands at 1740.13, 1638.49, 1605.18 and 1514.15 cm were not observed in
of 99.5% [35]. Table 6 shows the different grade of CMC with their the extracted cellulose. Particularly two absorption bands must be
1 1
applications and also shows that only extra-purified CMC is used as food emphasized: the bands at 1514 and 1249 cm . The band at 1514 cm was
additive. The percentages of CMC content and sodium salts in the prepared 1
not present and the band at 1249 cm was drastically reduced on the purified
CMC were determined and compared to that of standard CMC and these cellulose spectra. These two absorption bands were important because their
result are summarized in Table 7. It can be observed from Table 7 that the absence in the extracted cellulose spectra strongly indicates that most of the
percentages of sodium chloride and sodium glycolate in the prepared CMC lignin had been removed [38,39].
are very low, 0.009% and 0.001%, respectively. Sodium glycolate is toxic in
nature. It is reported in the literature [27,33] that sodium chloride and sodium
glycolate content in food additives should not exceed 0.5% individually or in
combination. The purity of prepared CMC was higher, at 99.99%, well above Table 7
the purity of 99.5% required for standard CMC and 98% required for Determination of CMC, NaCl and sodium glycolate contents.
commercial grade CMC. Parameters Content of CMC Content of Content of sodium
or purity(%) NaCl(%) glycolate (%)
CMC prepared 99.99 0.009 0.001
CMC standard 99.95 0.03 0.02
Table 8
Table 5
Concentration of heavy metals in the synthesized CMC.
Microbiological test of the prepared CMC.
Heavy metal Concentration in Concentration in ppm
ppm (studied (proposed permissible Tested organisms Cultural response
values) limit) [36,37] Total plate count (cfu/g) <100
As 0.0001 3 Mold (cfu/g) <100
Pb 0.0005 1 or lower in case of Yeast (cfu/g) <100
high consumption Colliform (g) Negative
Cd 0.001 1 Salmonella (g) Negative
Hg 0.0002 1 E. coli (g) Negative
Md.I.H. Mondal et al. / International Journal of Biological Macromolecules 79 (2015) 144150 149

Fig. 2. FTIR spectra of (a) raw corn husk powder and (b) purified extracted cellulose.

The infrared spectra of prepared CMC and standard CMC sam-ples have
been shown in Fig. 3. It is evident from Fig. 3b that the broad absorption band
at 3434.92 cm is due to the stretching fre-quency of the OH group and a
band at 2924.07 cm is attributable to C H stretching vibration. The presence
of a new and strong absorption band at 1620.16 cm confirms the stretching
vibra-tion of carboxyl groups (COO ) and 1423.81 cm is assigned to
carboxyl groups as salts [40,41]. The bands around 1329.32 cm and
1112.65 cm are assigned to -OH bending vibration and
C O C stretching, respectively. Wavelength 894 cm detected 1,4-
glycoside of cellulose [42]. The IR spectra of the standard CMC procured
from the market are also recorded in Fig. 3a and the pat-terns of two spectra,
prepared CMC and standard CMC are almost similar. Fig. 4. X-ray diffractogram of (a) pure husk cellulose and (b) carboxymethylated cellulose (DS
= 2.41).

3.2. XRD analysis

the small crystallites in cellulose granules, which conforms the theory of
X-ray diffraction (XRD) analysis is a special technique for estimating the XRD. This theory states that very small imperfect crystals give broadened
degree of crystallinity in polymer. Cellulose is semi-crystalline in nature. Fig. diffractions.
4 shows the diffraction pattern of pure husk cellulose and carboxymethylated The diffraction patterns of CMC show a destruction of the crys-talline
cellulose. The peaks correspond to the crystalline phase and the background structure of the original cellulose (Fig. 4). All characteristic peaks for native
corresponds to the amorphous phase. The peaks are broad due to cellulose have almost disappeared and trans-formed into an amorphous phase.
Therefore CMC has excellent

Fig. 3. FTIR spectra of (a) standard CMC (DS = 0.8 and (b) synthesized CMC (DS = 2.41).
150 Md.I.H. Mondal et al. / International Journal of Biological Macromolecules 79 (2015) 144150

Fig. 5. SEM image of (a) cellulose and (b) CMC at 500 magnification (200 m size bar).

solubility [43] as lower crystallinity represents higher solubil-ity [12]. During [13] O. Egbuchunam, E.E. Okicimen, Indian J. Chem. Technol. 10 (6) (2003) 619622.
the carboxymethylation process, the cellulose molecules are placed in an [14] Z. Nagieb, M.E. Sakhawy, K. Samir, Int. J. Polym. Mater. 50 (2001) 163173.
[15] I.A. Jahan, F. Sultana, M.N. Islam, M.A. Hossain, J. Abedin, Bangladesh J. Sci. Ind. Res.
alkaline solution. The swelling of the cellulose granules exert a tension on 42 (2007) 2936.
neighboring crystallines of cel-lulose molecules and tend to distort them. [16] H. Gu, J. He, Y. Huang, G. Guo, Fibers Polym. 13 (6) (2012) 748753.
Further swelling leads to uncoiling or dissociation of their double-helical [17] M.M. Uddin, M. Saifur, S. Yeasmin, M.M. Rahman, Md.I.H. Mondal, J. Innov. Dev.
Strategy 7 (2) (2013) 59.
region and the breakup of their crystalline structure [44]. [18] A.B.M.F. Alam, Md.I.H. Mondal, J. Appl. Polym. Sci. 128 (2) (2013) 12061212.
[19] Md.I.H. Mondal, M.M.U. Haque, J. Appl. Polym. Sci. 103 (2007) 23692375.
[20] A. Latif, T. Anwar, S. Noor, J. Chem. Soc. Pak. 29 (2) (2007) 143150.
[21] P. Rachtanapun, J. Kasetsart, Nat. Sci. 43 (2009) 259266.
3.3. SEM analysis
[22] T. Abel, K.N. Maurice, N.J. Noah, H.N. Ntede, M. Richard, N. Emmanuel, RASAYAN J.
Chem. 4 (2011) 17.
SEM analysis is a technique for examining granules morphol-ogy since it [23] B. Brandrup, E.H. Immergut, E.A. Grulke, Polymer Hand Book, fourth ed., John Wiley &
has a large depth of field, which allows a large amount of sample to focus at Sons, Inc, New York, NY, 1998, pp. VII/46.
[24] J.A. Larrauri, P. Ruperez, B. Borroto, S. Saura-Calixto, Food Sci. Technol. 29 (8) (1996)
one time. The SEM also produces images of high resolution, which means 729733.
that closely spaced features can be examined at high magnification. Fig. 5 [25] R. Rane, S. Patil, D. Gangolli, K. Ingawale, Res. J. Recent Sci. 1 (10) (2012) 5962.
represents the morphologi-cal structures of pure husk cellulose and prepared [26] O.H. Lin, R.N. Kumar, H.D. Rozman, M.A.M. Noor, Carbohydr. Polym. 59 (2005) 5769.

CMC with DS 2.4. The CMC molecules are rod-like (or ribbon shaped) which [27] JECFA, Compendium of food additive specifications, in: FAO Food and Nutrition Paper
is sim-ilar to other reported images for a typical CMC molecule [45,46]. Add 10, JECFA, Geneva, 2002, pp. 15 (Issue 52, 59th session).
Figures clearly show that the conversion of cellulose to CMC leads to [28] JECFA, Compendium of food additive specifications, in: FAO Food and Nutrition Paper,
Add 5, JECFA, Rome, 1997, pp. 5152 (Issue 52, 59th session).
changes in its ribbon shape. [29] K.K. Sharma, L.K. Sharma, A Textbook of Physical Chemistry, third ed., Vikas Publishing
House Pvt. Ltd., New Delhi, 1994, pp. 586.
[30] V.K. Varshney, P.K. Gupta, S. Naithani, R. Khullar, A. Bhatt, P.L. Soni, Carbohydr. Polym.
63 (2006) 4045.
4. Conclusion
[31] A.I. Yeh, Y.C. Huang, S.H. Chen, Carbohydr. Polym. 79 (2010) 192199.
[32] International oenological codex (2012 Issue), CODEX 2012 EN.pdf
While corn husks have been used on a small scale as a fuel for direct
[33] JECFA, Compendium of food additive specifications, in: FAO Food and Nutrition Paper,
combustion in cooking and heating, their use as chemical feedstock for large-
Add 5, JECFA, Rome, 1997, pp. 160 (Issue 52, 59th session).
scale production is a more modern concept. Yet this concept has potential to [34] A. Das, A Text Book on Medical Aspects of Bioinorganic Chemistry, CBS, Delhi, 1990,
help in reducing the pollution problem. -cellulose was extracted from corn pp. 1758.
[35] US International Trade Commission, Purified carboxymethyl cellulose from Finland,
husks and etheri-fication reaction was carried out by the infusion of cellulose
Mexico, Netherlands, and Sweden, Invs. Nos. 731-TA-1084-1087 (Final), in: USITC
with NaOH and monochloroacetic acid. High purity food-grade CMC was Publication 3787, US International Trade Commission, 2005, pp. 14.
successfully produced as an additive for pharmaceutical and food industries.
[36] JECFA, Specifications for the identity and purity of food additives and their toxicological
evaluation: some emulsifiers and stabilizers and certain other substances, in: Wld. Hlth.
Org. Techn. Rep. Ser. 10, No. 373, JECFA, 1967, pp. 11.

References [37] JECFA, Evaluation of certain food additives and contaminants, in: WHO Tech-nical
Report Series 53, No. 896, JECFA, 2000, pp. p. 11f.
[38] M.I. Khalil, A. Hasem, A. Habeish, Starch 42 (1990) 6063.
[1] Y. Choi, S. Maken, S. Lee, E. Chung, J. Park, B. Min, Korean J. Chem. Eng. 24 (2) (2007) [39] D. Bhattacharyya, R.S. Singhal, P.R. Kulkarni, Carbohydr. Polym. 27 (1995) 247253.
[2] K. Hattori, E. Abe, T. Yoshida, J. Cuculo, Polym. J. 36 (2) (2004) 123130. [40] A. Bono, P.H. Ying, F.Y. Yan, C.L. Muei, R. Sarbatly, D. Krishnaiah, Adv. Natl. Appl. Sci.
[3] M.P. Adinugraha, D.W. Marseno, M. Haryadi, Carbohydr. Polym. 62 (2005) 164169. 3 (1) (2009) 511.
[41] D.R. Biswal, R.P. Sing, Carbohydr. Polym. 57 (2004) 379387.
[4] M. Mohkami, M. Talaeipour, BioResources 6 (2) (2011) 19882003. [42] R.G.P. Viera, G.R. Filho, R.M.N. Assuncao, C.S. Meireles, J.G. Vieira, G.S. Oliveira,
[5] P. Mario, D.W. Adinugrada, M. Haryadi, Carbohydr. Polym. 62 (2005) 164169. Carbohydr. Polym. 67 (2007) 182189.
[6] V. Stigsson, G. Kloow, U. Germgard, Paper Asia 17 (10) (2001) 1621. [43] J. Zhang, D. Wu, J. Appl. Polym. Sci. 46 (1992) 369374.
[7] H.D. Heydarzadeh, G.D. Najafpour, A.A. Nazari-Moghaddam, World Appl. Sci. J. 6 (4) [44] M. Fang, A. Fowler, J. Tomkinson, S. Hill, Carbohydr. Polym. 47 (2002) 245252.
(2009) 564569. [45] P. Rachtanapun, R. Suriyatem, Value added of durian husk: synthesis of
[8] C. Barba, D. Montane, M. Rinaudo, X. Farriol, Cellulose 9 (2002) 319326. carboxymethyl cellulose from durian husk, in: Project Report, Chiang Mai Uni-versity,
[9] N. Olaru, L. Olaru, A. Stoleriu, D. Timpu, J. Appl. Polym. Sci. 67 (1998) 481486. Thailand, 2009, pp. 155.
[10] H. Togrul, N. Arslan, Carbohydr. Polym. 54 (2003) 7382. [46] M. Moosavi-Nasab, A.R. Yousefi, H. Askari, M. Bakhtiyari, World Acad. Sci. 14 (2010)
[11] J. Xue, M. Ngadi, Food Hydrocoll. 23 (2009) 286295.
[12] X. He, S. Wu, D. Fua, J. Nia, J. Chem. Technol. Biotechnol. 84 (2009) 427434.