LWT - Food Science and Technology 48 (2012) 52e58

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LWT - Food Science and Technology

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Carboxymethyl cellulose film from durian rind

Pornchai Rachtanapun a, b, c, *, Suwaporn Luangkamin d, Krittika Tanprasert e, Rungsiri Suriyatem a
a
Division of Packaging Technology, Faculty of Agro-Industry, Chiang Mai University, Chiang Mai 50100, Thailand
b
Postharvest Technology Innovation Center, Chiang Mai University, Chiang Mai 50200, Thailand
c
Materials Science Research Center, Faculty of Science, Chiang Mai University, Chiang Mai 50200, Thailand
d
Department of Chemistry, Faculty of Science, Chiang Mai University, Chiang Mai 50200, Thailand
e
Department of Printing and Packaging, King Mongkut’s University of Technology Thonburi, Bangkok 10140, Thailand

a r t i c l e i n f o a b s t r a c t

Article history: Cellulose from durian rind was converted to carboxymethyl cellulose (CMCd) by carboxymethylation using
Received 11 July 2011 sodium monochloroacetate (SMCA) and various sodium hydroxide (NaOH) concentrations (20e60 g/
Received in revised form 100 mL). The chemical structure of the cellulose and resulting polymers was then characterized using
29 February 2012
Fourier transform infrared spectroscopy (FTIR). Then, the properties of the CMCd materials were investi-
Accepted 29 February 2012
gated. The optimum condition for carboxymethylation was found to be 30 g/100 mL NaOH, which provided
the highest viscosity and degree of substitution (DS ¼ 0.87). Crystallinity of CMCd was found to decline
Keywords:
after synthesis. The L* value of the CMCd decreased with increasing NaOH concentrations (20e40 g/
Biopolymer
Carboxymethyl cellulose
100 mL). The trend of the a* and b* values varied inverses to the L* values. The CMCd films were
Durian rind prepared and tested, and the highest tensile strength (140.77 MPa) and WVTR (220.85 g/day$m2) were
Edible film found using the 30 g/100 mL NaOH-synthesized CMCd film. The percent elongation at break of the different
Sodium hydroxide CMCd films was not to significantly differ.
Ó 2012 Elsevier Ltd. All rights reserved.

1. Introduction material compositions occur in the range of approximately

40e55 g/100 mL cellulose, 15e35 g/100 mL lignin and 25e40 g/
Functionalized cellulose is a critical component for the 100 mL hemicellulose (dry basis). The association of cellulose
advancement and application of new biomaterials. The conversion with these other substances makes it difficult to obtain pure
of plant waste materials into advantageous products can provide cellulose. Cellulose can be utilized in many various forms including
relief for a variety of environmental problems. Plant wastes contain using its original unaltered fibers for textile and papers and with
more than 90% (w/w) carbohydrate polymers (polysaccharides) derivatives including cellulose nitrate and carboxymethyl cellulose
which can react to both biochemical and chemical modifications. (Thomas, Paquita, & Thomas, 2002).
The durian is well known as the “king of fruit”. The durian has Carboxymethyl cellulose (CMC) is an artificial-nature polymer
a unique odor and formidable thorn-covered rind. Durian rind, a by- derived from cellulose. CMC is a copolymer of two units: ß-D-glucose
product of durian fruit consumption, provides one such good source and ß-D-glucopyranose 2-O-(carboxymethyl)-monosodium salt
for cellulose. The cellulose materials can be isolated from the durian which are connected via b-1,4-glycosidic bonds. The substitution of
rind and carboxymethyl cellulose may then be synthesized using an a carboxymethyl group instead the hydroxyl groups is slightly
etherifying agent under alkaline condition. predominant at the C-2 glucose position (Charpentier et al., 1997).
Cellulose is a linear condensation of glucose units combined CMC is widely used in various industries including food (Boursier,
together by b-glycosidic bonds between the C-4 of one sugar unit Bossiere & Hughette, 1985), pharmaceutics (Koyama, 1988), and
and the anomeric C-1 of a second sugar. Cellulose normally appears non-foods such as cements (Ernandes de Brito, 2000), adhesives
in the cell walls of plants and often occurs in conjunction with (Gayrish, Saychenko, Kozlova, Melanichenko, & Liptuga, 1989),
lignin and hemicellulose. Depending on the type of plant, bulk textiles (Kniewske, Kiesewetter, Reinhardt, & Szablikowski, 1994),
pesticides (Lee, 1992), detergents (Leupin & Gosselink, 1999), paper
(Seiichi & Shosuke, 2000) and as a binder in ceramics (Rachtanapun,
Eitssayeam, & Pengpat, 2010). CMC is prepared by activation of
* Corresponding author. Materials Science Research Center, Faculty of Science,
cellulose with an aqueous NaOH in the slurry of an organic solvent
Chiang Mai University, 155 Moo 2, Mae-hea, Muang, Chiang Mai 50200, Thailand.
Tel.: þ665 3948224, þ6689 7903926; fax: þ665 3948224; Thailand.
which reacts with the cellulose and monochloroacetic acid as an
E-mail address: p.rachta@chiangmai.ac.th (P. Rachtanapun). etherifying agent. The first step in the carboxymethylation process is

0023-6438/$ e see front matter Ó 2012 Elsevier Ltd. All rights reserved.
doi:10.1016/j.lwt.2012.02.029
 P. Rachtanapun et al. / LWT - Food Science and Technology 48 (2012) 52e58 53

an alkalization where the hydroxyl groups of the cellulose chains are 2.3. Synthesis of carboxymethyl cellulose (CMCd) from cellulose of
stimulated and altered into more reactive alkaline form (CLLeOe). durian rind

CLLeOH þ NaOH/CLLeONa þ H2 O (1) CMCd was synthesized according to the procedure described by
Rachtanapun, Kumthai et al. (2007). Cellulose powder (15 g), 50 mL
This is followed by an etherification as in Equation (2) to obtain of NaOH (20, 30, 40, 50 and 60 g/100 mL) and isopropanol (450 mL)
CMC and a side reaction as in Equation (3), which results in sodium were mixed in the beaker and let stand for 30 min at ambient
glycolate (Heinze & Pfeiffer, 1999). temperature prior to adding 18 g of monochloroacetic acid. The
mixture was then stirred for 1.5 h and left standing in a beaker
CLLeONa þ CleCH2 eCOeONa/CLLeOeCH2 eCOONa þ NaCl covered with aluminum foil at 55  C for 3 h. During this time the
mixture separated into two phases. The liquid phase was discarded
(2)
and the solid phase was suspended in 70 mL/100 mL methanol
(100 mL) and neutralized using glacial acetic acid. The solid phase
NaOH þ CleCH2 eCOeONa/HOeCH2 eCOeONa þ NaCl (3) suspended in methanol was filtered and washed 5 times with
70 mL/100 mL ethanol (300 mL). It was then washed with absolute
methanol and filtered again. The residue from the filtration was
Many research projects have studied the production of CMC
dried at 55  C in a hot air oven overnight the resulting CMCd was
from agricultural waste cellulose sources such as cotton linters
obtained. The CMCd product was in powder form after synthesis.
(Xiquan, Tingzhu, & Shaoqui, 1990), sugar beet pulp (Togrul &
The yield, expressed as a percentage, was calculated based on the
Arslan, 2003), cashew tree gum (Silva et al., 2004), cavendish
amount of cellulose using Equation (4):
banana pseudo stem (Adinugraha, Marseno, & Hayadi, 2005), sago
waste (Pushpamalar, Langford, Ahmad, & Lim, 2006), papaya peel Weight of CMCðgÞ
(Rachtanapun, Kumthai, Yagi, & Uthaiyod, 2007), waste of mulberry Yield of CMCð%Þ ¼  100 (4)
Weight of celluloseðgÞ
paper (Rachtanapun, Mulkarat, & Pintajam, 2007) and Mimosa pigra
peel (Rachatanapun & Rattanapanone, 2011). All measurements were performed in triplicate.
However, to date, no research has presented the CMC film
preparation from durian rind. In this study, the effect of NaOH 2.4. Degree of substitution (DS)
concentrations of CMC synthesized from durian rind on the degree
of substitution (DS), chemical structure, viscosity, crystallinity, and The DS was measured using the USP XXXII method described for
color changes was evaluated. In addition to the effects of NaOH Croscarmellose sodium. This method included titration and
concentrations on CMC films produced from durian rind, several collection of the residue open ignition step as previously described
other properties were investigated including mechanical properties by Rachatanapun and Rattanapanone (2011).
(tensile strength and percent elongation at break), water vapor
transmission rate (WVTR), and sorption isotherms. 2.5. Fourier transform infrared spectroscopy (FTIR)

The functional groups of the cellulose and CMCd samples were

2. Experimental
determined using an infrared spectrophotometer (Bruker, Tensor
27, Germany). Pellets were made from cellulose and CMCd sample
2.1. Materials
(w2 mg) with KBr. Transmission levels were measured for wave
numbers of 4000e400 cm1.
Durian rind was obtained from Taladthai (Bangkok, Thailand).
All chemicals used in the preparation and analysis of CMC were
2.6. Viscosity
AR grade or the equivalent. Sodium hydroxide and glacial acetic
acid were purchased from RCI Lab-scan Co., Ltd. (Bangkok,
The viscosities of the samples were measured using a Rapid
Thailand). Isopropanol, ethanol and methanol were purchased
Visco Analyzer (Model: RVA-4, Newport Scientific, USA). Initially
from Union science Co., Ltd. (Chiang Mai, Thailand). Mono-
a sample solution (4 g/100 mL water) was prepared. Then the
chloroacetic acid was purchased from SigmaeAldrich (Steinheim,
viscosity was measured in two steps; first, the speed was set at
Germany). The hydrogen peroxide (30e32%) used in this experi-
960 rpm for 10 s at 30  C, and then the temperature was varied from
ment was from QReCÔ and was obtained from SAC Science
30, 40 and 50  C at 6 min with a speed of 160 rpm. All measure-
(Bangkok, Thailand).
ments were performed in triplicate.

2.2. Extraction of cellulose 2.7. X-ray diffraction (XRD)

The durian rind was first sun-dried and then ground into powder The X-ray diffraction patterns of the crystallinity of the cellulose
using a hammer mill (Armfield, England). The powder was then and CMCd were recorded on a JEOL JDX-80-30 X-ray diffractometer.
cooked in 10 g/100 mL NaOH (w/w of dried durian rind) at 100  C The powder samples were dried in a hot air oven at 105  C for 3 h
under a pressure of 413 MPa. The obtained black slurry was filtered before testing. The scattering angle (2q) ranged from 10 to 60 at
and washed with water. The resulting residue was then dried in an a scan rate of 5 /min.
oven at 55  C for 24 h to obtain the cellulose fibers. The fibers were
separated using a food processor (Mulinex, England) and bleached 2.8. Color
with hydrogen peroxide according to Rachtanapun, Mulkarat et al.
(2007). The bleached fibers were then ground again using the The color characteristic was assessed using a Color Quest XE
hammer mill to obtain a powder with a size below 70 mesh. The Spectrocolorimeter (Hunter Lab, USA) to determine the L* value
cellulose powders were then stored until used in a polyethylene (lightness), a* value (redness) and b* value (yellowness) of the
bag. powder samples. A white standard (tile: L* ¼ 93.24, a* ¼ 0.72, and
54 P. Rachtanapun et al. / LWT - Food Science and Technology 48 (2012) 52e58

b* ¼ 1.53) was used to calibrate the spectrocolorimeter before the consecutive weighings. The equilibrium moisture content (EMC) (g
measurement was taken. The sample was measured in triplicate water/100 g dry solid) of the films at each relative humidity was
and the average values of L*, a* and b* were averaged. Whiteness calculated using Equation (6):
(WI) and total color difference (DE) were also calculated using an  
equation previously described (Devani et al., 2009). The total color We
EMC ¼ ðMi þ 1Þ  100 (6)
differences (DE) were calculated in comparison to the L*, a* and b* Wi
value of the cellulose powders.
where We is the equilibrium weight of the film specimen (g), Wi is
the initial weight of the film specimen (g) and Mi is the initial
2.9. CMCd film preparation moisture content of the film specimen (g/g) (Rachtanapun, 2007;
Rachtanapun & Suriyatem, 2012). All measurements were per-
The CMCd (3.0 g) was dissolved in 100 mL of distilled water at formed in triplicate.
80  C for 10 min to prepare the film-forming solution. The solution
was cooled down to 25  C and cast onto a cellulose acetate sheet
2.13. Statistical analysis
(300 mm  150 mm). The thickness of the film was controlled by
the amount of solution (70 mL) being poured onto each sheet. The
Data were analyzed using a one-way analysis of variance
film was left to dry at room temperature for 36 h. The dried film was
(ANOVA) and Duncan’s multiple range test (p  0.05) using Sta-
then peeled and kept in a sealed polyethylene bag until being used.
tistica software version 11. All of the figures show the amount of
Thickness of films was measured using a micrometer model GT-
variation as the standard deviation for the appropriate values. The
313-A (Gotech testing machine Inc., Japan).
error bars for some data points overlap the mean values.

2.10. Mechanical properties

3. Results and discussion

The examined mechanical properties included tensile strength

3.1. Degree of substitution (DS) and percent yield of CMCd
(TS) and elongation at break (EB). The mechanical properties were
determined using an Instrong Universal Testing Machine Model
In general, CMC samples obtained from the alkalization of
1000 (H1K-S, UK) with the procedure according to ASTM D882-80a
cellulose followed by a carboxymethylation process using sodium
(ASTM, 1995) with the 24 h preconditioning and testing performed
monochloroacetate (NaMCA) as reagent usually produce DS values
at 27  2  C, 65  2% RH according to TIS 949-2533 (TIS, 1990). The
in the range of 0.4e1.3 (Adinugraha et al., 2005; Waring & Parsons,
film samples were cut into 15  140 mm rectangles to be used as
2001). The DS values found in this work were in the expected range
a test specimen. The initial grip separation and cross-head speed
of 0.56e0.87 (Fig. 1). The DS values increased with increasing NaOH
was set at 100 mm and 20 mm/min, respectively. There were ten
concentrations (20e30 g/100 mL) with the maximum DS of 0.87
sample measurements.
observed for 30 g/100 mL NaOH. For concentrations greater than
30 g/100 mL the DS values then decreased in value. The synthesis of
2.11. Water vapor transmission rate (WVTR) the CMCd used in this experiment yielded two main products. The
first product is produced from the reaction of cellulose hydroxyl
The water vapor transmission rate (WVTR) was investigated with NaMCA which formed the desired CMC, and the second
according to ASTM E96 (ASTM, 1993). The film sample was cut into product is formed from the conversion of NaMCA to sodium gly-
a circle with the diameter of 70 mm. Cups containing dried silica gel colate, as a by-product (Kirk & Othmer, 1967). The results found in
(10 g) were each covered with a specimen and then sealed with this study imply that NaOH concentration affects the two reactions
paraffin wax. The sealed cups were then weighed and kept at 25  C, differently. Low NaOH concentrations favor the former reaction
75% RH in a desiccator. A constant relative humidity was achieved where CMC is obtained while for concentrations greater than 30 g/
using a saturated sodium chloride solution according to ASTM E104 100 mL the latter reaction is favored, therefore reducing the DS
(ASTM, 2007). The cup was then reweighed daily for 14 days. The value of the obtained CMC. In addition, the lower DS value could be
slope of the linear relationship between time as an independent a result of polymer degradation at high NaOH conditions. A similar
variable and weight gain as a dependent variable was obtained
from the data and used for calculating the WVTR as described in
Equation (5):

slope
WVTR ¼ (5)
film area
All measurements were performed in triplicate.

2.12. Moisture sorption isotherm

The CMCd film was cut into a 30 mm  30 mm square and dried

in a hot air oven at 105  C for 3 h before being placed in desiccators
containing dried silica gel for 2 days. The specimens were then
placed in several different desiccators containing various kinds of
saturated salt solutions to maintain constant relative humidity at
16.1, 34.8, 55.0, 75.9 and 99.0%. In the desiccators containing salt
solution of high relative humidity, a cotton wool soaked with 95%
ethanol was used as a fungi static agent. The specimens were
weighed daily until inequilibrium was attained. “Equilibrium” was Fig. 1. Effect of NaOH concentration on DS (C) and percent yield (>) of CMCd
achieved when the change in weight did not exceed 0.1% for three synthesizing with various NaOH concentrations.
 P. Rachtanapun et al. / LWT - Food Science and Technology 48 (2012) 52e58 55

result was also observed in CMC from sugar beet pulp (Togrul & 2500
Arslan, 2003), banana pseudo stem (Adinugraha et al., 2005),
sago waste (Pushpamalar et al., 2006) and M. pigra peel
2000
(Rachatanapun & Rattanapanone, 2011).
The percent yield of CMCd as a function of NaOH concentration

Viscosity(cP)
trend result was similar to the results for the DS (Fig. 1). This 1500
observation was in agreement with previous results (Adinugraha
et al., 2005). This research found that the percentage of CMC
1000
from cavendish banana pseudo stem increased with increasing DS.

3.2. Fourier transform infrared spectroscopy (FTIR) 500

The frequency of the absorption bands of the representative

0
spectra of cellulose and carboxymethyl cellulose obtained from 0 10 20 30 40 50 60 70
various concentration of NaOH were similar indicating that cellulose NaOH concentration (g/100 mL)
and CMCd have similar functional groups (Fig. 2). The broad band at
3200e3600 cm1 is due to OeH stretching. The bands at 1450 and Fig. 3. Effect of NaOH concentration in CMCd synthesis and temperatures [30  C (C),
1000e1200 cm1 are due to eCH2 scissoring and eOe stretching, 40  C (-) and 50  C (:)] on viscosity of CMCd.

respectively. The band at 3000 cm1 is due to a CeH stretching

vibration. The band around 1600 cm1 is due to C]O stretching. The
the rate of molecular interchange causing the lower viscosity
band at 1060 cm1 is due to eCHeOeCH2 stretching (Kondo, 1997).
(Rachatanapun & Rattanapanone, 2011). At the same temperature,
The absorbent bands in the CMCd spectra were similar regardless of
the viscosity of CMCd increased with increasing NaOH concentration
NaOH concentration but they were different from those of cellulose.
(20e30 g/100 mL). The viscosity of CMCd diminished when the
The differences were observed at 1608, 1419 and 1055 cm1. This
NaOH concentrations used in the synthesis were greater than
indicates the presence of carboxymethyl substituents for the
30 g/100 mL. This viscosity trend agrees with the DS results previ-
absorption bands which were COOe, eCH2 and eOe, respectively
ously mentioned in this experiment. The larger DS values indicate
(Adinugraha et al., 2005; Rachtanapun & Tongdeesoontorn, 2009).
greater amounts of carboxymethyl groups, which are hydrophilic.
According to Adinugraha et al. (2005), the carboxyl groups (COOe)
Then, for equal concentrations of CMCd the larger DS values can help
and its salts have a wave number about 1600e1640 cm1 and
immobilize more water in the system. Therefore, the viscosity of
1400e1450 cm1. A similar observation for the absorption bands has
CMCd directs varies with the DS value. This relationship was also
previously been reported (Rachatanapun & Rattanapanone, 2011;
observed for CMC films of M. pigra peel (Rachatanapun &
Rachtanapun & Tongdeesoontorn, 2009) and the CMCd results for
Rattanapanone, 2011).
different NaOH concentrations were similar.

3.4. X-ray diffraction (XRD)

3.3. Viscosity
All of the CMCd samples had lower peak of intensity (au) values
It is well known that the viscosity of CMC is influenced by many than cellulose (Fig. 4) indicating that were less crystallin. This is
factors including CMC concentration (El Ghzaour, Trompette, most likely due to the cleavage of hydrogen bonds from the NaOH
Cassanas, Bardet, & Fabregue, 2001), sodium monochloroacetate (Adinugraha et al., 2005). The increased distance between cellulose
(NaMCA) concentration (Adinugraha et al., 2005), NaOH concen- polymer molecules makes the substitution of monochloroacetic
tration (Heinze & Pfeiffer, 1999) and temperature (Rachatanapun & acid molecules into the cellulose polymers easier comparisoned to
Rattanapanone, 2011). The viscosity of the CMCd solution (1 g/ cellulose without alkalization with NaOH. Thus, the crystallinity of
100 mL) decreased when the experiment temperature was increased the CMCd was reduced because of the effect of NaOH on the
(Fig. 3). This has been explained by the increase in temperature cellulose structure before the carboxymethylation reaction. This
which reduces the cohesive forces while simultaneously increasing result agrees with the crystallinity of CMC results found for cav-
endish banana cellulose, which were also found to decrease when
alkalizing by 15 g/100 mL NaOH (Adinugraha et al., 2005). Lin, Qu,
and Qi (1990) also found that the crystallinity of cellulose decreased
with an increasing DS and completely disappeared when the DS
was greater than 1. The crystallinity of cellulose extracted from
durian rind seems to be not highly affected by the level of NaOH
since the DS values for different CMCd samples were quite similar.

3.5. Color

Color measurements were carried out in order to determine

change in color due to the carboxymethylation reaction. The main
effects on the color value of the CMC samples was a decreased L*
value with increasing a* and b* values as NaOH concentration
increased up to 40 g/100 mL (Table 1). This indicates that the use of
NaOH with concentration ranging from 20 to 40 g/100 g yields
CMCd that is lighter and more yellowish and reddish. However the
Fig. 2. FTIR spectra of cellulose from durian rind and CMCd synthesized with various level of this effect cannot be observed with the naked eye. For NaOH
NaOH concentrations. with concentrations above 40 g/100 mL, the results were opposite
56 P. Rachtanapun et al. / LWT - Food Science and Technology 48 (2012) 52e58

Fig. 4. X-ray diffractograms of cellulose from durian rind and CMCd synthesized with various NaOH amounts.

those for concentrations below 40 g/100 mL. With an increasing which is directly related to the DS, the more the inter-molecular
NaOH concentration L* value decreased while a* and b* values forces between the polymer chains increased resulted in a greater
increased. The results for DE follow the same trend as the results of TS. The reduction of TS at higher NaOH concentrations has been
the a* and b* values while the result of whiteness (WI) value fol- found to be caused by the formation of sodium glycolate leading to
lowed the L* trend. These results are in agreement with the results polymer degradation (Adinugraha et al., 2005). The increased
from one of our previous studies (Rachtanapun, Simasatitkul, formation of sodium glycolate provided a reduction in the CMC
Chaiwan & Wathanaworasakun, in press). We found that carbox- content thereby lowering the inter-molecular forces (Barai, Singhal,
ymethyl rice starch film yellowness increased with alkaline pH. The & Kulkarni, 1997).
increase in yellowness of the CMCd alkalization with 20e40 g/
100 mL NaOH is most likely due to the characteristic color of the 3.7. Water vapor transmission rate (WVTR)
NaOH solution (Rachtanapun et al., in press). The decrease in yel-
lowness of the CMCd alkalization for NaOH values over 40 g/100 mL The relationship between changes in NaOH concentration and
are most probably due to the competitive reaction between NaOH alkalization on the water vapor transmission rate (WVTR) of CMCd
and monochloroacetic acid (Equation (3)). was investigated (Table 2). The WVTR of the CMCd films were
slightly different for each condition. The films created using 30 g/
3.6. Mechanical properties 100 mL NaOH showed the highest WVTR values. This is interesting
in that it correlates to the trend with our DS value result. WVTR is
It was found that the NaOH concentration had an affect on the another property that is directly related to the hydrophilic nature of
tensile strength (TS) but not on the elongation at break (EB) of the the film, i.e. more hydrophilic films will have greater WVTR (lower
CMCd films. TS increased with NaOH concentrations of 20 and 30 g/ water vapor barrier) (Bourtoom & Chinnana, 2008; Ferreira, Nunes,
100 mL were used. Beyond the 30 g/100 mL concentration, the TS of Delgadillo, & Lopes-da-Silva, 2009; Tongdeesoontorn, Mauer,
the films decreased. This followed the same trend as yield, DS and Wongruong, & Rachtanapun, 2009). This result can also be related
viscosity previously mentioned in this paper. It was also similar to to our result that the hydrophilic nature of the CMCd films increases
the tensile properties found for M. pigra peel (Rachatanapun & with increasing carboxymethyl groups. The greater DS, as obtained
Rattanapanone, 2011). The more carboxymethyl groups there are, from NaOH concentrations between 20 and 30 g/100 mL, indicates

Table 1
Color values of cellulose and CMC synthesized with various NaOH concentrations.

Type of samples L* a* b* DE WI
Cellulose 84.60  0.02 0.00  0.02 16.81  0.05 0.00  0.00 77.20  0.06
20 g/100 mL NaOHeCMCd 83.41  0.01 0.32  0.01 19.08  0.03 2.58  0.02 74.71  0.03
30 g/100 mL NaOHeCMCd 80.59  0.02 2.00  0.00 22.90  0.04 7.56  0.05 69.91  0.05
40 g/100 mL NaOHeCMCd 77.61  0.01 3.49  0.02 24.61  0.04 11.04  0.04 66.55  0.04
50 g/100 mL NaOHeCMCd 79.87  0.02 2.82  0.02 22.21  0.04 7.72  0.03 69.89  0.04
60 g/100 mL NaOHeCMCd 82.36  0.02 1.55  0.01 18.11  0.02 3.02  0.01 74.67  0.01
 P. Rachtanapun et al. / LWT - Food Science and Technology 48 (2012) 52e58 57

Table 2 from carboxymethyl rice starch (Rachtanapun et al., in press). It

Water vapor transmission rate (WVTR) and mechanical properties for CMCd films should be noted that the samples at 99%RH had water droplets on
synthesized with various NaOH concentrations at 25  C, 75% RH.
the film surface and the EMC of samples were above 200 g water/
Type of films Water vapor Tensile Elongation 100 g dry solid. Therefore, these data point were omitted.
transmission rate, strength (Mpa) at break (%)
WVTR (g/day m2)
20 g/100 mL NaOHeCMCd 205.52  4.60 141.16  8.32 2.32  0.26 4. Conclusions
30 g/100 mL NaOHeCMCd 220.85  4.13 255.54  30.02 2.20  0.81
40 g/100 mL NaOHeCMCd 211.06  4.22 140.77  14.43 2.07  0.50 Cellulose was first successfully extracted from durian rind. Then,
50 g/100 mL NaOHeCMCd 217.31  1.08 53.42  8.21 2.95  1.13
the cellulose was converted to CMCd films using carbox-
60 g/100 mL NaOHeCMCd 204.58  1.74 79.62  9.76 2.28  0.98
ymethylation with various NaOH concentrations. The DS value
initially increased with increasing NaOH concentrations (up to 30 g/
100 mL) and then gradually declined with further increases in
increased levels of carboxymethyl groups and therefore the
NaOH concentration. The maximum DS was 0.87 which was
resulting CMCd films had greater WVTR. Beyond this concentration
attained from CMCd synthesized with 30 g/100 mL NaOH. The DS
range, the CMCd films were more hydrophobic as the DS content
value was also related to the viscosity, the lightness of the CMCd
increased and thus became a better barrier to the water vapor.
films, WVTR, tensile strength and the sorption isotherm. The
crystallinity of the CMCd films was found to decrease after modi-
3.8. Moisture sorption isotherm fication. The highest tensile strength, WVTR and EMC were also
obtained from the CMCd film synthesized with 30 g/100 mL NaOH.
Many films have a characteristic sigmoid-shaped type II sorp- The only property unaffected by NaOH concentration and therefore
tion isotherm (Cho & Rhee, 2002; Jangchud & Chinnan, 1999; did not have a relationship with the DS values was the elongation at
Rachtanapun & Suriyatem, 2012; Rachtanapun & Tongdeesoontorn, break. The authors believe that this new biopolymer is useful for
2009; Tongdeesoontorn et al., 2009). This is also true for the industrial utilization possibly as a film-forming agent, binding
sorption isotherm of our CMCd films (Fig. 5). For equivalent NaOH agent, sustain release agent, gelling agent, and metal absorber and
concentrations, an increasing percent relative humidity (RH) also will increase the value of agricultural waste.
increased the equilibrium moisture content (EMC) of the CMCd
films. When compared at each RH, the EMC of the CMCd films
increased with increasing NaOH concentrations between 20 and Acknowledgments
30 g/100 mL with the maximum EMC obtained in a CMCd film
created using a 30 g/100 mL NaOH concentration (i.e. the greatest The authors gratefully acknowledge the financial support from
DS value). The CMCd film obtained from 30 g/100 mL NaOH had the Postharvest Technology Innovation Center, Chiang Mai University.
greatest hydrophilic nature and, therefore, could absorb more The authors also gratefully acknowledge the Thailand Research
moisture. The EMC value trended to decrease with increasing NaOH Fund (TRF) and the National Research University Project under
concentrations above 30 g/100 mL because the DS value decreased. Thailand’s Office of the Higher Education Commission (CHE),
This phenomenon is similar to previously published results in the Thailand for financial support.
literature such as that found with carboxymethyl cellulose films
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