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Key Engineering Materials
ISSN: 1662-9795, Vol. 751, pp 745-750
doi:10.4028/www.scientific.net/KEM.751.745
© 2017 Trans Tech Publications, Switzerland
Submitted: 2017-01-03
Revised: 2017-03-25
Accepted: 2017-04-12
Online: 2017-08-22
The Effect of Carboxymethyl Cellulose from Various Agriculture Wastes
on the Viscosity and Physical Properties of Low Concentration Solution
of Surfactant
Thritima Sritapunya1,a *, Gulisara Sommanas1,b, Hathairat Surachaijarin1,c
1
Division of Polymer Engineering Technology, Department of Mechanical Engineering Technology,
College of Industrial Technology, King Mongkut’s University of Technology North Bangkok,
Bangkok, Thailand
a
thritima.s@cit.kmutnb.ac.th, bs-gulisara@hotmail.com, cs.hathairat189@gmail.com
Keywords: Carboxymethyl Cellulose, Agriculture Wastes, Surfactant, Viscosity, Thickener.
Abstract. The goal of this work was the synthesis and the improvement of viscosity of surfactant
with carboxymethyl cellulose (CMC) from different types of agriculture wastes to reduce a quantity
of wastes. Cavendish banana peels, corn silk and bagasse as agricultural wastes were selected to
synthesis CMC by extraction with NaOH to cellulose. Then cellulose was modified by reacting with
monochloroacetic acid to obtain CMC which was investigated the functional group by Fourier
Transform Infrared Spectrometer (FTIR). Moreover, a 0.5 wt% of synthesized CMC was prepared in
14 wt% of sodium lauryl sulfate (SLS) solution to estimate viscosity by rotational viscometer,
transparency by visible spectrophotometer and stability by observation, comparing with commercial
thickener (PEG400). The results showed that CMCs of all three agriculture wastes can increase the
viscosity of the surfactant solution and more increase than solution with PEG400. The SLS solution
containing the CMC of corn silk provided the highest viscosity of 22.4 Cp by rotation speed of
250 rpm. However, the values of transparency and stability of surfactant solution with CMCs are
slightly lower than that of solution with PEG400, except for the addition of CMC from bagasse, it was
precipitated in yellow color in a short time.
Introduction
Growing demand for naturally-derived ingredients for personal care product is rapidly expanding
as a ‘greener’ and ‘safer’ alternative compared to conventional personal care ingredients from
synthetic chemicals. Due to consumer concern for safety of synthetic chemicals, it would appear that
the more ‘natural’ the ingredients, the more attractive the product is to consumers [1, 2]. For example,
polyethylene glycols (PEGs), which are widely used as thickeners and moisture-carriers in personal
care product, may be contaminated with significant amounts of dioxins [3]—which are known
endocrine disruptors, strongly linked to cancer and toxic to the organ system and human
development—referring to the EWG’s Skin Deep Cosmetic Database [4, 5].
In order to capture such changing consumer attitude, several PEG-free chemicals have been
developed for replacing PEGs in thickening application of various formulations e.g. hair conditioners
and shampoo formulations, even though PEG-free systems in general are difficult to thicken [6]. For
example, palmitic amido propyl trimethyl ammonium chloride in propylene glycol and sorbitan
sesquicaprylate (commercially available by Evonik under tradename VARISOFT® PATC [7] and
ANTIL® Soft SC [8], respectively), cetostearyl alcohol (commercially available by Croda under
tradename Crodacol™ CS50 [9]), cocamide DEA (commercially available by BASF under
tradename Comperlan® KD [10]), and hydroxyethyl cellulose (commercially available by Dow
Chemical under tradename CELLOSIZE® [11]) are developed to produce a thickening effect in
rinse-off applications e.g. hair conditioners and shampoo products [7-11]. To develop an application
of cellulose-type thickener or so-called “cellulosic thickener” for personal care product is technically
challenged because, in general, they are electrolyte-sensitive and lead to slimy appearance [6].
However, the cellulose is derived from a polysaccharide, (C6H10O5)n consisting of long straight chain
be parallel through hydrogen bonds providing high crystalline, consequently, cellulose is insoluble in
All rights reserved. No part of contents of this paper may be reproduced or transmitted in any form or by any means without the written permission of Trans
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746
Materials Science and Technology IX
water [12]. Therefore, the cellulose would be chemically modified to yield cellulose ether derivatives
to improve its water solubility [13]. To the best of our knowledge on literature review, none of the
academic research provides basic knowledge underlying application of cellulose ether thickener for
personal care products which is one of the key enablers, driving commercial success of specialty
chemical like this.
Thailand Industry 4.0 policy—shaping Thailand direction toward more specialty and value-added
of existing agricultural product as one of its target [14]—is a key motivation of this present work
whose objective is to study applications of bio-thickener from cellulose derivatives—carboxymethyl
cellulose (CMC) for personal care products, especially shampoo. In this research, three types of
agricultural wastes with potentially high feedstock availability in Thailand—including Cavendish
banana peels, sweet corn silk and sugarcane bagasse—were employed as cellulose source for CMC
thickener synthesis. The effect of agriculture wastes types on the thickening efficiency in aqueous
solution of sodium lauryl sulfate (SLS surfactant) with low concentration (14 wt%) since general
shampoo contained about 10-15% of anionic surfactant that gave quite low viscosity and needed
thickener adding to thicken [15].
Experimental
Materials. Corn silk (CS) inside ear of sweet corn, Cavendish banana peel and sugarcane bagasse
were collected from local fruit shops in Bangkok, Thailand and thoroughly washed with tap water in
order to remove impurities. After that, all washed agriculture residues were dried at 80°C overnight.
They were then ground into powder. Hydrochloric acid (HCl, 37% concentration) and ethanol
(C2H5OH, 95% concentration) were purchased from QREC Chemical Co., Ltd. and Merck-Chemica
Co., Ltd., respectively, used in lipid removal. Sodium hydroxide (NaOH, 40% concentration) was
purchased from Fisher Chemical Co., Ltd. used in alkali treatment for cellulose extraction. Sodium
hypochlorite (NaOCl, 10% concentration) and hydrogen peroxide (H2O2, 30% concentration) were
purchased from Vittayasom Shiracha and Fine Chemical Co., Ltd., respectively, used in beaching.
Monochloroacetic acid and citric acid were supplied by Loba Chemie Co., Ltd. used in
carboxymethylation. Polyethylene glycol (PEG400) was purchased from Tariko Company used as
commercial thickener. And sodium lauryl sulfate (SLS) was supplied by Ajax Finechemical Co., Ltd.
acted as surfactant. All chemicals were used without further purification.
Preparation of Cellulose [16, 17]. For corn silk and bagasse powders, they were treated with 1.2%
on weight of fiber (owf) of HCl with material to liquor ratio (MLR) of 1:30 at 90°C for 3 h, whereas
banana peel powder was treated with 95% of ethanol with MLR of 1:10 at 50°C for 24 h to remove
lipid and impurities followed by washing and drying. Then, all samples were boiled in 30 g/l NaOH
(MLR of 1:20) at 165°C for 2 h to remove protein. Next all alkali treated samples were bleached with
1% owf of NaOCl (MLR of 1:20) at room temperature for 2 h. After that, alkali extraction was
achieved by 4% owf of NaOH (MLR of 1:20) at 80°C for 1 h. In the last step, The bleaching was
carried out repeatly (3 more times) to ensure that all lignin was removed by using 7 g/l H2O2 (MLR of
1:15) at 90°C for 3 h., followed by washing with distrilled water after each treatment to remove all
excess solvents. The final product (cellulose) was dried at 80°C overnight. Finally, all types of
cellulose were ground.
Carboxymethylation of Cellulose [16]. Dried cellulose powder was added to a solution of 95%
ethanol with MLR of 1:20. A solution of 45% NaOH containing the required amount of alkali was
then added. The mixture was stirring at room temperature for 30 min. After that, the
monochloroacetic acid was added gradually during mechanical stirring with cellulose to acid ratio of
1:1. The reaction mixture was left overnight at room temperature. Next, the reaction mixture was
reheated at 60°C for 70 min and left it cool down to room temperature. The excess alkali was
neutralized with citric acid. The product was filtered off and rinsed with 80% ethanol to purify until it
was without salt. Finally, all products were dried and ground again and the CMCs would be obtained.
Preparation of Surfactant Solution and Characterization. At first, the functional groups of both
celluloses and CMCs synthesized earlier were chacterized using Perkin Elmer FTIR Spectrometer in
Key Engineering Materials Vol. 751
747
the transmission of a wavelength number range between 4000 and 400 cm-1. For the characterization
of synthesized CMC properties, the 0.5 wt% of CMCs or PEG400 prepared into 14 wt% SLS solution
were investigated viscosity, transparency and product stability (suspension) by rotational viscometer,
visible spectrophotometer and observation, respectively.
Results and Discussion
In this work, the cellulose was extracted from different types of agriculture residues including
Cavendish banana peel, corn silk and bagasse according to the previous procedure and synthesized
via carboxymethylation with monochloroacetic acid in the presence of sodium hydroxide. Cellulose
can be derived to carboxymethyl cellulose (CMC) as expressed by the following [18]:
Cellulose-OH + NaOH → Cellulose-O-Na + H2O
(1)
Cellulose-O-Na + Cl-CH2COOH → Cellulose-O-CH2COO-Na
(2)
All obtained CMCs had been confirmed the appeared functional group comparing to that of
extracted celluloses using FTIR as shown in Fig. 1 and 2. In addition, CMCs acted as bio-thickener
were added in low concentration (14 wt%) of SLS solution to characterize the physical properties
comparing with SLS solution with PEG400 (commercial thickener). The viscosity, transparency and
product stability were determined and reported in Fig. 3 and 4.
FTIR Spectra of Synthesized Celluloses and CMCs. Fig. 1 showed the FTIR spectra of cellulose
extracted from banana peel, corn silk and bagasse. In all three spectra, the broad peaks were observed
in range of 3200-3500 cm-1, corresponding to O-H of alcohol in cellulose. In comparison of Fig.1,
Fig. 2 revealed the FTIR spectra of CMCs derived from those celluloses, but the peaks of O-H
(3400-3500 cm-1) in CMC spectra are smaller than that in cellulose spectrum, indicating the
disappearance of alcohol end group of cellulose. In addition, all CMC spectra in Fig. 2 also evidenced
the significant increase in the intensity of the carbonyl group (C=O) at 1630 cm-1 and the ether group
(C-O) at 1030-1165 cm-1 in carboxyl group and methyl group (CH2 scissoring) at 1450 and 1375 cm-1,
indicating the presence of carboxymethyl substituent and its salts [19]. These results could be
confirmed that all CMCs were successfully prepared from banana peel, corn silk and bagasse by
carboxymethylation to substitute the O-H groups for carboxymethyl groups (CH2-COO-Na).
Moreover, Fig. 2 showed the intensity of carboxyl groups for bagasse CMC was highest meaning to
high degree of substitution of carboxymethyl group. This indicated that bagasse cellulose was mostly
swollen by sodium hydroxide (NaOH) compared with other celluloses, resulting in the highest
penetration of carboxymethyl group [20, 21].
C-O
C=O
O-H
(a)
(c)
% Transmittance
(b)
(a)
(b)
(c)
C-H
4000
3400
2800
2200
1600
Banana peel CMC
Corn silk CMC
Bagasse CMC
1000
400
Wavenumber (cm-1 )
Fig. 1 FTIR spectra of (a) banana peel cellulose
(b) corn silk cellulose and (c) bagasse cellulose.
Fig. 2 FTIR spectra of (a) banana peel CMC
(b) corn silk CMC and (c) bagasse CMC.
748
Materials Science and Technology IX
Fig. 3 Viscosity and transparency of SLS solution with various CMC types.
Viscosity and Transparency. For the study of CMC efficiency, the viscosity and transparency was
needed to investigate since viscosity was the main role of thickener. The concentration of CMCs and
PEG400 (commercial) thickeners in a 14-wt% of aqueous SLS solution was only studied at 0.5 wt%
to remain the transparency of solution [18]. The rotational speed of 250 rpm with spindle no. 4 was
carried out to determine the viscosity of aqueous solution. The results (Fig. 3) showed that the
viscosity of SLS solution was increased with adding of either CMCs or PEG400. Generally, for the
mechanism of a polymeric hydophillic thickener, the hydrophobic parts were incorporated into the
surfactant micelles and increased the micelle size by long polymer chains whereas another part
bridged to the other spherical micelles led to limit space moving, resulting in viscosity improvement
[6]. Therefore, the prepared CMCs were hydrocolloid polymer that had both hydrophilic part and
hydrophobic part could exhibit this mechanism to thicken. In another hand, CMC molecules outside
surfactant micelles could dispersed and arranged in uncoiled linear in aqueous solution, leading to
thickening. Moreover, it also was found that the corn silk CMC provided the highest viscosity of SLS
solution at 22.4 Cp with transparency of 98.8%. In comparison of PEG400, the corn silk CMC could
enhance the viscosity of SLS solution about 8.8% whereas the PEG400 just enhanced the viscosity
about 0.8% with transparency of 100%. Besides, the bagasse CMC added SLS solution revealed the
lowest viscosity and transparency. This is because bagasse CMC with high amount of anionic charges
of carboxymethyl groups, as referred in Fig. 2, might repulse to SLS molecule which is anionic
surfactant until surfactant could not micelle to thicken as well as some remained crystalline regions in
bagasse CMC molecules, which should be higher than other CMCs due to more observed toughness
of fiber, could not be swollen. From these reasons, the bagasse CMC with too high degree of
carboxymethyl substitution and high crystalline provided the lowest viscosity.
Product Stability. This method used the real time storage condition to observe the compatibility of
CMC in surfactant solution because the stability of CMC in aqueous surfactant solution is necessary
properties for applying in personal care products when they were aged on shelf. The 24 ml of SLS
solutions with either CMCs or PEG400 were left indoor at room temperature for 10, 20, 30, 40, 50
and 60 days to notice the appearance and color. The results in Fig. 4 showed that both banana peel and
corn silk CMCs provided clear solution through experiment (60 days) similar to PEG400. Whereas,
the SLS solution with bagasse CMC did not form a stable solution which revealed color change from
clear to yellowish color and separated directly since 10th day of experiment. Since a residual
crystalline region of bagasse CMC, referring in previous section, could form the chain aggregation
Key Engineering Materials Vol. 751
749
with strong H-bonding of undissociated carboxymethyl groups in solution, leading to precipitation
[22, 23]. So, the bagasse CMC might not be suitable for applying in personal care products.
a
b
c
d
e
a
b
10 days
a
b
c
c
d
e
a
b
20 days
d
e
a
b
c
c
d
e
d
e
30 days
d
e
a
b
c
40 days
50 days
60 days
Fig. 4 Product stability of SLS solution with various thickener types for 60 days.
Conclusions
The synthesis of CMCs from all three types of agriculture wastes including Cavendish banana
peel, sweet corn silk and sugarcane bagasse was successful, confirming from the increase of
carboxymethyl group band (C=O, C-O and CH2) in FTIR spectra. It was also found that the viscosity
of 14wt% SLS solution adding any prepared CMCs from all three agriculture wastes was higher than
that of one adding PEG400, which increased the viscosity of 0.8%. In addition, the corn silk CMC
provided the viscosity increasing of SLS solution of 8.8% revealed the highest solution viscosity with
moderately lower values of solution transparency than that with PEG400. For the product stability,
the result of both banana peel and corn silk CMCs were satisfying with clear solution similarly to
PEG400 over 60 days, whereas the bagasse CMC in SLS solution showed instability within 10 days
after solution preparation by precipitation in clear yellow color. In conclusion, the possibility of
application of corn silk CMC replaced PEG400 in personal care, especially shampoo, was the most
attractive and interesting.
Acknowledgements
This work was funded by Science and Technology Research Institute, King Mongkut’s University of
Technology North Bangkok, Bangkok, Thailand (Grant no. KMUTNB-60-GEN-38).
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Materials Science and Technology IX
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