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 firstname.lastname@example.org, email@example.com, firstname.lastname@example.org 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 —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 . For example, palmitic amido propyl trimethyl ammonium chloride in propylene glycol and sorbitan sesquicaprylate (commercially available by Evonik under tradename VARISOFT® PATC  and ANTIL® Soft SC , respectively), cetostearyl alcohol (commercially available by Croda under tradename Crodacol™ CS50 ), cocamide DEA (commercially available by BASF under tradename Comperlan® KD ), and hydroxyethyl cellulose (commercially available by Dow Chemical under tradename CELLOSIZE® ) 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 . 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 Tech Publications, www.scientific.net. (#103379131, University of Auckland, Auckland, New Zealand-12/11/17,14:35:22) 746 Materials Science and Technology IX water . Therefore, the cellulose would be chemically modified to yield cellulose ether derivatives to improve its water solubility . 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 —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 . 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 . 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 : 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 . 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 . 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 . 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). References  Information on http://www.cosmeticsbusiness.com/news/article_page/Five_personal_care_ingre dient_trends/123167 [cited Dec 30th, 2016]  Information on http://emea.ingredion.com/MeetIngredion/News/Personal-care-natural-products .html [cited Dec 30th, 2016]  R. E. Black, F. J. Hurley, D. C. Havery, Occurrence of 1,4-dioxane in cosmetic raw materials and finished cosmetic products, J. AOAC Int. 84(3) (2001) 666-670.  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