10 1016@j Carbpol 2016 03 030

Accepted Manuscript
Title: Recent Advances in Cellulose and Chitosan Based

Membranes for Water Purification: A Concise Review
Author: Vijay Kumar Thakur Stefan Ioan Voicu
PII: S0144-8617(16)30259-4
DOI: http://dx.doi.org/doi:10.1016/j.carbpol.2016.03.030
Reference: CARP 10867
To appear in:
Received date: 18-11-2015

Revised date: 19-2-2016
Accepted date: 14-3-2016
Please cite this article as: Thakur, Vijay Kumar., & Voicu, Stefan Ioan., Recent Advances
in Cellulose and Chitosan Based Membranes for Water Purification: A Concise
Review.Carbohydrate Polymers http://dx.doi.org/10.1016/j.carbpol.2016.03.030
This is a PDF file of an unedited manuscript that has been accepted for publication.
As a service to our customers we are providing this early version of the manuscript.
The manuscript will undergo copyediting, typesetting, and review of the resulting proof
before it is published in its final form. Please note that during the production process
errors may be discovered which could affect the content, and all legal disclaimers that
apply to the journal pertain.
1 Recent Advances in Cellulose and Chitosan Based Membranes for Water Purification: A Concise
2 Review
3 Vijay Kumar Thakura* vijayisu@hotmail.com, Stefan Ioan Voicub** svoicu@gmail.com
a
4 School of Mechanical and Materials Engineering, Washington State University, Pullman,
5 WA, United States
b
6 Faculty of Applied Chemistry and Materials Sciences, University Politehnica from Bucharest,
7 Bucharest 011061, Romania
*
8 Corresponding author.
**
9 Corresponding author.
10
11 Highlights
12 Natural polysaccharides are of great importance for advanced applications.
13 Biobased polymeric membranes performances can be improved using fillers.
14 Sustainable cellulose and chitosan membranes can efficiently purify water.
15
16 Abstract
17 Recently membrane technology has emerged as a new promising and pervasive technology
18 due to its innate advantages over traditional technologies such as adsorption, distillation
19 and extraction. In this article, some of the recent advances in developing polymeric
20 composite membrane materials for water purification from natural polysaccharide based
21 polymers namely cellulose derivatives and chitosan are concisely reviewed. The impact of
22 human social, demographic and industrial evolution along with expansion through
23 environment has significantly affected the quality of water by pollution with large quantities
24 of pesticides, minerals, drugs or other residues. At the forefront of decontamination and
25 purification techniques, we found the membrane materials from polymers as a potential
26 alternative. In an attempt to reduce the number of technical polymers widely used in the
27 preparation of membranes, many researchers have reported new solutions for desalination
28 or retention of organic yeasts, based on bio renewable polymers like cellulose derivatives
29 and chitosan. These realizations are presented and discussed in terms of the most important
30 parameters of membrane separation especially water flux and retention in this article.
31 Keywords: Biobased polymers; Membranes; Composite; Salts rejection; Water purification
32
33 Introduction
34 Membrane technology
35 Membrane technology has emerged as a new promising and pervasive technology
36 for water purification due to its innate advantages over traditional technologies such as
37 adsorption, distillation and extraction (Eminoglu, Beypinar, Kahraman, & Durmus, 2015;
38 Mondal & De, 2015; Said et al., 2015). Indeed due to the human social, demographic and
39 industrial evolution and expansion, the need for drinkable and pure water sources has
40 become a major challenge (Thakur & Thakur, 2015; Thakur & Thakur, 2014c; Pappu et al.,
41 2015). In the last few years, the impact of human activities to environment has affected the
42 quality of water by polluting with large quantities of pesticides, minerals, drugs or other
43 residues (Mondal & De, 2015; Zhao et al., 2015;Thakur, Vennerberg, & Kessler, 2014;Thakur
44 & Kessler, 2015). So new technologies and materials are being researched for water
45 purification. Different kinds of membranes from polymers are such potential materials and
46 the membrane technology is one such technology at the first line of decontamination and
47 purification techniques.(Khalil, Sheha, Hanafy, & Al-Hartomy, 2014; Ferreira, Caridade,
48 Mano, & Alves, 2014; He et al., 2015). A membrane, by definition is a selective barrier for a
49 certain species of particles, molecules, ions from a complex mixture (or solution) (Zhao et
50 al., 2015; Rahimnejad, Bakeri, Ghasemi, & Zirepour, 2014). A schematic representation of a
51 polymeric membrane and principle of use is represented in Figure 1 (a). The feed solution
52 (which contains the species to be removed) passes through the membrane and the
53 impurities are retained at the surface of the material. The separation occurs due to the
54 average diameter of pores which do not allow the species over a certain dimension to
55 pass.(Li et al., 2014) As a function of species dimensions, there are several known
56 membrane processes that include conventional filtration, microfiltration, ultrafiltration,
57 nanofiltration and reverse osmosis. In terms of water purification, the main role of each
58 process can be summarized as following:
59
60 Conventional filtration membranes separate eye-visible particles, like sand particles;
61 Microfiltration membranes separate particles with dimensions between 0,1 and 10 m, like
62 microorganisms;
63 Ultrafiltration separate membranes particles with dimensions between 10-1000 , like

64 macromolecules or colloids;
65 Nanofiltration and reverse osmosis membranes separate salts and ions.
66
67 Due to their unique property of selective separation, the membranes have found their use
68 in various domains like biomedicine, food industry, electronics, and sensors (Stamatialis et
69 al., 2008; Sivakumar et al., 2014; Jiang, 2014). In biomedicine, they are used as controlled
70 drug delivery systems(Stamatialis et al., 2008) osmotic systems(Wright et al., 2001),
71 transdermal patches(Guy, 1996) or ocular patches(Jain, Carvalho, & Banerjee, 2010) or
72 artificial organs as replacements for kidney(Sasaki, 2006) in the case of patients with
73 chronic kidney disease, artificial liver or lung(Kobayashi, Okitsu, Nakaji, & Tanaka, 2003).The
74 use of technical polymers in the preparation of membranes is preferred due to the
75 versatility in the properties of these polymers. Intensively studied polymers for the
76 membrane preparation includepolysulfone, polyether sulfone, polyethylene, polyimide,
77 poyetherketone, polyphenylene oxide and polyphenylene sulphate (Akther et al., 2015;
78 Choudalakis & Gotsis, 2009; Ravanchi, Kaghazchi, & Kargari, 2009; Pendergast & Hoek,
79 2011).
80 Synthesis of polymeric membranes

81 There are several methods that can be effectively used for the synthesis of polymeric
82 membranes, the most important being the precipitation of the polymer from a polymeric
83 solution film in the presence of a non-solvent for the polymer totally miscible with the
84 polymer solvent (Voicu et al., 2007). This process is called phase inversion technique and has
85 a significant importance because of the type of membranes that are obtained during this
86 technique. Depending on the geometry of pores, the membranes can be classified in
87 symmetric and asymmetric (Voicu et al., 2009). The symmetric membranes have cylindrical
88 pores with a poor value in separation techniques. The asymmetric ones have pores with
89 conic geometry and are the most suitable for separation processes. At asymmetric
90 membranes, during the formation of porous polymeric film, large quantities of polymers are
91 concentrated at the top surface of the membrane, with very small pores. This layer being
92 the active layer of the membrane play a crucial role in the separation process. The active
93 layer is very resistant at pressure and is sustained by large porous support layer. The
94 geometry in section of an asymmetric and a symmetric membrane is presented in Figure2
95 (Baicea et al., 2011); Voicu, Aldea , & Nechifor 2010) .
96
97 Composite membranes
98 For improving the separation performances, one of the foremost possibilities refers to the
99 synthesis of composite membranes (Luntraru et al., 2011. The fillers(graphene, carbon
100 nanotubes, magnetic particles, fullerenes, TiO2, zeolites, etc.) which are added to the
101 polymer play an active role in the separation process (Cho et al., 2014; Jafarzadeh, Yegani, &
102 Tantekin-Ersolmaz, 2015;Chen, Hong, & Gao, 2015). In this case, the membrane act more as
103 a support, membrane pores facilitating the access of solute to active separation centres of
104 filler. Another types of composite membranes can be obtained by coating a membrane
105 support with a very thick film which acts as an active layer. The advantage of this method is
106 given by the fact that the coating can be usually crosslinked, so the resulting material can
107 also be used for the filtration of solutions made in organic solvents (solvent resistant
108 nanofiltration membranes) (Corobea et al., 2015;Rusen et al., 2014;Ionita, Vasile, et al.,
109 2015;Voicu et al., 2013).The parameters which give the efficiency of membrane associated
110 to a separation membrane process are water (solvent) flux and retention. The water flux is
111 the quantity of water that can pass through the membrane in time. It is usually expressed in
112 L/m2h and indicates for which membrane processes, the porous obtained material is more
113 suitable (microfiltration, ultrafiltration, nanofiltration or reverse osmosis).Retention
114 expresses the capacity of membrane to retain on its active layer and the solute represents
115 the percent from total amount of solvent which is separated by the membrane. It is
116 calculated with the following formula:
117
Ci Cf
118 C % *100
Ci
119
120 where Ci is the concentration in permeate, andCfis concentration in retentate. The

121 determination ofCi, respectively Cf is determined by UV-Vis spectroscopy (Voicu,
122 Ninciuleanu, Muhulet, & Miculescu, 2014;Voicu, Dobrica, Sava, Ivan, & Naftanaila, 2012).
123 During the last few years, the researchers interest inbiobased and renewable polymers
124 hasincreased continuously and is also being proven by the number of documents indexed in
125 Scopus database forcellulose and chitosan during last 25 years (Figure 3) (Li et al., 2014).
126 This is justified by the abundance of these polymers and their natural sources (in
127 comparison with technical polymers, only if we are referring to cellulose and its derivatives,
128 the resources are practically unlimited,51011 tons being generated annually in the
129 biosphere(Voicu et al., 2014;Voicu et al., 2012)and to their impact to environment which is
130 much limited that in the case of technical polymers (including manufacturing processes and
131 degradation)(Thakur, Singha, & Misra, 2011;Singha & Thakur, 2010b;Singha & Thakur,
132 2009;Singha & Thakur, 2008a;Singha & Thakur, 2010a).In this article, we briefly present
133 some of the recent advances in developing polymeric composite membrane materials for
134 water purification from biobased and renewable polymers, like cellulose and chitosan. The
135 influence of different synthesis conditions and nature of fillers to water flux and retention
136 arealso presented and discussed.
137
138 2. Different Biobased Polymers for Membrane Applications

139 Different kinds of bio-based polymers are currently being explored for usage in membrane
140 applications. The prime reason for use of biobased polymers in any applications lies in their
141 environmental friendly advantages along with easy availability, biodegradability and low
142 cost to name a few (Thakur & Thakur, 2014a;Thakur, Thakur, & Gupta, 2014;Thakur,
143 Thakur, & Gupta, 2013b). In the following section, different bio-based polymers used in
144 membrane technology are discussed.
145
146 2.1 Cellulose based Membranes
147 Cellulose is the first most abundant polymers on the earth. It is the prime constituent of all
148 natural fibres (Figure 4) and primarily exists in two form namely cellulose I and II (V. K.
149 Thakur, Thakur, & Gupta, 2013a;Thakur & Singha, 2010;Singha & Thakur, 2008b). It is a non -
150 branched polysaccharide that is composed of D-anhydroglucopyranose units. These units
151 arejoined by -1, 4-glycosidic bonds (Figure5) (Pinkert, Marsh, Pang, & Staiger, 2009;Thakur,
152 Thakur, & Gupta, 2013c;Dhakal, Zhang, Bennett, Lopez-Arraiza, & Vallejo, 2014).Non
153 dissolution of cellulose in common organic solvents has been one of its biggest
154 disadvantages(Dhakal et al., 2015). Several solvents have been explored for its dissolution
155 but only few have shown a potential in this direction. In fact, the dissolution of cellulose is
156 must for carrying out its functionalization. Figure 6summarizes some of the solvents used in
157 the cellulose processing(Heinze & Liebert, 2001). Cellulose and cellulose derivatives are
158 among the most intensively studied natural source polymers for membranes preparation.
159 The properties of these membranes can be manipulated by several techniques like selection
160 of the polymer, solvent and non-solvent, thickness of the polymer solution film at the
161 precipitation of the membrane, addition of surfactants at the polymer solution or fillers for
162 composite membranes synthesis(Voicu, Muhulet, Antoniac, & Corobea, 2015). Different
163 morphologies for cellulose acetate (CA) membranes obtained from polymeric solution films
164 with thickness of 100 m, 200 m, 300 m or from polymer solution with surfactants
165 (dimethyl-dioctodecil ammonium bromide, alkyl-benzyl-dimethyl ammonium chloride, N-
166 dodecyl-pyridinium chloride) confirmed the changes in their morphology. The polymer
167 solution (12% wt.) was prepared in N, N-dimethylformamide. This type of pores
168 recommends the membranes for microfiltration and ultrafiltration processes, suitable for
169 proteins or macromolecular compounds separations. For improving salts rejection, an
170 elegant solution is the synthesis of composite cellulose acetate membranes with different
171 fillers, like carbon nanotubes (CA-MWCNT) or graphenes (CA-GO). The rejection mechanism
172 is based here on the adsorption of ions at the surface of fillers. Results obtained for Bovine
173 Serum Albumine (BSA) and NaCl rejection in different cellulose acetate membranes are
174 presented in Table 1. Carbon nanotubes and graphene oxide were added at polymer
175 solution at a 0.75, 1.5, 3% wt. concentration related to polymer. The thickness of the
176 polymer solution film for composite membrane was 200 m and retention tests were
177 performed during 120 min.Higher values for carbon nanotubes and graphene oxide can be
178 explained by smaller dimension of pores and high capacity for adsorption at the surface of
179 different chemical species via weak chemical interactions between delocalized electrons
180 from their surface and electrons from solute molecules(Voicu, Muhulet, Antoniac, &
181 Corobea, 2015).
182 2.1.1. Synthesis methods for cellulose based composite membranes
183 Two main methods are frequently used for preparing composite membranes: dispersion of
184 filler in polymer solution, or mixing a polymer solution with a filler dispersion and interfacial
185 polymerization (Rong et al., 2016); Tianyi et al., 2016).Polyvinyl alcohol/carboxymethyl
186 cellulose sodium blend composite membranes were obtained by interfacial polymerization
187 occurring between polyvinyl alcohol,carboxymethyl cellulose, sodium blended and 1, 6-
188 hexamethylene diisocyanate(Miao, Zhang, & Bai, 2015). The obtained composite membrane
189 was found to exhibit a negative charge and the contact angle of the membrane was found
190 to decrease with the extent of surfactant concentration as well as concentration of PVA and
191 CMC-Na. Subsequently 5mM concentration inorganic electrolyte solution was used to study
192 the permeation of the obtained PVA-CMC/PS membranes. The rejection degrees shown by
193 membranes for different salts were 93.7% for Na2SO4, 32.6% for NaCl, 24.5% for MgSO4,
194 respectively 8.6% for MgCl2. These values recommended the use of such type of membranes
195 for partial desalination process, due to the proper balance between water flux and salt
196 rejection.
197
198 2.1.2. Fillers for cellulose based composite membranes
199 From a wide variety of used fillers for developing composite membranes with application in
200 water purification, carbon nanotubes, graphene, silver nanoparticles or alginate has
201 attracted a special attention from researchers due to their improvement on membranes
202 properties (Miculescu, Thakur, Miculescu, & Voicu (2016). Among various nanomaterials,
203 carbon nanotubes are one of the most used chemical species for reinforcement of the
204 composites membranes, but are also used for their high capacity of adsorption at the
205 surface of a wide range of molecules (Miculescu, Muhulet, Nedelcu, & Voicu, 2014;
206 Nechifor, Voicu, Nechifor, & Garea, 2009; Balacianu, Nechifor, Bartos, Voicu, & Nechifor,
207 2009). Composite membranes based on cellulose acetate and polyethylene glycol with
208 multi-walled carbon nanotubes (MWCNTs) were used for NaCl rejection from salt water
209 (Sabir et al., 2015). The CNTs in this work were surface modified in strong acid medium to
210 make the multi-walled carbon nanotubes more compatible with polymer solution. Figure 7
211 shows the scheme for the surface modification of MWCNTs. These surface modified
212 MWCNTs were then uniformly dispersed in the loading percentage from 0.1 to 0.5% in the
213 solution of cellulose acetate/polyethylene glycol (CA/PEG400) to synthesize themembrane
214 using dissolution casting method (Figure 8). These synthesized membranes were thoroughly
215 investigated for their structural analysis using atomic force microscopy (AFM), Fourier
216 transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA),and scanning
217 electron microscopy (SEM) respectively. Figure 9 shows the AFM images of the membranes.
218 It was concluded from these characterizations that the modified MWCNTs were successfully
219 tethered in CA/PEG400 membrane. These nanocomposite membranes were then subjected
220 to permeation flux and salt rejection study in an effort to analyse their suitability in drinking
221 water treatment. For the composite membrane with 0.5 carbon nanotubes, the salt
222 rejection was 99.8% (from a saline solution with 1000 ppm NaCl) with a flux decrease of only
223 0.61 L/m2h (from an initial 25 L/m2h). Similar rejection degrees, around 98-99% were
224 achieved for other cellulose acetate-carbon nanotubes composite membranes (El-Din, El-
225 Gendi, Ismail, Abed, & Ahmed, 2015). In this work, the phase inversion technique was use to
226 prepare cellulose acetate (CA)/carbon nano tubes (CNTs) membranes. Different types of
227 membranes were prepared by dispersing diverse ratio of CNTs in the polymer solution. In
228 addition to study the effect of CNTs loadings, the effect of amount of polymer to solvent
229 was also studied. These membranes were then thoroughly characterized using scanning
230 electron microscopy and thermogravimetric analysis (TGA) and were usedin water
231 desalination studies. Along with the amount of CNTs, the concentration of polymer also
232 played a significant role in determining the overall performance of the membrane. The salt
233 rejection was found to be enhanced to 96% by the presence of CNTs due to the formation of
234 macro voids as well as the porous structures. It also lead to the significant improvement in
235 the pure water flux. Cellulose acetate-carbon nanotubemembranes were prepared for the
236 water filtration applications(El Badawi, Ramadan, Esawi, & El-Morsi, 2014). In this study,
237 membranes were fabricated employing phase inversion using multi walled carbon nanotube
238 in different ratios (0.0005 wt. % and 0.005 wt. %) of CNTs using 20 wt. % deionized water
239 asnon-solvent while acetone as the standard solvent. The functionalization of the CNTs was
240 also carried out in a strong acidic medium to have the uniform dispersion of CNTs within the
241 polymer matrix. Small amounts of the functionalized CNTs, namely 0.0005, 0.005, and 0.01
242 wt. % were used to prepare the membranes. The CNTs were randomly oriented and
243 uniformly dispersed within the membranes. Membranesmorphologies were investigated
244 using field emission scanning electron microscopy (FESEM) &nitrogen adsorption. A
245 decrease in the number of macro voids with increase in CNTs content was observed. Pore
246 sizes analysis was used to further verify this. Nanocomposite membrane permeation rates
247 and salt retention rates were studied employing a 1000 ppm NaCl solution. It was found
248 that the permeation rates increases to 54% with the lowermost CNTs content. Further
249 addition of CNTs was found to result in the reduction in permeation rates. Functionalization
250 of multi-walled carbon nanotube in an acid mixture of nitric and sulfuric acids was carried
251 out to prepare the blended cellulose acetate (fCNT-CA) membranes for application in
252 forward osmosis (FO) (Choi et al., 2015). Prime motive to carry out the functionalization in
253 such a strong acid was to improve the dispersion of the CNTs in the organic solvents.The
254 membranes were synthesized employing phase inversion and were characterized
255 throughFTIR, SEM, and water contact angle measurement. FTIR results clearly indicated the
256 hydrogen bonding interactions between the functionalized CNTs and the polymer. AFM
257 studyused to investigate alginate fouling mechanism revealed that the incorporation of the
258 fCNTsresults in increment in the alginate fouling resistance in FO (57% less normalized water
259 flux decline for 1% fCNT-CA membrane was observed than that for bare CA membrane). This
260 behaviour was attributed to the enhanced electrostatic repulsion among the CAmembranes
261 and the alginate. The water permeated flux and membrane hydrophilicity was also found to
262 be enhanced as a result of the carboxylic groups in the functionalized CNTs. This
263 functionalization resulted in 50% higher water-permeated flux in comparison to the pristine
264 CA membrane. It was concluded in this study that under fouling reduction consideration,
265 these membranes have high potential to be used in pre-treatment processes prior to the
266 desalination and wastewater treatment.
267 The mechanical/ thermal properties of composite membranes (cellulose/carbon nanotubes)

268 were further improved by adding another compatible polymer with the entire mixture
269 chitosan (Xiao et al., 2013). Instead of the traditional common organic solvents, in this study
270 authors had used ionic liquids namely 1-butyl-3-methylimidazolium chloride and 1-H-3-
271 methylimidazolium chloride. These ionic liquids were used to dissolve and disperse
272 themultiwalled carbon nanotubes (MWCNTs), chitosan and cellulose together. This mixture
273 was subsequently used to synthesize chitosan/cellulose/MWCNT composite membranes as
274 well asfibers. These membranes were investigated employing characterization techniques
275 such as thermogravimetric analysis,tensile testing, Fourier transform infrared spectroscopy,
276 wide-angle X-ray diffraction, scanning electron microscopy, and conductivity measurements
277 in order to investigate their different properties. The effect of the incorporation of various
278 loadings of MWCNTs on the membrane properties was also studied and it was found that
279 the addition of MWCNTs significantly improved the comprehensive performances with 4 wt
280 % MWCNTs giving the best results.
281 Composite membranes based on cellulose derivatives with graphenes have been
282 synthesized for optoelectronic applications using carboxymethyl cellulose (Wang, Feng, &
283 Zhan, 2014), high metal absorbtion(Zhang et al., 2014), flexible transparent conductive
284 paper using cellulose nanofibers (Gao et al., 2013) and flexible conductive film using
285 bacterial cellulose (Feng, Zhang, Shen, Yoshino, & Feng, 2012). For potential water
286 purification, cellulose triacetate/graphene oxide porous composite membranes were
287 synthesized using different loading of graphene oxide (0.25, 0.5, respectively 1% wt. related
288 to polymer) (Ionita, Crica, Voicu, Pandele, & Iovu, 2015). The membranes were synthesized
289 by the dispersing the graphene oxide in polymer solution under sonication, followed by the
290 membranes precipitation in water. With the increase of graphene oxide loading, the water
291 flux decreases due to the changes in membranes pore size and distribution, but the
292 retention of Bovine Serum Album increase from 78% to 99%. A cellulose acetate membrane
293 was also used to obtain a polymer-free graphene paper through a transfer process by
294 carbon vapour deposition onto the flexible polymeric membrane (Shinde et al., 2015). The
295 graphene film at the surface of cellulose acetate membrane was highly conductive having
296 huge potential to use the manufacturing of paper base electronics or separation of large
297 amount of heavy metals from various solutions.
298 Potential antibacterial properties of cellulose acetate asymmetric membranes by

299 incorporating silver nanoparticles were also studied (Sonawane, Terrien, Figueiredo, Clara
300 Gonalves, & De Pinho, 2015). The polymer nanocomposite membranes were obtained
301 usingcelulose acetate/acetone/formamide at a ratio 1.44:2.77 acetone: formamide. The
302 incorporation of silver nanoparticles in the CA membranes was ascertained by comparing
303 the FTIR spectra of the pristine CA and the Ag reinforced CA membranes. The presence of
304 silver nanoparticles in the membrane was found to result in an enhancement in hydraulic
305 properties. With the variation in the pore size and pH of the membrane, the surface charge
306 of the mixed CA membrane was also found to be varied.
307
308 2.1.3. Applications of cellulose based composite membranes for water purification
309 One of the possibilities in water purification using membranes techniques consist of the
310 removal of pure water instead of impurities. Highly compact poly (ethylene-co-vinyl
311 acetate)/cellulose membranes were synthesized using cellulose whiskers from banana fibers
312 and commercial poly (ethylene-co-vinyl acetate) from tetrahydrofuran by solvent
313 evaporation(Elanthikkal, Francis, Unnikrishnan, Varghese, & Guthrie, 2012). Water vapours
314 were separated from different mixtures with carbon tetrachloride (CCl4), chloroform (CHCl3),
315 and dichloromethane (CH2Cl2) and their vapor permeation characteristics were investigated
316 in detail. Composite membranes were prepared using different content (18 % & 40 %) of
317 poly (ethylene-co-vinyl acetate) (EVA) and cellulose that was extracted from banana waste
318 fibers. Polymer composite membranes with 40 % loading of poly (ethylene-co-vinyl acetate)
319 (EVA) were found to exhibit more permeating in comparison to the18 % loaded membranes
320 and this behaviour was attributed to the added amorphous nature of EVA40. The barrier
321 properties of EVA were also found to be enhanced by the incorporation of cellulose. On the
322 same principle, polyether sulfone (PES) membranes were coated with a thick layer of
323 cellulose acetate (CA)/poly (ethylene glycol) for removal of water vapours from H2O/N2
324 mixture(Kim et al., 2015). After the incorporation of poly (ethylene glycol), the water
325 vapours permeation through membrane increased significantly due to the changes in
326 polymer chain mobility as a result of the total free-volume increase. In comparison to the
327 PES/CA composite membrane, the addition of poly (ethylene glycol) in the CA solution
328 resulted in the improved performance of the hollow fiber membranes.
329 Electrospuncellulose acetatecomposite membranes with AgCl were used for photocatalytic
330 degradation of organic dyes (methylorange) from water under visible-light irradiation(Zhou
331 et al., 2016). A double diffusion technique was used to prepare the CA membranes with
332 Ag@AgCl crystalsat room temperature.Figure 10shows the schematic illustration of AgCl
333 crystals grown in situ on electrospunfibers. Different characterization techniques like X-ray
334 photoelectron spectroscopy measurements (XPS), X-ray powder diffraction (XRD),
335 attenuated total reflection-infrared intensity (ATR-IR), scanning electron microscopy (SEM),
336 ultravioletvisible (UVvis) diffuse reflectance spectra and energy dispersive spectrometer
337 (EDS) were used to investigate the morphology, crystal structure, composition, and
338 absorption light ability of the cellulose acetate supported Ag@AgCl. Figure 11shows the
339 SEM images of the studied crystals. Different types of crystals were investigated and it was
340 shown that cubic crystals can provide a much higher photocatalytic activity in comparison to
341 the octahedron crystals due to the semiconductor excitation and surface transfer of the
342 induced charge carriers.
343 For inducing a hydrophilic character to polysulfone(PSf) porous membranes, a cellulose-

344 based amphiphilic co-polymer with grafted myristyl groups was used as filler for a
345 polysulfone membrane(Zhong, Gao, Li, & Zhang, 2015). It was shown that there is a good
346 compatibility between the two polymers and the presence of amphiphilic cellulose increases
347 the water flow of the polysulfone membrane from 160 to 850 L/m2h (at a loading of 15%
348 amphiphilic cellulose) and the rejection capacity for Bovine Serum Albumin at 99% (at a
349 loading of 5% amphiphilic cellulose). Differential scanning calorimetry (DSC) was used
350 successfully to confirm the compatibility between amphiphilic cellulose and
351 polysulfone(PSf). It was concluded from the study that retention capacity and hydrophilicity
352 of the membrane can be significantly improved by the addition of a definite amount of
353 amphiphilic cellulose. Another composite membranes based on polyether sulfone were
354 prepared with cellulose acetate by dissolving both polymers in N, N-dimethylformamide
355 followed by the precipitation through phase inversion(Mahendran, Malaisamy, & Mohan,
356 2004). The maximum value for water flux was achieved in the case of composite membrane
357 with 75% cellulose acetate and 25% polyether sulfone 275.7 L/m2h. It was observed in this
358 study that blending of polyether sulfone and cellulose acetate results innew membranes
359 with enhanced ultrafiltrationcharacteristics especially lower Rmvalues associated with higher
360 pure water flux and higher water content. Another study performed on composite
361 membranes using amphiphilic cellulose as filler for a polysulfone membrane have also
362 shown the same conclusion, that with the increase of amphiphilic cellulose, the water
363 permeability of the membrane increases(Gao, Li, Zhong, Zhang, & Ding, 2014). In this work,
364 successful synthesis of nano-cellulose-based amphiphilic copolymer cellulose-graft-myristyl
365 was accomplished using a facile reaction and was successfully used as an additive in the
366 composite membranes from polysulfone (PSf). The dimensions of the amphiphilic cellulose
367 was determined using transmission electron microscopy (TEM) while its presence in the
368 polymer composite membranes was established using FTIR. With the increment in the
369 amount of amphiphilic cellulose, the water flux of the PSf membranes was found to be
370 increased. More than that, the amphiphilic cellulose improvesthe mechanical and thermal
371 properties of the initial polysulfone membrane due to the compatibility of the two polymers
372 at the synthesis of the membrane.
373 Cellulose nanofibers from the skin of beavertail cactus were used as reinforcement fibers for
374 polyvinyl alcohol by solvent evaporation from a solution in water of two polymers(Ramezani
375 Kakroodi, Panthapulakkal, Sain, & Asiri, 2015). The cellulose nanofibers in this work were
376 isolated from the skin of the beavertail cactus, OpuntiaBasilaris, employing chemo-
377 mechanical technique and were found to contain a high amount of cellulose in comparison
378 to the lignin. The content of cellulose fibres seriously improved the mechanical and thermal
379 properties of the polyvinyl alcohol membranes, but do not prove a significant advantage for
380 the separation properties of the composite membranes.
381 A composite membrane based on bacterial cellulose with alginate was developed for
382 separation of ethanol-water mixtures(Suratago et al., n.d.). Due to the azeotrope nature of
383 this mixture, the conventional distillation was impossible for realizing the separation of the
384 mixture components. The membrane was prepared by impregnation of a bacterial cellulose
385 hydrogel (BC) with sodium alginate followed by crosslinking with calcium chloride solution.
386 The hydrogel in this study was modified via impregnation by diffusion of sodium alginate
387 and cross-linking with calcium chloride solution. BC/alginate (BCA) membranes were
388 configured, characterized, and used for pervaporation of mixtures of ethanolwater.The
389 total permeate flux of water through membrane was measured at 33g/m2h, the average
390 pore size of the membrane being 27.7 (Suratago et al., n.d.). In another study, calcium
391 carbonate was used as inorganic filler in the direction of preparation of robust
392 membranes(He, Cho, & Won, 2016). The composite membranes were prepared using
393 cationic starch (C-starch), precipitated calcium carbonate (PCC) and cellulose nanofibrils
394 (CNF). The cellulose nanofibrilsin this work were used in two different forms to reveal their
395 effects on filler retention, flocculation, and the strength/ optical properties of the resulting
396 hand sheets. Although the paper filled with the precipitated calcium carbonate
397 (PCC)&cellulose nanofibrils (CNF)fillers exhibit more bursting and tensile strengths in
398 comparison to the conventional PCC loading, but the membranes did not showed
399 remarkable increasing properties useful for separation processes(He et al.,
400 2016).Biodegradable and recyclable ultrafiltration(UF) membranes were also prepared for
401 filtration application(Varanasi, Low, & Batchelor, 2015). These membranes in this study
402 were based on cellulose nanofibers and silica nanoparticles (with an average diameter of
403 22nm) and were synthesized using polyamide-amine-epiclorohydrin(PAE). Figure 12shows
404 the synthesis of the membranes. The role of the nanoparticles in this work was to act as
405 spacer in order to control nanofibrepore size. Figure 13 shows the mechanism of the silica
406 nano particle bridging between the nanofibres. The membranes in this study presented a
407 rejection degree for 300 kDa polyethylene glycol of 40%.The recyclability of the membranes
408 was studied and the performance of the resulting membranes was also compared with the
409 previously published work (Ma, Burger, Hsiao, & Chu, 2014;Viswanathan et al., 2006;Ma,
410 Burger, Hsiao, & Chu, 2012;Wang et al., 2005). It was demonstrated in this work that using
411 thenano particles, the pore size of the membranes can be easily controlled.
412 The retention of heavy ions from aqueous solution was also realized with cellulose
413 triacetate/silica composite membranes(Srivastava, Thakur, & Shahi, 2016). Acid catalyzed
414 solgel method was used to synthesize the phosphorylated cellulose triacetate (CTA)/silica
415 composite by using (3-aminopropyl triethoxysilane (APTEOS) as the inorganic precursor. The
416 studied heavy ions were Cu2+, Ni2+, Cd2+ and Pb2+. It was observed that silica particles used
417 as filler showing very good results in retention of these ions(Srivastava et al., 2016). The
418 antibacterial properties for cellulose derivatives based membranes were enhanced by
419 preparing a silver sulfadiazine loaded bacterial cellulose/sodium alginate composite
420 membrane(Shao et al., 2015). The membrane was obtained from a homogenous dispersion
421 in water of the components by a freeze-dried process at -40oC for 10 hours. The membrane
422 exhibited very good antibacterial properties for Escherichia Coli and Staphylococcus Aureus.
423
424 2.2 Chitosan based Membranes
425 Along with cellulose, chitosan is another most important biorenewable polymer that is
426 extensively being used in a number of applications (Thakur, Gupta, & Thakur, 2014;Thakur &
427 Thakur, 2014b;Wu, Hsu, Liao, & Cai, 2015). It isbiocompatible, non-toxic and biodegradable
428 in nature (Anitha et al., 2014;Wang et al., 2014). Chitosan (CS) is generally obtained from
429 chitin (CH) by the deacetylation reaction. Chitin is a natural polysaccharide that is consist of
430 unbranched chains of -(14)-2-acetoamido-2-deoxy-D-glucose(Antunes, Moreira, Gaspar,
431 & Correia, 2015). Figure 14 shows the structure of chitin & chitosan while Figure 15shows
432 the processing of CH and CS into different forms(Anitha et al., 2014).We have recently
433 summarized the different properties of chitosan based materials so will not be discussing
434 the properties in this section(Thakur & Thakur, 2014b). In addition to biomedical
435 applications of chitosan, itsuse also is being explored in membrane field (Song, Gao, Cheng,
436 & Xie, 2015;Chatterjee & Judeh, 2015).
437 2.2.1. Synthesis methods for chitosan based composite membranes
438 In comparison with cellulose derivatives which are soluble in a wide range of organic
439 solvents mixtures, chitosan is soluble in water with a small amount of acetic acid (Thakur &
440 Thakur, 2014b). This restricts the synthesis of composite membranes to blending method, or
441 dispersing the filler into a polymer solution. The process can be improved by the use of
442 surfactants, making more easy the dispersion phenomena and membrane synthesis by any
443 of known methods (casting or solvent evaporation) (Liu et al., 2016; Ding et al., 2015; Rassu
444 et al., 2016). Chitosan is the second most important biopolymers next to cellulose and is
445 used in wide range of applications.
446 For the advanced separation of heavy ions from aqueous solutions, composite nanofibers
447 chitosan/MWCNT/Fe3O4 were developed for the removal of Cr (VI)(Beheshti, Irani, Hosseini,
448 Rahimi, & Aliabadi, 2016). The nanofibrous composites were prepared by electrospinning
449 process and were characterized using TEM, SEM, XRD and FTIR analysis. A batch system was
450 used to study the effects of different sorption parameters namely temperature, initial
451 concentration and contact time. Langmuir isotherm models along with the pseudo-second-
452 order kinetic were used to analyse the equilibriumand kinetic data in this work. The
453 maximum retention of Cr (VI) was achieved at equilibrium time of 30 min, pH of 2 and
454 temperature of 45oC and had the value of 360.1 mg/g. Another interesting research
455 reported the synthesis of polyacrylamide-chitosan as coating for magnetite nanoparticles as
456 well as for the removal of heavy ions from aqueous solutions (Li et al., 2015). At a pH of 5,
457 the effective values of separation were 43.35 mg/g for Cu2+, 63.67 mg/g for Pb2+ and 263.9
458 mg/g for Hg2+. Despite the high costs for synthesizing these composites, for an advanced
459 decontamination of water, the material justified its synthesis.
460
461
462 2.2.2. Fillers for chitosan based composite membranes
463 Due to the versatility of synthesis methods, any kind of fillers can be used for the synthesis
464 of chitosan based composite membranes, like carbon nanotubes (Mohammadi et al., 2015;
465 Qi et al., 2015); graphene (Shirdast , Sharif , &Abdollahi M. (2016); or silica nanoparticles
466 (Lee , & Kim 2016).
467 For improving the fouling properties (i.e. fouling resistance), chitosan/graphene oxide
468 composite thin layer was coated on the surface of brackish water (BW30LE) thin-film
469 composite (TFC) membrane(Hegab, Wimalasiri, Ginic-Markovic, & Zou, 2015). In this work,
470 chitosan was functionalized with graphene (GO/f-Cs) and was applied as the modified layer
471 on (BW30LE) thin-film composite (TFC) membrane. Figure 16 shows the mechanism for
472 chemical reaction between graphene and chitosan while Figure 17 shows the schematic
473 diagram for reverse osmosis (RO) cross-flow setup. All the membranes samples including
474 the pristine and functionalized ones were thoroughly characterized using UV
475 spectrophotometer, contact angle, ATR-FTIR, scanning electron microscope and atomic
476 force microscopy. The modified membrane exhibited a water flux of 61.5 L/m2h (in
477 comparison with 56.1 L/m2h for unmodified commercial membrane) and a salt rejection of
478 95.6% (in comparison with 88.7) for NaCl. The higher rejection degree was attributed to the
479 more pronounced compactness of the composite chitosan active layer, this being the reason
480 also for the improvement of antifouling properties.
481
482 2.2.3. Applications of chitosan based composite membranes for water purification
483 Solvent resistant chitosan/poly(ether-block-amide) composite membranes were synthesized

484 by depositing a layer of chitosan onto a poly(ether-block-amide). Chitosan layer was
485 crosslinked with tetraethylorthosilicate and used for the pervaporation of n-methyl-2-
486 pyrrolidone/water mixtures (Prasad, Moulik, Bohra, Rani, & Sridhar, 2016) (Figure 18).
487 Tetraethyl orthosilicate (TEOS) was used to crosslink the composite barrier in order to have
488 control over the swelling characteristics as well increase the selectivity. To investigate the
489 selectivity and membrane flux, different parameters such as membrane thickness, permeate
490 pressure and feed water concentration were varied. The water flux for unmodified chitosan
491 was established at 0.024 kg/m2h and for the crosslinked chitosan was established at 0.019
492 kg/m2h, the selectivity of membranes for water being 182, respectively 225.Table 2
493 compares the performance of the studied membranes with that of the earlier reported
494 literature (Ghosh, Pradhan, & Adhikari, 2006;Tsai, Chen, Lee, & Lai, 2012;Sato et al.,
495 2012;Sunitha, Yamuna Rani, Moulik, Satyanarayana, & Sridhar, 2013). In addition to the
496 experimental study, theoretical studies were also carried out to predict the concentration
497 profile of the membrane.
498 Also the pervaporation characteristics of ethanol/water mixtures were studied using
499 different chitosan membranes(Uragami, Saito, & Miyata, 2015). Effect of deacetylation
500 degree as well as molecular weight of chitosan membranes on the characteristics
501 dehydration behaviour of ethanol/water was studied. It was concluded in this study that the
502 pervaporation rate decreases with increase in molecular weight up to 90 kDa, but over this
503 value, the pervaporation rate still increased. These observations are important for the
504 development of composite membranes with chitosan layer for different pervaporation
505 applications, especially in food industry for the manufacturing of alcohol free beer. In this
506 study, the different characteristics of chitosan membranes were also analysed w.r.t.
507 theirphysico-chemical characteristics namely the density, glass transition temperature,
508 contact angle, and degree of swelling.
509 For the removal of salts from water, chitosan was also used as coating layer for poly (1,4-
510 phenylene ether ether sulfone) PPEES membranes(Shenvi, Ismail, & Isloor, 2014). In this
511 work, the active chitosan layer of the membrane was crosslinked with sodium
512 trypolyphosfate(TPP), the crosslinking reaction being more effective in acidic media than
513 alkaline. SEM and EDX was used to study the cross sectional images and morphology of the
514 prepared membranes (Figure 19). In addition to SEM and EDX, infrared (IR) spectroscopy
515 also confirmed the crosslinking of surface of chitosan with sodium tripolyphosphate (TPP).
516 Water uptake studies, water flux and contact angle measurement were used to study the
517 changes in the surface of PPEES membrane as a result of chitosan crosslinking. The rejection
518 degrees were established at 55% for MgSO4 and 21% for NaCl. Despite the lower values of
519 separation process, these could be preferable in the case of partial desalination processes.
520 In order to removethe organic dyes from water, composite membranes of chitosan-cellulose
521 nanocrystals were synthesized through a freeze-dried technique followed by
522 compacting(Karim, Mathew, Grahn, Mouzon, & Oksman, 2014). Different characterization
523 techniques such as scanning electron microscopy (SEM) and Brunauer, Emmett and Teller
524 (BET) were used to study the nano-porous structure of the membranes. Thesynthesized
525 membranes successfully removed 98%, 84% and 70% respectively of positively charged dyes
526 like Victoria Blue 2B, Methyl Violet 2Band Rhodamine 6G, after a contact time of 24 h. The
527 outstanding performance of these membranes was attributed to the freeze-drying process
528 that resulted in well individualized CNCs. These CNCs subsequently act as functional entities
529 that are loosely bound together by chitosan polymer chains.
530
531 Conclusions and future perspectives

532 Applications and recent advances of composite membranes from biobased renewable
533 polymers (cellulose and chitosan) for water purification were briefly and systematically
534 presented in this article. The used synthesis methods varied from blending the components
535 (polymer-polymer composites) to interfacial polymerization (coating layer for a commercial
536 membrane) and fillers from silver nanoparticles to carbon nanotubes, graphenes, or
537 alginate. The compactness of majority of the presented membranes has been found to be
538 suitable for the retention of salts or organic compounds. Different types of membranes
539 reported in this study were recommended for ultrafiltration and nanofiltration membrane
540 processes. The interfacial polymerization allows the synthesis of active coatings for
541 ultrafiltration or microfiltration commercial membranes with the imperative advantage of
542 increasing the chemical resistance by crosslinking. Using this technique, a porous
543 microfiltration membrane is transformed into a solvent resistant nanofiltration one with
544 good performances in the domain of salts rejection. However, the biggest advantage of
545 these polymers can be justified by their easy availability, natural sources, abundance and to
546 their minimum impact on the environment which is much limited that in the case of
547 technical polymers (including manufacturing processes and degradation).
548 In the context and trend of lower impact of human activities to the environment, the use of
549 naturally source polymers for manufacturing membranes has become a major achievement.
550 The resistance and life cycle of biobased polymeric membranes at continuous use is lower in
551 comparison with technical polymers (like polysulfone or polyether imides), but the
552 resources are practically unlimited and the wastes can be easily re-processed (even in the
553 case of composite membranes, by dissolving the membrane in a proper solvent, both
554 polymer and filler can be recovered). Another huge advantage is given by the hydrophilicity
555 of cellulose and chitosan which assure higher fluxes for water (several times higher than in
556 the case of technical polymers) with best efficiency for separation process.
557 A future trend will be given by the incorporation of functionalized or derivatized nanofillers
558 (like carbon nanotubes or graphene derivatives) with enzymes, crown ethers,
559 macroheterocyclic compounds. This will allow the possibility to separate chemical species
560 which will interact chemically with the filler, species heavy to separate at this moment, but
561 representing a real problem for life quality (hormones, active pharmaceutical compounds,
562 organic pollutants, small amounts of heavy metals).
563 Another way to improve separation properties and selectivity of composite membranes will
564 be given by the use of surfactants at membranes synthesis that will also allow a better
565 dispersion of fillers inside membrane structure and the possibility to manipulate the shape
566 and dimensions of polymeric membrane pores.
567
568 Acknowledgement
569 This work was supported by a grant of the Romanian National Authority for Scientific
570 Research and Innovation, CNCS UEFISCDI, project number PN-II-RU-TE-2014-4-0292 -
571 Nanostructured membrane reactors for derivatization and doping of carbon nanotubes and
572 graphenes.
573
574
575 References
576 Akther, N., Sodiq, A., Giwa, A., Daer, S., Arafat, H. A., & Hasan, S. W. (2015). Recent
577 advancements in forward osmosis desalination: A review. Chemical Engineering Journal,
578 281, 502522. http://doi.org/10.1016/j.cej.2015.05.080
579 Anitha, A., Sowmya, S., Kumar, P. T. S., Deepthi, S., Chennazhi, K. P., Ehrlich, H.,
580 Jayakumar, R. (2014). Chitin and chitosan in selected biomedical applications. Progress in
581 Polymer Science, 39(9), 16441667. http://doi.org/10.1016/j.progpolymsci.2014.02.008
582 Antunes, B. P., Moreira, A. F., Gaspar, V. M., & Correia, I. J. (2015). Chitosan/arginine-
583 chitosan polymer blends for assembly of nanofibrous membranes for wound regeneration.
584 Carbohydrate Polymers, 130, 104112. http://doi.org/10.1016/j.carbpol.2015.04.072
585 Balacianu, F. D., Nechifor, A. C., Bartos, R., Voicu, S. I., & Nechifor, G. (2009). Synthesis and
586 characterization of Fe3O4 magnetic particles-multiwalled carbon nanotubes by covalent
587 functionalization. Optoelectronics and Advanced Materials-Rapid Communications, 3(3),
588 219222.
589 Baicea C., Nechifor A.C., Vaireanu D.I., Gales O., Trusca R., & Voicu S.I. (2011). Sulfonated
590 poly (ether ether ketone) activated polypyrrole composite membranes for fuel cells,
591 Optoelectronics and Advanced Materials Rapid Communications, 5(11), 1181-1185.;
592 Beheshti, H., Irani, M., Hosseini, L., Rahimi, A., & Aliabadi, M. (2016). Removal of Cr (VI) from
593 aqueous solutions using chitosan/MWCNT/Fe3O4 composite nanofibers-batch and column
594 studies. Chemical Engineering Journal, 284, 557564.
595 http://doi.org/10.1016/j.cej.2015.08.158
596 Chatterjee, S., & Judeh, Z. M. A. (2015). Encapsulation of fish oil with N-stearoyl O-
597 butylglyceryl chitosan using membrane and ultrasonic emulsification processes.
599 Chen, C., Hong, X., & Gao, Y. (2015). Electrosynthesis of poly(3-amino-4-hydroxybenzoic
600 acid) nanoparticles with electroactivity even in highly alkaline solutions. Journal of Applied
601 Polymer Science, 132(27), 42190. http://doi.org/10.1002/app.42190
602 Choi, H., Son, M., Yoon, S., Celik, E., Kang, S., Park, H., Choi, H. (2015). Alginate fouling
603 reduction of functionalized carbon nanotube blended cellulose acetate membrane in
604 forward osmosis. Chemosphere, 136, 204210.
605 http://doi.org/10.1016/j.chemosphere.2015.05.003
606 Choudalakis, G., & Gotsis, A. D. (2009). Permeability of polymer/clay nanocomposites: A

607 review. European Polymer Journal, 45(4), 967984.
608 http://doi.org/10.1016/j.eurpolymj.2009.01.027
609 Cho, Y.-S., Kim, Y.-K., Kim, S.-H., Lim, D. C., Lee, J.-G., Baek, Y.-K., & Yi, G.-R. (2014). Spherical
610 meso-macroporous silica particles by emulsion-assisted dual-templating. Materials Express,
611 4(2), http://doi.org/10.1166/mex.2014.1152
612 Corobea, M. S., Albu, M. G., Ion, R., Cimpean, A., Miculescu, F., Antoniac, I. V., Ghica, M. V.
613 (2015). Modification of titanium surface with collagen and doxycycline as a new approach in
614 dental implants. Journal of Adhesion Science and Technology, 29(23), 25372550.
615 http://doi.org/10.1080/01694243.2015.1073661
616 Dhakal, H. N., Sarasini, F., Santulli, C., Tirillo, J., Zhang, Z., & Arumugam, V. (2015). Effect of
617 basalt fibre hybridisation on post-impact mechanical behaviour of hemp fibre reinforced
618 composites. Composites Part a-Applied Science and Manufacturing, 75, 5467.
619 http://doi.org/10.1016/j.compositesa.2015.04.020
620 Dhakal, H. N., Zhang, Z. Y., Bennett, N., Lopez-Arraiza, A., & Vallejo, F. J. (2014). Effects of
621 water immersion ageing on the mechanical properties of flax and jute fibre biocomposites
622 evaluated by nanoindentation and flexural testing. Journal of Composite Materials, 48(11),
623 13991406. http://doi.org/10.1177/0021998313487238
624 Ding W., Liang C., Sun S., He L., & Gao D. (2015) On-Chip Fabrication of Carbon
625 NanoparticleChitosan Composite Membrane, Journal of Materials Science &Technology,
626 31, 10871093.
627 Elanthikkal, S., Francis, T., Unnikrishnan, G., Varghese, S., & Guthrie, J. T. (2012). Barrier
628 properties of poly(ethylene-co-vinyl acetate)/cellulose composite membranes. Polymer
629 Engineering & Science, 52(10), 21402146. http://doi.org/10.1002/pen.23172
630 El Badawi, N., Ramadan, A. R., Esawi, A. M. K., & El-Morsi, M. (2014). Novel carbon
631 nanotubecellulose acetate nanocomposite membranes for water filtration applications.
632 Desalination, 344, 7985. http://doi.org/10.1016/j.desal.2014.03.005
633 El-Din, L. A. N., El-Gendi, A., Ismail, N., Abed, K. A., & Ahmed, A. I. (2015). Evaluation of
634 cellulose acetate membrane with carbon nanotubes additives. Journal of Industrial and
635 Engineering Chemistry, 26, 259264. http://doi.org/10.1016/j.jiec.2014.11.037
636 Eminoglu, E. M., Beypinar, F., Kahraman, M. V., & Durmus, A. (2015). Fabrication of photo-
637 cross-linked polyethyleneimine-based barriers for CO2 capture. Polymers for Advanced
638 Technologies, 26(9), 10531058. http://doi.org/10.1002/pat.3525
639 Feng, Y., Zhang, X., Shen, Y., Yoshino, K., & Feng, W. (2012). A mechanically strong, flexible
640 and conductive film based on bacterial cellulose/graphene nanocomposite. Carbohydrate
641 Polymers, 87(1), 644649. http://doi.org/10.1016/j.carbpol.2011.08.039
642 Ferreira, C. S., Caridade, S. G., Mano, J. F., & Alves, N. M. (2014). Homogeneous poly(L-lactic
643 acid)/chitosan blended films. Polymers for Advanced Technologies, 25(12), 14921500.
644 http://doi.org/10.1002/pat.3391
645 Gao, K., Shao, Z., Wu, X., Wang, X., Li, J., Zhang, Y., Wang, F. (2013). Cellulose
646 nanofibers/reduced graphene oxide flexible transparent conductive paper. Carbohydrate
647 Polymers, 97(1), 243251. http://doi.org/10.1016/j.carbpol.2013.03.067
648 Gao, Y., Li, B., Zhong, L., Zhang, L., & Ding, Z. (2014). Effect of nano-amphiphilic cellulose as a
649 modifier to PSf composite membranes. Vacuum, 107, 199203.
650 http://doi.org/10.1016/j.vacuum.2014.01.029
651 Ghosh, U. K., Pradhan, N. C., & Adhikari, B. (2006). Pervaporative recovery of N-methyl-2-
652 pyrrolidone from dilute aqueous solution by using polyurethaneurea membranes. Journal of
653 Membrane Science, 285(12), 249257. http://doi.org/10.1016/j.memsci.2006.08.026
654 Guy, R. H. (1996). Current Status and Future Prospects of Transdermal Drug Delivery.
655 Pharmaceutical Research, 13(12), 17651769. http://doi.org/10.1023/A:1016060403438
656 Hegab, H. M., Wimalasiri, Y., Ginic-Markovic, M., & Zou, L. (2015). Improving the fouling
657 resistance of brackish water membranes via surface modification with graphene oxide
658 functionalized chitosan. Desalination, 365, 99107.
659 http://doi.org/10.1016/j.desal.2015.02.029
660 Heinze, T., & Liebert, T. (2001). Unconventional methods in cellulose functionalization.
661 Progress in Polymer Science, 26(9), 16891762. http://doi.org/10.1016/S0079-
662 6700(01)00022-3
663 He, M., Cho, B.-U., & Won, J. M. (2016). Effect of precipitated calcium carbonateCellulose
664 nanofibrils composite filler on paper properties. Carbohydrate Polymers, 136, 820825.
665 http://doi.org/10.1016/j.carbpol.2015.09.069
666 He, S., Lin, Y., Wei, Z., Zhang, L., Lin, J., & Nazarenko, S. (2015). Solvent-free fabrication of
667 proton-conducting membranes based on commercial elastomers. Polymers for Advanced
668 Technologies, 26(4), 300307. http://doi.org/10.1002/pat.3443
669 Ionita, M., Crica, L. E., Voicu, S. I., Pandele, A. M., & Iovu, H. (2015). Fabrication of cellulose
670 triacetate/graphene oxide porous membrane. Polymers for Advanced Technologies, n/a
671 n/a. http://doi.org/10.1002/pat.3646
672 Ionita, M., Vasile, E., Crica, L. E., Voicu, S. I., Pandele, A. M., Dinescu, S., Costache, M.
673 (2015). Synthesis, characterization and in vitro studies of polysulfone/graphene oxide
674 composite membranes. Composites Part B: Engineering, 72, 108115.
675 http://doi.org/10.1016/j.compositesb.2014.11.040
676 Jafarzadeh, Y., Yegani, R., & Tantekin-Ersolmaz, S. B. (2015). Effect of TiO2 nanoparticles on
677 structure and properties of high density polyethylene membranes prepared by thermally
678 induced phase separation method. Polymers for Advanced Technologies, 26(4), 392398.
679 http://doi.org/10.1002/pat.3466
680 Jain, D., Carvalho, E., & Banerjee, R. (2010). Biodegradable hybrid polymeric membranes for
681 ocular drug delivery. Acta Biomaterialia, 6(4), 13701379.
682 http://doi.org/10.1016/j.actbio.2009.11.001
683 Jiang, J. (2014). Molecular simulation studies on microstructure of phospholipid nano-carrier

684 for hydrophobic drug delivery. Materials Express, 4(3), 253257.
685 http://doi.org/10.1166/mex.2014.1169
686 Karim, Z., Mathew, A. P., Grahn, M., Mouzon, J., & Oksman, K. (2014). Nanoporous
687 membranes with cellulose nanocrystals as functional entity in chitosan: Removal of dyes
688 from water. Carbohydrate Polymers, 112, 668676.
690 Khalil, R., Sheha, E., Hanafy, T., & Al-Hartomy, O. (2014). Synthesis and characterization of
691 poly(vinyl alcohol)-acid salt polymer electrolytes. Materials Express, 4(6), 483490.
692 http://doi.org/10.1166/mex.2014.1197
693 Kim, K., Ingole, P. G., Yun, S., Choi, W., Kim, J., & Lee, H. (2015). Water vapor removal using
694 CA/PEG blending materials coated hollow fiber membrane. Journal of Chemical Technology
695 & Biotechnology, 90(6), 11171123. http://doi.org/10.1002/jctb.4421
696 Kobayashi, N., Okitsu, T., Nakaji, S., & Tanaka, N. (2003). Hybrid bioartificial liver:
697 establishing a reversibly immortalized human hepatocyte line and developing a bioartificial
698 liver for practical use. Journal of Artificial Organs: The Official Journal of the Japanese
699 Society for Artificial Organs, 6(4), 236244. http://doi.org/10.1007/s10047-003-0235-7
700 Lee E.-J., & Kim H.-E. (2016). Accelerated bony defect healing by chitosan/silica hybrid
701 membrane with localized bone morphogenetic protein-2 delivery, Materials Science and
702 Engineering C, 59, 339345.
703 Li, J., Gao, J., Sui, G., Jia, L., Zuo, C., & Deng, Q. (2014). Influence of a glycerin additive on the
704 structure and water vapor permeance of chitosan membranes. Materials Express, 4(6), 491
705 498. http://doi.org/10.1166/mex.2014.1200
706 Li, K., Wang, Y., Huang, M., Yan, H., Yang, H., Xiao, S., & Li, A. (2015). Preparation of
707 chitosan-graft-polyacrylamide magnetic composite microspheres for enhanced selective
708 removal of mercury ions from water. Journal of Colloid and Interface Science, 455, 261270.
709 http://doi.org/10.1016/j.jcis.2015.05.043
710 Liu H., Gong C., Wang J., Liu X., Liu H., Cheng F., Wang G., Zheng G., Qin C., & Wen S. (2016).
711 Chitosan/silica coated carbon nanotubes composite proton exchange membranes for fuel
712 cell applications, Carbohydrate Polymers, 136, 13791385.
713 Luntraru V.I, Gales O., Iarca L., Vasile E., Voicu S.I., &Nechifor A.C. (2011). Synthesis and
714 characterization of magnetite - titanium dioxide - 4-Benzene-azo--naphthylamine and
715 methylene blue composites, Optoelectronics and Advanced Materials Rapid
716 Communications, 5(11), 1229-1232.
717 Ma, H., Burger, C., Hsiao, B. S., & Chu, B. (2012). Highly Permeable Polymer Membranes
718 Containing Directed Channels for Water Purification. ACS Macro Letters, 1(6), 723726.
719 http://doi.org/10.1021/mz300163h
720 Ma, H., Burger, C., Hsiao, B. S., & Chu, B. (2014). Fabrication and characterization of
721 cellulose nanofiber based thin-film nanofibrous composite membranes. Journal of
722 Membrane Science, 454, 272282. http://doi.org/10.1016/j.memsci.2013.11.055
723 Mahendran, R., Malaisamy, R., & Mohan, D. R. (2004). Cellulose acetate and
724 polyethersulfone blend ultrafiltration membranes. Part I: Preparation and characterizations.
725 Polymers for Advanced Technologies, 15(3), 149157. http://doi.org/10.1002/pat.417
726 Miao, J., Zhang, R., & Bai, R. (2015). Poly (vinyl alcohol)/carboxymethyl cellulose sodium
727 blend composite nanofiltration membranes developed via interfacial polymerization.
728 Journal of Membrane Science, 493, 654663. http://doi.org/10.1016/j.memsci.2015.07.031
729 Miculescu, M., Muhulet, A., Nedelcu, A., & Voicu, S. I. (2014). Synthesis and characterization
730 of polysulfone - carbon nanotubes - polyethylene imine composite membranes.
731 Optoelectronics and Advanced Materials-Rapid Communications, 8(11-12), 10721076.
732 Miculescu M., Thakur V.K., Miculescu F., & Voicu S.I. (2016). Graphene based-polymer
733 nanocomposites membranes: a review, Polymers for Advanced Technologies, DOI:
734 10.1002/pat.3751.
735 Mondal, M., & De, S. (2015). Preparation, characterization, and performance of a novel
736 hollow fiber nanofiltration membrane. Polymers for Advanced Technologies, 26(9), 1155
737 1167. http://doi.org/10.1002/pat.3549
738 Mohammadi Z.A., Aghamiri S.F., Zarrabi A., &Talaie M.R. (2015). A comparative study on
739 non-covalent functionalization of carbon nanotubes by chitosan and its derivatives for
740 delivery of doxorubicin, Chemical Physics Letters, 642, 2228.
741 Nechifor, G., Voicu, S. I., Nechifor, A. C., & Garea, S. (2009). Nanostructured hybrid
742 membrane polysulfone-carbon nanotubes for hemodialysis. Desalination, 241(13), 342
743 348. http://doi.org/10.1016/j.desal.2007.11.089
744 Pappu, A., Patil, V., Jain, S., Mahindrakar, A., Haque, R., & Thakur, V. K. (2015). Advances in
745 industrial prospective of cellulosic macromolecules enriched banana biofibre resources: A
746 review. International Journal of Biological Macromolecules, 79, 449458.
747 http://doi.org/10.1016/j.ijbiomac.2015.05.013
748 Pendergast, M. M., & Hoek, E. M. V. (2011). A review of water treatment membrane
749 nanotechnologies. Energy & Environmental Science, 4(6), 19461971.
750 http://doi.org/10.1039/c0ee00541j
751 Pinkert, A., Marsh, K. N., Pang, S., & Staiger, M. P. (2009). Ionic Liquids and Their Interaction
752 with Cellulose. Chemical Reviews, 109(12), 67126728. http://doi.org/10.1021/cr9001947
753 Prasad, N. S., Moulik, S., Bohra, S., Rani, K. Y., & Sridhar, S. (2016). Solvent resistant
754 chitosan/poly(ether-block-amide) composite membranes for pervaporation of n-methyl-2-
755 pyrrolidone/water mixtures. Carbohydrate Polymers, 136, 11701181.
757 Qi X., Rui Y., Fan Y., Chen H., Ma N., & Wu Z. (2015). Galactosylated chitosan-grafted
758 multiwall carbon nanotubes for pH-dependent sustained release and hepatic tumor-
759 targeted deliveryof doxorubicin in vivo, Colloids and Surfaces B: Biointerfaces, 133, 314322.
760 Rassu G., Salis A., Porcu E.P., Giunchedi P., Roldo M., &Gavini E. (2016). Composite
761 chitosan/alginate hydrogel for controlled release of deferoxamine: A system to potentially
762 treat iron dysregulation diseases, Carbohydrate Polymers, 136, 13381347.
763 Rahimnejad, M., Bakeri, G., Ghasemi, M., & Zirepour, A. (2014). A review on the role of
764 proton exchange membrane on the performance of microbial fuel cell. Polymers for
765 Advanced Technologies, 25(12), 14261432. http://doi.org/10.1002/pat.3383
766 Ramezani Kakroodi, A., Panthapulakkal, S., Sain, M., & Asiri, A. (2015). Cellulose nanofibers
767 from the skin of beavertail cactus, Opuntia basilaris, as reinforcements for polyvinyl alcohol.
768 Journal of Applied Polymer Science, 132(36), n/an/a. http://doi.org/10.1002/app.42499
769 Ravanchi, M. T., Kaghazchi, T., & Kargari, A. (2009). Application of membrane separation
770 processes in petrochemical industry: a review. Desalination, 235(1-3), 199244.
772 Rong Ma, Yan-Li Ji, Xiao-DanWeng, Quan-Fu An, & Cong-Jie Gao (2016). High-flux and
773 fouling-resistant reverse osmosis membrane prepared with incorporating zwitterionic amine
774 monomers via interfacial polymerization, Desalination, 381, 100-110.
775 Rusen, E., Mocanu, A., Nistor, L. C., Dinescu, A., Clinescu, I., Mustea, G., Diacon, A.
776 (2014). Design of Antimicrobial Membrane Based on Polymer Colloids/Multiwall Carbon
777 Nanotubes Hybrid Material with Silver Nanoparticles. ACS Applied Materials & Interfaces,
778 6(20), 1738417393. http://doi.org/10.1021/am505024p
779 Sabir, A., Shafiq, M., Islam, A., Sarwar, A., Dilshad, M. R., Shafeeq, A., Jamil, T. (2015).
780 Fabrication of tethered carbon nanotubes in cellulose acetate/polyethylene glycol-400
781 composite membranes for reverse osmosis. Carbohydrate Polymers, 132, 589597.
783 Said, A., Daou, T. J., Limousy, L., Bikai, J., Halwani, J., Toufaily, J., Dutournie, P. (2015).
784 Surface energy modification of a Na-mordenite thin layer treated by an alkaline solution.
785 Materials Express, 5(5), 451456. http://doi.org/10.1166/mex.2015.1253
786 Sasaki, M. (2006). Development of vitamin E-modified polysulfone membrane dialyzers.

787 Journal of Artificial Organs, 9(1), 5060. http://doi.org/10.1007/s10047-005-0318-8
788 Sato, K., Sugimoto, K., Shimotsuma, N., Kikuchi, T., Kyotani, T., & Kurata, T. (2012).
789 Development of practically available up-scaled high-silica CHA-type zeolite membranes for
790 industrial purpose in dehydration of N-methyl pyrrolidone solution. Journal of Membrane
791 Science, 409410, 8295. http://doi.org/10.1016/j.memsci.2012.03.032
792 Shao, W., Liu, H., Liu, X., Wang, S., Wu, J., Zhang, R., Huang, M. (2015). Development of
793 silver sulfadiazine loaded bacterial cellulose/sodium alginate composite films with enhanced
794 antibacterial property. Carbohydrate Polymers, 132, 351358.
796 Shenvi, S., Ismail, A. F., & Isloor, A. M. (2014). Preparation and characterization study of
797 PPEES/chitosan composite membrane crosslinked with tripolyphosphate. Desalination, 344,
798 9096. http://doi.org/10.1016/j.desal.2014.02.026
799 Shinde, S. M., Kalita, G., Sharma, S., Zulkifli, Z., Papon, R., & Tanemura, M. (2015). Polymer-
800 free graphene transfer on moldable cellulose acetate based paper by hot press technique.
801 Surface and Coatings Technology, 275, 369373.
802 http://doi.org/10.1016/j.surfcoat.2015.04.040
803 Shirdast A., Sharif A., &Abdollahi M. (2016). Effect of the incorporation of sulfonated
804 chitosan/sulfonated graphene oxide on the proton conductivity of chitosan membranes,
805 Journal of Power Sources, 306, 541-551.
806 Singha, A. S., & Thakur, V. K. (2008a). Saccaharum Cilliare Fiber Reinforced Polymer
807 Composites. E-Journal of Chemistry, 5(4), 782791.
808 Singha, A. S., & Thakur, V. K. (2008b). Synthesis and Characterization of Pine Needles
809 Reinforced RF Matrix Based Biocomposites. Journal of Chemistry, 5(S1), 10551062.
810 http://doi.org/10.1155/2008/395827
811 Singha, A. S., & Thakur, V. K. (2009). Fabrication and characterization of S-cilliare fibre
812 reinforced polymer composites. Bulletin of Materials Science, 32(1), 4958.
813 http://doi.org/10.1007/s12034-009-0008-x
814 Singha, A. S., & Thakur, V. K. (2010a). Mechanical, Morphological, and Thermal
815 Characterization of Compression-Molded Polymer Biocomposites. International Journal of
816 Polymer Analysis and Characterization, 15(2), 8797.
817 http://doi.org/10.1080/10236660903474506
818 Singha, A. S., & Thakur, V. K. (2010b). Synthesis, Characterization and Study of Pine Needles
819 Reinforced Polymer Matrix Based Composites. Journal of Reinforced Plastics and
820 Composites, 29(5), 700709. http://doi.org/10.1177/0731684408100354
821 Sivakumar, B., Aswathy, R. G., Nagaoka, Y., Iwai, S., Hasumura, T., Venugopal, K.,
822 Sakthikumar, D. N. (2014). Augmented cellular uptake and antiproliferation against
823 pancreatic cancer cells induced by targeted curcumin and SPION encapsulated PLGA
824 nanoformulation. Materials Express, 4(3), 183195. http://doi.org/10.1166/mex.2014.1160
825 Sonawane, S. H., Terrien, A., Figueiredo, A. S., Clara Gonalves, M., & De Pinho, M. N.
826 (2015). The role of silver nanoparticles on mixed matrix Ag/cellulose acetate asymmetric
827 membranes. Polymer Composites, n/an/a. http://doi.org/10.1002/pc.23557
828 Song, K., Gao, A., Cheng, X., & Xie, K. (2015). Preparation of the superhydrophobic nano-
829 hybrid membrane containing carbon nanotube based on chitosan and its antibacterial
830 activity. Carbohydrate Polymers, 130, 381387.
832 Srivastava, N., Thakur, A. K., & Shahi, V. K. (2016). Phosphorylated cellulose triacetatesilica
833 composite adsorbent for recovery of heavy metal ion. Carbohydrate Polymers, 136, 1315
834 1322. http://doi.org/10.1016/j.carbpol.2015.10.047
835 Stamatialis, D. F., Papenburg, B. J., Girons, M., Saiful, S., Bettahalli, S. N. M., Schmitmeier,
836 S., & Wessling, M. (2008). Medical applications of membranes: Drug delivery, artificial
837 organs and tissue engineering. Journal of Membrane Science, 308(12), 134.
838 http://doi.org/10.1016/j.memsci.2007.09.059
839 Sunitha, K., Yamuna Rani, K., Moulik, S., Satyanarayana, S. V., & Sridhar, S. (2013).
840 Separation of NMP/water mixtures by nanocomposite PEBA membrane: Part I. Membrane
841 synthesis, characterization and pervaporation performance. Desalination, 330, 18.
843 Suratago, T., Taokaew, S., Kanjanamosit, N., Kanjanaprapakul, K., Burapatana, V., &
844 Phisalaphong, M. (n.d.). Development of bacterial cellulose/alginate nanocomposite
845 membrane for separation of ethanolwater mixtures. Journal of Industrial and Engineering
846 Chemistry. http://doi.org/10.1016/j.jiec.2015.09.004
847 Tianyi Ma, Yanlei Su, Yafei Li, Runnan Zhang, Yanan Liu, Mingrui He, Yang Li, Nanxi Dong,
848 Hong Wu, &Zhongyi Jiang (2016). Fabrication of electro-neutral nanofiltration membranes
849 at neutral pH with antifouling surface via interfacial polymerization from a novel zwitterionic
850 amine monomer, Journal of Membrane Science, 503, 101-109.
851 Thakur, M. K., Gupta, R. K., & Thakur, V. K. (2014). Surface modification of cellulose using
852 silane coupling agent. Carbohydrate Polymers, 111, 849855.
854 Thakur, V. K., & Kessler, M. R. (2015). Self-healing polymer nanocomposite materials: A
855 review. Polymer, 69, 369383. http://doi.org/10.1016/j.polymer.2015.04.086
856 Thakur, V. K., & Singha, A. S. (2010). Natural fibres-based polymers: Part I-Mechanical
857 analysis of Pine needles reinforced biocomposites. Bulletin of Materials Science, 33(3), 257
858 264. http://doi.org/10.1007/s12034-010-0040-x
859 Thakur, V. K., Singha, A. S., & Misra, B. N. (2011). Graft Copolymerization of Methyl
860 Methacrylate onto Cellulosic Biofibers. Journal of Applied Polymer Science, 122(1), 532544.
861 http://doi.org/10.1002/app.34094
862 Thakur, V. K., & Thakur, M. K. (2014a). Processing and characterization of natural cellulose
863 fibers/thermoset polymer composites. Carbohydrate Polymers, 109, 102117.
865 Thakur, V. K., & Thakur, M. K. (2014b). Recent Advances in Graft Copolymerization and
866 Applications of Chitosan: A Review. Acs Sustainable Chemistry & Engineering, 2(12), 2637
867 2652. http://doi.org/10.1021/sc500634p
868 Thakur, V. K., & Thakur, M. K. (2014c). Recent trends in hydrogels based on psyllium
869 polysaccharide: a review. Journal of Cleaner Production, 82, 115.
870 http://doi.org/10.1016/j.jclepro.2014.06.066
871 Thakur, V. K., & Thakur, M. K. (2015). Recent advances in green hydrogels from lignin: a
872 review. International Journal of Biological Macromolecules, 72, 834847.
873 http://doi.org/10.1016/j.ijbiomac.2014.09.044
874 Thakur, V. K., Thakur, M. K., & Gupta, R. K. (2013a). Graft copolymers from cellulose:
875 Synthesis, characterization and evaluation. Carbohydrate Polymers, 97(1), 1825.
877 Thakur, V. K., Thakur, M. K., & Gupta, R. K. (2013b). Rapid synthesis of graft copolymers
878 from natural cellulose fibers. Carbohydrate Polymers, 98(1), 820828.
880 Thakur, V. K., Thakur, M. K., & Gupta, R. K. (2013c). Synthesis of lignocellulosic polymer with
881 improved chemical resistance through free radical polymerization. International Journal of
882 Biological Macromolecules, 61, 121126. http://doi.org/10.1016/j.ijbiomac.2013.06.045
883 Thakur, V. K., Thakur, M. K., & Gupta, R. K. (2014). Graft copolymers of natural fibers for
884 green composites. Carbohydrate Polymers, 104, 8793.
886 Thakur, V. K., Vennerberg, D., & Kessler, M. R. (2014). Green Aqueous Surface Modification
887 of Polypropylene for Novel Polymer Nanocomposites. Acs Applied Materials & Interfaces,
888 6(12), 93499356. http://doi.org/10.1021/am501726d
889 Tsai, H.-A., Chen, Y.-L., Lee, K.-R., & Lai, J.-Y. (2012). Preparation of heat-treated PAN hollow
890 fiber membranes for pervaporation of NMP/H2O mixtures. Separation and Purification
891 Technology, 100, 97105. http://doi.org/10.1016/j.seppur.2012.09.005
892 Uragami, T., Saito, T., & Miyata, T. (2015). Pervaporative dehydration characteristics of an
893 ethanol/water azeotrope through various chitosan membranes. Carbohydrate Polymers,
894 120, 16. http://doi.org/10.1016/j.carbpol.2014.11.032
895 Varanasi, S., Low, Z.-X., & Batchelor, W. (2015). Cellulose nanofibre composite membranes
896 Biodegradable and recyclable UF membranes. Chemical Engineering Journal, 265, 138146.
897 http://doi.org/10.1016/j.cej.2014.11.085
898 Viswanathan, G., Murugesan, S., Pushparaj, V., Nalamasu, O., Ajayan, P. M., & Linhardt, R. J.
899 (2006). Preparation of Biopolymer Fibers by Electrospinning from Room Temperature Ionic
900 Liquids. Biomacromolecules, 7(2), 415418. http://doi.org/10.1021/bm050837s
901 Voicu S.I., Nechifor A.C., Serban B., Nechifor G., &Miculescu M. (2007).
902 FormylatedPolysulphone Membranes for Cell Immobilization, Journal of Optoelectronics and
903 Advanced Materials, 9 (11), 3423-3426.
904 Voicu S.I., Stanciu N.D., Nechifor A.C., Vaireanu D.I., & Nechifor G. (2009). Synthesis and
905 Characterization of Ionic Conductive Polysulfone Composite Membranes, Romanian Journal
906 of Information Science and Technology, 12 (3), 410-422.
907 Voicu S.I., Aldea F., &Nechifor A.C. (2010). Polysulfone-carbon nanotubes composite
908 membranes. Synthesis and characterization, Revista de Chimie, 61(9), 817-821.
909 Voicu, S. I., Dobrica, A., Sava, S., Ivan, A., & Naftanaila, L. (2012). Cationic surfactants-
910 controlled geometry and dimensions of polymeric membrane pores. Journal of
911 Optoelectronics and Advanced Materials, 14(11-12), 923928.
912 Voicu, S. I., Muhulet, A., Antoniac, I. V., & Corobea, M. S. (2015). Cellulose Derivatives Based
913 Membranes for Biomedical Applications. Key Engineering Materials, 638, 2730.
914 http://doi.org/10.4028/www.scientific.net/KEM.638.27
915 Voicu, S. I., Ninciuleanu, C. M., Muhulet, O., & Miculescu, M. (2014). Cellulose acetate
916 membranes with controlled porosity and their use for the separation of aminoacids and
917 proteins. Journal of Optoelectronics and Advanced Materials, 16(7-8), 903908.
918 Voicu, S. I., Pandele, M. A., Vasile, E., Rughinis, R., Crica, L., Pilan, L., & Ionita, M. (2013). The
919 Impact of Sonication Time Through Polysulfone-Graphene Oxide Composite Films
920 Properties. Digest Journal of Nanomaterials and Biostructures, 8(4), 13891394.
921 Wang, J., Feng, M., & Zhan, H. (2014). Preparation, characterization, and nonlinear optical
922 properties of graphene oxide-carboxymethyl cellulose composite films. Optics and Laser
923 Technology, 57, 8489. http://doi.org/10.1016/j.optlastec.2013.09.040
924 Wang, N., Wang, X., Jia, Y., Li, X., Yu, J., & Ding, B. (2014). Electrospun nanofibrous chitosan
925 membranes modified with polyethyleneimine for formaldehyde detection. Carbohydrate
926 Polymers, 108, 192199. http://doi.org/10.1016/j.carbpol.2014.02.088
927 Wang, X., Chen, X., Yoon, K., Fang, D., Hsiao, B. S., & Chu, B. (2005). High Flux Filtration
928 Medium Based on Nanofibrous Substrate with Hydrophilic Nanocomposite Coating.
929 Environmental Science & Technology, 39(19), 76847691. http://doi.org/10.1021/es050512j
930 Wright, J. C., Tao Leonard, S., Stevenson, C. L., Beck, J. C., Chen, G., Jao, R. M., Skowronski,
931 R. J. (2001). An in vivo/in vitro comparison with a leuprolide osmotic implant for the
932 treatment of prostate cancer. Journal of Controlled Release, 75(12), 110.
933 http://doi.org/10.1016/S0168-3659(01)00358-3
934 Wu, C.-S., Hsu, Y.-C., Liao, H.-T., & Cai, Y.-X. (2015). Antibacterial activity and in vitro
935 evaluation of the biocompatibility of chitosan-based polysaccharide/polyester membranes.
937 Xiao, W., Wu, T., Peng, J., Bai, Y., Li, J., Lai, G., Dai, L. (2013). Preparation, structure, and
938 properties of chitosan/cellulose/multiwalled carbon nanotube composite membranes and
939 fibers. Journal of Applied Polymer Science, 128(2), 11931199.
940 http://doi.org/10.1002/app.38329
941 Zhang, Y., Liu, Y., Wang, X., Sun, Z., Ma, J., Wu, T., Gao, J. (2014). Porous graphene
942 oxide/carboxymethyl cellulose monoliths, with high metal ion adsorption. Carbohydrate
943 Polymers, 101, 392400. http://doi.org/10.1016/j.carbpol.2013.09.066
944 Zhao, L.-B., Liu, M., Xu, Z.-L., Wei, Y.-M., Xu, M.-X., & Jiang, B.-H. (2015). Modification of
945 polysulfone hollow fiber ultrafiltration membranes using hyperbranched polyesters with
946 different molecular weights. Polymers for Advanced Technologies, 26(4), 353361.
947 http://doi.org/10.1002/pat.3460
948 Zhao, L., Cheng, C., Chen, Y.-F., Wang, T., Du, C.-H., & Wu, L.-G. (2015). Enhancement on the
949 permeation performance of polyimide mixed matrix membranes by incorporation of
950 graphene oxide with different oxidation degrees. Polymers for Advanced Technologies,
951 26(4), 330337. http://doi.org/10.1002/pat.3456
952 Zhong, L., Gao, Y., Li, B., & Zhang, L. (2015). Preparation of hydrophilic polysulfone porous
953 membrane by use of amphiphilic cellulose. Journal of Applied Polymer Science, 132(12), n/a
954 n/a. http://doi.org/10.1002/app.41664
955 Zhou, Z., Peng, X., Zhong, L., Wu, L., Cao, X., & Sun, R. C. (2016). Electrospun cellulose
956 acetate supported Ag@AgCl composites with facet-dependent photocatalytic properties on
957 degradation of organic dyes under visible-light irradiation. Carbohydrate Polymers, 136,
958 322328. http://doi.org/10.1016/j.carbpol.2015.09.009
959
960
961
962
963
964
965
966
967
968
969
970 Figure Captions
971 Figure 1Schematic representation of an asymmetric polymeric membrane and principle for
972 separation.
973 Figure 2Schematic representation for symmetric and asymmetric polymeric membranes
974 synthesis
975 Figure 3Number of documents in Scopus Database from 1990-2014 for cellulose, and
976 chitosan
977 Figure 4 Structure of cellulose.
978 Figure 5 Intra- and intermolecular hydrogen bonds in Cellulose.
979 Figure 6Classification of cellulose solvents suitable as medium for chemical functionalization
980 reactions.
981 Figure 7Preparation of surface engineered-multiwalled carbon nanotubes by oxidation

982 purification in strong acid medium.
983 Figure 8Tethering of surface engineered multiwalled carbon nanotubes with cellulose
984 acetate/polyethylene glycol polymer matrix.
985 Figure 9 AFM 3-dimensional image of PM and PM-CNTs membranes.
986 Figure 10 Schematic illustration of AgCl crystals grown in situ on electrospunfibers and the
987 photocatalytic degradation mechanism of organic dyes using the CA based Ag@AgCl crystals
988 under visible light irradiation.
989 Figure 11 SEM images of CA based Ag@AgCl crystals: (a) cubes, (b) octahedrons (c), CA
990 based cube Ag@AgCl crystals crystallization 24 h, (d) CA based cube Ag@AgCl crystals
991 crystallization 72 h, and (e) CA based cube Ag@AgCl crystals crystallization 168 h.
992 Figure 12Composite suspension preparation by direct addition (DA) method (top) and
993 controlled and simultaneous addition (CSA) method (bottom).
994 Figure 13 The mechanism of silica nano particle bridging between the nanofibers.
995 Figure 14 Structures of CT and CS.
996 Figure 15Schematic representation on the possibilities of processing CT and CS into different
997 forms.
998 Figure 16 Chemical reaction indicating the formation of amide bond between GO and Cs
999 chain, according to the nucleophilic addition mechanism and subsequent surface adsorption
1000 of GO/f-Cs coating material on the PA (TFC) membrane.
1001 Figure 17 Schematic diagram of RO cross-flow setup.
1002 Figure 18 Schematic of chitosan crosslinking with tetraethyl orthosilicate in the presence of
1003 acetic acid and laboratory pervaporation experimental setup.
1004 Figure 19Surface, cross sectional morphology and EDX analysis of the composite membrane.
1005
1006 Table Caption
1007 Table 1 Water flux, BSA and NaCl retention for studied cellulose acetate membranes.
1008 Table 2 Performance comparison of pervaporation membranes reported in literature with

1009 present chitosan/poly (ether-block-amide) composites for the separation of n-methyl-2-
1010 pyrolidone/water mixtures.
1011
1012
1013
1014
1015
1016
1017
1018 Figure 1Schematic representation of an asymmetric polymeric membrane and principle for
1019 separation.
1020
1021
1022
1023
1024
1025
1026
1027
1028
1029 Figure 2 Schematic representation for symmetric and asymmetric polymeric membranes
1030 synthesis
1031
10000
9000
8000
Number of Documents
Cellulose
7000
6000 Chitosan
5000
4000
3000
2000
1000
0
1990 1994 1998 2002 2006 2010 2014
1032 Year
1033
1034 Figure 3 Number of documents in Scopus Database from 1990-2014 for cellulose, and
1035 chitosan
1036
1037
1038
1039
1040
1041
1042
1043
1044
1045 Figure 4 Structure of cellulose
1046
1047
1048
1049
1050
1051
1052
1053
1054
1055
1056
1057
1058 Figure 5 Intra- and intermolecular hydrogen bondsin Cellulose. Reprinted with permission
1059 from (Pinkert, Marsh, Pang, & Staiger, 2009). Copy right 2009 American Chemical Society.
1060
1061
1062
1063
1064
1065
1066 Figure 6 Classification of cellulose solvents suitable as medium for chemical
1067 functionalization reactions. Reprinted with permission from(Heinze & Liebert, 2001). Copy
1068 right 2001Elsevier

1069
1070 Figure 7 Preparation of surface engineered-multiwalled carbon nanotubes by oxidation
1071 purification in strong acid medium.Reprinted with permission from (Sabir et al., 2015). Copy
1072 right 2015 Elsevier.
1073
1074
1075 Figure 8 Tethering of surface engineered multiwalled carbon Nanotubes with cellulose
1076 acetate/polyethylene glycol polymer matrix.Reprinted with permission from (Sabir et al.,
1077 2015). Copy right 2015 Elsevier.
1078
1079
1080
1081
1082 Figure 9 AFM 3-dimensional image of PM and PM-CNTs membranes.Reprinted with
1083 permission from (Sabir et al., 2015). Copy right 2015 Elsevier.
1084
1085
1086
1087
1088
1089
1090 Figure 10 Schematic illustrations of AgCl crystals grown in situ on electrospun fibers and the
1091 photocatalytic degradation mechanism of organic dyes using the CA based Ag@AgCl
1092 crystals under visible light irradiation. Reprinted with permission from (Zhou et al., 2016).
1093 Copy right 2016 Elsevier.
1094
1095
1096 Figure 11 SEM images of CA based Ag@AgCl crystals: (a) cubes, (b) octahedrons (c), CA
1097 based cube Ag@AgCl crystals crystallization 24 h, (d) CA based cube Ag@AgCl crystals
1098 crystallization 72 h, and (e) CA based cube Ag@AgCl crystals crystallization 168 h.
1099 Reprinted with permission from (Zhou et al., 2016). Copy right 2016 Elsevier.
1100
1101
1102
1103
1104 Figure 12 Composite suspension preparation by direct addition (DA) method (top) and
1105 controlled and simultaneous addition (CSA) method (bottom). Reprinted with permission
1106 from (Varanasi, Low, & Batchelor, 2015). Copy right 2015 Elsevier.
1107
1108
1109
1110
1111
1112 Figure 13 The mechanism of silica nano particle bridging between the nanofibers.Reprinted
1113 with permission from (Varanasi, Low, & Batchelor, 2015). Copy right 2015 Elsevier.
1114
1115
1116
1117
1118
1119 Figure 14 Structures of CH and CS.
1120
1121
1122
1123
1124
1125
1126
1127
1128 Figure 15Schematic representation on the possibilities of processing CT and CS into
1129 different forms.Reprinted with permission from (Anitha et al., 2014). Copy right 2015
1130 Elsevier.
1131
1132
1133
1134
1135
1136 Figure 16 Chemical reaction indicating the formation of amide bond between GO and Cs
1137 chain, according to the nucleophilic addition mechanism and subsequent surface adsorption
1138 of GO/f-Cs coating material on the PA (TFC) membrane. Reprinted with permission from
1139 (Hegab, Wimalasiri, Ginic-Markovic, & Zou, 2015). Copy right 2015 Elsevier.
1140
1141
1142
1143 Figure 17 Schematic diagram of RO cross-flow setup. Reprinted with permission from
1144 (Hegab, Wimalasiri, Ginic-Markovic, & Zou, 2015). Copy right 2015 Elsevier.
1145
1146
1147
1148 Figure 18 Schematic of chitosan crosslinking with tetraethyl orthosilicate in the presence of
1149 acetic acid and laboratory pervaporation experimental setup. Reprinted with permission from
1150 (Prasad, Moulik, Bohra, Rani, & Sridhar, 2016). Copy right 2016 Elsevier.
1151
1152
1153
1154
1155 Figure 19Surface, cross sectional morphology and EDX analysis of the composite
1156 membrane.Reprinted with permission from (Shenvi, Ismail, & Isloor, 2014). Copy right 2014
1157 Elsevier.
1158
1159
1160
1161 Tables
Membrane Water flux BSA NaCl

(L/m2h) Rejection (%) Rejection
(%)
CA (polymer solution film 100 m) 11241 41.3 17.3
CA (dimethyl-dioctodecil ammonium 10962 44.9 17.1
bromide)
CA (alkyl-benzyl-dimethyl ammonium 10856 44.8 17.9
chloride)
CA (N-dodecyl-pyridinium chloride) 11034 45.2 18.9
CA-MWCNT 0.75% 8453 88.2 46.2
CA-MWCNT 1.5% 8322 86.1 48.6
CA-MWCNT 3% 8114 91.2 52.1
CA-GO 0.75% 8253 87.4 61.2
CA-GO 1.5% 7998 90.5 64.7
CA-GO 3% 7653 95.2 67.8
1162 Table 1 Water flux, BSA and NaCl retention for studied cellulose acetate membranes.
1163 Adopted from (Stefan Ioan Voicu et al., 2015).
1164
1165
1166
1167
1168 Table 2 Performance comparison of pervaporation membranes reported in literature with
1169 present chitosan/poly (ether-block-amide) composites for the separation of n-methyl-2-
1170 pyrolidone/water mixtures.Reprinted with permission from (Prasad, Moulik, Bohra, Rani, &
1171 Sridhar, 2016). Copy right 2016 Elsevier.
1172
Membrane Feed mixture Temperature Total flux Selectivity Reference
NMP:water
(C) (kg/m2 h) ()
(wt %)
Polyurethane urea 45 0.013 3396 Ghosh,

Pradhan, and
Adhikari (2006)
PAN hollow fiber 70:30 25 0.18 Tsai, Chen, Lee,

and Lai (2012)
Calcined high silica 90:10 90 11.7 19 Sato et al.

zeolite (2012)
Poly(ether-block- 97:3 30 1.2 180 Sunitha et al.
amide) 2533 + 4A (2013)
zeolite + TDI
Chitosan/poly(ether- 98.7:1.3 30 0.02 838 (Prasad,
block-amide) Moulik, Bohra,
composite Rani, &
(uncrosslinked) Sridhar, 2016)
Chitosan/poly(ether- 98.7:1.3 30 0.02 1007 (Prasad,
block-amide) Moulik, Bohra,
composite (TEOS Rani, &
crosslinked) Sridhar, 2016)
1173
1174
1175
1176

10 1016@j Carbpol 2016 03 030

Hochgeladen von

Dokumentinformationen

Originaltitel

Copyright

Verfügbare Formate

Dieses Dokument teilen

Dokument teilen oder einbetten

Freigabeoptionen

Stufen Sie dieses Dokument als nützlich ein?

Sind diese Inhalte unangemessen?

Copyright:

Verfügbare Formate

10 1016@j Carbpol 2016 03 030

Hochgeladen von

Copyright:

Verfügbare Formate

Accepted Manuscript

Title: Recent Advances in Cellulose and Chitosan Based

Author: Vijay Kumar Thakur Stefan Ioan Voicu

Received date: 18-11-2015

12 Natural polysaccharides are of great importance for advanced applications.

13 Biobased polymeric membranes performances can be improved using fillers.

14 Sustainable cellulose and chitosan membranes can efficiently purify water.

31 Keywords: Biobased polymers; Membranes; Composite; Salts rejection; Water purification

60 Conventional filtration membranes separate eye-visible particles, like sand particles;

63 Ultrafiltration separate membranes particles with dimensions between 10-1000 , like

65 Nanofiltration and reverse osmosis membranes separate salts and ions.

80 Synthesis of polymeric membranes

120 where Ci is the concentration in permeate, andCfis concentration in retentate. The

138 2. Different Biobased Polymers for Membrane Applications

146 2.1 Cellulose based Membranes

182 2.1.1. Synthesis methods for cellulose based composite membranes

198 2.1.2. Fillers for cellulose based composite membranes

267 The mechanical/ thermal properties of composite membranes (cellulose/carbon nanotubes)

298 Potential antibacterial properties of cellulose acetate asymmetric membranes by

343 For inducing a hydrophilic character to polysulfone(PSf) porous membranes, a cellulose-

424 2.2 Chitosan based Membranes

437 2.2.1. Synthesis methods for chitosan based composite membranes

462 2.2.2. Fillers for chitosan based composite membranes

483 Solvent resistant chitosan/poly(ether-block-amide) composite membranes were synthesized

531 Conclusions and future perspectives

606 Choudalakis, G., & Gotsis, A. D. (2009). Permeability of polymer/clay nanocomposites: A

683 Jiang, J. (2014). Molecular simulation studies on microstructure of phospholipid nano-carrier

786 Sasaki, M. (2006). Development of vitamin E-modified polysulfone membrane dialyzers.

977 Figure 4 Structure of cellulose.

978 Figure 5 Intra- and intermolecular hydrogen bonds in Cellulose.

981 Figure 7Preparation of surface engineered-multiwalled carbon nanotubes by oxidation

985 Figure 9 AFM 3-dimensional image of PM and PM-CNTs membranes.

995 Figure 14 Structures of CT and CS.

1008 Table 2 Performance comparison of pervaporation membranes reported in literature with

1045 Figure 4 Structure of cellulose

1066 Figure 6 Classification of cellulose solvents suitable as medium for chemical

1068 right 2001Elsevier

1070 Figure 7 Preparation of surface engineered-multiwalled carbon nanotubes by oxidation

1072 right 2015 Elsevier.

1077 2015). Copy right 2015 Elsevier.

1093 Copy right 2016 Elsevier.

1119 Figure 14 Structures of CH and CS.

1128 Figure 15Schematic representation on the possibilities of processing CT and CS into

Membrane Water flux BSA NaCl

1163 Adopted from (Stefan Ioan Voicu et al., 2015).

Polyurethane urea 45 0.013 3396 Ghosh,

PAN hollow fiber 70:30 25 0.18 Tsai, Chen, Lee,

Calcined high silica 90:10 90 11.7 19 Sato et al.

Das könnte Ihnen auch gefallen