Journal of Membrane Science 453 (2014) 202211

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Journal of Membrane Science

journal ome!a"e# $$$%elsevier%com&locate&memsci

S'nt esis( c aracteri)ation an* a!!lication of novel i" +u+ ,membrane b' la'er.b'.la'er self.assemble* !ol'electrol'te
/an0aj /ar*es i( 1l0a 1% Mun"ra' n
De!artment of C emical 2n"ineerin"( S% 3% 4ational 5nstitute of 6ec nolo"'( Surat 375008( 9ujarat( 5n*ia

article info
1rticle istor'# :eceive* 21 Ma' 2013 :eceive* in revise* form 27 -ctober 2013 1cce!te* 2 4ovember 2013 1vailable online 11 4ovember 2013

abstract
,or t e *evelo!ment of for$ar* osmosis (,-) tec nolo"'( !ro+cient membranes are re>uire* for se!aration $it a!!ro!riate trans!ort c aracteristics% /ol'mer nanocom!osites ave been s o$in" a "reat +e+ibilit' for tailorin" membrane substrate% 1 la'er.b'.la'er (<b<) met o* of !ol'electrol'te as unveile* t e best o!tion for fabricatin" t e re>uire* se!aration la'er% 5n t is researc $or0( t e nanocom!osite of !ol'vin'l alco ol (/31) an* montmorillonite cla' (surface mo*i+e* $it 2530 $t? met 'l *i '*ro+'et 'l '*ro"enate* tallo$ ammonium (61) (MMt.61)) $as use* for membrane substrate fabrication% /article si)e $as measure* for ensurin" t e cla' si)e in nanoran"e% 6 e !ore formin" a"ent $as also a**e* to en ance t e !orosit' of ,- substrate% C itosan (C=) (!ol'cation) an* !ol'acr'lic aci* (/11c) (!ol'anion) $ere em!lo'e* as !ol'electrol'te for surface mo*i+cation of !re!are* substrate $it t ree la'ers of C=&/11c b' t e <b< met o*% 6 e !re!are* nanocom!osite membrane $as name* as @(/31&MMt.61&<iCl) 3<b<A% (/31&MMt.61&<iCl) as a substrate an* (/31&MMt. 61&<iCl) 3<b< as ,- membrane $ere c aracteri)e* b' scannin" electron microsco!' (S2M) for mor! olo"'% 6 ermo"ravimetric (691) anal'sis $as use* to un*erstan* t e t ermal be aviour of substrate as $ell as ,- membrane% Substrate membrane !orosit' $as also c ec0e*% (/31&MMt.61&<iCl) 3<b< membrane $as teste* on t$o fee* solution i%e% *eionise* $ater (D5) an* s'nt etic $aste$ater% Due to t e formation of t e i" '*ro! ilic substrate( membrane s o$e* i" $ater +u+ (38%B5 l m C 2 C 1 (<M=)) an* !ol'electrol'te active la'er restraine* *ra$ solute *iffusion from *ra$ solution to fee* solution% 5t s o$e* remar0able se!aration (0%2D13 " C 2 C 1("M=)) in active la'er facin" *ra$ solution (1<.DS) mo*e for D5 $ater as fee* an* 2 M 4aCl solution as *ra$ solution% Similarl'( for s'nt etic $aste$ater( t e +u+ $as 34%35 <M=% 6 is <b< a!!roac as reveale* t at it is !ossible to fabricate novel i" +u+ ,- membranes $it i" $ater !ermeabilit' an* lo$ reverse salt *iffusion% E 2013 2lsevier F%3% 1ll ri" ts reserve*%

;e'$or*s# ,or$ar* osmosis (,-) <a'er.b'.la'er /ol'electrol'te =i" +u+ :ejection

1% 5ntro*uction 6o*a' t e $orl* as been "oin" t rou" one of t e most inevitable !roblems affectin" !eo!le t at is ina*e>uate sources of s$eet an* clean $ater% 4atural resources of s$eet an* clean $ater ave been obsoletin" *a' b' *a'( $ ic means uman0in* $ill face a "lobal $ater crisis in t e u!comin" *a's% 6 e membrane base* !rocess as !roven t e !ro+cienc' in *esalination of brac0is &salt' $ater an* t e' ave become t e most !romisin" a!!roac to t e "lobal $ater crises !roblem G1(2H% 6 e current state.of.t e.art for $ater !uri+cation an* *esali. nation is reverse osmosis (:-)% :- is a membrane se!aration !rocess t at recovers !ure $ater from im!ure&saline $ater b' a!!l'in" '*raulic !ressure to a level above its osmotic !ressure%

/ressuri)ation of $ater is t e main cause of ener"' consum!tion in :-% /ressure re>uire* for se!aration is *irectl' relate* to t e *issolve* salt concentration an* t is !ressureconcentration rela. tion also affects t e scalin" of membranes% =i" cost of :membrane is also anot er factor% 6 erefore( :- is onl' suitable for treatin" nearl' !ure or brac0is $ater or it nee*s !re. treatment to fee* $ater G3H% =ence( t ere is t e nee* of *ifferent tec nolo"ies( $ ic can *eal $it i" soli* contents $ater or i" foulin" !otential% -ne researc "rou! com!ile* some e+cellent information on t e basic !rinci!les an* a!!lications of for$ar* osmosis (,-) an* unveile* t at ,- also can become a stron" o!tion for *esalination of $ater an* $aste$ater treatment G4H% Due to so man' uni>ue as!ects of ,- i%e% less ener"' in!ut G5H( lo$er foulin" ten*enc'( easier foulin" removal GB(8H an* i" er $ater recover' GDH( for$ar* osmosis tec nolo"' as become a os!itable tec nolo"' for !ro*uction of clean $ater% 5n ,- !rocess( transfer of $ater t rou" a semi.!ermeable membrane from a lo$ osmotic !ressure fee* solution to a i" osmotic *ra$ solution occurs *ue to osmotic

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038B.83DD&M . see front matter E 2013 2lsevier F%3% 1ll ri" ts reserve*% tt!#&&*+%*oi%or"&10%101B&j%memsci%2013%11%001

/% /ar*es i( 1%1% Mun"ra' & Journal of Membrane Science 453 (2014) 202211

203

!ressure *ifference( *urin" $ ic no e+ternal ener"' is re>uire* for mass transfer G7H% 5n t e !ast *eca*e( ,- !rocess $as success. full' use* for $aste $ater treatment GB(10H( sea$ater&brac0is *esalination G11(12H( foo* !rocessin" G13(14H( ! armaceutical a!!lication G15(1BH an* !o$er "eneration G18(1DH% 6o e+!lore ,- !otential as ne$ $ater !ro*uction tec nolo"'( follo$in" major ur*les are to be reco"ni)e*#

(i) 6 e ina*e>uate number of i" !erformance ,- membranes G7H% (ii) 6 e *eart of non.to+ic novel *ra$ solution $ ic can ma+imi)e osmotic !ressure an* can be effective an* easil' rec'cle* $it lo$ ener"' consum!tion G17(20H%

6 e membrane *evelo!ment over t e !ast four *eca*es as occurre* base* on t eir use in !ressure *riven( rat er t an osmoticall' *riven !rocesses% 6 is as meant *esi"nin" of membranes $it ver' t in (an* t erefore i" l' !ermeable) *ense la'ers $ ic reject t e un*esire* solute( an* ver' t ic0 !orous su!!ort la'ers $ ic mec anicall' su!!ort t is t in active la'er G21H% Since t e 17B0s( $ en t e <oebSourirajan membrane $as +rst *evelo!e*( in most of t e ,- stu*ies :- membrane a* been use*% 4evert eless( after t e 2000s( fe$ stu*ies ave been o!ene* for *evelo!ment of ,- membrane% =eretofore( ='*ration 6ec nolo"' 5nc% (=65) cellulose materials +at s eet ,- membranes $ere *ominatin" in commercial a!!lications% 4evert eless( cellulose base* membranes ave some *emerits li0e !oor salt rejection( lo$ $ater !ermeabilit' an* ma' be *e"ra*e* b' some micro. or"anisms G22H% 6 en +at s eet 6,C.,- membranes $ere +rstl' !re!are* via interfacial !ol'meri)ation of m.! en'lene*iamine (M/D) an* trimeso'l c lori*e (6MC) i%e% t e la'er of !ol'ami*e on !orous !ol'sulfone (/Sf) substrates t at $ere cast on !ol'ester non.$oven fabrics in 2limelec Ns lab G23H% 6 is !ol'ami*e 6,C membrane as been ful+lle* ,- !rocess re>uirements because in ,- bot t e la'er of membrane i%e% su!!ort la'er an* active la'er *o ta0e !art in se!aration unli0e :-% 5n :-( onl' t e active la'er !la's a vital role in t e se!aration% 5n ,-( mass transfer also *e!en*s on t e orientation of membrane% Fut some *ra$bac0s ave been foun* in 6,C.,- membrane% 1 major *ra$bac0 for suc as'mmetric structure is t e internal concentration !olari)ation (5C/) as a result of t e accumulation of fee* solutes or t e *ilution of *ra$ solutes in t e !orous su!!ort la'er *e!en*in" on t e membrane orientation G24H% Fecause of t e i" cost an* less commercial availabilit' of '*ro! ilic !ol'sulfone an* !ol'et ersulfone( t ere is a nee* to +n* an alternative for fabrication of ,- substrate $ ic can ful+l

t e ,- re>uirements% /ol'vin'l alco ol (/31) is a s'nt etic !ol'. mer $ ic as i" '*ro! ilicit' an* solubilit' in $ater t at allo$s for better *is!ersion of an' or"anic&inor"anic +ller% ,urt er. more( /31 +lms are +e+ible as $ell as !ossessin" "oo* *imen. sional stabilit' G25H% /31 is a ver' !o!ular !ol'mer to fabricate !erva!oration membrane for *e '*ration of or"anic solvents (e%"%( alco ols( et ers an* aci*s) G2B2DH% Can /31 become an alter. native for ot er substrates in ,- an* ave similar ,- !erformanceO 6o t e best of t e aut orNs 0no$le*"e( eretofore( no sin"le a!!reciable *ata are available about /31 bein" use* for tailorin" ,- membrane substrate% 6 erefore( an attem!t is ma*e to !re!are an ,- substrate b' usin" /31% 6 e insuf+cient mec anical !ro!erties an* !oor resistance in solvents ave limite* /31 a!!licabilit' in membrane an* in*ustrial a!!lications% 6 erefore( t ere is a nee* to mo*if' /31 for membrane !re!aration% Dis!ersion of nano+ller inor"anic !ol'mers can en ance a broa* ran"e of t e material !ro!erties( suc as mec anical( t ermal an* barrier !ro!erties G27H% Montmorillonite (MMt) nanocla' $it *ifferent c emical mo*i+cations as been use* in t e membrane mo*i+cation for *ifferent !ur!oses i%e% en ancement of $ater +u+ G30H an* to increase !ermselectivit' of C-2&C=4 G31H% Montmorillo. nite (MMt) is a '*ro! ilic( inor"anic material( $ ic contains '*rate* 4a I or ; I ions G32H% 6 erefore( montmorillonite (MMt) is onl' miscible $it '*ro! ilic !ol'mers( suc as !ol'vin'l alco ol (/31) G33H( !ol' (et 'lene o+i*e) (/2-) G34H etc% 6 erefore( *evelo!. ment of /31.base* nanocom!osite ,- membrane as been an emer"in" met o* to im!rove mec anical( t ermal an* !ermeabilit' !ro!erties of t e membrane% 6 is ma' offer a viable o!tion for ,membrane *evelo!ment% 1mon" so man' criteria for ,- membrane( one criteria is t at t e membrane (substrateIactive la'er) must be i" l' !orous an* '*ro! ilic% 6 erefore( t e !ore formin" a"ent $as a**e* to en ance t e !orosit' G35(3BH% <iCl in t e !ol'mer solution is use* as a !ore formin" a"ent for su!!ressin" microvoi* formation (0inetic effect) at a i" concentration( but at a lo$ concentration it o!erates as a !ermeate +u+ en ancer (t ermo*'namic effect) G38H% 6o en ance t e a!!licabilit' of t e for$ar* osmosis membranes one attem!t a* been ma*e b' mo*if'in" !ol'sulfone substrate $it !ol'*o!amine G3DH an* a**in" 6i-2 nano!articles in !ol'. ami*e t in.+lm nano+ltration (4,) membranes via in.situ inter. facial !ol'meri)ation G37H% Fut one !ossible a!!roac to mo*if' ,membranes is t e la'er.b'.la'er (<b<) assembl' of !ol'electrol'tes% 6 e la'er.b'.la'er (<b<) assembl' of !ol'electrol'tes means t at t e a*sor!tion of !ol'electrol'tes on soli* substrates is a surface ! enomenon $ ere lon".c aine* !ol'mer molecules $it c ar"e*

6able 1 Com!arison of !ol'electrol'te multila'er membranes for for$ar* osmosis% Sr no% Membrane name 4o% of la'ers 3 /ol'electrol'te name ,- $ater +u+ (<M=) 2D :everse salt +u+ ("M=) 1%78 Con*ition of e+!eriments ,ee*# D5 $ater Dra$# 0%5 M M"Cl2 ,ee*# D5 $ater Dra$# 0%5 M 4aCl :eferences

1%

<a'er.b'.la'er assemble* ,membrane on to! of '!erbranc e* !ol'et 'leneimine (/25) =i" l' crosslin0e* la'er.b'.la'er !ol'electrol'te ,- membranes

/ositivel' c ar"e* !ol'(all'lamine '*roc lori*e)( ne"ativel' c ar"e* blen* of !ol'(acr'lic aci*) (/11) /ositive !ol'electrol'te /1= an* ne"ative !ol'.electrol'te /SS !ol'(so*ium 4.st'rene sulfonate) /ositive !ol'electrol'te /1= an* ne"ative !ol'.electrol'te /SS !ol'(so*ium 4.st'rene sulfonate) /ositive !ol'electrol'te /1= an* ne"ative !ol'.electrol'te /SS !ol'(so*ium 4.st'rene sulfonate) /ositive !ol'electrol'te /1= an* ne"ative !ol'.electrol'te /SS !ol'(so*ium 4.st'rene sulfonate)

G43H

2%

1D

144%D2

G44H

3%

Double.s0inne* for$ar* osmosis membranes base* on la'er.b'.la'er assembl' <a'er.b'.la'er assemble* ,- ollo$ +bers on !ol'et ersulfone (/2S) ollo$ +ber substrate 3P<b<

42%3

,ee*# D5 $ater Dra$# 0%5 M M"Cl2 ,ee*# D5 $ater Dra$# 1 M M"Cl2

G45H

4%

41

13%5

G4BH

15( 20( an* 2D <&mQ

,ee*# D5 $ater Dra$# 0%1( 0%5( an* 1%0 M M"Cl2

G48H

204

/% /ar*es i( 1%1% Mun"ra' & Journal of Membrane Science 453 (2014) 202211

"rou!s (*ubbe* !ol'electrol'tes) bin* to a surface t at is c ar"e* in t e o!!osite !olarit'% 6 is met o* as been use* in nano+ltration an* !erva!ori)ation membrane s'nt esis !rocess to increase t e selectivit' of solute G40H% 6 ese membranes ave s o$n abilit' for i" $ater !ermeabilit' an* "oo* retention a"ainst *ivalent ions $ ic attract its attention to$ar*s t e ,- !rocess G41(42H% 9ener. all'( <b< !ol'electrol'te la'ers s o$ i" solvent resistance an* i" t ermal stabilit' G41H% ,or$ar* osmosis as been stu*ie* for a ran"e of a!!lications% Commercial a!!lications( t ou" are still limite* *ue to t e relativel' lo$ $ater +u+( i" reverse salt *iffusion an* i" cost of membranes% 6 erefore( t ere is a nee* to *evelo! effective an* c ea! membrane for ,- a!!lications( $ ic "ives i" $ater +u+ an* lo$ salt lea0a"e% 1mon" various ,- membrane !re!aration met o*s( <a'er b' <a'er assembl' is a versatile met o* for creatin" ultra.t in barrier la'ers assemble* b' o!!ositel' c ar"e* !ol'elec. trol'te% 5n t e literature( man' !a!ers are available b' usin" !ol'electrol'te multila'er for ,- membrane !re!aration% Some researc ers ave !re!are* ,- membrane an* t e com!ilation of t ese membranes is "iven in 6able 1% 6able 1 "ives clear i*ea about t e use of *ifferent t'!es of !ol'anion an* !ol'cation( *ifferent number of bila'ers( various e+!erimental con*ition( various *ra$ solution $it *ifferent concentrations etc% ,rom 6able 1 it can be conclu*e* t at some membranes "ive lo$ $ater +u+ (1<.,S mo*e)( $ ic nee* some mo*i+cation met o* to im!rove $ater +u+ (1<. ,S mo*e)% Some membranes "ive i" $ater +u+ (1<.,S mo*e) but at t e same time i" reverse salt *iffusion also( $ ic is un*esir. able% 6 erefore( i" $ater +u+( lo$ cost an* effective membranes must be furt er *evelo!e*% =ence( an attem!t is ma*e to *evelo! a ne$ 0in* of lo$ cost an* effective ,- membrane b' combination of *ifferent !ol'electrol'tes% 5n t is stu*'( /31&MMt.61 nanocom!osite substrate $as !re. !are* b' t e solution intercalation +lm castin" met o*% 1ctive la'er $as !re!are* b' a <b< assembl' of !ol'electrol'tes (C= as !ol'cation an* /11c as !ol'anion)% 6 ree la'ers (3<b<) of !ol'. electrol'te $ere a!!lie* on t e /31&MMt.61 substrate% 6 e main objective of t is $or0 $as to fabricate novel i" +u+ ,membrane ((/31&MMt.61&<iCl) 3<b<) an* e+amine its !erfor. mance in D5 $ater an* s'nt etic $aste$ater as fee*%

nanocla' !articles( $ei" e* se!aratel'( $ere *is!erse* in 10 ml of $ater( sonicate* for 30 min an* a**e* in t e !reviousl' !re!are* /31 solution% 6 e mi+ture $as stirre* for 24 an* cast usin" an automatic +lm a!!licator (S een 5nstrument <t*%( 3acuum base*( Mo*el number# 11334) at a s!ee* of 50 mm s C 1 after t e removal of bubbles% 6 e initial t ic0ness of t e caste* +lm $as a*juste* b' a four si*e* a!!licator $it a "a! si)e of 200 Rm% 1fter 2 *a's *r'in" in atmos! eric tem!erature( t e resultin" /31&MMt.61&<iCl sub. strate $as soa0e* in 1%5 M 4a-= at 45 1C for 1%5 % 6 e intension of t e 4a-= treatment $as to leave ne"ative c ar"es to t e substrate via !artial '*rol'sis( $ ic is im!ortant for t e subse>uent <b< assembl' G3BH%

2%3% Crosslin0in" of /31&MMt.61 substrate /31 as !oor stabilit' in a>ueous solution% 6 erefore( t e /31 must be insolubili)e* b' crosslin0in" to create a stable membrane $it consum!tion of some of -= "rou!s res!onsible for '*ro. ! ilicit' G4DH% 6 e substrate $as immerse* in t e crosslin0in" solution consistin" of 1%5 $t? "lutaral*e '*e (91)( 0%5 $t? sulfuric aci*( 4D $t? of acetone an* *eioni)e* $ater for 25 min% 6 en( t e membrane $as $as e* several times $it *eioni)e* $ater to remove t e traces of 91 G28H%

2%4% Mo*i+cation of /31&MMt.61&<iCl membrane substrate $it <b< assembl' -!erationall'( <b< met o* occurs t rou" sim!le( consecutive e+!osures of a substrate to !ol'cation an* !ol'anion solutions( $it rinsin" to remove una*sorbe* !ol'mer after eac *e!osition ste!% /rior to ma0in" t ree la'ers of C=&/11c !ol'electrol'te la'er( ne"ativel' c ar"e* /31&MMt.61&<iCl substrate $as cleane* $it D5 $ater for 5 min% F' e+!osin" onl' one surface of substrate( !ol'electrol'te *e!osition be"an $it a 30 min immersion of t e ne"ativel' c ar"e* substrate into a c itosan !ol'cation solution (2 $t? acetic aci*( 1 $t? c itosan in $ater) G28H% 1fter rinsin" $it D5 $ater for 5 min( t e substrate $as immerse* in a /11c !ol'anion solution (0%02 monomol&l of $ater) for 30 min an* rinse* $it D5 $ater for 5 min% 6 e !roce*ure $as re!eate* to allo$ t e *e!osi. tion of t ree la'ers of C=&/11c +lm on substrate an* t is +lm $as t en *rie* in t e atmos! eric tem!erature% ,inall' !re!are* ,membrane $as name* as ((/31&MMt.61&<iCl) 3<b<)A%

2% Materials an* met o*s 2%1% C emicals an* membrane materials /ol'vin'l alco ol (D5D7? '*rol')e*( t e $ei" t.avera"e molecular $ei" t# 200075(000) $as use* as t e !ol'mer mate. rial for t e fabrication of membrane substrate !urc ase* from ,is er Scienti+c 5n*ia% 6 e nanocla' use* in t is stu*'( MM6( 25 30 $t? octa*ec'lamine (-1) an* MM6( 2530 $t? met 'l *i '. *ro+'et 'l '*ro"enate* tallo$ ammonium (61) (1l*ric C em% Co%( TS1)( $ere use* as receive*% 9lutaral*e '*e (25? <:( for s'nt esis) $as use* as crosslin0in" a"ent !urc ase* from ,ine. C em 5n*ia limite*% ,or !ol'electrol'te la'er( c itosan (!ure( != 8 to 7( viscosit' o200 c!) $as use* as !ol'cation an* !ol'acr'lic aci* $as use* as !ol'anion !urc ase* from -tto C emical% ,or ,tests( so*ium c lori*e (4aCl) !urc ase* from ,541: rea"ent $as *issolve* in D5 $ater an* use* as t e *ra$ solution% 1cetic aci*( =Cl an* acetone $ere use* in e+!erimental !arts% 5n all e+!eri. ments an* for $as in" !ur!oses( ultra.!ure $ater (!= 5%7 80%2 an* con*uctivit' 1%0 (mS&cm)) $as use* (MilliV( Milli!ore( 5n*ia)%

2%5% C aracteri)ations 2%5%1% /article si)e measurement of or"anicall' mo*i+e* MMt.61 cla' Seta avera"e *iameter of cla' !articles *is!erse* in $ater $as measure* b' usin" Setasi)er laser li" t scatterin" e>ui!ment (Malvern Setasi)er( 4ano SS.70( T;)%

2%5%2% S2M anal'sis of membrane substrate an* ,- membrane Membrane surface an* cross.section mor! olo"' $ere e+am. ine* usin" a scannin" electron microsco!e (S2M( 2D1U U<.30)% ,or t e anal'sis( substrate an* !re!are* ,- membranes $ere cut into !ieces of various si)es an* $i!e* $it +lter !a!er% 6 ese !ieces $ere *i!!e* into li>ui* nitro"en for 2030 s an* fro)en% 6 e fro)en !ieces of t e membranes $ere bro0en an* 0e!t in *esicca. tors till t e' $ere use* for S2M anal'sis%

2%2% /re!aration of /31&MMt.61 nanocom!osite membrane substrate /ol'vin'l alco ol (10 $t?) an* <iCl (1 $t?) $ere *issolve* in $ater un*er constant stirrin" at 70 1C for 3 % 6 en 1 $t? of MMt.61

2%5%3% 6 ermal anal'sis of substrate an* ,- membrane 6 ermal anal'sis $as em!lo'e* to estimate t e t ermal stabilit' of t e !re!are* membrane $it /er0in.2lmer./'ris.1 691 at a eatin" rate of 10 1C&min un*er nitro"en atmos! ere in tem!erature ran"in" from 50 to B00 1C% 1ll t e s!ecimens $ere

/% /ar*es i( 1%1% Mun"ra' & Journal of Membrane Science 453 (2014) 202211

205

,i"% 1% Sc ematic of ,- e+!eriment setu!%

+rst *rie* in vacuum for 24 to remove $ater before t e 691 c aracteri)ation%

6able 2 S'nt etic $aste$ater com!onents use* in t e stu*' G44H% Com!onent Concentration(m"&< of D5 $ater) 3B0 810 D0 85 24 85 14 85 B0 85 1D 83 24 83

2%5%4% Membrane substrate !orosit' 6o measure t e !orosit' of /31( /31&<iCl an* /31&MMt.61&<iCl membrane substrate( *r' membranes $ere $ei" te* (m*r') an* same membranes $ere immerse* in $ater for 1 an* blotte* usin" tissue !a!er to remove t e e+cess $ater on t e surface% 6 e $et membranes $ere t en $ei" te* (m$et)% 6 en !orosit' W (?) of t e membranes $ere calculate* usin" t e follo$in" e>uation G35H%

9lucose /rotein 4a=C-3 ;=2/-4 4=4Cl CaCl2 M"S-4 ` 8=2-

WX

Ym$et C m*r' Z[\$ ] 100 ^m$et Cm*r' [\$ _ I m*r' [\m

Y1Z c an"e of t e fee* or *ra$ t e solution b' a3 J$ X at1m $ ere a3 is t e volume c an"e of fee* solution( at is t e measurin" time interval an* 1m is an effective membrane area% 6 e salt concentration in t e fee* $ater solution $as *eter. mine* from t e con*uctivit' measurement base* on t e stan*ar* concentrationcon*uctivit' curve for 4aCl% 6 e reverse salt *iffu. sion Js in " m C 2 C 1 (abbreviate* as "M=) from t e *ra$ solution to t e fee* si*e $as *etermine* from t e increase of t e fee* con*uctivit' usin" t e follo$in" e>uation# Y2Z

$ ere \$ an* \m are t e *ensit' of t e $ettin" solvent ($ater in t e current stu*') an* membrane( res!ectivel'%

2%5%5% ,- !erformance evaluation of (/31&MMt.61&<iCl) 3<b< membrane 6 e ,- !erformance of t e !re!are* membrane $as evaluate* usin" t$o e>ual.si)e com!artments (,i"% 1)% 6 e total li>ui* volume of eac com!artment $as 1%5 l% 6 e effective surface area of t e membrane $as 17 cm2% 6 e tem!erature of t e fee* an* *ra$ solution $as maintaine* at room tem!erature of about 2B 81 1C% Durin" osmosis e+!eriments t e *ra$ an* fee* solu. tions $ere not stirre*% (/31&MMt.61&<iCl) 3<b< membrane $as evaluate* un*er t$o *ifferent mo*es# (i) active la'er facin" *ra$ solution (1<.DS) an* (ii) active la'er facin" fee* solution (1<.,S)% 6 e follo$in" testin" con*itions $ere a*o!te* for ,evaluation#

aYC t 3 t Z Js X at1m $ ere Ct an* 3t are t e salt concentration an* volume at t e en* of ,- tests( res!ectivel' G35H%

Y3Z

Dra$ Solution (DS)# 4aCl at *ifferent concentrations (0%5 M( 1 M( 1%5 M an* 2 M)% ,ee* Solution (,S)# D5 $ater an* s'nt etic $aste$ater%

3% :esults an* *iscussion 3%1% 4anosi)e of MMt.61 cla' 5n membrane !re!aration( MM6 nanocla' $as use*% 6 erefore( to con+rm t e nano!articles si)e( Setasi)er laser li" t scatterin" e>ui!ment $as use*% 5t s o$e* 38%D4 nm si)es at 40%8 vol? as s o$n in ,i"% 2%

Com!onents containe* in s'nt etic $aste$ater are s o$n in 6able 2% 6 e $ater !ermeation +u+ from fee* solution to *ra$ solution $as calculate* from t e volume c an"e of t e fee* $ater b' observin" t e level c an"e on fee* com!artment% 6 e $ater +u+ (J$( < m C 2 C 1( abbreviate* as <M=) is calculate* from t e volume

20B

/% /ar*es i( 1%1% Mun"ra' & Journal of Membrane Science 453 (2014) 202211

3%2% Mor! olo"' of /31&MMt.61 substrate an* (/31&MMt.61&<iCl) 3<b< via S2M ,i"% 3(a)( (b) an* (c) s o$s to! surface S2M ima"es of /31 membrane( /31&cla'&<iCl nanocom!osite substrate an* (/31& MMt.61&<iCl) 3<b< membrane( res!ectivel'% 6 e to! surface S2M ima"es irra*iate* t e effect of a**ition of MMt.61 cla' an* <iCl on /31 membrane an* surface mo*i+cation of (/31&MMt.61&<iCl) nanocom!osite substrate via <b<% ,rom ,i"% 3(a) an* (b)( t e effect of MMt.61 cla' an* <iCl (!ore formin" a"ent) a**ition in /31 can

be clearl' observe*% -nl' /31 substrate $it out t e a**ition of MMt.61 cla' an* <iCl avin" ver' less !ores but /31 $it a**ition of MMt.61 cla' an* <iCl e+!ose* itself as a i" l' !orous substrate% 6 ese surface mor! olo"' *ifferences mi" t be *ue to t e "oo* *is!ersion of MMt.61 cla' in /31 matri+ an* mi" t be res!onsible in t e en ancement of t e !orosit' of t e substrate% 5t can be justi+e* b' t e stu*' con*ucte* b' bu+in et al% G47H( $ o investi"ate* t e effect of cla' in !ol'sulfone membrane as an a**itive an* conclu*e* t at cla' $as res!onsible for t e en ance. ment of !orosit'% 5n a**ition( ,i"% 3(c) *is!la's t e formation of *ense !orous uniform active la'er of !ol'electrol'tes on /31& MMt.61&<iCl substrate% 6 is is *ue to '*rol'sis b' 4a-= im!arts a ne"ative c ar"e on /31&MMt.61&<iCl substrate an* la'er.b'.la'er assembl' of !ositivel' c ar"e* c itosan an* ne"ativel' c ar"e* /11c% 6 e S2M ima"es of cross.section mor! olo"ies of t e /31 membrane( /31&MMt.61&<iCl nanocom!osite substrate an* (/31& MMt.61&<iCl) 3<b< membrane are s o$n in ,i"% 4(a)( (b)( an* (c)( res!ectivel'% Substrates s o$ s!on"' structure an* avera"e t ic0. ness of substrates is about 2B%433 mm (,i"% 4(b) an* (c))% 6 e S2M cross.section ima"e of (/31&MMt.61&<iCl) 3<b< a* t in s!on"e li0e s0in la'er (t ic0ness M 3 mm see ,i"% 4(c))% Micron.t ic0 ( M3 mm) la'er in t e cross.sectional ima"e of ,i"% 4(c) ma' be *ue to t e use of c itosan an* !ol'acr'lic aci* as !ol'electrol'te la'ers% 1mon" t ese( c itosan "ives t e viscous solution an* resulte* in t e t ic0 !ol'electrol'te +lm% 5n literature( some !a!ers ave active la'erNs t ic0ness in micron ran"e G48H% 6 is active la'er $as res!onsible for ver' lo$ reverse salt *iffusion (0%2D13 "M=) in 1<.DS mo*e G3BH%

,i"% 2% /article si)e measurement isto"ram of MMt.61%

,i"% 3% S2M ima"es of membrane surface mor! olo"'# (a) /31J (b) /31&MMt.61&<iClJ (c) (/31&MMt.61&<iCl) 3<b<%

/% /ar*es i( 1%1% Mun"ra' & Journal of Membrane Science 453 (2014) 202211

208

,i"% 4% S2M ima"es of membrane cross.section mor! olo"'# (a) /31J (b) /31&MMt.61&<iClJ (c) (/31&MMt.61&<iCl) 3<b<%

6able 3 /orosit' of membraneNs substrates% MembraneNs substrates /31 /31&<iCl /31&MMt.61&<iCl /orosit' (?) 38 8B D1

,i"% 5% 691 t ermo"rams of /31( /31&MMt.61&<iCl( (/31&MMt.61&<iCl) 3<b< membranes%

3%3% 2valuation of t ermal stabilit' b' 691 6 ermal stabilit' of /31( /31&MMt.61&<iCl an* (/31&MMt.61& <iCl) 3<b< membranes $ere *etermine* b' t e 691% 6'!ical 691 results for t e com!arison of t e /31( /31&MMt.61&<iCl( an* (/31&MMt.61&<iCl) 3<b< membranes are s o$n in ,i"% 5% 5n "eneral( major $ei" t losses are observe* in ran"e of 21D0 B00 1C for t ree t'!es of membrane% 5t is observe* t at t e onl' /31 membrane is stable u! to 1D0 1C be'on* $ ic a smoot *ecrease in $ei" t is *etecte* $ ile /31&MMt.61&<iCl membrane sta's stable u! to 250 1C% 6 is in*icates t at a**ition of cla' can en ance t ermal stabilit' G30H% 6 e c emical structure of MM6 contains t$o fuse* silica tetra e*ral s eets( san*$ic in" an e*"e.s are* octa e*ral s eet of eit er ma"nesium or aluminum

'*ro+i*e% 5ts stac0e* silicate s eets mi" t be res!onsible for increasin" t ermal stabilit' of /31% 1lso MMt.61 acts as a barrier to ma+imi)e t e eat insulation an* to minimi)e t e !ermeabilit' of volatile *e"ra*ation !ro*ucts t rou" t e material G50H% =ence( it is con+rme* from literature t at nanocla' a**ition increases t ermal stabilit' of membranes G51(52H% 6 e curve of (/31&MMt. 61&<iCl) 3<b< s o$s effect of 3<b< la'ere* b' sli" tl' increasin" stabilit' tem!erature (stable u! to 270 1C)( in*icatin" t at electro. static forces an* '*ro"en bon*in" bet$een t e o!!ositel' c ar"e* !ol'electrol'tes im!rove t ermal stabilit' of a membrane G53H% 6 at is $ ' it *oes not "ive rise to "reater mass loss $it tem!erature $it M 3 mm active la'er%

3%4% Membrane !orosit' Membrane !orosities are calculate* b' "ravimetric anal'sis for /31( /31&<iCl an* /31&MMt.61&<iCl substrates to reco"ni)e $ et er MMt.61 cla' or <iCl is res!onsible for !ore formation% /orosit' of *ifferent substrates is "iven in 6able 3% 6able 3 as unveile* t at /31 $it out MMt.61 cla' an* <iCl s o$s a lo$ !orosit' i%e% 38?( b' t e a**ition of <iCl it reac es a

20D

/% /ar*es i( 1%1% Mun"ra' & Journal of Membrane Science 453 (2014) 202211

i" er value of !orosit' (8B?)% 6 is is *ue to t e '*ro! ilic <iCl $ ic $or0s as a nonsolvent( re*ucin" t e t ermo*'namic mis. cibilit' of castin" solution( an* in*ucin" en ancement of li>ui*. li>ui* ! ase se!aration G38H% F' a**ition of cla' it is sli" tl' increase* (D1?)% 6 erefore sli" t increase in !orosit' (D1?) $as e+!ectable from /31&MMt.61&<iCl substrate because of t e '*ro. ! ilic nature of t e cla'%

3%5% ,- !erformance of (/31&MMt.61&<iCl) 3<b< membrane 3%5%1% 2ffect of membrane orientation in D5 $ater as fee* Mass transfer (i%e% t e $ater +u+ an* t e reverse salt +u+) in bot 1<.,S an* 1<.DS mo*es as a function of *ra$ solution concentration is *e!icte* ,i"% B(a) an* (b)% Most of t e e+istin" stu*ies re!orte* i" er $ater +u+ in 1<.DS mo*e com!are* to 1<.,S mo*e *ue to t e more severe *ilutive 5C/ in 1<.,S mo*e G4(53H% 5n 1<.DS mo*e '*ro! ilic an* i" l' !orous substrate face t e fee* solution $ ic as less concentration t an *ra$ solution an* *ense active la'er face t e concentrate* *ra$ solution% 5n t is con*ition $ater in fee* solution $ill face lo$ resistance to +o$ t rou" '*ro! ilic !orous substrate an* ma+imum $ater $ill +o$% 1not er factor $ ic can affect t e $ater +u+ is 5nternal Concentration /olari)ation (5C/)% 5n 1<.DS mo*e 5C/ is less because *ense active la'er faces t e concentrate* *ra$ solution an* it resists t e solute to !ass t rou" t e membrane% 6 erefore $ater +u+ in 1<.DS mo*e is i" er t an t e 1<.,S mo*e G54H% ,or B.la'er /2S substrate <F< membrane t e $ater +u+ $as 40%5 <&m 2 an* 1D%44 <&m2 in 1<.DS mo*e an* 1<.,S mo*e( res!ectivel' G55H% Some researc ers use* t in.+lm.com!osite !ol'ami*e +at s eet membrane for for$ar* osmosis% 6 e' also investi"ate* t at in 1<.DS an* 1<.,S mo*e t e $ater +u+ $as 48%5 an* 11%D <&m 2 ( res!ectivel' G5BH% 6 erefore( $ater +u+ in 1<.DS mo*e is i" er t an 1<.,S mo*e an* a same tren* is observe* in t e current stu*' also% 6 e internal concentration !olari)ation (5C/) insi*e t e su!!ort la'er of ,- membrane is *e!en*in" on t e su!!ort la'er structure% 4evert eless( 5C/ also affecte* b' t e active la'er b' a ! enomenon 0no$n as reverse *iffusion in*uce* 5C/ G35H% 5n t e

1<.DS mo*e( *iffusion of *ra$ solutes t rou" t e active la'er an* accumulation insi*e t e su!!ort la'er can become cause for 5C/ (even if t e fee* $ater contains no *issolve* solute or an' soli* materials)% 5n 1<.,S mo*e( *iffusion of *ra$ solutes t rou" t e active la'er can re*uce t e solute concentration insi*e t e su!!ort la'er an* t us can be res!onsible for en ancin" t e *e"ree of 5C/% 5n t e current stu*'( it can be seen t at bot t e $ater +u+ an* reverse salt +u+ increase almost linearl' $it t e increase of *ra$ solution concentration *ue to no foulin" an* lo$ concentration !olari)ation at relativel' lo$ concentration% =o$ever( bot $ater +u+ an* reverse salt +u+ in 1<.DS mo*e are i" er t an t at in 1<.,S mo*e( !articularl' at i" er concentration% 5n 1<.DS mo*e 38%B5 <M= $as obtaine* at 2 M 4aCl *ra$ solution( *ue to t e electrostatic interaction bet$een $ater molecules an* !ositivel' c ar"e* MMt.61 !articles t at are incor!orate* in t e /31 matri+ an* also MMt.61 cla' is '*ro! ilic( its !resence $ill create a**itional *iffusional !at s for >uic0 trans!ort of $ater molecules( t ereb' increasin" t e selectivit' to $ater to t e value of in+nit'% Fecause of t e intercalation la'er of MMt.61 cla'( more /31 c ains ten*e* to accommo*ate in t eir "alleries( t erefore a lar"e number of $ater molecules mi" t ave been absorbe* into t e !ol'mer matri+ G30H% Fut in 1<.DS mo*e( membrane unveile* t e more reverse salt +u+ (0%2D13 "M=) t an 1<.,S mo*e (0%0510 "M=)( because( t e membrane consists of !ositivel' an* ne"a. tivel' c ar"e* !ol'electrol'te la'ers in alternative se>uence% -n t e surface of t e active la'er( ca"e* la'er stron"l' interacts $it *ra$ solution ions (4a I an* Cl C ) b' rejectin" t e e>uall' c ar"e* ion an* attractin" t e o!!osite c ar"e* ion% 6 erefore( at t e active la'er surface t e ion concentration increases stron"l' an* solute concentration !ro+le *evelo!s from t e membrane surface to t e bul0 of t e *ra$ solution% Moreover( i" er solute concen. tration at t e active la'er surface causes a i" er concentration in t e membrane% 6 erefore more reverse salt +u+ observe*% 5n t e case of 1<.,S mo*e( t e !re!are* membrane $as able to !ass 25%5 <M=( $ ic is more t an commerciall' available =65 mem. brane (13 <M= as "iven in 6able 4) $it fee* $ater as D5 $ater an* 2 M 4aCl as *ra$ solution% 6 is ,- +u+ value (25%5 <M=) is lo$er

,i"% B% (a) cater +u+ an* (b) reverse salt +u+ of ,- membrane teste* in t e 1<.,S an* 1<.DS mo*e $it var'in" *ra$ solution concentration (4aCl) usin" D5 $ater as fee*%

6able 4 Com!arison stu*' of !re!are* membrane $it commerciall' available membrane% Sr no% 1 2 Membrane name /31&MMt.61&<iCl) 3<b< =65 (='*ration 6ec nolo"ies 5nc%) membrane ,- $ater +u+ (<M=) 25%5 13%0 /:- $ater +u+ (<M=) 38%B5 :everse salt +u+ (/:-) ("M=) 0%2D13 :eferences /resent stu*' GB0H

,ee* solution# D5 $aterJ Dra$ solution# 2 M 4aCl solution%

/% /ar*es i( 1%1% Mun"ra' & Journal of Membrane Science 453 (2014) 202211

207

6able 5 Com!arison of ,- membranes $it !re!are* membrane% Sr no% Membrane name ,- $ater +u+ (<M=) /:- $ater +u+ (<M=) :everse salt +u+ ("M=) (/:-) :eferences

/31&MMt.61&<iCl) 3<b<

25%5

38%B5

0%2D13

/resent stu*' G3DH G3DH

2 3 4 5 B 8

/Sf 6,C.,/D1L/Sf.1 6,C.,//ST (non.sulfonate*) s//ST.2(5 (2%5 mol? sDCD/S) s//ST.5 (5 mol? sDCD/S) 6,C.,- membranes (50 $t? sul! onate* material in t e membrane substrate) 6,C.,- castin" solution 1 (50 $t? S/2;) $it out D29 6,C.,- castin" solution 2 (50 $t? S/2;) $it D29

10 4D B2%D 21

8%5 24 10 54 8D%85 33 2%1 D%D 13%5 2%D

G58H G58H G58H G5DH

D 7

30 35

40 50

D 7

G57H G57H

,ee* solution# D5 $aterJ Dra$ solution# 2 M 4aCl solution%

t an 1<.DS mo*e (38%B5 <M=)% 6 is mi" t be *ue to t e *ense structure of t e active la'er( $ater a* to face some ur*le to +o$ t rou" t e membrane an* t e *iffusion of salt into t e substrate restraine* t e +o$ of $ater% 4evert eless( in 1<.,S mo*e lo$ reverse salt +u+ $as observe* (0%0510 "M=) t an in 1<.DS mo*e% 5n t is case salt molecules coul* *iffuse to t e boun*ar' la'er of substrate but $ere not able to *iffuse t e *ense an* c ar"e* active la'er of !ol'electrol'te% 6able 5 s o$s t e com!ilation of *ifferent ,- membranes alon" $it !re!are* membrane (,ee* $aterJ D5 $aterJ Dra$ a"entJ 2 M 4aCl)% 6able 5 clearl' in*icates t at s//ST. 5 (5 mol? sDCD/S) membrane "ave t e i" est amount of $ater +u+ B2%D <M= an* 8D%85 <M= in 1<.,S an* 1<.DS mo*e( res!ec. tivel' G58H% Fut at t e same time it "ave 13%5 "M= reverse salt +u+% //ST (non.sulfonate*) membrane "ave lo$est $ater +u+ in 1<.,S an* 1<.DS mo*e avin" reverse salt +u+ value 2%1 "M=% Com!ar. in" our $or0 $it ot er stu*'( it "ives a clear i*ea t at !re!are* membrane "ave avera"e +u+ (38% B5 <M= (1<.DS)( 25%5 <M= (1<. ,S)) $it lo$est value of reverse salt +u+ (0%2D13 "M=)%

,i"% 8% cater +u+ as a function of 4aCl concentration in bot 1<.DS an* 1<.,S mo*e usin" s'nt etic $aste$ater as fee*%

4% Conclusions 3%5%2% 2ffect of membrane orientation on s'nt etic $aste$ater $ater as fee* S'nt etic $aste$ater contains a variet' of ions suc as so*ium (4a I )( c lori*e (Cl C )( ma"nesium (M"2 I )( sul! ate (S-42 C )( calcium (Ca2 I )( an* !otassium (; I ) as $ell as trace level of or"anic matters% 1 recent stu*' as *emonstrate* t at ions or molecules $it lar"er si)es( lo$er a>ueous *iffusion coef+cients or i" er viscosities $ill cause more severe 5C/ $it in t e membrane su!!ort la'er GB0H% Since t e ions in t e s'nt etic $aste$ater ave *ifferent si)es( a>ueous *iffusion coef+cients an* viscosities( t e' ma' ave a com!le+ effect on 5C/ in t e ,- !rocess% 1**itionall'( t e or"anic matter in s'nt etic $aste$ater ma' intro*uce or"anic foulin"% 1s a result( in 1<.DS mo*e t e $ater +u+ in *esaltin" s'nt etic $aste$ater is muc lo$er t an t at $ en t e fee* solution is D5 $ater( an* in 1<.,S mo*e because of *ense structure of active la'er c ances of 5C/ $ere *ecrease*( as s o$n in ,i"% 8% cater +u+ in D5 $ater as fee* an* s'nt etic $aste$ater as fee* seems small% 6 is lesser *ifference a!!ears because of lo$ foulin" of membrane% 5t $or0e* ef+cientl' in t e case of "lucose as fee* solution% 6 e $ater +u+ $as almost constant an* *i* not var' muc $it time for a *ifferent 4aCl concentration as *ra$ a"ent% 6 erefore( initial $ater +u+es values are same as "iven in ,i"s% B (a) an* 8 for D5 $ater an* s'nt etic $aste$ater as fee* $it *ifferent *ra$ solution concentration% 5n t e !resent stu*'( /31&MMt.61 nanocom!osite as been use* to fabricate ,- membrane substrate( $ ic !la's a vital role in re*ucin" internal concentration !olari)ation an* im!rove t e !erformance of ,- membrane% 6o fabricate i" +u+ for$ar* osmosis membrane( to! surface of /31&MMt.61&<iCl $as carefull' coate* $it 3<b< assembl' of c itosan (C=) (!ol'cation) an* /11c (!ol'anion)% 6 is novel fabrication !rocess can !rovi*e a ne$ !ara*i"m for t e !re!aration of i" +u+ ,- membrane% 6 e follo$in" conclusion can be *ra$n from t is $or0#

6 is im!rove* !rocess results in ,- membrane $it en ance. ments in $ater !ermeabilit' an* s o$s t e tremen*ous *eclination of reverse salt *iffusion% 1 i" $ater +u+ (J$) of about 38%B5 <M= (1<.DS)( 25%5 <M= (,-) an* ver' lo$ reverse salt +u+ (Js) of about 0%2D13 "M= (1<.DS)( 0%0510 "M= (,-) a* been ac ieve* $ en usin" a 2 M 4aCl as t e *ra$ solution an* D5 $ater as fee* solution at 2B 81 1C% cit s'nt etic $aste. $ater( $ater +u+ (J$) of about 34%354 <M= (1<.DS) an* 22%245 <M= (,-) $as obtaine*% 6 e i" '*ro! ilic nature of /31&MMt.61&<iCl substrate !la's an im!ortant role in en ancin" $ater +u+ an* because of t e *ense nature of t e 3<b< surface coatin" on substrate lo$ salt lea0a"e coul* be ac ieve*%

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/% /ar*es i( 1%1% Mun"ra' & Journal of Membrane Science 453 (2014) 202211

5n a**ition( it is foun* t at selection of membrane orientation is basicall' in+uence* b' t e fee* solution com!osition% c en usin" ,- membrane for treats fee* solution $it i" er foulin"&scalin" ten*encies( 1<.,S mo*e is more favorable% c ile in case of 1<.DS mo*e( t e fee* solution $it lo$er foulin" ten*encies is !referable as a fee*%

:eferences
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G28H 1% Svan".1ri'as0ul( :%b%M% =uan"( /%<% Dou"las( :% /al( U% ,en"( /% C en( <% <iu( Flen*e* c itosan an* !ol'vin'l alco ol membranes for t e !erva!oration *e '*ration of iso!ro!anol( J% Membr% Sci% 2D0 (200B) D15D23% G2DH 9% :uili( =% C an"lai( /% ,us en"( c% =on"( J% S on"'i( /319/6MS&62-S 'bri* !erva!oration membrane for *e '*ration of et 'lene "l'col a>ueous solution( J% Membr% Sci% 2D1 (200B) 4544B2% G27H 2% Manias( 1% 6oun'( <% cu( ;% Stra$ ec0er( F% <u( 6%C% C un"( /ol'!ro!'lene& montmorillonite nanocom!osites% :evie$ of t e s'nt etic routes an* materi. als !ro!erties( C em% Mater% 13 (2001) 351B3523% G30H S%9% 1*oor( M% Sairam( <%S% Manjes $ar( ;%3%S%4% :aju( 6%M% 1minab avi( So*ium montmorillonite cla' loa*e* novel mi+e* matri+ membranes of !ol'(vin'l alco ol) for !erva!oration *e '*ration of a>ueous mi+tures of iso!ro!anol an* 1(4.*io+ane( J% Membr% Sci% 2D5 (200B) 1D2175% G31H S%1% =as emifar*( 1%,% 5smail( 6% Matsuura( 2ffects of montmorillonite nano. cla' +llers on /25 mi+e* matri+ membrane for C-2 removal( C em% 2n"% J% 180 (2011) 31B325% G32H :% ;ris namoorti( :%1 3aia( 2%/% 9iannelis( Structure an* *'namics of !ol'mer. la'ere* silicate nanocom!osites( C em% Mater% D (177B) 182D1834% G33H ;%2% Stra$ ec0er( 2% Manias( Structure an* !ro!erties of !ol' (vin'l alco ol)&4a I montmorillonite nanocom!osites( C em% Mater% 12 (2000) 27432747% G34H /% 1ran*a( 2% :ui).=it)0'( /ol' (et 'lene o+i*e).silicate intercalation materials( C em% Mater% 4 (1772) 13751403% G35H c% Jin"( V% C an">uan( b%6% C u'an"( c% :on"( 9%,% 1nt on'( S'nt esis an* c aracteri)ation of +at.s eet t in +lm com!osite for$ar* osmosis mem. branes( J% Membr% Sci% 382 (2011) 272302% G3BH V% Saren( V%V% C an"( b%6% C u'an"( S'nt esis an* c aracteri)ation of novel for$ar* osmosis membranes base* on la'er.b'.la'er assembl'( 2nviron% Sci% 6ec nol% 45 (2011) 5201520D% G38H ,% 2nrica( C%J% Jo annes( C% 1lessan*ra( C% 2frem( D% 2nrico( 2ffect of a**itives in t e castin" solution on t e formation of /3D, membranes( Desalination 172 (200B) 170178% G3DH 9% =an( S% Sui( <% Uue( c% 4atalia( C% 6ai.S un"( 6 in +lm com!osite for$ar* osmosis membranes base* on !ol'*o!amine mo*i+e* !ol'sulfone substrates $it en ancements in bot $ater +u+ an* salt rejection( C em% 2n"% Sci% D0 (2012) 217231% G37H =%S% <ee( S%J% 5m( J%=% ;im( =%J% ;im( J%/% ;im( F%:% Min( /ol'ami*e t in.+lm nano+ltration membranes containin" 6i- 2 nano!articles( Desalination 217 (200D) 4D5B% G40H S% Vian"( ,%1% Vuanfu( J% banli( V% Jin$en( 9% Con"jie( /ol'electrol'te com!le+ membranes for !erva!oration( nano+ltration an* fuel cell a!!lications( J% Membr% Sci% 387 (2011) 1745% G41H /% Fertran*( 1% Jonas( 1% <asc e$s0'( :% <e"ras( Tltrat in !ol'mer coatin"s b' com!le+ation of !ol'electrol'tes at interfaces# suitable materials( structure an* !ro!erties( Macromol% :a!i* Commun% 21 (2000) 31734D% G42H F% 6ie0e( ,% van 1c0ern( <% ;rasemann( 1% 6outianous ( Tltrat in self.assemble* !ol'electrol'te multila'er membranes( 2ur% / 's% J% 2 5 (2001) 2737% G43H b% Cui( =%c% =% can"( 6%S% C un"( Micro.mor! 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olo"' an* formation of la'er.b'.la'er membranes an* t eir !erformance in osmoticall' *riven !rocesses( C em% 2n"% Sci% 101 (2013) 132B%

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G55H C% <iu( c% ,an"( S% C ou( < S i( 1%9% ,ane( :% can"( ,abrication of la'er.b'.la'er assemble* ,- ollo$ +ber membranes an* t eir !erformances usin" lo$ concentration *ra$ solutions( Desalination 30D (2013) 148153% G5BH ;%b% can"( 6%S% C un"( 9% 1m'( Develo!in" t in.+lm.com!osite for$ar* osmosis membranes base* on t e !es&s!sf substrate t rou" interfacial !ol'meri)ation( 15C 2 J% 5D (3) (2012) 8808D1% G58H 4% ci*jojo( 6%S% C un"( M% ceber( C% Malet)0o( 3% car)el an( 1 sulfonate* !ol'! en'lenesulfone (s//ST) as t e su!!ortin" substrate in t in +lm com!osite (6,C) membranes $it en ance* !erformance for for$ar* osmosis (,-)( C em% 2n"% J% 220 (2013) 1523%

G5DH 4% ci*jojo( 6%S% C un"( M% ceber( C% Malet)0o( 3% car)el an( 6 e role of sul! onate* !ol'mer an* macrovoi*.free structure in t e su!!ort la'er for t in.+lm com!osite (6,C)for$ar* osmosis (,-) membranes( J% Membr% Sci% 3D3 (2011) 214223% G57H 9% =an( 6%S% C un"( M% 6orii*a( S% 6amai( 6 in.+lm com!osite for$ar* osmosis membranes $it novel '*ro! ilic su!!orts for *esalination( J% Membr% Sci% 423424 (2012) 543555% GB0H S% S uaifei( S% <in*a( M% Dennis( 2ffects of membrane orientation on !rocess !erformance in for$ar* osmosis a!!lications( J% Membr% Sci% 3D2 (2011) 30D315%