Water Sorption and Diffusion Through

8/7/2019 Water Sorption and Diffusion Through

1/16

2010 Ol Cit P blis i g, I c.P blis e b lice se er t e OCP Scie ce i pri t,

e ber o t e Ol Cit P blis i g Gro p.

I. J. Trans. Phenomena , Vol. 11, pp. 267282Repri ts v il ble irectl ro t e p blis erP otocop i g per itte b lice se o l

*Correspo i g t or: ppk923@ oo.co

267

IntroductIon

T e bio-co p tibilit bio- egr bilit o pol ers ve g i e c i port ce i t e l st

ew e rs [13]. So e rese rc gro ps i t e worl

ve se t r l oils or t e prep r tio o bio-pol ers [410]. W ter i sio sorptiobe vior i t r l oil b se pol ers is i terest-

W e S p i di si tLi see oil B se P ly e s

n -c p si es

VInay ShaRma 1,2, J. S. BanaIT 2 and P. P. Kundu 1,*

1

Department of Chemical Technology, Sant Longowal Institute of Engineering & Technology, Sangrur,Punjab-148106, India

2Faculty of Physical Sciences, Punjabi University, Patiala, Punjab-147002, India

a ew s ste o li see oil b se pol ers is i vestig te or t e sorptio i -sio st ies i w ter. T e ki etics o sorptio is st ie b si g t e eq tio o

tr sport p e o e . T e v l es o i tr sport eq tio re o to be betwee0.5 1, i ic ti g t e o -Ficki i sio i pol er. T e epe e ce o i -sio coe cie t o co positio te per t re s bee st ie or ll pol erics ples. T e i sio coe cie t i c tio ic s ples i cre ses wit i cre se it e oil co te ts i t e s ples. I t er l s ples, it ecre ses wit i cre se ioil co te ts. T e o-co posite s ples s ow less i sio coe cie t t pris-ti e pol er it ecre ses wit i cre si g o t o li see oil. T e i siocoe cie t i cre ses wit i cre se i te per t re or ll pol er s ples. T esorptio coe cie t s ows little c ge wit v ri tio i co positio s well ste per t re or ll t e s ples it is i r ge o 1. T e ctiv tio e erg or

i sio per e tio is positive or ll t e s ples. T e e t o sorptio is lsopositive or ll t e s ples, i ic ti g he r t pe o e o sorptio .

Keywords : W ter tr sport, i sio , sorptio , li see oil pol ers, o -Ficki be vior, ctiv tioe erg , e t o sorptio .

267-282 pp IJTP_MS08N-1078.indd 267 3/10/2010 1:16:30 PM


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268 P. P. Kundu et al.

i g s bject i bot c e ic i stri l elowi g to t e ve er bilit o t e petroc e ic ls. T esorptio i sio o w ter t ro g oil b sepol ers is o gre t i port ce e to t e prospec-tive se o t ese teri ls i co str ctio s, electro -ics, to obiles, etc [1114].

I t e prese t st , t e li see oil b se pol ers o-co posites ve bee st ie . T e e ect o

v rio s p r eters o t e pol er s ples is lsost ie b si g tr sport eq tio arr e i srel tio s ip.

ExPErImEntaL

m e i ls

Co o li see oil o co erci l gr e is pro-c re ro loc l rket co j g te li see oil(87% co j g tio ) is p rc se ro al or OilCo p , ny, uSa. St re e, cr lic ci , tetr ro-

r boro trif ori e iet l et er te co plexre p rc se ro merck C e ic l Co., Ger .

divi lbe ze e is p rc se ro Fl k C e ie.dic clope t ie e is p rc se ro hi e i L bo-r tories Pvt. Lt ., m b i (I i ).

SamPLE PrEParatIon

c i i s ple p ep i

Pol eric teri ls ve bee prep re b e ti g esire co ce tr tio o co o li see oil, st -

re e ivi lbe ze e i gl ss ol s. T e esireo t o st re e ivi lbe ze e is e to t e

li see oil t e ixt re is vigoro sl stirre . T e ,t e ixt re is coole t e i iti tor is e witco st t stirri g t low te per t re t e w ole

ss is tr s erre to t e gl ss ol . T e se le gl ss

ol is kept t roo te per t re or 12 o rs t e e te seq e ti ll t i ere t te per t res s cs 12 o rs t 60C, 24 o rs t 110C ll post

c re t 120C or 3 o rs. T e o e cl t re se it is work is b se o t e origi l co positio o re c-t ts (s ow i T ble 1).

thErmaL SamPLE PrEParatIon

Pol eric teri ls ve bee prep re b e ti g esire co ce tr tio o co j g te li see oil,cr lic ci ivi lbe ze e i gl ss vi l. T eesire o t o cr lic ci ivi lbe ze e is

e to t e co j g te li see oil t e ixt re isvigoro sl stirre . T e gl ss vi l is e te seq e -ti ll t i ere t te per t res s c s 6 o rs t 80C,12 o rs t 100C, 12 o rs t 120C ll postc re t 140C or 12 o rs. T e o e cl t re se it is work is b se o t e origi l co positio o re c-t ts (s ow i T ble 1).

modIfIcatIon of montmorILLonItE

mo t orillo ite Cl s re isperse i dI w terb stirri g. Cet l tri et l o i bro i e(CTaB) or ex ec l o i bro i e (hdaB) is

e to ispersio . T e w ole ispersio is e te t80C or 4 r. T e exc ge cl s re ltere w s e wit dI w ter, til it is ree ro bro i e(teste titr te b silver itr te). T e o i ecl is rie t 80C er v c . CEC (c tioexc ge c p cit ) c lc l te ro t e titre v l e orCTaB is 29.92 or hdaB 152.84 eq/100 g o cl .

nano-comPoSItE PrEParatIon

T e pol eric o-co posites re prep re be ti g t e esire ixt re o co j g te li see oil,cr lic ci dVB o i e o t orillo ite

i gl ss vi l. T e o i e o- llers o pre eter-i e q tit re isperse i co j g te li see

oil- cr lic ci - ivi lbe ze e. T e et ile co po-sitio s re reporte i T ble 1. T e ispersio is i -t i e b co st t g etic stirri g t 500 rp

(over ig t or proper i terc l tio ). T e ixt re ise te t 85C or 2 rs, ollowe b t 95C or 14rs s c t t t e viscosit o t e liq i (pre-pol er)

is s cie tl ig llers got tot ll ex oli te . att is co itio , t e llers will ot be sep r te ro t epre-pol er eve o stoppi g stirri g. T e w ole



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WaTER SORPTIOn and dIFFuSIOn ThROuGh LInSEEd OIL BaSEd POLymERS and nanO-COmPOSITES 269

ss is tr s erre to ppropri te o l p t i e te ove t 100C or 2 r 120C or 12 r

130C or 12 r.

SWELLIng ExPErImEntS

T e s ples re c t i to circ l r or si g ieo 10 i eter. T e t ick ess o s ple is e -s re b e s o screw g ge. T e r s ples reweig e o electro ic b l ce (Citize , CX 220)

t e kept i t e solve t i screwe bottles. T es ples re t ke o t o t e solve t t speci c i ter-

v ls t e excess solve t is r bbe o . T e s plesre t e weig e g i i erse i t e solve t

till eq ilibri is tt i e (i.e. 72 ). T e ti e ore s ri g weig t o t e s ple is kept i i l ( bo t

30 sec), so t t t e esc pe o t e solve t ro t e s -ple re i s egligible. Eq ilibri swelli g experi-

e ts t i ere t te per t res re c rrie o t t 20,

40, 55 70 C ( 1 C) to st t e e ect o te -per t re o t e swelli g. For te per t res ig er troo te per t re, t e s ples re kept i icropro-cessor co trolle ot ir ove .

T e ole perce t pt ke (Q t) t e c ti e i terv lis c lc l te b si g eq tio 1 [15].

TaBLE 1det ile co positio o t e pol er s ples prep re ro li see oil

S ple Id * Li seeOil (%)

St re e(%)

divi lbe ze e(%)

acr lic aci(%)

I iti tor(%)

dic clope -t ie e (%)

mo t orillo iteCl (%)

Li 30 30 46 15.5 ----- 8 ----- -----

Li 40 40 39 13 ----- 8 ----- -----

Li 50 50 31.5 10.5 ----- 8 ----- -----

Li 60 60 24 8 ----- 8 ----- -----

dCP7 40 38 7 ----- 8 7 -----

dCP16 60 ----- 16 ----- 8 16 -----

CLi 0 0 ----- 10 90 ----- ----- -----

Cli 10 10 ----- 10 80 ----- ----- -----

CLi 20 20 ----- 10 70 ----- ----- -----

CLi 30 30 ----- 10 60 ----- ----- -----

CLi 40 40 ----- 10 50 ----- ----- -----

CLi 50 50 ----- 10 40 ----- ----- -----

CLi 60 60 ----- 10 30 ----- ----- -----

CLi mOnT30 30 ----- 10 60 ----- ----- 5 (CTaB)

CLi mOnT40 40 ----- 10 50 ----- ----- 5 (CTaB)

CLi mOnT50 50 ----- 10 40 ----- ----- 5 (CTaB)

CLi mOnT60 60 ----- 10 30 ----- ----- 5 (CTaB)

CLi mOnT70 70 ----- 10 20 ----- ----- 5 (CTaB)

CTaB-mOnT2.5 50 ----- 10 40 ----- ----- 2.5 (CTaB)

CTaB-mOnT7.5 50 ----- 10 40 ----- ----- 7.5 (CTaB)

CTaB-mOnT10 50 ----- 10 40 ----- ----- 10 (CTaB)

hdaB-mOnT2.5 50 ----- 10 40 ----- ----- 2.5 (hdaB)

* CLi s ples co t i 87% co j g te li see oil.



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Q M

M M t t

r i

= 100 (1)

w ere m t is t e ss o t e solve t t ke p t ti e t,m r is t e rel tive olec l r ss o t e solve t m i is t e ss o t e r s ple. T e ole perce t pt ke

t 72 o rs is t ke s swelli g t i ite ti e (Q ).

rESuLtS and dIScuSSIon

Swelli P ly e S ples

T e ole perce t pt ke o t e w ter is plotteg i st sq re root o ti e. T e plots or t e ole per-

ce t pt ke re s ow i Fig res 1 2 or c tio ic,t er l o-co posite s ples t te per t reo 20 1C. I Fig re 1 , it is observe t t t e swell-i g o t e c tio ic s ples i cre ses wit i cre sei t e oil co te ts. T e s ple co t i i g 30% li seeoil s ows i i swelli g, w ere s t e s plewit 60% li see oil co te ts s ows xiswelli g. T is c be expl i e b ecre se i t erigi p rt wit i cre se i t e li see oil co te ts,res lti g i ore fexible r bber pol ericc i s. I itio to ivi lbe ze e (dVB), w e

ic clope t ie e (dCP) is e to t e ixt re, t eres lti g pol er s ows ecre se i swelli g. IdCP s ste , t e s ple wit 7% dCP co te t s ows

i i t e s ple wit 16% dCP co te t

0.01

0.02

0.03

0.04

0.05

0.06

0.07

0 1 2 3 4 5 6 7 8 9

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

a. Cationic Sample

Lin30Lin40

Lin50Lin60

DCP7DCP16

b. Thermal Sample

(Time) 1/2 in hrs

Q t

( m o

l % )

CLIn0

CLIn10CLIn20

CLIn30CLIn40

CLIn50CLIn60

FIGuRE 1T e sorptio c rves or i ere t pol ers s ples t 25C( ) C tio ic s ples (b) T er l s ples.

0.03

0.06

0.09

0.12

0.15

0.18

0.21

0 1 2 3 4 5 6 7 8 9

0.00

0.05

0.10

0.15

0.20

0.25

0.30

a. Variation in oil contentsMONTCLin30

MONTCLin40

MONTCLin50

MONTCLin60

MONTCLin70

b. Variation in Nano-clay contents Q t

( m o

l % )

(Time) 1/2 in hrs

CTABMONT0

CTABMONT2.5

CTABMONT5

CTABMONT7.5

CTABMONT10

HDABMONT2.5

FIGuRE 2T e sorptio c rves or o-co posite s ples t 25C( ) or s ples wit v ri tio i oil co te ts, (b) or s ples witv ri tio i cl co te ts.



5/16


s ows xi swelli g i.e. wit i cre si gdCP co te t, t e swelli g lso i cre ses. I ll t ec tio ic s ples, dCP7 s ows i i Li 60s ows xi swelli g. Fig re 1b s ows t e sorp-tio c rves or t er l s ples t 20 1C. T ei cre si g li see oil co te ts res lts i ecre se it e swelli g. Be o 30% o co j g te li see oil,

ll t e s ples s ow l ost egligible swelli g (lowert 0.5 ol %). T e s ple wit o t li see oil s ows

xi sorptio ecre ses wit t e i cre sei t e oil co te ts. T e cr lic pol ers re k ow ort eir w ter lovi g t re [1618]. as t e cr lic co -te ts ecre ses ro 90 to 20% t e bsorbe t proper-ties o t e li see pol ers ecre ses. T ese s pless ow ig er swelli g t c tio ic pol ers.

Fig re 2 s ows t e sorptio c rves or t e o-co posite s ples t 20 1C. Fig re 2 s owssorptio or t e s ples wit v r i g co j g te li -see oil co te ts t 5% o t orillo ite co te ts. It isobserve t t wit i cre se i t e oil co te ts, t eswelli g o w ter ecre ses. T e cr lic ci b sepol ers ge er ll s ow ig w ter bsorptio . T e

ecre se i t e cr lic ci co te ts res lts i lessswelli g. Fig re 2b s ows t e sorptio c rves or t es ples wit v r i g o t orillo ite co te ts ro0 to 10% si il r co positio s. I Fig re 2b, t epristi e pol er s ows xi swelli g t es ple wit 2.5% o-cl s ows i i swell-i g. T e s ples wit o-cl s ows six ol

ecre se i t e swelli g t t e pristi e pol er. Fort e s ples co t i i g o-cl , t e xi

i i swelli g is observe or t e s ples wit7.5% 2.5% cl co te ts ( o i e b hdaB),respectivel .

For t e swelli g o c tio ic s ples, t e r te o pt ke i cre ses s sorptio procee s, b t l terecre ses s t e l eq ilibri is ppro c e

(Fig re 1b). T ese c rves re o te re erre to s sig-oi sorptio c rves [19]. T e re ge er te e to

t e re so t t t e s r ce eq ilibri co itio s reot est blis e i st t eo sl . I t er l s ples,

two st ge sorptio is evi e t or ll t e s ples. It is

e to q si-eq ilibri , w ic rst re c es r pi lt t e pol er s r ce t e b si ple i siot ro g o t t e pol er s ple [20]. T e seco st geo sorptio is ssoci te wit i cre se i s r ceco ce tr tio , w ic occ rs slowl co p re to t e

i sio process is t e r te- eter i i g ctor or

sorptio . T e co ce tr tio is virt ll i ort ro g o t t e s eet i cre ses t r te, i epe -

e t o t e t ick ess.I t e o-co posite s ples, t e sorptio c rves

re sig oi l re i isce t o t er l s ples. W eco plex sorptio be viors like sig oi l s pes reobserve , it is s ll ss e t t o lo s or o -Ficki tr sport occ rs [21]. nevert eless, rorece t works, better r tio liz tio o t ese o -lo s be viors s bee c ieve , w ere co trib tio s

ro t e e ect o croscopic el stic co str i ts ris-i g ri g t e swelli g process (geo etric l e ects)i sorptio experi e ts ve bee poi te o t [22].I iti ll , t e s ple is co pletel r i ersei t e wet e viro e t (pe etr t). T e i sio o

pe etr t st rts i st t eo sl t e s ple st rtsswelli g. T e r ( o -swolle ) core o t e s pleexerts co pressive stress o t e o ter wet (swolle )l ers i eri g t e i sio [2122]. Si ce t e coreis still r , t e o l irectio to w ic t e s ple is

llowe to swell is perpe ic l r to t e s r ce (st geI). T is is prove b t e st i cre se i t ick ess o t e s ple, co p re to t e sq re root i cre se o t e re . as t e i sio ro t pe etr tes t e s ple,t e re ci g orce is less pro i e t lti tel

is ppe rs w e t e i sio ro t re c es i le o t e s ple. at t is poi t, t e swelli g o t e s ple is

ree to co e ce i ll irectio s (st ge II) t ei sio r te i cre ses, til it levels o (close to t eisse i tio poi t).

Fig re 3 s ows t e sorptio c rves or s pleswit 50% li see oil co te ts t i ere t te per -t res. For t e s ples prep re b c tio ic pol er-iz tio , Li 50 s ple s ows xi swelli g t70C ecre ses wit ecre se i te per t re. Fort er l s ples, t e CLi 50 s ple s ows i i-

swelli g t 20C xi swelli g t70C. T e o-co posite s ple CLi mOnT50s ows i i swelli g t 20C xiswelli g t 70C. I ll t e s ples, it is observe t tt e swelli g i cre ses wit i cre se i te per t re.T is is e to t e ct t t t e pol er c i s ows

ig er seg e t l obilit cco o ti g ig ero t o t e solve t.I or er to o t t e ec is o swelli g,

t e i sio t is tte i to e piric l eq tio(eq. 3), [23] erive ro t e eq tio o tr sportp e o e (eq. 2) [15]



6/16


Q

Qkt t n

= (2)

lQ

Q k n t t

= +l l (3)

w ere Q t Q re t e ole perce t pt ke o sol-ve t t ti e t t i it or eq ilibri . k is co st t, w ic epe s po t e solve t-pol er

i ter ctio t e str ct re o t e pol er. For ll t es ples, t e regressio coe cie t (r) v ries betwee0.96 0.99. T e v l es o co st t k obt i e ro t e eq tio (3) Q re reporte iT ble 2 3. T e v l e o gives i e o t e

ec is o sorptio [24]. For t e v l e o s 0.5,t e ec is o swelli g is ter e s Ficki tr s-port. T is occ rs, w e t e r te o i sio o solve tis s ller t pol er seg e t l obilit . I t ev l e o is ot eq l to 0.5, t e t e tr sport isco si ere s o -Ficki . I p rtic l r, i = 1,

0 1 2 3 4 5 6 7 8 9

0.00

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

0.55

0.60

CLin50@20 oCCLin50@40 oCCLin50@55 oCCLin50@70 oC

Q t

( m o

l % )

(Time) 1/2 in hrs

CLinMONT50@20 oCCLinMONT50@40 oCCLinMONT50@55 oCCLinMONT50@70 oC

Lin50@20 oCLin50@40 oCLin50@55 oCLin50@70 oC

FIGuRE 3T e sorptio c rves or c tio ic s ple (Li 50-ST31.5-dVB10.5-I 8), t er l s ple (CLi 50-aca40-dVB10) o-co posite s -ple (CLi mOnT50- aca40-dVB10-mOnT5) t i ere t te per t re.



7/16


TaBLE 2V l es o ole perce t pt ke t i ite ti e (Q ), , k st r evi tio (Sd) or i ere t s ples t 20 40C

Te per t re (C) S ple Id Q ( ol %) k Sd

20

Li 30 0.04278 0.69 6.064 0.029

Li 40 0.04892 0.65 5.718 0.079

Li 50 0.05772 0.61 5.381 0.067

Li 60 0.06579 0.56 5.012 0.071

dCP7 0.02874 0.82 7.406 0.042

dCP16 0.03525 0.72 6.046 0.024

CLi 0 3.8964 0.62 0.989 0.214

Cli 10 3.1519 0.74 1.632 0.305

CLi 20 2.36348 0.81 2.231 0.328

CLi 30 1.10813 0.72 2.661 0.291

CLi 40 0.49872 0.54 2.819 0.205

CLi 50 0.32068 0.59 3.408 0.214

CLi 60 0.21341 0.54 3.762 0.085

CLi mOnT30 0.21485 0.89 0.046 0.635

CLi mOnT40 0.13639 0.81 0.027 0.019

CLi mOnT50 0.08869 0.72 0.015 0.0102

CLi mOnT60 0.05126 0.71 0.006 0.005

CLi mOnT70 0.03659 0.55 0.003 0.003

CTaB-mOnT2.5 0.07574 0.91 0.011 0.008

CTaB-mOnT7.5 0.10665 0.82 0.022 0.016

CTaB-mOnT10 0.09802 0.87 0.019 0.014

hdaB-mOnT2.5 0.0635 0.68 0.008 0.007

40

Li 30 0.12577 0.65 4.56 0.24

Li 40 0.13428 0.62 4.35 0.27

Li 50 0.1473 0.59 4.09 0.28

Li 60 0.1698 0.53 3.76 0.26dCP7 0.09546 0.79 5.39 0.28

dCP16 0.11493 0.71 4.90 0.23

CLi 0 5.9719 0.81 1.29 0.28

Cli 10 3.6271 0.85 1.90 0.32

CLi 20 2.8547 0.93 2.47 0.43

CLi 30 0.908 0.89 3.49 0.42

CLi 40 0.4376 0.79 3.88 0.27

CLi 50 0.12796 0.48 3.80 0.22

CLi 60 0.0754 0.29 3.85 0.06

CLi mOnT30 0.42876 0.72 3.57 0.27

CLi mOnT40 0.3371 0.73 3.87 0.24

CLi mOnT50 0.20914 0.68 4.24 0.21

CLi mOnT60 0.0929 0.67 5.11 0.05

CLi mOnT70 0.0498 0.59 5.44 0.19CTaB-mOnT2.5 0.18347 0.71 4.47 0.22

CTaB-mOnT7.5 0.25164 0.66 3.96 0.23

CTaB-mOnT10 0.23867 0.69 4.15 0.24

hdaB-mOnT2.5 0.16793 0.77 4.81 0.20



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TaBLE 3V l es o ole perce t pt ke t i ite ti e (Q ), , k st r evi tio (Sd) or i ere t s ples t 55 70C

Te per t re (C) S ple Id Q ( ol %) k Sd

55

Li 30 0.1154 0.68 4.78 0.22

Li 40 0.1404 0.59 4.23 0.24

Li 50 0.1875 0.56 3.75 0.27

Li 60 0.2416 0.55 3.51 0.23

dCP7 0.1367 0.64 4.45 0.24

dCP16 0.1952 0.56 3.74 0.27

CLi 0 5.4344 0.64 0.71 0.27

Cli 10 3.9154 0.66 1.17 0.24

CLi 20 2.8335 0.72 1.76 0.23

CLi 30 1.5827 0.61 2.02 0.15

CLi 40 0.945 0.63 2.57 0.18

CLi 50 0.59116 0.57 2.70 0.21

CLi 60 0.30565 0.50 3.04 0.31

CLi mOnT30 0.6041 0.58 2.63 0.32

CLi mOnT40 0.5125 0.67 3.15 0.33

CLi mOnT50 0.37167 0.77 3.88 0.31

CLi mOnT60 0.19768 0.76 4.42 0.36

CLi mOnT70 0.12031 0.65 4.61 0.23

CTaB-mOnT2.5 0.32582 0.76 4.08 0.26

CTaB-mOnT7.5 0.44372 0.70 3.49 0.26

CTaB-mOnT10 0.41711 0.76 3.76 0.31

hdaB-mOnT2.5 0.27587 0.77 4.23 0.28

70

Li 30 0.2247 0.63 3.85 0.27

Li 40 0.24127 0.56 3.47 0.28

Li 50 0.2783 0.50 3.09 0.31

Li 60 0.31769 0.46 2.76 0.31dCP7 0.18166 0.78 4.69 0.29

dCP16 0.20349 0.72 4.33 0.28

CLi 0 4.0765 0.63 0.99 0.22

Cli 10 3.5618 0.73 1.54 0.24

CLi 20 2.9784 0.83 2.09 0.28

CLi 30 2.4574 0.94 2.72 0.27

CLi 40 1.37773 0.76 2.74 0.15

CLi 50 0.42436 0.53 2.91 0.19

CLi 60 0.25078 0.38 2.92 0.11

CLi mOnT30 0.77102 0.69 2.96 0.19

CLi mOnT40 0.70224 0.90 3.81 0.27

CLi mOnT50 0.50475 0.79 3.89 0.14

CLi mOnT60 0.30529 0.89 4.79 0.14

CLi mOnT70 0.15546 0.87 5.34 0.24

CTaB-mOnT2.5 0.44727 0.86 4.29 0.16

CTaB-mOnT7.5 0.64869 0.83 3.73 0.15

CTaB-mOnT10 0.59465 0.90 4.09 0.21

hdaB-m OnT2.5 0.4053 0.87 4.46 0.11



9/16


t e tr sport is c lle c se II tr sport [24]. It is speci l c se, w ere t e solve t ro t oves wit co -st t velocit . I lies betwee 0.5 1, t e itis c lle o lo s tr sport [24]. For o -Fickitr sport, i sio is ore r pi t t e pol errel x tio r te. For o lo s tr sport, t e i sio

rel x tio r tes re co p r ble [24]. I sorptio isless t 0.5, t e it is ter e s pse o-Ficki tr s-port. It is c r cterize b i iti l c rv t re o t e Q t vers s t 1/2 plots o t o t e origi co c ve to t e ti e

xis [2526]. Fro T ble 2 3, t e v l es o rebove 0.5, i ic ti g t e tr sport s o -Ficki or

o lo s tr sport.T e swelli g t is se to c lc l te t e i sio

coe cie t (d), w ic is e s re o t e bilit o t e

solve t olec les to ove t ro g t e pol er t e sorptio coe cie t (S), w ic gives i e bo tt e eq ilibri sorptio . T e i sio coe cie t (d)is c lc l te s [27]

D hQ

=

4

2

(4)

w ere = 3.14; is t e t ick ess o t e r s ple is t e slope o t e i iti l li e r portio o t e

c rve Q t vers s t; Q is t e ole perce t pt keo t e solve t t i ite ti e.

T e sorptio coe cie t (S) is c lc l te s [27]

S = mm p

(5)

w ere m is t e ss o t e solve t pt ke t eq ilib-ri m p is t e ss o t e r s ple. T e sorp-tio i sio coe cie ts re se to c lc l teper e bilit coe cie t (P) o t e s ples, w ic isgive b [27]

P D S= (6)

T e v l es o t ese coe cie ts re reporte iT ble 4 5. It is observe t t or c tio ic s ples,Li 60 s ple s ows t e ig est t e dCP7 s ples ows t e lowest i sio coe cie t. T e i siocoe cie t o t e c tio ic s ples i cre ses wit i cre se i t e oil co te ts ro 30 to 60% (T ble 4

5). T is be e to t e i cre se i t e oil p rt,w ic rel xes e sil t s provi i g sp ce to t esolve t t ereb , i cre si g t e i sio o sol-ve t i t e pol er etwork. T e i sio coe cie ti cre ses wit i cre se i t e te per t re or llc tio ic s ples. T e i cre se i t e i sio coe -cie t is e to t e o i ce o t e oil portio i t epol er trix. a i cre se i oil p rt ecre se i

ro tic or crossli ker p rt res lts i i cre se iseg e t l obilit e ce, provi i g ore sp ceto t e w ter olec les. W e dCP is e to t e s s-te , j st opposite be vior is observe . T e s plewit 40% li see oil s ows i i , w ere s t es ple wit 60% oil s ows xi i siocoe cie t. T is be ttrib te to t e prese ce o

dCP w ic is less re ctive t ivi lbe ze e, s ow-i g opposite tre . T e sorptio coe cie t s ows i cre se wit i cre se i oil co te ts te per -t re. T e i cre se i sorptio is q ite s ll l osteq l to o e or ll s ples t ll te per t res. T isi ic tes t t t ere is ver less c ge i t e sorptioproperties wit v ri tio i oil co te ts s well s te -per t re. T e per e bilit i t e s ples s ows t es e tre s t t or i sio coe cie t.

T e t er l pol ers s ow i cre se i t e i -sio coe cie t wit i cre se i t e oil co te t

(T ble 4 5). T is is e to t e prese ce o ig ero t o oil i t e s ples. T e ig er oil co te ts

res lts i fexible c i str ct re, w ic gives rise tol rge size icrovoi s. T ese l rge icrovoi s givee s p ss ge to t e s ll w ter olec les. T e sorp-tio coe cie t ecre ses wit i cre se i oil co -te ts i cre ses wit i cre se i te per t re. atzero or low li see oil co te ts, t e sorptio is e tot e cr lic ci , w ic s goo it or w ter. T ei cre se i oil co te ts res lts i et ecre se i

cr lic co te ts, re ci g t e sorptio i pol ertrix. T e per e bilit i t e s ples is observe to

s ow si il r tre s t t or i sio coe cie t.For o-co posite s ples, t e i sio coe -

cie t ecre ses wit i cre se i t e oil co te ts.CLi mOnT30 s ows xi , w ere s CLi -

mOnT70 s ows i i i sio coe cie t.T is is ex ctl opposite to t e be vior s ow b t epristi e pol er s ples. Ge er ll , wit i cre si goil co te ts i t e pol er, crossli ki g e sit

ecre ses, le i g to i cre se i t e solve t pt ke[28]. I t e prese t c se, t e ecre se i t e solve t



10/16


TaBLE 4di sio coe cie t (d), Sorptio coe cie t (S) Per e bilit coe cie t (P) i w ter or i ere t s ples t 20 40C

Te per t re (C) S ple Id d 10 2 (c 2 /sec) S (g/g) P 10 2 (c 2 /sec)

20

Li 30 0.96 1.005 0.96

Li 40 1.10 1.006 1.11

Li 50 1.22 1.009 1.23

Li 60 1.40 1.012 1.42

dCP7 0.46 1.015 0.47

dCP16 0.82 1.022 0.84

CLi 0 15.88 1.701 27.01

Cli 10 12.58 1.567 19.71

CLi 20 15.76 1.431 22.55

CLi 30 16.38 1.157 18.95

CLi 40 19.38 1.039 20.14

CLi 50 16.12 1.026 16.54

CLi 60 28.01 1.001 28.04

CLi mOnT30 26.39 1.039 27.42

CLi mOnT40 12.35 1.020 12.59

CLi mOnT50 11.28 1.008 11.37

CLi mOnT60 7.90 1.008 7.96

CLi mOnT70 5.54 1.004 5.56

CTaB-mOnT2.5 5.08 1.015 5.16

CTaB-mOnT7.5 13.24 1.010 13.37

CTaB-mOnT10 9.90 1.010 9.99

hdaB-mOnT2.5 14.40 1.012 14.57

40

Li 30 2.82 1.022 2.88

Li 40 2.63 1.022 2.69

Li 50 3.29 1.027 3.38

Li 60 3.69 1.031 3.80dCP7 1.46 1.018 1.48

dCP16 2.12 1.022 2.17

CLi 0 16.26 2.075 33.73

Cli 10 15.01 1.653 24.81

CLi 20 16.00 1.514 24.22

CLi 30 17.72 1.163 20.61

CLi 40 21.99 1.079 23.73

CLi 50 17.08 1.023 17.47

CLi 60 30.59 1.005 30.74

CLi mOnT30 42.38 1.079 45.73

CLi mOnT40 18.68 1.061 19.82

CLi mOnT50 13.04 1.033 13.47

CLi mOnT60 14.11 1.017 14.35

CLi mOnT70 12.66 1.009 12.77

CTaB-mOnT2.5 8.73 1.039 9.07

CTaB-mOnT7.5 21.97 1.036 22.76

CTaB-mOnT10 14.19 1.036 14.70

hdaB-mOnT2.5 25.11 1.034 25.96



11/16


TaBLE 5di sio coe cie t (d), Sorptio coe cie t (S) Per e bilit coe cie t (P) i w ter or i ere t s ples t 55 70C

Te per t re (C) S ple Id d 10 2 (c 2 /sec) S (g/g) P 10 2 (c 2 /sec)

55

Li 30 2.81 1.021 2.87

Li 40 3.21 1.025 3.29

Li 50 4.21 1.034 4.35

Li 60 3.58 1.043 3.73

dCP7 2.71 1.025 2.77

dCP16 5.14 1.035 5.32

CLi 0 17.38 1.978 34.37

Cli 10 17.25 1.705 29.41

CLi 20 17.44 1.510 26.33

CLi 30 19.69 1.219 24.00

CLi 40 26.29 1.113 29.26

CLi 50 19.42 1.037 20.13

CLi 60 32.24 1.011 32.59

CLi mOnT30 65.32 1.109 72.43

CLi mOnT40 19.99 1.092 21.83

CLi mOnT50 16.47 1.047 17.24

CLi mOnT60 24.06 1.027 24.71

CLi mOnT70 18.00 1.015 18.27

CTaB-mOnT2.5 9.68 1.063 10.29

CTaB-mOnT7.5 22.93 1.076 24.67

CTaB-mOnT10 15.53 1.073 16.66

hdaB-mOnT2.5 27.09 1.052 28.49

70

Li 30 4.35 1.040 4.52

Li 40 4.47 1.040 4.64

Li 50 6.07 1.050 6.37

Li 60 6.99 1.056 7.38dCP7 2.06 1.033 2.13

dCP16 3.14 1.036 3.25

CLi 0 21.17 1.734 36.71

Cli 10 18.35 1.641 30.11

CLi 20 19.43 1.536 29.84

CLi 30 21.52 1.442 31.03

CLi 40 28.01 1.136 31.82

CLi 50 23.58 1.052 24.81

CLi 60 34.10 1.019 34.74

CLi mOnT30 74.63 1.079 80.52

CLi mOnT40 21.56 1.126 24.27

CLi mOnT50 19.54 1.063 20.77

CLi mOnT60 29.46 1.059 31.19

CLi mOnT70 31.86 1.027 32.72

CTaB-mOnT2.5 13.03 1.095 14.27

CTaB-mOnT7.5 25.94 1.114 28.89

CTaB-mOnT10 17.69 1.093 19.33

hdaB-mOnT2.5 28.75 1.073 30.84



12/16


pt ke wit i cre se i t e oil co te ts c o l beexpl i e wit possible i cre se i t e crossli k e -sit e to t e prese ce o t e xe o t o o-

ller i t e co positio . T e prese ce o o-clpossibl i cre ses t e r te o re ctio o li see oil

ri g t e copol eriz tio , le i g to i cre se it e crossli k e sit .

T e bove e tio e i gs ve bee co r eri g t e t er l pol eriz tio o co j g te li -

see oil ixt re o o- ller wit co j g teli see oil. d ri g t e s e perio o 8 e ti g (t er-

l pol eriz tio ), it s bee observe t t t ei cre se i viscosit is c ig er i t e c se o

o-cl lle co j g te li see oil, co p re too l co j g te li see oil. T is i ic tes t e r te o

t er l pol eriz tio i cre ses lot e to t e pres-e ce o o- ller. T e o- llers re so i

g esi silic tes [m + (al 2- mg )(Si 4)O10(Oh) 2* h 2O]. T ese c tio s, ge er ll , elp i

r i g o li see oil [2931]. T e i cre se i clco te ts ro 0 to 10% res lts i i cre se i t e

i sio coe cie t. T e i cre se i te per t reres lts l ost two ol i cre se i t e i sio coe -

cie t. I t ese s ples, t e s ple wit o t cls ows xi t e s ple wit 2.5% cls ows i i swelli g. T e s ple wit 5, 7.5

10% o-cl s ows ig er solve t pt ke tt e s ples wit 2.5% o-cl co te ts. T is be e to t e re so t t t e s ple wit 2.5% cl

s xi co p tibilit s ows better w terresist ce properties. T e cl ( o t orillo ite) is

o i e b two s r ct ts, s c s cet l tri et lo i bro i e (CTaB) ex ec l o-

i bro i e (hdaB). T e s ple wit CTaB o -i e o t orillo ite s ows less i sio t t es ple wit hdaB o i e o t orillo ite. T ehdaB o i e o t orillo ite s ows t ree oli cre se i t e i sio coe cie t.

a i cre se i te per t re res lts i i cre se it e i sio coe cie t or ll t e s ples. T e sorp-tio coe cie t or ll t e s ples s ows ecre sewit i cre se i oil s well s cl co te ts. T is i i-

c tes t t t e solve t ssi il tio or t e bilit tobsorb solve t ecre ses e to t e i corpor tio o o- ller. T is i ic tes t e goo co p tibilit o

t e o-cl pol er trix. T e per e bilitcoe cie t s ows si il r tre s s is or i siocoe cie t.

di sio per e tio re t er ll ctiv teprocesses, t eir te per t re epe e ce c be

se to c lc l te t e ctiv tio e erg or t e processo w ter bsorptio . T e ctiv tio e erg or i -sio (E d ) or per e tio (E P) is c lc l te b

si g st r arr e i s rel tio s ip (eq tio 8)[3233].

X = X (eo E /RTX ) (7)

logX logX Eo X= / . .2 303 RT (8)

w ere X represe ts eit er d or P, X o is co st t rep-

rese ti g eit er d o or P o. E X is eit er E d or E P, w icepe s po t e swelli g process er co si er-tio . Fro t e li e r plot o log X vers s1/T, t e v l-es o EX c be c lc l te . Fig re 4 gives t e plot o

log d vers s 1/T Fig re 5 gives t e plot o log Pvers s 1/T or i ere t pol er s ples. T e v l eso Ed EP c lc l te ro Fig re 4 5 re s owi T ble 6. T e regressio coe cie t v l es i esti -tio re betwee 0.92 0.99. T e e t o sorptio(h S) is lso c lc l te si g t e eq tio 9[3233],

h E ES P d= (9)

T e v l es o h S provi e itio l i or tiobo t t e tr sport o solve t olec les t ro g t e

pol er trix. T e v l es o h S re give iT ble 6. all t e v l es re positive, i ic ti g he rsorptio i t e jorit (e ot er ic co trib tio tot e sorptio process) [34]. T is t pe o sorptio isco cer e wit t e or tio o ole o olec -l r size i t e pol er trix [34]. T e ctiv tioe erg or i sio is t e e erg ee e to e blet e issolve olec les to j p i to ot er ole.T e positive ctiv tio e erg o i sio or ll t epol er s ples i ic tes ig e erg req ire-

e t to j p ro o e ole to ot er. C tio ics ples ve t e ig est t er l s ples vet e lowest v l es o E d . T e t er l s ples req irelesser o t o ctiv tio e erg or i siobec se t e co t i cr lic ci i t eir co posi-tio s.



13/16


0.0029 0.0030 0.0031 0.0032 0.0033 0.0034

7.39

20.09

54.60

0.0029 0.0030 0.0031 0.0032 0.0033 0.0034

20.09

0.0029 0.0030 0.0031 0.0032 0. 0033 0.0034

1.00

2.72

7.39

0.0029 0.0030 0.0031 0.0032 0.0033 0.0034

7.39

20.09

L o g

D

1/T (K -1)

CLinMONT30

CLinMONT40

CLinMONT50

CLinMONT60

CLinMONT70

CLin50

CLin60

L o g

D

1/T (K -1)

CLin0

CLin10

CLin20

CLin30

CLin40

L o g

D

1/T (K -1)

Lin30

Lin40

Lin50

Lin60

DCP7

DCP16

CTAB7.5

CTAB10

HDAB2.5

1/T (K -1)

L o g

D

CTAB0

CTAB2.5

CTAB5

FIGuRE 4T e plot o log d vers s i verse o te per t re (1/T) or i ere t s ples.

concLuSIon

a ew s ste o li see oil b se pol ers is i ves-tig te or t e sorptio i sio st ies i w ter.T e ki etics o t e sorptio is st ie b si g t eeq tio o tr sport p e o e . T e v l es o i

tr sport eq tio re o to be betwee 0.5 1,s owi g t e o -Ficki i sio i t e pol er. T eepe e ce o t e i sio coe cie t o t e co po-

sitio te per t re s bee st ie or t e pol -eric s ples. T e i sio coe cie t i c tio ic

s ples i cre ses wit i cre se i t e oil co te ts i



14/16


t e s ples w ere s, or t er l s ples, it ecre seswit i cre se i oil co te ts. T e o-co posites ples s ow less i sio coe cie t t pristi epol er it ecre ses wit i cre si g o t o li -see oil. T e i sio coe cie t i cre ses wit i cre se i te per t re or ll pol er s ples. T e

sorptio coe cie t s ows ver little c ge witc ge i co positio s well s te per t re or ll t es ples it is i r ge o o e. T e ctiv tioe erg or i sio per e tio is positive or llt e s ples. T e e t o sorptio is lso positive or llt e s ples s owi g he r t pe o e o sorptio .

rEfErEncES

Elissee J, a set K, L ger R, hrk c JS. S t esis c r c-teriz tio o p oto-cross-li ke pol ers b se o pol (L-l c-tic ci -co-L- sp rtic ci ). m cro olec les 1997; 30:21822184.

h sirci V, Lew rowski K, Gresser Jd, Wise dL, Tr tolo dJ.Vers tilit o bio egr ble biopol ers: egr bilit i vivo pplic tio . Jo r l o Biotec olog 2001; 86:

135150.

h g SJ, Rob mS. Bio egr ble pol ers pol ( i e- re-t es). Jo r l o Bio ctive Co p tible Pol er 1986; 1:6171.

0.0029 0.0030 0.0031 0.0032 0.0033 0.0034

1.00

2.72

7.39

0.0029 0.0030 0.0031 0.0032 0.0033 0.0034

20.09

0.0029 0.0030 0.0031 0.0032 0.0033 0.0034 0.0035

7.39

20.09

54.60

0.0029 0.0030 0.0031 0.0032 0.0033 0.0034 0.0035

7.39

20.09

L o g

P

1/T (K -1)

Lin30

Lin40

Lin50

Lin60

DCP7

DCP16

CLin30

CLin40

CLin50

CLin60

L o g

P

1/T (K -1)

CLin0

CLin10CLin20

L o g

P

1/T (K -1)

CLinMONT30

CLinMONT40

CLinMONT50

CLinMONT60

CLinMONT70

CTAB10

HDAB2.5

L o g

P

1/T (K -1)

CTAB0

CTAB2.5

CTAB5

CTAB7.5

FIGuRE 5T e plot o log P vers s i verse o te per t re (1/T) or i ere t s ples.



15/16


TaBLE 6arr e i s p r eters e t o sorptio or i ere t pol ers i w ter

S ple Id E d 10 3 (kJ/ ol) E P 10 3 (kJ/ ol) h S 10 3 (kJ/ ol)

Li 30 16.29 16.70 0.40

Li 40 15.69 15.99 0.30

Li 50 18.03 18.46 0.44

Li 60 16.93 17.38 0.46

dCP7 18.78 18.91 0.13

dCP16 17.98 18.12 0.15

CLi 0 3.05 3.39 0.35

Cli 10 4.46 5.12 0.67

CLi 20 2.36 3.13 0.77

CLi 30 3.16 5.45 2.29

CLi 40 4.47 5.48 1.01

CLi 50 4.23 4.52 0.29

CLi 60 2.24 2.43 0.19

CLi mOnT30 12.46 12.99 0.53

CLi mOnT40 6.31 7.44 1.13

CLi mOnT50 6.42 7.02 0.60

CLi mOnT60 15.67 16.21 0.53

CLi mOnT70 19.53 19.78 0.25

CTaB-mOnT2.5 10.34 11.19 0.86

CTaB-mOnT7.5 7.48 8.61 1.13

CTaB-mOnT10 6.52 7.47 0.95

S r V, K PP. a itio pol ers ro t r l oils-a review.Progress i Pol er Scie ce 2006; 31: 9831008.

Li F, h so mV, L rock RC. So be oil- ivi lbe ze e t er o-setti g pol ers: s t esis, str ct re, properties t eir rel -tio s ips. Pol er 2001; 42: 15671579.

Wool RP, K se ogl Sh, P l ese GR, Z o R, K ot Sn. higo l s pol ers co posites ro pl t oils. u.S. P te t

6,121,398, 2000.

K ot Sn, L sc l JJ, C E, mor e SS, Willi s GI, P l ese GR,K se ogl Sh, Wool RP. develop e t pplic tio o trig-l ceri e-b se pol ers co posites. Jo r l o appliePol er Scie ce 2001; 82: 703723.

Zo K, So cek md. uV-c r ble org ic-i org ic bri l

co ti gs b se o epoxi ize c clo exe e eriv tize li seeoil. m cro olec l r C e istr P sics 2004; 204:20322039.

Zo g Z, So cek md, Li y, h J. C tio ic p otopol eriz tioo epox orbor e li see oils: T e e ect o il e ts. Jo r lo Pol er Scie ce. P rt a: Pol er C e istr 2003; 41:34403456.

L J, ho g CK, Wool RP. Bio-b se oco posites ro c-tio lize pl t oils l ere silic te. Jo r l o Pol erScie ce. P rt B: Pol er P sics 2004; 42: 14411450.

Sto V, Kli e t C. h rogels: Speci lit pl stics or bio e ic l p r ce tic l pplic tio s, Tec o ic P blic tio , B sel.

1996.

C rto C, Sc iller n, F l m, holl er a, We el a, noller K.develop e t o ig b rrier l s o fexible pol er s b-str tes. T i Soli Fil s 2006; 502: 99103.

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Wiesb e ah, W ll EP, Wiesb e GB. acr lic pol ers v-i g ig swell bilit i w ter. 1982, uS P te t 4337328.



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B gle E, Lo g Fa. Two-st ge sorptio esorptio o org icv pors i cell lose cet te. Jo r l o a eric C e ic l Soci-et 1955; 77: 21722178.

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Rossi G. m croscopic escriptio o solve t i sio i pol eric

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Cr k J. C pter 11. T e m t e tics o di sio ; 2 e . Cl re -o Press. Ox or 1975; 254265.

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Water Sorption and Diffusion Through

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