Adsorption Thermodynamics of Polyamidoamide Epichlorohydrin Polymer in an Aqueous Fibrous Suspension PAE

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(1)Journal of the Korean Chemical Society 2003, Vol. 47, No. 3 Printed in the Republic of Korea. PAE

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(4) (2003. 4. 10 !") †. ‡. #. Adsorption Thermodynamics of Polyamidoamide Epichlorohydrin Polymer in an Aqueous Fibrous Suspension Sung-Hoon Yoon*, Kwang-Suk Joo†, Tae-Won Lee‡, Kun-Han Kim#, and Byung-Bin Park Research Institute of Technology, Korea Minting and Security Printing Corporation, Daejon 305-713 Korea † Department of Environmental Management, Hyechon College, Daejon 302-715 Korea ‡ Korea Electric Power Research Institute, Korea Electric Power Corporation, Daejon 305-380 Korea # Environmental Geology Division, Korea Institute of Geoscience and Mineral Resources, Daejon 305-350 Korea Department of Chemistry, Kongju Nat'l University, Chungnam 314-701 Korea (Received April 10, 2003). . # $ %& -'()* PAE +, -. /012 Lanumuir 3 Freundlich4 /0 567 89: ;1< =>? @?A "BCDE. %&. FGH@: ;1I JK-: LM. NO@ PQ 7 .- ,RCD+, PAE +, /0SI +, -T). PCD :Q< U- PQCDE. PAE +, *VI W. NO@7 XY Z2< [\]^ *V _7$ NO@ à bc XY dOef gh. i jk ? lm'`< dO*DE. PAE +,$ no p$ ò7q r-Langmuir /0 sH< tAD]d ouc v c?Gq Freundlich "w(ν)x yz:]{ |}$ ~ dO*DE. PAE +,. Gibbs /0 &7{ "(N )$ ò7q 7~8. @{ dOe+ +, +. I 215 nm{q 10 C ouà7 - 9% vc?E. W * PAE +,. /0 $ −27~−29 kJ/molx^ n7 /0x =>CDE. : PAE, N, +, /0, , o. seg. ABSTRACT. This study was to examine the thermodynamic features of polyelecrolytic adsorption of polyamidoamine-epichlorohydrin(PAE) in a papermaking wet-end. The PAE adsorption experiments were conducted in a stirred jar containing an aqueous fibrous suspension and evaluated in terms of Langmuir and Freundlich parameters. The electrokinetic property of a stock was examined by measuring the zeta potential of each colloidal suspension. The polyelectrolytic PCD titration was employed to determine the adsorbed amounts of PAE polymer. The zeta potential of a stock, being varied significantly depending upon the addition of PAE polymer, showed initially a sharp increase and later an exponential decay as a function of time . The PAE adsorption exhibited a pseudo-Langmuir adsorption behavior at 20 oC, whereas its Freundlich power(ν) increased in a proportional way at an elevated temperature. The train numbers calculated on the basis of adsorption thermodynamics were 7 to 8. The length of the extended loop of PAE was calculated. 220.

(5) PAE

(6) . 221. as 215 nm at 20 oC and increased at a rate of 9% at every 10 oC rise in temperature. The PAE adsorption was proven to be an exothermic physisorption with the estimated adsorption enthalpy of −27 to −29 kJ/mol. Keywords: PAE, Papermaking, Polymer Adsorption, Langmuir, Enthalpy. . 3. "$ x. u(wet-strength) 2`g @- N7 q TC+ $ (wet-end) *VN{q . "d ¡¢£ "7 y- ¤1 3 ¥¦1 _(papermaking) §7qu 'x |E$ ¨ < ©+ E. PAE +,7$ azetidinium ªT¢ + «$ 4 aminochlorohydrinc 61C "T) *7q ¬xo1 +, -{q sH?Y C+ ®%& ¯G. °xo1 carboxyli Q: x ªT?A %& ¯G]{ x±+ Q0?Y ? $ ²< ©$E. PAE "c x. u 'g$³ ´ µ ¶. ·x A?$ ¸]{ ¥¹º $³ » ¤ ?d$ ,m. azetidinium ªTc E¼ ,m. 2 }£i ·?A , m h c~½< 61g$ ²x^ p ?d$ ,m7q 2¾ x`. azetidinium ªTc µ ¾. %& x7q ¿ %&. carboxyli ·?A %& h c~½< 61g$ ²xE. xÀ ·I + o. §Q7q xÁ ^ x *V +,. (curing) p$ Â1]{ ¯'E. 7q %&7 PAE +,. /0²I u '< ~Q ? @ 1: x ÃÄ7 +,. /0 12 I _g +,. t¶(retention) ~Q?$ # ¢+ Å " + %& ¯G. °xo1, ® Æu, /0 gh, +, *VÇ 3 ® +-u(beating degree) È. 7 Z2< ÉY ÊE. Ë¢q %& '( ) *7q %&7 PAE +, . /0 ;1 < x-?$ ¸I ´: QbÇ &i Ì2`< @ ÍÎ. ÏB §]{ Ð¿Å " ]^ x @- , /0 ¾Ñ. _ : ·T . Ò 1x µ ÊE. '()7q. %& p$ y%& ÓW7 ¿ +, . /07 {$ CMC7 ¬xo1 FGÔ1N p$ ¬1 ,. /07 3 ÕÖ{×Ø7 ¬xo1 polyacrylamide. /07 , ÕÖ{×Ø %& Polyamidoamine-epichlorohydrin(PAE). 1. 2. 2003, Vol. 47, No. 3. 7 ¬1,. /0;1, ¯Ù }Ú ® 7 polyacrylamidei polyethylenimine. /0 ; 17 , È< yÛ?A X¢® ®7 - ¬xo1 polyacrylamide. /07 , ® 3 ÜN7 ¬1,. /0;1 , kaolin clay 7 poly(acrylate). /07 , Polystyrene T)7q poly(vinyl alcohol). /07 , X7 polyethylene/polypropylene oxide ÝÞ ¤ ½ß. /07 , °xo]{ ?Ê montmorillonite7 ¬xo1 +,. /07 . È E"c Ó?^ , /0 +,. Æu à 7 Èo /0S. à PQ ¸x U:xE. + , . /0 '`7 áuâ: {q ÕÖ {×Ø %&7 polyethylenimine. /0 áu , ¯Ù }Ú ®7 polyethylenimine. /0 áu 7 , ¯Ù }Ú®7 polyethylenimine /0. ZH: b7 , ÕÖ{×Ø % &7 ¬xo1 +,-. /0 áu7 . , ã¶ JK7q. ®%&7 ¬xo1 +, -. /0 áu7 , ã¶ §7q. ä7 +, /0, , Óå2, ¾8 áu È7 3 Polystyrene ¢æØ T)7q. polyallylamine. /0 áu7 È E". ~ c t+Ê ç E. G u "{q PAE +, . *V TÇx ´è 'né vc?+ °7u ê. ?+ ®%&7 PAE +,. /0 ;17 : $ ë `ì{q PAE +,. ´: ·T< @ : Wc ¿íé C+ $ QxE. Ë¢q, # $ NQ F7q . PAE +, -. /0 12 FGH: ;1 3 Langmuiri Freundlich¬4. /0 567 89 : ;1< =>? @?A "BCDE. 3,4. 5. 6. 7. 8. 9. 10. 11. 4,12. 4,13. 14. 15. 16,17. 18. *V +,$ Hercules { NÉI ¸ ]{q ,Sx 50f a.m.u.x+ ?îu$ 4.92 PAE.

(7) !". 222. gW T?E. ¿ W$ 0.5%{ 1 `ì7q /0 ï< "B?]^ 1 ï7q$ o u 20, 30 3 40 C. 3 "r]{ ð?A Èo / 0< g?E. 2 ï7q$ /0 -ñNN{ PAC ¿¿ Al O r 0, 0.013, 0.025 3 0.05% Vc ?A ò ó PAE +, 07q 16 mg/g-fiberô vcg^ /0 ï< õB?+, ¿ gW$ 300 rpm. áu7q 3,h ·gh< &?E. / 0-·x öã gW$ ÷, ó `È)< 10 mL øù?+ ú ?PQ(particle charge detector, PCD-O3 pH) T?A `È)* û& PAE +,S < PQ?$³ :Q)I 0.001N PES-Na +, T)< 2_ü 0.02 mL áu{ ú?Gq ¤ ô :Q?E. PAE +, *V W(paper stock)$ 0.2% Æu. '()]{ 1 ó 72 mesh ýþ7q _?A r 5S 100 g/m . "_{ N ª?E. _g W ,1I M/K ÿ êu (non-uniformity index, NUI) PQ ó » . 9" { , u(uniformity index, UI) ?A T?E. UI . F L4I 4 (1)7 dO ç i E. meq/g. o. 2. 3. 2. µ 1 UI = ---------- = -----I NUI σI. (1). A7q µ 3 σ $ PQÊ . u ,7 ¿¿. 5 ¯r . < dOE. N O @PQ< @- %& '(). Æu 2.05%{ Æ g+ PQg 250 g< øù?A 300 rpm]{ ?Gq x

(8) (TiO ) xä#< Vc ó PAE *V?A gW N?E. ¿ gW$ 5,h ·g v¶" 750 g< c?A 0.5%. R)] { ó JK@(streaming potential) PQ(Model: SZP-04) T?A NO@ PQ?E. I. I. 2. "$ N 7 *V g +, 7 Ó?$ azetidinium ion* 4c }£. ªT7 .- ¬ xo1 +, -{q sH?Y C+ W *7q °?. ®%&i Q: x ªT?A %& ¯G]{ x± /0?Y ÊE. _g *V +, PAE. PAE. Fig. 1. Hypothetical model of a PAE polymer chain adsorbed from a aqueous phase on a fiber surface.. c %&¯G7 /0?A 7 t¶C$ Qu$ _ bÇ x 1< ~Q?$ ¤ {q ªTÅ }¢ [ t¶² "(drainage) ;1, _"Ç(papermachine yield) 3 Ù"(white water) . (u È7 Z2?A ÌI â NQ. : N1< ?Y ÊE. T)*7q +, - x +ß ¯G7 /0?$ xâ: I Hesselink 7 .- NC CD+ x ès{ ¬xo1 PAE +,c °xo1 %&¯G7 - /0Å " $ 6ì. c`. < dO*G Fig. 1 E. Fig. 17 Ê çi x %& ¯G7q. +, /06ì$ )`]{ Y ¨- $ +(loop), %&¯G /0?A ! p$ ~½?+ $ (train) , »+ 6ì{ öd$ !(tail) , È 3 @{ ,?A "># " E. /0 +, . + @$ @ x7 µ+ $:] { 61C ÃÄ7 . ¾"$ /0. u i yz?Y C+ G +. ¨@i yz?$ F ©Y ÊE. +. ¨@$ W*7q % %&. &H: ;1< å?Y C+ p %&h : `$ªT7 Z2< [&$ ]{ ªTÅ " Y Cf # +7q$ +'I Ð (E. Fig. 2$ PAE ". %& ¯G7 /0 ;1< dO »)]{q PAE VcS "rx 0.8~0.9% ô$ 100% /0< tA+ ]d » x`7q$ /0*x l ?+ °< dO* + E. » )7qi x PAE /0 ;1I %,ÿ /0. Langmuir4 /0Q< tA+ $³ x$ /0ß 19,20. Journal of the Korean Chemical Society.

(9) PAE

(10) . 223. `ì¢ «^ xÃ$ *VÊ Ì ßc Ò(paper 7 t¶C /+ ýþ(wire), (press felt), 0 1Ø(dryer canvas) p$ Î ¯G(roll surface) È7 ð ¢2 ×3< ]$ è]{ ªT?u E. Fig. 37q$ PAE +, úÇx 0.2% "r7q N O@c 0 mV 4q+ » x`. *V "r7q $ ¯G?c °7q ¬. ]{ C$ '`< t A+ E. »Àd, .. PAE +, úÇ7 - dOã NO@$ 5: I }^ W, + -u, WÆu 3 !gh È7 .- àH# " $ à"xE. ;é !gh7 - NO@$ "j" : lmb dO*$ ;1< ©+ ÃÄ7 6 §x H ¬xo1 +,. *V _7$ , ¬. ]{ dOdf ghx ?Gq ° . ]{ ?Y ÊE. Fig. 4$ PAE +,. *V 7ó gh. 7 Ë¢ NO@c à ?$ '`< tA+ $³ 0.3% PAE +, *V _7$ ¬ . < tA+ Fig. 3. ~i &?d gh x 2~3, Ê ó7$ 0 mV d Eg °. ]{ C+ $ '`< tA+ E. PAE +,c /0Ê ó gh. j"{q ¯G @ c lm?$ 'Ì /0Ê +,c %&¯G c ôx7q /0 6ì Óå8?+ %& ¯G7 Ó? $ [8< U- ,mc *{ ? ÃÄ ¸]{ ¥¹º E. web). Fig. 2. Adsorption characteristics of PAE polymer adsorbent on fiber; the solid line indicates the hypothetical 100% adsorption.. Fig. 3. Zeta-potential change of fiber suspension as a function of PAE polymer addition level.. c +ßG )`7q 8: 56`ì7 Y C^ ´ /0Sx ÓE$ ¸< +-+ E. Fig. 3I PAE +,. *VS7 %&. NO @ .u dO »)]{q PAE +,. VcSx vcj7 Ë¢ NO@u vc?+ °< tA+ E. NO@$ %& ¯G. - x¤ÿ(electric double layer) * &H: %G7q PQC$ FGH@: @{q úh , ·,7 `$ªT7 ~Q?$ ¯{ T# " E. N O@c °. Z97 $ $ úh ·, tE$ ,1x `ìxd 0 mV7 cô-" Þ ·,12x vc?+ 0 mVc CG ´ 7 !è ?Y C _g ´:. t¶u dO*Y ÊE. ¬ xo1 +,c Ò x`]{ *VÊ NO@ c ¬. < ©Y C+ x .-¬?(over-cation) 2003, Vol. 47, No. 3. 21. PAE Langmuir . %& -'(). %& ¯G7 /0Ê PAE +, c )`7 &Ê PAE +,i 89: 56F7. Fig. 4. Charge decay exhibited by 0.3% PAE adsorbed onto fibers..

(11) !". 224. $ `ì c`?G E° x PAE ,. /0 Q< Q·]{ ?+ 0 Q< 9·]{ 564< u4Å " E. PAE ( l) + S f ⇔ PAE ⋅ Sf + H 2 O ; kads , k des. (2). A7q PAE(l), S 3 PAE9S $ ¿¿ )`7q & `ì PAE +,, %& ¯G. Ô1@(active site) 3 PAE-%&. /0 `ì dO*^ k i k $ ¿¿. áu`"7 -üE. )`7 Ó?$ PAE +, x %& ¯G]{ /0Å " $ Qu +,. ,Ç(θ){q E° x Q.Å " $³, f. f. ads. ΓPAE θ = -------------Γ PAE, ∞. des. (3). A7q Γ 3 Γ $ ¿¿ %& ¯G7 /0Ê +,. .. S 3 ´ S< dOE. +, ,Çx '()`7 Ó?$ PAE +, . Æui +,c /0 c² %& /0@. ¬ x7q QS: j" F dOE+ Å " $³ x Langmuir 64]{ ¯'?G E° I PAE +,. /0 Èo4 x :õE. PAE. PAE,. PAE. 22. K adsθ C PAE = -----------1–θ. (4). @ 47q C $ )`* %& § ¤S< r]{ ¯' PAE +, Æux^ K I PAE +,. %& /07 56`"{q k /k 7 -ü?+ + , ,Ç$ ;<: xE. 4 (4) θ7 Q?+ 4 (3)< ú?G E° 4x :õE. PAE. ads. ads. des. 1 1 1 -  -------------------------1 - -----------------------  ------------ = + ΓPAE Γ PAE,∞  K ads ΓPAE ,∞   C PAE . (5). 4 (5) T?A ï:]{ PQ Γ . 9"7 C . 9" ug?G 5 ]{ PAE +, PAE. PAE. ´ /0S(Γ )x ~Q# " + ={ +, /056`"(K )c FÊE. Table 1I W. ou 20, 30, 40 C. "r]{ ð?A PAE +, /0 ï< B?+ »Ã :õ W 4 (5)7 ès?A >? ,R ~{q Langmuir È o/0 `"i jk dO ¯xE. Table 17 dOã çi x W. ou$ PAE + ,. /07 Z2< [&$ x^ W o uc |}@7 Ë¢ %&7 ´ /0S(M ) I l ?$ G /0 56`". (K )I vc?$ ¸< dO* + E. PAE,. PAE. ads. o. PAE,. ads. PAE Freundlich . W -'()* ®%&. PAE +, /07 Langmuir4 !è LM7 q$ %& ¯G7 Ó?$ 6 Ô1@c ?^ Ë¢q /0Ê PAE +,c ©$ ~½7$ /0 @&7 FAx w ` Q?E$ cQ7 èsÊ ¸xE. »Àd, Bî .[7q W '() * ®%&$ E¬ ¶. 4 { 1C + p ¾¾. %&7 -qu C. : 1 [g: p ê Å " ÃÄ7 D7q. cQ]{ Langmuir Èo /0xâI 7 Ë¢ h. "Qx # " u E. H ® %&¢ Å¢u /0 @7 PAE +,. /0I xE?$ Ô1 @. PAE /0ß ÓA7 F Z2< É< "u Y ÊE. W '() * PAC +,. Æuc GI (K C H1) Langmuir64. /0Èo4I E° x % Ê 6ì{ # " E. ads. PAE. θ = K ads C PAE. (6). »Àd , GI Æu7qu @ 4x »{ :T C$ $ I ÃÄ7 Langmuir 64. /0 È o4< E¼ LM]{ "Q< c?A E°.. Table 1. Results of regression analysis for Langmuir isothermal adsorption of PAE polymers on fiber surfaces at three different temperatures. Regresson data. Langmuir parameters. Temp. (oC). y-intercept. slope. R. MPAE, . Kads. 20 30 40. 0.0174 0.0232 0.0318. 0.878 0.840 0.790. 0.98 0.98 0.98. 57.471 43.104 31.447. 0.020 0.028 0.040. 2. Journal of the Korean Chemical Society.

(12) PAE

(13) . 225. Table 2. Results of regression analysis for Freundlich isothermal adsorption of PAE polymers on fiber surfaces. Regresson data. Freundlich parameters. Temp. (oC). y-intercept. slope. R. ν. Kads. 20 30 40. −3.6732 −3.2974 −2.8920. 0.8103 0.7634 0.7095. 0.97 0.96 0.98. 1.22 1.32 1.41. 0.025 0.037 0.055. 64. /0Èo4 6ì fJ K "c 23. Freundlich. E. L,. 2. ΓPAE 1 v -------------- = Kads ( CPAE) ⁄ Γ PAE,∞. (7). A7q "w. ν$ ?d. `"{q Langmuir È o/04x x`: `ì7q. /056< EM ¸x¢ + EG ν$ /0. x`1]{ Nã Qu dOO " $ Pu7 -üE. ν$ %& ¯G /0 @ QI Ô1@ h. 1< QS:]{ dO* R " $ ¸]{q ¾ 1tE F < ©$ ¸x tUxE. ν. x 17 cô= "Þ Langmuir Èo /0 xâ47 :½?+ 1tE Xsd ªI < dO O"Þ %& ¯G Ô1 @. êuc |I ¸x E. @ 4. ¬à< {»{ ù?G E° E. ΓPAE 1 ln  --------------- = ln K ads + --- ln C PAE ν ΓPAE,∞. (8). 4 (8)7 ès?G lnC ln(Γ / Γ )7 ?A ugS< Ã :$ 7Ï. ={ PAE +, . ®%& /07 x`1. Pu ν /0 56`" - O " E. Table 2$ @7q TU L4]{ Freundlich `" >?,R ~i j k dO ¯xE. Table 27 dO çi x ò(20 C). W. PAE +, /07 Freundlich "w(ν) x 1.22{q Langmuir /0. x`17 côV < dO *D]d Wouc |}@7 Ë¢ Freundlich u jk vc?$ 6ì tA+ E. Freundlich " w. ou-.u$ +u. 7Ï: yzF(R =0.999) ©+ ]^(Fig. 5) »)7q >?7Ï< WX- # s. 0 C èò7q Langmuir4 +, /0x c ²?Y ÊE$ ¸< g?+ E. xÀ ~$ o uc àj7 Ë¢ /0 PAE +, . 8VHx vc?+ ! +,. /0 å87 [&$ Z2x PAE. PAE. 2. 2003, Vol. 47, No. 3. Hg7 vc? ÃÄ ¸]{ WÊE. PAE

(14) /056`"i /0 Gibbs &7i. F$ E° 4]{ dOO " $³,. PAE,. o. o. Fig. 5. Temperature-dependence of Freundlich power in PAE polymer adsorption on fiber.. ∆Gads = –RTlnK ads. (9). A7q ∆G I /0Q7q "Ê Gibbs & 7 à x^ Table 1 p$ 27q. /056`" T?G PAE +,. %& /07 Gibbs & 7 à ¥ " Y ÊE. Hoever 3 Silberbergxâ 7 ès?G %&7 PAE +, / 0. Gibbs &7(∆G )wI E°. EY ¶ . w]{ 1ÊE+ ">Å "c E, L ads,1. 24,25. ads. 26,27. 5. ∆G ads = ∑ ∆G ads, i. (10). i=1. A7q, ∆G I )`7q Z[\ 6ì. +, c + 61?Gq @ %&¯G7 /0 Å Ã +, . 6ì: à6 ]Ê ]{ %& ¯G. `$ªT 7c A7 jÊ E. ∆G $ FG7q. 1 µk ÿ(δ)7q /0Ê ads,1. ads,2.

(15) !". 226. 3 T h. `$ªT 7 x^, ∆G $ )`7 ¨Ê +i h. `$ª T 7xE. ∆G $ PAE +,. ?Ê + i ~Ê ?Ê @c ?Ê %&. FG @7 /0# Ã %&. x¤ÿ7 & 7 à Sx+ ∆G $ y?Ê +, @c ?Ê %&¯G @i /0Csd p$ ?Ê +, @c y?Ê %&¯G @i /0# Ã Ð?$ &7{q x$ ^8 p$ ,, 8 b{ C$ ?îu7 .?$ xE. PAE +, /07 q +, . ,5 (segment)ü C$ /0 &7 0.5 kT { ? G E° 4 (11)7 ès?A +, x /0Å Ã %&¯G !- $ ,5. ¾" 4 1(N ). Fx c²-õE. L, ads,3. ads,4. ads,5. 17). seg. ∆G ads Nseg = ------------------------( 0.5 kT )N A. (11). A7q k$ K_f `"(=1.38`10 J/oK)x^ N $ }tcI{ "(=6.02`10 /mol) dOE. F 4 (9) 3 (11)< T?A PAE +,. Langmuir6 4 /07 /0 &7(∆G )i 4 1(N ) ou "r í{ ¿¿ F?+ » ~ Table 37 dO*DE. Table 37 dO ~7 .?G PAE /07 / 0 &7i 41$ µ ouc vc?G q 7Ï:]{ l ?$ 6ì tA+ $³ x$ ou à jk /0Ê PAE +,m. +i ! ,7q. 8VH Xc vc? ÃÄ ¸]{ Ð ¿Å " + %@ +,ü %&¯G7q. !@ c l j]{a /0ß$ çb]{ cd © Y C^ »{- /0 +,. |}õ &u$ /0 {(∆S ). vc7 A ¸]{ -RÅ " Y ÊE. PAE ". ,S< 50f amu¢+ ?G + , ü azetidinium xox jÊ e%@c 1,026 −23. A. ¾{ FC^ e%@ 1?$ h W6 s (zigzag distance) 0.126 nm{ EG PAE +, ¾ü x$ 3.36 µmc ÊE. Ë¢q 20oC. PAE +, x "{ df /0 + ¾ü x F- tG 430 nmc C+ %& ¯G 7q. I ( » ¸. 5 215 nmc ÊE. 30 C 3 40 C. $ ¿¿ 234 nm 3 257 nm {q ou 10 C vc7 - +, I 9% vc?$ gx ÊE. o. o. o. PAE %&¯G7 PAE +,. /0Q7q W { /"Csd W{ ÐC$ 7 à / 08 p$ /0 7{ ¯'Å " ]^ x U56`ì7q /0ß PAE +,i %& Ô1@ h. 89: ~½ `ì7 Qtc : " Y ÊE. ¯G7q. /0ß. /0Q7 ou .17 ">I E° I Gibbs-Helmholtz. F4]{ Å " $³, 21. 23. ads. seg. ads. Table 3. Calculation results of adsorption Gibbs free energy and train numbers for PAE polymer on fibers at three different stock temperatures. Temp. (oC). ∆Gads, kJ/mol. Nseg. 20 30 40. 9.558 9.046 8.365. 7.849 7.184 6.531. ∂ ( ∆G ads ⁄ T ) ∆H ads -------------------------- = – ------------2 ∂T T. (12). A7q ∆H I /0Q7q "Ê /0 dOE. 4 (9) 4 (12)7 új]{a E° I Clausius-Clapeyron F4x :Y ÊE. ads. d ln Kads ∆H ads( T ) ----------------- = – --------------------d( 1 ⁄ T) R. (13). @ 4 (9)7 ès?A lnK < 1/T7 ?A ug?G 7Ïx :+ 7Ï. ={ /08 ∆H c F# " Y ÊE. Fig. 6$ W * PAE +,. /0`"7 Clausius-Clapeyron F Langmuir /0i Freundlich /07 - ug?A dO ») xE. :]{ +ß ¯G7 , /0I /0 ª 7 Ë¢ µ ¶{ ,?A /0ß(adsorbate)i 0 ß(surface)h. ç¥Ø hx ªT?$ /0 &~½. Ð7 . /0]{ df K " $³, /0I /0ßi 0ß h. sc / 0. tE$ i s7q ÐC^ `$ªT7 c GI ¸x ;jx+ , /0]{ ÐC$ 8I · -(condensation enthalpy, ~20 kJ/mol)i s. ads. ads. Journal of the Korean Chemical Society.

(16) PAE

(17) . 227. ùÅ ß: ¬7$ à ] /$E. # 7q$ W. -'() `ì7q. ® % & ¯G7 PAE +, -. /0x : à Qx "C /$ n-7. /0 < =>?E. %& ¯G7q. PAE +, /07 c`. ,: 6ì Fig. 77 dO*DE.. Fig. 6. Clausius-Clapeyron plots for the determination of PAE adsorption enthalpy.. yk ¬]{ ¥¹º E. G /07q$ & ~½. Ð]{ /07c 200 kJ/mol{q |+ /0ß. 6ìc XY à6C$ ;1< ©+ E. Fig. 67 dO u¯. >?4. ={ PAE +,. /0- F?$³ Langmuir 4 /07q$ -27 kJ/mol{ CD+ Freundlich 4 /07q$ xtE h |I -29 kJ/mol{q µ /07q. /087 -üE+ Å " $ X x^ p ÕÖ{×Ø %&. " ~½7( 20 kJ/ mol) i è!?$ ¬x¢+ Å " E. xi x /07q ÐC$ 7$ { ~Ql. õH 7{ /"C^ xq 8. 6ì{ à7 LC + x Ã. 7$ ,h ~½ ¾8 g7 $ m ¬xn{ /07q$ ¯G7q /0ß . 6ìc +6ì{ osd À$ 6ì 21. 21. # $ %& '()* PAE +,. *Vb{ q +, /012 Lanumuir 3 Freundlich ¬4. /0 567 89: ;1< >? @?A " BCDE. PAE +, *V7 %&. FGH@ : ;1I JK-: LM. NO@ PQ7 .,RCD+, %&7 PAE +, /0SI W ÷,i +, -T). PCD :Q< U- PQ CDE. ~ ?G E° E: 1. W*7q. PAE +, *VI _7 %&. NO@ à7 X Y Z2< [&f gh. i jk 'n ? lm'`< dO*DE; 2. PAE +,$ no7q 6: Langmuir /0 ¬47 côV sH< tAD ]d ouc vc?G Freundlich νx |}@] {q Langmuir /0 x`1]{ p$ ~ dO*DE; 3. PAE +,7 Gibbs /0 &7 { "(N )$ ò7q 7~8 . @{ dOe+ ouc vc?Gq l ? E; 4. +, +. I 215 nm{ FC D+ 10 C ouà7 - 9% vc?E; 5. Clausius-ClapeyronF47 .- Ê /0 $ −27~−29 {q PAE +,. %&7 /0x 8·x^ n7 /0< =>?E. seg. o. . Fig. 7. Molecular conformation of PAE polymer on fiber surface: adsorption occurs with an aid of the electrical interaction between the azitidinium ion in a PAE repeating unit and the carboxyl group of fiber surface. 2003, Vol. 47, No. 3. 1. Marton, J.; Marton, T., Tappi J., 1976, 59(12), 121. 2. Lindstrom, T.; Soremark, C., Adsorption of cationic polyacrylamides on cellulose. J. Coll. Int. Sci., 1976, 55(2), 305. 3. Horn, D., Progr. Colloid & Polymer Sci., 1978, 65, 251. 4. Horn, D.; Melzer, J.; in Fibre-Water Interactions in Papermaking. Transactions of the Sixth Fundamental Research Symposium, BPBIF, Oxford, 1977, 135. 5. Tanaka, H.; Tachiki, K.; Sumimoto, M.; Tappi J., 1979, 62(1), 41..

(18) 228. !". 6. Marton, J., Tappi J., 1980, 63(4), 87. 7. Jarnstrom, L.; Steniun, P.; Colloids Surfaces, 1990, 50(1), 47. 8. Chibowski, S., J. Coll. Int. Sci., 1990, 143(1), 174. 9. Laurila, M.; The Adsorption of Nonionic Surfactants and Polyacrylic Acid on Talc: Lic. Techn. Thesis, Department of Forest Products Technology, Helsinki University of Technology, Espoo, Finland, 1996. 10. Jonsson, B.; Lindman, B.; Holmberg, K.; Kronberg, B.; Surfactant and Polymers in Aqueous Solution, John Wiley & Sons, New York, 1998, 303. 11. Kindler, W. A.; Swanson, J. W.; J. Polymer Sci., 1971, 9(A-2), 853. 12. Horn, D.; Progr. Coll. Polymer Sci., 1978, 65, 251. 13. Horn, D.; in Polymeric Amines and Ammonium Sults, ed. E. J. Goethals, Pergamon Press, Oxford, 1980, 333. 14. Mahanta, D.; Chaliha, B.C.; Baruah, J.N.; Coll. and Surf., 1987, 25, 101. 15. Falk, M.; Odberg, L; Wagberg, L.; Risinger, G.; Coll. and Surf., 1989, 40, 115. 16. Tanaka, H.; swerin, A.; Odberg, L.; Tappi J. 1993, 75(5), 157. 17. Odberg, L.; Tanaka, H.; Glad-Nordma; G., Swerin, A.; Coll. and Surf., A: Physicochem. Eng. Aspects, 1994,. 86, 201. 18. Matthhew H. Lang; Robert A. Stratton; Polyelectrolyte adsorption kinetics, Tappi 1995 Papermakers Conference Proceedings, TAPPI Press, Atlanta, 1995, 101. 19. Hessselink, F.; Th.; J. Electroanal. Chem., 1972, 37, 317. 20. Hesselink, F. Th.; J. Coll. Int. Sci., 1977, 60, 448. 21. Scott, W. E.; Principles of Wet End Chemistry, Tappi Press, Atlanta, 1996, 64. 22. Atkins, P. W.; Physical Chemistry, 2nd Ed., Oxford University Press, W.H. Freeman and Company, San Francisco, 1982, 1012 23. Hunter, R.J.; Introduction to Modern Colloid Science, Oxford University Press, New York, 1993, 164. 24. Hoeve, C.A.J.; J. Polym. Sci., 1971, 34(C), 1. 25. Silberberg, A.; J. Chem. Phys., 1968, 48, 2835. 26. Parfitt, G.D.; Rochester C.H.; Adsorption from solution at the Solid/Liquid Interface, Academic Press, New York, 1983, 388. 27. P. Stenius, “Macromolecular, Surface and Colloid Chemistry,” in Forest Products Chemistry, Vol. 3, Papermaking Science and Technology, Fapet Oy. Helsinki, p227(2000).. Journal of the Korean Chemical Society.

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Adsorption Thermodynamics of Polyamidoamide Epichlorohydrin Polymer in an Aqueous Fibrous Suspension PAE  

Adsorption Thermodynamics of Polyamidoamide Epichlorohydrin Polymer in an Aqueous Fibrous Suspension PAE