Li cm n! Vi lng bit n su sc, ti xin chn thnh cm n: GS. TS Ng Duy Cng PGS.

TS Phan Vn Ninh giao ti, tn tnh hng dn v to mi iu kin thun li nht ti hon thnh bn lun vn thc s ny. Xin chn thnh cm n cc thy c trong t b mn Ha l, cc thy c trong Khoa Ho, cc bn ng nghip trong phng th nghim cao phn t Khoa Ha hc, Trng i hc Khoa hc T nhin, i hc Quc gia H Ni gip , ng vin ti trong sut qu trnh lm vic. Ti cng xin chn thnh cm n lnh o Vin Ha hc - Vt liu, Vin Khoa hc - Cng ngh Qun s, B Quc phng. Phng th nghim cao phn t, Vin Ha hc - Vt liu, cng cc bn ng nghip trong Vin to mi iu kin tt nht gip ti hon thnh bn kho lun ny. Xin chn thnh cm n!
Hc vin

Phm Nh Hon

M u

Trong nhng nm gn y, vic nghin cu ch to ra nhng loi vt liu mi c nhiu tnh nng u vit nhm p ng nhng yu cu, i hi ca cc ngnh cng ngh cao nh cng ngh thng tin, in t, cng ngh hng khng v tr, cng ngh qun s, cng ngh sinh hc, y dc l mt trong nhng mc tiu hng u ca nhiu Vin nghin cu, phng th nghim trn th gii. Khoa hc v cng ngh nano l mt trong nhng hng chnh ch to ra cc vt liu c bit ny. Vt liu polyme nanocomposit trn c s nanoclay c ch to bng cng ngh bc tch cc lp clay c cu trc nano v phn tn u cc nanoclay trong polyme hu c. y l loi vt liu c nhiu tnh nng c l vt tri m cc loi vt liu polyme composit thng thng khng c c. Vi mong mun tip cn hng nghin cu trong lnh vc mi ny nhm to ra vt liu polyme nanocomposit c cc tnh nng u vit, chng ti chn ti : Nghin cu qu trnh trng hp acrylamit v axit acrylic trong lp nanoclay nhm tm ra iu kin ti u ch to vt liu poly(acrylamit - co - axit acrylic) clay nanocomposit v polyacrylamit clay nanocomposit bng phng php ng trng hp v trng hp xen lp vi s c mt ca nanoclay.

Mc ch

- Nhm tip cn hng nghin cu, ch to vt liu polyme clay nanocomposit trn c s phn ng trng hp cation monome acrylamit xen trong khong gia cc lp MMT ca clay. - Ch to nanoclay hu c. - Ch to polyacrylamit clay nanocomposit. - Nghin cu, kho st iu kin thch hp cho qu trnh ng trng hp gia acrylamit v axit acrylic vi s c mt ca nanoclay hu c. - Kho st kh nng hp th nc ca vt liu.
Nhim v ca lun vn

Vi nhng mc ch th yu cu, nhim v ca bn lun vn gm cc phn chnh sau: - Kho st kh nng v cc yu t nh hng ti kh nng chn acrylamit vo trong khong gia hai lp ca MMT. - Nghin cu qu trnh trng hp acrylamit vi s c mt ca nanoclay hu c, kho st cu trc ca vt liu thu c. - Ch to mng ph polyacrylamit clay nanocomposit, kho st cc tnh nng c l ca mng. - Kho st qu trnh ng trng hp ca acrylamit v axit acrylic trong s c mt ca nanoclay hu c. - Kho st kh nng hp th nc v cc dung dch mui c nng khc nhau ca sn phm thu c.

Chng 1 - Tng quan

1. Polyme cu trc nano v vt liu nanocomposit 1.1 - Polyme c cu trc nano

Nhng nm cui ca th k 20, cc nh ha hc polyme thnh cng trong vic pht trin cc cng c nhm iu khin cc thng s cu trc phn t khc nhau trong cc hp cht cao phn t tng hp nh trng lng phn t, tnh a phn tn, tnh n nh lp th v tnh n nh khu vc, a hnh hc ca tnh lin kt n v tun hon nh trong trng hp dendrimer v thm ch l c s phn b chui copolyme. Tuy nhin, vic iu khin mc t chc cao nh hnh dng mch v sau sp xp cc mch c kch thc v m l vic kh khn hn. Vic iu khin t chc phn t trong kch thc nanomet v sau sp xp li nhm ch to polyme c cu trc nano. [7,14] Vt liu polyme c cu trc nano bao gm cc polyme c cu trc ht, xp, si, ng, mng mng v vt liu composit m kch thc ca chng t t 10 100 nm. c bit vi cu trc kch thc nano s lm cho vt liu c nhng thay i quan trng trong tnh cht ni ti ca vt liu. Nhng khc bit trong yu t kch c, s phn b kch thc, thnh phn vt liu v s tp hp li ca chng s dn n nhng thay i khc bit ng k v tnh cht, bn l ho u vit m cc vt liu polyme v polyme composit truyn thng khng c c. Ngy nay, xu hng pht trin trong lnh vc nghin cu vt liu nano l tm ra cc phng php tng hp, ch to vt

liu c kch thc nano. Trong lnh vc ha hc cc hp cht cao phn t, th phng php t c vt liu nano v cao phn t c kch thc nano l cc phng php trng hp mch sng (living), phn ng trng hp khi, trng hp nh tng, trng hp phn tn, trng hp huyn ph. Bng phng php lng ng ha hc CVD (Chemical Vapor Deposition) ch to si nano. Trong gia cng polyme bng phng php Blending c th ch to vt liu composit cu trc nano hoc phng php Templating ... [11].
1.2 - Vt liu nanocomposit (NC)

Vt liu composit truyn thng cha cc loi ct liu gia cng nh bt v c, hu c, cc loi si ... c phn tn trong pha lin tc hay cn gi vt liu nn. Vi s xut hin ca cc cht n gia cng c kch thc nano to ra s khc bit rt ln so vi cc cht n thng thng. Trc ht l do kch thc nh hn hng trm n hng nghn ln v kh nng to ra cc tng tc vt tri gia pha lin tc vi cht n. Do c kch thc nano m cc cht n gia cng ny khc phc c rt nhiu cc hn ch ca vt liu composit truyn thng nh trong, bn c l c ci thin, kh nng bn nhit tt hn ... Khi phn tn u cc cht n ny trong nn polyme chng s to ra din tch tng tc ln gia cc tiu phn nano v polyme nn. Din tch ny c th t n hng trm m2/g. Khi , khong cch gia cc phn t nano s tng ng vi kch thc ca chng v to ra nhng tng tc khc bit khc so vi cc cht n truyn thng. Vt liu v c dng trong nanocomposit gm hai loi:
5

- Vt liu c kch thc ht nano nh cc ht v c Au, Ag, TiO2, SiO2 - Vt liu c cu trc nano nh bentonit, cacbon nanotube, nanofiber, nano xp. Vi vt liu nanocomposit tu thuc vo s lin kt t nhin gia pha lin tc v vt liu gia cng m ngi ta c th chia chng ra thnh 3 loi: - NC - 1: Cc ht nano v c c phn tn u trong hp cht polyme hu c (vt liu nn) dng tch lp. - NC - 2: Nhng polyme hu c c a vo trong cu trc nano ca vt liu v c dng xen lp. - NC - 3 : Phn tn NC - 2 trong polyme hu c to vt liu nhiu thnh phn.

a. Dng tch pha

b. Dng xen lp

c. Dng bc tch lp

Hnh 1.1 - S minh ho cu trc cc dng vt liu nanocomposit Trong s cc vt liu c kch thc hay cu trc nano th nanoclay thu ht c s quan tm ch ca rt nhiu cc nh khoa hc bi cc c tnh u vit ca n nh din tch b mt ring ln c 700 800 m2/g, gi thnh r ... Ch vi mt l-

ng nh c 2% th tch c a vo polyme ngi ta c th nng cao gn gp i modul ko m khng lm suy gim bn va p, lm tng cng vng, kh nng chng chy, nng cao h s chng thm kh ln rt nhiu ln m khng lm tng ng k trng lng ca vt liu.

Hnh 1.2 - Cc cht n c kch thc nano Hng Toyota ch to vt liu nanocomposit trn c s polyamit 6 vi khong st, khi so snh vi polyamit thng thng th vt liu nanocomposit ch to c c cc tnh cht c l tt hn nh bn nn tng 40%, bn un tng 60%, modul ko tng 68%, modul un tng 120%[1].
1.3 - Vt liu polyme clay nanocomposit

1.3.1 - Nano clay hu c 1.3.1.1 - Gii thiu khong st Bentonite - clay Khong st l hp cht thuc h alumosilicat tn ti trong t nhin thnh m. N c cu trc lp bao gm lp ca nhm oxit v lp ca silic oxit. Cc lp c lin kt vi nhau qua cu nguyn t oxi. Tinh th khong st ca lp silic c cu to t

cc t din oxi silic sp xp thnh mng lc gic, lin kt vi cc mng bt gic. Ht st khi phn tn trong nc to huyn ph c kch thc rt nh khong mt vi micromet. Khong st ngm nc mm do [6]. Thnh phn ha hc ca cc loi khong st bao gm nguyn t silic chim t trng ln nht sau l nguyn t nhm. Ngoi ra cn c cc nguyn t khc nh Fe, Mg, Na, Ca ... Bng 1.1 - Cc loi khong st v thnh phn cu to ch yu
TT Tn khong st Thnh phn cu to ch yu

tonit) 2 Saponit Si, Al, Mg 3 Baidellit Si, Al 4 Vermiculit Si, Al, Mg, Fe2+ 5 Illit Si, K, Al, Fe2+, Mg2+ 6 Glauconit Si, K, Fe2+, Fe3+ 7 Nontronit Si, Fe3+ 8 Celaconit Si, Al, Mg, K, Fe2+, Fe3+ 9 Chlorit Si, Mg, Al, Fe 10 Kaolinit Si, AL 11 Sepionit Si, Al, Mg 12 Talc Si, Mg, Fe2+ 13 Palygorskit Al, Mg Da vo kh nng trng n trong nc ca khong st, c th chia khong st thnh hai nhm: nhm trng n v nhm khng trng n. - Nhm trng n bao gm: Bentonit, Saponit, Nontronit, Vermiculit ... - Nhm khong st khng trng n gm: Illit, Chlorit, Kaolinit ...
8

Montmorillonit

(Ben Si, Al, Mg2+, Fe2+

V cu trc, khong st t nhin c cu trc lp. Trong cu trc khong st hnh thnh t hai n v cu trc c bn: + Cu trc t din ca silic + Cu trc bt din ca oxit nhm

Ion Si Oxi Hnh 1.3 - Cu trc t din SiO2 Cu trc bt din MeO6

Cation : Al, Mg Oxi Hnh 1.4 -

Trong khong st m cc lp t din sp xp theo mt trt t k tip nhau lin tc th s hnh thnh nn cu trc kiu 1:1, y l cu trc tinh th ca Caolin. Nu xen k gia hai lp t din oxit silic l lp bt din ca nhm oxit (hydroxyt) th khong st thuc nhm khong st c cu trc 2:1, in hnh l Bentonit v Vermiculit

Hnh 1.5 - Kiu cu trc mng tinh th 2:1 Thnh phn ch yu ca khong st Bentonit l Montmorillonit (MMT) c cng thc tng qut Al2Si4O10(OH)2. Montmorillonit chim khong t 60 - 70%, cn li l cc loi khong st khc nh Saponit, Beidellit, Mica ... v cc mui, cc cht hu c khc. V thnh phn chnh trong Bentonit l Montmorillonit nn Bentonit c gi theo tn khong vt chnh l Montmorillonit (MMT). Mi lp MMT c dy 1 nm, chiu di cc lp t 30nm cho ti vi micromet v tch in m, gia cc lp MMT tn ti cc ion kim loi tch in dng nh Na+, K+, Ca2+, Fe2+, Mg2+ ... To nn cu trc MMT - Me trung ho v in. Ch mt phn rt nh cc cation ny (Na+, K+ ...) nh v mt ngoi ca mng, cn phn ln nm vng khng gian gia cc lp. Trong khong MMT cc cation ny c th trao i vi cc cation ngoi dung dch vi dung lng trao i khc nhau tu thuc vo mc thay th ng

10

hnh trong mng. Lng trao i ion ca MMT dao ng trong khong 70 - 150 mdl/100g. Cc lp trong cu trc ca MMT c lin kt vi nhau qua cu nguyn t oxi. Trong khng gian cc lp cn tn ti nc v nc c xu hng to v hydrat vi cc ion trong . Khi phn ly trong nc MMT d dng trng n v phn ly thnh cc ht nh c micromet v dng trng thi lng theo lc ht Van der Waals [6].

Hnh 1.6 - Cu trc mng tinh th 2:1 ca MMT Qu trnh trng n v qu trnh xm nhp nhng cation khc vo khong xen gia
Na+ Na+ Na+ Na+ Na+

mng v lm thay i
Na+ Na+ > 10 A0 < 10 A0

khong cch gia chng theo s sau:

11

Hnh 1.7 - Qu trnh xm nhp cation vo trao i cation Na+ trong khong gia hai lp MMT Qu trnh xm nhp cation vo khng gian hai lp MMT l dn khong cch c s (t mt phng Oxy ca lp Si n lp tip theo) t 9,6 A0 n vi chc A0 tu thuc vo loi cation th. Vit Nam khong st Bentonit c hai ngun chnh l Di Linh - Lm ng v Tuy Phong - Bnh Thun. St Di Linh - Lm ng l st cha ion kim th (Ca2+, Mg2+), st Tuy Phong cha ion kim (Na+, K+) nn trng n cao hn, c kh nng trao i ion ln hn. Cc kt qu ca nhiu tc gi [6,11] cho thy rng kh nng trao i ion ca khong st Tuy Phong - Bnh Thun t 96 - 105 mgdl/100g. Trong khi , dung lng trao i ion trong Bentonit ca hng Southerm Clay Co l 110 115 mgdl/100g, ca hng Merck khong 100 - 120 mgdl/100g. Thnh phn ha hc ca Bentonit c nh gi theo phng php phn tch thng thng c a ra bng sau: Bng 1.3 - Thnh phn ha hc ca Bentonit Tuy Phong - Bnh Thun[11]
Thnh phn ha hc Hm lng (%)

SiO2 Al2O3 Fe2O3

12

51,90 15,60 2,83

FeO CaO, MgO K2O, Na2O Thnh phn khc MKN* MKN+ : Mt khi nung

0,21 4,05 4,05 7,62 15,67

Cht lng ca Bentonit c nh gi qua cc thng s nh: Hm lng MMT, phn tn, din tch b mt, dung lng trao i ion CEC (cation exchange capacity - CEC) 1.3.1.2 - Bin tnh hu c khong st Khong st Montmorillonit c nhiu ng dng trong thc t l do vic bin tnh b mt ca khong st rt d dng. Gn y cc nh khoa hc s dng khong st vi thnh phn chnh l MMT lm vt liu gc ch to ra vt liu nanocomposit hu c lai v c. y l mt loi vt liu mi c nhiu kh nng ng dng trong thc t bi cc tnh nng u vit ca mnh. Mc ch ca vic bin tnh khong st bng phn ng hu c ha MMT l nhm to ra vt liu t dng a nc sang dng a du vi nhng gc th khc nhau v c kh nng trng n trong dung mi hu c, khuch tn v tng hp tt trong cc polyme thng qua qu trnh ho tan trong dung mi hu c hoc qu trnh nng chy. Vic hu c ho MMT thng qua phn ng trao i gia cc cation kim loi c trong cu trc khong st vi cc cation amoni hu c. y chnh l qu trnh trao i ion Na +, K+ vi nhm mang in tch dng phn u ca hp cht hu c m in hnh l nhm ammonium cation vi phn ui l cc gc hu c khc nhau.
13

Nhm u N+ Nhm ui R

Phn ui ca hp cht ny c tnh a du v l tc nhn lm dn cch gia cc lp khong st theo m hnh sau:

Hnh 1.8 - S m hnh hu c ha khong st Qu trnh dn khong cch cc lp MMT l tng kh nng xm nhp ca cc cht hu c, polyme vo khong xen gia cc lp. Tip theo khi cc cht hu c hay polyme khong gia cc lp MMT - hu c thc y qu trnh khuch tn phn ly c nano MMT - lai hu c trong dung mi hu c hoc trong polyme. Cc tc nhn hu c hay c s dng bin tnh khong st c lit k trong bng 1.4. Bng 1.4 - Cc cht ha c dng lm tc nhn bin tnh MMT
Cng thc ha hc Tn gi im chy (0C)

CH3N+ClCH3(CH2)2NH2 CH3(CH2)3NH2 CH3(CH2)7NH2 CH3(CH2)9NH2

Methylamine hyrochloride Proyl amine Butyl amin Octyl amine Decyl amine
14

228 - 83 -50 -3 13

CH3(CH2)11NH2 CH3(CH2)15NH2 CH3(CH2)17NH2 HOOC(CH2)5NH2 HOOC(CH2)11NH2

Dodecyl amine Hexadecyl amine Octadecylamine Axit 6 - Aminohexanoic Axit 12 - Aminododecanoin Tetramethyl ammonium CH3N+Clchloride N - Methyl octadecyl CH3(CH2)17NH(CH3) ammonium bromide CH3(CH2)17N+(CH3)3Br Octaecyl trimethy ammonium bromide CH3(CH2)11N+(CH3)3Br Dodecyl dimethyl ammonium bromide (CH3(CH2)17)2N+ Dimethyl benzyl octadecyl (CH3)2Br aminium bromide CH3(CH2)17N+ (C6H5)CH2 Bis(2-hydroxyethyl)methyl (CH3)2Br CH3(CH2)17N+(HOCH2 Octadecyl ammonium chloride CH2)2CH2CICH3(CH2)14CH2(C6H5N 1 - Hexadecylpyridium bromide + )BrH2N(CH2)6NH2 1,6 - Hexamethylene diamine H2N(CH2)12NH2 1,12 - Dodecane diamine

30 46 57 205 186 > 300 45 246 69 44 70

Tnh cht quan trng ca cc tc nhn hu c thng c mch hydro cacbon di. c tnh ca cc ion amonium l tnh a hu c, kh nng trng n v s hnh thnh h sol - gel thun nghch trong cc dung mi hu c. Trong dung dch nc phn ng hu c ho khong st ph thuc nhiu vo qu trnh trng n ca MMT. Qu trnh trng n ny c chia lm ba giai on. giai on 1: Kt

Hnh 1.9 - Trng thi phn ly ca khong st trong dung dch

15

tinh mng st c gi nguyn, khong cch gia chng tng t 1 - 2,2A0 lc ny nguyn nhn trng n do hin tng thy phn ion dng Na+, K+, Li+... tn ti gia cc lp st. giai on 2, MMT c cha ion dng ha tr 1 tip tc trng n. giai on ny hnh thnh lc pht tn trn b mt ca lp st do qu trnh hnh thnh in tch p gia hai lp. Lc ny ln hn lc lin kt Vander Waals, kt qu qu trnh tch ly cc lp MMT xy ra, lc ny lc lin kt chnh tn ti l lc gia phn cui nhnh di ca lp trn vi b mt trn ca lp di. Trng thi ny hnh thnh nh dng paste hay dng gel. Nu hm lng nc cng tng th lin kt di trn cc lp yu i v trng thi tch ly th ba sinh ra nh hnh sau: [6]

Phn ng hu c ha MMT xy ra theo phng trnh sau: R - N+H3Cl- + Na+ - MMT MMT - N+ - R + Na+ClKh nng khuch tn ca cc mui alkyl ammonium ph thuc vo in tch th bc ca mui amoni v cu to gc R. Cc gc R cng cng knh th kh nng khuch tn cng kh, nhng kh nng lm dn khong cch gia hai lp MMT

16

cng cao. Vi khong dn cch cng cao ny th kh nng khuch tn ca nanoclay trong polyme cng ln. Phn ng trao i ny ch xy ra vi khong st c cu trc 2:1 c bit l Montmorillonit v Vermiculit c dung lng trao i ln. * Cng ngh hu c ho khong st c thc hin qua cc bc sau: Bc 1: Khong st dng bt c khuch tn trong nc v c khuy trn mnh trong nhiu gi. Cc ht clay dng huyn ph trng n lm khong cch cc lp dn rng to c s cho qu trnh thc hin phn ng trao i cation. Bc 2: Thc hin phn ng trao i gia tc nhn alkyl ammonium vi ion Na+ trong clay 800C Bc 3: Lc ra, sy kh thu hi sn phm. Clay dng bt

Khuch tn trong nc Thnh phm

Khuy trn

Trao i ion, 800C

Tc nhn alkyl amonium

Sy kh

Phn ng

Lc, ra 17

Lc

Hnh 1.10 - S cng ngh ch to vt liu nanoclay hu c

1.3.2 - Cng ngh ch to vt liu polyme clay nanocomposite Khc vi cc loi vt liu composit truyn thng l s dng cc loi cht n gia cng thng thng c kch thc ht ln c vi micromet. Th vt liu nanocomposit s dng cht n gia cng c kch thc c nano em n cho loi vt liu composit ny c nhng tnh cht c l vt qua tm ca vt liu composit truyn thng nh: bn c hc, trong sut, kh nng chu nhit v khng tch pha v t n mc vt liu thng minh. Do , cng ngh ch to vt liu polyme clay nanocomposit c nhng nt c trng ring v tri qua cc giai on sau: + La chn khong st c cha MMT + Bin tnh hu c ha khong st (MMT - hu c hay organoclay) +Tin hnh khuch tn MMT - hu c vo trong polyme bng cc phng php sau: - Phng php dung dch - Phng php trn hp - Phng php trng hp + To nanocomposit trng thi xen lp (Intercalanted state)

18

+ To nanocomposit trng thi tch lp (Exfoliated state) Hnh 1.11 l quy trnh cng ngh ch to vt liu nanocomposit t khong st v polyme. * Phng php dung dch: Polyme nn c ho tan trong dung mi hu c. Tip theo cho khuch tn MMT - hu c vo dung dch polyme. Dung mi hu c xm nhp vo cc lp MMT hu c ha. Vi tnh a du, MMT hu c t t khuch tn trong dung dch polyme theo cc giai on, cui cng c hn hp dung dch c cc phn t MMT khuch tn u trong polyme. * Phng php trn hp Khc vi phng php dung dch, phng php trn hp c tin hnh cho khuch tn trc tip MMT lai hu c trong dung dch polyme nng chy. Phng php ny thng p dng cho mt s loi polyme nh epoxy, polyeste v phi dng n my trn siu cao tn. Theo phng php ny th u tin hu c ha MMT bng hp cht hu c c gc cation sau a tip cht ng rn nhn c nanocomposit nhit rn. [46] * Phng php trng hp y l phng php trng hp polyme c tin hnh trong cc lp MMT ca khong st. Ban u ngi ta tin hnh a monome c in tch dng vo trong cc lp MMT ca khong st. Sau tin hnh trng hp polyme xen k trong cc lp MMT. Phng php ny c hn ch l ch tin hnh c phn ng trng hp cation [11,43]

Hnh 1. 11 - Quy trnh ch to vt liu nanocomposit t k khong st v polyme

19

20

Polyacrylamit clay nanocomposit c th c ch to bi phn ng trng hp cation monome acrylamit xen gia trong khong gia hai lp MMT ca clay. Qu trnh trng hp c thc hin qua cc giai on sau: * a monome acrylamit vo gia hai lp MMT ca khong st: Gia cc lp MMT trong khong st tn ti cation kim loi Na+, K+, Li+. Nhng ion ny ng vai tr trung ho in tch trong clay. Bng phn ng trao i cation gia monome acrylamit v ion kim loi ta thu c clay nano bin tnh acrylamit. * Trng hp cation polyacrylamit clay nanocomposit Polyacrylamit clay nanocomposit nhn c bng phn ng trng hp cation vi s c mt ca cht xc tc oxy ha nh: amoni pesunfat, kali pesunfat theo c ch nh hnh sau:
CON+H3

Xc tc CON+H3

H2C CH

H2C CH

H2C = CH

H2C = CH

CON H3

CON H3

CON+H3

Hnh 1.12 - S trng hp cation acrylamit xen gia cc lp MMT Tuy nhin, trong thc t khi cho lng acrylamit vo hn hp clay ngoi cc monome xm nhp vo khong gia cc lp MMT cn c cc monome bn ngoi. Khi tin hnh phn ng trng hp cation ta thu c c polyacrylamit bao quanh MMT.

21

1.4. Gii thiu chung v vt liu polyme a nc

1.4.1 - Polyacrylamit Polyacrylamit l vt liu polyme c s dng rt rng ri trong i sng. Trong cng nghip vt liu c dng sn xut ph gia chng thm cho b tng, lm tng kh nng bt mu ca vi si, lm vt liu hp th thu hi du m, lm vt liu siu hp th nc gi m cho cy, chng si mn cho t ... Polyacrylamit kh l cht rn mu trng gin. Vt liu polyacrylamit c chia lm ba loi: polyme nonionic (cha nhm amit trung tnh), polyme anionic (cha nhm anion cacboxylat) v polyme cationic (cha nhm cation amoni bc 4)[8]. CH2 O CH C NH2 n CH2 O CH C NH2 n CH2 O CH C ONa m

Polyme nonionic CH2 O CH C NH2 n CH2 O C(CH3) C O H3C C2H4 N

+

Polyme anionic

CH3 R X-

Polyme cationic R: alkyl c mch cacbon t C1 - C16,, arylalkyl Cc tnh cht vt l ca polyacrylamit khng ion c trnh by bng sau
22

Bng 1.5 - Tnh cht vt l ca polyacrlamit rn

Tnh cht Gi tr

T trng, g/cm Nhit chuyn ha thy tinh, 0C Sc cng b mt ti hn, mN Tinh th Cc dung mi Phi dung mi Ct phn on dung mi Cc kh kt hp trong khng kh

1,302 188 35 - 40 V nh hnh Nc, etylenglycol, formamit Xeton, hydrocacbon Nc - methanol H2, CO, CO2, NH3, NO, NO2

Polyacrylamit c iu ch bng phng php trng hp ca acrylamit vi s c mt xt tc. Qu trnh phn ng xy ra theo s sau: CH2 O CH C NH2
xt

CH2 O

CH C NH2 n

Qu trnh trng hp acrylmit c th c tin hnh theo nhiu phng php khc nhau nh: trng hp trong dung dch, trng hp khi, trng hp nh tng ... * Trng hp khi Theo phng php ny, acrylamit c un nng khng c dung mi, hoc trn acrylamit rn vi cht khi mo oxy ha kh hay cc cht khi mo azo. Theo phng php ny th polyme thu c rt tinh khit, trong sut nhng c nhc im l nht ca hn hp phn ng ln, kh nng dn nhit km
23

nn s thot nhit kh khn dn ti hin tng qu nhit cc b. Do polyme thu c khng ng nht v khi lng phn t. V nhng hn ch ny m phng php trng hp khi t c s dng trong cng nghip. * Trng hp nh tng y l phng php s dng nc lm mi trng phn tn to nh tng du nc. Pha du thng l cc hydrocacbon nh benzen, xylen, toluene ...[41] Cc cht to nh c s dng l xetyl, hexadexyl natriphtalate, sorbital monooleat hay sorbital monostearat. Trng hp nh tng thng xy ra vi tc ln v nhit tng i thp. iu ny cho php thu c polyme c khi lng phn t ln vi ng u tng i cao, nhng nhc im l sn phm c sch khng cao. * Trng hp dung dch Trng hp trong dung dch l phng phng php ph bin tng hp polyacrylamit. Qu trnh trng hp acrylamit trong dung dch nc l qu trnh ta nhit nn hn hp monome phi c khuy mnh trnh hin tng qu nhit cc b. Trong qu trnh trng hp dung dch, khi lng phn t polyme ph thuc rt nhiu vo iu kin tin hnh phn ng nh nng monome, nhit , thi gian, pH ca mi trng cng nh nng v loi cht khi mo ... Thng thng nng monome s dng tng hp polyacrylamide thay i trong phm vi rng t 5 - 20% hay 20 - 50% thm tr 70 -80% [16].

24

Cc cht khi mo c s dng trong phn ng trng hp cng rt a dng, nhng cht thng hay c s dng l: - Cc cht khi mo dng oxy ha nh K2S2O8, (NH4)2S2O8, H2O2 H khi mo oxi ha kh: K2S2O8/Na2SO3, (NH4)2S2O8/Na2SO3 - Cc cht azo: azo - bis - isobutylronnitril, 2,2 - azo - bis amidino - propan hydroclorua. Ngoi ra ngi ta cn s dng tia phng x nh tia ca Co66 khi mo cho qu trnh trng hp hay sng siu m. Ty thuc vo h cht khi mo v thi gian phn ng m qu trnh trng hp c th tin hnh nhit t 10 1200C. Thng thng qu trnh polyme ha 400C trong khong thi gian 4 - 10 gi, hay 50 - 600C trong thi gian 3 - 6 gi, cn 70 - 850C trong 2 gi. 1.4.2 - Poly(acrylic axit) Cng ging nh cc loi polyme a nc khc, polyacrylic axit cng c nhiu ng dng trong thc t. Poly(acrylic axit) l vt liu gin, cng vi trong sut khng c c. Polyme (acrylic axit) tan nhiu trong nc. Tuy nhin, nu polyme kh cng, c bit l nhit cao, tan ca chng gim mnh.

25

Bng 1. 6 - tan ca poly(acrylic axit)

Dung mi tan

Nc Dioxan Dimethylfocmande hyt Etanol Metanol 2 - propanol Axeton Propylen cacbonat Etylen cacbonat Etyl ete Benzen Xyclohexan

Tan Tan Tan Tan Tan Tan Khng tan Khng tan Khng tan Khng tan Khng tan Khng tan

Poly(acrylic axit) c iu ch t qu trnh trng hp ca axit arylic vi s c mt ca cht khi mo phn ng nh: benzoyl peoxit, kali pesunfat, ammonium persulfat ... phn ng c tin hnh nhit 80 - 1000C. ng hc ca qu trnh trng hp axit acrylic trong dung dch c rt nhiu tc gi nghin cu. Robert A.Scott v Nikolaos A. Peppas [42] nghin cu ng hc, cc yu t khc nhau nh hng n qu trnh trng hp. Cc tc gi s dng phng php phn tch nhit tin hnh kho st ng hc ca phn ng trng hp dung dch axit acrylic cc iu kin phn ng khc nhau v nhn thy rng tc phn ng gim khi pH
26

tng. iu ny c gii thch l do s gim tng i hot tnh ca axit acrylic b ion ha so vi cc monome khng b ion ha. pH > 6 ng hc qu trnh ngt mch c quyt nh bng s khuch tn, nh vy mc ion ha khng nhng ch tc ng ln hot tnh ca cc ht trong dung dch m cn tc ng ln c tnh khuch tn ca cc gc pht trin mch [9]. Axit acrylic d dng ng trng hp vi nhiu monome khc. iu ny l do kh nng phn ng cao ca ni i cng nh tnh d tan ca cc monome trong c pha nc v pha du. Hng s ng trng hp r1 v r2 ca axit acrylic vi mt s loi monome khc c trnh by di bng sau [45]. Bng 1.7 - Hng s ng trng hp r1 v r2 ca axit acrylic
TT Monome, M1 Comonome, M2 Dung mi

r1 1,15 0,77 1,63 1,43 0,35

r2 0,3 5 0,2 1 0,5 9 0,6 1,1 1,3 8 0,3 3 1 2,3

1 2 3 4 5 6 7 8 9

Acrylic axit Natri acrylat Metacrylic axit Acrylic axit Natri acrylat Acrylic axit Metacrylic axit Acrylic axit Natri

Acryloitrin Acryloitrin Metacrylonitrin Acrylamit Acrylamit Acrylamit Metacrylamit Natri styrensunfonat Natri styrensunfonat

Nc Nc Khi Nc Nc

Axeton 0,36 Nc Nc Nc 2 0,1 0,34

27

acrylat 10 Acrylic axit 11 Metacrylic axit 12 Acrylic axit 13 Acrylic axit 14 Acrylic axit 15 Metacrylic axit 16 Metacrylic axit 17 Metacrylic axit 18 Natri acrylat

Styren Styren n - butyl acrylat n - butyl metacrylat N, N dimetylacrylamit n - butyl acrylat n - butyl metacrylat Dimetylaminoetylmeta crylat Dimetylaminoetylmeta crylat

Khi Khi Etanol Etanol

0,35 0,7 0,58 0,29

- Dioxan 0,4 Etanol Etanol Nc Nc 1,31 0,75 0,98 0,08

0,2 1 0,1 5 1,0 7 3,6 7 0,5 0,3 5 1,2 0,9 0,6 5

Poly(acrylic axit) cng c tng hp theo nhiu phng php khc nhau nh : trng hp trong dung dch, trng hp khi, trng hp nh tng ... Mi phng php u c nhng thun li v nhng bt li ring ca mnh. Tu thuc vo mc ch yu cu sn phm thu c m la phng php tin hnh trng hp cho ph hp.
1.5 - Vt liu polyme siu hp th nc

Polyme siu hp th nc (hay cn gi l cht gia m, polyme hydrogel) l cc polyme a nc c to li nh c th hp th, trng v gi nc ti vi trm ln khi lng ca chnh n, thm ch di p lc. Trong mi trng nc mch polyme hp th nc to ra mt mng ba chiu cc chui mch polyme. Ti
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 mt vi phn c solvat ha bi cc phn t nc, nhng phn cn li lin kt vi nhau bng lin kt ha hc hay lin kt vt l. [7]

Hnh 1.13 - Hnh nh ca mt polyme siu hp th trc v sau khi trng n Polyme siu hp th nc biu hin thuc tnh d hp th nc dn ti lm trng n, nhng khng ho tan trong mi trng nc. Mc trng n, bn ca gel ph thuc vo cu trc, bn cht ca monome v cng ngh ch to. Polyme siu hp th nc c s dng rng ri trong nhiu lnh vc khc nhau nh cc sn phm chm sc c nhn, trong nng nghip, h vn chuyn thuc, t nhn to cho thu canh, tc nhn nh chm cho phn bn v thuc tr su, nha trao i ion, cht mang xc tc, chng thm, nng cao kh nng thu hi du, tuyt nhn to, truyn dn thuc trong y hc [15]. Ngy nay, c nhiu phng php khc nhau tng hp ra vt liu polyme siu hp th nc nhng thng c chia thnh

29

hai nhm chnh l ng trng hp c cht to li trong dung dch v trng hp huyn ph ngc. Qu trnh ng trng hp dung dch ca acrylamit v axit acrylic trung ho mt phn vi s c mt ca cht to lin kt ngang bao gm 2 giai on: din ra chm giai on u v sau din ra rt nhanh giai on 2. Cc monome v cht to lin kt ngang c ho tan vo nc nng thch hp. Dung dch ca hn hp cc monome ny c loi b oxy bng cch thi qua mt kh tr dng bong bng, cht khi mo c thm vo vi lng thch hp. Sau iu chnh nhit tin hnh trng hp. Ngoi phng php trng hp dung dch, cc phng php truyn thng khc c s dng tng hp polyme siu hp th nc l trng hp nh tng ngc, huyn ph ngc. Mc d cc phng php ny c th khc phc mt s nhc im ca phng php trng hp dung dch nh vn kh truyn nhit v khuy trn khi nht ca khi phn ng tng nhng qu trnh trng hp vn khng n nh bi s ng t v keo t vn c th xy ra do kch thc ht ln. Wan v cng s [47] tin hnh tng hp polyme siu hp th nc bng qu trnh trng hp vi nh ngc. u im quan trng ca qu trnh trng hp vi nh ngc l d phn tn nhit v nht thp hn. Hn na, qu trnh c th din ra vi tc nhanh hn v thu c polyme c trng lng phn t cao hn, n nh hn do cc ht c kch thc nh hn. Mt s ng dng ca polyme siu hp th nc

30

* Trong nng nghip Polyme siu hp th nc c bit t nhng nm 1950 cng vi vic a cc cht a in ly tng hp lm bn v gia cng cu trc t. Vt liu ny c kh nng hp th nc cao v y chnh l mt ngun nc d tr trong t cy trng hp th [18]. Vic s dng polyme siu hp th nc gi m v dinh dng, s dng nc v phn bn hiu qu ngy cng tr nn quan trng c bit khi ngun nc sn c b hn ch, hay nhng vng kh hn ko di. Polyme siu hp th nc c kh nng ci to tnh cht t nh hp th mt lng ln nc. Cc nghin cu ch ra rng, polyme siu hp th nc c th gip cy trng sinh trng v pht trin trong vng t c nguy c b hn hn. Polyme ny cng lm tng kh nng gi nc ca t ct v lm chm thi im cy ho khi nc b bay hi mnh. B sung polyme siu hp th nc cng lm gim tc bay hi nc ca t. Nhiu nghin cu ch ra rng, vt liu polyme hp th nc em li nhiu li ch khi s dng nh gim t l cht ca thc vt gn 100%, gim s chm sc thc vt ti 80%. Khi b sung polyme siu hp th nc vo t c th c cc tc dng sau: chng xi mn t v dng chy mt, tng kh nng thm, tng kh nng gi nc, ci thin kh nng sng st ca cy trng chu hn, ci thin kh nng thu hi dinh dng t phn bn s dng v gim tn sut ti. * Trong x l mi trng

31

Ngy nay, vn nhim mi trng l mt trong nhng thch thc ln ca nhn loi. C rt nhiu ngun gy nhim mi trng nhng ch yu l do qu trnh sn xut cng nghip v luyn kim. S c mt ca cc ion kim loi nng trong mi trng do qu trnh sn xut cng nghip v luyn kim gy ra l mt nguy c nghim trng do c tnh ca chng i vi nhiu c th sng. Vic tch loi cc ion kim loi c hi trong nc thi cng nghip c quan tm c bit trong thi gian gn y do nhng tiu chun quy nh v vn ny ngy cng nghim ngt. C nhiu phng php c s dng tch loi ion kim loi nng khi nc thi nh: chit, kt ta ho hc, trao i ion n gin v trao i to phc, hp thu, tch cht bng mng. Cc phng php nh kt ta ho hc hay thm thu ngc khng tch loi c hon ton cc ion kim loi. Hn na, cc qu trnh ny tiu tn nhiu nng lng v ho cht, ng thi li phi x l bn thi c hi sinh ra. Mt trong nhng phng php an ton v hiu qu v mt kinh t tch loi cc cht c hi dn ti s pht trin cc loi vt liu polyme c kh nng loi b cc ion kim loi theo c ch to phc v trao i ion. Hu ht cc vt liu polyme s dng cho mc ch ny thng l nha, tc l cc polyme to li c mc trng nh hn 100%. Ngoi cc loi nha trao i ion, th polyme siu hp th nc cng c s dng cho mc ch tch loi ion kim loi. Kh nng lu gi cc cation kim loi ca polyme siu hp th c

32

th din ra nh cc qu trnh trao i ion hoc to phc tu thuc vo cu trc ho hc v cc nhm chc ca chng. Cc nhm chc to phc l cc nhm chc cha mt hoc nhiu nguyn t cho electron nh N, S, O v P, cu trc ho hc ca chng rt khc nhau v thng phc tp. Cc nhm chc ny thng d dng a vo mng li polyme nh qu trnh trng hp hoc bin tnh sn phm sau trng hp. Polyme siu hp th nc c bn nhit v bn ho cht nn d tch khi mi trng phn ng khin cho qu trnh tch loi d dng v c kh nng ti sinh. Dng vt l ca cc polyme siu hp th to phc c th thay i t vt liu cng nh n dng gel mm. Cc tnh cht mong mun ca hydrogel to phc bao gm: - Dung lng hp ph cao - chn lc cao - ng hc v cn bng hp ph nhanh i vi dung dch cha kim loi - bn c hc cao v tnh tr ca cc ht trao i ion/to phc Heitz v cng s nghin cu qu trnh hp ph v gii hp ion crom bng gel polyacrylic axit. S lu gi crom tng theo pH theo 2 c ch. Trong khong pH thp, vng m cc phn t crom tan, qu trnh lu gi din ra qua s lin kt ion trong ton b th tch ca gel. pH cao hn, vng m cc ht crom hydroxit khng tan c to thnh, qu trnh lu gi l do hp ph trn b mt gel. Gii hp cc phn t crom trong

33

iu kin axit cng c nghin cu v ph thuc nhiu vo c ch lu gi v thi gian tn ti ca phc polyme - crom. Khi qu trnh lu gi din ra do lin kt ion, qu trnh gii hp ch t c mt phn vi thi gian tn ti rt ngn. Ngc li, qu trnh gii hp rt nhanh khi qu trnh lu gi din ra qua hp ph trn b mt ca gel polyme. [22] Xie v cng s nghin cu qu trnh hp th v hp ph ca hydrogel poly(acrylic axit-co-acrylamit) trong c 2 dung dch CuCl2 v FeCl3. S hp th ln nht tng ng i vi Cu v Fe l 247 v 173mg/g. Kt qu cng cho thy rng s hp th ca Cu2+ v Fe3+ ln hydrogel tng ng k khi pH ca dung dch thay i tng ng t 2,3 ln 4,2 v t 1,0 ln 2,1.
1.6 - Tnh hnh nghin cu trong v ngoi nc

1.6.1 - Vt liu polyme nanocomposit Khoa hc v cng ngh nano c nghin cu t lu trn th gii v n c coi nh mt trong nhng cuc cch mng ln nht ca khoa hc cng ngh hin i. T cui nhng nm 80, u nhng nm 90 nhiu nh khoa hc tin hnh cho cc monome hoc nhng oligome tn cng trc tip vo khong gia cc lp MMT - bin tnh hu c to vt liu nano composit, trong ni tri ln l cng trnh ca gio s Giannelis i hc Cornel ch to polystyren khong st bng qu trnh nng chy [11]. Nm 1987 hng Toyota thnh cng trong vic ch to vt liu nano polyamit trn c s s dng cht 1,2 - aminolauric lm tc nhn hu c ha MMT ... c bit ch vi 4,2% khong st trong polyamit th cng va p khng gim, trong khi
34

 bn ko t, n hi tng gp 100 ln. Trong khi vt liu composit vi bt n gia cng truyn thng th bn ko t v n hi khng thay i hoc gim i.

35

Bng 1.8 - Tnh hnh nghin cu v pht trin vt liu nanocomposit trn th gii N m
196 3 196 5 197 3 197 4 197 6 198 1 198 7 198 8 199 3

Tc gi
D. J. Greenland

Ni dung

c tnh
ISa = 5,2 A0 IS = 7,6 A0 IS = 20 A0 IS = 9,6 A0 IS = 13,1 A0

199 4

PVA xen trong cc lp MMT bng phng php dung dch Trng hp PMMA xen k trong A.Blumstein cc lp MMT B.W. Francis PVP xen k trong cc lp MMT (Oak Ridge) bng phng php dung dch K.K. Parikh Trng hp PAN xen k trong cc (Lowell) lp MMT Trng hp polyamit s dng T. Sakamoto caprolactam v 6 - amino caproic axit trong cc lp MMT Trng hp PS trong cc lp MMT H. Takahara dng cht (Waseda stearytrimethylamonium lm Univ.) tc nhn hu c ha Polyamit nano composit trng O. Kamigaito hp t caprolatam v 12 (Toyota) aminolauric axit trong cc lp MMT C. Kato Trng hp PAN xen trong cc lp (Waseda cao lanh (Kao - PAN) Univ) E.P. Cho PS nng chy xen k trong Giannelis cc lp MMT s dng (Cornnell ioctaecyldimethylamonium Univ.) ion lm tc nhn hu c ha To nano composit t MMT E.P. Epoxy s dng ankyl Giannelis ammonium mch ngn lm (Cornnell tc nhn hu c ha Univ.) To nano composit t cc T.J. Pinnavaia ankyl ammonium mch di (n (M.S.U) 12) lm tc nhn hu c ha

IS ~ 2,2A0

ISa = 5,2 A0 IS = 51 210A0 IS = 7,1 A0 IS ~ 2,2 A0 trng lng 35000 400000 trong 5h/1650C Tng bc ng rn, phn tn

199 4

36

199 6 199 6 199 7

Nano composit t MMT - Phng php Polycaprolactone s dng nhng chm aminododecanoic axit lm tc h. Phn nhn hu c ha tn Ch to nano composit t cao IS = 4,0 A0 lanh - PEG bng phng php trng lng nng chy PEG 1000 - 3400 Ch to nano composit MMT - Phng php O. Kamigaito PP bng phng php hn hp c l c (Toyota) bit

E.P. Giannelis (Cornnell Univ.) C. Deterllier (U. of Ottawa)

Trong phng php trng hp polyme, u tin monome xm nhp vo khong gia hai lp MMT nh vai tr cht hu c ha MMT. Phn ng khi mo c tin hnh qua qu trnh dch chuyn ca nguyn t hydro trong monome. Tip theo phn ng trng hp c tin hnh, cui cng thu c vt liu nanocomposit vi nhng polyme xm nhp vo khong gia hai lp MMT. Vit Nam, khoa hc v cng ngh nano c bt u quan tm v trin khai cch y gn 10 nm. i u trong lnh vc ny l cc nh vt l hc vi nhng ti nghin cu c bn v cng ngh nano. Cc nh khoa hc Vit Nam tip cn vi cng ngh nano, trin khai nghin cu vi s cng tc ca cc phng th nghim Nht Bn, Hn Quc, M, Php ... cng nh thc hin nhiu nghin cu c lp trong nc v bc u thu c mt s kt qu sau: - Nghin cu ch to nano TiO2 v mng TiO2 dit khun trn nn gch men ( ti cp Tp. HCM v i hc Quc gia H Ni nm 2006). - Vt liu nanocomposit PU cha bt Ag x l ngun nc nhim bn.
37

- Nghin cu to vt liu nano trn nn C (hp tc Vit Nam - Hn Quc, 2007 - 2009). - Nghin cu ch to vt liu bn dn pht quang trn saphia. - Nhiu tc gi Vit Nam tp trung nghin cu s dng bt nanoclay (nhp ngoi hay ch to t khong st Bnh Thun) gia cng cho nn polyme (PA, PE, PP ...). Cc k thut s dng l cn trn nng chy hoc dng my n hai trc ( ti ca trung tm Polyme/i hc Bch Khoa H Ni v Tp. HCM). - Trong khun kh chng trnh KC 02/06 - 10 c ti s dng vt liu nano lm cm bin hi ha hc (Vin ITIMS). Ti Vin Khoa hc - Cng ngh Qun s, cng ngh nano c nghin cu do GS. TSKH Nguyn c Hng ch tr ( ti thm d CNN), tip sau l ti c lin quan ti ch to mng xp Al2O3 anod ha c l xp c nano dng trong k thut nhum mu [1]. Cng ti Vin Khoa hc - Cng ngh Qun s, nhm tc gi do GS. TS Nguyn Vit Bc ch tr nghin cu ch to nanopolyme dn in (Polyanilin, Polypyrol) v composit PAni.FexOy, PAni.MMT cho kt qu tt. Mt s kt qu c cng b t 2006 - 2008. Vt liu nano composit t khong st - polyme c nhng c tnh c l ha u vit m cc vt liu thng thng khng c nh bn, khng lm gim tnh trong sut, tng cng vng, n hi, c kh nng c ch qu trnh thm thu ca kh v nc, chu mui, chu mi mn, chu nhit ... Do

38

, trong tng lai m ra rt nhiu trin vng ng dng khoa hc ca loi vt liu ny. Vic tng hp ra vt liu polyme siu hp th nc c s tham gia ca khong st hu c ha s to ra mt loi vt liu mi c nhiu ng dng hu ch trong thc tin. 1.6.2 - Vt liu polyme siu hp th nc Vt liu polyme siu hp th nc c bit ti ln u tin ti M l tc nhn gi nc trong nng nghip v c pht trin Nht Bn vo gia thp nin 1970 trong cc sn phm v sinh v chm sc c nhn. Ngoi ra, polyme siu hp th nc cn c s dng trong nng nghip, h vn chuyn thuc, t nhn to cho thu canh, tc nhn nh chm cho phn bn v thuc tr su, nha trao i ion, cht mang xc tc...Ban u polyme siu hp th nc c ch to trn c s qu trnh trng hp ghp cc vinyl monome a nc ln cc polyme sinh hc nh tinh bt, xenluloz, chitosan hay cc polysaccarit khc. Sau ny, polyme siu hp th nc ngun gc t nhin dn c thay th bi cc polyme tng hp c thi gian s dng ko di, kh nng hp th nc v bn gel ln. Vt liu polyme siu hp th nc c ch to trn c s cc loi polyme a nc thu ht c s quan tm ca nhiu nh khoa hc trn th gii. Raju v cng s tng hp polyme siu hp th nc trn c s cc monome acrylamit, canxi acrylat v natri acrylat s dng cht khi mo amoni pesunfat (APS) v cht to li N,N- metylenbisacrylamit (MBA). Copolyme c tng hp bng cch thay i nng

39

monome, cht to li v cht khi mo. Kt qu thc nghim cho thy rng polyme siu hp th nc c hp th cao c trong nc ct v trong dung dch NaCl (Qmax= 384g H2O/g mu). Vi xut hin ca khong st, th vic nghin cu ng dng n trong lnh vc ch to vt liu polyme siu hp th nc c rt nhiu nh khoa hc trn th gii nghin cu. Francisca Santiago v cng s tng hp vt liu siu hp th nc trn c s qu trnh trng hp axit acrylic trung ho mt phn vi cht an li l N, N - methylen bisacrylamit, octadecylammonium chlorit l tc nhn xen lp MMT. Kt qu ch ra rng vi 14% MMT th kh nng hp th nc ct v cc dung dch mui NaCl ln lt l 995g/g v 215g/g [21]. An Li v cng s tng hp polyme composit siu hp th nc trn c s phn ng ng trng hp ca axit acrylic trung ho mt phn v acrylamit, vi cht an li l N, N metylen bisacrylamit, cht khi mo phn ng l amoni persulfat. Kt qu cho thy vi 10% khong st th kh nng hp th nc ct v cc dung dch mui ca vt liu t c ln lt l 1414g/g i vi nc ct v 117g/g vi dung dch NaCl 0,9% [15]. Ji Zhang v cng s tng hp vt liu polyme composit siu hp th nc trn c s qu trnh trng hp axit acrylic trung ho mt phn vi cht an li l N, Nmethylen bisacrylamit, tc nhn khi mo phn ng l amoni persulfat vi bentonit c cc t l khc nhau. Kt qu cho thy

40

vi hm lng bentonit l 20% th kh nng hp th ca vt liu trong nc ct v dung dch NaCl 0,9% ln lt l 150 g/g v 35g/g [27]. Vit Nam, Vin Ho hc- Vin KH&CN Vit Nam bt u nghin cu v polyme siu hp th nc t nhng nm 1997 - 1998. n nm 2001 trin khai thnh ti KHCN trng im cp Nh nc. Sn phm c ch to trn c s qu trnh trng hp ghp gc t do axit acrylic v mui acrylat ln tinh bt sn c mt cht to li divinyl. Sn phm c kh nng hp th khong 350 ln trong nc ct v 65 ln trong nc mui sinh l. Thi gian phn hu hon ton trong t t 12 - 15 thng v c th pht huy tc dng t 2 - 3 v. Polyme siu hp th nc do Vin Ho hc ch to c th nghim cho nhiu loi cy, ti nhiu a phng nh cy bng ng Nai, c sa Ph Th, ch, c ph Ngh An, ng, lc, u tng H Ni, nho, tiu Ninh Thun, c ph c Lc...cho hiu qu cao trong vic gi m, chng hn, tng kh nng s dng nc v phn bn, tng nng sut cy trng v em li hiu qu kinh t [12]. Nm 2004, Trung tm nghin cu v trin khai cng ngh bc x (VINAGAMMA) nghin cu ch to ch phm c tn gi Gam-sorb. y l gel polyme t tinh bt sn bin tnh, c kh nng hp th nc cao khong vi trm ln so vi khi lng kh ca chng dng bt, ht, vy iu ho m. Thi gian phn hy ca loi Gam-sorb ny kh di. Sau 9 thng chn trong t, sn phm t phn hy 85,5%. Theo

41

nhm tc gi th sn phm ny thch hp vi mt s loi cy trng nh: cy du ty, cy thng , cy ci ngt, cy rau mung ... l nhng cy trng ngn ngy, c nhu cu tng v vo nhng thi im kh hn cc vng nh Ty Nguyn v Trung Trung B [12]. Bn cnh nhng c gng nghin cu v trin khai cng ngh, mt s n v cn tm cch nhp khu cng ngh v thit b ch to polyme siu hp th nc. Vin Khoa hc Nng nghip tm cch nhp khu dy truyn sn xut polyme siu hp th nc t Trung Quc nhng nhng n lc ny n nay vn cha thnh cng. n nay c rt t cng trnh trong nc nghin cu ch to vt liu polyme siu hp th nc trn nn nanoclay nhm ci thin kh nng hp th nc cng nh gim gi thnh sn phm nhm p ng tt nhu cu thc tin. Trong tng lai khng xa, khoa hc v cng ngh nano s c trin khai nghin cu su rng khp Vit Nam v s thu c cc kt qu nghin cu v ng dng tt p.

42

Chng 2 - thc nghim

2.1 - Thit b, dng c v ha cht

2.1.1 - Ha cht - Acrylamit (Merck, M = 71) - Axit acrylic: loi Pa, Trung Quc, d = 1,045 (M=72) - N, N - metylen bisacrylamit (Merck), M = 154 - Axit HCl: loi Pa, Trung Quc, d = 1,185 - Amonipersulfat: Loi Pa, Trung Quc, M = 228,2 - NaOH: Loi Pa, Trung Quc, M = 40 - Mui FeCl3.6H2O: Loi Pa, Trung Quc, M = 270,29 - CaCl2.6H2O: Loi Pa, Trung Quc, M = 219,08 - Dung dch nc mui sinh l 0.9% - Bentonit tinh khit: Vin Cng ngh X him (sn phm ca ti KC.02.06./06 - 10), Bnh Thun, Vit Nam. Hm lng MMT > 90%, kch thc ht < 10 micron, dung lng trao i ion 105 mldg/100g, m <5%, thnh phn ho hc: Al2O3 60,5%, Fe2O3 < 0,5%. - Etanol, Metanol, Nc ct - Kh nit: 99,99% 2.1.2 - Thit b, dng c - My khuy t: IKA - Gold Fish, tc 0 1500 vng/pht - T sy, bp in, t ht chn khng: SPt 200 (Horyzont, Ba Lan) - My li tm: Universal 32 (Hettich, c) - Bnh cu 3 c 250ml, 500ml, sinh hn thng
43

- ng ong, cc thy tinh, bnh nh mc, phu lc - Cn in t: Scientech (M), chnh xc 0,001 (g) - My khuy c, my nghin bi - Tiu bn mu thp CT3: 15x7,5x0,1 cm, chi qut. 2.1.3 - Cc thit b phn tch, o c - Thit b ghi ph hng ngoi: FT - IR Impact 410 Nicolet USA - Thit b phn tch nhit: My DSC - TGA 131, Setaram - Thit b phn tch nhiu x tia X: My AXS , SIEMENS D5005, Brucker - Thit b knh hin vi in t qut: My Hitachi S 4800, Nht - Nht kt Ubbelohde.
2.2 - Phng php tin hnh

2.2.1 - Tng hp polyacrylamit nguyn gc Theo nhiu ti liu nghin cu th iu kin thch hp thng s dng trong qu trnh polyme ha acrylamit l nng monome t 16% - 20%, hm lng cht khi mo phn ng 1% so vi lng monome, nhit phn ng, thi gian tin hnh phn ng l 700C/2h [52]. Trong khun kh ca kho lun chng ti cng tin hnh trng hp acrylamit iu kin: nng monome 20%, lng cht khi mo phn ng, iu kin phn ng nh trn v tin hnh xc nh khi lng phn t, ph hng ngoi v bn nhit, nh SEM v cc tnh nng c l ca mng ph ca polyacrylamit tng hp c nhm so snh cc tnh cht ca polyacrylamit nguyn gc

44

vi vt liu polyacrylamit clay nanocomposite s tng hp sau ny. Quy trnh: Ho tan 20g acrylamit v 0,2g amonipersulfat vo 80 ml nc ct. Sau , cho vo bnh cu ba c, c np sinh hn, cnh khuy. H phn ng c khuy mnh trong 30 pht c sc kh nit ui ht oxy trong dung dch phn ng. Qu trnh trng hp c tin hnh 700C/2h. Trong sut qu trnh trng hp h lun c sc kh nit v c khuy mnh. Sau khi kt thc phn ng, lm lnh v tho thit b cho sn phm kt ta trong etanol loi b cc monome d. Sy, ht chn khng 800C cho n khi khi lng khng i. 2.2.2 - Ch to clay hu c. Clay hu c c ch to thng qua phn ng trao i ion gia cc cation Na+ trong cu trc MMT vi cation ankyl amonium, tc nhn trao i y l acrylamit c mui ha bng dung dch HCl 1M. Quy trnh: - Dung dch huyn ph bentonit c chun b nh sau: Ho 5g Clay vo 500 ml nc ct, v c khuy mnh trong nhiu gi. Sau , xa lng 24h, loi b phn xa lng bn di. Dung dch huyn ph thu c em xc nh li hm kh tin hnh hu c ha. - Cn 1 lng xc nh acrylamit ho tan trong nc ct. Khuy mnh v c mui ha bng dung dch HCl 1M. Sau 1 gi khuy, mi lng acrylamit mui ha trn c nh t t

45

vo dung dch huyn ph bentonit c chun b t trc. Hn hp c khuy trong 24 gi tin hnh phn ng trao i. - Clay hu c ho c thu hi bng phng php ly tm, sau lc ra vi ln bng nc ct loi b ht ankyl amonium v Cl- d. Sy, ht chn khng 300C cho n khi khi lng khng i (khong 3 ngy). +) Kho st hm lng acrylamit ti u n qu trnh hu c ha khong st, chng ti tin hnh ly acrylamit c hm lng khc nhau l: 10%, 20%, 30%, 50% so vi lng clay c trong dung dch. +) kho st nh hng ca nhit ti qu trnh hu c ha khong st, chng ti tin hnh cc nhit khc nhau: 300C, 400C, 600C v 800C. +) Tng hp polyacrylamit trn nn nanoclay hu c c ch to nh sau: Ho tan 1 lng acrylamit thch hp vo nc ct, sau b xung thm lng nanoclay hu c theo t l nh sau: 2%, 3% v 4% so vi monome acrylamit. Thm mt lng thch hp cht khi mo v qu trnh trng hp c tin hnh iu kin chn. +) Mng ph clay nanocomposit c ch to theo s Clay hu Dung dch quy trnh sau: c Polyacrylamit

Nghin bi Polyacrylamit clay nanocomposit

46

To mng

2.2.3 - ng trng hp ca acrylamit v axit acrylic vi s c mt ca nanoclay - Trc tin, chng ti tin hnh nghin cu qu trnh ng trng hp ca acrylamit v axit acrylic, vi N, N - metylen bisacrrylamit l tc nhn an li. Quy trnh: Cho hn hp dung dch gm mt lng axit acrylic xc nh trung ho mt phn, acrylamit v N, N - metylen bisacrylamit vo bnh cu 3 c c lp sinh hn, cnh khuy v nhit k. Hn hp c khuy v sc kh nit trong 30 pht cho n khi h thnh ng th. B xung 1 lng thch hp cht khi mo phn ng vo h. Trong sut qu trnh phn ng h lun c sc kh nit v c khuy n nh. Sn phm c ra vi ln bng hn hp dung mi etanol/nc vi t l 9/1 theo th tch loi b cc monome d. Sn phm c sy, ht chn khng 800C cho n khi khi lng khng i.

47

Chng ti tin hnh kho st cc yu t nh hng n tnh cht ca sn phm nh: T l mol ca cc monome, hm lng cht an li v hm lng cht khi mo phn ng. Tip theo, chng ti tip tc tin hnh nghin cu phn ng ng trng hp ca acrylamit v axit acrylic vi s c mt ca nanoclay hu c cng c tin hnh tng t trn vi hm lng clay hu c t 2 5% so vi tng lng monome.
2.3 - Cc phng php phn tch, nh gi vt liu

2.3.1 - Xc nh trng lng phn t trung bnh ca polyacrylamit nguyn gc Trng lng phn t trung bnh ca polyacrylamit c xc nh bng phng php o nht, s dng nht k Ubbelohde, tin hnh o 300C. Trng lng phn t trung bnh c tnh theo phng Mark - Houwink nh sau: [] = K.M

Vi: K = 6,8.10-4 v = 0,66 0,05 2.3.2 - Xc nh trng ca sn phm bng phng php ti ch Cn chnh xc 50mg polyme siu hp th cho vo ti ch sau ngm trong cc ng 500ml nc ct hay cc dung dch mui c nng khc nhau trong 8 gi, nhit phng. Sau , ly ra ro nc, xc nh kh nng hp th nc theo cng thc sau: Q = (m2 - m1)/m0 Trong : Q: trng ca polyme, g/g

48

m0: Khi lng polyme kh, g m1: Khi lng ti vi, g m2: Khi lng ti vi v polyme sau khi trng, g 2.3.3 - Kho st cu trc sn phm 2.3.3.1 - Nghin cu cu trc bng k thut o ph hng ngoi (FT - IR) Ph hng ngoi c ghi trn my quang ph hng ngoi vi di sng t 400 4000 cm- 1 Thit b phn tch: FT - IR Impact 410 Nicolet USA, Vin Khoa hc Cng ngh Vit Nam. 2.3.3.2 - Nghin cu cu trc bng phng php nhiu x tia X Gin nhiu x tia X c ghi trn my phn tch nhiu x tia X vi gc qut t 20 500 Thit b phn tch: My AXS SIEMENS D5005, Bruker 2.3.3.3 - Nghin cu cu trc hnh thi hc bng k thut knh hin vi in t qut (SEM) Kch thc v hnh thi hc ca vt liu c th c xc nh bng k thut chp nh trn knh hin vi in t qut pht x trng (PE - SEM) vi gii hn kch thc c th phn bit c trong phm vi 5 10nm. Thit b phn tch: My Hitachi S - 4800, Nht 2.3.3.4 - Nghin cu thnh phn, bn nhit ca vt liu bng k thut phn tch nhit (TGA)

49

Nghin cu bn nhit trn thit b phn tch nhit DSC - TGA 131, Sertaram Labsys, Khoa ha hc, Trng i hc Khoa hc T nhin, HQG HN Ch o: Nhit : t 25 - 8000C Tc nng nhit: 100C/pht Mi trng o: Khng kh
2.4 - Cc phng php kho st tnh nng ca mng.

2.4.1 - Xc nh bn va p ca mng bn va p ca mng ca mng ph c xc nh trn my Erischen model 304 theo tiu chun ISO D - 58675, Vin Vt liu - Vin Khoa hc v Cng ngh Vit Nam. 2.4.2 - Xc nh b un ca mng bn un do ca mng c xc nh theo tiu chun ASTM 1737 trn dng c Erischen model 266, Vin Vt liu Vin Khoa hc v Cng ngh Vit Nam. 2.4.3 - Xc nh bn co xc bn co xc c nh gi theo tiu chun ISO 1518 trn dng c Erischen model 3239/I, Vin Vt liu - Vin Khoa hc v Cng ngh Vit Nam. 2.4.4 - Xc nh bm dnh bm dnh ca mng c xc nh theo tiu chun ASTM D - 4541 trn dng c Erischen model 525, Vin Vt liu - Vin Khoa hc v Cng ngh Vit Nam.

50

Chng 3 - kt qu v tho lun

3.1 - Tng hp polyacrylamit

iu kin tng hp polyacrylamit c la chn nh trn. Di y l ph hng ngoi ca acrylamit v polyacrylamit tng hp c.

Hnh 3.1 - Ph hng ngoi ca acrylamit

Hnh 3.2 - Ph hng51 ngoi ca polyacrylamit

Bng 3.1 - Tn s dao ng c trng ca acrylamit v polyacrylamit Dao ng NH CH C O C=C CH pic dao ng c trng NH, S sng, cm-1 Acrylamit 3371 3250 2812 1673 1612 1428 CH, C O, C=C Polyacrylamit 3423 2941 2931 1633 1596 1423

T d kin trn ph hng ngoi v bng 3.1 ta thy cc trong phn t acrylamit v polyacrylamit u xut hin nhng c s x dch i cht. Trn ph hng ngoi ca monome acrylamit c xut hin pic dao ng c trng ca lin kt i C=C 1612 cm-1 vi cng mnh. Trong khi pic dao ng c trng ca lin kt i C=C trn ph hng ngoi ca polyacrylamit cng xut hin 1596 cm-1 vi cng thp. Chng t mt lng ln lin kt i b m. iu c ngha l xy ra phn ng trng hp acrylamit to ra polyacrylamit. Trng lng phn t ca polyacrylamit c xc nh bng phng php o nht v c gi tr 3,1.105.
3.2 - Kt qu bin tnh hu c ha khong st

3.2.1 Kt qu kho st kh nng chn acrylamit vo gia cc lp MMT nghin cu kh nng chn acrylamit vo khong gia cc lp MMT, chng ti tin hnh phn ng trao i cation

52

trong khong gia cc lp MMT vi acrylamit c mui ho bng HCl 1M, c hm lng thay i t 10%, 20%, 30% v 50% so vi MMT c trong dung dch. Kt qu c nu cc hnh t hnh 3.3 n hnh 3.7. Tng hp kt qu phn tch nhiu x tia X c tng hp trong bng 3.2 sau: Bng 3.2 - Dn cch (d001) ca cc mu c hm lng acrylamit khc nhau Hm lng acrylamit Dn cch lp (d001), A0 0% 12,94 7 10% 14,94 7 20% 14,96 8 30% 14,72 8 50% 14,36 0

T kt qu trn, ta thy dn cch (d001) gc nhiu x (2) ca cc mu cao hn dn cch (d001) ca MMT ban u. iu ny chng t c s trao i ion gia cc cation trong cu trc MMT vi cc monome acrylamit. Hay cc monome ny c chn vo khong gia cc lp ca khong st. Cng t kt qu trn, ta thy dn cch (d001) t c gi tr cao nht l 14,968 A0 mu c hm lng acrylamit 20% so vi cc mu c hm lng acrylamit khc. S khc nhau v s dn cch ny c th do nhiu nguyn nhn nh: s monome c trao i l khc nhau, s sp xp caPAM-10-60 monome gia cc lp trong cc M au
6 00

khong st l n lp hay a lp ... Mt khc, do acrylamit l kh nng trng hp bn ngoi to thnh polyme cng ngn cn
4 00 d=12.967

mt monome d trng hp ngay c iu kin thng. Do ,

5 00

cc monome khc tip tc khuch tn vo khong gia ca

3 00 d=4.451 d=7.191 d=2.432

cc mu Bentonit ban u v gin ca cc mu bentonit

1 00

0 2 1 0 20 30 40 50

2-Theta - Scale
File: H oan K18 mau P AM-1 0-60.raw - Type: Locke Coupled - Sta 2.0 - End: 50.000 - Step: 0.020 - S time: 0.7 s - Tem 25 C (R d rt: 00 tep p.: oom) - Time Started: 2 s - 2-Theta: 2.00 - The 1.000 - C 0 ta: h 00-003-0014 (D - M ) ontmorillon - MgOAl2 ite O35 SiO2xH2O - Y: 22.60 %- d x by 1. - WL: 1.540 : 6 00-033-1161 (D - Q ) uartz, syn - SiO2 - Y: 26.50 % - d x by: 1. - WL: 1.5406 - Hexag onal - a 4 340 - b 4 .91 .91340 - c 5.4 0530 - a lpha 90 .000 - beta 9 00 - gam 120.0 - Prim 0.0 ma 00 itive - P 3221 (1 54) - 3 - 113.

53

Hnh 3.3 - Gin nhiu x tia X ca MMT

d=2.543

2 00

d=3.555

d=3.327

khong st. Di y l hnh nh gin nhiu x tia X ca

Lin (Cps)

 c chn acrylamit vi hm lng khc nhau: 10%, 20%, 30% v 50%.

54

400

Mau 2 PAM-40
d=14.947

300 d=3.330

Lin (Cps)

d=4.230

d=4.019 d=3.936

d=3.751

d=3.231 d=3.177

200

d=4.449

d=2.979

d=2.554

d=2.447

100

0 2 10 20 30 40 50

2-Theta - Scale
File: Hoan K18 mau 2 PAM-40.raw - Type: Locked Coupled - Start: 2.000 - End: 50.000 - Step: 0.030 - Step time: 1. s - Temp.: 25 C (Room) - Time Started: 11 s - 2-Theta: 2.000 - Theta: 1.000 - Chi: 00-003-0014 (D) - Montmorillonite - MgOAl2O35SiO2xH2O - Y: 28.13 % - d x by: 1. - WL: 1.5406 00-033-1161 (D) - Quartz, syn - SiO2 - Y: 33.00 % - d x by: 1. - WL: 1.5406 - Hexagonal - a 4.91340 - b 4.91340 - c 5.40530 - alpha 90.000 - beta 90.000 - gamma 120.000 - Primitive - P3221 (154) - 3 - 113.

Hnh 3.4 - Gin nhiu x tia X ca MMT c chn 10% acrylamit

500

Mau 3 BT-05

400 d=14.968

300

Lin (Cps)

200

d=4.479

d=4.244

d=3.341

d=3.770

d=3.476

d=3.238 d=3.181

d=4.025

100

0 2 10 20 30 40 50

2-Theta - Scale
File: Hoan K18 mau 3-BT-05.raw - Type: Locked Coupled - Start: 2.000 - End: 50.000 - Step: 0.020 - Step time: 0.8 s - Temp.: 25 C (Room) - Time Started: 10 s - 2-Theta: 2.000 - Theta: 1.000 - Chi: 00-003-0014 (D) - Montmorillonite - MgOAl2O35SiO2xH2O - Y: 28.12 % - d x by: 1. - WL: 1.5406 00-033-1161 (D) - Quartz, syn - SiO2 - Y: 32.98 % - d x by: 1. - WL: 1.5406 - Hexagonal - a 4.91340 - b 4.91340 - c 5.40530 - alpha 90.000 - beta 90.000 - gamma 120.000 - Primitive - P3221 (154) - 3 - 113.

Hnh 3.5 - Gin nhiu x tia X ca mu clay chn 20% acrylamit

55

d=2.991

d=2.551

d=1.881

400

Mau 4-PAM-80

300

d=14.728

Lin (Cps)

200

d=4.454

d=4.227

d=3.333 d=4.018 d=3.756 d=3.450 d=3.227 d=3.183

100

0 2 10 20 30 40 50

2-Theta - Scale
File: Hoan K18 mau 4 PAM-80.raw - Type: Lock ed Coupled - Start: 2.000 - End: 50.000 - Step: 0.030 - Step time: 1. s - Temp.: 25 C (Room) - Time Started: 11 s - 2-Theta: 2.000 - Theta: 1.000 - Chi : 00-003-0014 (D) - Montmorillonite - MgOAl2O35SiO2xH2O - Y: 31.24 % - d x by: 1. - WL: 1.5406 00-033-1161 (D) - Quartz, syn - SiO2 - Y: 36.64 % - d x by: 1. - WL: 1.5406 - Hexagonal - a 4.91340 - b 4.91340 - c 5.40530 - alpha 90.000 - beta 90.000 - gamma 120.000 - Primitive - P3221 (154) - 3 - 113.

Hnh 3.6 - Gin nhiu x tia X ca mu clay chn 30% acrylamit

Mau 3 PAM-60
400 d=14.360

300 d=3.332

Lin (Cps)

d=3.461

d=3.227 d=3.181

d=4.233

200

d=4.456

d=3.762 d=3.654

d=2.960

d=2.538

d=2.543

100

0 2 10 20 30 40 50

2-Theta - Scale
File: Hoan K18 mau 3 PAM-60.raw - Type: Locked Coupled - Start: 2.000 - End: 50.000 - Step: 0.030 - Step time: 1. s - Temp.: 25 C (Room) - Time Started: 11 s - 2-Theta: 2.000 - Theta: 1.000 - Chi: 00-003-0014 (D) - Montmori llonite - MgOAl2O35SiO2xH2O - Y: 27.16 % - d x by: 1. - WL: 1.5406 00-033-1161 (D) - Quartz, syn - SiO2 - Y: 31.86 % - d x by: 1. - WL: 1.5406 - Hexagonal - a 4.91340 - b 4.91340 - c 5.40530 - alpha 90.000 - beta 90.000 - gamma 120.000 - Primitive - P3221 (154) - 3 - 113.

Hnh 3.7 - Gin nhiu x tia X ca mu clay chn 50% acrylamit

56

d=2.122

3.2.2 - nh hng ca nhit ti kh nng hu c ha khong st kho st nh hng ca nhit ti qu trnh hu c ho MMT chng ti la chn mu c hm lng acrylamit bng 20% so vi MMT c trong dung dch v tin hnh phn ng trao i ion cc nhit khc nhau l: 300C, 400C, 600C v 800C. Cc iu kin tin hnh, mui ha c gi c nh. Kt qu c nu ra trong bng 3.3 v hnh 3.8 n hnh 3.11 Bng 3.3 - nh hng ca nhit ti kh nng hu c ha MMT Nhit Dn cch lp (d001), A0 300C 400C 600C
800C

14,968 15,063 14,733

14,181

T kt qu thu c bng trn, ta thy dn cch (d001) ca cc mu tng khi nhit tng t 30 400C. iu ny c th gii thch l khi nhit tng th phn ng trao i ion xy ra thun li hn. Tuy nhin, khi nhit tng cao hn 400C khong cch gia cc lp li gim. S gim dn cch lp ny c th gii thch l do nhit cao trn 600C, tc phn ng trng hp ca acrylamit to thnh polyacrylamit trong dung dch din ra mnh lit hn so vi tc ca phn ng trao i ion. Chnh v iu ny cn tr cc monome acrylamit tip tc khuch tn
500

Mau 3 BT-0 5

vo khong gia cc lp st dn n d001 gim. T cc kt qu

400

cho thy nhit ti u cho phn ng hu c ha khong st

Lin (Cps)

trong trng hp ny l 400C. Di y l hnh nh gin nhiu

d=4.244 d=3.770 d=3.476 d=3.238 d=3.181 d=4.025

300

d=14.968

khc nhau:
100 0 2 10 20

Hnh 3.8 - Gin 57 nhiu x tia X ca mu clay chn 20% acrylamit 300C
30 40

d=2.991

d=2.551

x tia X cc mu c tin hnh phn ng trao i cc nhit

200

d=4.479

d=3.341

50

2-Theta - Scale

File: Hoan K18 mau 3-BT-05.raw - Type: Locked Coupled - Start: 2.000 - End: 50.000 - Step: 0.020 - Step time: 0.8 s - Temp.: 25 C (Room) - Time Started: 10 s - 2-Theta: 2.000 - Theta: 1.000 - Chi: 00-003-0014 (D) - Montmorillonite - MgOAl2O35SiO2xH2O - Y: 28.12 % - d x by: 1. - WL: 1.5406 00-033-1161 (D) - Q uartz, syn - SiO2 - Y: 32.98 % - d x by: 1. - WL: 1.5406 - Hexagonal - a 4.91340 - b 4.91340 - c 5.40530 - alpha 90.000 - beta 90.000 - gamma 120.000 - Primitive - P3221 (154) - 3 - 113.

58

600

M 4 AM 0 au 3

500

400

Lin (Cps)

d=15.063

300

d=3.340 d=4.469 d=4.244 d=4.020 d=3.770 d=3.460 d=3.235 d=3.188

200 d=7.168

100

0 2 10 20 30 40 50

2-Theta - Scale
File: H oan K18 mau 4-AM-30.raw - Type: Locked Coupled - Start: 2.000 - End: 50.000 - Step: 0.030 - Step tim 1. s - Tem 25 C (R e: p.: oom) - Tim Started: 10 s - 2-Theta: 2.000 - Theta: 1.000 - Chi: e 00-003-0014 (D) - M ontmorillonite - MgOAl2O35SiO2xH2O - Y: 19.42 %- d x by 1. - WL: 1.5406 : 00-033-1161 (D) - Q uartz, syn - SiO2 - Y: 22.78 % - d x by: 1. - WL: 1.5406 - Hexagonal - a 4.91340 - b 4.91340 - c 5.40530 - alpha 90.000 - beta 90.000 - gam ma 120.000 - Prim itive - P3221 (154) - 3 - 113.

Hnh 3.9 - Gin nhiu x tia X ca mu clay chn 20% acrylamit 400C
Mau PAM -10-8 0-0,5
500

400

Lin (Cps)

300

d=4.485

200

d=14.733

d=3.346

100

0 2 10 20 30 40 50

d=7.236

d=4.983

2-Theta - Scale
File: Hoan K18 mau PAM-10-80-0,5.raw - Type: Locked Coupled - Start: 2.000 - End: 50.000 - Step: 0.020 - Step time: 0.8 s - Temp.: 25 C (Room) - Time Started: 10 s - 2-Theta: 2.000 - Theta: 1.000 00-003-0014 (D) - Montmorillonite - MgOAl2O35SiO2xH2O - Y: 34.49 % - d x by: 1. - WL: 1.5406 00-033-1161 (D) - Quartz, syn - SiO2 - Y: 30.34 % - d x by: 1. - WL: 1.5406 - Hexagonal - a 4.91340 - b 4.91340 - c 5.40530 - alpha 90.000 - beta 90.000 - gamma 120.000 - Primitive - P3221 (154) - 3 - 113.

Hnh 3.10 - Gin nhiu x tia X ca mu clay chn 20% acrylamit 600C

59

d=2.573

d=2.557

5 00

M A4 -1 au M 0

4 00

Lin (Cps)

3 00

d=14.181

d=4.452

2 00 d=7.123 d=4.908

d=3.322

1 00

0 2 1 0 2 0 3 0 4 0 50

2-Theta - S cale
File: H an K18 ma A -10.raw- Type: Locked C pled - S o u 4M ou tart: 2 .000 - En 50.000 - Ste 0 d: p: .020 - Step tim 0.7 s - Te .: 2 C (R e: mp 5 oom - Tim S ) e tarted 16 s - 2-Theta: 2 0 - The 1.0 - C i: : .00 ta: 00 h 0 0-00 3-001 (D - M 4 ) ontmo rillonite - Mg OAl2O SiO 35 2xH2 - Y: 3 9 %- d x by 1. - W : 1.540 O 3.9 : L 6 0 0-03 3-116 (D - Q 1 ) uartz, syn - SiO2 - Y: 29 .90 % - d x by: 1 - W 1.5 . L: 406 - H exagon - a 4 340 - b 4 al .91 .91340 - c 5.4 0530 - a lpha 90.00 - be 9 00 - gam 120.000 - Prim 0 ta 0.0 ma itive - P 3221 (154) - 3 - 1 . 13

Hnh 3.11 - Gin nhiu x tia X ca mu 3.2.3 - Nghin cu 20% trc nanoclay hu c bng ph MMTchn cu acrylamit 800C hng ngoi Phng php ph hng ngoi l phng php phn tch nhanh, nhy c th nghin cu cu trc MMT hu c. Chng ti tin hnh chp ph hng ngoi mu MMT ban u, acrylamit v mu MMT c hu c ha bng acrylamit 20% 400C. Kt qu c trnh by bng 3.4 sau:

Hnh 3.12 - Ph hng ngoi ca Acrylamit

60

d=2.549

Hnh 3.13 - Ph hng ngoi ca Bentonit ban u

Bng 3.4 - Tn s dao ng c trng ca MMT ban u, Hnh 3.14 - Ph hng ngoi ca Clay acrylamit v MMT hu c ha hu c

61

S sng, cm-1 Dao ng OH NH CH C O C=C NH CH Si-O Al-OH CH Si-O-Al 2926 Clay 3628 3449 3371 3250 2812 1673 1612 1428 Acrylamit Clay hu c 3642 3427 3220 1674

1042 920 819 788

1347 1034 921 801

Trn ph hp th hng ngoi ca mu MMT ban u, ta thy cc dao ng ha tr OH 3642 cm-1 v 3449 cm-1 trong mng tinh th lin kt vi cc cation Al3+, Mg2+ v Fe2+ trong nhm bt din, v dao ng c trng ca Si - O 1042 cm-1

62

trong mng tinh th t din. Cn trn ph hng ngoi ca mu MMT - hu c, ngoi cc dao ng c trng ca cc nhm trn ta cn thyxut hin cc dao ng c trng ca N - H 3410 cm-1 v 3220 cm-1, dao ng c trng ca nhm C - O 1674 cm-1 v dao ng bin dng ca C - H 1347 cm-1. Kt qu phn tch ph hng ngoi ca mu MMT c hu c ha bng acrylamit ca cc mu vt liu trn chng minh c s hnh thnh MMT - hu c t phn ng hu c ha clay vi tc nhn hu c ha l acrylamit. 3.2.4 - Nghin cu hnh thi hc ca nanoclay hu c b xung cho vic chng mnh cu trc ca nanoclay hu c chng ti tin hnh nghin cu hnh thi hc ca vt liu bng phng php knh hin vi in t qut (SEM). Di y l hnh nh SEM c phn gii cao ca cc mu MMT ban u v MMT hu c vi tc nhn hu c ha l acrylamit.

Hnh 3.15 - nh SEM ca MMT ban u

63

Hnh 3.16 - nh SEM ca MMT- hu c Trong nh SEM ca clay ban u cho thy cc ht MMT c dng tm v c xp thnh cc lp, kh phn bit c ranh gii gia cc lp. Trong khi , nh SEM ca clay hu c cc ht MMT cng c dng tm xp lp nhng cc lp ny dn rng ra v hnh nh cc tm ny sc nt hn so vi MMT ban u. iu ny chng t tc nhn hu c ha acrylamit amonium thay th c cc ion Na+ trong cu trc MMT, khong cch gia cc lp c y ra xa. Nh vy, xen k gia cc lp ny l tc nhn hu c ho m y s dng l acrylamit.
3.3 - Kt qu tng hp polyacrylamit clay nanocomposit

64

Vt liu polyme clay nanocomposit c ch to trn c s qu trnh trng hp acrylamit vi s c mt ca nanoclay hu c c hm lng thay i t 2%, 3%, v 4%. Cc kt qu nghin cu c trnh by trong cc phn tip theo.
3.3.1 - Nghin cu cu trc polyacrylamit clay nanocomposit bng nhiu x tia X.

Phng php nhiu x tia X c s dng ph bin nghin cu nh gi nhng thay i v cu trc ca vt liu. Kt qu phn tch nhiu x tia X ca cc mu polyacrylamit clay nanocomposit c hm lng nanoclay hu c khc nhau c trnh by cc hnh t 3.17 n 3.19 v c tng hp bng 3.5. Bng 3.5 - Kt qu phn tch nhiu x tia X ca cc mu c hm lng clay hu c khc nhau Hm lng clay hu c, % Dn cch lp (d001), A0 2% 15,779 3% 15,586 4% 15,377

T kt qu phn tch nhiu x tia X thu c ta thy: cc mu c hm lng nanoclay hu c t 2 - 4%, dn cch lp (d001) ng vi gc nhiu x (2) u ln hn so vi dn cch lp ca MMT - hu c ban u (15,036 A0). iu chng t cc monome acrylamit bn ngoi dung dch tip tc khuch tn vo khong gia cc lp MMT - hu c v trong qu trnh trng hp cc monome ny kt hp vi cc monome c sn trong trong khong gia cc lp ca MMT - hu c to thnh polyacrylamit. Chnh iu ny dn ti khong cch hai lp MMT c dn rng ra.

65

Thc t th polyacrylamit clay nanocomposit thu c ngoi cc monome acrylamit khuch tn vo trong hnh lang ca khong st trng hp to thnh polyacrylamit xen gia cc lp MMT. Ta cn nhn c c polyacrylamit bao quanh cc ht MMT hu c bn ngoi. Cc mu c dn cch lp dao ng t 15,377 15,779 A0, tng ng kch thc mch polyacrylamit xp thng hng trong khong gia cc lp st. Kt qu thu c ph hp vi cc kt qu o c ca nhiu tc gi khc [2,11]. Trong cc mu polyacrylamit clay nanocomposit thu c th mu c hm lng MMT - hu c 2% c khong dn cch lp l ln nht. Chng ti s s dng mu c hm lng MMT - hu c l 2% nghin cu cu trc vt liu tng hp c. Gin nhiu x tia X ca cc mu c trnh by di y.
1000

VNU-HN-SIEMENS D5005 - Bentonite-Mau AM-20

900

800

700

600

Lin (Cps)

500

d=15.779

400

d=4.504

d=4.268

200

100

0 2 10 20 30 40 50

File: Hoan-Vien HHVL-AM-20.raw - Type: 2Th/Th locked - Start: 2.000 - End: 50.000 - Step: 0.030 - Step time: 1.0 s - Temp.: 25.0 C (Room) - Anode: Cu - Creation: 09/25/09 14:50:11 33-1161 (D) - Quartz, syn - SiO2 - Y: 19.80 % - d x by: 1.000 - WL: 1.54056 03-0014 (D) - Montmorillonite - MgOAl2O35SiO2xH2O - Y: 8.79 % - d x by: 1.000 - WL: 1.54056

Hnh 3.17- Gin nhiu x tia X ca mu c 2% nanoclay hu c

66

d=3.789

2-Theta - Scale

d=3.248 d=3.202

300

d=3.354

1000

VNU-HN-SIEMENS D5005 - Bentonite-Mau BM-20

d=15.586

900

800

700

Lin (Cps)

600

500

400

d=4.505

d=3.355 d=4.270
20

200

100

0 2 10 30 40 50

2-Theta - Scale
File: Hoan-Vien HHVL-BM-20.raw - Type: 2Th/Th locked - Start: 2.000 - End: 50.000 - Step: 0.030 - Step time: 1.0 s - Temp.: 25.0 C (Room) - Anode: Cu - Creation: 09/25/09 14:12:53 33-1161 (D) - Quartz, syn - SiO2 - Y: 18.00 % - d x by: 1.000 - WL: 1.54056 03-0014 (D) - Montmorillonite - MgOAl2O35SiO2xH2O - Y: 11.93 % - d x by: 1.000 - WL: 1.54056

Hnh 3.18 - Gin nhiu x tia X ca mu cha 3% nanoclay hu c

VNU-HN-SIEMENS D5005 - Bentonite-Mau 1 AM-20

700

600

500

Lin (Cps)

400

300

d=15.377

d=3.489

300

d=4.480

d=4.245

d=4.031

d=3.479

d=3.242 d=3.192

200

d=3.343

d=3.253 d=3.203

100

0 2 10 20 30 40 50

2-Theta - Scale
File: 1Mau1 AM-20.raw - Type: 2Th/Th locked - Start: 2.000 - End: 50.000 - Step: 0.030 - Step time: 1.0 s - Temp.: 25.0 C (Room) - Anode: Cu - Creation: 09/25/09 14:14:48 33-1161 (D) - Quartz, syn - SiO2 - Y: 10.33 % - d x by: 1.000 - WL: 1.54056 03-0014 (D) - Montmorillonite - MgOAl2O35SiO2xH2O - Y: 7.15 % - d x by: 1.000 - WL: 1.54056

Hnh 3.19 - Gin nhiu x tia X ca mu cha 4% nanoclay hu c

67

d=2.1538 d=2.1286

3.3.2 - Nghin cu cu trc polyacrylamit clay nanocomposit bng ph hng ngoi Ph hng ngoi ca mu polyacrylamit clay nanocomposit a ra hnh 3.20

Hnh 3.20 - Ph IR mu polyacrylamit cha 2% MMT - hu c

Trn ph hng ngoi ca mu polyacrylamit cha 2% MMT - hu c cho thy, cc pic dao ng c trng ca OH 3638 cm-1, NH 3411 cm-1 ca nhm amit, CH 2944 cm-1, CO 1666 cm-1, CH 1460 cm-1, SiO 1038 cm-1, Al-OH 920 cm-1 u xut hin khng nh c s c mt ca hai thnh phn ca h composit. Ngoi vic to thnh polyacrylamit bao quanh cc ht MMT - hu c th hin bng cc dao ng c trng ca nhm amit vi cng mnh, th vic to thnh polyacrylamit xen trong khong cch gia cc lp MMT - hu c cng c xc nh th hin bng s x dch cc vch ph c trng v thay i cng ca chng. S x dch v thay i cng ca ca cc vch

68

ph ny c th l do s tng tc gia nhm chc amit phn cc vi cc nhm chc c trong cu trc MMT khi chng c iu kin c tip xc gn nhau. iu ny l minh chng kh th v cho vic hnh thnh vt liu polyme nanocomposit bng phn ng trng hp cation acrylamit nanoclay . 3.3.3 - Kt qu nghin cu hnh thi hc ca polyacrylamit clay nanocomposit K thut knh hin vi in t qut (SEM) l mt trong nhiu phng php dng nghin cu cu trc b mt ca vt liu nanocomposit nhm xc nh ln ca cc ht trong cu trc nano. Chng ti la chn mu polyacrylamit clay nanocomposit c dn cch lp (d001) t gi tr ln nht l 15,779 A0 v mu polyacrylamit khng cha nanoclay tin hnh nghin cu cu trc b mt ca vt liu tng hp c, di y l hnh nh SEM ca hai mu vt liu . khi c mt

Hnh 3.21a - nh SEM ca mu polyacrylamit

Hnh 3.21b - nh SEM ca mu polyacrylamit cha 2% MMT - hu c

69

Trn hnh nh SEM 3.21 a, ta thy cu trc b mt ca vt liu l khi lin khng c 1 polyacrylamit Figure: Experiment: au cc ht dng tm. Cn P T 100mu Atmosphere: M Crucible:vi l Air cha 2% nanoclay hu c th b mt ca vt liu c cc ht MMT TG/% H eatFlow/ V dTG/% /min
11.2 0 dng tm, xp lp v dn rng ra bi qu trnh khuch tn
Peak :661.68 C Labsys TG 13/11/2009 Procedure:RT ----> 800C (10C.min-1) (Zone 2) Mass (mg): 81.78

Exo

polyacrylamit trong khong xen gia cc lp MMT. Cc ht ny phn

8.4
Peak :535.72 C

-2

5.6 tn u trong nn polyacrylamit v c kch thc c 200nm. -20

3. 3. 4 - Kt qu phn tch bn nhit ca polyacrylamit 2.8

Peak :150.49 C

-4

clay nanocomposit 0.0

-40 Tnh cht nhit ca polyacrylamit clay nanocomposit c xc -2.8
Mass variation: -7.64 % nh bng phng php phn tch nhit TGA. Trong qu trnh nung

-6

-5.6

nng tnh cht v cu trc ca polyacrylamit clay nanocomposit thay -60 i. Nhng thay i ny km theo qu trnh thu nhit hay to
Mass variation: -2.40 %

-8.4

-8

nhit. Di y l gin phn tch nhit ca mu bentonit ban u, mu polyacrylamit v mu polyacrylamit clay nanocomposit. Hnh 3.22 - Gin TGA ca bentonit ban u
Figure: Labsys TG Experiment:Mau 2 Crucible:PT 100 l Atmosphere: Air Mass (mg): 23.71 13/11/2009 Procedure: RT ----> 800C (10C.min-1) (Zone 2)

-11.2

Mass variation: -1.79 %

100

200

300

400

500

600

700

Furnace temperature /C

TG/% 56
Peak :147.24 C Peak :286.12 C

HeatFlow/V 20 Exo

d TG/% /min

42
Peak :410.08 C

-10

28

0 -20

14

0
Mass variation: -8.18 %

-20

-30

-14

Mass variation: -17.31 %

-28 -40 -42

Mass variation: -30.32 %

-40

-50 -56 0 100 200 300 400

70

Hnh 3.23 - Gin TGA ca polyacrylamit

500

600

700

Furnace t emperature /C

Figure: Labsys TG

Experiment:Mau 3

Crucible:PT 100 l

Atmosphere:Air Mass (mg): 13.96

13/11/2009 Procedure: RT ----> 800C (10C.min-1) (Zone 2)

TG/%

HeatFlow/V Exo 10 Peak :731.16 C

Peak :436.49 C Peak :153.22 C Peak :283.44 C

d TG/% /min

40

20

-10

-5 0
Mass variation: -8.19 %

-10

-20

Mass variation: -16.76 %

-15

-20

Mass variation: -15.34 %

-20

-40 -25
Mass variation: -5.87 %

100

200

300

400

500

600

700

Furnace temperature /C

Trn gin Gin phn tch nhit ca mu ban Hnh3.24 - phn tch nhit ca mu bentonit u ta thy polyacrylamit 60 1500C xy ra qu trnh khong nhit clay nanocomposit tch nc hp th vt l trong mu v t cc i 150 0C, vi

71

tn hao khi lng l 7,64%. Tip theo l qu trnh mt nc trong cu trc tinh th 1,79%. Cn trn gin phn tch nhit ca mu polyacrylamit ta thy qu trnh phn hu nhit din ra qua ba giai on r rng. nhit 1470C xy ra qu trnh mt nc, tn hao khi lng l 8,18%. Ti nhit 2860C th polyacrylamit bt u phn hu vi tn hao khi lng l17,31%, n nhit 4100C polyacrylamit phn hu mnh nht vi tn hao khi lng l 30,32% v nhit trn 4100C phn hy xy ra hon ton. Trn gin phn tch nhit ca mu polyacrylamit clay nanocomposit ta thy ti nhit 1530C xy ra qu trnh tch nc, vi tn hao khi lng l 17,31%. Ti nhit t 2830C 4360C l giai on polyacrylamit clay nanocomposit b phn hy vi tn hao khi lng ln lt l 6,76% v 15,34%. Ta thy giai on ny qu trnh phn hu nhit din ra thnh hai giai on. iu ny c th gii thch l do s c mt ca nanoclay hu c ngn cn s khuch tn xy vo tip cn vi mch polyacrylamit. Dn ti qu trnh phn hu nhit gian on ny xy ra khng lin tc m c s thay i. nhit 7310C xy ra qu trnh tch nc trong cu trc mng tinh th v c th l c qu trnh phn hy polyacrylamit xen trong khong gia cc lp MMT, tn hao khi lng giai on ny l 5,87%. T cc kt qu phn tch nhit trn y ta thy rng ch vi 2% hm l6610C vi tn hao khi lng l

72

ng MMT hu c th kh nng bn nhit ca vt liu polyacrylamit c ci thin ng k. 3.3.5 - Kt qu xc nh trng lng phn t ca polyacrylamit clay nanocompsit Chng ti tin hnh kh st nh hng ca hm lng nanoclay n trng lng phn t ca sn phm theo phng php o nht. Kt qu c trnh by bng 3.6 sau: Bng 3.6 - S ph thuc ca trng lng phn t polyacrylamit vi hm lng nanoclay hu c. Hm lng nanoclay hu c, % 0 2 3 4 5 Trng lng phn t x103 310 306 302 298 295

T kt qu trn, cho thy cng iu kin tin hnh phn ng th trng lng phn t ca cc mu thay i khng ng k so vi trng lng phn t ca mu polyacrylamit khng cha MMT - hu c khi hm lng MMT hu c tng t 2 - 5% . iu ny c th gii thch nh sau: Vi hm lng MMT - hu c c trong polyme khng nhiu v cc ht MMT - hu c c kch thc rt nh c nano v c phn tn u trong nn polyme. Do , cc ht MMT - hu c ny khng gy nh hng ng k ti nht ca dung dch polyme dn ti trng lng phn t trung bnh ca cc mu polyacrylamit clay nanocomposit tng hp c thay i
73

khng nhiu. T kt qu xc nh trng lng phn t ca cc mu tng hp c th mu c cha 2% MMT - hu c c trng lng phn t gn bng trng lng phn t ca polyacrylamit nguyn gc l do vi hm lng nh v kch thc rt nh th cc ht MMT - hu c d dng khuch tn vo trong nn polyacrylamit tt hn so vi cc mu c hm lng MMT - hu c cao hn.
3.4 - Kt qu nghin cu ng trng hp acrylamit v axit acrylic

Cng nh cc phn ng tng hp polyme khc, phn ng ng trng hp ca acrylamit v axit acrylic chu nh hng ca cc yu t nh: nng cht khi mo, t l mol gia hai cu t, nhit phn ng ... Trong khun kh ca bn lun vn ny, do thi gian c hn chng ti ch la chn nghin cu nh hng ca mt vi yu t quan trng nht, cn cc iu kin phn ng khc c tham kho theo ti liu v c gi c nh. 3.4.1 - nh hng ca hm lng cht khi mo n trng ca sn phm Kt qu kho st nh hng ca hm lng cht khi mo n trng ca sn phm c trnh by bng 3.7 v hnh 3.25. iu kin tin hnh phn ng 700C trong 2gi, hm lng cht an li l 0,2%, mc trung ho ca axit acrylic l 75%, t l mol gia AM/AA l 0,5, hm lng cht khi mo thay i t 0,2 1,4%. Bng 3.7 - nh hng ca hm lng cht khi mo n trng ca sn phm

74

Hm lng cht khi mo, % 0,2 0,5 0,7 1 1,2 1,4

500
trng, g/g

trng, g/g 302 338 365 432 269 234

400 300 200 100 0 0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6
H l ngcht kh m o , % m i

Hnh 3.25 - nh hng ca hm lng cht khi mo n trng ca vt liu T kt qu bng 3.7 v hnh 3.25, cho thy khi hm lng cht khi mo phn ng tng th trng ca sn phm cng tng. Nhng trng ca sn phm ch tng ti mt gi tr nht nh sau li gim xung. iu ny c th gii thch: khi tng hm lng cht khi mo phn ng th s gc t do to thnh s tng ln, s trung tm hot ng cng tng dn ti tc phn ng chung tng ln. Tuy nhin, khi hm lng cht khi mo tng qu cao s lm cho s gc t do to thnh cng phn hy nhanh hn, tng tc ngt mch ca

75

phn ng, dn n trng lng phn t ca sn phm gim do trng gim. T kt qu trn chng ti la chn hm lng cht khi mo phn ng l 1% so vi tng lng monome thc hin cc kho st tip theo. 3.4.2 - nh hng ca hm lng cht an li ti trng ca sn phm Kt qu nghin cu kho st nh hng ca cht an li ti trng ca sn phm c trnh by bng 3.8 v hnh 3.26, phn ng c tin hnh 700C trong 2 gi, hm lng cht khi mo phn ng l 1%, mc trung ho axit acrylic l 75%, t l mol AM/AA l 0,5, hm lng cht an li thay i t 0,2 1%.

76

Bng 3.8 - nh hng ca hm lng cht an li ti trng ca sn phm Hm lng cht an li, % 0,2 0,4 0,6 0,8 1,0
500

trng, g/g 432 214 123 106 95

400 trng, g/g 300 200

100 0

Hnh 3.26 - nh hng ca hm lng cht an Hm l ng cht l i, % li an ti trng ca sn phm T kt qu trong bng 3.8 v hnh 3.26, cho thy trng ca sn phm gim khi hm lng cht an li tng t 0,2 1%. iu ny c th gii thch nh sau: vi hm lng cht to li nh to cho sn phm c s lin kt ngang gia cc mch copolyme thp, cc phn t nc c th d dng khuch tn vo trong copolyme v y cc mch mm do ra xa nhau,

0.2

0.4

0.6

0.8

1.2

77

nn sn phm thu c c trng cao. Khi lng cht an li tng ln s lm cho cc mch copolyme c an li cht ch hn, lm gim khong khng gian cha nc ca sn phm, dn n trng ca sn phm gim. thun li cho vic nghin cu kho st tip theo, chng ti chn t l cht an li l 0,2% so vi tng monome c trong dung dch. 3.4.3 - nh hng ca t l mol gia hai cu t acrylamit v axit acrylic Kt qu nghin cu kho st nh hng ca t l mol gia cc cu t ti trng ca sn phm c nu ra bng 3.9 v hnh 3.27, phn ng c tin hnh 700C trong 2 gi, hm lng cht khi mo phn ng l 1%, mc trung ho axit acrylic l 75%, hm lng cht an li 0,2 %. T l mol gia acrylamit/ axit acrylic (AM/AA) thay i t 0,2; 0,3; 0,5; 0,7 v 0,9. Kt qu c nu bng 3.8 v hnh 3.28: Bng 3.9 - nh hng ca t l mol gia cc cu t ti trng ca sn phm T l mol AM/AA 0,2 0,3 500 0,5 0,7 400 0,9
300 200 100 0 0 0.2 0.4 0.6 0.8 1 Tlm l AM/AA o Hnh 3.27 - nh hng ca t l mol 78 AM/AA ti trng ca sn phm

trng, g/g

trng, g/g 274 328 432 311 289

T cc kt qu trn, cho thy trng ca sn phm tng khi t l mol gia acrylamit/axit acrylic tng t 0,2 - 0,5 sau li gim khi m t l mol gia hai cu t li tng. iu ny c th gii thch: Khi t l s mol ca AM/AA tng t 0,2 0,5 tc l tng nhm a nc (CONH) trong mch copolyme dn n kh nng gi nc tng dn ti trng ca copolyme tng. Nhng nu tip tc tng AM th lc tng tc gia cc mch polyme thng qua lin kt cu hydro tng, chnh iu ny dn ti s lin kt ngang trong mch copolyme tng lm gim khng gian cha nc ca sn phm, dn n trng ca sn phm gim. Khi trong cu trc ca vt liu thu c tn ti c ba nhm a nc l - COO-, - COONa, - CONH vi mt t l thch hp, n c tc dng lm gim nh hng gia cc ion v dn ti kh nng hp th nc ca vt liu tng [27]. T kt qu th nghim thu c chng ti la chn t l AM/AA ti u l 0,5 tin hnh cc nghin cu kho st tip theo.
3.5 - Kt qu kho st qu trnh ng trng hp ca acrylamit v axit acrylic vi s c mt ca nanoclay hu c.

3.5.1 - Kt qu kho st nh hng ca hm lng nanoclay n kh nng trng ca sn phm T kt qu kho st nh hng ca cc yu t nh: t l mol AM/AA, hm lng cht an li, hm lng cht khi mo

79

phn ng n tnh cht ca sn phm phn trn, chng ti chn c t l ti u: AM/AA = 0,5, hm lng cht khi mo phn ng 1%, hm lng cht an li l 0,2%. Phn ng tin hnh 700C trong 2 gi. Chng ti tin hnh phn ng ng trng hp gia cc cu t vi s c mt ca nanoclay hu c vi hm lng nanoclay hu c thay i t 0%, - 5% so vi lng monome c trong dung dch. Kt qu c trnh by bng 3.10 v hnh 3.28 sau:

80

Bng 3.10 - nh hng ca hm lng nanoclay hu c ti trng Hm lng nanoclay hu c, % 0 1 2 3 4 5

600

trng, g/g 432 522 545 416 363 275

tng, g/g

500 400 300 200 100 0

Hnh 3.28 - nh hng ca hm lng % nanoclay u nanoclayh c n trng ca sn phm

T kt qu trn cho thy trng ca sn phm tng khi hm lng nanoclay hu c tng t 0 - 2%, sau li gim khi hm lng nanoclay hu c tip tc tng. iu ny c th gii thch nh sau: Trong clay c cha cc nhm chc OH trn b mt, cc nhm ny c th tng tc vi cc nhm chc COOca polyme to thnh cc lin kt trong mng li ca vt liu. y clay ng vai tr gn ging nh tc nhn to lin kt ngang. Vi hm lng nanoclay hu c thp (1 - 2%) th

81

nanoclay hu c d dng phn tn vo trong polyme, lm cho mch polyme mm do v dn rng ra, dn n trng ca polyme tng. Nhng khi hm lng nanoclay hu c tng ln th lc tng tc gia polyme v nanoclay hu c tng dn ti mt lin kt ngang ca polyme tng ln dn n lm gim kh nng hp th nc ca vt liu. 3.5.2 - Kt qu kho st trng ca sn phm trong cc dung dch mui c nng khc nhau tin hnh nghin cu kho st kh nng hp th ca sn phm i vi cc dung dch mui c nng khc nhau, chng ti tin hnh la chn hai sn phm c v khng c nanoclay hu c c kh nng hp th nc ct cao nht so snh. Kt qu c trnh by trong bng 3.11 v hnh 3.29, 3.30 di y. Bng 3.11 - trng ca vt liu vi cc dung dch mui c nng khc nhau trng, g/g PAAM
Nng , % Dung dch

PAAM2 0,3 0,5 0,7 52 15 13 0,9 44 9 7

0,3 NaCl CaCl2 80 FeCl3

trng, g/g

0,5 53 8 11

0,7 45 7 5

0,9 39 6 3

71 15 19

88 65 31 18 42 NaCl 22
FeCl3 CaCl2

Ghi ch:

60

PAAM: Poly(acrylamit - co - axit acrylic )

PAAM240Poly(acrylamit - co - axit acrylic ) cha 2% naoclay hu c. :

20

0 0 0.2 0.4 0.6 0.8 1

Hnh 3.29 - trng ca PAAM Nng % , 82 trong cc dung dch mui c nng khc nhau n

 NaCl FeCl3 CaCl2

Hnh 3.30 - trng ca PAAM2 trong cc dung dch mui c nng khc nhau T kt qu thu c cho thy trng ca PAAM v PAAM2 gim khi nng ion trong cc dung dch mui tng (Na+, Ca2+, Fe3+). iu ny c th gii thch l do s gim chnh lnh p sut thm thu gia gel vi dung dch bn ngoi. T cc th trn cho thy kh nng hp th ca c hai sn phm trong cc dung dch mui khc nhau l khc
8 83

nhau. Kh nng hp th trong dung dch NaCl cao hn so vi hai dung dch CaCl2 v FeCl 3 nguyn nhn l do kh nng to phc ca cc cation Ca2+, Fe3+ vi nhm cacboxylate ca vt liu kt qu l lm tng mt an li ca hydrogel dn ti trng gim[15,21]. Kt qu cho thy trng ca PAAM2 trong cc dung dch mui cao hn ca PAAM. iu ny c th gii thch l hm lng nhm chc COOH ca vt liu PAAM 2 t hn so vi PAAM l do nhm chc ny tng tc vi cc nhm chc OH c trong cu trc clay trong qu trnh ng trng hp. Dn n kh nng to phc ca vt liu PAAM 2 vi cc ion trn t hn so vi vt liu PAAM. 3.5.3 - Kt qu nghin cu cu trc ca poly(acrylamit co - acrylic acid) clay nanocomposit bng ph hng ngoi. Ph hng ngoi l phng php nhanh nhy c th nghin cu cu trc ca sn phm thu c. Chng ti tin hnh chp ph hng ngoi ca hai loi sn phm PAAM v PAAM2. Kt qu c trnh by cc hnh 3.31, 3.32 v c tng hp trong bng 3.12.

84

Hnh 3.31 - Ph hng ngoi ca mu PAAM

Hnh 3.32 - Ph hng ngoi ca PAAM2 Bng 3.12 - Tn s dao ng c trng ca hai loi sn phm

85

Dao ng OH OH NH CH CO NH CH Si-O Al-OH CH Si-O-Al

S sng, cm-1 MMT - hu PAAM c 3642 3427 3220 1674 1347 1034 920 788 3446 3261 2934 1638 1448 1366

PAAM2

3449 2926 1661 1450 1321 1046 832

883

T kt qu trong bng 3.12 cho thy, cc nh c trng cho dao ng ha tr ca cc nhm chc nh: NH, CH, CO, NH u xut hin trong c hai sn phm PAAM v PAAM 2. Trong khi sn phm PAAM2 cn xut hin thm dao

86

ng ha tr Si-O trong cu trc bentonit. Kt qu o ph hng ngoi ca vt liu PAAM v PAAM2 chng t c s hnh thnh ca vt liu nanocomposit t phn ng ng trng hp gia acrylamit v axit acrylic vi s c mt ca nanoclay hu c. 3.5.4 - Kt qu nghin cu cu trc vt liu bng nhiu x tia X Phng php phn tch nhiu x tia X c dng nh gi cc thay i v cu trc vt liu trong qu trnh tng hp vt liu nano composit. Chng ti tin hnh la chn cc mu c kh nng hp th nc tiu biu v mu nanoclay chn 20% acrylamit phn tch nhiu x tia X. Trn gin nhiu x tia X ca mu nanoclay hu c ta thy gc quay 2 = 4 - 60, khong cch d001 c trng cho gi tr dn cch lp tinh th l 15,063 A0. Cn trn gin nhiu x tia X ca cc mu c cha 2%, 5% nanoclay hu c th dn cch lp (d 001) ln lt l 19,983 A0 v 20,912 A0. iu ny cho thy mch copolyme
600

1500 1400 1300

c xp a lp trong khong gia cc lp MMT ca clay. VNU-HN-SIEMENSMau 4 AM3 D5005 - Bentonite-Mau B8-OA 0 iu ny s c khng ng thm bng vic nghin cu hnh thi hc ca vt liu phn sau.
900 800
d=15.063

500

1200 1100

400

Lin (Cps)

Lin (Cps)

300

600 500
d=4.469 d=4.484 d=3.460 200 400 d=4.244 d=4.257

d=3.350 d=3.340
d=4.020 d=3.770

700

d=19.983

1000

d=3.235 d=3.188

300 200
100

100 0 2
0 2 10 20

10

d=7.168

20

30

d=2.557

40

50

2-Theta - Scale

File: Hoan K18 mau 4-A M-30.raw - Type: Locked Coupled - Start: 2.000 - End: 50.000 - Step: 0.030 - Step time: 1. s - Temp.: 25 C (Room) - Time S tarted: 10 s - 2-Theta: 2.000 - Theta: 1.000 - Chi: 00-003-0014 (D) - Montmorillonite - MgOAl2O35SiO2xH2O - Y: 19.42 % - d x by: 1. - WL: 1.5406 00-033-1161 (D) - Q uartz, syn - SiO2 - Y: 22.78 % - d x by: 1. - WL: 1.5406 - Hexagonal - a 4.91340 - b 4.91340 - c 5.40530 - alpha 90.000 - beta 90.000 - gamma 120.000 - Primitive - P 3221 (154) - 3 - 113.

File: Hoan-Vien HHVL-B8-OA.raw - Type: 2Th/Th locked - Start: 2.000 - End: 50.000 - Step: 0.030 - Step time: 1.0 s - Temp.: 25.0 C (Room) - Anode: Cu - Creation: 09/25/09 15:08:49 33-1161 (D) - Quartz, syn - SiO2 - Y: 24.24 % - d x by: 1.000 - WL: 1.54056 2-Theta - Scale 03-0014 (D) - Montmorillonite - MgOAl2O35SiO2xH2O - Y: 15.71 % - d x by: 1.000 - WL: 1.54056

30

40

50

Hnh 3.34 - Gin nhiu x tia X ca mu Hnh 3.33 - Gin nhiu x tia X ca mu clay PAAM2 chn 20% acrylamit

87

1500 1400 1300 1200 1100 1000 900 800 700 600 500 400 300 200 100 0 2 10

VNU-HN-SIEMENS D5005 - Bentonite-Mau B7-OA

Lin (Cps)

d=20.912

d=4.429

20

d=3.323

30

40

50

2-Theta - Scale
File: Hoan-Vien HHVL-B7-OA.raw - Type: 2Th/Th locked - Start: 2.000 - End: 50.000 - Step: 0.030 - Step time: 1.0 s - Temp.: 25.0 C (Room) - Anode: Cu - Creation: 09/25/09 14:39:37 33-1161 (D) - Quartz, syn - SiO2 - Y: 16.26 % - d x by: 1.000 - WL: 1.54056 03-0014 (D) - Montmorillonite - MgOAl2O35SiO2xH2O - Y: 15.71 % - d x by: 1.000 - WL: 1.54056

Hnh 3.35 - Gin nhiu x tia X ca mu PAAM5

3.5.5 - Kt qu nghin cu hnh thi hc ca PAAM v PAAM2 Mt trong nhng phng php nghin cu cu trc b mt ca vt liu nanocomposit xc nh ln ca cc ht trong cu trc nano bng knh hin vi in t c phn gii cao nh knh hin vi in t qut (SEM). T hnh nh SEM ca mu PAAM ta thy mu c cu trc khi mn tng i cht st v khng thy xut hin cc l xp. Trong khi mu PAAM2 c xut hin cc l xp c kch thc c micro v cu trc cc ht MMT c dng tm xp lp, c dn rng ra v cc ht MMT - hu c phn tn u trong nn polyme. iu ny lm cho kh nng hp th nc ca mu PAAM2 cao hn ca mu PAAM. V cng ph hp vi kt qu thc nghim thu c. Di y l hnh nh SEM ca hai sn phm PAAM v PAAM2.
88

Hnh 3.36 - nh SEM ca PAAM

Hnh 3.37 - nh SEM ca mu PAAM2

89

3.5.6 - Kt qu phn tch bn nhit ca PAAM v PAAM2 bn nhit ca vt liu c xc nh bng phng php phn tch nhit TGA. Trong qu trnh nung nng vt liu, cu trc PAAM v PAAM2 thay i. Nhng thay i ny km theo qu trnh thu nhit hay to nhit. Di y l gin phn tch nhit ca PAAM PAAM2.
Figure: Labsys T G Experiment: SAP Crucible:PT 100 l Atmosphere:Air Mass (mg): 12.28

30/11/2009 Procedure: 30 ----> 800C (10C.min-1) (Zone 2)

TG/%

HeatFlow/V Exo

d TG/% /min

60
Peak :177.98 C

Peak :349.79 C

20 -10

40 0 -20 -20 0
Mass variation: -17.84 %

20

-30 -40

-20 -40
Figure: Experiment: SAP-2

-40

Labsys T G

30/11/2009

Mass variation: -51.93 % Procedure: 30 ----> 800C (10C.min-1) (Zone 2)

Crucible: PT -60 l 100

Atmosphere: Air Mass (mg): 15.91

TG/%

HeatFlow/V Exo -80

Peak :116.61 C Peak :577.35 C

d TG/%/min -50

-60 60

20

0
40

100

200

300

400 500 Peak :430.89 C

600

700

Furnace temperature /C

-6

Hnh3.38 - Gin phn tch nhi mu PAAM 0

20 -12 0
Mass variation: -12.43 %

-20

-20 -40

-18

-40

Mass variation: -54.65 %

-24 -60 -60

100 200 300 400 700 Furnace Hnh3.39 - Gin 90 500 tch nhit ca temperature /C phn 600

mu PAAM2

Trong gin TGA ca mu PAAM ta thy nhit 1770C xy ra qu trnh tch nc vi tn hao khi lng l 17,84%. Ti nhit 3490C PAAM bt u phn hu, vi tn hao khi lng l 51,93%. Qu trnh phn hy PAAM din ra t t, khng c t bin no trn ng cong TGA. iu ny cho thy PAAM khng b chy hay xy ra t bin no khc. Cn vi mu PAAM2 khi c tng hp ra cho thy c nhng thay i ng k trong cu trc qua vic phn tch nhiu tia X, IR, SEM. Vi s c mt ca nanoclay hu c cho php copolyme xen lp vo khong gia cc lp st v c th dn ti thay i bn nhit ca vt liu. Kt qu phn tch nhit ch ra rt r iu . Trn gin phn tch nhit ca mu PAAM2 ta thy nhit 1160C l qu trnh tch nc, vi tn hao khi lng l 12,43%, sau qu trnh phn hy bt u xy ra nhit 430 0C v n 5770C th phn hy hon ton vi tn hao khi lng giai on ny l 54,65%. Qu trnh phn hu PAAM2 din ra khng t t m trn ng cong TGA c nhng on gp khc. iu ny c th l gii l khi c mt nanoclay hu c kh nng

91

bn nhit ca vt liu tng ln l do nanoclay c tc dng bo v, ngn cn s khuch tn xy vo tip cn vi mch copolyme. Mt khc vi kch thc hp gia cc lp clay cng hn ch s dn nhit lm phn hy, t gy sm ca mch copolyme. Tc dng chung l lm tng kh nng ng k bn nhit ca vt liu tng hp c. Tm li ch vi mt lng nh nanoclay hu c (2%) khng nhng lm tng kh nng hp th nc ca vt liu m cn ci thin ng k bn nhit ca vt liu. iu ny khng nh tnh u vit ca vt liu nanocomposit.
3.6 - Kt qu nghin cu kho st mt s tnh nng c l ca mng ph polyacrylamit.

Polyacrylamit l mt polyme phn cc d ho tan trong nc v c rt nhiu ng dng trong thc t. Trong khun kh ca kho lun chng ti tin hnh nghin cu ng dng ca polyacrylamit trong vic to mng ph. y l mt hng nghin cu mi. Vi li th l mt polyme phn cc d ho tan trong nc l dung mi r tin, ph bin v khng gy nhim mi trng. Nhng hn ch ca vt liu ny chnh l kh nng d b phn hy khi tip xc vi mi trng nc v mng ph c tnh nng c l khng cao. Vi mc ch nhm nng cao tnh nng c l ca mng ph. Chng ti tin hnh nghin cu ch to mng vi s gia cng ca nanoclay vi cc t l thay i 0%, 2%, 3%, 4% v 5%. Kt qu kho st mt s tnh nng c l ca mng c trnh by di bng v hnh sau: Bng 3.13 - Mt s tnh nng c l ca mng ph polyacrylamit
92

Nanocl ay (%) 0 2 3 4 5

bm dnh (%) 100 100 100 100 100

bn un (mm) 2 2 3 3 3

bn va p (KG.cm) 31 38 36.5 33 32

bn co xc (kg) 0.3 0.6 0.45 0.4 0.3

bn va p, KG.cm

40

30

20

10

0 0 1 2 3 4 5 6

bn co xc, kg

0.8

m u , Hnh 3.40 H l ng nanoclay h % - ng biu din c bn va p ca mng vi hm lng nanoclay hu c

0.6

0.4

0.2

0 0 1 2 3 4 5 6

Hnh 3.41 - ng biu 93 din bn co xc ca mng vi hm lng nanoclay hu c

H l ng nanoclay, % m

T kt qu thu c ta nhn thy rng cc tnh nng c l ca mng ph t gi tr ln nht mu c hm lng nanoclay l 2%. Sau li gim khi hm lng nanoclay tng ln. iu ny c th gii thch l khi hm lng nanoclay 2% th kh nng phn tn ca nanoclay vo trong nn polyacrylamit l tt nht. Cn khi hm lng nanoclay tng ln th mt lng nht nh nanoclay khng phn tn u vo trong nn polyacrylamit m chng khuch tn vo trong nn theo phng php trn hp composit thng thng. Chnh v vy m cc tnh nng c l ca mng ph thay i. Trn c s la chn mu c cc tnh nng c l tt nht trong cc mu polyacrylamit clay nanocomposit ch to c (mu cha 2% MMT - hu c), chng ti tin hnh nghin cu cu trc vt liu bng phnng php SEM kt qu thu c cc hnh sau:

94 Hnh 3.43- nh SEM ca mu Hnh 3.42- nh SEM ca mu polyacrylamit/clay polyacrylamit nanocompossit

Qua cc hnh nh SEM, ta thy mu polyacrylamit khng c cha MMT - hu c c cu trc khi v tng i cht xt, khng thy xut hin cc ht dng tm xp lp. Cn vi mu polyacrylamit clay nanocomposit th cc ht nanoclay hu c phn tn vo trong polyacrylamit kh ng u. iu ny chng minh tnh nng c l ca mng polyacrylamit clay nanocomposit tng ng k so vi mng polyacrylamit khng c n nanoclay. Tuy nhin mng ph trn c s polyacrylamit clay nanocomposit thu c c bn c l cha cao, v cn nhiu hn ch khi s dng lm mng bo v trong thc tin. Xong bc u gp phn nghin cu v khng nh tnh u vit ca vt liu nanocomposit.

95

Kt lun ti: Nghin cu qu trnh trng hp acrylamit v axit acrylic trong lp nanoclay nghin cu ch to c vt liu nanocomposit. y l mt ti i theo hng nghin cu mi l cng ngh nano v vt liu nanocomposit. Sau mt thi gian nghin cu, chng ti thu c mt s kt qu sau: - nghin cu tm ra t l v nhit ti u n kh nng chn ca acrylamit vo gia cc lp MMT l 20% v 400C. tng hp c vt liu polyacrylamit clay nanocomposit bi phn ng trng hp cation monome

acrylamit xen trong khong gia hai lp MMT hu c. - kho st nh hng ca nanoclay n tnh nng c l ca mng ph polyacrylamit. Vi t l 2% nanoclay hu c cc ch tiu c l ca mng ph nanocomposit u c ci thin ng k so vi mng ph khng c nanoclay hu c. - tng hp c vt liu siu hp th nc trn c s phn ng ng trng hp ca acrylamit v axit acrylic c v khng c MMT hu c. trng ca PAAM t 432g/g i vi nc ct cn vi dung dch NaCl 0,9%, CaCl 2 0,9% v FeCl3 0,9% ln lt l 39g/g, 6 g/g, 3 g/g. Cn ca PAAM2 trong nc ct, NaCl 0,9%, CaCl2 0,9% v FeCl3 0,9% ln lt l 545 g/g, 44 g/g, 9g/g, 7g/g.

96

Ti liu tham kho Ti liu ting vit [1]. Nguyn Vit Bc v ctv.(2009), Nghin cu ch to polyme dn trn nn nanoclay, Bo co tng kt Khoa hc k thut, Vin Ha hc - Cng ngh Qun s. [2]. Lu Vn Bi (2008), Nghin cu ch to v ng dng polyacrylamit lm vt liu chng ng cn cho cc ni hi, Bo co tng kt ti khoa hc v cng ngh cp thnh ph, i hc Quc gia H Ni. [3]. Ng Duy Cng (2004), Ha hc cc hp cht cao phn t, NXB i hc Quc gia, H Ni. [4]. Ng Duy Cng (2008), Nghin cu ch to vt liu polyme c cu trc nano, Bo co nh k kt qu ti, B Khoa hc v Cng ngh, [5]. Nguyn Vn Khi (2007), Polyme a nc ha hc v ng dng, NXB Khoa hc T nhin v Cng ngh H Ni, Vin Khoa hc v Cng ngh Vit Nam. [6]. Nguyn c Ngha (2007), Ha hc nano cng ngh nn v vt liu ngun, NXB Khoa hc T nhin v Cng ngh, Vin Khoa hc v Cng ngh Vit Nam.

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[7]. Nguyn c Ngha (2009), Polyme chc nng v vt liu lai cu trc nano, NXB Khoa hc T nhin v Cng ngh H Ni, Vin Khoa hc v Cng ngh Vit Nam. [8]. Phm Cng Ng (2007), Nghin cu, ch to polyacrylamit clay nanocomposit v ng dng to mng ph, Lun vn tt nghip i hc, i hc Khoa hc T nhin, i hc Quc gia H Ni. [9]. Nguyn Thanh Tng (2003), Nghin cu phn ng ng trng hp axit acrylic v dn xut trong s c mt ca cht to li, Lun vn thc s khoa hc ha hc, i hc Quc gia H Ni. [10]. Nguyn nh Triu (2001), Cc phng php phn tch vt l v ha l, NXB Khoa hc K thut. [11]. Quch ng Triu v ctv. (2003), Nghin cu ch to v ng dng vt liu nano polyme - composit, Bo co tng kt Khoa hc v K thut, Trung tm Khoa hc t nhin & Cng ngh Quc gia, Ting Anh
[12].http://www.vista.gov.vn/portal/page?

_pageid=33,298797&_dad=portal&_schema=PORTAL [13].http://www.vista.gov.vn/pls/portal/url/ITEM/308FDFA4850 84B55E040A8C00512675 [14]. P. M. Ajayan, L.S. Schadler, P.V. Braun, (2003), Nanocomposite Science and Technology, J. Wiley - VCH, Weinhein, 230p.

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[15]. An Li, Aiqin Wang, (2005), Synth. And properties of clay - bases superaborbent composite, Eur. Polym. J., Vol.41, pp. 1630 - 1637. [16]. Barvenik F. W., (1994), Polyacrylamide characteristics related to soil applications, Soil Sci. , Vol. 158, pp. 235 - 243. [17]. Bharat Bhushan et al., (2004), Hanbook of Nanotechnology, Springer, NY, 1258p. [18]. Bouranis D. L., Theodoropoulus A. G. and Drossopoulus J. B., (1995), Designing synthetic polymers as soil conditioner, Communications in Soil Science and Plant Analysis, Vol. 26, p. 1455 - 1480. [19]. Daniel Schmidt et al., (2002), New advances in polymer/layered silicate nanocomposites, Current Opinion in solid state and Materials Science, Vol. 6, pp. 205 - 212. [20]. Elton N. Kaufmann, Characterization of materials, J. Wiley - Interscience, Vol. 1, 1413p. [21]. Francisca Santiago et al., (2007), Preparation of composites and nanocomposites bases on bentonite and poly(sodium acrylate). Effect of amount of bentonite on the swelling behaviour, Eur. Polym. J., Vol. 43, pp. 1 - 9. [22]. Heitz C., Binana - Limbele W., Francois J., Biver C., (1999), Absorption and desorption of Chromium ions by Poly(acrylic acid) gels, Journal of Applied Polymer Science, Vol 72, pp. 455 - 466.

99

[23]. Hua Zou et al., (2008), Polymer/Silica Nanocomposites: Preparation, Characterization, Properties, and Applications, Chem. Rev., Vol. 108, p. 3893 - 3957. [24]. Ignacio Rintoul, Chritine Wandrey, (2005), Polymerization of ionic monomers in polar solvents: kinetics and mechan. Of the free radial copolymerization of acrylamide/acrylic acid, Polym., Vol. 46, p. 4525 - 4532. [25]. Jamal Aalaie et al., (2008), Effect of montmorillonite on gelation and swelling behavior of sulfonated polyacrylamide nanocomposite hydrogels in electrolyte solutions, Eur. Polym. J., Vol. 44, p. 2024 - 2031. [26]. James E. Mark, (1998), Polyme data Handbook, Oxford University Press, 1102p. [27]. Ji Zhang et al., (2007), Preparation and properties of polyacrylate/bentonite [28]. Junzhong Wang and superbsorbent et al. hybrid via intercal. of Polymerization, Materials Letter, Vol. 61, pp. 316 - 320. (2004), Preparation polyacrylamide gamma zirconium phosphate

nanocomposites by intercalative polymerization, Ultrasonics Sonochemistry, Vol. 11, p. 301 - 306. [29]. Kazutoshi Haraguchi, (2007), Nanocomposite hydrogels, Current Opinion in Solid State and Materials Science, Vol. 11, pp. 47 - 54. [30]. Kun Xu et al., (2007), Study on the synthesis and performance of hydrogels with ionic monomers and montmorillonite, Appl. Clay science, Vol. 38, pp. 139 - 145.

100

[31].

Lszl

Janovk,

(2009),

Swelling

properties

of

copolymer hydrogels in the presence of montmorillonite and alkylammonium montmorillonite, Applied Clay Science, Vol. 43, p. 260 - 270. [32]. W. Li et al., (2002), Synthesis and characterisation of a polyacrylamide - polyacrylic acid copolymer hydrogel for environmental analysis of Cu and Cd, Reactive & Functional Polymers, Vol. 52, pp. 31 - 41. [33]. Lucilene Betega de Paiva et al., (2008), Organoclays: Properties, preparation and applications, Applied Clay Science, Vol. 42, pp. 8 - 24. [34]. J. Madejova, (2003), FTIR techniques in clay mineral studies, Vibrational Spectroscopy, Vol. 31, pp. 1 - 10. [35]. Makoto Ogawa et al., (1992), Solid - state intercalation of acrylamide into smectites and Na - taeniolite, Appl. Clay Science, Vol.7, p. 291 - 302. [36]. Michael Alexandre, Philippe Dubois, (2000), Polymerlayered silicate nanocomposites: preparation, properties and uses of a new class of materials, Materials Science and Engineering, Vol. 28, p. 1 - 63. [37]. Mohammad J. Zohuriaan - Mehr * and Kourosh Kabiri, (2008), Superabsorbent polymer materials, Iranian Polym. Journal, Vol. 17, pp. 451 - 477. [38]. D. R. Paul and L.M. Robeson, (2008), Polymer nanotechnology: Nanocomposites, Polymer, Vol.49, pp. 3187 - 3204.

101

[39]. S. Pavlidou, (2008), A review on polymer - layered silicate nanocomposites, Progress in Polymer Science, Vol. 33, pp. 1119 - 1198. [40]. Peng Li, (2008), Novel with PAAm/Laponite cationic clay dye nanocomposite 763. [41]. F. Rodrigue and R. D. Givey, (1956), Polymerization of acrylamite with persulfate - metabisufate initiator, US. Patent 3853802. [42]. Scott R. A. and Peppas N.A, (2007), Kinetic study of acrylic acid sodium polymerization, Aiche Journal, Vol. 43, pp. 135 - 144. [43]. Suprakas Sinha Ray et al, (2003), Polymer/layered silicate nanocomposites: a review from preparation to processing, Prog. Polym. Sci., Vol. 28, pp. 1539 - 1641. [44]. Yian Zheng et al., (2007), Study on superabsorbent composite XVI. Synthesis, poly(sodium 1698. [45]. Thomas W.M., (1067), Encyclopedia of polymer science and technology, Vol. 1, p. 177 - 226. characterization and swelling behaviors of acrylate)/vermiculite superabsorbent 1691hydrogels improved

adsorption behavior , Composites: Part B, Vol. 39, pp. 756 -

composites, European Polymer Journal, Vol. 43, pp.

102

[46]. S.C. Tjong, (2006), Structural and mechanical properties of polymer nanocomposites, Materials Science and Engineering R, Vol. 53, pp. 73 - 197. [47]. Wan T. et al., (2008), Preparation of poly(AA-AM) water superabsorbent by inverse microemulsion polymerization, Journal of Applied Polymer Science, Vol. 110, p. 3859 - 3864. [48]. Youjun Deng and et al., (2006), Colloids Bonding and between A: polyacrylamide smectite, Surface

Physicochem. Eng. Aspects, Vol. 281, pp. 82 - 91. [49]. Deyu Gao & Robert B. Heimann, (1993), Structure and mechanical properties of superabsorbent poly(acrylamide) Montmorillonite composite hydrogels, Polym. Gels and Networks, Vol. 1, pp. 225 - 246. [50]. Zhiqi Shen et al., (2002), Comparison of solutionc intercalation [51]. and melt intercalation of polymer clay nanocomposites, Polymer, 43, pp. 4251 - 4260. Zhaohui Tong (2007), Water-based suspension of School of Chemical and Biomolecular Polymer Nanoclay Composite Prepared via Miniemulsion Polymerization, Engineering Georgia Institute of Technology. [52]. Dietrich B., Cheroro H., Kern V., (1971), Techniques of polymer syntheses and charaterization, Wiley - Interscience, New York.

103