B GIO DC V O TO

I HC NNG

CHU VN TI

NGHIN CU IU CH CHITOSAN
T CHITIN V GH
V NG DNG LM PH GIA M KM IN HA

Chuyn ngnh: Ha hu c
M s

: 60 44 27

TM TT LUN VN THC S KHOA HC

Nng Nm 2013

Cng trnh c hon thnh ti

I HC NNG

Ngi hng dn khoa hc: PGS.TS. L T HI

Phn bin 1: TS. BI XUN VNG

Phn bin 2: TS. NGUYN NH ANH

Lun vn s c bo v trc Hi ng chm Lun vn tt

nghip thc s khoa hc hp ti i hc Nng vo ngy 31 thng
05 nm 2013.

* C th tm hiu lun vn ti:

- Trung tm Thng tin- Hc liu, i hc Nng.
- Th vin trng i hc S phm, i hc Nng.

M U
1. L do chn ti
Nc ta c ngun thy sn di do, lng v gip xc ph liu
hng nm rt ln (nm 2005 l 70.000 tn). Trong c v cua gh.
Chitosan (CTS) iu ch t chitin tch t v tm, cua, gh l
mt polymer sinh hc c rt nhiu ng dng trong i sng, cc lnh
vc nh y t; sinh hc; cng - nng nghip; cng ngh mi trng
Mt c tnh ca CTS l ha tan trong mi trng axit long
to gel cation:
(ChitNH2)n + nH3O+ (ChitNH3+)n + nH2O
Nm 2006, E.C. Dreyer - Hoa K to thnh cng v nghin
cu lp mng CTS trn b mt catot bng phng php in ha
ng dng trong bo qun thc phm.
Nhiu nghin cu trong v ngoi nc cho thy CTS c ch n
mn kim loi tt, kh nng to phc kim loi cao.
Hin nay vn bo v kim loi trc s n mn l vn bc
thit, trong c bo v vt liu thp bng phng php m in. Lp
m kim loi-polymer c s dng nhng cha nhiu v hin trong
nc cha c cng trnh nghin cu c cng b v ng dng ca
CTS trong m in.
Km l kim loi m tt trn thp v tnh chu ng n mn c
hc, chu bin dng, tnh m thut v kh nng lm anot hy sinh. Nu
to c lp m kt hp tnh nng bo v bng nguyn tc anot hy sinh
v lp mng CTS th kh nng chng n mn s rt cao. Chnh nhng
l do trn m ti quyt nh chn ti Nghin cu iu ch chitosan
t chitin v gh v ng dng lm ph gia m km in ha lm
ti lun vn tt nghip ca mnh.

2
2. Mc ch nghin cu
- Nghin cu iu ch CTS t chitin tch t v gh ph liu
ch bin thu sn vi hiu qu v mc deacetyl cao.
- Nghin cu ng dng CTS to lp ph m composite ZnCTS trn thp bng phng php in ho.
3. i tng v phm vi nghin cu
- CTS chit tch t v gh ph liu ch bin thu sn
- Cht lng lp m in ho composite Zn-CTS
4. Ni dung v phng php nghin cu
Nghin cu l thuyt
- Nghin cu ngun gc, trng thi tn ti ca chitin.
- Nghin cu cc tnh cht ho l ca chitin, CTS.
- Phng php chit tch chitin, iu ch CTS.
- Nghin cu quy trnh c im ca cng ngh m kim loi
in ho, cc phng php m km in ho.
- Nghin cu kh nng s dng CTS trong m km in ho.
Nghin cu thc nghim
- Ti u ho iu ch CTS t chitin v gh vi hiu sut cao
v deacetyl ph hp vi mc ch nghin cu.
- Nghin cu m km in ho trn thp xy dng vi s tham
gia ca CTS lm ph gia, kim tra so snh cht lng lp m v s
chng n mn vi lp m km khng c CTS trong cng iu kin.
5. ngha khoa hc v thc tin ca ti
ngha khoa hc
- Nghin cu ng dng mi ca CTS.
- ra mt hng mi to lp m in cht lng cao, thn
thin vi mi trng v kh nng ng dng tt ca n trong thc t.

3
ngha thc tin
- To cht liu m mi trn thp m bo yu cu k thut v
m thut.
- Gim vn ngun cht thi m in gy nhim mi
trng, bng cch s dng loi cht m tt c th thay th nhiu loi
cht m l kim loi nng c hi khc.
6. Cu trc lun vn
Lun vn gm 78 trang v 6 ph lc. Trong c 14 bng v
24 hnh. Phn m u gm 3 trang, kt lun v kin ngh gm 2
trang, s dng 27 ti liu tham kho. Ni dung lun vn c 3 chng:
Chng 1 - Tng quan, 32 trang.
Chng 2 - Nguyn liu v phng php nghin cu, 17 trang.
Chng 3 - Kt qu v tho lun, 21 trang.
CHNG 1

TNG QUAN
1.1. TNG QUAN V CHITIN V CHITOSAN
1.1.1. Lc s nghin cu chitin CTS
1.1.2. S tn ti ca chitin v CTS trong t nhin
1.1.3. c im cu to v tnh cht ca chitin CTS
a. c im cu to v tnh cht vt l ca chitin
b. c im cu to v tnh cht vt l ca CTS
c. Tnh cht ha hc ca chitin CTS
1.1.4. Tnh hnh nghin cu sn xut chitin v CTS trong
nc v trn th gii
a. Tnh hnh nghin cu chitin v CTS trn th gii
b. Tnh hnh nghin cu sn xut chitin v CTS trong nc
1.2. L THUYT N MN V BO V KIM LOI

4
1.2.1. n mn kim loi
a. nh ngha v phn loi cc qu trnh n mn
b. Cc ch tiu nh gi tc n mn
1.2.2. Cc phng php bo v kim loi
a. Bo v bng phng php in ha
b. Bo v bng cht c ch (cht lm chm n mn)
c. S dng lp ph bc ngn chn n mn
1.3. M IN
1.3.1. Khi nim c bn v m in
a. C s chung
b. Thnh phn dung dch v ch m
1.3.2. M km
a. Gii thiu chung v lp m km
b. Tnh cht v ng dng ca lp m km
c. Mt s dung dch m km thng dng hin nay
d. nh gi cht lng lp m
CHNG 2

NGUYN LIU V PHNG PHP NGHIN CU

2.1. NGUYN LIU, HA CHT, DNG C
2.1.1. Nguyn liu
Nguyn liu c s dng l v mai gh, ch yu l gh ba
mt, (tn khoa hc l Portunus sanguinolentus) (Hnh 2.1), c thu
mua ca tiu thng ti ch Non Nc, qun Ng Hnh Sn, thnh
ph Nng. y l loi gh ph bin cc tnh ven bin Vit
Nam, c bit l min trung, loi ny sng y bn ct ven bin
vi su nc t 5 25 mt.

(a)

(b)

Hnh 2.1. Gh ti (a) v mai gh (b)

2.1.2. Ha cht
2.1.3. My mc, dng c th nghim.
2.2. PHNG PHP NGHIN CU
2.2.1. Nghin cu ti u ha qu trnh iu ch CTS
a. Quy trnh tch chitin t v gh
Quy trnh c m t theo s trong hnh 2.2.

Hnh 2.2. S tm tt quy trnh tch chitin t v gh

- Loi khong: V gh kh sch b mnh 1x1(cm), ngm o
trong dung dch HCl 10%; t l rn/lng (w/v): 1/10; nhit phng;
thi gian 11h. Sau ra trung tnh, sy kh.
- Loi protein: Sn phm ngm trong dung dch NaOH 10%; t
l w/v=1/5; nhit phng; thi gian 24h. Sau ra sch, kim tra
protein vi thuc th Biure, sy kh, thu c chitin v gh.

6
b. Quy trnh iu ch CTS
Quy trnh theo s trong hnh 2.3.

Hnh 2.3. S tm tt quy trnh iu ch CTS

- Deacetyl ho: Kho st ti u cc iu kin C%NaOH (Z1):
40% 50%, thi gian (Z2) t 5h8h; nhit (Z3): 800C1000C;
w/v=1/20 thu CTS. S dng k hoch thc nghim bc mt hai
mc ti u ton phn (2k) kho st. Gi Zj (j = 1; 2; 3) l mc gii
hn ca vng nghin cu, tm k hoch Z 0j c xc nh theo cng
thc:
Z j max Z j min
(2.1)
Z 0j
2
Trong Zjmax l mc gii hn trn, Zjmin l mc gii hn di.
Khong bin thin cc yu t xc nh theo cng thc:
Z j max Z j min
Z j
2
Xy dng c iu kin th nghim theo bng 2.1.
Bng 2.1. iu kin th nghim iu ch CTS c chn
Cc mc
Zjmax

Z1 (%)
50

Cc yu t nh hng
Z2 (h)
8

Z3 (0C)
100

(2.2)

7
Zj0
Zjmin
Zj

45
40
5

6,5
5
1,5

90
80
10

Thc hin vi 11 mu th nghim c khi lng 5g mi mu

trong cc bnh cu 250ml, s liu th hin trong bng 2.2.
Bng 2.2. S liu thc nghim kho st iu ch CTS
STT th
nghim
Z1 (C%)
Z2 (h)
Z3 (0C)

Th nghim theo cc phng n

1
40
5
80

2
50
5
80

3
4
40 50
8
8
80 80

5
40
5
100

6
7
8
50 40
50
5
8
8
100 100 100

Th nghim ti
tm
9
10 11
45 45 45
6,5 6,5 6,5
90 90 90

- Tinh ch: Sau cc kho st trn, ra sch sy kh, ghi li

khi lng mi mu. Sau ho tan mu CTS thu c bng dung
dch CH3COOH 1% (dung dch A) c dung dch CTS/A (dung
dch B) c nng 1%, lc v kt ta li bng dung dch NaOH 10%
n pH>7, lc ra bng cn 96% n ht kim, ngm trong cn tuyt
i 500C-600C trong 5 gi, ra li bng axeton. Sn phm em sy
kh v xc nh hiu sut deacetyl ha.
2.2.2. Xc nh mt s ch tiu ha l ca CTS
Vic xc nh mt s ch tiu ha l ca CTS nhm kim tra
v so snh cht lng CTS vi tiu chun ca CTS thng mi v
theo yu cu dng m in.
a. Xc nh m
b. Xc nh hm lng tro ca CTS
c. Hm lng cht khng tan
2.2.3. Phn tch nh tnh CTS
a. Phn tch hm lng nguyn t nit xc nh
deacetyl
b. Ph hng ngoi

8
c. Ph cng hng t ht nhn proton
2.2.4. Nghin cu ng dng CTS lm ph gia m km in
ha
a. C s nghin cu
CTS l mt polymer sinh hc, mang in tch dng trong mi
trng axit long, c bit tan tt trong dung dch axit acetic long.
Do khi cho dng in chy qua dung dch, th cc cation (ChitoNH3+)n s di chuyn v pha catot v nhn in t gii phng H2 theo
phn ng: 2(Chito-NH3+)n + 2ne 2(Chito-NH2)n + nH2
S dng CTS lm ph gia trong dung dch m km c th to
c lp ph composite ZnCTS. Lp m mi ny c th kt hp
c tnh nng ca km v CTS va ng vai tr l mt lp ph hiu
qu v bn vi mi trng, bn c hc, va tng kh nng ngn cn
n mn kim loi do tnh nng c ch n mn kim loi ca CTS.
b. Chun b dng c, dung dch m, vt liu m v x l s
b vt liu m
- B dng c m
Lp t h thng m nh trong hnh 2.4.

Hnh 2.4. B tr h thng m km in ha trong phng th nghim

9
- Dung dch m
Chun b hai loi dung dch m: Dung dch m th cha
ZnSO4.7H2O (250 gam/lt); NaCl (40 gam/lt), H3BO3 (30 gam/lt).
Dung dch m nghin cu: Dung dch m th c thm CTS.
Dng dung dch H2SO4 10% v NaHCO3 iu chnh pH.
CTS c pha ch thnh dung dch 1% trong CH3COOH 1%.
- Vt liu m
Chn vt liu m th nghim l loi thp tm CT3, kch thc
45 x 25 x 0,5 (mm). Anot lm bng Zn 99%.
- X l b mt vt liu m
c. Quy trnh m
X l dung dch m vi mt dng 1A/dm2 ti khi c lp
m sng. M lp km th pH: 3,5; Dc 4,5A/dm2. Lp m composite
Zn-CTS kho st: pH: 2,55,0; mt dng: 3A/dm2 8A/dm2;
nng CTS: 0,52,0 gam/lt; ti u ha theo k hoch thc nghim
bc mt hai mc ti u ton phn, s liu th hin bng 2.3.
Bng 2.3. S liu thc nghim kho st ch m Zn-CTS
STT
pH
Dc(A/dm2)
C. CTS (g/l)

TN theo cc phng n
1 2 3 4 5 6 7 8
2,5 5,0 2,5 5,0 2,5 5,0 2,5 5,0
3 3 8 8 3 3 8 8
0,5 0,5 0,5 0,5 2,0 2,0 2,0 2,0

TN ti tm
9
10
11
3,5 3,5 3,5
5,5 5,5 5,5
1,25 1,25 1,25

(TN: Th nghim; C. CTS: Nng CTS)

M 20 pht/th nghim, tnh ton ti u ha hiu sut dng.
2.2.5. Kim tra nh gi kh nng chng n mn ca lp
m
a. nh gi b mt v kim chng bng hnh nh SEM
Sau qu trnh m, chp SEM, so snh mn, hnh thi cu trc
lp m Zn vi lp m composite Zn-CTS.

10
b. nh gi bng phng php kim tra gim khi lng
So snh gim khi lng ca lp m Zn vi lp m
composite Zn-CTS theo chu k 24h trong 10 ngy khi nhng trong
dung dch NaCl 3,5% nhit phng.
Sau 10 ngy kim tra so snh hnh nh SEM b mt hai lp
m.
c. nh gi bng phng php o tng tr in ha (EIS)
Trong lun vn s dng phng php o tng tr in ha
nh gi mc chng n mn kim loi ca lp m composite cc
nng chitosan khc nhau bng cch so snh vi lp m thng.
CHNG 3

KT QU V THO LUN
3.1. TCH CHITIN T V GH
Thc hin tch chitin t v gh vi 600 gam v gh kh. Sn
phm cho kt qu nh trong bng 3.1 v hnh 3.1.
Sn phm
Khi lng (g)
% sn phm
Mu sn phm

Bng 3.1. Kt qu x l t 600 gam v gh

Sau kh khong
Sau kh protein
104,65
77,47
17,44
12,91
Hng
Pht hng

11
Hnh 3.1. Chitin thu c t v gh
Nhn xt: Thnh phn ch yu trong v gh kh l cht
khong, (CaCO3, Ca3(PO4)2 v mt s cht v c khc). Ngoi ra cn
c chitin, protein v cc cht mu hu c. Trong qu trnh kh
khong, cc hp cht v c b ha tan v mt phn protein cng b
thy phn. Khuy lin tc tng tc phn ng. Qu trnh kh
protein bng NaOH 10% ngoi kh protein cn kh mt phn hp
cht mu khin mu nht hn.
3.2. QU TRNH DEACETYL HA CHITIN
Kho st theo phng n k hoch trc giao cp I nh trnh
by mc 2.2.1.2. Phng trnh hi quy ca k hoch c dng:
= b0 + b1x1 + b2x2 + b3x3 + b12x1x2 + b13x1x3 + b23x2x3 +
b123x1x2x3

(3.1)

Trong x1; x2; x3 ln lt l bin m ha nng NaOH;

thi gian v nhit v c xc nh bi cng thc (3.2).
xj

Z j Z 0j

(3.2)

Z j

Lp ma trn k hoch 23 nh bng 3.2 v bng ma trn k

hoch bin s hng 3.3.
Bng 3.2. Ma trn k hoch 23cho qu trnh iu ch CTS
STT
1
2
3
4
5
6
7
8

Gi tr thc
Z1(%)
Z2(h)
Z3(0C)
45
5
80
50
5
80
45
8
80
50
8
80
45
5
100
50
5
100
45
8
100
50
8
100

Gi tr m ha
x1
x2
x3
+
+
+
+
+
+
+
+
+
+
+
+

Hm mc tiu
y (%)
52,24
57,94
60,30
61,26
58,44
60,78
60,92
58,32

12

Bng 3.3. Ma trn k hoch qu trnh iu ch CTS vi bin s hng

STT
1
2
3
4
5
6
7
8

x0
+
+
+
+
+
+
+
+

x1
+
+
+
+

x2
+
+
+
+

Bin m ha
x3 x1x2 x1x3 x2x3 x1x2x3
+
+ +
+
+
+
+
+
+ +
+
+
+
+
+
+ +
+
+
+

Hm mc tiu
y (%)
52,24
57,94
60,30
61,26
58,44
60,78
60,92
58,32

T tnh c cc gi tr hng: b0 = 58,775; b1 = 0,8; b2 =

1,425; b3 = 0,84; b12 = -1,21; b13 = -0,865; b23 = -1,42; b123 = -0,025.
Gi tr hm mc tiu ti tm phng n: y10 57,36 %;
0

y 20 58,82 %; y30 58,4 %, gi tr trung bnh: y 58,19 %.

Phng sai lp: S u2 1

(y
m 1

0
a

y 0 ) 2 = 0,565, lch chun

a 1

Sbj = ( S u2 / 8)1/ 2 0,266 ; bc t do lp: f2 = m-1 = 2.

Vi mc c ngha p = 0,05, bc t do lp f2=2, tra bng c
chun s Student: t0,05;2 = 4,30. Nh vy bj c ngha khi b j S bj .t bj
1,142. Chn c: b0; b2; b12 v b23. Vy phng trnh hi quy bin
m: = 58,775 + 1,425x2 1,21x1x2 1,42x2x3
Ti cc im thc nghim: 1 = 54,72; 2 = 57,14; 3 = 62,83;
4 = 60,41; 5 = 57,56; 6 = 59,98; 7 = 59,99; 8 = 57,57.
N
Phng sai d: S du2 1 ( yi )2 = 4,189; ch s Fisher:
N l i 1
F

S du2
4,189

7,414 . Vi f1 = N l = 4 v f2 = m 1 = 2, mc
2
S u 0,565

13
c ngha p = 0,05, tra bng thu c Fp,f1,f2 = 19,3 > F. Vy phng
trnh hi quy va thit lp tng thch vi bc tranh thc nghim.
Khai trin cng thc (3.2) sang bin thc Zj vi cc gi tr
tng ng trong bng 2.1, c cc gi tr xj:
Z 45
Z 6,5 ;
;
x1 1
x2 2
5
1,5

x3

Z 3 90
10

Thu c phng trnh theo bin thc: y = 49.97 + 1,049z1 +

16,73z2 + 0,615z3 0,161z1z2 0,095z2z3

(3.3)

Gii phng trnh (3.3) vi phn mm Matlab 5.3, kt qu thu

c gi tr hiu sut cc i l 62,37%, ti cc iu kin: Nng
NaOH: 41,00%; thi gian un: 8,00h; nhit : 810C
Nhn xt: Trong qu trnh iu ch CTS t chitin, ngoi nhm
acetyl b tch ra t chitin, cn mt phn phn t CTS b ct mch v
ha tan theo dung dch, dn n gim hiu sut qu trnh iu ch.
nhit thp, nng NaOH thp, nhm acetyl t cc mt
xch khng b tch nhiu dn n deacetyl khng t yu cu.
nhit cao, nhm acetyl b tch ra nhiu tuy nhin km theo l
s ct mch. Thc t kho st cho thy khi s dng nhit cao,
nng NaOH cao th dung dch CTS to thnh to kt ta vi dung
dch ZnSO4, dn n vic cn tr nghin cu s dng CTS m
km. Nh vy s dng cc gi tr min nh hng nh kho st l
hp l. Hnh nh CTS thu c nh hnh 3.2.

14

Hnh 3.2. CTS tinh ch

Sau qu trnh tinh ch, sn phm thu c l CTS bt, hnh
kim, mu trng c. C s kh mu ny l cc qu trnh kh
khong, kh protein v deacetyl lm mt i mt phn mu sc. S
to thnh dung dch CTS/CH3COOH tch c ring thnh phn
mu v thnh phn CTS, khi kt ta li CTS bng NaOH, phn mu
c tch ra v ra tri bi C2H5OH.
3.3. MT S CH TIU HA L CA CTS
3.3.1. m
Kt qu xc nh m ca CTS l 10,13%, gn vi mc tiu
chun thng mi (lch 0,13%), ngoi kh nng ht m cao ca CTS
th nguyn nhn cn do nh hng ca m phng th nghim.
3.3.2. Hm lng tro
Kt qu xc nh hm lng tro ca CTS c l 0,027%, sn
phm t ch tiu v hm lng tro. Hm lng tro thp chng t
qu trnh kh khong v gh c thc hin tng i trit .
3.3.3. Hm lng cht khng tan
Kt qu xc nh hm lng cht khng tan ca CTS l 7,12%,
p ng c ch tiu CTS thng mi. Cht khng tan y ch
yu l mt phn chitin cha phn ng ht (v v gh dy).
Nh vy v c bn, cc ch tiu v m, ha tan v hm
lng tro ca CTS iu ch t c yu cu ra.

15
3.4. PHN TCH NH TNH CTS
3.4.1. deacetyl ha
Kim tra deacetyl mu CTS theo phng php TCVN
6498:1999, kt qu cho thy hm lng % ca nit trong mu t
8,45%. deacetyl ca mu CTS xc nh theo cng thc (2.7)
c 88,83%. Nhn xt: deacetyl ph hp vi yu cu ca thc
nghim v t ch tiu ca CTS thng mi.
3.4.2. Ph hng ngoi
Ph hng ngoi (KBr), max(cm-1): 3521,83; 2931,15; 1664,16;
1628,88; 1436,18; 1381,90; 1319,48; 1172,92; 1053,50; 887,94;
757,66; 651,81; 592,10; 505,25.
Theo trn, nh hp th cc i 3521,83 cm-1 c trng ca
nhm -OH, nh hp th 2931,15 cm-1 v di ln cn trong khong
3000 2800cm-1 c trng cho nhm CH2, CH3 v nhm CH; nh
hp 1664,16 cm-1 v 1628,88 cm-1 ln lt c trng cho dao ng
bin dng ca -NH trong amid bc mt v NH2, lin kt COCH3
c th hin bi dao ng khu vc 1436,18 cm-1 v ln cn, nh
hp th 1053,50 cm-1 c trng cho dao ng ca nhm C-O, nh
hp th 888 cm-1 c trng cho dao ng ca lin kt glycozit.
3.4.3. Ph cng hng t ht nhn 1H-NMR
Ph 1H-NMR (500MHz, D2O).

16

Hnh 3.4. Ph 1H-NMR ca CTS iu ch t chitin v gh

Trong hnh 3.4, cm peak A th hin c trng cho H ca -CH3
trong nhm acetyl cn li sau khi deacetyl ha, cm peak E th hin
c trng cho H v tr C(1) trong vng pyranose. Cc cm peak khc
ng vi H trong cc cacbon cn li. i vi mch polymer ca CTS,
do cc mt xch khc nhau v s c mt ca nhm acetyl hay nhm
amino, cng nh s khng tun hon ca cc mt xch m khng c
mt ph xc nh, ch c th kim tra bng xc nh s c mt ca
cc nhm peak cc v tr c trng. Da vo cc d kin v c
im ph 1H-NMR v ph IR, v so snh vi nhiu ph CTS
cc ti liu tham kho c khng nh cht m chng ti iu ch l
CTS vi mc deacetyl nht nh.
3.5. KT QU NGHIN CU KH NNG CA CTS LM
PH GIA M KM
3.5.1. Kho st s dng CTS lm ph gia m km in ha
a. Kt qu to lp m thng

17
- Lng Zn kt ta trn catot tnh theo cng thc (1.8), chiu
dy tnh theo cng thc (1.11). M lp m thng trong thi gian
20 pht. Khi lng lp m theo l thuyt 0,4226 gam, thc t c
0,4057 gam. Hiu sut t 96%. dy lp m tnh c 24,37 m.
b. Kho st lp m km c ph gia chitosan
- Kho st lp m km c ph gia CTS theo phng n k
hoch trc giao cp I. Phng trnh hi quy ca k hoch nh sau:
= b0+b1x1+b2x2+b3x3+b12x1x2+b13x1x3+b23x2x3+b123x1x2x3 (3.4)
Trong x1; x2; x3 ln lt l bin m ha ca pH, mt
dng v nng CTS.
Vi hm mc tiu y l hiu sut dng thu c t cc th
nghim, lp c ma trn k hoch 23 nh trong bng 3.7 v bng
ma trn k hoch vi bin s hng 3.8.
Bng 3.7. Ma trn k hoch 23cho qu trnh m km
STT
1
2
3
4
5
6
7
8

Gi tr thc
Z1 Z2 (A/dm2) Z3 (g/l)
2,5
3,0
0,5
5,0
3,0
0,5
2,5
8,0
0,5
5,0
8,0
0,5
2,5
3,0
2,0
5,0
3,0
2,0
2,5
8,0
2,0
5,0
8,0
2,0

Gi tr m ha
x1
x2
x3
+
+
+
+
+
+
+
+
+
+
+
+

Hm mc tiu
y (%)
95,50
94,16
98,94
91,07
97,95
95,39
92,86
90,23

(Z1: pH; Z2: mt dng; Z3: nng CTS)

Bng 3.8. Ma trn k hoch cho qu trnh m km vi bin s hng
STT
1
2
3
4

x0
+
+
+
+

x1
+
+

x2
+
+

Bin m ha
x3 x1x2 x1x3
+
+
+
+
-

x2x3 x1x2x3
+
+
+
+
-

Hm mc tiu
y (%)
95,50
94,16
98,94
91,07

18
5
6
7
8

+
+
+
+

+
+

+
+

+
+
+
+

+
+

+
+

+
+

+
+

97,95
95,39
92,86
90,23

Tnh c cc gi tr hng: b0 = 94,763; b1 =-1,55; b2 = -0,988;

b3 = - 0,655; b12 = -0,575; b13 = 0,253; b23 = -1,575; b123 = 0,558.
Th nghim ti tm phng n thu c cc gi tr hm mc
tiu: y10 96,99 %; y 20 95,12 %; y30 95,82 %. Gi tr trung bnh:
95,98 %; phng sai lp: S u2 0,893; lch chun: Sbj =
( S u2 / 8)1 / 2 0,334 ; bc t do lp: f2 = m-1 = 2.
Vi mc c ngha p = 0,05, bc t do lp f2=2, tra bng c
chun s Student: t0,05;2 = 4,30. Nh vy bj c ngha khi
b j S bj .t bj 1,436. Chn c b0; b23. Vy phng trnh hi quy bin
m: = 94,76 1,55x1 1,575x2x3
Tnh c gi tr ti cc im thc nghim: 1 = 93,60; 2 =
94,75; 3 = 95,925; 4 =94,775; 5 = 96,750; 6 = 97,9; 7 = 92,775;
8 = 91,625. Phng sai d: S du2 5,13; ch s Fisher: F = 5,747.
Vi f1 = N l = 5 v f2 = m 1 = 2, mc c ngha p = 0,05,
tra bng thu c Fp,f1,f2 = 19,3 > F. Vy phng trnh hi quy bin
m trn tng thch vi bc tranh thc nghim.
Mi lin h gia bin m vi bin thc Zj:
x1

Z 1 3,75 ;
1,25

x2

Z 2 5,5 ;
2,5

x3

Z 3 1,25
0,75

Vy phng trnh theo bin thc: y = 93,638 1,55z1 + 1,05z2

+ 4,62z3 0,84z2z3
Gii phng trnh bin thc trn vi phn mm Matlab 5.3,
c hiu sut cc i l 96,62 %, ti cc iu kin: pH: 2,8; mt
dng: 8,00 A/dm2, CTS: 0,55gam/lt

19
Nhn xt: Qua kho st nhn thy khi pH thp sinh nhiu kh
H2; khi pH qu cao th lp m nhum mu ti ng thi b mt lp
m x x. Mt dng qu cao lm gim hiu sut dng v cht
lng lp m do sinh nhiu bt kh H2. Nng CTS cao gy tng
nht dung dch, cn tr dng in, mt khc CTS tp trung ln b
mt catot gy cn tr s kt ta Zn. Kt qu m in cc ch ti
u thu c lp m mn, sng.
3.5.2. Cht lng lp m nh gi qua hnh nh
Hnh nh SEM so snh cc mu th hin hnh 3.5 v hnh 3.6
vi k hiu mu A: Lp m Zn; mu B: Lp m Zn-CTS.

Hnh 3.5. nh SEM hai mu m phng i 200 ln

Hnh 3.6. nh SEM hai mu phng i 5000 ln

20
Nhn xt: Lp m c ph gia (B) cu trc cht ch hn lp m
thng (A), hnh nh th hin lp m c ph gia mn hn lp m
khng s dng ph gia CTS. Cc mm Zn trn lp m composite ZnCTS c CTS bao ph bi lp mng mng ca n.
3.5.3. Kh nng chng n mn ca lp m composite trong
mi trng c NaCl
a. Kt qu o ph tng tr in ha (EIS)
Ph tng tr in ha ca mu thp m Zn v m composit Znchitosan cc ch khc nhau c trnh by trong hnh 3.7.

(d)

(a)

(b)

(c)

Hnh 3.7. Ph EIS ca mu thp m Zn (a) v composite Znchitosan cc nng chitosan: 2g/l (b); 1g/l (c); 0,55g/l (d)
Ph tng tr in ha Nyquist cho thy, trong trng hp c
s dng chitosan th lp m composite Zn-chitosan thu c c vng
cung ln hn so vi lp m Zn. iu ny cho thy, lp m composite
c kh nng chng n mn tt hn v t ti u khi nng chitosan
l 0,55g/l.
b. Kt qu nghin cu chng n mn qua kim tra
gim khi lng

21
Kt qu biu din trong bng 3.9 v hnh 3.8:
Bng 3.9. Theo di n mn cc lp m trong dung dch NaCl 3,5%
gim khi lng (10-5g/cm2.ngy)
STT
Zn
Zn-CTS
1
7,860
5,890
2
6,721
4,746
3
5,883
4,243
4
5,517
4,155
5
5,472
3,982
6
5,244
3,928
7
4,928
3,784
8
4,829
3,556
9
4,540
3,550
10
4,458
3,471

Biu so snh mt dng n mn ca hai lp m km v

Zn-CTS nh trong hnh 3.8.
8
Km

Km - chitosan

gim khi lng (10 g/cm .ngy)

-5

6
5
4
3
2
1
0
1

10

Thi gian (ngy)

Hnh 3.8. Biu mt dng n mn ca hai lp m

Cc lp m sau n mn c chp SEM, kt qu trn hnh 3.9,
cc k hiu mu C: Lp m Zn, mu D: Lp m Zn-CTS.

22

Hnh 3.9. nh SEM hai mu m sau n mn

phng i 2000 ln
Nhn xt: Hnh nh so snh trn hnh 3.9 cho thy trn lp m
composite Zn-CTS sau 10 ngy n mn, phn Zn b hao mn ng
thi vi mng CTS nhng Zn vn c bao ph bi lp mng mn.
Lp mng ny tip tc ngn cn s n mn i vi thnh phn Zn.
Mi trng mui trung tnh NaCl l mi trng c vai tr tng
tc n mn kim loi, kt qu nghin cu chng n mn ca lp m
Zn-CTS v so snh vi lp m Zn trong mi trng dung dch NaCl
th hin bng 3.9 v th hnh 3.8 cho thy tc n mn xy
ra trn b mt lp m composite mi chm hn so vi lp m ch c
Zn. Ban u tc n mn nhanh v sau gim dn theo thi gian.
C ch ca n mn lp m km c ngh: Trong dung dch in
ly NaCl, s tip xc ca b mt Zn vi kim loi tp cht v cc ion
Na+, Cl- gy s phng in trn anot v catot (kim loi tp):
Zn Zn2+ + 2e;

H2O + 2e OH- + H2

M qu trnh m lp Zn s dng CTS lm ph gia, trn b mt

catot xy ra ng thi cc qu trnh kh:
Zn2+ + 2e Zn
2(Chito-NH3+)n + 2ne 2(Chito-NH2)n + nH2
CTS v Zn ng thi kt ta ln b mt catot to lp m
composite Zn CTS. Khi b n mn trong mi trng trung tnh, lp

23
mng CTS ngn cn s xm thc ca mi trng, cn tr qu trnh
oxi ha Zn do vy lm chm qu trnh n mn. Nhc im ca CTS
l b ha tan trong mi trng axit long, tuy nhin cc ion SO42-,
PO43- c ch c qu trnh ny, nn kh nng chng chu b ha tan
ca CTS tng i tt trong mi trng t nhin. CTS c
thng mi ha, vic m cng n gin, do vy vic s dng lp m
ny vo thc tin l kh quan.

KT LUN V KIN NGH

Kt lun
1. Kho st cc iu kin ti u v nng dung dch NaOH,
thi gian phn ng v nhit cho qu trnh iu ch CTS (ng vi
hiu sut ti a) thu c kt qu nh sau:
- Nng dung dch NaOH: 41,00 % (vi t l rn/lng =
1/20)
- Thi gian cho phn ng deacetyl ha: 8,00 gi
- Nhit s dng: 810C
Hiu sut iu ch CTS t chitin v gh trong cc iu kin
trn t ti a l 62,37%.
2. Qua kim tra ph hng ngoi v ph cng hng t proton
cho thy CTS iu ch c cng thc ph hp vi l thuyt, kt
qu thu c CTS vi cht lng nh sau:
- m: 10,13%

- Lng tro: 0,027%

- Lng cht khng tan: 7,12 %

- deacetyl: 88,83%

Nh vy cht lng CTS iu ch ph hp vi yu cu cht

lng ti thiu ca CTS thng mi, kt qu ny cng ph hp vi

2
24
ng dng trong nghin cu thc nghim lm ph gia m km in
ha.
3. to thnh cng lp m composite Zn-CTS trn thp CT3
quy m phng th nghim vi quy trnh n gin. Vi dung dch
nn to bi ZnSO4.7H2O (250 gam/lt); NaCl (40 gam/lt), H3BO3
(30 gam/lt) v CTS lm ph gia. Kho st v to c lp m ZnCTS gi tr ti u cc iu kin nh hng:
- pH: 2,8

- Mt dng: 8,00 A/dm2

- Nng CTS: 0,55gam/lt

- Hiu sut cc i 96,62%

4. Nghin cu kh nng chng n mn ca lp m Zn-CTS

bng cc phng php kim tra. Cc kt qu hnh nh SEM v th
nghim chng n mn cho thy hiu qu chng n mn ca lp m
Zn-CTS cao hn so vi lp m Zn trong c mi trng dung dch
nc v mi trng m cha NaCl.
Kin ngh
1. Nghin cu y hn na nh t l chitin/dung dch
NaOH n deacetyl, kho st cc yu t nh hng n nht
ca dung dch CTS iu ch t chitin v gh.
2. Kho st thm v nh hng ca deacetyl, nht ca
dung dch CTS ti lp m.
3. Kt hp vi cc chuyn ngnh bn lnh vc vt l kho
st cc yu t ti u t cu trc lp m tt nht, cng nh bn,
cng, bm ca lp m ln vt cn c m.