B GIO DC V O TO

TRNG I HC CN TH

ti:
CH TO V KHO ST TNH CHT
CA CHT LNG T FERIT CoFe2O4
LUN VN THC S
CHUYN NGNH: VT L K THUT

Hng dn khoa hc: TS. Nguyn Khnh Dng

Hc vin thc hin : Hunh Th Thu H
4/26/2014

Cn Th Thng 10/2008

Sng Th Vi

Nc ti 1 cng x bn b ro
4/26/2014
Cng Ty Vedan

Nc bn Cng Ty Vedan

Nc thi ti ming cng ca

Cng Ty Vedan

Ferit coban c:
t ha bo ha cao.
Tnh d hng t cao.
t b oxy ha hn ferit st.
CoFe2O4 v Fe3O4 c nhng thng s gn bng nhau:
Vt liu

KLPT
(g)

Cu
trc

Hng s
mng
( Ao)

Fe3O4

231,54

spinel

8,39

858

477

-13

CoFe2O4 234,63

spinel

8,38

793

398

180

TC Ms
( K) (KA.m-1)

K1
(KJ.m-3)

ti : Ch to v kho st tnh cht ca cht lng t ferit

CoFe2O4
4/26/2014

MC TIU CA TI
To ra cht lng t CoFe2O4 c:

t ha v cm t cao.
Cc cht kch hot b mt phi dng huyn ph trong
cht lng mang.

ng dng cht lng t to ra vo vic x l nhng kim loi

nng trong nc b nhim bn.

4/26/2014

Ni dung trnh by gm c 5 phn:

Phn 1: Ht nano t v cht lng t.

Phn 2: Thc nghim tng hp ht nano t v cht

lng t CoFe2O4.
Phn 3: Kt qu nghin cu v bin lun.
Phn 4: ng dng ht nano t v cht lng t
CoFe2O4 vo vic x l kim loi nng trong nc b
nhim bn.
Phn 5: Kt lun chung v hng pht trin.
4/26/2014

PHN 1: HT NANO T V CHT LNG T

Ht CoFe2O4:

Ferit t cng.
Cu trc tinh th lp phng spinel
ngc.
L nhng ht n men
men

Vch
men

V tr t din

xi.
V tr bt din
V tr bt din.
V tr t din.

4/26/2014

Cht lng t
Cht lng t l mt huyn ph gm cc ht vt liu t
nh b (kch thc c nano mt) v cht lng mang cc ht
t ny.
Cht lng t gm ba thnh phn chnh:

Cht lng mang (cn gi l dung mi).

Ht vt liu t kch thc nano (ht nano t).

Cht kch hot b mt (cht c nh b mt).

4/26/2014

Axit Oleic
Cng thc phn t: C18H34O2
Cu trc

Tnh cht vt l:
Cht lng nh du mu vng nht hay vng hi nu, c mi
ging m ln, khng ha tan trong nc m ha tan trong nhexan, kerosene v ethanol
Nhit nng chy: 13- 14oC.
Nhit si: 360oC( 760 mmHg).
T trng: 0.895- 0.947 g/cm3.
4/26/2014

Cc phng php tng hp ht nano t

Phng php Vt L:
Bc bay nhit trong l .
Nghin bi.
Thu nhit.
Phn x.
Bc bay nhit trong chn khng.
Phn ng pha rn.
Ngui nhanh.
Phng php ho l:
in ho.
Ngng t.
in ho siu m.
Phn ng trong ng thp
nhit cao.
4/26/2014

Phng php ho hc:

ng kt ta.
Vi nh tng.
Sol-gel.
Ho siu m.
Ho vi ba.

Phng php ng kt ta
MeCl2 + 2FeCl3 + 8NaOH MeFe2O4 + 8NaCl + 4H2O
MeCl2 + 2FeCl3 + 8NH4OH MeFe2O4 + 8NH4Cl + 4H2O
CoCl2.6H2O + 2 FeCl3.6H2O + 8 NaOH CoFe2O4 + 8NaCl + 22H2O

u im:
Ch to n gin.
Phn ng xy ra nhanh.
C th to ra ht nano vi ng nht, phn tn kh cao, rt
thch hp cho phn ln cc ng dng trong nhiu lnh vc.

4/26/2014

10

ng dng ca cc ht nano t v cht lng t

1. ng dng trong y sinh hc
Phn tch v chn lc t bo
Nng thn nhit cc b
Dn truyn thuc
Tng tnh tng phn cho nh cng hng t (MRI)

2. ng dng trong vic kho st cu trc men t

4/26/2014

11

3. ng dng trong mi trng

Ht nan kt hp vi mui Al2(SO4)3 lm sch nc bng lng ng cht bn

Cc cht bn
trong nc
phi sau thi
gian di mi
lng ng.

4/26/2014

Al2(SO4)3
to thy
phn to keo
Al(OH)3 ko
cc cht bn
lng ng
xung di.

Ht nano t tnh
gip keo
Al(OH)3 lm
lng ng cht
bn nhanh hn
khi dng mt t
trng ngoi.
12

PHN 2: THC NGHIM

Qui trnh tng hp ht nano t CoFe2O4
20 ml ddCoCl2.6H2O
FeCl2.6H2O
80_- 90 oC

St kh N2

dd NaOH
80 - 90 oC

Rung siu m 1 h
Khuy trn

Ht CoFe2O4

ng kt ta

Dung dch kt ta mu
en

Cho vi git
HCl lang

Lng bng nam chm v

ra vi nc ct

Ly tm 15 pht
( 3000 rpm)
4/26/2014

13

Bng cc mu tin hnh thc nghim

Mu

Nng NaOH
(mol/l)

VNaOH
(ml)

VMui
(ml)

pH[1]

pH[2]

pH[3]

t(oC)

Thi
gian
(pht)

Ghi ch

HAo

150

20

10

9,1

67

50

60

Sc N2

HA1

150

20

10

9,2

67

80

65

HA2

150

20

10

67

80

65

HA3

150

20

10

67

90

60

HA4

150

20

10

67

90

80

HA5

2,5

60

20

11

9,5

67

80

65

HA6

2,5

60

20

11

9,5

67

80

60

HA7

2,5

60

20

11

9,4

67

90

55

HA8

2,5

60

20

11

9,8

67

90

65

HA9

3,5

43

20

13

11,5

67

80

75

HA10

3,5

43

20

13

11

67

80

60

HA11

3,5

43

20

13

11,5

67

90

60

3,5

43

20

13

12

67

90

45

4/26/2014

HA12

Sc N2

Sc N2

Sc N2

Sc N2

Sc N2

Sc N2

14

Qui trnh tng hp cht lng t CoFe2O4

2,35 g
CoFe2O4
80 ml nc ct
pH = 10,5
Khuy, un nng
n 80oC

15 ml NH4OH

20 ml axit Oleic

Khuy trn 1 h

un nng
100 ml ethanol
Khuy, un nng
n 80oC

Gn, cht

4/26/2014

Cht lng t
CoFe2O4

15

Bng cc mu ht tin hnh ph

Mu

Mu
ht

V
(Oleic)
(ml)

HL4

HA4

16

30

1: 23: 4,8

15

n-hexan(30%)

100

HL4*

HA4

16

30

1: 50: 4,8

15

ethanol (30%)

100

HL8

HA8

20

30

1: 72: 6

n-hexan

100

HL10

HA10

20

30

1: 170: 6

15

ethanol

100

HL10*

HA10

20

80

1: 50: 6

ethanol (30%)

100

HL12

HA12

20

80

1: 170: 6

15

ethanol

100

4/26/2014

t
T l mol V(NH4OH) Dung mi
(Oleic) gia
(ml)
(oC) ht,dung
mi, cht
ph

V (Dung
mi)
(ml)

16

Cc thit b s dng kho st ht nano t

v cht lng t

Knh hin vi in t qut (SEM)

My o ph nhiu x tia X

T k mu rung

M hnh my o ph hp th hng ngoi -FT-IR.

4/26/2014

Knh hin vi in t truyn qua (TEM

17

PHN 3: KT QU V BIN LUN

Kho st cu trc ht
CoFe2O4
(113)

CoFe2O4
(113)
CoFe2O4
(220)

CoFe2O4
(220)

CoFe2O4
(024)

CoFe2O4
(110)

CoFe2O4
(033)

CoFe2O4
(110)

Ph X-Ray ca mu HA8

Co
Fe2O4
(220)

CoFe2O4
(110)

CoFe2O4
(024)

CoFe2O4
(033)

Ph X-Ray ca mu HA10

CoFe2O4
(113)

CoFe2O4
(033)

CoFe2O4
(024)

Mu

Nng
NaOH (mol/l)

Nhit
(oC)

Kch thc
(nm)

HA8
HA10
HA12

2,5
3,5
3,5

90
80
90

13,9 15,3
13,1 16,2
15,3 16,2

Kch thc cc mu ht thay i khng

nhiu.
Ph X-Ray ca mu HA12

4/26/2014

Hng s mng a = 8,402 Ao.

18

Kho st t tnh ca ht
t ha bo ha ph thuc vo
nng NaOH.

Trong khong nng NaOH

13,5 M, nng cng tng th
t ha cng gim.
ng cong t ha ca mu HA4, HA8, HA12
Mu

HA4
HA8
HA12
4/26/2014

Nng
NaOH
(mol/l)

Nhit
(0C)

Ms
(emu/g)

Hc(Oe)

Ghi ch

1
2,5
3,5

90
90
90

57
51
50,5

881
895
920

Sc N2
Sc N2
Sc N2

19

Kho st t tnh ca ht (tip theo)

t ho ph thuc
nhit .

ng cong t ha ca mu HA10, HA12

Mu Nng NaOH Nhit Ms (emu/g)
(mol/l)
( oC)
HA10
HA12
4/26/2014

3,5
3,5

80
90

55
50,5

Hc(Oe)

Ghi
ch

828
920

Sc N2
Sc N2
20

Kho st t tnh ca ht (tip theo)

Vic sc kh N2 c nh
hng rt ln n t ha
bo ha ca mu

ng cong t ha ca mu HA11, HA12

Mu

Nng
NaOH
(mol/l)

Nhit
(oC)

Ms (emu/g)

Hc(Oe)

HA11
HA12

3,5
3,5

90
90

31
50,5

1751
920

4/26/2014

Sc N2

Khng
C
21

 t ha bo ha ca cc mu ht
60

57

iu kin tng hp ht
tt nht:

55
51

50.5

t ha (emu/g)

50
HA4

40
31
30
20

HA8
HA10
HA11
HA12

Nng NaOH 1 M.
Nhit : 8090oC.
Sc kh nit.

10
0

Biu biu th t ha ca cc mu ht

4/26/2014

22

Kho st dng hnh hc

nh SEM mu HA8 - giai o 200 nm

4/26/2014

nh SEM mu HA8 - giai o 500 nm

23

Kho st dng hnh hc (tip theo)

nh TEM mu HA8 - giai o 50 nm

4/26/2014

nh TEM mu HA8 - giai o 100 nm

24

Kho st mu cht lng t

Kho st cu trc ht trong cht lng t
nh ph cc
i l (113) trng
khp vi nh ph
ca cc mu ht.
Lp ph Oleic
khng lm thay
i cu trc pha
ca ht nano t
CoFe2O4
4/26/2014

Ph X-Ray ca mu HL4, HL8, HL10

25

Kho st t tnh ca cht lng t

ng cong t ha ca mu HL4, HL8, HL10

Mu

Dung mi

Nhit
(0C)

Ms (emu/g)

Hc(Oe)

HL4

n-hexan (30 %)

80

27

780

HL8

n-hexan

80

21

1450

4/26/2014

26

HL10

ethanol

80

41

1294

So snh t tnh ca mu ht v mu cht lng t

ng cong t ha ca mu HA4 v HL4

ng cong t ha ca mu HA8v HL8

Mu

HA4

HL4

HA8

HL8

HA10

HL10

Ms
(emu/g)

57

27

51

21

55

41

HC ( Oe)

881

780

895

1450

828

1294

ng cong t ha ca mu HA10 v HL10

4/26/2014

27

 t ha (emu/g)

t ha bo ha ca mu ht
v mu ph
60
40

57

HA4

55

51

41

27

21

20

HL4
HA8
HL8

0
1

HA10
HL10

Biu biu th t ha ca cc mu ht v mu ph

4/26/2014

28

So snh s n nh t tnh ca mu ht nano t

CoFe2O4 c ph Oleic vi ht nano t oxit st Fe3O4
ph Dextran

t ha (emu/g)

t ha ca mu nano t ferit
coban v oxit st
80
60
40
20
0
1

Mu

t ha
(emu/g)

HA10

55

HA10

HL10

41

HL10

H6

71,77

H6

DH2

39,7

DH2

Biu biu th t ha ca mu

bin thin t ha
(emu/g)
14
32,07

Mu CoFe2O4 n nh t tnh tt hn
mu Fe3O4

CoFe2O4 v mu Fe3O4
4/26/2014

29

Kho st dng hnh hc

nh SEM mu HL4 - giai o 1 m

4/26/2014

nh SEM mu HL4 - giai o 300 nm

30

Kho st dng hnh hc (tip theo)

nh SEM mu HL8 - giai o 300 nm

4/26/2014

nh SEM mu HL4 - giai o 500 nm

31

Kho st dng hnh hc (tip theo)

nh SEM mu HL10 - giai o 500 nm

4/26/2014

nh SEM mu HL10 - giai o 1 m

32

Kho st dng hnh hc (tip theo)

nh TEM mu HL8 - giai o 50 nm

4/26/2014

nh TEM mu HL8 - giai o 200 nm

33

Ph hp th FT-IR
O
C
O

Ht
nan

S gn kt ca Oleic ln b mt ht
CoFe2O4

s hin din
ca axit Oleic ln b
mt ht.
C

Ph FT-IR ca mu HA4, Oleic v mu HL4

4/26/2014

C s gn
gia lp ph v
th hin qua lin
COO-ht nano
CoFe2O4.

kt
ht
kt
t
34

 nht v t trng ca cht lng t

Dng nht k v t trng k xc nh : Mu cht lng t HL8 c
nht l 13,62 cst v t trng l 0,893 g/ml.

KT LUN
Cht lng t CoFe2O4 c ch to gm:
Cc ht ferit CoFe2O4:
* n pha.
* Hng s mng a = 8,402 Ao.
* Kch thc: 15 20 nm
* Ms = 50 57 emu/g , HC: 828 1751 Oe.
Lp ph: Axit Oleic.
Dung mi: Ethanol gip n nh t tnh tt, Ms: 41 emu/g.
Cc ht sau khi ph c kch thc t 25 30 nm.
T l gia ht, dung mi v cht ph thch hp m bo yu cu
ca cht lng t.

nht l 13,62 cst, t trng: 0,893 g/ml.

4/26/2014
35

PHN 4: NG DNG

Dng ht nano t v cht lng t CoFe2O4 kh nhng kim loi nng

trong nc b nhim bn.
Kim loi nng:
Kim loi c nguyn t lng cao.

Thng c c tnh i vi s sng nh As, Cd, Pb, Hg, Cr, Ni,

Zn
Triu chng khi b ng c kim loi nng:

Ch:au bng, tiu chy, n khng ngon ming, bun nn v co c.

Km: kh chu, nn, m hi lnh, mch p kh.
Nhim Asen mn tnh: tc hi n chc nng ca nhiu c quan nh
thn kinh, tim mch, tiu ha, sinh sn, nghim trng hn l ung th
bng quang, gan , thn, rut, lm ri lon gen.
4/26/2014

36

C ch hp ph kim loi nng ca cc ht CoFe2O4

A
s
N
i

N
i

N
i
F
e

Niken

F
e
Z
n

Z
n

A
s

HtCoFe2O4

A
s

Km

St
Asen

F
e
Z
n

N
4/26/2014

S
37

Qui trnh x l kim loi nng i vi cc mu nc pha ch

phng th nghim
Dd in phn: pH = 8
(0,85 g NaNO3, 10ml Tris
buffer (pH = 8), 990 ml nc
ct)

NaOH hoc HNO3

Kim loi nng

(DD2)

Ht CoFe2O4
rung siu m 10
pht (DD1)

Khuy trn
4rpm, 24 h

Lng mu bng
nam chm

Dng mng lc

Ly tm 4000 rpm,
30 pht
4/26/2014

38

Sn phm

Qui trnh x l mu nc thc t b nhim st

0,625 g ht CoFe2O4
20 ml nc ct
1 ml Tris buffer 8.0

250 ml nc b nhim st

Lc th

Rung siu m 10 pht

3 ml
Tris buffer 8.0
Dd nc cn x l pH=8
( DD1)

DD2

Khuy trn 4 rpm

Lng mu bng nam chm

Mng lc

Ly tm 4000 rpm, 30 pht

Sn phm
4/26/2014

39

Kt qu
Bng kt qu ca cc mu nc c iu ch
trong phng th nghim trc v sau khi x l
K hiu
mu

Ch
tiu
phn
tch

Loi
mu

T
trng
lng

Thi
gian
lng

Nng

trc
x l
(mg/l)

Nng
sau
x l
(mg/l)

Nng

chun
(mg/l)

Hiu
sut
kh
( %)

HZn

Zn

Lng

0,15 T

24 h

9,89

< 0,02

99,8

HNi

Ni

Lng

0,15 T

24 h

5,96

< 0,04

0,1

99,3

HPb

Pb

Lng

0,15 T

24 h

41,3

KPH*

0,015

100

HLPb

Pb

Lng

0,15 T

24 h

41,3

0,067

0,015

99,8

HHH

Zn

Lng

0,15 T

24 h

17,3

KPH*

100

HHH

Ni

Lng

0,15 T

24 h

6,42

KPH*

0,1

100

HHH

As

Lng

0,15 T

24 h

5,448

0,038

0,01

99,3

4/26/2014

KPH* : Khng pht hin

40

Bng kt qu ca mu nc thc t b nhim st trc v sau

khi x l
K hiu
mu

Ch
tiu
phn
tch

Thi
gian
khuy
(gi)

T
trng
lng

Thi
gian
lng
(gi)

HFeR
HFe1
HFe2

Nng

(mg/l)

Nng

chun
(mg/l)

Hiu
sut
kh
( %)

0,5

99,8

15,07
Fe

12

0,15 T

0,03

0,15 T

17

KPH*

100

Nhn xt
Cc ht CoFe2O4 hp ph tt c cc kim loi nng kho st.

Kh nng hp ph cc kim loi nng ca ht CoFe2O4 rt tt.

Hiu sut hp ph: 99,3% 100 %.
S dng cc ht CoFe2O4 kh cc kim loi nng trong nc b nhim bn s
c hiu
sut rt cao nhng chi ph x l thp .
4/26/2014
41

M hnh x l nc b nhim kim loi nng

Bm nc ln

Bn cha
nc

B phn lc 1

Ht
CoFe2O4

B phn hp ph
kim loi nng ca
cc ht CoFe2O4
Nc cn
x l

B phn lc 2

Ht CoFe2O4
hp ph kim loi
nng

Thit b
kh trng

4/26/2014

42

Nc sch

KT LUN CHUNG
1. Bng phng php ng kt ta ch to c cc ht nano t CoFe2O4:
* n pha, cu trc tinh th lp phng spinel.
* Kch thc t 15 20 nm, hng s mng a = 8,402 Ao.
* Ms = 50 57 emu/g, HC = 828 1751 Oe
2. tng hp c cht lng t ferit gm:
* Cc ht nano t CoFe2O4, kch thc trung bnh: 25 30 nm.
* Cht ph Oleic.
* Cht lng mang ethanol.
* T l mol gia ht, dung mi, cht ph l 1: 170: 6.
* t ha bo ha cao 41 emu/g.
* nht 13,62 cst.
* T trng: 0,893 mg/l.
3. ng dng cc ht nano t v cc ht cht lng t CoFe2O4 x l mu
nc b nhim asen, ch, km, niken, st vi hiu sut: 99,3 100 %.

a ra m hnh x l nc ha hn vi chi ph thp.

4. Cc ht nano t CoFe2O4 ny chiu x bng ngun bc x gamma t thit b
SvST-Co60 quan st thy thay i v mt s tnh cht t ca vt liu, v
t ha bo ha, t d v lc khng t.
4/26/2014

43

HNG PHT TRIN

Kho st kh nng hp ph cc kim loi nng
da vo:
Kch thc ht nano t CoFe2O4.
Thi gian khuy.
T trng lng.
Thi gian lng.
a ra iu kin hp ph kim loi nng tt nht.
Dng ht nano t v cht lng t CoFe2O4 x
l nc nhim kim loi nng ngoi thc t.
Dng cht lng t ny kho st cu trc
men t ca vt liu.
Nghin cu ng dng vo lnh vc y sinh hc.
4/26/2014

44

 Cc kt qu trong lun vn s c bo co ti
hi ngh Khoa Hc i Hc Quc Gia TP.HCM
thng 11 nm 2008.
Kt qu ny l mt phn ca bi bo
Researching of absorbability of As and heavy
metal of magnetic nano particles coated with Oleic
and Chitosan. s c bo co vo ngy 10-13/12/
2008 ti Hi Ngh Asian Magnetics Conference
2008, Busan, Hn Quc.

4/26/2014

45

XIN CHN THNH CM N !

4/26/2014

46