MN HC

N MN V
BO V VT LIU
1.1 Khi nim chung
1.1.1 Tnh hnh n mn vt liu
Vt liu c th c chia thnh bn nhm chnh: kim loi v hp kim, gm s, polyme v
composit.
Tt c cc loi vt liu u c th b n mn v ph hy.
Tuy nhin qu trnh n mn kim loi v hp kim ng vai tr quan trng trong thc t s dng,
do loi vt liu ny c dng nhiu nht v km n nh nht khi tip xc vi mi trng.
n mn l kt qu ca s tng tc ha hc hay vt l gia vt liu v mi trng.
n mn kim loi gy thit hi ln cho nn kinh t quc dn.
- Theo bo co ca y ban n mn v bo v Anh th thit hi do n mn Anh chim
3,5 % tng sn lng quc dn.
- M th chi ph ny vo nm 1982 c nh gi khong 126 t la mi nm.
- Vit nam c kh hu nng, m v t l s dng kim loi trong cng nghip cn rt ln
cho nn thit hi do n mn cn c th ln hn na.
- Tnh chung trn ton th gii tn tht do n mn gy ra trn 4,5% GDP:
. Thay th cc cu thnh b n mn.
. S dng hp kim chng n mn.
. S dng cc lp ph hoc cht c ch.
. Cc bin php in ha bo v kim loi.
n mn dn n s nhim mi trng.
Nm 2000, tu Erika 25 tui chm cch
b bin nc Anh 40 dm, gy nhim
nng n.
- Nm 1974, Flixborough (Anh),
mt l phn ng xyclohexan
(trong mt dy chuyn gm 6 l)
b thng do n mn. V n xy ra,
28 ngi thit mng.
1.1.2 nh ngha n mn
n mn l s ph hy kim loi do tng tc ha hc hoc in ha gia kim loi v mi
trng xung quanh.
n mn dn n s thoi ha kim loi v s nhim mi trng.

1.1.3 Chi ph chng n mn
Chi ph trc tip: thay th thit b, chi tit b n mn.
Chi ph gin tip: sa cha, thit hi do ngng sn xut.
V d: Chi ph thay th sa cha mt thit b trao i nhit trong nh my in ht
nhn < mt mt do ngng sn xut. Chi ph thay mt ng nc nng trong tng ca
mt ta nh > chi ph ca ng (gi ng)
Chi ph bo v: dng vt liu chu n mn th u t cao hn, chi ph to cc lp ph
bo v, chi ph bo v in ha.
Chi ph phng nga: phi dng vt liu c kch thc ln hn, chi ph kim tra, bo
dng.
n mn ha hc

- Phn ng oxy ha v phn ng kh xy ra
trong cng mt thi im trn cng mt v
tr.

- Khng c s xut hin ca dng in.

- Sn phm n mn to thnh trc tip
trong vng phn ng ca kim loi vi mi
trng xung quanh.

Th d:

Si + O
2
SiO
2


Mg + CO
2
MgO + CO


n mn in ha

- Phn ng oxy ha v phn ng kh xy ra
ng thi trn hai vng ring l ca b mt
kim loi.

- C s xut hin ca dng in.

- Sn phm n mn l kt qu ca mt s
phn ng th cp.


t
0

t
0

1.2 Cc dng n mn v ph hy vt liu phi kim
1.2.1 n mn v ph hy vt liu polyme
S n mn v ph hy vt liu polyme l do t lin kt gia cc phn t trong
polyme.
Cc lin kt ny l lin kt cng ha tr, nng lng lin kt nh nn rt d b ph
hy di cc tc ng ha hc v vt l nh nhit, chm tia nng lng cao.
1.2.2 n mn vt liu gm
Vt liu gm c phn thnh ba nhm chnh: gm s v vt liu chu la, thy tinh
v gm thy tinh, xi mng.
V d: thy tinh silicat rt km bn trong mi trng kim do c phn ng thy phn
lm t cc lin kt trong phn t v ph hy b mt.
Si O Si
O O
OH
O O
Si OH
O
O
Si O
O
O
+
+
Cc vt liu xy dng (btng, xi mng, gch ) thng b n mn theo c ch ha
tan cacbonat.
Trong bu kh quyn nhim cng nghip, khi c mt ca nc, SO
2
s to thnh
H
2
SO
4
. Axt ny s tc dng vi cacbonat canxi CaCO
3
trong vt liu to thnh
thch cao (CaSO
4
.2H
2
O).
Do thch cao c th tch ln hn cacbonat canxi, khi to thnh s lm trng phng
b mt, gy nt v bong trc b mt.
Cc vt nt s cho php nc v axt xm nhp cng su vo trong vt liu, gy t
gy cc lin kt v ph hy vt liu.
St b n mn
1.3 n mn kim loi
1.3.1 Phn ng n mn
Tc nhn n mn
S n mn kim loi l do phn ng oxy ha kh khng thun nghch gia kim loi
v mt tc nhn oxy ha trong mi trng.
Kim loi + tc nhn oxy ha kim loi b oxy ha + tc nhn oxy ha b kh.
V d: Fe (r) + 2HCl (dd) FeCl
2
(dd) + H
2
(k)
Fe + 2H
+
Fe
2+
+ H
2

H
+
: tc nhn oxy ha
Mi trng axt: O
2
+ 4H
+
+ 4e = 2H
2
O
Mi trng trung tnh: O
2
+ 2H
2
O + 4e = 4OH
-


Cation kim loi c tnh oxy ha: Cu
2+,
Fe
3+,
Sn
4+
Anion c tnh oxy ha NO
2-
, NO
3-
, CrO
4
2-
, MnO
4
-
, OCl
-
Kh oxy ha ha tan: O
3
, Cl
2
, SO


Trong mi trng kh kh, nhit cao
Tc nhn oxy ha c th l
Kh oxy
CO
2

Hi nc
Hp cht ca lu hunh S
2
, SO
2
, SO
4
2-

Mi trng m, tc nhn oxy ha l:
1.3.2 Tc n mn
Cc inh lut c bn
Phng trnh Nernst
R: hng s kh = 8,314 J/mol.K
T: nhit tuyt i (K)
F: hng s Faraday = 96500 C/mol
n: s in t trao i
: hot ion kim loi trong dung dch.

: th in cc tiu chun ca kim loi ng vi hot dung dch bng 1
hoc p sut kh bng 1 atm.
Theo qui c Stockholm nm 1953, th in cc tiu chun tnh cho cc phn ng
in cc c vit dng kh theo chiu t tri sang phi
V d: Cu
2+
+ 2e = Cu, E
o
(Cu
2+
/Cu) = + 0,337 V so vi SHE.
n
Me
a
0
Me / Me
n
E



n n n n
Me
0
Me / Me Me
0
Me / Me
rev
a lg
n
059 , 0
E a ln
nF
RT
E E
Khng th xc nh c gi tr tuyt i ca bt k th in cc no m phi o
th in cc so vi th ca mt in cc so snh.
Cc in cc so snh thng l in cc hydr chun SHE, in cc calomel bo
ha SCE, in cc Cu/CuSO4.
Theo quy c, th in cc tiu chun ca in cc hydr chun l 0 V
in cc hydr chun (SHE), quy c bng E
SHE
= 0 V, 25
0
C


in cc Calomen
bo ha
in cc Cu/CuSO
4

in cc Ag/AgCl
E = 0,222 V (SHE)
E = 0,241 V (SHE) E = 0,318 V (SHE)
A: Nguyn t (phn t) lng ca kim loi
F: hng s Faraday I = iS cng dng in (A)
i: mt dng in (A/m
2
) S: din tch (m
2
)
: Thi gian in phn (giy) n: s in t trao i
nh lut Faraday
iS
nF
A
I
nF
A
m
CC PHNG PHP TNH TC N MN KIM LOI
gim khi lng ca mu / n v din tch / n v thi gian (g/cm
2
.h)




su n mn (cm)


W: gim khi lng mu (g).
A: Din tch b mt kim loi (cm
2
).
D: Khi lng ring ca kim loi (g/cm
3
).
W: gim khi lng mu (g).
A l din tch b mt kim loi (cm
2
).
T l thi gian (gi).
i
corr
: mt dng n mn (A/cm
2
).
M l khi lng mol ca kim loi (g/mol).
F l hng s Faraday (96500 C/mol).
n l s in t trao i.
D l khi lng ring ca kim loi (g/cm
3
).
Th d:

Cho mu km vo dung dch HCl. Sau 2 gi thu c 1000 ml H
2
iu kin tiu
chun. M
Zn
= 65,37; d
Zn
= 7,14 g/cm
3
. Tc n mn (g/cm
2
h) khi din tch lm
vic ca mu l 2 dm
2
l bao nhiu?

Gii:
Phng trnh phn ng: Zn + 2HCl = ZnCl
2
+ H
2

n (Zn) = n (H
2
) (ktc) = 0,1/22,4 (mol)
Khi lng km tan tng ng vi kh H
2
thot ra l:

W (Zn) = 65,37.(0,1/22,4) = 0,2918 (g)
Tc n mn theo khi lng l:
Vy tc n mn l 7,295.10
-4
(g/cm
2
.h)
1.3.3 Cc yu t nh hng n s n mn
1.3.3.1 nh hng ca th in cc
Chiu v tc ca phn ng in cc ph thuc vo th in cc.
V d: Dung dch cha 1 mol Fe
2+
, Fe
3+
tip xc vi in cc Pt th phn ng xy ra
l Fe
3+
+ e = Fe
2+
cn bng, in th in cc l 0,77 V.
Nu < 0,77 V s chuyn phn ng t Fe
3+
Fe
2+
(qu trnh kh)

> 0,77 V s chuyn phn ng t Fe
2+
Fe
3+
(qu trnh oxy ha)

1.3.3.2 nh hng ca sn phm n mn
Bn cht vt l ca cc sn phm n mn nh hng mnh n tc n mn.
1.3.4 Phn loi cc dng n mn
1.3.4.1 Phn loi theo c ch n mn
1.3.4.1.1 n mn in ha
L s n mn kim loi trong mi trng in ly
Xy ra do qu trnh trao i in t gia cht oxyha v cht kh.
1.3.4.1.2 n mn ha hc
L s n mn trong mi trng kh, cn gi l n mn trong kh kh
Xy ra do phn ng ha hc ca kim loi vi mi trng kh xung quanh c cha cc
tc nhn gy n mn nh oxy, lu hunh, clo
V d kim loi khi nung nhit cao trong khng kh s b oxyha theo phn ng:
2 Me + O2 MeO
n mn ha hc

- Phn ng oxy ha v phn ng kh xy ra
trong cng mt thi im trn cng mt v
tr.

- Khng c s xut hin ca dng in.

- Sn phm n mn to thnh trc tip
trong vng phn ng ca kim loi vi mi
trng xung quanh.

Th d:

Si + O
2
SiO
2


Mg + CO
2
MgO + CO


n mn in ha

- Phn ng oxy ha v phn ng kh xy ra
ng thi trn hai vng ring l ca b mt
kim loi.

- C s xut hin ca dng in.

- Sn phm n mn l kt qu ca mt s
phn ng th cp.


t
0

t
0

1.3.4.2 Phn loi theo mi trng n mn
n mn trong kh quyn
n mn trong mi trng nc ngt
n mn trong mi trng nc bin
n mn trong mi trng t
n mn trong kim loi lng
1.3.4.3 Phn loi theo phm vi n mn
1.3.4.3.1 n mn u v n mn cc b
n mn u
Xy ra ng nht trn tt c b mt ca kim loi, mc v m, khng phn bit
c khu vc ant, khu vc catt.
B mt ca kim loi va l catt va l ant.
n mn cc b
Xy ra ti mt ni trn b mt, ch c phn ng ant.
C th phn bit r rng khu catt, khu ant.
Trong thc t n mn cc b l do tnh d th ca vt liu hoc ca mi trng.
+ n mn galvanic (galvanic corrosion) (vi pin):
- n mn gia hai kim loi do to thnh pin in ha gia chng.
- Kim loi c th m hn s b n mn.
+ n mn hc (crevice corrosion):
- Do s khc nhau v nng oxy hai phn ca mt cu trc, to
thnh pin in ha gia chng.
- Thng gp trn cc khe ca kim loi hoc trn cc vng m oxy t
c kh nng thm vo.
+ n mn l (pitting corrosion):
- To nn bi mt vi anion (ch yu l Cl-) trn cc kim loi c
bo v bi mt lp mng th ng.
- Thng to cc l hng c ng knh khong vi chc m
+ n mn gia cc ht (intergranular corrosion):
- n mn c chn lc trn bin gii ht.
- C lin quan n cc pha b kt tinh trong qu trnh x l nhit.
+ n mn chn lc (selective corrosion):
- n mn do oxyt ha mt cu t ca hp kim to thnh mt cu trc
kim loi xp.
+ n mn xi mn (erosion corrosion):
- Do tc ng kt hp gia mt phn ng in ha v bo mn c
hc.
- Dng ny thng xy ra khi cc kim loi t trong dng cht lng
chy nhanh.
+ n mn di ng sut (stress corrosion cracking):
- l s kt hp gia mt ng sut c hc v mt phn ng in ha
to nn cc vt nt trn kim loi