TEACHING NOTES

1 CORROSION FUNDAMENTALS
1.1 Defnition of Corrosion
Corroson Engneerng appcaton of scence and art to prevent
or contro corroson damage economcay and safey
Destructon or deteroraton of matera because of reacton wth
envronment
1.2 Corrosion Damae
A!!earan"e. Rusted surfaces not peasng to eye
Bady corroded equpment poor mpresson
Maintenan"e an# o!eratin "osts. Substanta savngs
use of corroson resstant materas
E.g.: Chemca pant annua savng >$10000 by changng
bot matera
Waste recovery pant operated n red unt corroson probem
soved
Appcaton of cathodc protecton can cut eak rates n
underground ppenes to n arge savngs n repar costs
Cooperaton between corroson engneer and process and desgn
personne before a pant s but emnate or reduce
mantenance costs
Sght changes n process reduce corrosveness of pant quors
permttng use of ess expensve materas
Changes made after pant s n operaton, but orgna preventve
measures more desrabe
Corroson dmcutes "desgned out" tme orgna desgn
Easer and cheaper to erase nes than to repar or repace faed
equpment
$%ant S&'t#o(ns. Pants shut down or portons of a
process stopped unexpected corroson faures
Sometmes shutdowns caused by corroson nvovng no change n
process condtons, but by changes n operatng procedures
erroneousy regarded as ncapabe of ncreasng severty of
corrosve condtons
Some mnor change n process or addton of a new ngredent
changes corroson characterstcs
E.g. Producton of chemca compound
To ncrease producton, temperature of coong medum n heat-
exchanger system owered tme decreased. Lowerng
temperature more severe therma gradents across wa. Induced
hgher stresses. SCC occurred pant shut down wth producton
deayed
Corroson montorng hepfu n preventng unexpected corroson
faures. By perodcay examnng corroson specmens exposed
to process or usng corroson probe records corroson rate
Perodc nspecton durng schedued downtmes prevent
unexpected shutdown
Contamination of !ro#'"t. Market vaue reated to
purty and quaty
Freedom from contamnaton vta factor n manufacture and
handng of transparent pastcs, foods, drugs, and
semconductors
Very sma amount of corroson, whch nduces certan meta ons
nto souton, may cause cataytc decomposton e.g.
manufacture and transportng of concentrated H
2
O
2
or hydrazne
Lfe of equpment not mportant where contamnaton or
degradaton of product concerned
Ordnary stee may ast many years, but more expensve matera
used because presence of rust undesrabe from product
standpont
Loss of )a%'a*%e !ro#'"t Sght osses of uranum
compounds hazardous and costy
Utzaton of more expensve desgn and better materas of
constructon warranted
E+e"ts on safet, an# re%ia*i%it,. Handng of hazardous
materas toxc gases, hydrouorc acd, concentrated suphurc
and ntrc acds, exposve and ammabe materas, radoactve
substances, and chemcas at hgh temperatures and pressures
demands use of constructon materas that mnmze corroson
faures.
Stress corroson of a meta wa separatng fue and oxdzer n
msse premature mxng oss of mons of rupees and persona
n|ury
Faure of sma component or contro faure or destructon of
entre structure
Corrodng equpment can cause harmess compounds to become
exposve.
Economzng on materas of constructon not desrabe f safety s
rsked.
Other heath consderatons aso mportant contamnaton of
potabe water.
Corroson products coud make santzng more dmcut
E.g. mk and other dary product pants. Newer pants use n-
pace ceanng and santzng whch requre corrosve chemcas, -
chorde ons and pttng. Use of pt-resstant staness stees
type 316
Corroson mportant n medca metas used for hp |onts,
screws, pates, and heart vaves. Reabty of mportance
Experence mportance of safety consderatons. Large carbon
stee was ceaned, washed, and entered for mantenance.
Workman asphyxated and ded ar became O
2
-decent
created by rapd rustng
$ro#'"t %ia*i%it,. Dsturbng trend puttng bame and
ega responsbty on producers of any tem or equpment that
fas because of corroson or any other reason.
Increase of product abty cams aarmng
Exampe bamng auto manufacturer f car corroded because
you drove through ake of hydrochorc acd
Corroson engneer douby sure that faure w not occur n
actua envronment and shoud be aware of ega abty aspects
- Stan#ar# E.!ressions for Corrosion Rate
To compare materas on the bass of corroson resstance, rate of
attack expressed quanttatvey
Corroson rates expressed varety of ways percent weght
oss, mg/sq. cm./day, gm/sq.n./hr.
These do not express n terms of penetraton
From engneerng pont of vew, rate of penetraton predct fe
In most cases, asde from contamnaton probems, prmary
concern s fe of equpment nvoved
Good corroson rate shoud nvove (1) famar unts, (2) easy
cacuaton wth mnmum opportunty for error, (3) ready
converson to fe n years, (4) penetraton, and (5) whoe numbers
wthout cumbersome decmas
Ms per year (mpy) now wdey used
Ms per year = 534W/DAT
where W = weght oss, mg
D = densty of specmen, g/cm
3
A = area of specmen, sq. n.
T = exposure tme, hr
Converson from other unts to obtan ms per year s
Multiply By
n./yr 1000
n./month 12,100
mg/dm
2
/day (mdd) 1.44/specc gravty
mpy popuar because t expresses corroson rate n terms of
penetraton usng sma ntegers
Some equvaent metrc penetraton rates are:
1 mpy = 0.0254 mm/yr = 25.4 m/yr = 2.90 nm/hr = 0.805
pm/sec
Corroson rates of usefuy resstant materas range between 1
and 200 mpy
Tabe 4-5 compares mpy wth above metrc expressons
Mmetres/year yeds fractona numbers, whe m/yr produces
arge ntegers
Nm/hr smaer numbers
Pm/sec very cose to mpy rates
Unts chosen to avod decmas
Nm/hr and pm/sec provde sma whoe numbers, requre
addtona converson before reated to dmensons of
engneerng structures
Mcrometers/yr and mm/yr most usefu cacuated from weght-
oss data:
m/yr = 87,900W/DAT
mm/yr = 87.9W/DAT
where W weght oss n mg, D densty n g/cm
3
, A area n cm
3
,
and T tme of exposure n hours
Corroson rates determned by eectrochemca technques are
expressed current densty converted nto penetraton rates by
foowng expresson based on Faradays aw:
Corroson penetraton rate = Ka/nD
Where a atomc weght; current densty n a/cm
2
; n
number of eectrons ost (vaence ost); D densty n g/cm
3
; K
constant dependng on penetraton rate
For mpy, m/yr, mm/yr, K - 0.129, 3.27, and 0.00327, respectvey
n s determned by anayss of souton or measurng potenta and
pH and referrng to potenta-pH dagram
Atomc weght a and n vaues for aoys from weghted averages
of components
Iron corrodng n ar-free acd at 1 A/cm
2
Dssoves as ferrous ons, n = 2
Corroson rate n mpy:
Penetraton rate = 0.129 (55.8) (1)/(2) (7.86) = 0.46 mpy
/ C%assif"ation of Corrosion
Cassed n many dherent ways
One method ow-temperature and hgh-temperature corroson
Another drect combnaton (or oxdaton) and eectrochemca
corroson
Preferred (1) wet corroson and dry corroson
Wet corroson occurs when qud s present. Invoves aqueous
soutons or eectroytes and accounts for greatest amount of
corroson. Common exampe s corroson of stee by water
Dry corroson n absence of qud. Vapours and gases
corrodents. Assocated wth hgh temperatures. Exampe s attack
on stee by furnace gases
ELECTROCHEMICAL AS$ECTS
E%e"tro#e $otentia%s
Potenta of eectrode measured aganst a reference
eectrode Eectrode meta n contact wth an eectroyte serves
as a ste where an eectrca current enters or eaves t to enter
the eectroyte S.C.E., Copper-Copper Suphate Eectrode, and
Patnum-Hydrogen Eectrode.
Referen"e e%e"tro#es
E%e"tro#e $otentia% 0s. NHE
1
203
Hg/Hg
2
C
2
, KC (1.0M)
(Norma Caome Eectrode,
NCE)
0.2810
Hg/Hg
2
C
2
, KC (3.5M)
(Saturated Caome
Eectrode, SCE)
0.2412
Ag/AgC, KC (0.1M) 0.2811
1 In aqueous soutons at 25
0
C (298 K)
Eectrode potenta represents reversbe work to remove unt
charge from eectrode surface through souton to reference
eectrode
Fg. 1.2 Expermenta technque for measurng eectrode
potenta
Eectrode potenta tabuated eectromotve seres usefu n
determnng whch of the two metas undergo corroson n the
presence of the other.
E%e"tromoti)e Series of Meta%s
Meta% Ion forme# $otentia%
Lthum L
+
2.96
Rubdum Rb
+
2.93
Potassum K
+
2.92
- - -
- - -
- - -
Iron Fe
+++
0.04
Hydrogen H
+
0.00
Antmony Sb
+++
-0.10
- - -
- - -
- - -
Patnum Pt
++++
-0.86
God Au
+
-1.36
God Au
+++
-1.50
Ga%)ani" Ce%%s
Ces consstng of two dssmar metas n contact wth each
other and wth a common eectroyte
Ga%)ani" Series
Me#i'm4 Sea Water
A"ti)e or Ano#i" En#4 Mg
Zn
A
-
-
-
Staness stee (Actve)
-
-
-
Brass
Cu
Bronze
Staness stee (Passve)
-
-
Graphte
Au
Pt: No*%e or Cat&o#i" En#
A!!%i"ations of Ga%)ani" Series
1. Metas and aoys at nobe end corroded east whe they at
actve end are corroded to maxmum extent
2. The farther apart meta and aoy are, the greater s potenta
generated. Metas and aoys farther apart shoud not be
connected together
3. When metas and aoys wth same group are couped, tte
danger of corroson
4. Same meta or aoy can assume dherent postons
Limitations of Ga%)ani" Series
1. Specc for each envronment
2. Corroson depends not ony on how far the metas and aoys
are n gavanc seres but to what extent they are poarzed
3. Gavanc seres cannot be used to predct ehect of change n
souton pH on corroson tendency
M + nH
2
O = M(OH)
n
+ nH
+
+ ne
M + 2n(OH)
-
= MO
n
-n
+ nH
2
O+ ne
E%e"tro"&emi"a% Rea"tions
Eectrochemca nature ustrated attack on Zn by hydrochorc
acd
When Zn n dute HC vgorous reacton; H
2
evoved Zn
dssoves, - souton of ZnC
2
. Reacton:
Zn + 2HC ZnC
2
+ H
2
(4.1)
C
-
not nvoved n reacton, equaton wrtten:
Zn + 2H
+
Zn
2+
+ H
2
(4.2)
Zn oxdzed to Zn
2+
and H
+
reduced to H
2
Eq. (4.2) dvded nto two reactons:
Oxdaton (anodc reacton) Zn Zn
2+
+ 2e (4.3)
Reducton (cathodc reacton) 2H
+
+ 2e H
2
(4.4)
Oxdaton ndcated producton of eectrons
Consumpton of eectrons reducton
(4.3) and (4.4) parta reactons both occur smutaneousy and
at same rate
Leads to one of most mportant basc prncpes of corroson:
during metallic corrosion, rate of oxidation equals rate of
reduction
Fg. 2-3
Corroson of Zn n HC eectrochemca process
Any reacton dvded nto two (or more) parta reactons of
oxdaton and reducton eectrochemca
A corroson cassed nto a few generazed reactons
Anodc reacton n corroson reacton oxdaton of meta to ts
on:
M M
+n
+ ne (4.5)
Number of eectrons produced equas vaence of on
Severa dherent cathodc reactons encountered n metac
corroson:
Hydrogen evouton 2H
+
+ 2e H
2
(4.6)
Oxygen reducton (acd soutons) O
2
+ 4H
+
+ 4e 2H
2
O
(4.7)
Oxygen reducton (neutra or
basc soutons) O
2
+ 2H
2
O + 4e 4OH
-
(4.8)
Meta on reducton M
3+
+ e M
2+
(4.9)
Meta deposton M
+
+ e M
(4.10)
Above parta reactons used to nterpret a corroson probems
Consder ron s mmersed n water exposed to atmosphere
Anodc reacton:
Fe Fe
2+
+ 2e (4.11)
Medum contans dssoved O
2
Cathodc reacton:
O
2
+ 2H
2
O + 4e 4OH
-
(4.12)
Overa reacton:
2Fe + O
2
+ 2H
2
O 2Fe
2+
+ 4OH
-
2Fe (OH)
2

(4.13)
Compound unstabe n oxygenated souton:
2Fe (OH)
2
+ H
2
O + O
2
2Fe (OH)
3
(4.14)
Product rust
Exampe repacement reacton nteracton of Zn wth CuSO
4

souton meta deposton:
Zn + Cu
2+
Zn
2+
+ Cu
(4.15)
as parta reactons:
Zn Zn
2+
+ 2e (4.16)
Cu
2+
+ 2e Cu (4.17)
Zn ntay pated wth Cu and eventuay products are Cu sponge
and ZnSO
4
souton
Durng corroson, more than one oxdaton and one reducton
reacton may occur
When aoy s corroded, component metas go nto souton as
ther respectve ons
Consder corroson of Zn n aerated HC
Two cathodc reactons possbe: evouton of H
2
and reducton of
O
2
Fg. 2-4
Snce rates of oxdaton and reducton must be equa, ncreasng
tota reducton ncreases Zn souton. Hence, acd soutons
contanng dssoved O
2
more corrosve than ar-free acds
Same ehect oxdzer present n acd soutons
Metas corrode more rapdy n mpure acd because two
cathodc reactons, H
2
evouton and Fe
3
reducton:
Fe
3+
+ e Fe
2+
Snce anodc and cathodc reactons are mutuay dependent,
possbe to reduce corroson by reducng rate of ether reacton
Fe not corrode n ar-free water or sea water
If surface of meta coated wth pant, rates of both reactons
reduced and corroson retarded
Corroson nhbtors functon by nterferng wth anodc or cathodc
reactons or both
Hgh-moecuar-weght amne retard H
2
evouton reacton
Good conductvty mantaned durng corroson reacton
Very pure water ess corrosve than mpure waters
$o'r*ai. #iarams
Potenta pH pots of varous systems
$o'r*ai. #iarams
Potenta pH pots of varous systems
Constructed from cacuatons based on Nernst equaton:
E = E
0
+ 2.3 (RT/nF) og (a
oxd
/a
red
)
and soubty data for varous meta compounds
For Fe-H
2
O system
Possbe to determne areas n whch ron, ron hydroxde, ferrous
rons etc are thermodynamcay stabe
That s these forms represent of owest free energy
Uses:
(1) To predct spontaneous drecton of reactons
(2) To estabsh compostons of corroson products
(3) To predct envronmenta changes whch w prevent or
reduce corrosve attack. E.g. regon abeed Fe ron nert
under these condtons of potenta and pH
Lmtaton same as any thermodynamc cacuaton
Represent equbrum condtons and shoud never be used to
predct veocty of a reacton
E%e"tro#e 5ineti"s
In engneerng, ma|or nterest knetcs or rate of corroson
Potenta of eectrode shfted from equbrum potenta when
net oxdaton and reducton processes occur
Ths devaton !o%ari6ation
Magntude o)er)o%tae 273
Zn eectrode after coupng potenta = 0.66V
q = 0.76 0.66 = 0.10V
E."&ane "'rrent #ensit,
At equbrum, r
1
= r
2
=
0
/nF

0
= Exchange current densty
0aria*%es a+e"tin i
8
1. Redox Reacton
S,stem E%e"tro#e
materia%
So%'tion i
8
9 A:"m
2
Ce
+4
/Ce
+3
Pt H
2
SO
4
3.99x10
-5
Fe
+3
/Fe
+2
-Do- -Do- 2.52x10
-3
2. Eectrode Composton (Fg.)
3. Temperature
Increases wth temp.
4. Surface Roughness

0
expressed n terms of pro|ected surface area.
Hence, dependent on surface roughness
For H
+
/H
2
,

0 (Pt, brght)
= 10
-3
A/cm
2

0 (Pt, Patnzed)
= 10
-2
A/cm
2
5. Surface Impurtes
E.g., For H
+
/H
2
system,
0
s reduced by As, S, & Sb
Mi.e#;$otentia% T&eor,
Conssts of two hypotheses:
1. Any eectrochemca reacton dvded nto two or more parta
oxdaton and reducton reactons
2. No net accumuaton of eectrc charge durng eectrochemca
reacton
Frst hypothess expermentay demonstrated
Second statement of aw of conservaton of charge
During corrosion of electrically isolated metal, total rate of
oxidation must equal total rate of reduction
Mi.e# E%e"tro#es
- those n contact wth two or more oxdaton-reducton
systems
Fg. 9-18 Eectrode knetc behavour of pure Zn n acd
souton.
Fg. 2 Corroson of a meta under reducton-dhuson contro
So far, smpest corroson systems, meta n contact wth a
snge redox system.
Actua condtons envronment more compcated
Basc prncpe of mxed eectrode theory appy to compex
systems
In gure 9-20, tota rate of oxdaton foows meta dssouton
rate unt reversbe hydrogen potenta s reached and an
ncrease s noted because of the addton of hydrogen-oxdaton
currents
In a smar fashon, tota rate of reducton s determned by
summng the tota reducton currents correspondng to ferrc
on reducton, hydrogen on reducton, and meta on reducton.

corr
=
(Fe
+3
Fe
+2
)
+
(H
+
H2)
Addton of an oxdzer shfts corroson potenta to E
corr
and
subsequenty ncreases corroson rate from `
corr
to
corr
and
decreases hydrogen evouton from `
corr
to
(H
+
H2)
.
Ths phenomenon depoarzaton.
$o%ari6ation
Rate of eectrochemca reacton mted by physca & chemca
factors
Reacton poarzed or retarded by these envronmenta factors
Poarzaton dvded nto two actvaton and concentraton
Actvaton process controed by reacton sequence at meta-
eectroyte nterface
Iustrated by hydrogen-evouton reacton on Zn Fg. 2-5
Speces must rst be adsorbed to surface before reacton can
proceed step 1
Foowng ths, eectron transfer (step 2) must occur
Step 3 two hydrogen atoms then combne to form a bubbe (step
4)
Speed controed by sowest step
Concentraton poarzaton eectrochemca reactons controed
by dhuson Fg. 2-5
No. of ons sma
Reducton controed by dhuson
Actvaton poarzaton controng factor n meda contanng
hgh concentraton of actve speces (concentrated acds)
Concentraton poarzaton predomnates when concentraton of
reducbe speces sma (dute acds, aerated sat soutons)
Concentraton poarzaton durng meta dssouton negected
Dependng on what knd of poarzaton s controng reducton
reacton, envronmenta varabes produce dherent ehects
E.g., any changes that ncrease dhuson rate w decrease
ehects of concentraton poarzaton ncrease reacton rate
Increasng veocty or agtaton ncrease rate f cathodc
process s controed by concentraton poarzaton
E)an<s Diarams
Poarzaton characterstcs provde the bass for a convenent
graphca method of presentng nformaton on corroson n the
form of corrosion velocity diagrams, ntroduced by Evans
Method dspay on the same dagram the poarzaton
characterstcs of a eectrode processes that contrbute anodc
and cathodc reactons
Constructon:
1. Equbrum potentas, E` for possbe reactons are
determned, appyng Nernst equaton for prevang
actvtes.
E.g. Corroson of ron n neutra aerated water
Eectrochemca reactons:
Fe
2+
+ 2e
-
= Fe
1/2O
2
+ H
2
O + 2e
-
= 2OH
-
Assume - pH of water s 7, saturated wth O
2
, & a
Fe
2+
= 10
-6
Appy Nernst equaton
E`
Fe
2+
= -0.62 V SHE and E
O2
= 1.0V SHE
2. Axes abeed E and drawn Fg. 3.13
3. Equbrum vaues of E` marked on potenta axs and
overpotentas potted as functons of for anodc and
cathodc poarzaton
Meta acqures a potenta between E`
Fe
2+
and E`
O2
, caed
corrosion potential, E
CORROSO!
Conservaton of eectrons determnes that corroson potenta
has a vaue at whch tota anodc and cathodc currents are
equa
Anodc current corrosion current, i
CORROSO!
and meta s
dssoved at Faradacay equvaent rate
Sometmes, anodc reacton s sustaned by two cathodc
reactons, e.g., n aerated dute acd, where both oxygen
reducton and hydrogen dscharge can contrbute to tota
cathodc current
Corroson potenta assumes a vaue at whch anodc current
equas sum of currents from cathodc reactons
E.am!%e
Usng the foowng data, show that the absorpton of oxygen
s the domnant cathodc reacton sustanng the corroson of
ron n neutra water n equbrum wth ar.
Data" For the reacton Fe
2+
+ 2e
-
= Fe:
E
0
= -0.44 V SHE
a
Fe
2+
= 10
-6
(assume)
Tafe constants: b = 0.06 V/decade,
0
= 10
-11
A cm
-2
.
For the reacton 2H
+
+ 2e
-
= H
2
on ron:
E
0
= 0.00 V SHE.
Tafe constants: b = 0.12V/decade,
0
= 10
-10
A cm
-2
at
pH 7
Corroson potenta, E
CORROSION
, on ron n aerated water
at pH
7: -0.45 V SHE
SOLUTION:
#nodic Current Density Due to Dissolution of ron"
Appyng the Nernst equaton yeds the equbrum
potenta, E`
Fe
2+
:
E`
Fe
2+
= -0.44 (0.0591/2)og(1/10
-6
) = -0.62 V SHE
Appyng the Tafe equaton yeds the anodc dssouton
current for ron:
q
ANODIC
= -b og
0
+ b og
ANODIC
Substtutng for q
ANODIC
, b and
0
:
E
CORROSION
E`
Fe
2+
= -0.06 og 10
-11
+ 0.06 og
ANODIC