In galvanostatic method, current flowing between specimen and a Pt

auxiliary electrode is changed using a variable resistance and electrode

potential of specimen is measured as a function of time
In potentiostatic method, electrode potential is changed using potentiostat
and current flowing is recorded as a function of time
For normal metals, both methods give same results
For active-passive metals, potentiostatic anodic polarization curves preferred
Polarization curves to measure corrosion rate
Corrosion current density obtained converted to corrosion rate through
Faradays law!
Corrosion rate "mpy# $ "%&'(x%)
*
+
e
,i
corr
#,-
Corrosion rate "mdd# $ .&/(x%)
*
+
e
, i
corr
+here +
e
$ 0lectrochemical e1uivalent "mg,coulomb#
i
corr
$ Corrosion current density "2,cm
'
#
- $ -ensity "gm,cm
3
#
-etermination of polarization curves and hence corrosion rate is very 1uic4
Complete curve determined in less than one hour several days or wee4s
rate of corrosion by weight loss measurements
-ue to their versatility, polarization measurements used to!
%& 5tudy the effect of change in material composition or environment on
corrosion rate
'& -evelop alloys with improved corrosion resistance
3& Control 1uality during manufacture of specific material of 4nown
behaviour
(& 6easure corrosion rate of structures which are not easily accessible, e&g&
underground pipeline, tan4s, and large chemical plant components
7& -etermine very low corrosion rates "8)&%mpy# important food,
pharmaceuticals etc& measured 1uic4ly and accurately
Following polarization measurement methods to determine corrosion rate
3.4.1 Polarization break method
9asis anodic and cathodic polarization curves straight line segments having
different slopes
Current at which change in slope "brea4# occurs in cathodic and anodic curves i
c

and i
a
i
corr
$ i
a
&i
c
,"i
a
: i
c
# "3&%#
Provides additional data
0xamination of curves corrosion under which control
In Fig& 7&%%, Polarization curve of iron cathodic control
Curve of stainless steel mixed control
3.4.2 Tafel extrapolation method
;his method is based on the fact that away from corrosion potential, there is a
potential region in which experimentally determined cathodic and anodic
polarization curves superimpose the true polarization curves&
;his potential region Tafel region, - slope, Tafel slope.
Fig&7&%' ;afel region for cathodic and anodic polarization curves of a corroding
metal, assuming that cathodic reaction is <
:
reduction&
Clear from Fig&7&%' that extrapolating line representing ;afel region in either
cathodic or anodic polarization curve to corrosion potential corrosion current
density, i
corr
, - used to calculate corrosion rate&
Further extrapolation of ;afel region in cathodic polarization curve to reversible
hydrogen electrode potential exchange current density for <
:
,<
'
e1uilibrium in
the given electrolyte&
+hen <
:
reduction is the only cathodic reaction occurring, then,
0
corr
0
<:
,
<'
$
cathodic
=r, 0
corr
: )&)7' p< $ - log "i
corr
, i
) <:,<'
#
2bove e1uation used to calculate either i
) <:,<'
if 0
corr
and i
corr
are 4nown or i
corr
if
0
corr
and i
) <:,<'
are 4nown&
>imitations!
a& 2ssumption total specimen surface is acting as either cathode or
anode& ;his could lead to wrong results& 0&g& if a specimen is
corroding with %!% cathode to anode area ratio, then amount of
current actually flowing to the cathodic areas would only be one-
half of that estimated by extrapolation method& ;hus, estimated
corrosion rate, would be double the actual corrosion rate&
b& For accurate extrapolation, ;afel region must extend over a
considerable current range& <owever, when there is either a strong
concentration polarization or resistance polarization or more than
one reduction reaction "due to the presence of impurities#, ;afel
region becomes less distinct& In some cases, effect of concentration
polarization can be reduced by either stirring or flowing
electrolyte or rotating electrode& ?esistance polarization may be
reduced by using properly designed >uggin probe and modifying
the galvanostatic circuit& <owever, in many cases, non-linearity of
these regions might cause a serious limitation to the applicability
of this method&
c& ;hough faster than weight loss method, still several hours are
re1uired to obtain data for each polarization curve& ;his may not be
convenient in many cases especially in plant applications&
d& Polarization of test specimen by several hundred millivolts
from the corrosion potential can disturb the system enough to
distort further periodic measurements, which might be made using
the same specimen&
3.4.3 Linear Polarization Method
>imitations of ;afel extrapolation method overcome by linear polarization
method also 4nown as polarization resistance method&
6ethod was discovered in mid-%@7)s&
Aow widely used to monitor corrosion in plants&
Commercial instruments available - give direct read-on of corrosion rate in mpy&
Principle summarized within %) mB more noble or more active than corrosion
potential, applied current density linear function of electrode potential Fig&7&%3&
Corrosion potential is used =vervoltage reference point and plot of =vervoltage versus applied
anodic or cathodic current is shown on a linear scale&
5lope related to 4inetic parameters!
"0,I
app&
# $ "
a

c
,'&3 i
corr
"
a
:
c
#
"0,I
app&
# in ohms&
5lope controlled by i
corr
2ssuming that values of )&%'B represent average of all corrosion systems,
"0,i
app&
# $ )&)'/, i
corr
2dvantages of electrochemical corrosion rate measurementsC particularly linear
polarization techni1ue!
%& Permit rapid corrosion rate measurements& Can be used to monitor corrosion
rate in various process streams&
'& 6ay be used for accurately measuring very low corrosion rates "less than )&%
mpy#& Important in nuclear, pharmaceutical, and food processing industries,
where trace impurities and contamination are problems&
3& 6ay be used to measure the corrosion rate of structures that cannot be
visually inspected or subDected to weight loss tests& 0&g& underground pipes
and tan4s and large chemical plant components&
4 CORROSO! PROT"CTO!
Corrosion prevented by
i& 6aterials 5election
ii& 2lteration of 0nvironment
iii& -esign Factors
iv& Cathodic and 2nodic Protection
v& Coatings
4.1Material# Sele$tion
Following points!
%& 6etals and alloys
'& 6etal Purification
3& Aonmetallics
4.1.1 Metal# and allo%#
6ost common method of preventing corrosion selection of proper metal or
alloy
5everal EnaturalF metal-corrosive combinations!
%& 5tainless steels nitric acid
'& Aic4el and nic4el alloys caustic
3& 6onel hydrofluoric acid
(& <astelloys hot hydrochloric acid
7& >ead dilute sulphuric acid
/& 2luminium atmospheric exposure
*& ;in distilled water
.& ;itanium hot strong oxidizing solutions
@& ;antalum ultimate resistance
%)& 5teel concentrated sulphuric acid
1.
2. 4.1.2 Metal p&rifi$ation
Corrosion resistance of pure metal better than one containing impurities or
other elements
Pure metals expensive, soft and wea4
Good example of pure metal not expensive 2l
Commercially pure metal is used for handling <
'
=
'
>ocalized attac4 if iron impurity separates
6ax& iron content limited
2nother example is arc-melted Hr, - more corrosion resistant than induction
melted Hr more impurities
Hr important in atomic energy application where a little corrosion is too much
4.1.3 !onmetalli$#
Involves integral or solid nonmetallic construction and also sheet linings or
coverings of substantial thic4ness
7 general classes!
"%# rubbers
"'# plastics
"3# ceramics
"(# carbon and graphite
"7# wood
?ubbers and plastics as compared to metals and alloys wea4er, softer, more
resistant to chloride ions and <Cl, less resistant to strong <
'
5=
(
and
oxidizing acids such as <A=
3
, less resistant to solvents and have low
temperature limitations
Ceramics excellent corrosion and high temperature resistance
disadvantages brittleness and lower tensile strength
Carbons show good corrosion resistance, electric and heat conductivity
fragile
+ood attac4ed by aggressive environments
4.2'lteration of "n(ironment
4.2.1 Chan)in) media
;ypical changes!
"%# >owering temperature
"'# -ecreasing velocity
"3# ?emoving oxygen or oxidizers
"(# Changing concentration
Lo*erin) temperat&re
Isually causes pronounced decease in corrosion rate
Inder some conditions temperature changes have little effect
Fig& '-%%
In other cases increasing temperature decreases attac4
2s hot fresh or salt water raised to boiling point result of decrease in
oxygen solubility with temperature
9oiling sea water less corrosive than hot sea water
+e$rea#in) (elo$it%
=ften used as a practical method
Belocity generally increases corrosive attac4 some exceptions Fig& ' -%)
6etals that passivate stainless steels better resistance to flowing media
than stagnant solutions
Bery high velocities avoided erosion corrosion
Remo(in) ox%)en or oxidizer#
Bery old corrosion control techni1ue
9oiler feed water was deaerated by passing through large mass of scrap steel
6odern practice vacuum treatment, inert gas sparging or oxygen
scavengers
nhibitor# and pa##i(ator#
Inhibitor substance which when added in small concentrations to
environment decreases corrosion rate
Inhibitor - considered as retarding catalyst
Passivators oxidizing inhibitors
Possible to classify inhibitors according to their mechanism and composition
'd#orption t%pe inhibitor#. ?epresent largest class of inhibiting substances
=rganic compounds which adsorb on metal surface and suppress metal dissolution
and reduction reactions
;ypical organic amines
2dsorption inhibitors commonly used in acid pic4ling of hot rolled products to
remove blac4 mill scale 4nown as pic4ling inhibitors
2lso used to clean steel water pipes clogged with rust and clean boiler tubes
encrusted with CaC=
3
or iron oxide scales
Ise results in!
"%# saving of acid
"'# saving of steel and
"3# reduction in acid fumes caused by <
'
evolution
=ils, greases or waxes containing small amounts of organic inhibitors used for
protecting steel surfaces temporarily from rusting during storage or shipment
slushing compounds
5lushing compounds include organic amines and various oxidation products of
al4ali and al4aline earth salts of sulphonated oils
,%dro)en e(ol&tion poi#on#. 5ubstances 2s and 5b ions retard <
'

evolution reaction
Bery effective in acid solutions ineffective in environments where other
reduction processes =
'
reduction controlling cathodic reactions
S$a(en)er#. 2ct by removing corrosive reagents from solution
0xamples sodium sulphite and hydrazine which remove dissolved =
'
from
a1ueous solutions!
'Aa
'
5=
3
: =
'
'Aa
'
5=
(
"7&%#
A
'
<
(
: =
'
A
'
: '<
'
= "7&'#
+or4 in solutions where =
'
reduction is controlling corrosion cathodic reaction
not effective in strong acid solutions
Oxidizer#. 5ubstances as chromate, nitrate and ferric salts
Ised to inhibit corrosion of metals and alloys which demonstrate active-
passive transitions iron and its alloys and stainless steels
>imitations!
- suitable only when concentration is sufficient to achieve passivity& If
insufficient, - dangerous since critical passivation potential not exceeded
corrosion occurs at enhanced rate
- >ocal brea4down of passivity due to inhibitor depletion could result in
pitting corrosion
=ccurs in crevices and at base of screw threads where passivator
depletion is most li4ely
Aitrites are used as inhibitors for antifreeze cooling waters
2lso used ")&% 'J# to inhibit cutting oil water emulsions employed in machining
of metals
Inhibition of internal surfaces of pipelines transporting gasoline and other
petroleum products also accomplished by continuously inDecting 7-3)J AaA=
'

solution into the line
Chromates ")&)(-)&%J# applied mostly as inhibitors for recirculating cooling
towers, internal combustion engines, rectifiers etc&
<igher concentrations of sodium dichromate is used in fresh waters of high
chloride concentrations above %) ppm or at higher temperatures
.apo&r Pha#e nhibitor#. Bery similar to organic adsorption type inhibitors
and possess very high vapour pressure
Ised to inhibit atmospheric corrosion of metals without being placed in the
vicinity of metal to be protected and transferred by sublimation and condensation
to metal surface
0ffective if used in closed spaces inside pac4ages or interior of machinery during
shipment
0xamples dicyclohexylamine chromate and benzotiazole for protecting Cu,
phenyl thiourea and cyclohexylamine chromate for brass
2t metal surface, it dissolves in minute traces of any moisture present
6echanism electrochemical consists of retardation of either anodic or cathodic
processes
Inhibitors specific in terms of metal, environment, temperature and concentration
range
Concentration and type of inhibitor to be used in a specific corrosive determined
by testing
+hen two or more inhibiting substances are added, inhibiting effect greater than
that which would be achieved by either of the two "or more# substances alone
synergistic effect
Aot possible to add inhibitors to all corrosive systems because they contaminate
the environment
6any inhibitors toxic and application limited to those media which will not be
used in the preparation of food or other products which will come in contact with
humans
2rsenic salts powerful inhibiting effect in strong acids limited application
Inhibitors used in closed systems corrosive environment either contained or
recirculated
Aot practical in Eonce throughF systems
>ose effectiveness as concentration and temperature of environment increase
4.3+e#i)n
2s important as choice of materials
-esign should consider mechanical and strength re1uirements together with
allowance for corrosion
/.3.1 0all thi$kne##
5ince corrosion penetrating action, - necessary to ma4e allowances for
reduction in thic4ness in designing pipes, tan4s and other components
In general, wall thic4ness made twice the thic4ness that would give desired life
/.3.2 +e#i)n r&le#
6any followed for best corrosion resistance
"%# +eld rather than rivet tan4s and other containers
"'# -esign tan4s and other containers for easy draining and cleaning
"3# -esign system for easy replacement of components that are expected to
fail rapidly in service
"(# 2void excessive mechanical stresses and stress concentrations in
components exposed to corrosive media
"7# 2void electric contact between dissimilar metals to prevent galvanic
corrosion&
Ise similar materials or insulate different materials
"/# 2void sharp bends in piping systems
Important in systems susceptible to erosion corrosion lead, Cu and their
alloys
"*# 2void hot spots during heat transfer operations
".# -esign to exclude air
"@# 6ost general rule! avoid heterogeneity
-issimilar metals, vapour spaces, uneven heat and stress distributions
and other differences between points in the system lead to corrosion
damage
In design attempt ma4e all conditions as uniform as possible
throughout entire system
4.4Cathodi$ and 'nodi$ Prote$tion
/.4.1 Cathodi$ prote$tion
Principle explained by considering corrosion of a typical metal 6 in acid
environment
0lectrochemical reactions dissolution of metal and evolution of hydrogen gas!
6 6
:n
: ne "7&3#
'<
:
: 'e <
'
"7&(#
Cathodic protection achieved by supplying electrons to metal
;wo ways!
"%# by external power supply
"'# by galvanic coupling
Fig&/-% protection by impressed current
0xternal dc power supply connected to underground tan4