TK 5021 PROSES &

PENGENDALIAN KOROSI

ENVIRONMENTS
 ATMOSPHERIC CORROSION

Atmospheric corrosion = corrosion of materials exposed to

air + its pollutants, immersed in a liquid
Can be classified into : dry, damp and wet categories
Damp & wet atmospheric corrosion corrosion in the
presence of moisture films (microscopic & visible electrolyte
layers) on the surface : damp moisture film is produced at a
critical humidity level by adsorption of water molecules,
while the wet film dew, ocean spray, rain water, water
splashing
TYPES OF ATMOSPHERES & ENVIRONMENTS
severity of atmospheric corrosion depends on environments
which are classified as rural, urban, industrial, marine, or its
combinations
Rural
The least corrosive, does not contain chemical pollutants but
organic & inorganic particulates ; principal corrodents are
moisture, oxygen, CO2
Urban
There is little industrial activity ; contaminants + SOx & NOx
from motor vehicles & domestic fuel emissions
Industrial
heavy processing facilities ; contains SO2, Cl-, PO43-, NO3-
Marine
fine windswept Cl- particles deposited on surface
highly corrosive ; corrosiveness depends on wind direction, wind
speed & distance from the coast
Bandung, Cibinong, Menteng, Anyer, Kemayoran dan Tanjung Priok
PETA KOROSIVITAS ATMOSFER
 Maps of atmospheric corrosiveness has been made for some
regions, e.g. South Africa, based on 20 years of atmospheric
exposure testing
 The coastal regions (4 5 km inland) : the most corrosive
atmospheres due to windswept Cl- + high humidity level
Effects of rainfall : provides moisture necessary for corrosion
reactions, but also cleans by washing out or diluting corrosive
surface species
In urban regions, deicing salts applied to road surfaces in winter
are responsible for high corrosion rates

THEORY OF ATMOSPHERIC CORROSION

Electrochemical corrosion process requires the presence of an
electrolyte on metal surface
Thin-film invisible electrolytes form on metal surface under
atmospheric exposure with certain critical humidity level
Critical humidity for iron = 60 % in atmosphere free of SO2
Critical humidity depends on the corroding material, the tendency
of corrosion products & surface deposits to absorb moisture and
the presence of atmospheric pollutants
without SO2
 In the presence of thin-film electrolytes, atmospheric corrosion
proceeds by balancing anodic and cathodic reactions: anodic
oxidation reaction = dissolution of the metal, cathodic reaction =
the oxygen reduction reaction
2Fe 2Fe2+ + 4e-
O2 + 2H2O + 4e- 4OH-

Corrosive contaminant concentrates in the thin electrolyte films,

especially under alternating wet & dry conditions; O2 from the
atmosphere is also available in the electrolyte film
Cathodic processes
Surface electrolyte = neutral or slightly acidic hydrogen
evolution reaction can be ignored
The most important cathodic reaction is the reduction of
atmospheric oxygen : O2 + 2H2O + 4e- 4OH-
Atmospheric oxygen diffuses through electrolyte film to metal
surface diffusion limited current density, but applicable only to
an electrolyte-layer thickness ~ 30 m under isothermal cond.
Calculated il of oxygen reduction in 30 m thick electrolyte-
layer > observed corrosion rates overall atmospheric
corrosion rates to be controlled by anodic reaction(s)
Anodic Process
General anodic reaction : M Mn+ + ne-
Overall rate of anodic metal dissolution depends on :
- corrosion products formation
- solubility of corrosion products in surface electrolyte
- passive film formation
 Passive film corrosion products, this film is
- more tightly adherent
- of lower thickness
- provide a higher degree of protection
- attack on surface protected by passive film localized corrosion
Corrosion product formation & breakdown processes = complex
reaction sequences to explain observed atmospheric corrosion
rates: kinetic model rather than equilibrium
Theoretical treating of atmospheric corrosion phenomena based on
6 regimes GILDES-type model : gaseous region (G), gas-to-liquid
interface (I), surface liquid (L), electrodic layer (E) and corroding
solid (S)
Gaseous-layer : entrainment detrainment of species across liquid
interface, chemical transformations in gas phase, effects of solar
radiation on photosensitive reactions, temperature effects on gas
phase reaction kinetics
 Interface regime : molecule transfer
into liquid layer prior to its chemical
interaction in the liquid phase,
species from liquid phase are
volatilized into gas phase
Liquid regime : aqueous film thickness
& its effect on species concentration,
chemical transformations, reactions
of metal ions produced by
electrochemical corrosion
Deposition zone : accumulation of
corrosion products & their
nucleation on the substrate.
Corrosion products naturally
formed minerals ; the most
thermodynamically stable = the
dominant species
 Inner electrolyte = solution trapped inside/under deposited corrosion
products ; corrosion product layers = membranes with various
resistance to ionic transfer ; passive films = high resistance membrane
Corroding surface has a complex charge distribution microscopic
layer of adjacent electrolyte with chemical & physical properties
bulk electrolyte electrodic regime influencing reaction kinetics
Solid regime: mechanistic steps of solid dissolution & their kinetics
Important Practical Variables in Atmospheric Corrosion

Time of Wetness
= presence of electrolyte on corroding surface, determines the
duration of electrochemical processes ; depends on critical relative
humidity : primary CH clean surface, secondary CH
hygroscopic corrosion products, tertiary CH capillary
condensation of moisture in corrosion products electrolyte
formation in microscopic surface cracks & metal surface dust
particle interface
other sources of surface electrolyte : chemical condensation by Cl-,
SO42-, CO32-; adsorbed molecular water layers, direct moisture
precipitation (ocean spray, dew, rain)
rain effects are ambiguous: providing electrolyte for corrosion
reactions, but wash out / diluting corrosive surface species
 Sulfur Dioxide
product of the combustion of sulfur containing fossil fuels
adsorbed on metal surfaces, has a high solubility in water, tends to
form sulfuric acid in the presence of surface moisture films
SO2 + O2 + 2e- SO42-
Electrons are originated from anodic dissolution reaction and from
oxidation Fe2+ Fe3+
SO42- formation of FeSO4 (corrosion product in industrial
atmosphere, found in layers at metal surface) which is hydrolyzed
by reaction FeSO4 + 2H2O FeOOH + SO42- + 3H+ + e-
The sulfate ions lead to autocatalytic type of attack on iron
H+ may accelerate corrosion, but countered by the buffering
effects of hydroxide & oxide corrosion products
Zn: SO42- stimulate corrosion without autocatalytic effect, because
corroding Zn is covered by protective ZnO and Zn(OH)2
Moderate atmosphere: SO42- in Zn corrosion products is slightly
soluble
 Chlorides
atmospheric salinity increases atmospheric corrosion rates
enhances surface electrolyte formation by hygroscopic salts such as
NaCl and MgCl2
Ferrous metals: Cl- impedes formation of Fe(OH)2 (stable passive
species); while Fe-Cl complexes is soluble further attack
Zn & Cu: their chloride salts are less soluble less prone to Cl-
induced corrosion damage
H2S is very corrosive to most metals
Cl2 & HCl + moisture more corrosive than Cl salts because of its
acidic character
NOx (emmited by combustion processes) accelerate atmospheric attack;
its deposition rate < SO2 lower importance
The effects of ozone are neglected for Fe & Zn, but accelerates attack on
Al & Cu
Solid matter deposits stimulate atmospheric corrosion by :
- reducing critical humidity level
- provide anions
- microgalvanic effects of more noble deposits
 Temperature
T reactions & diffusion rate corrosion rate
T relative humidity , evaporation rate time of wetness
(TOW) corrosion rate
Indoor atmosphere: RH , T corrosion rate , example :
AC without dehumidifier T atmospheric corrosion
T < Tmelt,H2O electrolyte film solidify electrochemical
corrosion 0, example : atmospheric corrosion rates in very cold
climates are very low

ATMOSPHERIC CORROSIVENESS & CORROSION

RATES

ISO Methodology
ISO classification is based on assumption that TOW & corrosive
pollutants (SO2 & Cl-) level determine atmospheric corrosiveness
On April 28, 1988 a nineteen-year-old
Boeing 737 aircraft, operated by Aloha
airlines, lost a major portion of the
upper fuselage near the front of the
plane, in full flight at 24,000 feet.
 TOW (h/yr) for T > 0 C
& RH > 80 %
TOW 10 T1
10 < TOW 250 T2
250 < TOW 2500 T3
2500 < TOW 5500 T4
5500 < TOW T5

Airborne Salinity (Cl

deposition rate, mg.m2-
.day1-)
S 60 S1
60 < S 300 S2
300 < S S3

2 fundamental approaches to classify atmospheric corrosiveness

 SO2 concentration (g.m-3) SO2 deposition rate (mg.m-2.day-1)
PC 40 PD 35 P1
40 < PC 90 35 < PD 80 P2
90 < PC 80 < PD P3

corrosion rate categories :

ISO corrosiveness category can be
determined using 3 key variables
category (Table 2.2 & 2.3)

Different corrosiveness categories

apply to different types of metal

Atmospheric corrosion rate can be

estimated for the determined
corrosiveness category

Atmospheric corrosion rates are not

linear with time initial rate ( 1
year exp) & stabilized longer term
rates for different metals
ATMOSPHERIC CORROSION RATE AS A FUNCTION
OF TIME

Buildup of corrosion products reduce corrosion rate over time

Pourbaix: linear bilogarithmic law, applicable to rural / urban /
marine / industrial atmospheres and for C-steels/weathering steels
/galvanized steels/aluminized steels

where p = corrosion penetration & t = exposure time

The mean corrosion rate :

Instantaneous corrosion rate :

atmospheric behavior of a material at a location can be defined

by parameters A & B :
- initial corrosion rate st year exposure, described by A
- B = measure of the long-term decrease in corrosion rate :
 B = 0.5 law of corrosion penetration increase = parabolic with
diffusion through corrosion product layers as rate controlling step
B < 0.5 corrosion products = protective, passive character
B > 0.5 nonprotective corrosion products (loosely adherent,
flaky rust layers)
Linear bilogarithmic law can predict long-term corrosion from
short exposure tests ; this extrapolation valid for 20 30 years
 NATURAL WATERS
1980: water required for US industries 525 billion liters/day
with make-up of 140 billion liters daily
Water properties :
- universal solvent contains various impurities (source of
troublesome deposit in water lines / boilers / ), dissolved
oxygen = corrosive on metals
- rain/snow = precipitation containing dissolved gases & suspended
mineral matter of the atmosphere
- sources of fresh water : surface water and groundwater
- surface water flows across the land surface solubilizes
minerals, fine particles & organic matter in suspension
- ground water (source of well & spring water) : constant T, no
suspended matter, higher mineral content
WATER CONSTITUENTS AND POLLUTANTS

The important constituents can be classified as :

a. dissolved gases (O2, N2, CO2, NH3, SOx)
surface waters ~ saturated with O2 ; + green algae super
saturation ; underground water + Fe(HCO3)2 O2-free ; natural
waters + dissolved solids 1000 ppm O2 solubility
 H2S & SO2 : result of pollution or bacterial activity, initiate or
accelerate corrosion of most metals
CO2 bicarbonate content ; normal carbonate is rarely found
naturally ; Ca(HCO3)2 is the most abundant, CaCO3 if heated
CO2 < required to keep Ca(HCO3)2 in solution water is
supersaturated with CaCO3, pH scaling ; deposit is
continuous & adherent metal surface is isolated from water
protected from corrosion ; CO2 >> no deposition of CaCO3
& existing deposit will be dissolved no protection by CaCO3
scale
b. dissolved mineral salts : Ca2+, Mg2+, Na+, HCO3-, SO42-, Cl-, NO3-
electrical conductivity
Cl- : effectiveness of natural protective films
NO3- : similar effects as Cl- but in smaller concentration
SO42- : behave similarly on C-steels; high-sulfate waters attack
concrete; adversely affect some inhibitor performance; nutrient of
corrosive anaerobic bacteria
 silica : present as colloidal suspension & dissolved silicates ;
sometimes applied as corrosion inhibitor, but also have trivial
effect, depend on its form/molecular structure
hardness : determined by Ca- & Mg-salts content ; mineral salts
make water more basic more aggressive to metals ; presence
of salts in lime scale deposits = cause of corrosion damage in
water pipelines & boilers
c. pH of water : in the range of 4.5 8.5 ; copper is slightly
corroded in acidic water green staining, redeposition of
copper galvanic corrosion on Al or galvanized steels
pitting ; critical pH value for most waters: 7.0, soft water +
organic acids higher pH
d. pollutants (heavy metals) : As, Cd-, Cr-, Cu- (from corrosion of
alloys & plated surfaces, electroplating wastes, industrial
discharges, exterior paints & stains), Pb (from leaded gasoline,
batteries, paints), Hg (from natural erosion & industrial
discharges), Zn (from tires, galvanized metal, paints)
 some heavy metals have a maximum contaminant limit (MCL) :
Cd (+Zn) from corrosion of galvanized pipes & fittings
Sb (+ Pb as hardening agent) from corrosion of lead pipes &
fittings, rarely detectable
Pb, the most significant heavy metal, from corrosion of plumbing
materials and joints of copper pipes & fittings
Cu + Pb commonly used in plumbing materials, corrodible
1.3 ppm Cu or 15 ppm Pb in tap water = corrosive water

SATURATION & SCALING INDICES

CaCO3 = scaling compound at equilibrium: solubility product, Ksp
= ion-activity product : aCa.aCO3 ; the saturation level of water = ratio
of IAP to Ksp

Water is saturated with CaCO3 when it will neither dissolve nor

precipitate CaCO3 scale at constant T and undisturbed, SL = 1.0
Water is undersaturated if it can still dissolve CaCO3, SL < 1.0
Supersaturated water will precipitate CaCO3 in static condition, SL
> 1.0 driving force for CaCO3 crystal formation & growth
Thick layer deposit protective layer = layer of negligible
thickness which do not impede water / heat flow & self-healing
Water in equilibrium of CaCO3 is corrosive to steel because it
cannot form CaCO3 deposit
Supersaturated water may inhibits corrosion if its scale is adherent &
nonporous
The Langelier Saturation Index (LSI)
LSI = pH pHs ; pHs = pH at saturation of CaCO3
pHs = (pK2 pKs) + pCa + pAlk where
pK2 = - log K2 = - log ([H+] [CO32-]/[HCO3-])
pKs = - log Ksp ; pCa = - log [Ca2+]
pAlk = - log (total alkalinity)
based on these reactions pH of 1 unit [CO32-] 1/10 x
IAP 1/10 x SL = IAP/Ksp 1/10 x &
LSI by 1 unit
 LSI < 0 water is undersaturated of CaCO3
SL-indices: potential for scale formation in unperturbed water for
infinite period of time ; LSI stability of existing CaCO3 scale,
indicator of corrosiveness toward steel / construction materials
Supersaturated water film of CaCO3 scale as corrosion barrier
of mild steel in highly buffered water. LSI do not guarantee this
behavior. Low buffer capacity water, supersaturated with CaCO3
tubercular deposits do not inhibit corrosion.

Ryznar Stability Index

RSI = 2 pHs pH
RSI < 6 : index scale tendency
RSI > 7 : CaCO3 formation protective corrosion inhibitor film
RSI > 8 : mild steel corrosion
Puckorius Scaling Index
PSI quantify the relationship between saturation state & scale
formation by incorporating buffering capacity of water into index
Water with high Ca IAP, + low alkalinity & buffering capacity
high SL ; plot of IAP vs precipitate : Ca precipitated pH
due to low buffering capacity
[CO32+] IAP tend to form scale but its quantity is <<
PSI = 2 pHeq pHs
pHeq = 1.465 x log [alkalinity] + 4.54
[alkalinity] = [HCO3-] + 2[CO32-] + [OH-]

Larson-Skold Index
describes water corrosiveness toward mild steel
= ratio of equivalent per million (epm) of SO42- & Cl- to CO32- +
HCO3- alkalinity
the index is a useful tool to predict the aggressiveness of once-
through cooling waters useful as indicator of applicability of
corrosion inhibitor that rely on natural alkalinity & film-forming
capacity of cooling water
index < 0.8 Cl & SO4 will not interfere natural film formation
0.8 < index < 1.2 Cl & SO4 may interfere natural film formation ;
higher corrosion rate can be anticipated
index > 1.2 index tend to have high corrosion rates of
local type