Filiform Corrosion

Filamentary corrosion occuring on metal surface. This is a special form of crevice corrosion.
Normally they appear under protective films and also referred as Underfilm Corrosion.
Commonly seen in enameled or lacquered surfaces of food and beverage cans exposed to
atmosphere.
Steel, Magnesium, and Al surfaces covered with tin silver, gold, phospate, enamel and lacquer
coatings, polymers etc. are prone to Filliform corrosion.
It is not that dangerous, but degrades the surface from aesthetic point of view.

Filiform Corrosion

1
 Mechanism of Filiform Corrosion

O2 H2O
H2O O2
Thin coating

Head
Hydrolysis, Low O2
pH, O2 Fe(OH)3

Steel substrate

 Special case called Self propagationg Crevice. Blue green head and brown tail.
 While growing, the head is supplied by water through osmosis process due to higher
concentration of Fe ions.
 Water is removed at the tail by osmosis as there is low amount of soluble products.
 O2 is present at all points but the center point is higher as there is more chance of lateral
movement, hence the anodic part is restricted to head alone.
 The hydrolysis of corrosion product lowers pH at head.

Humidity effects Filiform Corrosion

 Humidity influences the filiform corrosion.

 A humidity between 65% to 90% favours filiform corrosion.

 Coatings with low water permeability will suppress filiform corrosion.

 The corrosion filament has no correlation with metallurgical structure of metal.

However, it follows the grinding and polishing marks.

 There is no biological organisms involved in this process.

Prevention

 Low humidity.

 Coating with brittle films.

 Low permeable coatings.

2
 Pitting Corrosion

 Form of extremely localised attack resulting holes in metals.

 Cavity or hole with a surface diameter, the same or less to that of the depth.

 Destructive and insidious forms of corrosion.

 Ascribed to a well-defined heterogeneity associated with the metal/environment.

 Pits usually grow in the direction of gravity.

 Develop on horizontal surface and grow downwards.

 Requires an extended initiation period for visible pits to appear.

 Incubation period ranges from months to years; specific to metal and

environment.

 Once started it penerates in ever increasing rate.

Pitting Corrosion

3
 Pitting Corrosion

 surface finish influences pitting and other localised corrosion

polished surfaces pit lesser than ground surfaces
PREN = % Cr + 3.3(% Mo +0.5 % W) + 16 (% N)
percents are in weight percent of elements IN SOLID SOLUTION

304 SS :- Cr: 17.0-19.5; N : 0.11: PREN =17.0-20.8

316/316L:- Cr: 16.5-18.5; Mo: 2.0-2.5; N: 0.11: PREN = 23.1-28.5

Pits Growth and Shape

 Pit is similar to crevice, where it creats its own crevice.

 Crevice occurs in most corrosive media, however pit occurs in specific environement, i.e. in
the aggressive anions, Cl-

Source: Shrier, Corrosion 1/ Metal- environment reactions

4
 Pits Growth – Autocatalytic nature

 Rapid dissolution at pit leads excessive +ve ions, compensated by migration of Cl-.
 Formation of metal chloride.
 Hydrolysis of metal choride leads to formation of H+ ions.
 H+ and Cl- stimulate the metal dissolution and process accelerate with time.
 No O2 reduction at pits.
 Pits with tubular corrosion products can be explained with this mechanism.
 All systems that show pitting are susceptible to crevice, however the reverse is not true.
 Crevice susceptible systems need not be attacked by pitting when freely exposed.

Pits Growth – Autocatalytic nature

Na+ Cl-
O2 Na+ O2
O2 Cl- O2
O2
O2
Na+
OH- OH- OH- OH-

H+ Cl- Cl- Cl-

e- Cl- Cl-
H+ H+ e-
Cl-
M+ M+
e- M+ Cl- M+
M+ e-
M+

Unique anodic reaction. Autocatalytic- Pitting process is stimulating and of

continuous nature.
M-pitted in NaCl solution. Rapid dissolution takes place at pit and reduction reaction
occurs at adjacent surfaces.
Self-stimulating and self propogating.

5
 Pitting Corrosion of Metals

Pitting Corrosion of Al alloys

Zaid et al. / Corrosion Science 50 (2008) 1841–1847

Four stages of pitting corrosion can be distinguished:

(1) processes occurring on the passive film, at the boundary of the passive film and the
solution.
(2) processes occurring within the passive film, when no visible microscopic changes occur in
a film.
(3) formation of so-called metastable pits which initiate and grow for a short period of time
below the critical pitting potential and then repassivate (this is an intermediate step in
pitting).
(4) stable pit growth, above a certain potential termed the critical pitting potential.

6
 Pitting in NiTi SMAs
L.Neelakantan et al., Research work

Pitting corrosion on a NiTi SMA in 0.9% NaCl after a polarisation study

Environmental effects & local chemistry

Task for you people: Corrosion tube growth mechanism.

Pitting corrosion occurs only in the presence of aggressive anionic species, and chloride ions are
usually, although not always, the cause.
The severity of pitting varies with the logarithm of the bulk chloride concentration.

WHY CHLORIDE IONS?

Chloride is an anion of a strong acid, and many metal cations exhibit considerable solubility in
chloride solutions. Acid forming tendency.
Chloride is a relatively small anion with a high diffusivity, it interferes with passivation, and it is
present at anytime as a contaminant.
The presence of oxidizing agents in a chloride-containing environment is extremely detrimental,
and will further enhance localized corrosion. Cupric ( CuCl2) and Ferric (FeCl3) ions. Get
reduced as they are electron acceptors.
An ASTM standard for testing the pitting resistance of materials by exposing them to 6% FeCl3,
solution that combines both high chloride content and high oxidizing power

7
 Alloy effects

 The alloy composition and microstructure has a strong effects on the tendency for an alloy to
pit.
 Cr concentration plays the dominant role in passivity to ferrous alloys. The pitting potential
correspondingly increases dramatically with increase in Cr content above the critical 13%
value needed to create stainless steel.
 Increasing concentration of Ni, which stabilizes the austenitic phase, moderately improves the
pitting resistance of Fe-C.
 Small increases in certain minor alloying elements, such as Mo and N in stainless steels, can
greatly reduce pitting susceptibility. Mo is particularly effective, but only in the presence of Cr.
 Mo acts by adsorbing on the surface as molybdate or by blocking active sites during active
dissolution.
 Pits almost always initiate at some chemical or physical heterogeneity at the surface, such as
inclusions, second phase particles, solute-segregated grain boundaries, flaws, mechanical
damage, or dislocations.
 Many different forms of dissolved sulfur species can decrease the pitting potential of stainless
steel in chloride solution.

Alloy effects

The surface finish of metal would influence the pitting resistance. Smoother surface would
have higher pitting resistance.

Severe Cold working increases pitting attack in 18-8 SS in ferric chloride solution.

304 and 316 SS exposed to sensitization temperature are susceptible to pitting attack.

Prevention

 Methods that combat crevice would work.

 Addition of Mo in 18-8 SS has better pitting resistance.

 Adding inhibitors is helpful (if and only if pitting is completely stopped)

8
 Pitting Resistance of Stainless Steels

Calculated pitting resistance numbers

The table below shows a range of calculated PREN values for comparison.

304 SS :- Cr: 17.0-19.5; N : 0.11

PREN =17.0-20.8

316/316L:- Cr: 16.5-18.5; Mo: 2.0-2.5; 0.11

PREN = 23.1-28.5

The values are rounded for convenience of display.

For example, the equivalent ASTM grade or the specifications of the oil and gas industry e.g.
NORSOK or NACE typically require a minimum of PREN =40.

Pitting Susceptibility by Polarisation Method

Several methods may be used in polarisation of specimens for corrosion testing.

Potentiodynamic polarisation is a technique where the potential of the electrode is varied at a

selected rate.

It is probably the most commonly used polarisation testing method for measuring corrosion
resistance and is used for a wide variety of functions:

Cyclic polarisation tests or Cyclic voltammetry:

This involves sweeping the potential in a positive direction until a predetermined value of
current or potential is reached, then the scan is immediately reversed toward more negative
values until the original value of potential is reached. In some cases this scan is done
repeatedly to determine changes in the current-potential curve produced with scanning.

These tests are often used to evaluate pitting susceptibility.

The potential is swept in a single cycle (or slightly less than one cycle), and the size of the
hysteresis is examined along with the differences between the values of the starting open
circuit corrosion potential and the return passivation potential.

9
 Selective Leaching

The removal of one element from a solid alloy by corrosion process.

Simplest example: Selective removal of Zinc from Brass alloys (Dezincification).

Similar process occur in alloys where Al, Fe, Co, Cr elements are removed.

Also refered as Parting.

Brass is 30 % Zn and 70% Cu. The alloy assumes red or Cu colour that contrasts original
yellow.

Two type:

1) Uniform – layer type attack. 2) Localised or plug type.

Overall dimensions does not change because of dezincification.

Metal structure and composition are important for dezincification.

Selective Leaching- Mechanism

 Dissolution of Zn from Brass matrix, leading to formation of vacant sites. But this could not
be proved as the depth of attack would be impossible or very slow as diffusion of solutions
and ions would be difficult from small vacant sites.

 Involves 3 steps
i) Brass dissolves (Zn and Cu dissolves)
ii) Zn ions stay in solution
iii) Cu plates back or redeposited.
 Zn is active; Cu is noble. Zn dissolves in pure water by cathodic ion reduction of H2O
forming H2 gas and OH- ions. Hence O2 is not required for selective leaching, if present will
enhance the dissolution.The porous structure of doposit permits easy contactg with solution
and the brass.

Prevention

 Reducing aggressiveness of environment

 Addition 1% Sn to Brass (Admiralty Metal). Also, P, As, Sb as inhibitors

 Critical parts Cupronickels can be used as alternative for Brass

10
 Intergranular Corrosion

 Grain boundaries are high energy areas and are more reactive nature.
 In certain cases, the grain interfaces are very reactive and intergranular corrosion results.
 Localised attack at and adjacent to grain boundaries, with relatively little corrosion of
the grains is termed as Intergranular corrosion (IGC).
 Alloy disintegrates and grain falls and / or loses its strength.
 IGC is caused by impurities at grain boundaries, where enrichment of one alloying
element occurs, or there is depletion of one of these elements at the grain boundary
areas.
 Small amounts of Fe in Al, precipitates or seggregrates at grain boundaries and causes
IGC.
 Depletion of Cr in grainboundary region results in IGC of stainless steel.
 Austenetic SS is prone to IGC. (18-8)
 Heated to senzitisation temperature (427–899 °C)

Intergranular Corrosion

 The theory of IGC is due to improvishment or depletion of Cr in grain boundary areas.

 Normally Cr is responsible for the corrosion resistance of steel and 10% Cr is required to
make steel stainless.
 However, at sensitisation temperature range, where steel is sensitised and stress
relieved the tendency of formation carbide is higher.
 The Cr reacts along with Carbon to form Cr23C6 precipitates.
 There exists a critical C content of 0.02 -0.03 wt % below carbide formation would be
less.
 At 0.03 even if carbide forms, the depletion of Cr would be negligible, making steels with
low Carbon immune to IGC.
 Slowly cooling from annealing temperature, relieving stress in the sensitizing range, or
welding may cause carbide precipitation.
 Longer time at annealing temperatures can cause sensitization of the complete material.
 Shorter times at welding temperature can result in sensitization of a band adjacent to but
slightly away from the weld. This region is known as the heat-affected zone (HAZ).

11
 Intergranular Corrosion

Carbon readily diffuses to grain boundaries at sensitizing temperatures, but as chromium

is less mobile. The grain boundary facilitates the formation of carbide particles.

Grain boundaries

Chromium carbide

Chromium depleted zone

Grain boundary in sensitized type 304 SS

The Cr level at boundary drops to even 2 %; Corrosion resistance is lowered.
Two dissimilar metal compositions, unfavourable area effect.

Intergranular Corrosion

Effect of carbon content on the carbide Sensitised Stainless Steel

formation. Carbide formation occurs within the
C curve
Source: Web

12
 Weld decay

Welded stainless steel were often prone to IGC.

The welded structure failed more often near the weld due to IGC, which is named as Weld Decay.

Weld decay is a zone / band in the parent base plate somewhat away from weld.

Temperature profile

There exists a temperature profile across the weld.

The base metal is subjected to metling temperatures at welding line and the adjacent areas
are subjected to lower temperature. i.e. Sensitization region.

These correspond to weld decay zone.

13
 T / °F
Time-Temperature profile

B A

C B
C
D
D

Time / s

Time - Temperature curve for an electric arc welding of 304 SS

Weld decay

Time and temperature relationship would depend on geometry of the specimen, i.e., the
thickness of material and type of welding.

Electric arc welding is used more than gas welding for SS.

Higher and intense heating in shorter times in the case of Arc welding.

The gas welding would have a wider zone of metal in sensitising range for longer time leading to
greater carbide formation.

It is a environment specific failure. i.e. If sensitised SS does not fail in all environments.

Control for Austenitic SS

3 ways

1) Use high temperature solution heat treatment. Quench-annealing or solution-quenching.

2) Adding stabilisers ( Elements that are more stronger carbide formers, Ti, Niobium etc.

3) Lower the C content in the alloys, less than 0.3%.

14
 Controlling IGC in Aust. SS

1) Heat up to higher temperature approx-1900-2000 F, and quench it in water.

The carbides melt and homogenous alloy is obtained. In case of welding quench annealing
would eliminate the weld decay. This is limited with size of the equipment. Rapid cooling from
Solution temperature is very important. Slow cooling would make specimen prone to IGC.

2) Strong carbide formers of stabilising elements like Nb + tantalum or titanium can be

used. These types of alloys are 347 and 321 SS respectively. The higher affinity of these elements
for C compared to Cr, would steal the C forming these carbides thereby avoiding depletion of Cr.

3) Lowering the C level < 0.03 (304L SS) helps to avoid IGC. Lower the carbon content lower
would be the carbide formation tendency. Also called as extra low carbon steels (ELC).

4) The susceptibility of SS to IGC can be reduced by severe cold-working the alloy.

Severe cold working would reduce the grain size and many slip lines, which provides larger
Surface for carbide formation.

5) Carbon pick up while casting of SS is a great issue. This occurs when steels are casted in
Carbonaceous meterials, like binders etc... The hot metal absorbs carbon from these enviroments.

More carbon pick up would lower corrosion resistance in terms of IGC.

Also pitting resistance would be lowered.

Knife Line Attack (KLA)

Refer Fontanna: Table 3-9. Media where Aust SS is prone to IGC.

Even stabilised aust. SS is attacked by IGC under certain conditions due to chromium carbide
formation. Why?

Type 347 SS drum that held fuming HNO3.. IGC attack in a narrow line on both sides of weld,
immediately adjacent to it.

Weld decay and KLA are both cases of IGC associated with welding, so what is the difference?

KLA occurs a narrow band in the parent metal immediately adjacent to the weld, whereas the
weld decay at a certain distance away from weld.

KLA occurs in Stabilised steels.

The thermal history of metal is different.

15
 Knife Line Attack (KLA)
Mechanism for failure of drum

Based on the solubility of Niobium in steel.

The Nb and its carbides are metled at very high temperatures and remain in solution while
quenching the metal.

When heated to sensitisation temperature, the Nb stays in solution and hence does not
participate in carbide formation, hence Cr-carbide is formed.

Metal behaves as if it is 18-8 unstabilised alloy.

At molten zone temperature is 3000 °F and immediately adjacent it is 2700 °F. Sharp thermal
gradient occurs in SS and therfore rapidly cools.

The immediate zone cools rapidly so that Nb carbide is in solution and then heated to
sensitisation range where Cr- carbide is formed. This temperature is not high enough for Nb
carbide to form.

Remedy for KLA:

Heat the complete alloy to a temperature where Nb carbide is formed and Cr-carbide dissolves. Ti
stabilised steels (321) are also prone to KLA.

Erosion / Flow Induced Corrosion

elementary processes of particle induced flow corrosion

passive film

damage to
erosion repassivation corrosion
passive layer / matrix

quick breakdown of surface layer

 difficult to get information of single event
(quick transient of small current) metal substrate

The flow induced corrosion problems are generally termed erosion corrosion. This
covers flow enhanced dissolution and impingement attack.
“erosion” applies to deterioration due to mechanical force
Here the corrosion problems involve situations where the environment moves, this
may increase or decrease the rate of corrosion. The fluid can be aqueous or
gaseous, single or multiphase.

16
 Erosion / Flow Induced Corrosion

1 µm

50 mm

Erosion / Flow Induced Corrosion

17
 Erosion / Flow Induced Corrosion

Does all electrochemical processes are affected by flow?

Activation controlled processes are immune to electrolyte flow.

The processes involve, the loss due to corrosion and to those where mechanical loss
dominates.

Erosion corrosion leaves its foot prints. Grooves, i.e., scooped-out rounded areas, horseshoe-
shaped depressions, gullies, or waves, all of which often show directionality. At times, attack
may be an assembly of pits.

All equipment exposed to flowing fluid is subject to erosion corrosion, but piping systems and
heat exchangers are the most commonly affected.

Erosion corrosion is affected by velocity, turbulence, impingement, presence of suspended

solids, temperature, and prevailing cavitation conditions.

The acceleration of attack is due to the distribution or removal of the protective surface film by
mechanical forces exposing fresh metal surfaces that are anodic to the uneroded neighbouring
film.

Influencing Factors
The formation nature and breakdown of protective surface films depends on both material and
environmental parameters both influences the erosion corrosion.

18
 Influencing Factors

Nature of metal or Alloy

Chemical composition, corrosion resistance, hardness.

Composition determines the corrosion resistance.
The corrosion resistance for an active metal/ alloys is due to its ability to form and maintain a
protective film.
More noble metals form inherently corrosion resistance.
80% Ni - 20% Cr is superior to 80% Fe - 20% Cr. Ni-Cu alloys better than Ni-Zn alloys.

Alloying with third element could be beneficial. Addition of Mo to SS is an example.

Formation of a stable protective film on surface.
Soft metals are susceptible to erosion corrosion because they undergo mechnical wear. But
this need not be always the case for erosion corrosion. Solid solution hardening. Fe-Si (14 %
Si)

Combating Erosion Corrosion

Better materials.

Design paramters.

The size, shape, geometry etc. Increasing diameter of pipe leads to decrease in
velocity and fluid flow would be laminar. Increasing diameter and streamlining bends avoids,
impingement effects. Increase thickness and vulnerable areas.

Alteration of environment.

Deareation and addition of inhibitors. Settling and filtration for removing solids.
Temperature can be lowered.

Coatings.

Resilient barrier coatings. Hard facings etc.

Cathodic protection.

Helps to reduce attack, however is not used for erosion corrosion problems.

19
 Cavitation damage
Cavitation corrosion refers to the progressive deterioration of a surface
under the combined action of corrosion and the implosion of
cavitation bubbles.

During turbulent flow bubbles form whenever a local low-pressure zone

is created.

The pressure drops below the vapour pressure of the fluid, a small
amount of liquid can evaporate, leading to the formation of a vapour
bubble, called a cavitation bubble.

The diameter of the bubbles can vary between several micrometer and
millimeter.
.
These bubbles grow from particular sites, related to surface topography
or to the presence of inclusions. Because of the pressure fluctuation,
the cavitation bubbles implode when the local pressure increases
again. `
During a short period of several microseconds, the pressure at the metal surface can thus reach
very high values, up to 1000 MPa. The repetition of this mechanism induces fatigue at the metal
surface, and thus causes irreversible damage.

Cavitation damage

1) Cavitation bubble formed on a protective film.

2) The bubble collpases and distrupts the film.
3) New area is exposed and corrodes and film formed.
4) A new cavitation bubble forms at same spot.
5) Repeat of 2-4 steps, leading to formation of deep holes.

Prevention:
Similar to erosion corrosion, change in design to reduce fluid pressure.
Smoother surface.
Resilient coatings like rubber and plastic.
Cathodic protection.

20
 Cavitation Erosion Tests

Mass loss data of Ni Mass loss data of Ti

Weight Weight Weight Weight Weight Weight
Time /h Measure/g loss/g loss/mg Time /h Measure/g loss/g loss/mg
0 1,3785 0 0
0 0,5488 0 0
1 1,3778 0,0007 0,7
1 0,5486 0,0002 0,2
3 1,3726 0,0059 5,9
5 0,5484 0,0004 0,4
5 1,368 0,0105 10,5
10 0,5466 0,0022 2,2
20 1,3338 0,0447 44,7
25 1,3276 0,0509 50,9 25 0,5418 0,007 7

40 1,312 0,0665 66,5 30 0,5389 0,0099 9,9

70
Ni
60
Ti
50 NiTi(M)
Dm / mg

40
30
20
10
0
0 20 40 60 80 100
t/h

Cavitation Erosion Tests

Cavitation erosion tests can be carried out in de-ionized water at 25°C according
to ASTM standard G32-92 using an ultrasonic cavitation facility (Bandelin
Sonoplus - UW 2200).

Mean erosion rate MER = ΔW/10ρAΔt µmh-1

Cavitation erosion resistance Re = 1 / MER hµm-1

ΔW is weight loss in mg
Δt is the time interval in hours
A is the cavitated area in cm2
r is the density in gcm-3

In the calculation of MER, it was assumed that the depth of damage was uniform
across the affected area.

21
 Fretting Corrosion
 Fretting is corrosion occuring at contact areas between materials under load subjected
to vibration and slip.
 It leaves pits and grooves in metal surrounded by corrosion products.
 Also called as friction-, wear- oxidation, chafing and false brinelling.
 Observed in engine components, automative parts, bolted parts and also in biomedical
field.
 Special case of erosion corrosion, however occurs in atmosphere.
 Very detrimental as the metal component is destructed and debris is formed.
 Also causes fatigue failure, as it imparts excessive strain and pits act as stress raisers.
 Requirements for fretting to occur
 The interface must be under laod.
 Vibration or repeated relative motion between surfaces.
 The load and relative motion of interface should produce slip or deformation
on the surfaces.

Fretting Corrosion

 A diplacement as 10-8 cm would be enough to cause fretting damage.

 It does not occur where continous motion between parts.
 Two major mechanisms had been proposed.
 Wear oxidation: Cold weld or fusion at interface due to pressure and
subsequent relative motion leads to rupture and fragments of metal are
removed. These small fragments are oxidised during heating.
 Oxidation wear theory: Atmospheric oxidation causes a protective film on
surface and metals in contact and load when subjected to relative motion, the
oxide layer fails and causes debris.

22
 Fretting Corrosion

Prevention
 Lubrication.
 Increase hardness of one of the components.
 Increase roughness. Normally coated with Pb and it wears out.
 Use of gaskets.
 Higher load to avoid slip.
 Increase the relative motion.

23