Erosion Corrosion

EROSION-CORROSION
(Flow-Assisted or Flow-Accelerated Corrosion)

An increase in corrosion brought about by a high relative velocity

between the corrosive environment and the surface.
Removal of the metal may be:
as corrosion product which spalls off the surface because of
the high fluid shear and bares the metal beneath;
as metal ions, which are swept away by the fluid flow before
they can deposit as corrosion product.
N.B. Remember the distinction between erosion-corrosion and
erosion:
erosion is the straightforward wearing away by the mechanical
abrasion caused by suspended particles . . . e.g., sand-blasting,
erosion of turbine blades by droplets . . .
erosion-corrosion also involves a corrosive environment . . . the
metal undergoes a chemical reaction.
2

Erosion-corrosion produces a distinctive surface finish:

grooves, waves, gullies, holes, etc., all oriented with respect to the fluid flow
pattern . . . scalloping...

Erosion-corrosion of stainless alloy pump

impeller.
Erosion-corrosion of condenser
tube wall.

Impeller lasted ~ 2 years in oxidizing

conditions;
after switch to reducing conditions, it lasted
~ 3 weeks!
3

Most metals/alloys are susceptible to erosion-corrosion.

Metals that rely on protective surface film for corrosion protection are
particularly vulnerable, e.g.: Al
Pb
SS
CS.
Attack occurs when film cannot form because of erosion caused by suspended
particles (for example), or when rate of film formation is less than rate of
dissolution and transfer to bulk fluid.

- aqueous solutions;
- gases;
- organic liquids;
- liquid metal.
If fluid contains suspended solids, erosion-corrosion may be aggravated.
Vulnerable equipment is that subjected to high-velocity fluid, to rapid
change in direction of fluid, to excessive turbulence . . .
viz. equipment in which the contacting fluid has a very thin boundary
layer
- high mass transfer rates.
Vulnerable equipment includes:
Erosion-Corrosion found in:

- pipes (bends, elbows, tees);

- valves;
- pumps;
- blowers;
- propellers, impellers;
- stirrers;
- stirred vessels;
- HX tubing (heaters, condensers);

- flow-measuring orifices, venturies;

- turbine blades;
- nozzles;
- baffles;
- metal-working equipment (scrapers, cutters,
grinders, mills);
- spray impingement components;
- etc.
5

Surface film effects

Protective corrosion-product films important for resistance to erosion-corrosion.
Hard, dense, adherent, continuous films give good resistance, provided that they
are not brittle and easily removed under stress.
Lead sulphate film protects lead against DILUTE H2SO4 under stagnant conditions,
but not under rapidly moving conditions.

Erosion-corrosion of hard lead

by 10% sulphuric acid (velocity
39 ft/sec).

pH affects films in erosion-corrosion of low-alloy steel.

Effect of pH of distilled water on

erosion-corrosion of carbon
steel at 50C (velocity 39 ft/sec).

Scale generally granular Fe3O4 (non-protective). But at pH 6 & pH 10, scale

Fe(OH)2/Fe(OH)3 . . . hinders mass transport of oxygen and ionic species.
7

N.B. Dissolved O2 often increases erosion-corrosion . . .

e.g. copper alloys in seawater. . . BUT . . . on steels, dissolved O2 will inhibit
erosion-corrosion . . . utilized in boiler feedwater systems.

Effects of temperature and dissolved O2 on the weight-loss of AISI 304

stainless steel exposed for 800 hours in flowing water at 3.7 m/s.

Effect of oxygen dosing on erosioncorrosion and potential of carbon

steel in water at 150C, pH at
25oC= 7.8.

Good resistance of Ti to erosion-corrosion in:

- seawater;
- Cl- solutions;
- HNO3;
and many other environments.
Resistance depends on formation and stability of TiO2 films.

10

Chromium imparts resistance to erosion-corrosion to: - steels;

- Cu alloys.

Effect of chromium additions on

seawater impingement-corrosion
resistance of copper-nickel alloys. 36day test with 7.5 m/s jet velocity;
seawater temperature: 27C.

Such tests have led to the marketing of a new alloy for condenser tubes . .
CA-722 . . . previously IN-838 . . . with constituents . . . Cu-16Ni-0.4Cr.
11

Velocity Effects

Schematic showing the

effect of flow velocity on
erosion-corrosion rate.

N.B. Turbulent flow regime for V < Vc is sometimes called

Flow-Assisted Corrosion regime.
12

Relationship between flow velocity, v, and erosion-corrosion rate, w, may be

written as . . .
w = kva
where k and a are constants that depend on the system.
DISCUSS:

What happens when v = 0 ?

How do we express no dependence on velocity?

The exponent a varies between . . .

0.3 (laminar flow) and
0.5 (turbulent flow)...
occasionally reaching > 1.0 for mass transfer and fluid shear
effects.
For mechanical removal of oxide films (spalling), the fluid shear stress at the
surface is important, and a > 1.0 . . . (may reach 2 - 4).

13

Erosion-Corrosion in Carbon Steel and Low-Alloy Steels

N.B. these materials are used extensively in boilers, turbines, feed-water
heaters in fossil & nuclear plants, CANDU feeders.
High velocities occur in single-phase flow (water) and two-phase flow (wet
steam).
Single-phase E-C seen in H.P. feedwater heaters, SG inlets in AGRs, feedwater
pumps, and CANDU feeders.
Two-phase E-C more widespread . . . steam extraction piping, cross-over piping
(HP turbine to moisture separator), steam side of feedwater heaters, and
CANDU feeders.

14

Material effects low-alloy steel . . .

Cr additions reduce E-C.

Erosion-corrosion loss as a function of time for mild steel and 1 Cr 0.5 Mo

steel in water (pH at 25C = 9.05) flowing through an orifice at 130C.
15

Flow dependence (single phase)...

Erosion-corrosion rate of carbon steel

as a function of flow rate of
deoxygenated water through orifice at
pH 9.05 and at 149C.

16

Mechanism... for E-C of C.S. in high temperature de-oxygenated water...

- magnetite film dissolves reductively
Fe3O4 + (3n-4) H2O + 2e
3Fe(OH)n(2-n) + (3n-8)H+
- high mass transfer rates remove soluble Fe II species;
- oxide particles eroded from weakened film by fluid shear stress;
- metal dissolves to try and maintain film.

17

Mass transfer characteristics correlated by expressions such as...

Sh

= kRea Scb

Re

dv

Sh = Sherwood Number =
Re = Reynolds Number

kd
D

Sc
Shear stress

correlatedDby .
=

= f
2

v
and at high Re, f independent of velocity so

Sc = Schmidt Number

f = friction factor

v2
18

Temperature and pH dependence for single-phase E-C of CS . . .

Effect of temperature on the

exponent of the mass transfer
coefficient for the erosioncorrosion of carbon steel in
flowing water at various pHs.

19

Prevention of Erosion-Corrosion

design (avoid impingement geometries, high velocity, etc.);

chemistry (e.g., in steam supply systems . . . for CS or lowalloy steel add O2, maintain pH > 9.2, use morpholine
rather than NH3);

materials (use Cr-containing steels);

use hard, corrosion-resistant coatings.

20

CAVITATION DAMAGE
Similar effect to E-C: mechanical removal of oxide film caused by collapsing
vapour bubbles.

High-speed pressure oscillations (pumps, etc.) can create shock waves > 60,000
psi. Surface attack often resembles closely-spaced pitting.

21

FRETTING CORROSION
Similar to E-C but surface mechanical action provided by wear of another
surface . . . generally intermittent, low-amplitude rubbing.
Two theories . . . with same overall result . . .

22

Effects in terms of materials COMBINATIONS

Fretting resistance of various materials
Poor
Aluminum on cast iron
Aluminum on stainless steel
Magnesium on cast iron
Cast iron on chrome plate
Laminated plastic on cast iron
Bakelite on cast iron
Hard tool steel on stainless
Chrome plate on chrome plate
Cast iron on tin plate
Cast iron on cast iron with
coating of shellac

Average
Cast iron on cast iron
Copper on cast iron
Brass on cast iron
Zinc on cast iron
Cast iron on silver plate
Cast iron on silver plate
Cast iron on amalgamated
copper plate
Cast iron on cast iron with
rough surface
Magnesium on copper plate
Zirconium on zirconium

Good
Laminated plastic on gold plate
Hard tool steel on tool steel
Cold-rolled steel on cold- rolled
steel
Cast iron on cast iron with
phosphate coating
Cast iron on cast iron with
coating of rubber cement
Cast iron on cast iron with
coating of tungsten sulfide
Cast iron on cast iron with rubber
gasket
Cast iron on cast iron with
Molykote lubricant
Cast iron on stainless with
Molykote lubricant

Source: J.R. McDowell, ASTM Special Tech. Pub. No. 144, p. 24, Philadelphia, 1952.
23

Prevention of Fretting Corrosion

lubricate;

avoid relative motion (add packing, etc.);

increase relative motion to reduce attack

severity;

select materials (e.g., choose harder

component).
24

Stress Corrosion

25

Stress Corrosion
STRESS CORROSION

(Stress Corrosion Cracking - SCC)

Under tensile stress, and in a suitable environment, some metals and

alloys crack . . . usually, SCC noted by absence of significant surface
attack . . . occurs in ductile materials.

26

Transgranular SCC (TGSCC)

Cross section of stress-corrosion

crack in stainless steel.
27

Intergranular SCC (IGSCC)

Intergranular stress corrosion

cracking of brass.
28

Two original classic examples of SCC:

season cracking of brass;
caustic embrittlement of CS;

both terms obsolete.

29

Season Cracking
Occurs where brass case is crimped onto bullet, i.e., in area of high residual stress.
Common in warm, wet environments (e.g., tropics).
Ammonia (from decomposition of organic matter, etc.) must be present.

Season cracking of German

ammunition.

30

Caustic Embrittlement
Early steam boilers (19th and early 20th century) of riveted carbon steel. Both
stationary and locomotive engines often exploded.
Examination showed:

cracks or brittle failures around rivet holes;

areas susceptible were cold worked by riveting (i.e., had high residual stresses);
whitish deposits in cracked regions were mostly caustic (i.e., sodium hydroxide
from chemical treatment of boiler water);
small leaks at rivets would concentrate NaOH and even dry out to solid. SCC
revealed by dye penetrant.

Carbon steel plate from a caustic storage tank failed by

caustic embrittlement.

31

Factors important in SCC:

environmental composition;
stress;
metal composition and microstructure;
temperature;

necessary

e.g., brasses crack in NH3, not in Cl-;

SSs crack in Cl-, not in NH3;
SSs crack in caustic, not in H2SO4, HNO3, CH3COOH, . . .
etc.

32

STRESS
The greater the stress on the material, the quicker it will crack.

(N.B. in fabricated components, there are usually RESIDUAL STRESSES

from cold working, welding, surface treatment such as grinding or shot
peening, etc., as well as APPLIED STRESSES from the service, such as
hydrostatic, vapour pressure of contents, bending loads, etc.).

33

Composite curves illustrating the relative stress-corrosion-cracking resistance

for commercial stainless steels in boiling 42% magnesium chloride.

DISCUSS:
how would you obtain such a curve and what does it mean?

34

The MAXIMUM stress you can apply before SCC is formed

(c.f.

MINIMUM stress to be applied compressively to prevent SCC) depends on

alloy (composition and structure), temperature, and environment
composition.
Such THRESHOLD stresses may be between 10% & 70% of the yield

stress - Q.V.
N.B. residual stresses from welding steel can be close to the yield point.
N.B. corrosion products can induce large stresses by wedging.

35

N.B. small-radius notch tip and even smaller-radius crack tip are STRESS
RAISERS
A wedging action by corrosion products of 10 ksi (10,000 psi) can induce
300 ksi (300,000 psi) at the crack tip.

36

Corrosion product wedging denting of S.G. tubes in some PWRs . . .

Boiling in crevice concentrates
impurities - can lead to acid + Cl- at
seawater-cooled sites.

Hour-glassing of Alloy-600 tubes led

to severe straining and cracking of
tubes. Surrey PWR in U.S. was first to
replace S.Gs., because of denting.

37

Time to Failure

Major damage during SCC

occurs in late stages as
cracks progress, crosssectional area decreases,
stress increases until final
failure occurs by mechanical
rupture.

38

Environmental Factors
No general pattern, SCC common in aqueous solutions, liquid metals; also
found in fused salts, nonaqueous inorganic liquids . . .
N.B. Coriou (France) cracked Inconel-600 in pure water at 300C in 1959!!!

39

Environments that may cause stress corrosion of metals and alloys

Material
Aluminum alloys
Air, Water vapor
Copper alloys

Environment
NaCl-H2O2 solutions
NaCl solutions
Seawater

NH3 (g & aq)

Amines
Water, Water vapor
Gold alloys
FeCl3 solutions
Acetic-acid-salt solutions
Inconel
Caustic soda solutions
Lead
Lead acetate solutions
Magnesium alloys NaCl-K2CrO4 solutions
Rural and coastal
atmospheres
Distilled water
Monel
Fused caustic soda
Hydrofluoric acid
Hydrofluosilicic acid
Nickel
Fused caustic soda

Material

Environment

Ordinary steels
NaOH solutions
NaOH-Na2SiO2 solutions
Ca, NH3, and NaNO3
solutions
Mixed acids (H2SO4-HNO3)
HCN solutions
Acidic H2S solutions
Seawater
Molten Na-Pb alloys
Stainless steels
Acid chloride solutions
such as MgCl2 and BaCl2
NaCl-H2O2 solutions
Seawater
H2S
NaOH-H2S solutions
Condensing steam from
chloride waters
Titanium alloys
Red fuming HNO3, N2O4,
seawater, methanol-HCI
40

Increasing temperature accelerates SCC:

Effect of temperature on
time for crack initiation in
types 316 and 347
stainless steels in water
containing 875 ppm NaCl.

Most susceptible alloys crack 100C; Mg alloys crack at room

temperature.
Alternate wetting and drying may aggravate SCC - accelerate crack growth
(possibly because of increasing concentration of corrosive component as
dryness is approached).

41

Some Data for Recommending Service of CS or Ni Alloy in Caustic

NACE caustic soda chart super-imposed over the data on which it is based.

Area A:
Carbon steel, no stress relief
necessary; stress relieve welded
steam-traced lines;
Area B:
Carbon steel; stress relieve welds
and bends;
Area C:
Application of nickel alloys to be
considered in this area; nickel alloy
trim for valves in areas B and C.
42

Metallurgical Factors in IGSCC

In austenitic SS and Ni alloys, sensitization is of major importance in
determining susceptibility to IGSCC . . . depletion of grain boundaries in Cr
because of carbide precipitation makes them vulnerable to attack. e.g., IGSCC
of recirculation piping in BWRs (type 304 SS) induced by 200 ppb dissolved
oxygen in the otherwise pure H2O coolant resulted in a major replacement
problem. Plants using L-grade experienced very much less SCC.
Al alloys (e.g., with Mg and Zn) are also susceptible to IGSCC because of
precipitation within grain boundaries . . . Mg-rich precipitates can denude the
grain boundaries of Mg, make them susceptible to attack in aqueous media.
N.B. In grain-boundary-precipitate mechanisms for inducing IGSCC, very local
galvanic effects between precipitates and matrix are important:
some precipitates are ANODIC;
some precipitates are CATHODIC.
43

Grain boundary segregation of alloy constituents or impurities (without

precipitation of separate phases) can also induce IGSCC.
e.g., Mg enrichment of grain boundaries in Al alloys is a factor in IGSCC
- promotes local dissolution and hydrogen entry (maybe to form hydride,
MgH);
- also . . . grain boundary enrichment of impurities and/or C in Fe-base alloys,
Ni-base alloys and austenitic stainless steels can contribute to IGSCC;
- segregation of P, Si, S, N, B reported; only clear link with IGSCC reported for P
in austenitic SS in oxidizing aqueous solutions, for P in ferritic alloys in nitrate
and caustic solutions.

44

Transgranular SCC
Lattice structure in metal/alloy matrix important: dislocation emergence,
movement along slip planes under stress, and similar factors that can disrupt
passivating films, will promote dissolution of metal at highly localized and
strained areas.
Irradiation-Assisted SCC (IASCC)

Since 1987, some in-reactor components have cracked in LWRs . . generally in

core-support structures at the top of the vessel (austenitic SS, Ni alloys). More
widespread in BWRs than PWRs . . . radiolytic chemical species (especially
oxidizing radicals) seem to be the cause.
IASCC of Alloy-600 (Inconel) penetrations in several PWR vessel heads have led
to leaks and boric-acid corrosion of RPV head steel (e.g., Davis Besse). Heads
replaced.
45

Mechanism of SCC
SCC is very complex; probably no single mechanism, but several operating at
the same time. Models (scientific descriptions) of mechanisms of two types:
dissolution;
mechanical fracture.
Dissolution Models of Crack Propagation

Major model is based on Film Rupture . . . (slip-dissolution) . . . high stresses

at crack tip create local area of plastic deformation - ruptures passive films,
exposed metal dissolves rapidly . . . some say periodic dissolution and repassivation, some say crack tip always bare.

46

periodic rupture

Schematic representation
of crack propagation by the film
rupture model.

47

Mechanical Fracture Models of Crack Propagation

Corrosion Tunnel;
Corrosion tunnel models.
(a) Schematic of tunnel
model showing the
initiation of a crack by the
formation of corrosion
tunnels at slip steps and
ductile deformation and
fracture of the remaining
ligaments.

(b) Schematic diagram of the

tunnel mechanism of SSC
and flat slot formation.
48

Adsorption of impurities at the crack tip promotes the nucleation of dislocations;

lead to shear-like fracture (seemingly brittle).
Tarnish Rupture;
Cracks propagate by alternate film growth and (brittle) film fracture, followed by rapid film
formation over exposed metal.
Film-Induced Cleavage;
thin film forms;
brittle crack initiates in layer;
crack moves from film into matrix;
crack continues through ductile matrix until it blunts and stops;
process repeats.
Adsorption-Induced Brittle Fracture;
Species adsorbing at crack tip alter inter-atomic bond strengths, lower stress required for
fracture; propagation should be continuous.
Hydrogen Embrittlement;
Cathodic processes involving hydrogen-ion reduction can inject H into matrix . . . this can
embrittle metal, promote cracking . . . most likely in ferritic steels but also possible in Nibase, Ti and Al alloys (contributes to SCC of carbon steel feeders at Point Lepreau ?).
49

Prevention of SCC
1. Lowering the stress below the threshold value if one exists. This may be done by
annealing in the case of residual stresses, thickening the section, or reducing the load.
Plain carbon steels may be stress-relief annealed at 590 to 650C, and the austenitic
stainless steels are frequently stress-relieved at temperatures ranging from 820 to 930C.
2. Eliminating the critical environmental species by, for example, de-gasification,
demineralization, or distillation.
3. Changing the alloy is one possible recourse if neither the environment nor stress can be
changed. For example, it is common practice to use Inconel (raising the nickel content)
when type 304 stainless steel is not satisfactory. Although carbon steel is less resistant to
general corrosion, it is more resistant to stress-corrosion cracking than are the stainless
steels. Thus, under conditions which tend to produce stress-corrosion cracking, carbon
steels are often found to be more satisfactory than the stainless steels. For example, heat
exchangers used in contact with seawater or brackish waters are often constructed of
ordinary mild steel.
50

4. Applying cathodic protection to the structure with an external power supply or

consumable anodes. Cathodic protection should only be used to protect installations
where it is positively known that stress-corrosion cracking is the cause of fracture, since
hydrogen embrittlement effects are accelerated by impressed cathodic currents.
5. Adding inhibitors to the system if feasible. Phosphates and other inorganic and organic
corrosion inhibitors have been used successfully to reduce stress-corrosion cracking effects
in mildly corrosive media. As in all inhibitor applications, sufficient inhibitor should be
added to prevent the possibility of localized corrosion and pitting.
6. Coatings are sometimes used, and they depend on keeping the environment away from
the metal - for example, coating vessels and pipes that are covered with insulation. In
general, however, this procedure may be risky for bare metal.
7. Shot-peening (also known as shot-blasting) produces residual compressive stresses in the
surface of the metal. Very substantial improvement in resistance to stress corrosion found
as a result of peening with glass beads. Type 410 stainless was exposed to 3% NaCl at room
temperature; type 304 to 42% MgCI2 at 150C; and aluminum alloy 7075-T6 to a water
solution of K2Cr2O7-CrO3-NaCl at room temperature.
51

Corrosion Fatigue The fatigue fracture of a metal aggravated by a corrosive

environment or the stress corrosion cracking of a metal aggravated by cyclic
stress.
N.B. Fatigue fracture usually occurs at stresses below the yield point but after
many cyclic applications of the stress.
Typical S-N curves:

52

Fatigue-fractured material often shows most of the fracture face shiny

metallic, with the final area to fracture (mechanically by brittle fracture of a
reduced cross-section) having a rough crystalline appearance . . .

If corrosion-fatigue occurs, the shiny-metallic area might be covered with

corrosion products; BUT normal fatigue fractures may also develop corrosion
products - depends on environment, stress pattern, etc.
53

N.B. In normal fatigue, the frequency of the stress cycles is not important.
(can do accelerated fatigue tests at high frequency - the total number of
cycles determines fatigue).
BUT in corrosion fatigue, low-cycle stresses are more damaging than highfrequency stresses.
Environment is important.
e.g., in seawater:

Al bronzes and type 300 series SS lose 20-30% of normal fatigue

resistance;

high-Cr alloys lose 60-70% resistance.

N.B. Cyclic loads mean lower allowable stresses, this must be designed into
components; if there is also a corrosive environment, the allowable stresses
are EVEN LOWER.
54

Prevention of Corrosion Fatigue

change design so as to reduce stress and/or cycling.

reduce stress by heat treatment (for residual stress), shot peening (to
change surface residual stresses to COMPRESSIVE).
use corrosion inhibitor with care!
use coatings . . . electrodeposited

Zn;
Cr;
Ni;
Cu;

and

nitrided layers (heating of steels in contact with Ncontaining material e.g., NH3, NaCN, etc.).

55