Corrosion Failures of Stainless Steel

Industrial Components

V. S. RAJA
Institute Chair Professor
Department of Metallurgical Engineering and
Materials Science
Indian Institute of Technology Bombay
Powai, Mumbai – 400 076, India
Email: vsraja@iitb.ac.in

Course “Stainless Steels” (CoSS-2015)

February 26-27, 2015
 Materi Environme
al nt

Corrosi
on

Desig
n

VS Raja, Aqueous Corrosion Lab,

Corrosion Basics IITB
Corrosion: Deterioration of
materials in presence of a
chemical environment leading to
loss in their function.

VS Raja, Aqueous Corrosion Lab,

IITB
Corrosion Tendency
Metal

Energy
level

Ore

VS Raja, Aqueous Corrosion Lab,

State/time
IITB
 H+

HH
H 2 H+

Fe Fe2+
e-eFe
ee -
Fe2+ H+
e- HH
-
H 2 H+

Environment
Metal / Electrolyte with H+ ions
Why Corrosion Failures
Occur?

Negligence

Process Modification

Materials Environment
Compatibility

Inadequate Fabrication Compliance

Notion Some Alloys are Always
“Better Alloys”

Ignoring the Associated Units
Waste Heat N Methyl Propylene Boiler
Failure-Material Mix-up (Analyze even the
unfailed tubes)

Failed Tubes were 304L

Tubes MOC: 316L; Temp: 300 oC, fire on shell-side, NMP solvent
for Wax (for Lube Oil Manufacture)
HP Heater Failure in a Co-Gen!
-Neglected Water Treatment

Aqueous Corrosion Laboratory

Tubes Details
Corrosion fatigue,
Erosion Corrosion

Type of heater: Vertical
channel down

Design pressure: 150 bar

Tube materials: SS SA
213TP304

Tube size: 15.87 mm OD.

Number of tubes:496

Overall dimensions:
949 mm dia and 9389
mm length
Aqueous Corrosion Laboratory
Aqueous Corrosion Laboratory
Aqueous Corrosion Laboratory

Chloride in Feed water
(3.5 ppm) & and
condensate pH: 7.5.

High hardness value
responsible for SCC of the
tubes

Water conductivity: 11 µS

Aqueous Corrosion Laboratory

Problem and solution

Water purity is vital for high

temperature and high purity water
Failure of Condenser Tubes

Negligence to
Clean the Tubes
Adequately
 HP Feed water heaters - details of losses

Heater installation period - delayed supply

Loss of Heater Loss of Loss
rev (Rs unavailabi HR due HR
Crs) lity (No of (Kcal/kwh) (Rs Cr)
From To Loss of MW Loss MU Days )
Htr5 17-Mar-10 19-Apr-10 12 9.50 3.449952 33 35 1.58
40
Htr6 18-Mar-10 19-Apr-10 13 9.98 3.624192 32 1.54
7.074144 3.12
Total loss due to delay in delivery: Rs. 10 Cr

Aqueous Corrosion Laboratory, IIT

Bombay
 Poor fabrication Practice

• Following foreign material was

collected after opening the HP
heaters :

• 3 kg of debris consisted of
metallic mandrill, pieces of
rubber hoses & o-rings, plastic
plugs & powder material

• Water collected from heater

was highly acidic in nature (pH
4.2).

Aqueous Corrosion Laboratory, IIT

Bombay
Clues

Water treatment is being
carried out as per the
required practice. Water
analysis report during
this period confirms this

chloride levels of 74
pH of water from the

ppm and 1.01 %. heaters were

Fluoride level is abnormally low,
about 292 ppm and even after long
the nitrate is 4 ppm. duration of flushing


Aqueous Corrosion Laboratory
Plot of pitting temperature versus oxygen content of
backing gas for Fe-22Cr-5.5Ni-3.0Mo-0.15N and Fe-
23Cr-4Ni-0.1N duplex stainless steel tested in 3.5 %
NaCl and 01% NaCl solutions, respectively, both at
anodic potential of 300mV [Odegard etal.,1990]
Effect of shielding and backing gas on critical
pitting temperature (CPT) of duplex
weldments in ferric chloride solution
 Post weld clean-up of SS
Contamination Prevention
during welding
Weld spatter: protective film is
penetrated and tiny crevices are
created within the weakened film.
Repair welds: Ground weld spatter,
spatter prevention paste.
Heat tint: pickling by immersion; Pickling
paste. Electro polishing.Glass bead
blasting, use clean beads; over
roughen is detrimental.
Slag : Careful wire brushing; C-steel and
(coated electrodes) . 400 grade steels
contaminate the surface so the weld
 Cleaning after welding (See ASTM
A380)
A. Degrease in solvent or caustic
B. Descale (remove heat tint,slig residue)

Mechanical descale (avoid iron)
 Grind
 Sand
 Grit Blast
 Power brush
C. Chemical descale (pickling)
• 10-25% HNO3 + 2%HF
• Pickle pastes containing HNO3 + HF
• 10% H2SO4 followed by 10% HNO3

D. Electrochemical(electropolishing)(not in ASTM A380)

• 50% H3PO4 (85%concentration)-
• 50%H2SO4 (concentrated)
2
• 12 volts DC power,3000 amps per m
• stainless as anode ,copper cathode
EFFECT OF Pickling
Application of paste
PICKLING IN BATH
Pickling by spray
Failure of Elbow of 14 inch Diameter
Steam line in Hydrogen Generation
Unit (Stainless Steel was a part of
the problem- Carbon Steel Can Serve
Better!)
Nozzle Failure of the
Steam line in Hydrogen
Generation Unit
Material specification is as
follows

PIPE: 14” Dia, Sch 100 material
confirming to ASTM A-312 TP
304, BW Seamless.

ELBOW: 14” Dia, Sch 100 material
confirming to ASTM A-403 GR.
WP304-S, BW Seamless
The cross-sectional photograph of the pipeline
obtained across the crack is shown. It looks the crack
is quite straight and flat until it crossed about 5 mm
along the thickness of the pipeline. There after, it
branched

Transgranular cracking also

indicates that the alloy is not
sensitized
Appearance of crack in the nozzle is shown. The crack
seems to emanate from the pipeline-nozzle joint. Stress
concentration seems to be the reason for the cracking
Clear indication of intergranular path of cracking.
Welding led to sensitization Fig. (a)
Welding spree!

Aqueous Corrosion Laboratory

Chemical Process Industry
Leaks in Dichlorobutene Production Plant

Chlorine is used as one of the raw materials

Aqueous Corrosion Laboratory
Aqueous Corrosion Laboratory
Life is less than a year

Aqueous Corrosion Laboratory

4 IN
4C
4 Out
pipe cross section
pipe cross section
Quality of Stainless Steels

Aqueous Corrosion Laboratory

Aqueous Corrosion Laboratory
Environments and their corrosion
characteristics

S.No. Medium Corrosion Characteristics

1. Chlorine
2 Moisture: 9-14 ppm
3 Hydrochloric acid: 0.06-
0.4%
4 Oxygen: 2.6-3.0 ppm
5 Dichloro butane (Process
fluid)
6 Butadiene (Process fluid)
Aqueous Corrosion Laboratory
Corrosive, if wet
Assist corrosion tendency of
chlorine
Corrosive below the due point
Probable that it promotes corrosion
if wet
Literature not available. Probably
Non-corrosive
Literature not available. Probably
Non-corrosive
Are you going to change process
parameters?

Aqueous Corrosion Laboratory

Caustic inlet nozzles

Sulphonic acid inlet nozzles

Orifice of
3.5 mm
 Sulphate Mass Entry Nozzle

We provide 7 mm I.D Teflon sleeve in

nozzle.Nozzle I.D 14 mm
 Rotor
Blades fitted
circumferenc
e
Rotor
Shaft
Blades
damages
Material marks
stick on
rotor
Blades Failure
“Design” Plays a Major Role

•Pressure reactor failure of a

surfactant manufacturing company
•Water pump-jamming

Aqueous Corrosion Laboratory

Schematic of the reactor

Aqueous Corrosion Laboratory

Back ground information

316L ss reactor was used to produce
intermediates for surfactants.

The process resulted in the generation
of about 6wt% NaCl as a by product

Operated at 85 Deg. C with 2.5kg/cm2
pressure

The process liquid was stirred causing
the liquid to move at a relative velocity
of 4m/s

Aqueous Corrosion Laboratory

…..Back ground information

The reactor was heated and
cooled externally through welded
baffles

After four years of use the baffle
supports became weak and
rewelding became not possible

The reactor was declared unfit
due to pitting?

An investigation was undertaken
Aqueous Corrosion Laboratory
So called pits on inside surface

Aqueous Corrosion Laboratory

Evaluation for IGC

Aqueous Corrosion Laboratory

Branched SCC cracks

Aqueous Corrosion Laboratory

Transgranular cracking

Aqueous Corrosion Laboratory

Aqueous Corrosion Laboratory
Data analysis

Aqueous Corrosion Laboratory

Location of the cracks

Aqueous Corrosion Laboratory


Such a thing is possible as baffles
act as source of heat when the
reactor is heated. Localized heat
caused SCC

The company has raised the
temperature of the reactor
further to 125 Deg. C in order to
increase the productivity!!!

Aqueous Corrosion Laboratory

Conclusions

The process liquid is aggressive to
cause pitting and stress corrosion
cracking, as it generates 6wt%
chloride

The reactor failed by TGSCC

The rise in temperature has
aggravated the failure

The baffles acted as heat sink and
caused high rise in inner surface
temperature

Aqueous Corrosion Laboratory

Recommendations

Use high alloy stainless steels:
duplex stainless steel, 2205, 2507
or 254 SMO

Weld baffles to the outer jacket of
the reactor

Aqueous Corrosion Laboratory

Modified design of the reactor

Aqueous Corrosion Laboratory

Remarks

Stainless Steels are Meant for Resisting
Uniform Corrosion

But if not handled carefully, the prematurely
fail and in some cases worse than carbon steel.

Handling
 Storage
 Fabrication
 Operation
 Maintenance
Thank You