Seminar with PhD Students

Stainless Steels
Nuclear Materials
Non Destructive Evaluation
Superalloys
Nagaoka University, Japan, May-June 2009
 Lectures delivered by

Baldev Raj
Distinguished Scientist & Director
Indira Gandhi Centre for Atomic Research
Kalpakkam, India
&
Senior Professor
Homi Bhabha National Institute (University)

Contact details
Tel: +91-44-27480267, Fax: +91-44-27480060
Email: secdmg@igcar.gov.in
 High Temperature Performance
Thermal expansion
Diffusion
Oxidation
Environmental Degradation
Yield Strength
Ultimate Tensile Strength
Creep
Fatigue
Thermal Stresses

Synergy of degradation mechanism is difficult to assess

 Possibilities and Solutions
9Thermal Barriers
9Cooling
Optimisation
9Corrosion Barriers &
9Alloy Compositions Improvements
9Thermo Mechanical Treatments
- Microstructures
9Modelling
9Characterisation for Performance
9Experiments
9Performance Monitoring
- Analysis & Measurements
9Learning from Failures and Successes
9New Directions – Ceramics rather than Alloys
 Lecture - I

Stainless Steels
 Outline of the Lecture
9 Invention, Properties and Applications of Stainless Steels
9 Manufacturing of Stainless Steel Products
9 Basics of Stainless Steels and their Classification
9 Nitrogen Effects, Passive Films, and Localised Corrosion
9 Surface Finish and Treatment of Stainless Steels
9 Mechanical Properties of Stainless Steels
9 Weldability of Stainless Steels
9 Stainless Steel Marketing and Current Scenario
9 Summary, References, Videos
 “Steel Family” E.Haynes, USA & Becket &
Dantsizen, USA, 1911-14
Austenitic steel with <1%
C, <20% Ni and 15-40% Cr,
E.Maurer and B.Strauss,
FRG, 1912-1914
Developments……….

Martensitic steel with

12.8% Cr and 0.24% C,
Harry Brearley, UK, 1913
Harry Brearley E. Stuart – ‘stainless’
Fe-Carbon Fe-Low Carbon (< 0.15%)- First ever ‘stainless steel’
Steels High Cr Alloy, Minimum Cr – 10.5% & Mo
Fe-C, P, S, Brustlein, France,1875 effect, P.Monnartz and
Mn Alloys Fe-high C-30-35%Cr-2%W W.Borchers, FRG, 1911
Delhi Iron Alloy, First Patent Fe-Ni-Cr Alloys, L.Guillet,
Pillar Woods & Clark, UK, 1872 France, 1904-06
400 A.D Fe-high C-low Cr Alloy Aluminothermic Reduction
PreHistoric M. Faraday, UK, P. Berthier, process for Carbon-free Cr,
Iron France (1820-21) H. Goldschmidt, FRG, 1895

‘Iron Alloys’ ‘Alloy Steels’ ‘Stainless Steels’

 Why stainless steels are ‘stainless’ ?
NewYork Times, 31-01-1915
¾ Presence of nonrusting thin surface layer
provides a ‘stainless’ nature to steel
¾ This ‘Passive film’ layer is made of Cr2O3 and
it forms when Cr content is > 10.5 % in steel
¾ The corrosion resistance and other useful
properties are enhanced by increased
chromium content, and the addition of
molybdenum, nickel and nitrogen.

Benefits from SS
Corrosion Resistance
High Temperature properties
Low Temperature Properties
Hygiene & Aesthetic Appearance
Ease of Fabrication
Toughness & Impact Resistance
Cost and Life Cycle Cost
Stainless Steels Everywhere ………..
Manufacturing of Stainless Steels
STEP I
¾Melt the charge (Fe,C,Cr&Ni) in electric arc furnace
¾Scrap SS can also be used as starting material
¾Melting occurs around 1500ºC
I

STEP II
¾Transfer the molten mass to a Converter
(Argon Oxygen Decarburization vessel)
¾Decrease the carbon by blowing out with oxygen
¾Add alloying elements to match the composition
II
STEP III
¾Pour the molten mass vertically into a mould
¾As solidification occurs, series of rolling is made to
produce slabs upto 2 m wide & upto 300 mm thick
III ¾Cut suitable size for hot rolling after slab grinding
 Manufacturing Flow Sheet

CHARGE MELTING CASTING WORKING PRODUCTS

Allotropy of Iron –Genesis for SS
 Manifestation of Stainless Steels
Austenitic (65-70%) Ferritic (20-25%) Martensitic (7%)
Precipitation Hardening (2%) Duplex (1%)
minimum 8% to stabilise ‘austenite’ phase;
Maintain chromium beyond 18%, add nickel

enhance corrosion resistance and toughness

(% of use of 150 types of stainless steels)

and hardenability
‘martensite’ phase; for enhancing strength
or no nickel, high C, and transform to
Maintain chromium between 12%-15%, less
1100˚C

Maintain carbon ≤ 0.1%, chromium more than 18%,

and NO nickel to arrive ‘ferrite’ structure for achieving
strength and moderate corrosion resistance
 Properties of Stainless Steels
Materials Types Advantages Disadvantages
Austenitic 304, 316 Widely used, cost, fabricability,
fabricability, Limited work hardening, poor
good corrosion resistance SCC resistance

Ferritic 410, 430, Moderate corrosion resistance, Limited corrosion resistance,

low cost strength and weldability
446
Martensitic 420, 431 Hardenable by heat treatment Poor corrosion resistance,
weldability

Duplex 1.442 Localised corrosion resistance, Limited temperature

good mechanical properties applications

Precipitation 17-4 PH Hardenable by heat treatment, Limited weldability and

Moderate corrosion resistance availability
Hardening
 Austenitic Stainless Steels
DESIGN PARAMETERS

• Alloying element;
• Grain size;
• Thermo-mechanical treatment - % cold work,
type & extent;
• Stability at service conditions
• Weldability
• Life assessment strategies
 Austenitic Stainless Steels
APPLICATIONS IN INDUSTRY

™ High temperature applications with required strength;

™ Wide range of operating stress – 200 to 2000 MPa;

™ Good corrosion and oxidation resistance;

™ Good formability & weldability;

™ Can be used from cryogenic temp. to ~ 1000 ºC.

™ Adoptable to multifaceted environments –

Food to Aero Space
Role of Alloying Elements for 304 SS
 Superaustenitic Stainless Steels
Superaustenitic stainless steels have the same structure as the
common austenitic alloys, but they have enhanced levels of
elements such as chromium, nickel, molybdenum, copper, and
nitrogen, which give them superior strength and corrosion
resistance.
Typical applications are:
• Pulp bleaching equipment and piping
• Sea water heat exchangers
• Chemical process tanks and pipelines
• Brewery equipment
• Reverse osmosis desalination equipment
and pumps
• Offshore oil and gas process systems
• Food processing equipment
• Pharmaceutical process pipes & vessels
 Role of Passive Films on SS
Thin, adherent and self-healing passive
Stainless steel films offer protection against halide ions
Passive film by quickly reforming the passive film.
Cl-
Film
SS
Surface damage

However, localised damage is caused to

the film by chloride ions at weak sites
leading to ‘localized corrosion’.

‘Localised Corrosion’ like pitting, crevice

Localised corrosion, intergarnular corrosion, stress
corrosion corrosion cracking, corrosion fatigue etc.
caused due to the destruction of passive
films are the root cause of failure of SS
components in industrial service.
 Pitting Corrosion of Stainless Steels
Passive film is damaged by chloride ions at
local defects and pitting is initiated; it grows
by an autocatalytic mechanism leading to
growth of pits

How to improve pitting resistance ?

9Add Mo, N, Ni to slow down the pit kinetics
9Laser melting/alloying on the surface
9Add inhibitors to the corrosive medium

Case study of pitting failure in type 304 SS

cryogenic condenser in chemical industry:
Failure occurred within six months of service as
compared to the guaranteed life of 5 to 10 years.
Coil is filled with 70% methanol brine with 30%
water, and the outside of the coil was exposed to
acetone vapour containing nitrogen.
Reasons for failure
Ingress of ordinary water with high chloride
content into DM water cooling system
Intergranular Corrosion of Austenitic Stainless Steels

sensitized

HAZ
HAZ

annealed

Weld Decay
Formation of chromium-rich M23C6 carbides at grain boundaries during slow
heating/cooling of austenitic stainless steels between 400-750°C leads to
development of chromium-depleted zones (< 9% Cr) along the grain boundaries.
This is known as Sensitisation
Any sensitised microstructure will undergo selective localised corrosion along
grain boundaries leading to Intergranular Corrosion
 Breakdown Potential, mV Benefits of Nitrogen Addition to Stainless Steels

T. Misawa et al., 1996

Increasing nitrogen content increases the breakdown potentials and
enhance the resistance to pitting, and crevice corrosion resistance by
stabilizing the passive film
[N] + 4 H+ + 3e → NH4+

NH4+ ions formed increase the pH at pit site, favour the formation of
inhibiting nitrate compounds, and provide ‘local inhibition’ for the
growth of pits.
Role of Nitrogen on Stress Corrosion Cracking

Increasing nitrogen content improves resistance to stress corrosion

cracking of austenitic stainless steels in chloride media
Increasing stability of passive films against damage, formation of
favourable microstructure are the reasons for improved SCC resistance
 Role of Nitrogen on Intergranular Corrosion
wt% I(316) II(316) III(316LN)
C 0.054 0.043 0.030
N 0.053 0.075 0.086

• Cold working up to 15% reduces time to

initiate sensitization (ts)
• Reduction in Carbon and addition of
Nitrogen increases the ts
• Nitrogen decreases M23C6 precipitation
kinetics and thereby tendency for
sensitisation.

Increasing nitrogen content improves resistance to intergranular

corrosion of austenitic stainless steels
Delaying of M23C6 carbide formation, Increasing stability of passive
films are the reasons for improved intergranular corrosion resistance.
 Grain Boundary Engineering to Avoid Sensitization
N o a ttack P a rtia l a ttack A ttack

Grain boundary engineering approach 900

850
M o d ifie d 3 1 6 (N )
C ritic a l c o o lin g ra te - 1 6 0 K / h
3 1 6 (L )
C ritic a l c o o lin g ra te - 1 K / h
1173
1 1 23

TEMPERATURE, °C
helps to identify and produce grain

TEMPERATURE, K
800 1 0 73

750 1 0 23

structures not favourable for the 700

650 3 1 6 (L)
973

923

continuous growth of M23C6 carbides

M o d ifie d 3 16(N )
600 873

550 823

providing interconnected Cr-depleted zones 500

0 .1 1 .0 10 100
773
1 00 0
T IM E , h

Type 316LN Stainless steels (similar chemical composition) but different

processing routes (Alloy A and Alloy B)
Alloy A: Intermediate Alloy B: No intermediate
warm working temp., warm working temp.,
annealing during annealing during rolling
rolling process process
uniform non-uniform
grain size grain size
Minimum Time for Minimum Time for
sensitisation : sensitisation :

about 200 h more than 2000 h

Percentage of Coincidence Site Lattice (CSL) boundaries increased to 70% in

Alloy B from 25% in Alloy A; Time for sensitisation is increased by 10 times.
Sensitization resistance increases with increase in low angle coherent
boundaries connectivity length
Effective Grain Boundary Energy (EGBE) & Role of Copper
Type 316LN SS with 0.08% and 0.529% Cu were subjected to 22 different thermal
treatments to alter the grain boundary nature significantly. Studies include
Double Loop EPR (Degree of sensitization) and EBSD (grain boundary nature)
Linear trends, between DOS and individual parameters, were often weak and
inconsistent. Effective grain boundary energy approach was made.
▼ Grade which contain higher % of copper show lower DOS
⎡⎛ ⎛ ∆θ i ⎞ ⎞⎛ 4 ⎞⎤
▼ EGBE = ⎢⎜⎜ ∑ F γi i
⎜⎜
⎝ θ Maximum
⎟⎟ ⎟⎜ ⎟⎥
⎟
⎠ ⎠⎝ d ⎠⎦⎥
was correlated to DOS
⎣⎢⎝

R
R
o

• As the EGBE increases DOS increases up to a critical value, beyond which

extreme randomisation helps to reduce DOS. This critical EGBE value is also
affected by copper content of the alloy.
• Copper reduces the EGBE, and improves passivity; Special heat treatment
results in very high resistance to sensitization due to different EGBE value.
 Microbiologically Influenced Corrosion

Deposition of
cells in flow

MIC refers to corrosion

and ensuing loss of
metal caused by
MOB biological organisms.
Crevice attack
Biofilm on 304SS
MIC is a common
problem in industrial
processes due to the
presence of microbes,
adequate nutrients and
corrosive byproducts.
 In-situ Study of Corrosion Process of AISI 304L SS in Nitric Acid
Medium using Electrochemical Atomic Force Microscope

0.1N HNO3: With increase in potential, surface 1N HNO3: Smooth passive film; with
reconstruction lead to film with platelet like increase in potential, grain boundaries
structure in the form of moiŕe pattern; platelet size start dissolve; Selective dissolution of
increase as the potential increased film at high potential

Voltammogram 1400 mV 1
5
2 6

Height, nm
3
4
Frequency

1400 mV

Area, µm2 Distance, µm

 Surface Finish of Stainless Steels

Rough Surface – Ra > 1 µm, Poor corrosion performance

Various Surface Finish

Smooth Surface – Ra~ 0.3 µm, Good corrosion performance & Pitting Resistance

Mechanical Finish Electroplolishing

240 Grit Smooth finish High Cr enrichment in pickled and passivated
surface provides excellent corrosion resistance
 Handling and Finishing of Stainless Steels
• Avoid embedding surface with carbon steel
– Causes local rust spots
– Scraping with steel tools or surfaces
– Grinding debris
– Contamination can be removed by pickling
• Done using oxidising acid solutions or pickling paste
• Passivating is necessary to restore oxide film

• Required for aggressive environments, food or pharmaceutical

industries
• Avoid or remove embedded iron
– Test surface for contamination (Ferroxyl Test)
– Pickling with acid or paste, passivation
• Remove heat tint by pickling
• Remove surface contaminants such as slag, dirt and paint,
which lead to crevice corrosion risk
 Mechanical Properties of Stainless Steels
M echanical Properties
(Anneale d condition)
Tensile Strength Yield Strength Elongation Hardness
Stainless ksi MPa ksi MPa

410 70 483 45 310 25 B80

430 75 517 50 345 25 B85
304 84 579 42 290 55 B80
316 84 579 42 290 50 B79
Elongation in 2" (50.80 mm)
Hardness in Rockwell B

Material Thermal Cycling Continuous Service

Service Temperature, ˚C Temperature, ˚C
Austenitic
Service 304 870 925
316 870 925
Temperatures 310 1035 1150
for
Martensitic
Stainless 410 815 705
Steels 420 735 620
Ferritic
430 870 815
 Creep Damage Assessment
500
Temperature: 873 K
400

Stress, MPa
300

200

316L(N) - Superphenix, France

316FR - DFBR, Japan
316L(N) - Germany
316L(N) - PFBR, India
316 - ORNL, USA
316L(N) - RCC-MR design curve
100
1 2 3 4 5
10 10 10 10 10
Rupture time, h

400
316LN
873 K
300

Applied stress, MPa

200

base metal
weld metal
weld joint
RCC-MR average on weld joint

100
10 100 1000 10000

Creep damage and fracture in 316 SS Rupture life,h

Trace Elements Control for Improving Creep Cavitation
Resistance in Stainless Steels

160
1023 K

100
90

Applied stress, MPa

80
70
60
304 } Cavitation
resistant
50

Precipitation
304Ti

hardened
304Nb
40 304NbCu
304TiBCe
}Precipitate
hardened
30

Cavitation
304NbBCe

resistant
304NbTiBCe
304NbCuBCe
304NbTiCuBCe
20
100 1000 10000 100000
Rupture life, hours

Ce and B prevent segregation of S on cavity surface.

B retards cavity growth rate: increases life & ductility
 Effects of Microstructure on LCF Properties of 304 SS

Uniform Matrix Cavitation

Scientific investigations established optimum grain size and cold work for better fatigue resistance of
reactor components and led to identification of new damage mechanism of uniform matrix cavitation
during high temperature fatigue.
 Fatigue Life Prediction Approaches

Prediction of LCF life using ANN model 100000

Modified 9Cr-1Mo steel
NIMS (316 SS)
IGCAR (316LN SS)
KAERI (316LN SS)
10000

Predicted life
10000
Predicted

factor of 2

1000
1000
Factor of 2

NIMS
IGCAR

100
100
100 1000 10000 100000
100 1000 10000

Experimental
Experimental life, h
Prediction of LCF life of 316LN Life prediction using Ostergreen’s
Stainless Steel using Artificial Neural frequency modified damage function
Network (ANN) model approach

Extrapolation of laboratory data to design conditions using numerical and

mechanistic approaches.
 Welding of Austenitic Stainless Steels

Macrostructure of Weld

Austenitic stainless steel Æ readily weldable materials

Welding results in the formation of a heterogeneous microstructure
Two major problems encountered during welding
X Hot Cracking of Weld Metal
Y Sensitisation at Heat Affected Zone
Deterioration in SS Weldments Due to Evolution of
Secondary Phases

Cr-rich carbides

DF image of δ-ferrite Brittle σ-phase-

SS316 weld/600ºC-5000h
Recommended range for amount of δ-ferrite ;
Strict Welding Procedure and Quality Control Procedures
 Hot Cracking Susceptibility of Austenitic Stainless Steels
100

90

80
highly susceptible
70 (0.19N)
60
D9

BTR (K)
50µm 50
(316L+Ni) susceptible
40
not susceptible
30 316L+N
•Segregation impurity or 20 316L+Ni (0.04N)
316LN+N
minor alloying elements in 10 PFBR 316 WM
A AF FA
the inter-dendritic region 0
(0.07-0.13N)

is crucial to cracking 0.6 0.8 1.0 1.2 1.4 1.6 1.8

WRC Creq/Nieq

•Maximum crack length

Brittle temperature range (BTR) estimated
(MCL), and total crack
from MCL and cooling curve and Creq and
length (TCL), are the
Ni eb obtained from composition are used
parameters obtained from
to evaluate the susceptibility of the
varestraint test to
material for hot cracking.
evaluate the susceptibility
(A – Austenite, F – Ferrite)
to cracking
 Penetration Enhancing Flux Assisted TIG Welding

Diffused arc Increase in the

Material Impact
IR Thermal image

in normal penetration in
Toughness, J
TIG
single pass PEFA-
Type 316LN
111 TIG welding of
PEFA-TIG Weld stainless steels is
Constricted arc due to
Type 316LN
in PEFA-TIG 77
Multi-pass • Arc constriction &
Weld
• Reversal of
Marangoni flow

7 passes 1 pass

10 mm

Weld bead in multi-pass TIG Weld bead in PEFA-TIG

 Manufacturing of Stainless Steel Components
Form Tolerances achieved for
the large diameter thin vessels
(main vessel, safety vessel
and inner vessel) < ½ wall
thickness (specified < wall
thickness).
Fabrication of vessels with
insignificant weld repair
Main vessel

Safety vessel

Ø Stainless steels are key materials for

fast breeder reactors
Ø Manufacturing technology established
for fabrication of critical components
Ø Capability of Indian industries to
manufacture high technology nuclear
components demonstrated (main
vessel, safety vessel, steam generator,
grid plate) PFBR will be commissioned by Sept 2010
 Deformation Processing Window for 316L SS
25

Grain Size Variance,

20
Refined window

Minimum variance is noticed in

15

µm
10

‘Refined Window’
800 900 1000 1100 1200

Temperature, oC

Grain Size Variance in stainless steel 316L

600

Refined window
600

Activation energy contours for type 316L UTS Variance in stainless steel 316L
 Alloy Design using Artificial Neural Networks with
Optimised Chemical Composition
ANN model for accurate prediction of the Ferrite Number in Stainless Steel Welds

Application of
the model:
Alloy design of
electrodes and
welding
consumables
to get desired
Ferrite Number
in Stainless
Steels
(a) Entire training dataset (b) Test dataset
Effect of alloying elements on FN has been quantified for 316L, 308L,
309L, and alloy 2205 and 255 Duplex stainless steels
• Behaviour at each scale directly or indirectly affects other scales and so
it is necessary to model simultaneously at all relevant scales.
• Modelling at different scales is therefore essential for alloy design and
thermo-mechanical processing to achieve desired properties.
 Challenges in Austenitic Stainless Steel Research
• Grain Boundary Engineering for enhancing performance
parameters in various applications
• Large size plate welding with minimum HAZ
• Manufacturing robustness with economics
• Clean steel technology for thin sections
• New generation SS with superior corrosion resistance
• Ageing management strategies for high temperature and long
life applications
• Enhancing weld performance for hot cracking
• Intelligent remote welding
• Modelling of alloy development
• Surface engineering with novel alloys and cladding
• High performance and cost effective new generation SS
Stainless Steels – Current Scenario and Future Growth

Source: Intl. Stainless Steel Forum

Stainless Steels- Bright Future & High Stakes
Hig
h qu
new ality s
Manufacturing of e ta
valu r prod inless
components with e ad ucts stee
stringent
d
exp ition p rov ls for
ort a ide
specifications, pot nd hug s
enti e
al
High market potential Stainless
and capacity additions Steel
Industry

Manufacturing Researchers Innova

tive R&
efforts
Technology & for new D
of S S t ty
Academia hrough pes
scale c la
ollabor rge
with re ations
search
academ a nd
ic insti
Synergy between global leadership in SS tutes
production and application has to be ensured
to realise benefits for industry and society
 References for Further Study
¾ Hand Book of Stainless Steels, D. Warren, USA

¾ ASTM Standards, Philadelphia, USA, 2001

¾ ASM Metals Hand Book Series

¾ Corrosion of Stainless Steels, A.J. Sedriks, John-Wiley, USA, 1998

¾ http://www.steel.org

¾ http://www.stainless-online.com

¾ http://www.nickelinstitute.org/

¾ http://www.worldstainless.org/ISSF/

¾ http://www.assda.asn.au/

¾ http://www.bssa.org.uk/

¾ Wikipedia, the free encyclopedia