IIW-AWS

Technical Lectures
The Cr-Mo Steels
January/February 2006
J. F. Henry
Temper Embrittlement
Lesson 3
IIW-AWS
January/February 2006


Temper Embrittlement


Lesson 3
IIW-AWS
January/February 2006


Temper Embrittlement is defined as the shift in the
ductile-brittle transition temperature (DBTT) that
results when certain alloy steels are held within, or
cooled slowly through, a critical temperature range
(~700-1000 F).

An IIW document summarized that temper
embrittlement affects the toughness of Cr-Mo steels
that are exposed to temperatures 660-1110 F.

Slow cooling through the critical range following
tempering or PWHT, or service exposure in that
temperature range, can lead to embrittlement.
Temper Embrittlement Defined


Lesson 3
IIW-AWS
January/February 2006


Temper embrittlement is a major cause of degradation
of toughness of ferritic steels.

Numerous otherwise sound components must be
retired due to severe embrittlement during elevated
temperature service, since under these conditions the
critical crack size can become very small.

Effects of Temper Embrittlement

Lesson 3
IIW-AWS
January/February 2006


Effects of Temper Embrittlement

Lesson 3
IIW-AWS
January/February 2006


A significant number of components are designed to
operate in the susceptible temperature range, so that
temper embrittlement can occur during service. This
group involve components of all section sizes,
including boiler headers, steam pipes, turbine casings,
pressure vessels, blades, fasteners, HP-IP rotors, &
turbine disks.

In the case of massive components, such as LP rotors,
generator rotors, and retaining rings, some
embrittlement may be inevitable as a result of slow
cooling following heat treatment.
Service and Heat Treatment

Lesson 3
IIW-AWS
January/February 2006


Temper embrittlement has been identified in a wide
range of alloys, including low alloy steels, higher
strength alloy steels and stainless steels.

Risk is higher with components produced using older
methodologies. Increased susceptibility is related to:

Higher normalizing temperature larger grain size
Steel making practices higher levels of impurities
Material Affected

Lesson 3
IIW-AWS
January/February 2006


In general, the increased risk of rapid brittle
fracture is not a major concern during steady
operation at elevated temperature --- sufficient
fracture toughness.

Problems have been encountered during hydrostatic
testing of headers & piping or during operational
transients, where fracture toughness is critical.

The risk of failure should also be considered during
steady operation in the case that stable crack growth
can lead to instability during subsequent operational
transient.

Reduction in upper shelf energy.
Operational Risks

Lesson 3
IIW-AWS
January/February 2006


Decrease Of Critical Flaw Size For Brittle Fracture Of A 2 Cr-1Mo
Reactor Vessel At 50 F Due To Temper Embrittlement
Operational Risks

Lesson 3
IIW-AWS
January/February 2006


Occurs within a specific temperature range.

Related to compositional changes in grain
boundaries.

Intergranular fracture.

Increase in FATT or in DBTT, but strength &
hardness are largely unaffected.

Can be avoided or eliminated by heat-treating
above the susceptible temperature range
followed by rapid cooling through that range.
Characteristics Of Temper
Embrittlement
Lesson 3
IIW-AWS
January/February 2006


I ntergranular Fracture Produced
By Temper Embrittlement
I n A Cr-Mo Steel
Fracture Behavior in Embrittled
Material

Lesson 3
IIW-AWS
January/February 2006


Shift In Transition Curve
Due To Temper Embrittlement
Lesson 3
IIW-AWS
January/February 2006


Temper embrittlement occurs by equilibrium grain boundary (GB)
segregation of major alloying elements and impurities occurring in
the susceptible temperature range.

Impurities reduce the cohesive strength of grain boundaries, creating
an easy path for fracture.

When the GB energy of a material is reduced by the presence of of an
alloy element, the concentration of the element in the GB is higher
than in the matrix due to the disordered state of the GB compared
to the matrix.

Segregation effect is usually confined to one to two atomic layers and
decays exponentially away from GB.

Segregation is reversible at temperatures above the susceptible
temperature range

Mechanisms Related To Temper
Embrittlement
Lesson 3
IIW-AWS
January/February 2006


In GB segregation theory, GB solute concentration X
b
is
approximately given by Langnuir-Mclean equation:






Where is the free energy released per mole when a solute atom
is released from the matrix to the GB. is usually positive and
increases as the size difference between the solute and the matrix
atoms increases.

) exp(
0
RT
G
X X
b
b

b
G
b
G
Mechanisms Related To Temper
Embrittlement
Lesson 3
IIW-AWS
January/February 2006


Auger Spectra From A Ni-Cr Steel I n The (a) Embrittled And (b) Non-Embrittled
Conditions, Showing Segregation Of Phosphorus Onto Grain Boundary
Embrittled
Non-Embrittled
Segregation Effect During
Embrittlement

Lesson 3
IIW-AWS
January/February 2006


Dependence Of GB Concentration Of Phosphorus On Annealing Temperature
For Fe-P Alloys With Different Levels of Phosphorus
GB segregation of P decreases with
increasing temperature and
decreasing bulk concentration

Temperature/Concentration
Dependence

Lesson 3
IIW-AWS
January/February 2006


GB Concentration Of P and C I n Fe-0.17%P Alloys With Different Carbon Levels
GB concentration of P
decreases with increasing
free carbon content

The Plateau shows at a
carbon level of 55 ppm
(solubility limit at 660 C)

Carbon-Phosphorus Interaction
Lesson 3
IIW-AWS
January/February 2006


Effects Of C and Cr On GB Concentration Of P After Annealing
At Different Temperatures With About The Same Bulk Concentration of P
The level of P segregation
dramatically decreases when
carbon is added to Fe-P

With the addition of 2%Cr,
the segregation of P is nearly
the same level as in the alloys
without carbon

C-Cr-P Interaction
Lesson 3
IIW-AWS
January/February 2006


In Seah-Hondros segregation theory, GB enrichment ratio is
inversely proportional to atomic solubility of the element in the
parent lattice.
The solubility in turn is inversely proportional to the term ( ) in
the Gibbs absorption formula:




Where is the GB concentration of the impurity in excess of
the bulk concentration C. is reduction in GB energy with the
the concentration of the impurity at temperature T.

Mechanisms Related To Temper
Embrittlement
dC
d
dC
d
kT
C

2
2

dC
d
Lesson 3
IIW-AWS
January/February 2006


Correlation Of Predicted GB Enrichment Ratios For Various Solutes
With The I nverse Of Solid Solubility
Effect of Matrix Solubility of Potential
Embrittling Agents
Lesson 3
IIW-AWS
January/February 2006


Time-Temperature relationship for temper embrittlement follows
C-Curve behavior---Diffusion-Controlled Process.
C-Curve Behavior For A 2 Cr-1 Mo Steel
Showing I sothermal FATT Contours
Embrittlement Kinetics
Lesson 3
IIW-AWS
January/February 2006


No significant segregation of impurity elements had been found
in carbon steels, presumably due to sufficient free C in solution.
Embrittlement can occur when carbon is tied up as carbides.

Embrittlement occurs in commercial alloy steels due to
segregation of P during slow cooling from high temperatures
involved with normalizing, during controlled step-cooling and
on holding in the temperature range (650-1000 F)

Factors Affecting Temper
Embrittlement
Lesson 3
IIW-AWS
January/February 2006


I ncrease I n Brittle Behavior, As Measured By I ncreasing Values Of FATT
With I ncreasing Levels Of Bulk P Content I n Three Rotor Steels
Effects of Alloy Content
Lesson 3
IIW-AWS
January/February 2006


Sn, Sb & As can also lead to embrittlement in some special alloys,
especially when P is absent. When P is present, it appears to exhibit
the dominant effect. Presence of C can further lower the tendency to
embrittle.

GB segregation of Sn in Fe-0.2%Sn Alloy
GB segregation of Sn in Fe-Sn-C Alloys
Factors Affecting Temper
Embrittlement
Lesson 3
IIW-AWS
January/February 2006


Embrittlement Data For A Range Of 2CrMo Weld Metals
Mn & Si in combination
appear to affect the level of
embrittlement when P is
present.
Mn is believed to reduce the
GB strength
Si is believed to promote the
segregation of P
A systematic effect of
greater embrittlement due
to P at higher levels of the
sum of Mn & Si
The presence of Mo Acts to
slow down the embrittlement
due to P
either because Mo & P
atoms tend to associate and
prevent P segregation
or because Mo increases the
coherency of GB Structure
Factors Affecting Temper
Embrittlement
Lesson 3
IIW-AWS
January/February 2006


The rate of embrittlement with time follows a parabolic relationship
(diffusion-controlled process).
Variation of FATT
With Time Of Aging at
850 F For A CrMoV
Rotor Steel
Segregation effects are reversible and embrittlement can be removed
by higher-temperature heat-treatment followed by rapid cooling.
Factors Affecting Temper
Embrittlement
Lesson 3
IIW-AWS
January/February 2006


Temperature of exposure is an important factor for embrittlement ---
C-Curve Behavior
A steep segregation gradient in
GB area -- peak segregation
occurs within 2-3 atomic planes,
indicating that energy
considerations limit segregation
to within the peak regions of GB
structure
There appears to be a trend in
decreasing susceptibility to
embrittlement from martensitic
to bainitic to ferritic structure.
AES results showing S, P & Sn
GB segregation pattern
Factors Affecting Temper
Embrittlement
Lesson 3
IIW-AWS
January/February 2006


Grain size appears to be an important factor, since available GB area
is governed by grain size.
Variation of FATT With Prior
Austenite Grain Size At Fixed
Hardness and I mpurity Levels
Factors Affecting Temper
Embrittlement
Lesson 3
IIW-AWS
January/February 2006


Compositional Effects on Embrittlement
Lesson 3
IIW-AWS
January/February 2006


Significant Improvement In The Levels Of
Trace Element In Modern Steels
Reduction Of The Level Of Trace Elements With Time For 2 Cr-1 Mo Steel Components
Impact of Steel-Making Practice
Lesson 3
IIW-AWS
January/February 2006


Since temper embrittlement is mainly related to material chemistry,
susceptibility can be quantitatively evaluated in terms of composition.

J Factor

J = (Mn+Si)(P+Sn) x 10
4
(%)

FATT (C) = 0.38 J 45

X Factor

= (10P+5Sb+4Sn+As)/10
2
(ppm)
X = (8P+10Sb+4Sn+As)/10
2
(%)





Prediction Of Temper Embrittlement
X
___
Lesson 3
IIW-AWS
January/February 2006


P
E
Factor
P
E
= C+Mn+Cr/3+Si/4+3.5 (10P+5Sb+4Sn+As)

FATT Factors
FATT (C)= 7524P+7194Sn+1166As-52Mo-450,000(P x Sn) (%)

FATT (C)= 4.8P+24.5Sn+13.75 (7-GS)
+2 (Rc-20)+0.33 (Rc-20)(P+Sn)
+ 0.036 (7-GS)(Rc-20)(P+Sn) (%)

Where: GSGrain Size I n Form Of ASTM Number,
Rc---Hardness (HRC)

Prediction Of Temper Embrittlement
Lesson 3
IIW-AWS
January/February 2006



FATT (C)= 4.8P+24.5Sn+13.75 (7-GS)+2 (Rc-20)+0.33 (Rc-20)(P+Sn)
+ 0.036 (7-GS)(Rc-20)(P+Sn) (%)

Where: GSGrain Size I n Form Of ASTM Number,
Rc---Hardness (HRC)
Prediction Of Temper Embrittlement
Lesson 3
IIW-AWS
January/February 2006


EF Factor
EF = %Si + %Mn + %Cu + %Ni x Y
Y = (10P+5Sb+4Sn+As)/10
2
(ppm)

50%FATT Factor (C-Mn Steels)
50% FATT (C) = 19 + 44 (%Si) + 700 (%free nitrogen)
1/2

+ 2.2 (%pearlite) + 11.5 d
1/2

Where: dlinear ferrite grain size (mm)

* The influence of elements on FATT was also assessed in an overall ranking of
1% Si: FATT + 44 C
0.01% N: FATT + 70 C
1%Sn: FATT + 136 C
1%P: FATT + 459 C
Prediction Of Temper Embrittlement
Lesson 3
IIW-AWS
January/February 2006


Step Cooling
An Accelerated Embrittlement Process
A commonly used procedure for the assessment of
pressure vessel steels in the petroleum industry
According to API results, FATT in such a step-
cooling treatment is approximately one third of what
might be expected after 30 years of service in an actual
reactor vessel.

Long-Term Isothermal Aging


Evaluation Of Susceptibility To Temper
Embrittlement (Laboratory Methodology)