HeatTreatmentTechnology

Dr.SantoshS.Hosmani
DEPT. METALLURGY & MATERIALS SCIENCE,
COLLEGE OF ENGINEERING, PUNE
The role of alloying elements in Steels
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3
Classification of iron alloy phase diagrams:
(Ref.: Wever, Archiv fr Eisenhttenwesen 2, 193, 19281929)
Fe-Ni system
Ni, Mn, Co
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Ni, Mn, Co
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C, N, Cu, Zn, Au
Si, Al, Be, P,
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Si, Al, Be, P,
Ti, V, Mo, Cr
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B,
Ta, Nb, Zr
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Ref.: Book by H.K.D.H. Bhadeshia & R.W.K. Honeycombe
9 Ref.: Book by H.K.D.H. Bhadeshia & R.W.K. Honeycombe
Effect on Fe-C phase diagram
i bili i l i Austenitestabilizingelements:Ni,Mn,Co,C,N
Ferritestabilizingelements:Cr,Si,Mo,W,V
A
1
temperature is lowered by the austenite-formers (e.g. Ni,
Mn, Co) and raised by the ferrite-formers (e.g. Cr, Si, Mo, ) y ( g
W, V).
A chrome steel containing 12% Cr and 0.4% C requires a g % % q
higher austenitizing temperature than a eutectoid carbon
steel, whereas a 3% Ni steel will already begin to
austenitize below 700 C austenitize below 700 C.
This state of affairs is clearly of great practical importance
h th t l b i d t t t d when these steels are being used at temperatures around
A
1
.
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Effect on Fe-C phase diagram
Influence of alloying element addition on eutectoid temperature and ue ce o a oy g e e e t add t o o eutecto d te pe atu e a d
eutectoid carbon content is displayed in following figure:
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What are your observations from the following phase-diagrams ? at a e you obse at o s o t e o o g p ase d ag a s
The amount of Ti required to close the -phase loop is much less than
the required for Cr in binary Fe-alloys
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the required for Cr in binary Fe alloys
Hardening effects of alloying elements in solid solution in fully
annealed ferrite
Here, factors affecting hardness are:
Size difference between solute Size difference between solute
and solvent atoms,
Concentration of solute atoms
Elastic modulus of solute
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Classification of alloying additions
A useful grouping is based upon the effect of the element on:
(a) the stability of the carbides and
(b) the stability of the austenite/ferrite.
1. Elements which tend to form carbides: Cr, W, Ti, Nb, V, Mo and Mn.
2. Elements which tend to graphitise the carbide: Si, Co, Al and Ni. 2. Elements which tend to graphitise the carbide: Si, Co, Al and Ni.
Only a small proportion of these elements can be added to the steel
before graphite forms during processing.
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15
3 Elements which tend to stabilise austenite: Mn Ni Co and Cu
Classification of alloying additions
3. Elements which tend to stabilise austenite: Mn, Ni, Co and Cu.
These elements alter the critical points of iron in a similar way to
carbon by lowering the A
3
point, thus increasing the range in which
austenite is stable, and they also tend to retard the separation of austenite is stable, and they also tend to retard the separation of
carbides.
They have a crystal lattice (f.c.c.) similar to that of -iron in
which they are more soluble than in -iron which they are more soluble than in iron.
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Classification of alloying additions
4. Elements which tend to stabilise ferrite: Cr, W, Mo, V, Si and Ti. 4. Elements which tend to stabilise ferrite: Cr, W, Mo, V, Si and Ti.
These elements are more soluble in -iron than in -iron. They
diminish the amount of carbon soluble in the austenite and thus tend
to increase the volume of free carbide in the steel for a given carbon
content. On the binary equilibrium diagram of these elements with
pure iron the A
3
point raised (although it may be lowered initially), until
the two points merge to form a closed gamma loop.
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r
e
m
p
e
r
a
t
u
Cr
T
e
m
18 Fe C
Animation: S.S. Hosmani
One convenient way of illustrating quantitatively the effect of an alloying element
on the -phase field of the FeC system is to project on to the FeC plane of the
Classification of alloying additions
on the phase field of the Fe C system is to project on to the Fe C plane of the
ternary system the -phase field boundaries for increasing concentration of a
particular alloying element. This is illustrated in Figure below for titanium and
chromium, from which it can be seen that just over 1wt% Ti will eliminate the -
l hil 20 t% C i i d t h thi i t Oth t t loop, while 20wt% Cr is required to reach this point. Other ternary systems
can be followed in the same way, e.g. in FeVC, vanadium has an effect
intermediate between that of titanium and of chromium.
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Thus above a certain
Classification of alloying additions
Thus, above a certain
amount of each of these elements
the austenite phase disappears
and ferrite exists from the melting- and ferrite exists from the melting
point down to room temperature.
No critical points exist and such
steels (e.g. 18% chromium irons) ( g )
are not amenable to normal heat
treatment, except recrystallisation
after cold work.
Isomorphous phase diagram of
This effect, however, can be
counteracted by adding certain
elements, like 2% of nickel is
Isomorphousphasediagramof
FeCrsystem
Here, in Fe-Cr phase diagram, we
can note that for Cr > 12 7% the
elements, like 2% of nickel is
added to the 18% chromium
stainless steel to enable it to be
refined by normal heat-treatment;
can note that, for Cr > 12.7%, the
ferrite phase becomes stable over
the entire temperature range up to
the melting point. If C is present
in the alloy then more Cr content
carbon has the same effect.
in the alloy, then more Cr content
is required to nullify carbons
austenite stabilizing effect.
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Stainless steels are categorized into four groups on the basis of
composition and crystal structure:
ferritic,
austenitic,
martensitic and
duplex stainless steels.
Stainless steels contain not less than 10 12 % Cr and often Ni in Stainless steels contain not less than 10-12 % Cr and often Ni in
addition.
The effect of other elements present in Cr-Ni steels can be
expressed as Ni equivalent (if they stabilize the austenite) and as Cr
equivalent (if they stabilize ferrite):
25N 30C 03C 05M C Ni i l t Ni 25N 30C 0.3Cu 0.5Mn Co Ni equivalent Ni + + + + + =
W 0.75 1.5Ti 1.75Nb 5.5Al 5V 1.5Mo 2Si Cr equivalent Cr + + + + + + + =
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The Schaeffler diagram depicts the phases present in the alloy as e Sc ae e d ag a dep cts t e p ases p ese t t e a oy as
a function of Ni and Cr equivalents:
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Fe-Ni-Cr Phase diagram: In order to control crystal structure the Fe-Ni-Cr Phase diagram: In order to control crystal structure, the
effect of ferritic and austenitic stabilizing alloying elements should
be taken into account.
s
m
a
n
i
S
.
S
.

H
o
s
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Formationofduplexmicrostructureduringsolidificationofthemelt
Duplexstainlesssteelssolidify100%ferrite(ferrite). p y ( )
Uponcoolingtheferritestartstopartiallydecomposeinto
t it th t l t d fi t t th i austenitethatnucleatesandgrowsfirstatthegrain
boundariesofferrite,followingfavorablecrystallographic
orientationsinsideofthegrains.
Asthetemperaturelowerstheferritecontentdecreases
asausteniteincreases(andcarbidesandseveralintermetallicphases
may also form during cooling: depending upon cooling rate) mayalsoformduringcooling:dependinguponcoolingrate)
Many literature prefers to denote ferrite in DSSs as ferrite rather than ferrite because DSSs
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Many literature prefers to denote ferrite in DSSs as ferrite rather than ferrite because DSSs
contain ferrite which is resulted (transformed) from liquid and not from austenite (refresh memory for
FeC diagram).
Duplex stainless steels (DSSs) are in between the austenitic and the ferritic grades,
b h b h l ( ll
SomeoftheimportantaspectsofDSSs
combining the best mechanical and corrosion resistance (especially, pitting, stress
corrosion cracking) properties of both.
A lt f th i hi h h i l t th d th l d ti it d ll t As a result of their high mechanical strength, good thermal conductivity and excellent
corrosion resistance DDSs are extensively used both in pulp and paper industries, in
chemical and petrochemical plants. They also find some applications in food and
biomedical fields as well.
The wide use of DSSs is closely connected to their specific microstructure, formed by
roughly 50%50% austeniteferrite ratio: higher yield and ultimate tensile strength than
the austenitic grades, with good ductility and toughness. But, on the other hand, the
microstructural anisotropy of the hot rolled materials can result in variability of
mechanical properties, such as tensile strength and fracture toughness.
Theaustenite+ferritematrixisattainablebycombiningvariousphasestabilizingelements.
CrandMo:ferritestabilizers.Ni(andN):austenitestabilizers.
Some economical advantages as a result of lower nickel content than the austenitic
grades.
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Pittingresistanceequivalentnumber(PREN):
PREN=%Cr+3.3x%Mo+17x%N
Figure:NominalPRENvaluesfordifferentstainlesssteels
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Ref.[$$]:D.S.Bergstrom,J.J.Dunn,J.F.Grubb,W.A.Pratt:PatentNumberUS20036551420B1(2003).
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It i ll k th t it ll i i t l d i t f ti l ti
Nickelfreeduplexstainlesssteels
It is well known that nitrogenalloying in steel produces a variety of exceptional properties
such as high strength, high ductility and resistance to stress corrosion cracking (SCC).
Nickel could be completely replaced by nitrogen in order to enhance SCC resistance and
reduce the alloying element cost.
A much lower nitrogen content is needed to maintain a 50% austenite phase compared
with the necessary addition of nitrogen to reach a 100% austenitic microstructure.
Except for nonmagnetic applications, nickelfree DSS are definitely promising in regard to
their properties and cost, and thus are suitable, for example, as reinforcing steels or
corrosion resistant structural materials corrosion resistant structural materials.
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Nickelfreeduplexstainlesssteels
Table: Chemical Composition, AusteniteContent and Calculated PREN Values of theDSSs.
Steel D10 is intended to have the lowest possible alloying element cost with about 22% Cr Steel D10 is intended to have the lowest possible alloying element cost, with about 22% Cr,
10%Mn and 0.35%N.
Steel D103 contains additionally about 3%Mo together with the further elevated nitrogen
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concentration of 0.45% in oder to improve the corrosion resistance.
Nickelfreeduplexstainlesssteels
Figure: The calculated nitrogen section of
the phase diagram of alloy Fe-22Cr-10Mn-N
b Th C l
Figure: The calculated nitrogen section of
the phase diagram of alloy Fe20Cr10Mn
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by Thermo-Calc.
3MoN by ThermoCalc.
D 10 D 10-3
Nickelfreeduplexstainlesssteels
Figure: The dependence of the ferrite
content on annealing temperature.
In comparison with commercial Duplex 2304 and Duplex 2205, the D10 and D103 alloys
show a more stable austenite content at high temperatures:
Due to its potent austenitic stabilization and rapid diffusion rate in FeCr alloys, nitrogen in
such nickelfree DSS increases the microstructural stability at high temperatures.
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Also compare phase diagrams on previous slide with the phase diagram on Slide # 48 or 49.
Nickelfreeduplexstainlesssteels
Table: Typical Room-temperatureMechanical Propertiesof theInvestigatedAlloys. Table: Typical RoomtemperatureMechanical Properties of theInvestigated Alloys.
In comparison with commercial Duplex 2304 and Duplex 2205, the D10 and D103 alloys
show a more yield strength (without affecting other mechanical properties) show a more yield strength (without affecting other mechanical properties).
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Nickelfreeduplexstainlesssteels
Table: Results of Pitting and CreviceCorrosion Tests of theExperimental DSS.
Tccc: critical crevicecorrosiontemperature
In comparison with commercial Duplex 2304 and Duplex 2205, the D10 and D103 alloys
have poor Crevice Corrosion Resistance.
With respect to corrosion properties, D103 alloy seems to be better choice than D10
ll d i h bl l 220
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alloy; and properties are somewhat comparable to Duplex 2205.
Nickelfreeduplexstainlesssteels
Table: Typical Composition and Costs of DSS and Austenitic Stainless Steels.
D10 and D103 Steels possess the highest ratio of PRE value to alloying cost due to a high p g y g g
nitrogen content and the absence of nickel.
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Intermetallic phases like sigma () chi () and G etc can form during casting or high
ProblemsassociatedwithDSSs(Warnings)
Intermetallic phases, like sigma (), chi () and G etc, can form during casting or high
temperature processing and can degrade the mechanical and corrosion properties of the
DSS.
During welding of DSS parts, such undesirable phases can form in heat affected zone (HAZ).
Therefore, welding of DSS parts is challenging task.
DSSs are characterized by two embrittling temperature ranges (Cshaped curves) which exhibit
several secondary phases, carbides and nitrides precipitation at different holding times:
475C b ittl t 475Cembrittlement
a spinodal decomposition of the a ferrite in two
phases: an Crrich phase and an Ferich phase.
nucleation and growing of NiSiMo rich f.c.c. G
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Figure: TypicalTTTdiagramforDSSs
g g f f
phase, characterised by a very slow precipitation
kinetic (the overall concentration in Gforming
elements increases from 40 to 60% between 1000
and 30000 h at 350C).
The stability of a given secondary phase usually depends on Fe, Cr, Mo and Ni contents in
the steel the steel.
The effect of alloying elements on the formation of those phases is indicated in the
following Figure:
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BSE and XEDS analysis
Howtoidentifysecondaryphasesinmicrographs?
y
can help in identification.
Figure: BSE micrograph of CD3MWCuN
ll l d 825C C
Figure: BSE micrograph of CD3MN
k 850C f 30 d h alloy annealed at 825C. Contrast
difference can be seen between and .
EDS scanning assured the brighter phase
as enveloped by .
taken at 850C after 30day heat
treatment.
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p y
Forverysmallsize(tiny)particles:TEMcan,ofcourse,helpinidentification
IdentifythefollowingtypesofStainlesssteelsusingtheirmicrostructures:
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