Cobalt--Based Alloys

Cobalt

History of CoCo-based Alloys

Originated from investigations in the early 1900s,
when p
patents covering
g alloys
y from the systems
y
CoCr and Co-Cr-W were issued.
The resulting alloys have been under development
every since.
C
Common trade
t d names such
h as Stellite
St llit and
d Hastelloy
H t ll
(both developed by the Haynes Corp.).
Very important for cutlery, machine tools, and wearresistant hardfacing applications.

History
1930s
Co-Cr-Mo alloy Vitallium developed for dental prosthetics.

1940
1940s
s
HS-21 (derived from Vitallium) becomes important for
turbochargers and gas turbine applications.
Wrought Co-Ni-Cr
Co Ni Cr alloy S-816
S 816 used for gas turbine blades and
vanes.
Co-Ni-Cr-W alloy X-40 developed in 1943. Still used in gas
turbine vanes.

1950-1970
1950 1970
Ni-based superalloys strengthened by developed. Rapidly
surpassed capabilities of Co alloys. Co-based alloys lack
comparable precipitation hardening mechanism (doesnt
( doesn t this
sound similar to Mg alloys?)

2000s
Discovery of something new and exciting!

Some typical CoCo-based Alloys and uses

Co
FSX-414
Bal.
Stellite 21
Bal.
Stellite 31
Bal.
MarM302 Bal.
MarM509 Bal.
Haynes-188 Bal.

Ni
10.5
2
10

10
22

Cr
29.5
28
20
21.5
23.4
22

Al

Ti

0.25

Mo

5.5

W
7

15
10
7
14.5

Ta

9
3.5

B
0.012

0.005

*maximumamount

Characteristics & Uses

FSX-414
Stellite 21
Stellite 31
MarM302
MarM509
Haynes-188

Gas turbine vanes

Wear resistance
Wear resistance
Jet engine blades
blades, vanes
Jet engine blades, vanes
Better oxidation resistance than Hastelloy X

PredominantlycomposedofCo,Ni,Cr,W

Zr

0.015
0.35

C
0.25
0.3
0.1
0.85
0.6
0.1

Other
2 Fe

3 Fe*
0 90La
0.90La

Advantages vs. NiNi-based Alloys

Higher melting points and flatter stress-rupture
curves.
curves
Results in higher stress capability to higher absolute
temperatures than Ni-base (or Fe-base) alloys.

Better hot corrosion resistance in contaminated

gas turbine atmospheres due to their higher Cr
contents.
Better weldability and better thermal fatigue
resistance than Ni-base alloys.

Disadvantages vs. NiNi-based Alloys

Lower strength
Lower ductility and fracture toughness at
ambient
bi t ttemperatures.
t
Li
Limited
it d opportunity
t it ffor iimprovementt off currentt
alloys.*

Chemistry of CoCo-Based Alloys

Chemical compositions are analogous to
stainless steels
steels.
Th
The roles
l off the
th major
j and
d minor
i
alloying
ll i
elements are virtually identical as both are
austenitic
austenitic (i.e.,
(i e FCC-based)
FCC based) alloy systems
systems.

General Characteristics
Austenitic matrix (FCC crystal structure)
20 30% Cr is added to provide oxidation and hot
corrosion resistance. This is the most important
addition.
dditi
C
Cr also
l provides
id some solid
lid solution
l ti strengthening
t
th i and
d
is of vital importance in precipitation strengthening.
Additional solid solution strengthening is provided via
additions of Ta,, W,, Nb,, Mo.

General Characteristics contd

Precipitation hardening via carbide formation.*
Co alloys generally contain 0.25-1.0%C.
Co-base
C b
alloys
ll
are h
heatt ttreated
t d tto control
t l precipitation,
i it ti
which controls properties.

Ni or Fe (up to 20%) are added to stabilize the FCC

phase, thus suppressing the transformation to HCP
Co at low temperatures.
Can be prone to TCP phase formation, in particular for
high Cr contents (>58%)
*NOTE:Nitrogenisoftensubstitutedforcarboninthecarbidephases.

Physical Properties of Co
HCP when T<421C
FCC when T>421C

Co is also ferromagnetic
Tmp is 50C greater than Ni

AlloyingElement

ChangeinMeltingTemperature(F)

Raise
Tungsten

+1

Lower
Nitrogen

Iron

Chromium

Molybdenum

Vanadium

15

Manganese

15

Aluminum

20

Tantalum

30

Zirconium

30

Sulfur

40

Titanium

65

Niobium

70

Silicon

75
75

Boron

115

Carbon

120

Phase Equilibria

BCC
FCC

HCP

A.M.Beltran;CobaltBaseAlloys;inSuperalloysII,C.T.Sims,N.S.Stoloff,
A
M B l
C b l B
All
i S
ll
II C T Si
N S S l ff
andW.C.Hagel,editors;(JohnWiley&sons,NewYork,1987)p.139.
Predel,B.: CoCr(CobaltChromium).Madelung,O.(ed.).SpringerMaterials
TheLandoltBrnstein Database(http://www.springermaterials.com).DOI:
10 1007/10086082 907
10.1007/10086082_907

MostalloysarepredominantlycomposedofCo+Cr,Ni,and/orW

Functions of Alloying Elements

Nickel

Chromium

Tungsten
g

Ti,Zr,Nb,
, , , Ta C

Principal
function

Austenite
stabilizer

Surface
stability+
carbide
former

Solidsolution
strength

MCformers

Carbide
formation

Problems

Lowers
corrosion
resistance

FormsTCP
phases

FormsTCP
phases

Harmssurface
stability

Decreases
ductility

X40

10

25

7.5

0.45

MM509
MM
509

10

24

70
7.0

3.5Ta,0.5Zr,
3
5 Ta 0 5 Zr
0.2Ti

0 60
0.60

L605

10

20

15.0

0.10

HS188

22

22

14.0

0.08

whenaddedin
excess

Examples

Small amounts of Aluminum (~ 5 wt.%) has been added to improve oxidation and hot corrosion
resistance. Used extensively in coatings.
Additions of Titanium,
Titanium have been shown to form a phase,
phase (Co
(Co,Ni)
Ni)3Ti.
Ti but to also stabilize undesirable
HCP-Co3Ti or Co2Ti-Laves phases).
Rare earth additions (0.08-0.15 wt.%) increases oxide scale adhesion and reduces oxidation
kinetics(RE effect).

Phase Equilibria

BCC
FCC

HCP

Predel,B.: CoCr(CobaltChromium).Madelung,O.(ed.).SpringerMaterials
TheLandoltBrnstein Database(http://www.springermaterials.com).DOI:
10.1007/10086082_907

A.M.Beltran;CobaltBaseAlloys;inSuperalloysII,C.T.Sims,N.S.Stoloff,
A
M B l
C b l B
All
i S
ll
II C T Si
N S S l ff
andW.C.Hagel,editors;(JohnWiley&sons,NewYork,1987)p.141.

AlloyingadditionsselectedtostabilizeFCCorHCPphases
oy g add o s se ec ed o s ab e
o
p ases
Rememberourdiscussionofalloydesign.
FCC/HCPtransition PossibilityofStackingFaults

Alloying

A.M.Beltran;CobaltBaseAlloys;inSuperalloysII,C.T.Sims,N.S.Stoloff,andW.C.Hagel,editors;(JohnWiley&sons,NewYork,1987)p.142.

Dislocationinteractionw/faultsproducesstrengthening.
Faultsarealsopreferentialnucleationsitesforcarbides;candegradeproperties.
Faults are also preferential nucleation sites for carbides; can degrade properties.
FCCstabilizingadditions(e.g.,Ni)areaddedtoinhibitSFformation&carbide
formationduringHTexposure.

Carbides in CoCo-based alloys

Primary
Pi
strengthening
t
th i precipitate:
i it t incoherent
i
h
t cubic
bi carbides.
bid
Comparative C contents:
Austenitic stainless steel
Ni-base superalloy (cast)
Co-base superalloy (cast)

0.02-0.20 wt.%
0.05-0.20 wt.%
0.25-1.0 wt.%
Solubilitylimitsat1260C

A.M.Beltran;CobaltBaseAlloys;in
SuperalloysII,C.T.Sims,N.S.Stoloff,andW.C.
Hagel,editors;(JohnWiley&sons,NewYork,
1987) 144
1987)p.144.

Carbides in CoCo-based Alloys

A.M.Beltran;CobaltBaseAlloys;in
SuperalloysII,C.T.Sims,N.S.Stoloff,andW.C.
Hagel,editors;(JohnWiley&sons,NewYork,
1987)p.145.

Carbide
CarbideformerscomefromgroupstotheleftofCointheperiodictable
formers come from groups to the left of Co in the periodic table
(Goldschmidtscriteria).Theseelementsaremoreelectronegativeandthus
morereactivethanCo.

Classes of Carbides
M3C2, M7C3, and M23C6 Carbides.
These are basically chromium carbides containing Co
Co, W
W, or Mo
in place of Cr.
M3C2 has a rhombic crystal structure and forms via a peritectic
reaction with Cr. It has been observed in some of the early
superalloys with low Cr contents.
M7C3 has a trigonal crystal structure and forms at low Cr/C
ratios. It can be dissolved during solution treating and in some
cases transforms to M23C6 during aging
aging.

Classes of Carbides
M3C2, M7C3, and M23C6 Carbides.
M23C6 generates very potent precipitation strengthening
strengthening. It is the
result from decomposition of the M7C3 carbides via reactions of
the form:

23C 7 C3 7C
23Cr
7Cr23C6 27C
6C+23Cr Cr23C6

decomposition
Reprecipitation

In M23C6 carbides, some heavier atoms often substitute for Cr

yielding the following formulae:

(Co,Ni) x (W,Mo) y (C,B,Si) z

Cr18Co3Mo 2 C6
Cr17 Co 4 W2 C6

Classes of Carbides
M3C2, M7C3, and M23C6 Carbides.
Tend to form via a eutectic type reaction:

In
I castt alloys
ll
M23C6 comes outt interdendritically.
i t d d iti ll
Specific carbide morphology depends upon cooling rate.

M3C2, M7C3, and M23C6 Carbides.

Morphology will depend on alloy
chemistry and cooling rates.

M3C2, M7C3, and M23C6 Carbide Morphology

Cast alloys:

Interdendritic
M23C6

In interdendritic areas, slow cooling results in a eutectic

microstructure consisting of alternating plates of (FCC) and
((M23C6) p
phases.
Fast cooling leads to change in morphology of M23C6.

Classes of Carbides
M6C and MC Carbides
These carbides are rich in refractory elements. They are used to
strengthen wrought and investment cast Co
Co-base
base alloys.
MC carbides are typically of the form: TaC, HfC, NbC, etc.,
Similar to Ni-base alloy systems, M6C carbides are generally
found in low-Cr alloys with Mo and/or W levels > 46 at.%.
M6C carbides are typically of the form:

M 3 M3C or M 4 M3C
(Co 0.45Cr0.3Ta 0.15 W0.1 )C

Classes of Carbides
M6C and MC Carbides
M6C carbides often form during
g service via a decomposition
p
reaction:

MC + austenite M 6 C
Example:

TaC + (Co,Ni,Cr,C) (Co,Ni) 4 (Cr,Ta) 2 C

Microstructural Variants MC Carbides

Chinese script eutectic carbide

Blocky or acicular carbides

Blockycarbidestend todevelop
whenN2 ispresent.

Other phases
We stated that it was possible to form , just not the same as
a Ni-base superalloy.
In
I these
h
alloys
ll
= (Co,Ni)
(C Ni)3Ti.
Ti
However, the phase is unstable
above 760C.
Also, once you add Cr, it no
longer forms.

Mechanical Working
We want to break down the coarse carbides that
form during
g solidification. This can be done by
y
mechanical working.

FiguretakenfromCo:
CobaltinSuperalloys,The
CobaltDevelopment
Institute:1985;page10

Solution Treatment and ReRe-PPTn.

FiguretakenfromSims,
Figure
taken from Sims
Stoloff,andHagel;
SuperalloysII,JohnWiley
&Sons:1987;page155

Canworkwithcertaindrawbacks.

ItisalsopossibletoformTCPphases(,,
Laves).
Laves)

Stepsmustbetakentoavoidthem.Theyare
undesirableastheyaresitesfortheinitiation
d
bl
h
f h
offracture.

Carbidesstrengthenthesealloys,butarealso
potentialsitesforfractureinitiation.

Something New!
Co-based - Alloys
Based on ternary Co-Al-W
Co Al W

Off
Offer potential
t ti l for
f superalloy
ll type
t
performance
f
at higher temperature.