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3.0: SUPER-ALLOYS:
Super-alloys are heat-resistant, corrosion-resistant and creep-resistant material,
They are iron, cobalt and nickel base alloys with some chromium for resistance to
oxidation and hot corrosion and other elements (columbium, molybdenum, tungsten
and tantalum) for strengthening.

They form extensive component-base in the aircraft industry, oil and gas industry,
chemical plant industry. Generally super-alloys exhibit good resistance to corrosion,
creep, fatigue, thermal shock, impact, cavitation and erosion and in addition have
good fracture properties, forming characteristics and weld ability.

The variety of uses of super-alloys include

♦ Chemical and Oil/Gas Industry:

Bolts

Valves

Reaction vessels

Piping

Pumps etc.

♦ Steam Turbine power plants

Bolts

Blades

♦ Aircraft gas turbines

Disks

Bolts

Shafts

Cases

Blades

Vanes

Burner cars

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Thrust reverses.

Super-alloys are also used in reciprocating engines, metal processing industries,

space vehicles, medical applications, heat-treating equipment, nuclear power
systems etc.

3.1 SUPER-ALLOY TYPES.

(Ref. Metals Handbook Vol 3 P. 210 9th Edition)

♦ Iron-base solid solution alloys.

16-25-6 16Cr 25Ni 6Mo

Incoloy 800 21Cr 33Ni 46Fe Balance Ti, Al, C, Cu.

Incoloy 801 205Cr 32Ni 46.5Fe Balance Ti, Al.

Incoloy 802 21 Cr 20Ni 44.8Fe Balance Ti, Al, C.

♦ Cobalt-base solid solution alloys:

Haynes 25 (L-605) 20Cr, ION] 50Co 15W 3Fe Balance: Mn, C.

Haynes 188 22Cr 22NI 37Co 14.5 W 3maxFe, Balance: La, C.

♦ Nickel base solid solution alloys

Hastelloy B 1 Cr 63NI 2.5 Co 28Mo 5Fe Balance: C, V.

Hastelloy B-2 1Cr 69NI 1Co 28Mo He Balance: C.

Inconel 600 15.5Cr 76Ni 8Fe Balance: C, Cu.

Inconel 601 23Cr 60.5Ni 1.35Al 14.1Fe Balance: C, Cu.

Inconel 604 16Cr 74NI 2.25Ni 7.517e Balance: C, C u.

Nimonic 75 19.5Cr 75NI 0.4Ti 0.15A1 2.5 Fe Balance: C, Cu.

♦ Iron-base precipitation-hardening alloys

Discaloy 15Cr 26Ni 1.25Mo 2ti 0.2Al 55.2 Fe Balance C, B, and V.

Haynes 556 22Cr 21Ni 20Co 3Mo 2.5W O.1Nb 0.3Al 29 Fe Bal: Ta,La,Zr,C.

lncoloy 903 0.1Cr 38Ni 15Co 0.1 Mo 3Nb 1.4Ti 0.7Al 41 Fe Balance: C.

♦ Cobalt-base precipitation hardening alloys

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AR - 213 19 Cr 0.5Ni 65 Co 4.5 W 0.5 Fe Balance: C, Ta, Zr, Y.

MP-35N 20Cr 35Ni 35 Co 10 No

♦ Nickel base precipitation hardening alloys:

Astrology 15 Cr, 56.5 Ni 15 Co 5.25 Mo 3.5 Ti, 4.4A1 0.317e Balance: C,B,,Zr.

In 100 I 1OCr, 60Ni, 15 Co 3Mo 4.7 Ti 5.5A1 0.6 Fe Balance: C,V,Zr,B.

Nimonic 80A19.5('r 73Ni 1('0 2.25 Ti 1.4A1 I.5 Fe Balance: C,Cu

3.1.1. Typical applications of stainless steels and super alloys in 0

and G operations:

3.2 METALLURGY OF SUPER-ALLOYS

The properties associated with super-alloys derive from the following

♦ Solid Solution strengthening

♦ Precipitation strengthening

♦ Oxide dispersion strengthening

The strengthening and mechanical strength at high temperatures are as a result of 6

the type of alloying elements in the system as illustrated in the Tables below.

Oxide dispersion strengthened super alloy are listed below.

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Table 1 Oxide dispersion strengthened super-alloy (ODS)

The role of various elements and their effects on the metallurgy of super-alloys are
shown on Tables 2 and 3

Table 2: Role of alloying elements on super-alloys

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(a) Not all these effects necessarily occur in a given alloy. (b) hardening by
precipitation of Ni3Ti also occur if sufficient NI is present. (c) if present in large
amounts, borides are formed.

Table 3 Effects of elements in iron-base super-alloys

3.2.1 SPECIFIC SUPER-ALLOYS

Iron base super-alloys

♦ Major constituent is iron.

♦ Its face-centred cubic matrix (austenite form close packed phases, namely
sigma, Mu, Laves and chi)------- which are resistant to time temperature
dependent deformation process (creep) or temperature above 540° C (1 000
degrees Fahrenheit).

♦ They are used in gas turbines as blades, disks, casings and fasteners.

♦ Lower cost substitutes for nickel - and cobalt super-alloys.

♦ Carbon along with carbide phases (M23 C and M6 C) on the grain boundary
and grain body to promote strength in these regions.

Cobalt - base super-alloys.

♦ Major constituent is cobalt -

♦ Made up of three major groups Viz

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o Alloys for use at temperature from 650° C to 6500 C (1200 to 2100° F)

o Fastener alloys for use at temperature, close to 6500.C

o Wear resistant alloys.

♦ All alloys at heat-treated and softened condition have FCC crystal structures,
some however develop close packed hexagonal structure during thermo -
mechanical processing.

♦ All contain secondary phases Me, M23C, M7C3 or Me) or intemetallic

compounds.

♦ Possess high hot hardness through the formation of complex carbides thus
they are used as erosion shields and wear pads for bends in tube systems
carrying particulate matter at high temperature sand high velocities.

Nickel Base Super-Alloys

♦ Major component is Nickel

♦ Possess greater resistance to high temperature than low- alloy steels and
stainless steels.

♦ Contain small amounts of Al, Ti, Nb, Mo, W to enhance strength or corrosion
resistance

♦ Used in high temperatures chemical processing equipment like hydrocarbon

reformers and crackers.

♦ One source of their strength is through solid solution strengthening and by

various heat treatments, optimum tensile, fatigue, creep - rupture properties of
temperature more than 650°C are produced.

♦ The other source of their strength is through precipitation hardening with the
aid of elements like Al, Ti, Nb, giving rise to the precipitation of second phases
- gamma prime or gamma double prime thus increasing the strength and
hardness of the alloy for engineering applications.

♦ Incoloy 903, an iron - nickel - cobalt super-alloy has high strength and low
constant coefficient of expansion.

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For " Properties and the Average Costs of Super-alloys, Stainless Steels,

Polymers and Ceramics)”, Refer to " Appendices B and C of Materials

Science & Engineering ----------An Introduction"; by William D. Canister,

Jnr.; Fifth Edition, John Wiley & Sons Inc.

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3.3 OTHER FEATURES OF SUPER-ALLOYS:

Super-alloys especially Nickel-chromium base super-alloys possess better creep and

oxidation resistance than Stainless Steels. Chromium, tungsten or molybdenum are
extensively used to enhance sheet fabrication of super-alloys. Carbon and minor
elements control workability and the microstructure of super-alloys. Creep strength in
nickel base super-alloys derive from gamma prime, an ordered FCC precipitated
phase formed by the following alloying elements: aluminium, titanium, tantalum and
columbium. Hafnium is a new addition to super-alloys for workability and hot ductility,
which is a problem in very high creep strength alloys. Columbium in large
percentage forms a precipitate in super-alloys designated " gamma double prime"
which enhances fabricability and weldability in super alloys. Welded super-alloys
suffer from post weld heat treatment (PWHT) cracking if the right solute elements are
not added in the right quantity, if the welding and heat treatment are not well
sequenced and if the right filler material is not used. Thus in the choice of
super-alloys for application many factors must be considered.

3.4 HIGH TEMPERATURE FAILURE OF SUPER-ALLOYS

OVERHEATING occurs when an alloy is exposed to excessively high temperatures

for short periods of time. Allowable metal temperatures for wrought heat resistant
alloys in structural applications generally do not exceed about 950°C. In applications
where the component does not bear load, allowable temperature may exceed
1200°C. In general any temperature can be considered to be in the over-heating
range when it

(a) causes melting

(b) causes strengthening phases to dissolve in the matrix or

(c) causes extensive oxidation or corrosion. Results of overheating depend on

the maximum temperature reached by the alloy.

Nickel base and cobalt base super alloys generally have incipient melting
temperatures above 1200°C. Over heating may deplete alloy elements that
provide oxidation resistance. Surface corrosion results and even for coated
components, the mechanical properties of the material are adversely affected. At
temperatures that cause neither incipient melting nor surface degradation, alloy

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strength may still be reduced because strengthening phases are taken into
solution For Stainless Steels, especially ferritic stainless steels embrittlement
results when they are exposed for long times below 480°C. Martensitic Stainless
Steels also suffer from embrittlement around such temperatures. For Stain less
Steels at 565°C and above the load carrying abilities decrease from thermal
exposures of 100000 hours in the unstressed condition.

3.5 OVER HEATING, CREEP AND ALLOY STABILITY IN

SUPERALLOYS

Heat resistant alloys normally respond to heat treatment, and thus exposure of these
alloys to elevated temperatures with or without stress can cause micro-structural
changes and resultant changes in properties. Generally the higher the exposure
temperature the more rapid the structural changes. As the exposure temperature
decreases the type of micro structural degradation may change. At the highest
exposure temperatures, an alloy may be subject to incipient melting. In addition
oxidation and surface corrosion will take place at all temperatures for which these
alloys are normally specified. Below are illustrations of incipient melting in some
super alloys:

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Fig. 9. Effect of Incipient melting on microstructure of two nickel-base super alloys

Table 6 Incipient melting temperatures of selected wrought super alloys

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3-6: HYDROGEN SULFIDE AND STEEL

SOUR SERVICE - (Hydrogen Sulphide)

NACE Material Requirement MR-O1-75 defines gas as "sour" if the partial pressure
of Hydrogen Sulphide is 0.05 psia or more.

At 10000 psi, this translates to 5 parts per million (ppm) or 0.0005 Mol% of hydrogen
sulphide.

MR-O1-75 does not address pressures in excess of 10000 psi or partial pressures
less than 0.05 psia. The NACE definition of "sour" is in Figure 10. Sulphide-stress
cracking of particular steel depends on the amount of Hydrogen Sulphide present
and also on the amount of tensile stress in the steel.

Steel at low stress can tolerate more Hydrogen Sulphide than it can at high stress.
The "threshold stress" is the maximum stress that the steel can tolerate without
brittle 'fracture.

The Threshold Stress decreases as the amount of Hydrogen Sulphide increases.

Similarly, steel at high temperature can tolerate more Hydrogen Sulphide than it can
at lower temperatures.

Manufacturers usually classify a steel as "sour service" if the minimum Threshold

Stress is 80% or more of the yield stress in tests at room temperature.

Figure 10

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