Materials behavior and

degradation
mechanisms at high
temperatures.
Objectives & Subjects of interest
Objectives:

This chapter provides the understanding of materials behavior and

degradation mechanisms at high temperatures.

Subjects of interest

• Introduction to materials under high temperature condition

• Some main High Temperature Degradation Mechanisms:

- Graphitization
- Spheroidization
- Creep
- Oxidation
- Carburization
- Sulfidation
Materials under high temperature condition

The effect of service environment on material performance at elevated

temperature can be divided into three main categories :

• Microstructural effects, such as grain growth & over aging.

• Chemical effects, such as oxidation.
• Mechanical effects, such as creep & stress rupture.
In high temperature applications, the environment plays an important role
in determining the performance of component.

 Selecting the material that will resist the environment, controlling the
environment, or protecting the surface is essential for prolong service.

 It become clear that the service temperature has a considerable influence

on the strength of material and, consequently, on the working stress used
in design.

 Depending on the temperature range, the design can based on :

• Short-time properties of the material, as described by the yield
strength and UTS , for moderate temperature.
• Both short-time and creep properties for intermediate temperature
Materials under high temperature condition

In addition of creep, other factors which must be taken into account when
designing for elevated temperature include :

• Metallurgical & microstructure change which occur in the material due to

long-time exposure to elevated temperature.

• Influence of method of fabrication, especially welding, on creep behavior.

• Oxidation & hot corrosion.

Design guideline:
• For design purposes, properties usually presented on plots which yield
reasonable straight lines. Common methods of presentation is log-log plots
of stress vs steady state creep rate.
• Change in microstructure of the material, will change in creep properties
and consequently a change in the slope of the line.
• Generally, designing under high temperature condition is carried according
to well-established codes:
E.g ASME Boiler & Pressure Vessel Code
BS 806:1975 (piping for land boilers)
Materials under high temperature condition

At high temperature, Materials tend to :

• Atoms move faster diffusion-control process.

This affects mechanical properties of materials.

• Greater mobility of dislocations (climb).

• Increased amount of vacancies.

• Deformation at grain boundaries.

• Metallurgical changes, i.e., phase transformation, precipitation,

oxidation, recrystallization.

.
Materials under high temperature condition

Selection of Materials:

Room T to 150°C:
• Most engineering metals & alloys except lead.

150 - 400°C:
• Plain C or Mn-C steel, or if very long-service low-alloy steel.

Up to 250°C:
• high-grade cast irons, Al alloys.

400 - 600°C:
• Low-alloy steel & Ti alloys are main materials used in this
range.
• Low-alloy steel is inexpensive & used if no restriction on
weight.

600 - 1000°C:
• stainless steels,
Main High Temperature Degradation Mechanisms:
Graphitization

- A change in the microstructure after long

term operation in the range (427°C to
593°C) that may cause a loss in strength,
ductility, and/or creep resistance.
- At elevated temperatures, the carbide
phases are unstable and may decompose
into graphite nodules.
Affected Materials
Some grades of carbon steel and 0.5Mo
steels.
Critical Factors
a)The most important factors chemistry,
temperature, and time of exposure.
b)There are two general types of
graphitization.
• Random graphitization in which the
graphite nodules are distributed
randomly throughout the steel.
• The second and more damaging type of
Main High Temperature Degradation Mechanisms:
Spheroidization

- Change in microstructure in the 440°C-

760°C range were the carbide phases are
unstable and agglomerate to a spheroidal
form in low alloy steels.
Causes loss of strength and or creep
resistance.
Affected Materials
All commonly used grades of carbon steel and
low alloy steels.
Critical Factors
- Metal chemistry, microstructure, exposure
and temperature
- The rate of Spheroidization depends on
temperature and initial microstructure.
- Spheroidization can occur in few hours at
600 °C but can take several years at 450
°C.
- Coarse grain are more resistant than fine
grain.
Main High Temperature Degradation Mechanisms:
Main High Temperature Degradation Mechanisms:
Creep

- At high temperatures, metal components can slowly and continuously deform

under load below the yield stress.
- Creep is define as time dependent deformation which occurs under stress.
• Creep occur as a result of the motion of dislocation within the grains,
grains boundary rotation and grains boundary sliding.
• When reach certain value, fracture occur.
• Creep rupture (also called stress rupture) usually takes place at strains
much less than the fracture strain under tension test at room
temperature.

Affected Materials
All metals and alloys.

Critical Factors
- The rate of creep deformation is a function of the material, load, and
temperature.
- Temperature at which materials start to creep depends on the melting point:
T > 0.3 – 0.4Tm
• Because atomic mobility becomes sufficient to cause softening of cold-
worked structure and coarsening of unstable precipitates.
Main High Temperature Degradation Mechanisms:

Movement of dislocations in the crystal lattice causes permanent deformation

initiating:

Microvoids, string of microvoids, microcracks, macrocracks then failure.

1. Annihilation:
Diffusion assisted climb
poof !
climb
2. By passing obstacles:

glide

glide climb
Main High Temperature Degradation Mechanisms:


grain boundary

diffusion
d

bulk crystal

diffusion
d
Main High Temperature Degradation Mechanisms:

Stages of Creep:

Primary creep (I) The deformation of the material causes strain

hardening (by the increase the number of dislocations) which decreases
the creep rate.

Secondary creep (II) The creep rate is constant because the number of
dislocations generated by strain hardening equals the number of
dislocations removed by annihilation.

Tertiary creep (III) By the subsequent formation of creep cavities (voids),

the linking of voids into void chains and creep cracks the creep rate
increases until rupture.

Tertiary creep can be caused by: –

• Reduction of cross-sectional area of component due to cracking or
necking.
• Oxidation and other environmental effects, which reduce the cross
Main High Temperature Degradation Mechanisms:
Main High Temperature Degradation Mechanisms:

Creep damage starts

c
tertiary
creep

time
Main High Temperature Degradation Mechanisms:

Replica Investigation
Main High Temperature Degradation Mechanisms:

Would you identify the stages??

Main High Temperature Degradation Mechanisms:

Would you
identify the
stages??
Main High Temperature Degradation Mechanisms:

Creep voids in Incoloy 800H

Main High Temperature Degradation Mechanisms:

Consider the following to have a design against creep:

• Minimize T / Tmelting to slow diffusion, climb, and creep.

• Arrange for large grain sizes to slow diffusion.

• Use precipitates (oxide particles) and solid solutions to slow dislocations.

Main High Temperature Degradation Mechanisms:
Oxidation

- Reaction of oxygen with metal/alloy at high temperature converting the

metal/alloy to oxides.

Affected Materials
a) All iron based materials including carbon steel and low alloy steels, both cast
and wrought.
b) All 300 Series SS, 400 Series SS and nickel base alloys also oxidize to varying
degrees, depending on composition and temperature.

Critical Factors
• The primary factors affecting high temperature oxidation are metal
temperature and alloy composition.
• Rates of metal loss increase with increasing temperature.
• In general, the resistance of carbon steel and other alloys is determined by
the chromium content of the material. Increasing chromium levels produce a
more protective oxide scale.
• The presence of water vapor can significantly accelerate oxidation rates of
some steels.
Main High Temperature Degradation Mechanisms:

Oxide
Unalloyed steel
Metal

Cr2O3
Cr alloyed steel

Cr2O3, SiO2 , Al2O3

Cr, Si, Al alloyed steel

Important elements for oxidation resistance are:

Cr Si Al Ce(REM)
Mo, V and W are detrimental
 Rare Earths (Cerium , Lanthanum etc.) increase Si diffusion to surface.
Main High Temperature Degradation Mechanisms:

Influence of alloying elements:

Chromium as well as Nickel, Silicon and Aluminum are used as alloying

elements to improve the oxidation resistance in alloys.

In many oxidation-resistant materials a combination of Chromium and Nickel is

used, resulting in an austenitic structure.

The influence of other elements is in most cases rather small.

Main High Temperature Degradation Mechanisms:
Main High Temperature Degradation Mechanisms:
Main High Temperature Degradation Mechanisms:

API RP-571
Main High Temperature Degradation Mechanisms:
Main High Temperature Degradation Mechanisms:

Appearance or Morphology of Damage

a) Most alloys, including carbon steels and low alloy steels, suffer general
thinning due to oxidation. Usually, the component will be covered on the
outside surface with an oxide scale, depending on the temperature and
exposure time.

b) 300 Series SS and nickel alloys generally have a very thin dark scale unless
exposed to extremely high temperatures where metal loss rates are
excessive.
Main High Temperature Degradation Mechanisms:
Carburization

- Carbon is absorbed into a material at elevated temperature while in contact

with a carbonaceous material or carburizing environment.

Affected Materials
Carbon steel and low alloy steels, 300 Series SS and 400 Series SS, cast stainless
steels, nickel base alloys with significant iron content.

Critical Factors
• Three conditions must be satisfied:
1) Exposure to a carburizing environment or carbonaceous material.
2) Temperature high enough to allow diffusion of carbon into the metal
[typically above 593°C].
3) Susceptible material.

• Carburization can result in the loss of high temperature creep ductility, loss
of ambient temperature mechanical properties (specifically
toughness/ductility), loss of weldability, and corrosion resistance.
Main High Temperature Degradation Mechanisms:

Mechanism of carburization
• Diffusion of C into metal lattice and conversion of primary carbides:

M23C6 + C M7C3

M7C3 + C M3C2

Formation of secondary carbides (growing on primary carbides):

M23C6 M7C3 M3C2

• Increase in volume and embrittlement and decrease in creep strength and

reduction in residual life.

Prevention / Mitigation
a) Select alloys with adequate resistance to carburization including alloys
with a strong surface oxide (silicon and aluminum).

b) Reduce the carbon activity of the environment through lower temperatures

and higher oxygen/sulfur partial pressures. Sulfur inhibits carburization and is
Main High Temperature Degradation Mechanisms:

CO,CH2  C Cr carbides

Embrittlement
Decreased corrosion resistance

 The metal cracks or “dusts” due to excessive carbide formation.

 Good oxidation resistance = Good carburization resistance
Main High Temperature Degradation Mechanisms:

Carburization depends on : Metal temperature, Alloy composition.

Defects in protective Attack due to

oxide layer Carburization

Line of defense: Oxide scale : Cr , Si , Al

Main High Temperature Degradation Mechanisms:

Temperature effect :

Ovalisation, bulging, tube bending from uneven carburization.

Main High Temperature Degradation Mechanisms:

Temperature: Increase of temperature increases the carburization rate

exponentially. Coke deposition results in increase of temperature.

Carbon activity: in steam cracking processes the carbon activity ac is always

>1. Carburization will occur if thermodynamically a decomposition reaction
resulting in carbon formation is possible.

Contamination of feed stock: presence of CI, Na and S (above 200 ppm) is

harmful.

Alloying elements:

Beneficial:

Cr, Si, Ti, W, Zr

Harmful:
S, Mn
Main High Temperature Degradation Mechanisms:
Sulfidation

- Corrosion of carbon steel and other alloys resulting from their reaction with
sulfur compounds in high temperature environments. The presence of
hydrogen accelerates corrosion.
- This mechanisms is also known as sulfidic corrosion.

Affected Materials
• All iron based materials including carbon steel and low alloy steels, 300
Series SS and 400 Series SS.
• Nickel base alloys are also affected to varying degrees depending on
composition, especially chromium content.
• Copper base alloys form sulfide at lower temperatures than carbon steel.

Critical Factors
• Major factors affecting sulfidation are alloy composition, temperature and
concentration of corrosive sulfur compounds.
• Susceptibility of an alloy to sulfidation is determined by its ability to form
protective sulfide scales.
• In general, the resistance of iron and nickel base alloys is determined by the
Cr content of the material. Increasing the Cr content significantly increases
Main High Temperature Degradation Mechanisms:

• At high temperatures (more than 260°C),

sulphur compounds react with metals to
form complex sulphides and/or oxides.
This causes very severe attack unless the
chromium content is very high.

• The protective oxide scale is dissolved

and then Sulphur diffuses into the metal
substrate forming metal sulfides then the
metal cannot rebuilt a new protective
oxide layer.

• At the scale-metal interface the activity

of sulphur exceeded that of both carbon
and oxygen and the grain boundary
chromium carbide network was
converted to chromium sulphide.
Main High Temperature Degradation Mechanisms:

Nickel sulphides –
with low melting
points (650°C)

Cr, Mn, Al, Si are important elements

Ni is detrimental
Main High Temperature Degradation Mechanisms:

Chromium sulfides –
reducing the protectiveness
of the Cr-oxide scale

The internal sulphidation would

deplete the chromium needed
to maintain a chromium oxide
scale. Once started the process
is self-maintaining and attack
by oxidation accelerates rapidly.

Sulfidation of a high (32%) Cr-alloy with the

formation of Cr-sulfides, reducing the
adhesion of the Cr-oxide film.
Main High Temperature Degradation Mechanisms:

Sulfidation failure of carbon steel on the right after 2 years in

operation. Original thickness is shown on left for comparison. Material
was supposed to be 9Cr-1Mo (API 971).
Main High Temperature Degradation Mechanisms:

The most practical course of action would be to:

• Closely monitor H2S concentration in the furnace effluent stream

and control DMDS injection into the feed accordingly.

• Monitor the thickness of all transfer lines during scheduled

turnarounds to reduce the likelihood of unscheduled failures.