HIGH TEMPERATURE

MATERIALS

BY
M. SANTHOSH,
Lecturer,
Department of Aeronautical Engineering
Contact:mkkksans@yahoo.co.in
 MATERIAL
Material is synonymous with substance, and is anything made of matter
hydrogen, air and water are all examples of materials

The basis of materials science involves relating the desired properties and
relative performance of a material in a certain application to the structure of
the atoms and phases in that material through characterization.

The major determinants of the structure of a material and thus of its

properties are its constituent chemical elements and the way in which it has
been processed into its final form.

The manufacture of a perfect crystal of a material is currently physically

impossible. Instead materials scientists manipulate the defects in crystalline
materials such as precipitates, grain boundaries, interstitial atoms,
vacancies or substitutional atoms, to create materials with the desired
properties.
 CRYSTALLOGRAPHY

What is a crystal?
In materials science a crystal is a solid substance in which the
atoms, molecules or ions are arranged in an orderly repeating pattern extending in
all three spatial dimensions - length, width and height.

The process of forming a crystalline structure from a fluid or from materials

dissolved in the fluid is often referred to as crystallization.
Various types of crystal structures in interest

1. SC
2. BCC
3. FCC
4. HCP
 SIMPLE CUBIC STRUCTURE (SC)
Cubic unit cell is 3D repeat unit
Rare (only Po has this structure)
Close-packed directions (directions along which atoms touch each other)
are cube edges.

(Courtesy P.M. Anderson)

 BODY CENTERED CUBIC
STRUCTURE (BCC)
Coordination # = 8

Adapted from Fig. 3.2,

(Courtesy P.M. Anderson) Callister 6e.

Close packed directions are cube diagonals.

--Note: All atoms are identical; the center atom is shaded
differently only for ease of viewing.
 FACE CENTERED CUBIC
STRUCTURE (FCC)
Coordination # = 12

Adapted from Fig. 3.1(a),

(Courtesy P.M. Anderson) Callister 6e.

Close packed directions are face diagonals.

--Note: All atoms are identical; the face-centered atoms are shaded
differently only for ease of viewing.
 HEXAGONAL CLOSE-PACKED
STRUCTURE (HCP)

Ideally, c/a = 1.633 for close packing

However, in most metals, c/a ratio deviates from this value
Some metals & their crystal structures
 CRYSTAL DEFECTS
A perfect crystal, with every atom of the same type in the
correct position, does not exist. All crystals have some defects.
Defects contribute to the mechanical properties of metals
There are basic classes of crystal defects:
Point defects, which are places where an atom is missing or irregularly
placed in the lattice structure. Point defects include lattice vacancies,
self-interstitial atoms, substitution impurity atoms, and interstitial
impurity atoms
Linear defects, which are groups of atoms in irregular positions. Linear
defects are commonly called dislocations.
Planar defects, which are interfaces between homogeneous regions of
the material. Planar defects include grain boundaries, stacking faults
and external surfaces.
 POINT DEFECTS

A self interstitial atom is an extra atom that has crowded its way into an
interstitial void in the crystal structure.
A substitutional impurity atom is an atom of a different type than the bulk
atoms, which has replaced one of the bulk atoms in the lattice.
Substitutional impurity atoms are usually close in size (within
approximately 15%) to the bulk atom.
An example of substitutional impurity atoms is the zinc atoms in brass. In
brass, zinc atoms with a radius of 0.133 nm have replaced some of the
copper atoms, which have a radius of 0.128 nm.
Interstitial impurity atoms are much smaller than the atoms in the bulk
matrix. Interstitial impurity atoms fit into the open space between the bulk
atoms of the lattice structure. An example of interstitial impurity atoms is
the carbon atoms that are added to iron to make steel. Carbon atoms, with a
radius of 0.071 nm, fit nicely in the open spaces between the larger (0.124
nm) iron atoms.
Vacancies are empty spaces where an atom should be, but is missing. They
are common, especially at high temperatures when atoms are frequently
and randomly change their positions leaving behind empty lattice sites. In
most cases diffusion (mass transport by atomic motion) can only occur
because of vacancies
 LINEAR DEFECTS
Dislocations are another type of defect in crystals. Dislocations are areas
were the atoms are out of position in the crystal structure. Dislocations are
generated and move when a stress is applied. The motion of dislocations
allows slip plastic deformation to occur.
In the early 1900s scientists estimated that metals undergo plastic
deformation at forces much smaller than the theoretical strength of the
forces that are holding the metal atoms together.
There are two basic types of dislocations,
the edge dislocation
the screw dislocation.

EDGE DISLOCATIONS

The edge defect can be easily visualized as an extra half-plane of atoms in a

lattice.
The dislocation is called a line defect because the locus of defective points
produced in the lattice by the dislocation lie along a line.
This line runs along the top of the extra half-plane.
The inter-atomic bonds are significantly distorted only in the immediate
vicinity of the dislocation line.
Dislocation motion is analogous to movement of a caterpillar
SCREW DISLOCATIONS

The motion of a screw dislocation is

also a result of shear stress, but the
defect line movement is perpendicular
to direction of the stress and the atom
displacement, rather than parallel.
The image aside shows the screw
dislocation
 Planar Defects in Solids
One case is a twin boundary (plane)
Essentially a reflection of atom positions across the twin
plane.

Adapted from Fig. 5.14,

Callister & Rethwisch 3e.

Stacking faults
For FCC metals an error in ABCABC packing sequence
Ex: ABCABABC
16
 GRAIN BOUNDARY CONCEPT
If you were to take a small section of a common metal and examine it under a microscope,
you would see a structure similar to that shown in figure.
Each of the light areas is called a grain, or crystal, which is the region of space occupied by a
continuous crystal lattice.
The dark lines surrounding the grains are grain boundaries. The grain structure refers to the
arrangement of the grains in a metal, with a grain having a particular crystal structure.
The grain boundary refers to the outside area of a grain that separates it from the other grains.
The grain boundary is a region of misfit between the grains and is usually one to three atom
diameters wide.
A very important feature of a metal is the average size of the grain. The size of the
grain determines the properties of the metal. For example, smaller grain size increases
tensile strength and tends to increase ductility. A larger grain size is preferred for improved
high-temperature creep properties.
Some of the more important physical and chemical properties
from an engineering material standpoint will be discussed in the
following sections.
Phase Transformation Temperatures
Density
Specific Gravity
Thermal Conductivity
Linear Coefficient of Thermal Expansion
Electrical Conductivity and Resistivity
Magnetic Permeability
Corrosion Resistance
 You should be familiar with the following
terms which you would have studied in lower
classes.
1. Engineering stress
2. Engineering strain
3. True stress
4. True strain
5. Yield strength
6. Yield point
7. Ultimate point
And some basic definitions related to strength of materials
What is meant by loading a material?
The application of a force to an object is known as loading. Materials can
be subjected to many different loading scenarios and a materials
performance is dependant on the loading conditions.
There are five fundamental loading conditions; tension, compression,
bending, shear, and torsion.
Tension is the type of loading in which the two sections of material on
either side of a plane tend to be pulled apart or elongated.
Compression is the reverse of tensile loading and involves pressing the
material together.
Loading by bending involves applying a load in a manner that causes a
material to curve and results in compressing the material on one side and
stretching it on the other.
Shear involves applying a load parallel to a plane which caused the material
on one side of the plane to want to slide across the material on the other
side of the plane.
Torsion is the application of a force that causes twisting in a material.
If a material is subjected to a constant force, it is called static loading. If the
loading of the material is not constant but instead fluctuates, it is called
dynamic or cyclic loading. The way a material is loaded greatly affects its
mechanical properties and largely determines how, or if, a component will
fail; and whether it will show warning signs before failure actually occurs.
PROBLEMS FACED BY
MATERIALS OPERATED
AT
ELEVATED
TEMPERATURES
 The mechanical strength of metals decreases with increasing temperature
and the properties become much more time dependent.
In the past the operating temperatures in applications like steam power
plant, chemical plant and oil refineries seldom exceeded 500oC, but since
the development of the gas turbine in the 1940's successive designs have
pushed this temperature up to typically 1000 oC.
Developments in high temperature alloys with improved high temperature
strength and oxidation resistance have had to keep pace with these
demands, and applications like rocket engines present greater problems.
At homologous temperatures of more than 0.5, creep is of engineering
significance
HIGH TEMPERATURE
>0.3TM

Creep
High temperature fracture
Corrosion
Fatigue
Embrittlement
These are the factors affecting the functional
or service life of components at elevated
temperatures
CREEP
 CREEP
Creep is the tendency of a solid material to slowly move or
deform permanently under the influence of stresses.
It occurs as a result of long term exposure to levels of stress that are below
the yield strength of the material. Creep is more severe in materials that are
subjected to heat for long periods, and near the melting point.
Creep always increases with temperature.
The rate of this deformation is a function of the material properties,
exposure time, exposure temperature and the applied structural load.
The temperature range in which creep deformation may occur differs in
various materials.
the effects of creep deformation generally become noticeable at
approximately 30% of the melting point for metals and 4050% of melting
point for ceramic
Creep deformation is important not only in systems where high
temperatures are endured such as nuclear power plants, jet engines and heat
exchangers
In steam turbine power plants, pipes carry steam at high temperatures (566
C or 1050 F) and pressures (above 24.1 MPa or 3500 psi). In jet engines,
temperatures can reach up to 1400 C (2550 F) and initiate creep
deformation in even advanced-coated turbine blades. Hence, it is crucial for
correct functionality to understand the creep deformation behavior of
materials.
 Creep data for general design use are usually obtained under
conditions of constant uniaxial loading and constant temperature.
Results of tests are usually plotted as strain versus time up to
rupture.
As indicated in the image, creep often takes place in three stages. In
the initial stage, strain occurs at a relatively rapid rate but the rate
gradually decreases until it becomes approximately constant during
the second stage.
This constant creep rate is called the minimum creep rate or steady-
state creep rate since it is the slowest creep rate during the test. In
the third stage, the strain rate increases until failure occurs.
Creep in service is usually affected by changing conditions of
loading and temperature and the number of possible stress-
temperature-time combinations is infinite. While most materials are
subject to creep, the creep mechanisms is often different between
metals, plastics, rubber, concrete.
High homologous temperatures (Tservice/Tmelting)
Unlike brittle fracture, creep deformation does not occur suddenly
upon the application of stress. Instead, strain accumulates as a result
of long-term stress. Creep deformation is "time-dependent"
deformation.
MECHANISMS OF CREEP IN METALS

There are three basic mechanisms that can

contribute to creep in metals, namely:
(i) Dislocation slip and climb.
(ii) Grain boundary sliding.
(iii) Diffusional flow
 DISLOCATION CREEP
Dislocations slip is hindered by obstacles such
(i) grain boundaries,
(ii) impurity particles,
(iii) the stress field around solute atoms in
solution or
(iv) the strain fields of other dislocations.
DIFFUSIONAL CREEP
 GRAIN BOUNDARY SLIDING

The onset of tertiary creep is a sign that structural damage has

occurred in an alloy.
Rounded and wedge shaped voids are seen mainly at the grain
boundaries and when these coalesce creep rupture occurs.
The mechanism of void formation involves grain boundary
sliding which occurs under the action of shear stresses acting
on the boundaries
Voids in creep ruptured Nimonic 80A. Showing scratch lines displaced across a grain
boundary in Aluminium.
A model for the formation of cracks
due to grain boundary sliding

The formation of wedge cracks

during grain boundary sliding.
DATA EXTRAPOLATION METHODS
LARSEN MILLER PARAMETER
AN EXAMPLE
 STRAIN HARDENING
Strain hardening (also called work-hardening or cold-working)
is the process of making a metal harder and stronger through
plastic deformation.
When a metal is plastically deformed, dislocations move and
additional dislocations are generated. The more dislocations
within a material, the more they will interact and become
pinned or tangled. This will result in a decrease in the mobility
of the dislocations and a strengthening of the material. This
type of strengthening is commonly called cold-working. It is
called cold-working because the plastic deformation must
occurs at a temperature low enough that atoms cannot
rearrange themselves.
When a metal is worked at higher temperatures (hot-working)
the dislocations can rearrange and little strengthening is
achieved.
Strain hardening can be easily demonstrated with piece of wire
or a paper clip. Bend a straight section back and forth several
times. It increases the strength of the wire. This is said to be
strain hardened wire.
 Effects of Elevated Temperature on Strain
Hardened Materials
When strain hardened materials are exposed to elevated temperatures, the
strengthening that resulted from the plastic deformation can be lost. This
can be a bad thing if the strengthening is needed to support a load.
Heat treatment can be used to remove the effects of strain hardening. Three
things can occur during heat treatment
Recovery
Recrystallization
Grain growth
 RECOVERY

When a stain hardened material is held at an elevated temperature an

increase in atomic diffusion occurs that relieves some of the internal strain
energy.
Remember that atoms are not fixed in position but can move around when
they have enough energy to break their bonds.
Diffusion increases rapidly with rising temperature and this allows atoms in
severely strained regions to move to unstrained positions. In other words,
atoms are freer to move around and recover a normal position in the lattice
structure. This is known as the recovery phase and it results in an
adjustment of strain on a microscopic scale.
Internal residual stresses are lowered due to a reduction in the dislocation
density and a movement of dislocation to lower-energy positions. The
tangles of dislocations condense into sharp two-dimensional boundaries
and the dislocation density within these areas decrease. These areas are
called sub grains. There is no appreciable reduction in the strength and
hardness of the material but corrosion resistance often improves.
 RECRYSTALLIZATION
At a higher temperature, new, strain-free grains nucleate and grow inside
the old distorted grains and at the grain boundaries. These new grains grow
to replace the deformed grains produced by the strain hardening. With
recrystallization, the mechanical properties return to their original weaker
and more ductile states.
Recrystallization depends on the temperature, the amount of time at this
temperature and also the amount of strain hardening that the material
experienced.
The more strain hardening, the lower the temperature will be at which
recrystallization occurs. Also, a minimum amount (typically 2-20%) of
cold work is necessary for any amount of recrystallization to occur. The
size the new grains is also partially dependant on the amount of strain
hardening. The greater the stain hardening, the more nuclei for the new
grains, and the resulting grain size will be smaller (at least initially).

GRAIN GROWTH

If a specimen is left at the high temperature beyond the time needed for
complete recrystallization, the grains begin to grow in size. This occurs
because diffusion occurs across the grain boundaries and larger grains have
less grain boundary surface area per unit of volume.
Therefore, the larger grains lose fewer atoms and grow at the expense of
the smaller grains. Larger grains will reduce the strength and toughness of
the material.
 SOLID SOLUTION STRENGTHENING
Solid solution strengthening is a type of alloying that can be used to
improve the strength of a pure metal. The technique works by adding atoms
of one element (the alloying element) to the crystalline lattice another
element (the base metal). The alloying element diffuses into the matrix,
forming a solid solution
Depending on the size of the alloying element,
Substitutional solid solution or
Intersitial solid solution
Substitutional solid solution strengthening occurs when the solute atom is
large enough that it can replace solvent atoms in their lattice positions.
According to the Hume-Rothery rules, solvent and solute atoms must differ
in atomic size by less than 15% in order to form this type of solution.
When the solute atom is much smaller than the solvent atoms, an interstitial
solid solution forms. This typically occurs when the solute atoms are less
than half as small as the solvent atoms. The smaller solute atom essentially
"crowds" into the spacings within the lattice structure, causing defects in
the material. Elements commonly used to form interstitial solid solutions
include H, N, C, and O. Carbon in iron (steel) is one example of interstitial
diffusion.
FRACTURE
 FRACTURE
A separation of an object into two or more pieces in response
to active stresses below the melting temperature of the
material.
Two steps in the process of fracture:
Crack initiation
Crack propagation
 Types of Failure in Materials
FIGURE 3.20 Schematic illustration of
types of failure in materials: (a) necking
and fracture of ductile materials; (b)
buckling of ductile materials under a
compressive load; (c) fracture of brittle
materials in compression; (d) cracking
on the barreled surface of ductile
materials in compression. (See also Fig.
6.1b)
FIGURE 3.21 Schematic illustration of
the types of fracture in tension: (a)
brittle fracture in polycrystalline metals;
(b) shear fracture in ductile single
crystals (see also Fig. 3.4a); (c) ductile
cup-and-cone fracture in polycrystalline
metals (see also Fig. 2.2 ); (d) complete
ductile fracture in polycrystalline
metals, with 100% reduction of area.
DUCTILE AND BRITTLE FRACTURE
Ductile Fracture
TRANSGRANULAR CREEP
FRACTURE
INTERGRANULAR CREEP
FRACTURE
PURE DIFFUSIONAL FRACTURE
RUPTURE
HIGH TEMPERATURE
CORROSION
 BASICS
CORROSION is the deterioration of a material by its reaction with the
surroundings. It adversely affects those properties that are to be preserved.
At higher temperature, this mode of degradation is known as oxidation or
dry corrosion or scaling. Metals and alloys sometimes experience
accelerated oxidation when their surfaces are covered with a thin film of
fused salt in an oxidizing atmosphere at elevated temperatures. This mode
of attack is called hot corrosion, where a porous, non-protective oxide
scale is formed at the surface and sulphides in the substrate
High temperature corrosion is a form of corrosion that does not require the
presence of a liquid electrolyte.
In general, the names of the corrosion mechanisms are determined by the
most abundant dominant corrosion products. For example:
Oxidation implies oxides,
Sulfidation implies sulfides,
Sulfidation/oxidation implies sulfides plus oxides, and
Carburization implies carbides
 High temperature corrosion is a widespread
problem in various industries such as:
power generation (nuclear and fossil fuel)
aerospace and gas turbine
heat treating
mineral and metallurgical processing
chemical processing
refining and petrochemical
automotive

pulp and paper

waste incineration
 During operation, blades and vanes of gas
turbines are subjected to high thermal stresses
and mechanical loads.
In addition, they are also attacked chemically by
oxidation and/or high-temperature corrosion.
Only composite materials are able to meet such a
demanding spectrum of requirements; the base
material provides the necessary mechanical
properties and coatings provide protection against
oxidation and corrosion
 Hot corrosion
Hot corrosion may be defined as an accelerated corrosion, resulting
from the presence of salt contaminants such as Na2SO4, NaCl, and
V2O5 that combine to form molten deposits, which damage the
protective surface oxides
Hot corrosion occurs when metals are heated in the temperature
range 700900C in the presence of sulphate deposits formed as a
result of the reaction between sodium chloride and sulphur
compounds in the gas phase surrounding the metals.
At higher temperatures, deposits of Na2SO4 are molten (m.p.
884C) and can cause accelerated attack on Ni- and Co-based
superalloys. This type of attack is commonly called hot corrosion.
Accelerated corrosion can also be caused by other salts, viz.
vanadates or sulphates vanadate mixtures and in the presence of
solid or gaseous salts such as chlorides
CHARACTERISTICS AND MECHANISM OF
HOT CORROSION
Hot corrosion can occur at high temperatures,
where the deposit is in the liquid state right
from the beginning, or the solid deposit turns
into liquid during exposure as a result of
reaction with the environment.
These two types of hot corrosion processes are
termed as
High Temperature Hot Corrosion (HTHC) or Type I
Low Temperature Hot Corrosion (LTHC) or Type II
respectively
 TYPES OF OXIDE LAYERS
High temperature oxidation usually results in formation of an
oxide layer on the surface of the oxidizing metal. Thin oxide
layers (commonly thinner than 3000 ) are called films. Thicker
oxide layers (above 3000 ) are called scales.(1.0 = 10-10 m)
Oxide scale may be composed of several layers of different
oxides. At the temperatures above 1050F (566C) iron scale
consists of three layers: FeO (the layer adjacent to iron), Fe3O4
(middle layer) and Fe2O3 (surface layer).

Depending on their structures, the scales may be categorized into

two groups: protective scales and non-protective scales.
Protective scale prevents access of oxygen to the metal surface
due to non-porous continuous structure of the oxide layer.
Non-protective scale has loose porous structure providing free
access of oxygen to the underlaying metal.
 The scales type may be determined by the Pilling- Bedworth rule:

The scale is protective (adherent and non-porous) if the volume of the

oxide is not less than the volume of metal, from which the oxide was
formed.
The scale is non-protective (porous) if the volume of the oxide is less than
the volume of metal, from which the oxide was formed.

Oxides with volume much greater (twice and more) than the volume of
metal, from which the oxide was formed cause developing compressive
stresses. The stresses may lead to cracking and spalling of the scale, which
result in faster penetration of oxygen to the metal surface.
 Non protective
Protective oxides
oxides
Be 1.59 K 0.45
Cu 1.68 Ag 1.59
Al 1.28 Cd 1.21
Cr 1.99 Ti 1.95
Mn 1.79 Mo 3.40
Fe 1.77 Hf 2.61
Co 1.99 Sb 2.35
Ni 1.52 W 3.40
Pd 1.60 Ta 2.33
Pb 1.40 U 3.05
Ce 1.16 V 3.18
 Effect of oxide structure on oxidation

Most of oxides are not ideal. Their compositions

differ from the stoichiometric ratios. The oxide
structure may be divided into two groups:
n-type oxides with anion deficiency (ZnO, ZrO2, MgO,
Al2O3, SiO2, SnO2, PbO2). Anion: negatively charged ion
(oxygen).
p-type oxides with cation deficiency (NiO, CoO, FeO,
PbO, MnO, Cu2O). Cation: positively charged ion (metal).
 Additions of alloying elements having a valencies, which
differ from the valency of the base metal may effect on the
oxidation rate if it is controlled by diffusion:

In n-type oxides.
Addition of higher valency cation (eg. addition of Al to Zn)
results in lowering the oxidation rate.
Addition of lower valency cation (eg. addition of Li to Zn)
results in increasing the oxidation rate.
In p-type oxides.
Addition of higher valency cation (eg. addition of Cr to Ni)
results in increasing the oxidation rate.
Addition of lower valency cation (eg. addition of Ni to Cr)
results in lowering the oxidation rate.
 Kinetics laws of oxidation
Three basic kinetic laws have been used to
characterize the oxidation rates of pure metals.
Parabolic rate law
Logarithmic rate law
Linear rate law
SUPER ALLOYS
 The different materials used in a Rolls-Royce
jet engine. In blue, titanium is ideal for its
strength and density, but not at high
temperatures, where it is replaced by nickel-
based superalloys (red). In orange: steel used
for the static parts of the compressor.
SINGLE CRYSTAL SOLIDIFICATION