Engineering Materials
Ch.E 311
Lecture 4
Thermal Properties
• By “thermal property” is meant the response of a material to the
application of heat.
• As a solid absorbs energy in the form of heat, its temperature rises
and its dimensions increase.
• The energy may be transported to cooler regions of the specimen if
temperature gradients exist, and ultimately, the specimen may melt.
• Properties of solids:
• Heat capacity
• Thermal expansion
• Thermal conductivity
Heat Capacity
• Indicative of a material’s ability to absorb heat from the external
surroundings; it represents the amount of energy required to produce
a unit temperature rise.
• In mathematical terms, the heat capacity C is expressed as follows:
One is the heat
capacity while
maintaining the specimen
volume constant, Cv
Heat capacity types
the other is for constant
external pressure, Cp
Temperature dependence
• The Cv is zero at 0 K, but it rises rapidly with temperature; this
corresponds to an increased ability of the lattice waves to enhance
their average energy with ascending temperature.
• At low temperatures the relationship between Cv and the absolute
temperature T is:
Thermal Expansion
• Most solid materials expand upon heating and contract when cooled.
The change in length with temperature for a solid material may be
expressed as follows:
• linear coefficient of thermal expansion; it is a material property that
is indicative of the extent to which a material expands upon heating,
and has units of reciprocal temperature [°C-1 or F-1].
• Metals: linear coefficients of thermal expansion for some of the
common metals range between about 5x10-6 and 25x10-6 these values
are intermediate in magnitude between those for ceramic and
polymeric materials.
• Ceramics: low coefficients of thermal expansion 0.5x10-6 and 15x10-6
• Polymers: Some polymeric materials experience very large thermal
expansions upon heating as indicated by coefficients that range from
50x10-6 to 400x10-6.
Thermal Conductivity
• Thermal conduction is the phenomenon by which heat is transported
from high- to low-temperature regions of a substance. The property
that characterizes the ability of a material to transfer heat is the
thermal conductivity.
• It is best defined in terms of the expression:
• Metals: good conductors of heat
• Range between 20 and 400 W/m-K
• Ceramics: Nonmetallic materials are thermal
insulators in as much as they lack large
numbers of free electrons.
• Range between 2 and 50 W/m-K
• Polymers: 0.3 W/m-K
• Polymers are often utilized as thermal
insulators because of their low thermal
conductivities.
• As with ceramics, their insulative properties
may be further enhanced by the introduction
of small pores, which are ordinarily
introduced by foaming during polymerization.
• Foamed polystyrene (Styrofoam) is commonly
used for drinking cups and insulating sheets.
Thermal Stresses
• Thermal stresses are stresses induced in a body as a result of changes
in temperature.
• An understanding of the origins and nature of thermal stresses is
important because these stresses can lead to fracture or undesirable
plastic deformation.
• Upon heating (Tf > To) the stress is compressive (σ < 0) since rod
expansion has been constrained.
• Of course, if the rod specimen is cooled (Tf < To) a tensile stress (σ > 0)
will be imposed.
Thermal Shock of Brittle Materials
• For ductile metals and polymers, alleviation of thermally induced
stresses may be accomplished by plastic deformation.
• However, the non-ductility of most ceramics enhances the possibility
of brittle fracture from these stresses.
• Rapid cooling of a brittle body is more likely to inflict such thermal
shock than heating, since the induced surface stresses are tensile.
• The capacity of a material to withstand this kind of failure is termed
its thermal shock resistance.
Phase Diagrams
• The understanding of phase diagrams for alloy systems is extremely
important because
• There is a strong correlation between microstructure and mechanical
properties
• The development of microstructure of an alloy is related to the characteristics
of its phase diagram.
• In addition, phase diagrams provide valuable information about
melting, casting, crystallization, and other phenomena.
• Component is frequently used in this discussion; components are
pure metals and/or compounds of which an alloy is composed.
• For example, in a copper–zinc brass, the components are Cu and Zn.
• Another term used in this context is system, which has two meanings.
• First, “system” may refer to a specific body of material under consideration
(e.g., a ladle of molten steel).
• Or it may relate to the series of possible alloys consisting of the same
components, but without regard to alloy composition (e.g., the iron–carbon
system).
Solubility Limit
• For many alloy systems and at some specific temperature, there is a
maximum concentration of solute atoms that may dissolve in the
solvent to form a solid solution; this is called a SOLUBILITY LIMIT.
The addition of solute in excess results in the formation of another
solid solution or compound that has a distinctly different composition.
Example
• Example : The sugar–water system (Figure)
• Initially, as sugar is added to water,
a sugar–water solution or syrup forms.
• As more sugar is introduced, the solution
becomes more concentrated, until the
solubility limit is reached.
• At this saturation point, the solution is not capable of dissolving any more sugar, and
further additions simply settle to the bottom of the container.
• Thus, the system now consists of two separate substances: a sugar–water syrup liquid
solution and solid crystals of undissolved sugar.
• The solubility limit at some temperature is the composition that corresponds to the
intersection of the given temperature coordinate and the solubility limit line.
• For example, at 20°C the maximum solubility of sugar in water is 65 wt%.
Phase
• A phase can be defined as a physically distinct and chemically
homogeneous portion of a system that has a particular chemical
composition and structure.
• Every pure material is considered to be a phase; so also is every solid,
liquid, and gaseous solution.
• Example: Water in liquid or vapor state is single phase. Ice floating on
water is an example of two phase system.
• When water and ice are present in a container, two separate phases
exist; they are physically dissimilar (one is a solid, the other is a liquid)
but identical in chemical makeup.
• For example, the sugar–water syrup solution just discussed is one
phase, and solid sugar is another.
• Each has different physical properties (one is a liquid, the other is a
solid); furthermore, each is different chemically (i.e., has a different
chemical composition); one is virtually pure sugar, the other is a
solution.
• If more than one phase is present in a given system, each will have its
own distinct properties, and a boundary separating the phases will
exist across which there will be a discontinuous and abrupt change in
physical and/or chemical characteristics.
• When two phases are present in a system, it is not necessary that
there be a difference in both physical and chemical properties; a
disparity in one or the other set of properties is sufficient.
Microstructure
• In metal alloys, microstructure is characterized by:
• the number of phases present
• their proportions
• the manner in which they are distributed or arranged
• The microstructure of an alloy depends on such variables as:
• the alloying elements present
• their concentrations
• the heat treatment of the alloy (i.e., the temperature, the heating time at
temperature, and the rate of cooling to room temperature).
Equilibrium
• Equilibrium is another essential concept that is best described in terms of a
thermodynamic quantity called the free energy.
• In brief, free energy is a function of the internal energy of a system, and also
the randomness or disorder of the atoms or molecules (or entropy).
• A system is at equilibrium if its free energy is at a minimum under some
specified combination of temperature, pressure, and composition.
• In a macroscopic sense, this means that the characteristics of the system do
not change with time but persist indefinitely; that is, the system is stable.
• A change in temperature, pressure, and/or composition for a system in
equilibrium will result in an increase in the free energy and in a possible
spontaneous change to another state whereby the free energy is lowered.
Phase Equilibria
• The term phase equilibrium, often used in the context of this discussion, refers to
equilibrium as it applies to systems in which more than one phase may exist. Phase
equilibrium is reflected by a constancy with time in the phase characteristics of a system.
• Suppose that a sugar–water syrup is contained in a closed vessel and the solution is in
contact with solid sugar at 20C.
• If the system is at equilibrium, the composition of the syrup is 65 wt% (Figure 9.1), and
the amounts and compositions of the syrup and solid sugar will remain constant with
time.
• If the temperature of the system is suddenly raised—say, to 100C this equilibrium or
balance is temporarily upset in that the solubility limit has been increased to 80 wt%.
• Thus, some of the solid sugar will go into solution in the syrup.
• This will continue until the new equilibrium syrup concentration is established at the
higher temperature.
• liquid–solid system
• In many metallurgical and materials systems of interest, phase
equilibrium involves just solid phases.
• In this regard the state of the system is reflected in the characteristics
of the microstructure.
Phase or Equilibrium Diagram
• Important parameters:
• Temperature
• Pressure
• Composition
One-component (or unary) phase
diagrams
• Simplest and easiest
• for a one-component system,
in which composition is held
constant (i.e., the phase
diagram is for a pure
substance); this means that
pressure and temperature are
the variables
• a two-dimensional plot of
pressure versus temperature
• Triple point
Binary Phase Diagram
• Temperature and composition are variable parameters, and pressure is held constant—
normally 1 atm.
• The line above which the alloy is liquid is called the liquidus line. At temperature just
below this line crystals of solid solution start forming.
• The line below which solidification completes is called solidus line. Hence, only solid
solution exists at any temperature below the solidus line.
• The intermediate region between liquidus and solidus lines is two-phase region where
liquid and solid coexist.
• It can be noted that the if two metals are soluble in each other in the entire range of
compositions in both liquid and solid state, this kind of system is known as ‘Isomorphous’
system.
• This complete solubility is explained by the fact that both Cu and Ni have the same crystal
structure (FCC), nearly identical atomic radii and electronegativities.
The copper–nickel phase diagram
Interpretation of Phase Diagram
• For a binary system of known composition and temperature that is at
equilibrium, at least three kinds of information are available:
(1) the phases that are present
(2) the compositions of these phases
(3) the percentages or fractions of the phases
Determination of Phase Compositions
The composition of the individual phases in
the two phase region is found as follows:
1. A tie line is constructed across the two-phase
region is drawn and its intercepts on the liquidus
and solidus lines at the temperature of the alloy.
2. The intersections of the tie line and the
phase boundaries on either side are noted.
3. Perpendiculars are dropped from these intersections
to the horizontal composition axis, from where
composition of each phase is determined.
4. The lever rule (or the inverse lever rule) is applied Let
to calculate the compositions. Co = The overall alloy composition be
Lever rule (or the inverse lever rule) located along the tie line and denoted as
• The tie line is constructed across the two-phase region at the temperature Co
of the alloy. WL = the lever rule mass fractions
• The overall alloy composition is located on the tie line.
• The fraction of one phase is computed by taking the length of tie line from
the overall alloy composition to the phase boundary for the other phase,
and dividing by the total tie line length.
Related Example:
35 wt% Ni–65 wt% Cu alloy where at 1250oC both solid and liquid phases are
present. Compute the fraction for each phase.
Solution:
The overall alloy composition is Co
Thus, the lever rule may be employed to determine the relative amounts or fractions of
phases in any two-phase region for a binary alloy if the temperature and composition are
known.
Assignment
9.7 Given here are the solidus and liquidus temperatures for the
germanium-silicon system. Construct the phase diagram for this
system and label each region.
Draw on Excel.
A copper-nickel alloy of composition 70 wt% Ni-30 wt% Cu is slowly
heated from a temperature of 1300°C (2370°F).
(a) At what temperature does the first liquid phase form?
(b) What is the composition of this liquid phase?
(c) At what temperature does complete melting
of the alloy occur?
(d) What is the composition of the last solid remaining prior to complete
melting?
Solution
(a) Heating from 1300°C, the first liquid phase forms at phase
boundary-1345°C
(b) The composition of this liquid phase corresponds to the intersection
with the phase boundary 59wt% Ni
(c) Complete melting is at 70 wt% Ni( ) i.e 1380 °C
(d) At same temp 1380 °C is 79 wt% Ni
Related Problems
• 9.11, 9.12, 9.16, 9.17
Reference
• Chapter 19, Thermal Properties
• Chapter 9 Phase Diagrams
• Material Science And Engineering - An Introduction By William D.
Callister.
