The Microstructural Forms of Materials

Lesson #2: THE MICROSTRUCTURAL FORMS OF MATERIALS

Learning Objectives:
At the end of this lesson, the learner will be able to:
Explain the Fundamental Concepts of Microstructure of Materials and differentiate
Components, Systems and Phases.
Characterize Crystallographic Directions and Planes and quantify Phase Compositions
and Amounts as well as Phase Distributions and Equilibrium that occurs inside a material
as it undergoes heating and cooling processes.
Describe the Development of Microstructures and Phase Transformation in reference to
the Fundamental Aspects of Structural Transformation and Kinetics of Phase
Transformation of material products.

Course Materials:
Etymology and Definition
Microstructure comes from the words “micro + structure” which pertains to the smallest scale
structure of a material, as exposed using an optical microscope above 25× magnification. The
microstructure of a material (such as metals, polymers, ceramics or composites) serves as
stimulus of the physical properties such as strength, toughness, ductility, hardness, corrosion
resistance, high or low temperature behaviour or wear resistance, which all defines the application
of each material.
Furthermore, nanostructures of biological specimens also exist, which are referred as
ultrastructure.
Photomicrograph showing the
microstructure of a lead–tin alloy of
eutectic composition. This
microstructure consists of
alternating layers of a leadrich -
phase solid solution (dark layers),
and a tin-rich -phase solid solution
(light layers). 375x.

Source:
Materials Science and Engineering
An Introduction by William D.
Callister Jr. and David G. Rethwisch

Watch: What is grain, grain boundary and microstructure in YouTube, Properties and Grain
Structure in YouTube, Lecture 17 Microstructures on eutectic and eutectoid phase diagram in
YouTube, Muddiest Point- Phase Diagrams I: Eutectic Calculations and Lever Rule in YouTube,
Muddiest Point-Phase Diagrams II: Eutectic Microstructures in YouTube, Introduction to Kinetics
of Phase Transformation in YouTube, Phase Diagrams of Water & CO2 Explained - Chemistry -
Melting, Boiling & Critical Point in YouTube

Important Terms
Isothermal Transformation Diagrams - also termed as time-temperature-transformation(T-T-T)
plots, whereby isothermal means conditions of constant temperature.

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 The Microstructural Forms of Materials

Athermal Transformation - is a reaction that is not thermally activated, and usually diffusionless,
as with the martensitic transformation. Normally, the transformation takes place with great speed
(i.e., is independent of time), and the extent of reaction depends on temperature.
Continuous Cooling Transformation Diagram - is a plot of temperature versus the logarithm
of time for a steel alloy of definite composition. Used to indicate when transformations occur as
the initially austenitized material is continuously cooled at a specified rate; in addition, the final
microstructure and mechanical characteristics may be predicted.
Austhenite - is the Face-centered cubic iron; also iron and steel alloys that have the FCC crystal
structure.
Pearlite - is a two-phase microstructure found in some steels and cast irons; it results from the
transformation of austenite of eutectoid composition and consists of alternating layers (or
lamellae) of α-ferrite and cementite.
Fine pearlite - is a pearlite in which the alternating ferrite and cementite layers are relatively thin.
Coarse pearlite - is a pearlite for which the alternating ferrite and cementite layers are relatively
thick.
Bainite - is an austenitic transformation product found in some steels and cast irons. It forms at
temperatures between those at which pearlite and martensite transformations occur. The
microstructure consists of α-ferrite and a fine dispersion of cementite.
Spheroidite - is a microstructure found in steel alloys consisting of spherelike cementite particles
within an α- ferrite matrix. It is produced by an appropriate elevated-temperature heat treatment
of pearlite, bainite, or martensite and is relatively soft.
Martensite - is a metastable iron phase supersaturated in carbon that is the product of a
diffusionless (athermal) transformation from austenite.
Tempered Martensite - The microstructural product resulting from a tempering heat treatment of
a martensitic steel. The microstructure consists of extremely small and uniformly dispersed
cementite particles embedded within a continuous α-ferrite matrix. Toughness and ductility are
enhanced significantly by tempering.
Cementite - is an Iron carbide phase (Fe3C).

A. Basic Concepts
Component - pure and/or compounds of which an alloy is composed
e.g. Copper and Zinc in a Cu-Zn brass
System - refers to the specific body of material under consideration
e.g. a ladle of molten steel
- refers to the series of possible alloys consisting of same components, regardless of alloy
composition.
e.g. the iron-carbon system
Solute - one component or element of a solution present in minor concentration which is
dissolved in solvent.
Solvent - the component of a solution present in the greatest amount which dissolves a solute

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 The Microstructural Forms of Materials

Solubility Limit - the maximum

concentration of solute atoms that
may dissolve in the solvent to form a
solid solution, for alloy systems at
specific temperature. Adding more
solute in excess of solubility limit
results in the formation of another
solid solution or compound that has a
distinctly different composition.
e.g. The solubility of sugar
(C12H22O11) in a sugar-water syrup
(C12H22O11 - H2O)
Source: Materials Science and Engineering,
An Introduction by William D. Callister Jr.
and David G. Rethwisch

Solid Solution - a homogeneous crystalline phase that contains two or more chemical species
Microstructure - geometric arrangement of grains and phases in material
- describes the structure level visualize as it is subjected to a microscope, may be optical
microscope (up to x 2,000 or micrometer level) or even electron microscope (up to 50,000
or nanometer level)
- characterized by the number of phase present, their proportions, and the manner in which
they are distributed or arranged, therefore it varies with respect to the AMOUNT, SIZE,
SHAPE, and DISTRIBUTION of these structural features.
Polycrystalline - material with multiple crystals and accompanying grain boundaries
Amorphous Structures - amorphous substances (non-crystalline)
- lack of systematic and regular arrangement of atoms over relatively large atomic distances
- lack any conventional microstructure
Metals: normally form crystalline solids
Ceramic: some are crystalline (the inorganic glasses are amorphous)
Polymers: maybe completely crystalline, completely amorphous or a combination.
Grains - individual crystals in a polycrystalline material

Phase - homogeneous part of a materials system that has uniform physical and chemical
characteristics
A. Single-phase system - is termed homogeneous
B. Multi-phase systems - is composed of two or more phases and are termed mixtures or
heterogeneous systems. Most metallic alloys, ceramic, polymeric, and composite
systems are heterogeneous. Ordinarily, the phases interact in such a way that the
property combination of the multiphase system is different from, and more attractive
than, either of the individual phases.
A. Single Phase Material
- Materials composed of only one phase
- Some of which are amorphous therefore have no conventional microstructure
- Some are single crystals thereby no microstructure in conventional sense
- Majority of which however are polycrystalline possessing microstructure; contain
many grains of same phase with a variety of possible microstructure

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 The Microstructural Forms of Materials

- Materials whose microstructures may be varies with respect to the Size, Shape,
and Orientation of the grains
- Its grain size increases with time as the applied temperature produces significant
atom movements
e.g. window glass, transparent polystyrene drinking cups; Silicon boules, ruby
gems; brass products, MgO ceramics
Grain Boundary - the zone where two mismatch crystals meet
Microstructural Variables of Single-Phase Materials
1. Grain Size
- Size of individual grains, varies inversely with the grain boundary area
- Grain boundary area affects the properties of the material (diffusion, nucleation,
strength, corrosion)
- Measured by the ASTM grain-sized number
- Dictated by time, temperature and other kinetic considerations
ASTM Grain-Sized Number
N(0.01 in. )2= N(0..0645 mm2 ) = 2n-1
where N = the number of grains observed in an area of 0.0645 mm2 (1 in2 at x100)
n = grain size number
Note:
At normal temperature Fine-grained materials are stronger than coarse-
grained materials thereby grain boundaries interfere with slip. But at high
temperature grain boundaries can withstand dislocations and results into creep,
therefore, coarse-grained materials are stronger than Fine-grained materials.
1
Mean Chord Length ( L ) = ------
- Index of grain size PL
- Reciprocal of the number of boundary intersection points per unit length, PL
- Can be determine easily by placing a random line of known length across a
polished and etched microstructure
Grain-Boundary Area per Unit Volume (Sv) = 2 PL
2. Grain Shape - maybe equiaxed, platelike, columnar, or dendritic (i.e. tree-like)
3. Preferred Orientation
Grain Growth - is such a characteristic that al crystalline materials whether or nonmetal
may exhibit
- Happens when material is heated at a temperature that produces atom movement
- Driving force the grain growth is the energy released as a atom moves across the
boundary from the grain with the convex surface to the grain with the concave; a s
as result of atom movement, boundaries move towards the surface
- Since small grains tend to have surfaces of sharper convexity than do large grains,
they disappear because they feed the larger grains.
- Highly dependent on temperature; increase in temperature increases growth rate;
but decreases in temperature does not reverse the process
- Determines the size and shape of grains
B. Multi-Phase material - materials composed of two or more phases
Microstructural Variables of Multi-Phase Materials
1. Relative Amounts of the Several Phases
2. Distribution of the Phases

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 The Microstructural Forms of Materials

3. Size and Shape of the Phases

B. Phase Distribution
Precipitation - separation of a minor phase form a supersaturated (supercooled) solid solution
Precipitation Rate R = f (GN)
where: N = nucleation rate G = growth rate
Note: @ intermediate temperatures, the faster the rate the shorter the precipitation times
C-type is for isothermal precipitation and common to variety of solid-state reactions. It describes the
kinetics of phase separation and aids the analysis of the origin of the microstructures

Pb - Sn Phase Diagram
Schematic representations of the equilibrium microstructures for a lead–tin alloy of composition
C4 as it is cooled from the liquid-phase region.

Source:
Materials Science
and Engineering
An Introduction
by William D. Callister Jr.
and David G. Rethwisch
C. Phase Transformation involved some alteration of the microstructure
Binary Systems - systems composed of two components
Component - chemically distinct and essentially indivisible substance.
e.g. (1) elements: Fe C (2) stoichiometric compounds: NaCI)
Phase Diagram
- is a graphical representation of the phase present of the ranges in composition,
temperature and pressure over which the phases are stable.
- collections of curves showing solubility limits
- also called equilibrium phase diagrams
Phase
- part of material that is distinct from other in structure and/or composition
- chemically and structurally homogenous region
Uses of Phase Diagram

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 The Microstructural Forms of Materials

1. Predict what phases for selected alloy compositions at desired temperatures

2. Determine the chemical composition of each phase
3. To calculate the quantity of each phase present
Equilibrium - the state at which all net reaction ceases
Solution - is a phase with more than one phase
Mixture - is a material with more than one phase
Solubility Limit - maximum solute addition without super-saturation
LSL - solubility limit in a liquid solvent
SSL - solubility limit in a solid
Solid solubility may be due:
1. One atom may be substituted for another in the phase structure
2. Atoms may be placed in the interstices
Observations on phase Diagrams
1. Solubility limit decreases with decreasing temperature
2. Intermediate compositions have melting points lower than those of pure components
3. As one goes across the phase diagram (isothermal cut) and cuts across boundaries,
alternating 1-2-1 phase fields will be encountered
Liquids - the locus of temperatures above which all compositions are liquid; the temperature at
which a liquid begins to freeze during equilibrium conditions
Solids - locus of temperatures below which ll compositions are solid; the temperatures at which
a liquid phase disappears
Phase Names - for solid solutions; use Greek letter (a, b, y)
- for liquids use L1, L2
Equilibrated phases
a. Chemical Compositions of Equilibrated Phases
One - Phase Areas
- chemical composition of a single phase is equal to the composition of the alloy
Two - Phase Areas
- chemical composition are located at the two ends of the isotherm, or tie-line, across the
two-phase area
- read composition of phase at the end of the tie line
b. Quantities of Phases in Equilibrated Mixtures
One - Phase Areas
- quantity of one phase is equal to the quantity of the alloy
Two - Phase Areas
- quantities are obtained by interpolating the composition of the alloy along the tie-line
between the composition of two phase
- use the Inverse Lever Rule
Inverse Lever Rule
Equations that enables one to calculate the relative amounts of two phases present in a
two-phase mixture in terms of the composition and the phase present.
Steps:

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 The Microstructural Forms of Materials

1.) Define the alloy composition and temperature

2.) Set tie-line between the compositions at the ends of the tie line.
3.) To find the amount of one phase, use this equation:
(composition at other end of tie-line - composition of alloy)
% amount, 1 phase = --------------------------------------------------------------------------------
Composition difference at the tie-line
Types of Phase Transformation Reactions
1. Invariant Reactions
- reactions in which there are zero degrees of freedom
- happens at only one temperature, specific compositions and phases
2. Eutectic Reactions
- transformation of a liquid phase isothermally and reversibly into two solid components
L1 ---------------→ S1 + S2
- at the eutectic point, three phases are simultaneously present
e.g. α (80.8 Pb) + β (2.5 Pb) ---------------→ liquid (38.1 Pb) at 183 O֯C
- reaction proceeds to completion at a constant temperature
Eutectic System
Eutectic point - point in the phase diagram where eutectic reaction happens
Solvus line / boundary - separate single-phase solid region from two-phase solid region
Hypoeutectic - compositions to the left of the eutectic point (less)
Hypereutectic - compositions to the right of the eutectic point (more)
Eutectic Isotherm - isothermal line passing through the eutectic point
Phase Rule or Gibb’s Phase Rule
- represents a criterion for the number of phases that will coexist within a system of
equilibrium
- Equation that relates the number of degrees of freedom F at equilibrium to the number of
components C in the system, the number of phases in the equilibrium
P and the two-state variables temperature and pressure E.
F + P = C + E or F + P = C + 1
Since only one variable is controlled like temperature
Degrees of Freedom (F) - the number of independent variables needed to specify equilibrium
- number of externally controlled variables that can be changed independently without
altering the number of phases that coexist in the equilibrium,
e.g. For a three-phase system; P = 3
F=C+1–P
F=2+1–3
F=0
which means that in a three-phase system (e.g. at the eutectic point), there is no
freedom in specifying variable for equilibrium
Other Variant Reactions
Eutectoid S1 → S2 + S3
Peritectic S1 + L1 → S2
Peritectoid S1 + S2 → S3
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 The Microstructural Forms of Materials

Monotectic L1 → S1 + L2
Syntetic L1 + L2 → S1
Iron Carbon System
- possibly the most important of all binary system
Two important diagrams in the Fe - C Systems
1. Iron-Cementite (Fe-Fe3 C) - used for steels
2. Ion-Graphite (Fe-C graphite) - used for cast irons
* these two represents the most technologically used metals and alloys called ferrous alloys
Steels - ferrous alloys with as much as 2 wt% carbon
Cast Irons - ferrous alloys with carbon contents less than 2-4.3%
1. Iron-Cementite System
Boundaries of the system:
100% Fe (0% C ) - 100% Fe3C (6.69% C )
Allotropic Changes
Alpha BCC ( ferrite) → γ FCC (austenite) at 912 OC
Lambda FCC (ferrite) → ẟ FCC (austenite) at 1394 OC
Melting point: 1538 O֯C Boiling point: 2880 OC
Three Invariant Reactions
A region of the
copper–zinc phase
diagram that has
been enlarged to
show eutectoid and
peritectic invariant
points, labeled E
(560C, 74 wt% Zn)
and P (598C, 78.6
wt% Zn),
respectively.
Source:
Materials Science
and Engineering
An Introduction by
William D. Callister Jr.
& David G. Rethwisch

a. Eutectoid reaction at 727 OC

- Eutectoid reaction for the iron–iron carbide system
The product of the eutectoid reaction is a two-phase microstructure, which is
composed of alternating ferrite, and cementite lamellae called pearlite.

- is fundamental to the development of microstructure in steel alloys. Upon cooling,

austenite, having an intermediate carbon concentration, transforms to a ferrite
phase, having a much lower carbon content, and also cementite, with a much

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 The Microstructural Forms of Materials

higher carbon concentration. Pearlite is one microstructural product of this

transformation. Temperature plays an important role in the rate of the austenite-
to-pearlite transformation.

Isothermal transformation
diagram for a eutectoid
iron–carbon alloy, with
superimposed isothermal
heat treatment curve
(ABCD). Microstructures
before, during, and after the
austenite-to-pearlite
transformation are shown.

Source:
Materials Science
and Engineering
An Introduction by William D.
Callister Jr. & David G.
Rethwisch

Photomicrographs of (a)
coarse pearlite and (b) fine
pearlite. 3000x.

Source:
Materials Science
and Engineering
An Introduction by William D.
Callister Jr. & David G.
Rethwisch

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 The Microstructural Forms of Materials

Transmission electron
micrograph showing the
structure of bainite. A
grain of bainite passes
from lower left to upper
right corners; it consists of
elongated and needle-
shaped particles of Fe3C
within a ferrite matrix. The
phase surrounding the
bainite is martensite.

Source: Materials Science and Engineering, An Introduction by William D. Callister Jr. & David G. Rethwisch

Bainite are other microconstituents that are products of the austenitic transformation. The
microstructure of bainite consists of ferrite and cementite phases, and thus diffusional processes
are involved in its formation. Bainite forms as needles or plates, depending on the temperature of
the transformation; the microstructural details of bainite are so fine that their resolution is possible
only using electron microscopy.
b. Eutectic reaction at 1148 OC
L4.30%C → γ2.11%C + (Fe3C) 6.69%C
c. Peritectic reaction at 1495 OC
ẟ0.09%C + L0.53%C → γ0.17%C

2. Iron-Graphite System
Similar Equilibrium diagram as Fe - Fe3C but no Fe3C line at 6.69% C. Addition
of silicon brings about precipitation of carbon as graphite

D. Kinetics of Phase Transformation

Equilibrium diagrams are valuable because they tell us which way a reaction will
proceed, but they give no indication of the time requirement.
Kinetics - refers to the rate a process occurs
- primary variables are time and temperature
Nucleation
Homogeneous Nucleation
unaided nucleation within a pre-existing surface; random nucleation in the parent phase
For a nucleus of radius, r, to form, the net energy for nucleation, ΔG:
ΔFn = ΔG = 4πr2 ẟγ + (4/3) πr3 ΔFv
where:
γ - energy per unit area that is required for new boundary ( + )
- value of γ does not vary much with the temperature
Fv - energy per unit volume released when new phase is created ( - )
- becomes significantly more negative as temperature is decreased.

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 The Microstructural Forms of Materials

At the start, when r is small, 4πr2γ > (4/3) πr3 Fv and ΔG is positive. Thus, energy is
needed to start nucleation and reaction is non-spontaneous. Only after a critical radius,
rc, develops the growth proceed automatically.

Homogeneous nucleation is affected by the amount of under-cooling; i.e. the greater the
under-cooling, the smaller rc becomes, and nucleation occurs faster (more nucleation
points) However, since temperature is lower growth is slow.

Heterogeneous Nucleation
nucleation on a preexisting surface (or by introduction of ‘seeds’).
The presence of irregularities in crystal structure, such as point defects and dislocations,
impurities, innoculants (‘seeds’), and grain boundaries facilities nucleation.
Heterogeneous nucleation occurs generally faster.

E. Diffusion
- the movement of atoms or molecules in a material
- for atom movement to occur, there is an energy, called activation energy, that needs to
be attained.
Diffusion can be described by this equation:
Fick’s First law: dC
J = - D (-------)
dx
where: J - Diffusion flux, atoms/m2-sec
D- diffusivity, (m2/sec)
C- concentration (atoms/m3)
X- distance, m
(negative sign indicates that movement of atom is from higher to a lower
concentration)

Observations of Diffusion:
Diffusion proceeds more rapidly:
a) At higher temperatures, because the atoms have higher thermal
energies and therefore greater probability of being activated over the
energy barrier between atoms;
b) When the diffusing atom is small;
c) When the packing factor of the host structure is low (bcc vs fcc);
d) When the bonds of the host structure are weak;
e) When there are imperfections in the material (e.g. grain boundaries,
vaccines)

Problem:
For a 99.65ω% Fe - 0.35 ωt% C alloy at a temperature just below the
eutectoid, determine the following:
a) The function of total ferrite and cementite phases
b) The function of the proentectoid ferrite pearlite
c) The function of entectoid ferrite

Glass Transition Temperature (Tg)

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 The Microstructural Forms of Materials

Metallic Glasses
- fabricated by Prof. Dumez in 1960
- can be made if molten metal is cooled at an extremely high cooling rate (106 C/s)
- unusual mechanical properties, very high strength combined with high toughness
- extremely low magnetic losses- good for transformers
- high hardness, excellent corrosion resistance

Microstructure Properties
Microstructure Tensile Strength (Mpa) Toughness (J)
Annealed (a+carbide)
Pearlite 655 55
Over tempered martensite 480 110
Martensite ~1400 <3
Tempered martensite
500 OC , 1 hr 1275 55
600 OC , 1hr 1035 110

Photomicrograph showing the martensitic

microstructure. The needleshaped grains are
the martensite phase, and the white regions
are austenite that failed to transform during
the rapid quench. 1220x

The complete isothermal transformation diagram

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Superimposition of isothermal and
continuous cooling transformation
diagrams for a eutectoid iron–carbon alloy
Continuous cooling transformation
diagram for a eutectoid iron–carbon alloy
and superimposed cooling curves,
demonstrating the dependence of the
final microstructure on the
transformations that occur during cooling.
The Microstructural Forms of Materials
for an iron–carbon alloy of eutectoid composition:
A, austenite; B, bainite; M, martensite; P, pearlite.
Moderately rapid and slow cooling curves
superimposed on a continuous cooling Transformation
diagram for a eutectoid iron–carbon alloy
Continuous cooling transformation
diagram for an alloy steel (type
4340) and several superimposed cooling
curves demonstrating dependence of the
final microstructure of this alloy on the
transformations that occur during cooling.
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 The Microstructural Forms of Materials

Summary of Microstructures and Mechanical Properties for Iron–Carbon Alloys

Source: Materials Science and Engineering, An Introduction by William D. Callister Jr. & David G. Rethwisch

Activities/Assessment to work at home:

1. Research and discuss the Advantages and Disadvantages of the Continuous Cooling
Transformation.
2. Illustrate the major parts and explain the functions, mode operations of Spectrometer.
3. Download a research study (research article) related to materials’ microstructure, briefly
describe the research problem, materials used, significant benefits of the study, and
conclusion of the research.
4. Briefly describe Dolomites, identify its hazards and justify its benefits.
5. Interview a Materials Engineering Practitioner, and learn how Electronics Engineers could
have a job in such Field.

Reading and Viewing Materials:

1. Materials Science and Engineering, An Introduction 8th Edition by William D. Callister Jr.
and David G. Rethwisch
2. The Science and Design of Engineering Materials 2nd Edition by James P. Schaffer, Ashok
Saxena, Stephen D. Antolovich, Thomas H. Sanders Jr., Steven B. Warner
3. Elements of Materials Science and Engineering 6th Edition by Lawrence H. Van Vlack
4. What is grain, grain boundary and microstructure in YouTube,
5. Properties and Grain Structure in YouTube,
6. Lecture 17 Microstructures on eutectic and eutectoid phase diagram in YouTube,
7. Muddiest Point- Phase Diagrams I: Eutectic Calculations and Lever Rule in YouTube,
8. Muddiest Point-Phase Diagrams II: Eutectic Microstructures in YouTube,
9. Introduction to Kinetics of Phase Transformation in YouTube,
10. Phase Diagrams of Water & CO2 Explained - Chemistry - Melting, Boiling & Critical Point
in YouTube

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