Materials for Mechanical Engineers

機電材料
MEME106B
CHAPTER III: MICROSTRUCTURE & PHASES
Dr. Bo-Shiuan Li
Office: EN3034-2
Phone: 4285
Email: [email protected]
Office hour: Tue & Thu 1500~1700
INTRODUCTION nm

- INTRODUCTION

- GRAINS AND GRAIN BOUNDARIES

- DEFECTS

- INTRODUCTION OF PHASES

- SOLID SOLUTION

- PHASE DIAGRAM
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INTRODUCTION nm

- Microstructure is the microscopic structures of materials which are often observed

using optical of electron microscopes

- Material properties are strongly influenced by its microstructure, therefore, it is crucial

for material engineers to understand the microstructure-to-property relationships

- Typically, microstructure is composed of grains, grain boundaries, defects, and

phases, spanning over a wide range of length scales
(a) (b) (c)

(a) Optical micrograph of an as-cast HEA rod, (b) SEM image of a HEA showing the various grain structure, (c) SEM image of a W/Fe
alloy with various composition, image courtesy of myself
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GRAIN AND GRAIN BOUNDARIES nm

- A grain is a portion of the crystalline material within which the atomic arrangement
are nearly identical, can range from couple nm to hundredth of µm

- A grain boundary is the surface that separates individual grains; it is a narrow zone
where the atoms are not properly arranged

- Each grain can have the same crystal structure but different crystallographic
orientations, e.g. the grains in below figures are all BCC but are oriented differently
(a) (b) (c) (d)

BCC
FCC

(a) Schematic showing the boundaries of three adjacent grains, (b) SEM image of an as-cast HEA showing three grains with dendritic
structure, (c) phase map shows all grains are of BCC structure, (d) orientation map (IPF-Z) showing the grains are of different
crystallographic orientations, image courtesy of myself
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GRAIN AND GRAIN BOUNDARIES nm

- Grain boundaries are surface defects in crystalline materials, and tend to decrease
the electrical and thermal conductivity of materials

- Grain boundaries are preferential sites for corrosion, precipitation, and creep (via
grain boundary sliding)

- Grain boundaries also act as obstacles for dislocation motions, so reducing the
grain size in an effective method to improve strength, as described by the Hall-
Petch relationship:

1
−2
𝜎𝑦 = 𝜎0 + 𝐾𝑑

where σy is the yield strength, d is the average diameter of the grains, σ0 and K are material constants

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GRAIN AND GRAIN BOUNDARIES nm

Exercise 1: the Hall-Petch effect

The yield strength of mild steel with average grain size of 0.05 mm is 138 MPa. The
strength of the same steel with grain size of 0.007 mm is 276 MPa. What will be the grain
size of the same steel with a yield strength of 207 MPa?

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GRAIN AND GRAIN BOUNDARIES nm

- Low-angle grain boundary (LAGB):

1. LAGB is array of dislocations that produces a small misorientation between adjacent crystals
2. LAGB has smaller energy than regular grain boundaries therefore are less effective in blocking
dislocation motions

- Twin boundaries:
1. Twin is a plane across which there is a special mirror image of misorientation within the crystal
2. Twinning occurs during deformation (deformation twin) or heat treatment (annealing twin)
3. Twin boundaries also impede dislocation motion hence increase material strength

Schematic of the LAGB produced by an array of dislocations, Schematic and orientation map showing the atomic
and the distribution of LAGB/HAGB in a SLM 316L SS arrange of a twin, caused by deformation
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DEFECTS nm

Point defects

- Point defects are localized disruptions in perfect atomic arrangements in a crystal;

despite being called point, their disruption affects a region involving several atoms

- These imperfections may be introduced by movement of atoms when they gain

energy from heating or processing, or by introduction of impurities (present in
raw materials, dopants, or from alloying)

- There are three types of point defects: vacancies, interstitials, and substitutionals
(a) (b) (c) (d)

Schematic drawings of different types of point defects: (a) vacancy, (b) interstitial,
(c) small substitutional atoms, and (d) large substitutional atoms
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DEFECTS nm

Point defects: vacancies

- A vacancy is produced when an atom is missing from its original lattice site,
increasing the overall entropy and thermodynamic stability of the material

- All crystalline materials have vacancies; they are introduced during solidification, or
as a consequence of radiation damage

- At room temperature, the concentration of vacancies is small, but increases

exponentially as temperature increases, followed by the Arrhenius equation:

−𝑄𝑣
𝑛𝑣 = 𝑛𝑒 𝑅𝑇

where nv is the number of vacancies per m3, n is the number of atoms per m3, Qv is the energy required to produce
one mole of vacancies (J/mol), R is the gas constant 8.314 J/mol∙K, T s the temperature in K

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DEFECTS nm

Point defects: interstitials

- An interstitial is formed when an extra atom is inserted into the crystal structure at a
normally unoccupied site

- Carbon are intentionally added to iron to make steel; carbon interstitials introduce
stresses within the distorted region of the crystal, increasing the strength of iron

- Unlike vacancies, once introduced, number of interstitial atoms within the structure
remain nearly constant, even at elevated temperatures

- FCC and BCC crystal lattice have octahedral and tetrahedral interstitial sites

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DEFECTS nm

Point defects: interstitials

Z Z
Octahedral sites

Tetrahedral sites
1 1
0, , 1 0, , 1
2 2

1 1 1
, , 1 1
2 2 2 , 1,
2 2
1 3 1
, ,
4 4 4
Y Y
1 1
1, ,
2 4

X
FCC X
BCC

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DEFECTS nm

Point defects: substitutional defects

- A substitutional defect is introduced when atom is replaced by a different type of atom

- The substitutional defect distorts the surrounding crystal, causing strengthening of

metallic materials. Larger atomic size mismatch causes larger lattice strain,
hence stronger strengthening effect

The effects of several alloying

elements on the yield strength of
copper alloys. Nickel and zinc atoms
are about same size as copper
atoms, but beryllium and tin atoms
are much different in size from the
copper atoms. Increasing the atomic
size difference increases the
strengthening effect

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DEFECTS nm

Homework 2: effect of temperature on vacancy concentration

Calculate the concentration of vacancies in copper at room temperature (25 °C). What
temperature is required to heat copper such that the concentration of vacancies
produced will be 1000 times higher than the concentration at room temperature? Assume
83680 J are required to produce a mole of vacancies in copper

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DEFECTS nm

Dislocations

- Dislocations are line defects in perfect crystals, typically introduced during

solidification or plastic deformation. They are being used to explain plastic
deformation in metallic materials

- Despite theory being developed by Voltera, Taylor, Orowan in the 1930s,

experimental validation was not available until the 1950s, when Hirsch et al. used
transmission electron microscopy to observe dislocations from Al foil

- There are three types of dislocations: edge, screw, and mixed

- The Burgers vector (b), is used to describe the displacement vector necessary to
close a stepwise loop, which will be shown more clearly later

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DEFECTS nm

Edge dislocation

- Illustrated by slicing partway through a perfect crystal and partly filling the cut with an
extra plane of atoms. The bottom edge of the half plane is the edge dislocation

- Start at point X, travel an equal atom spacing in each direction clockwise, we finish
at point Y, which is one atom spacing from X. The vector required to close the loop
is the Burgers vector, which is perpendicular to the dislocation line

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DEFECTS nm

Screw dislocation

- Illustrated by cutting partway through a perfect crystal and skew the crystal by one
atom spacing. The axis around which the path is traced is the screw dislocation

- Start at point X, travel an equal atom spacing in each direction clockwise, we finish
at point Y, which is one atom spacing below X. The vector required to close the
loop is the Burgers vector, which is parallel to the dislocation line

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DEFECTS nm

Mixed dislocation

- Most dislocations in actual materials are mixed dislocations, having both edge and
screw components, with a transition region in between

- The Burgers vector remains the same for all portion of the mixed dislocation

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DEFECTS nm

Animations of dislocations

https://www.youtube.com/watch?v=Upcc70OZ8Z4&ab_channel=DrGray%27sAnimations
https://www.youtube.com/watch?v=RD40OtchSVg&ab_channel=DrGray%27sAnimations
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DEFECTS nm

Seeing dislocations via TEM

Prof. Sir Peter B Hirsch FRS Prof. Michael J Whelan FRS

https://www.youtube.com/watch?v=J1ydWe63GGo&ab_channel=RiArchives
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DEFECTS nm

Exercise 3: the bubble raft experiment

Substitutional solute

Interstitial solute Edge dislocation

Vacancy

The bubble raft experiment, showing examples of vacancy, interstitial solute, substitutional solute, and
dislocation, image courtesy of DoITPoMS, University of Cambridge (https://www.doitpoms.ac.uk/index.php)

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DEFECTS nm

Dislocation motion

- A plane containing both dislocation line and the Burgers vector is the slip plane

- When a large shear stress acting parallel to the Burgers vector is applied to a
crystal containing dislocation, the dislocation can move through a process called slip

- Combination of slip plane and slip direction is called a slip system

Shear stress

Slip plane
Unit step of slip = 1 b

From left to right: when shear stress is applied to a crystal containing a dislocation, the atom are displaced, causing the dislocation
to move one Burgers vector in the slip direction, continue movement of dislocation to the material surface eventually creates a step
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DEFECTS nm

Slip and slip plane

- Stress required to move dislocation increases exponentially with the length of the
Burgers vector, hence the slip directions are often the closed-packed directions

- Stress required to move dislocation decreases exponentially with the interplanar

spacing of the slip planes, hence slip planes are often the closed-packed planes

- Dislocations do not move easily in materials with covalent and ionic bonds, due to
the higher strength and directionality of the bonds, hence they are often brittle
Crystal Structure Slip Plane Slip Direction
FCC 111 110
BCC 110 , 112 , 123 111
HCP 001 100
Diamond cubic (Si) 111 110
Slip planes and directions of common crystal structures
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DEFECTS nm

Significance of dislocations

- Plastic deformation is the cumulative effect of numerous slip; they are the
movement of many dislocations under significant stresses

- Slip explains why the strength of metal is much lower than theoretical value, since
only a tiny fraction of all the bonds need to broken at any one time

- Slip provides ductility in metals; if no dislocations were present, metals will be brittle
and cannot be shaped or deformed by metalworking processes

- Metallic materials can be strengthened through hindering dislocation motions,

common practices are alloying, cold-working, and introducing fine precipitates

- Dislocations also influence electrical and optical properties of materials, e.g.

resistivity of pure copper increases with increasing dislocation density
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DEFECTS nm

Visualization of slip and dislocation using SEM

From left to right: numerous slip lines in a SLM 316L SS at ε=3%, higher magnification of the slip lines where the surface steps are
clearly seen, TEM image showing the dislocation lines gliding on the slip plane showing the equal spacing

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INTRODUCTION OF PHASES nm

- A phase can be defined as any portion of a system that is physically homogeneous

within itself and bounded by a surface that separate it from other portions

- For example, water has three phases: liquid water, solid ice, and gaseous steam

- A phase has the following characteristics:

1. Same structure or atomic arrangement throughout
2. Roughly the same composition and properties throughout
3. A definite interface between the phase and any surrounding phases

Illustration of phases and solubility: (a) three forms of water, gas, liquid, and solid (b) water and alcohol have unlimited solubility (c)
salt and water have limited solubility (d) oil and water have almost no solubility
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INTRODUCTION OF PHASES nm

Phase rule

- The phase rule describes the relationship between number of components (C) and
number of phases (P) for a given system and conditions (F)

2+𝐶 =𝐹+𝑃

C is the number of chemically independent components

F is the degree of freedoms (temperature, pressure) that are allowed to change without changing the number of equilibrium phases
P is the number of phases present

- Phase rule assumes thermodynamic equilibrium. The phases do not always have to
be solid, liquid, and vapor. It can exist as different crystal structures

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INTRODUCTION OF PHASES nm

- Below figure shows the unary (C=1) phase diagram of pure magnesium, depending
on the temperature and pressure, there may be 1~3 phases present

- At point A, Mg is all liquid (P=1), using the phase rule, the degrees of freedom are:

2+1=𝐹+1→𝑭=𝟐

- Thus we can change pressure, temperature, or both, and still be in the liquid phase

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INTRODUCTION OF PHASES nm

- At point B, the boundary between solid and liquid, the component is still 1 but the
number of phases is 2

2+1=𝐹+2→𝑭=𝟏

- There is only one degree of freedom; if temperature is changed, then pressure must
also be changed if we want to stay on the boundary where liquid and solid coexist

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INTRODUCTION OF PHASES nm

- At point X, all three phases coexist, component is 1 but number of phases is 3

2+1=𝐹+3→𝑭=𝟎

- There is no degree of freedom; all three phases can only coexist if both temperature
& pressure are fixed

- Point X is also called a triple joint, where all three phases coexist in equilibrium

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SOLID SOLUTION nm

- Solubility is important as it provides information on how much of each material we

can add without producing an additional phase

- Unlimited solubility means regardless of how much the solute is added, only one
phase (solvent) is produced, e.g. alcohol in water, Ni in Cu

- Limited solubility means when excessive amount of solute is added, additional

phases (other than the solvent phase) will form, e.g. salt in water, Zn in Cu

(a), (b) Cu & Ni are complete soluble in each other in liquid & solid phase (c) Cu-Zn alloy containing more than 30% Zn, a second
phase form due to limited solubility of Zn in Cu Right: Solubility of Zn in Cu, showing two phases coexist when excessive Zn is added
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SOLID SOLUTION nm

Solid solution strengthening

- Solid solution strengthening (SSS) is caused by increased resistance to dislocation

motion, through addition of alloying elements

- Degree of SSS depends on two factors

1. Atomic size difference between the original (solvent) atom and the added (solute) atom; larger
size difference increases the strengthening effect
2. Amount of alloying element added; the more alloying element added, the greater the
strengthening effect. However, adding beyond the solubility limit can precipitate out additional
phases, causing a different strengthening mechanism called dispersion strengthening

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SOLID SOLUTION nm

Solid solution strengthening

- Effects of SSS on properties of metals include the following:

1. The yield strength, tensile strength and hardness of alloys are greater than those of pure metal
2. The ductility of alloy is less than that of pure metal
3. Electrical conductivity of alloy is much lower than that of pure metal
4. Creep resistance at elevated temperatures can be improved by SSS

Left: effects of alloying elements on the yield strength of copper-based alloys, showing significant effect on the atomic size difference
Right: effect of additions of Zn to Cu on the properties of SSS alloy, the increase in elongation with increasing Zn is not typical
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PHASE DIAGRAMS nm

- Phase diagram shows the phases and their composition at any combination of
temperature and alloying composition, but often at atmospheric pressure (1 atm)

- Isomorphous phase diagram is used when the two alloying elements are
miscible (mixable) at solid state as well as liquid state at any composition

- In the Cu-Ni & NiO-MgO systems, only one solid phase forms, the two components
in the system display complete solid solubility

The equilibrium phase diagrams for the Cu-Ni and NiO-MgO system. Liquidus & solidus temperature are shown for a Cu-40%Ni alloy
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PHASE DIAGRAMS nm

Composition of each phase

- For each phase, we can specify a composition, expressed as the percentage of

each element in the phase, usually in wt%

- When only one phase is present, the composition of the phase equals to the overall
composition of the material; when two phases coexist, their composition differ
from one another and also differ from the overall composition
Single
phase

Two
phases

Binary phase diagram with A & B. When an alloy is present in the 2 phase region, a tie line at constant temp fixes the composition of the 2 phases
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PHASE DIAGRAMS nm

Exercise 4: composition of phases in the Cu-Ni phase diagram

Determine the composition of each phase in a Cu-40%Ni alloy at 1300 °C, 1270 °C,
1250 °C, and 1200 °C

- 1300 °C: only liquid phase is present, so the liquid contain 40% Ni

- 1270 °C: two phases are present. End point of the horizontal line in
contact with the liquidus phase is at 37% Ni, endpoint in contact
with the solidus phase is at 50%. Hence, the liquid contains 37% Ni,
and the solid contains 50% Ni

- 1250 °C: the horizontal line at this temperature shows that the liquid
contains 32% Ni, and the solid contains 45% Ni

- 1200 °C: only solid phase is present, so the solid contain 40% Ni

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PHASE DIAGRAMS nm

Amount of each phase

- Previously, we calculate the composition in each phase, but we also like to know the
relative fraction of each phase in the alloy

- The lever rule is used to calculate the relative fraction of a phase in a two-phase
mixture, which can be expressed as:

𝑜𝑝𝑝𝑜𝑠𝑖𝑡𝑒 𝑎𝑟𝑚 𝑜𝑓 𝑙𝑒𝑣𝑒𝑟

𝑷𝒉𝒂𝒔𝒆 𝒑𝒆𝒓𝒄𝒆𝒏𝒕 = × 100
𝑡𝑜𝑡𝑎𝑙 𝑙𝑒𝑛𝑔𝑡ℎ 𝑜𝑓 𝑙𝑒𝑣𝑒𝑟

- The lever rule is applicable in any two-phase region of a binary phase diagram

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PHASE DIAGRAMS nm

Exercise 5: application of the lever rule

Calculate the amount of solidus (α) and liquidus (L) phase at 1250 °C of the Cu-40%Ni
alloy shown in the figure below
- Assume x is the fraction of solidus (α) phase, y is the fraction of liquidus (L) phase, using the lever rule:

𝟒𝟎 − 𝟑𝟐 𝟖
𝒙= = = 𝟎. 𝟔𝟐
𝟒𝟓 − 𝟑𝟐 𝟏𝟑

𝟒𝟓 − 𝟒𝟎 𝟓
𝒚= = = 𝟎. 𝟑𝟖
𝟒𝟓 − 𝟑𝟐 𝟏𝟑

- Therefore, at 1250 °C, the alloy contains 62% solidus phase and 38% liquidus phase

- The concentration of Ni in the solidus phase is 45%, concentration of Ni in the liquidus phase is 32%

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PHASE DIAGRAMS nm

- When an alloy is melted & cooled, solidification occurs, using Cu-40%Ni as example:
1. At start of freezing (1280 °C), the liquid contains 40% Ni, and the solid contains 52% Ni
2. After cooling to 1250 °C, the liquid contains 32% Ni and the solid contains 45% Ni
3. At the solidus temperature (1240 °C), the liquid contains 28% Ni and the solid contains 40% Ni

- Sufficient time must be permitted for the copper and nickel atom to diffuse and
produce the composition given by the phase diagram, reaching equilibrium state

Change in structure of a Cu-40%Ni alloy during equilibrium solidification. Nickel and copper atoms must diffuse during cooling to
satisfy the phase diagram and produce a equilibrium structure
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