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# CHAPTER 9: PHASE DIAGRAMS

When we combine two elements...
what equilibrium state do we get?

Greek Alphabet

## In particular, if we specify... then...

--a composition (e.g., wt%Cu - wt%Ni), and --a temperature (T) How many phases do we get? What is the composition of each phase? How much of each phase do we get?

## Definitions Component - The elements or compounds which are mixed initially

(e.g., Al and Cu, Fe and C)

9.2

## THE SOLUBILITY LIMIT

10 0 Temperature (C) 80 60 40 20 0
Pure Water

Solubility Limit:
Maximum concentration for which only a solution occurs.

Solubility Limit

L
(liquid)

## Phase A homogeneous portion of a system that has uniform physical

and chemical characteristics. Solids can have multiple phases. Liquids depends on their solubility (oil and water do not mix)

L
(liquid solution i.e., syrup)

## Example: Water-Sugar System Phase Diagram

Question: What is the
solubility limit at 20oC?

+ S
(solid sugar) 10 0
Pure Sugar

Regions, which differ in structure and/or composition from another region are different phases.
A phase will have a definite interface and be able to be mechanically separated from its surroundings.

## 20 40 6065 80 C o =Composition (wt% sugar)

If Co < 65wt% sugar: sugar (1 phase) If Co > 65wt% sugar: syrup + sugar. (2 phases)

## Solubility limit increases with T:

e.g., if T = 100oC, solubility limit = 80wt% sugar.

## EQUILIBRIUM PHASE DIAGRAMS

Tell us about phases as function of T, Co, P. (Pressure = 1 atm) For this course: -binary systems: just 2 components. -independent variables: Temperature and Composition - Pressure is fixed (P = 1 atmosphere) The microstructure generated from these phases influences the properties of the material.

## Phase Diagram (Pressure Temperature) of Water - Ice

Point where the densities of liquid and vapor become equal and the interface between the two vanishes. Above this point, only one phase can exist.

## Conditions dictate the phase present

Triple point
Fun Facts: Ice is less dense than water, thus the liquid state is more compact than the solid state. Increasing pressure will favor compactness of the molecules, thus will favor the liquid state. Increasing the pressure will lower the temperature at which the solid will melt. Using a pressure cooker allows us to increase temperature above boiling

Fast forward for a minute to 9.17 The Gibbs Phase Rule (System in equilibrium)

P+F=C+N
P = number of phases present
Usually = 2 -solids, liquids... F = number of degrees of freedom - # of variables not controlled by nature, or the number of independent variables that we can change (density, conductivity, pressure, temperature, composition, electrical, magnetic......)

P = number of phases present F = number of degrees of freedom C = number of components N = number of noncompositional variables

P+F=C+N

## 1 component system (C=1)

C = 1, N = 2 gives P + F = 1 + 2 or P = 3 F. - if P = 1, F = 2 (liquid water, ice, steam) can change Temperature or Pressure. - if P = 2, F = 1. You will be on a LINE between two phases (Ice-water) you can ONLY change temperature OR pressure to stay at that point. - if P = 3, F = 0. This point is defined as a Critical Point. You cant change anything, nature dictates its existence.

C = number of components
- can be elements, compounds or solutions

## N = number of noncompositional variables

- temperature, pressure N=2

P = number of phases present F = number of degrees of freedom C = number of components N = number of noncompositional variables

P+F=C+N

Two general types of binary phase diagrams will be studied in this class Binary alloy only contains two elements ISOMORPHOUS EUTECTIC

## 2 component system (binary system)

C = 2, N = 2 gives P + F = 2 + 2 or P = 4 F. we need a 3-D diagram to show this, but usually we fix pressure at 1 ATM, so we only need a slice of the 3-D diagram. - if P = 1, F = 3 We can change 3 independent variables - if P = 2, F = 2. We can change 2 independent variables - if P = 3, F = 1. We can change 1 independent variables - if P = 4, F = 0. We can not change anything (if F = 0, conditions (like triple point) fixed by nature.)

A third general type is called Peritectic, but will not be emphasized Diagram looks like this

100% Ag

## The Phase Diagram - construction Melting point and melting range

The Eutectic Reaction all liquid to all solid from Greek "eutektos" meaning "easily melted" Figure 9.13

## We perform many experiments

Typical cooling curve of a solid-solution alloy. Note that freezing (L2 to S2) occurs over a range of temperatures rather than at one temperature.

The phase diagram allows us to determine the following: 1) Phases Present (L, , ...) (9.8, page 260) 2) Composition (what the phases are made of (elements)) (Page 260) 3) The amount of phases present (L, , ...)(page 261)

## - SINGLE PHASE REGION -

A = 75% Ni, (100 75 = 25% Cu) B = 40% Ni, (100 40 = 60% Cu)

C = 2 phase region, covered later D = 35% Sn, (100 35 = 65% Pb) E = 63% Sn, (100 63 = 37% Pb) F = 86% Sn, (100 86 = 14% Pb)

2) Using Phase Diagrams to Determine Composition - DUAL PHASE REGION Determining the composition in regions with two phases is performed using the same procedure with one additional step.

## Procedure: Page 261

-An isothermal (iso = constant, thermal = temperature) line, or tie line is drawn horizontally through the point of interest. - At the intersection of the tie line and the nearest SINGLE PHASE BOUNDARY (on each end) a vertical line is dropped to the horizontal axis from which the composition of the phases is determined. - The composition from the horizontal axis will correspond to the single phase boundary from which it came from (alpha = 5% beta, 95% alpha and the liquid phase is 34% beta, 66% alpha).

## Example: Phase composition in a two-phase region CO = 39%, 1250 OC

Use of the Phase Diagram to Determine Phase Amounts (How much of each phase is present)

Cu

Ni 39 31.5 42.5

We need to know how much of each phase exists at a given temperature. The ratio of the two phases present can be found by using the LEVER RULE. (Sometimes called the Inverse lever rule)

Point B

- CL = 31.5% Ni (100 - 31.5 = 68.5% Cu) - Calpha = 42.5% Ni (100 - 42.5 = 57.5% Cu)

As in Figure 9.3, anywhere along this tie line will have the same composition, but the amounts of phases will change

## Procedure on Page 261

100%

100% Liquid

100%

100% Liquid

Basically, the proportions of the phases present are given by the relative lengths of the tie line. So, the proportions of alpha and liquid present on the diagram (showing a portion of the whole phase diagram) are: X X+Y and Y but which equation goes with which phase? X+Y

Now, consider the same alloy as it crosses the liquidus line. At this line it will be 100% liquid. Looking at the diagram Y1 is very small and so must be the amount of liquid that has been transformed into alpha. Similarly X1 is relatively large and so it corresponds to the amount of liquid. So, the left side of the tie line gives the proportion of the liquid phase (or the single phase to the right), and the right side of the line gives the proportion of the alpha phase (or the single phase on the left)

## Example: Phase composition in a two-phase region CO = 39%, 1250 OC

Cu
For example, on the diagram, the percentage of alpha present can be calculated from the three pieces of composition data given. Fraction of alpha = (34 23) / (34 5) = 11/29 = 0.379, or 37.9% alpha as the alpha and liquid make up 100% of the alloys composition Percentage of liquid = 100 37.9 = 62.1% liquid.

Ni 39 31.5 42.5
Equation 9.1a, b

## Point H - CL = 31.5% Ni, Calpha = 42.5% Ni, CO = 39% Ni

WL = (U/(T+U)) = (42.5-39)/(42.5-31.5) = 0.32 Walpha = (T/(T+U)) = (39-31.5)/(42.5-31.5) = 0.68 Equation 9.2a,b

## Intermetallic compounds are usually hard and brittle

Figure 9.19 1 phase

2 phase 1 phase

## 2 Mg2Pb is a single phase line

Mg2Pb
2 phase

Some of the phase diagrams may appear complex, but you can reduce them to simple ones, like the ones previously shown. Every SINGLE (1) phase field has a TWO PHASE (2) field next to it. Every TWO PHASE field has SINGLE PHASE fields on either side of it.

Figure 9.20

Note: intermetallic compound forms a line - not an area because stoichiometry (i.e. composition) is exact.

Not all phase diagrams will have a beta solid solution (ie: Al Si) Aluminum silicon phase diagram

## Information on the phase diagrams in the book

Copper - Nickel ("cupro - nickels")
Most common alloys - Cu + 10% Ni - cooling circuits, ammunition - Cu + 30% Ni - desalination plants, chemical pipe - Cu + 25% Ni (+0.05 - 0.4 Mn) - coins, medals - Cu + 45% Ni (constantan) thermocouples (type J) strain gages General properties - outstanding corrosion resistance, particularly in sea water - good resistance to biofouling (90/10 slightly better than 70/30) - 70/30 stronger, better impingement corrosion resistance - ductile, hardened only by cold working - E = 120 - 156 GPa (aluminum = 70 GPa, steel = 207 GPa) - UTS = 267 - 624 MPa, density = 8.5 - 8.95 g/cm3

NO beta phase

Aluminum has zero solid solubility in silicon at any temperature. This means that there is no beta phase and so this phase is replaced by pure silicon.

## Information on the phase diagrams in the book

Copper - Silver
Most common alloys - 34% Cu + 50% Ag + 16% Zn - typical brazing alloy - 92.5% Ag + 7.5% Cu - Sterling silver - 90% Ag + 10% Cu - Silver coins - 60-70% Ag, 18-25% Sn + 2 - 14% Cu - Dental fillings General properties - many alloys have pleasing silver-like appearance

Copper - Zinc
Most common alloys - Cu + 15% Zn - red brass (C23000) - architectural, jewelry (UTS - 260-630 MPa, Elongation 50%, HV 65-170) - Cu + 30% Zn - cartridge brass (C26000) -highest elongation of all brasses. Ammunition, deep drawn applications. (UTS - 300-830 MPa, Elongation 55%, HV 65-200) - Cu + 40% Zn - Muntz metal (C28000) - good working properties. (named for its inventor.) (UTS - 340-500 MPa, Elongation 45%, HV 90-150) - Cu + 50% Zn - brazing solder

## Information on the phase diagrams in the book

Magnification 75X

Most common alloys (pre 2005, lead-free laws now in effect) - Pb + 40% Sn - Plumbers solder (pre- 2005) On slow cooling the liquid metal solidifies as lead rich dendrites at approximately 265C. The remaining liquid becomes increasingly tin rich with cooling until it solidifies at the eutectic composition at the eutectic temperature (183C). This temperature freezing range allows for the liquid to be "wicked" into the plumbing joint. - Pb + 62% Sn - electrical solder (eutectic, pre-2005) Most used pre-2005 plumbing and electrical

## PHASE DIAGRAM EXAMPLES

(Same type of questions that are in the exams) 779oC - T, 5% Ag

## Phases present Composition

_____ 5% Ag _____

## 100% Amount of Phases _____

1000oC, 25% Ag

779oC - T, 80% Ag

% = 91.2 - 80 91.2 - 8 % = 80 - 8 91.2 - 8 Multiply by 100 to get % Phases present Composition L _____ 25% Ag _____ Phases present Composition _______ _______ 8% Ag _______ 91.2% Ag _______

## 86.5% 13.5% _______ Amount of Phases _______

779oC - T, 60% Ag

## 850 oC, 20% Ag

% = 91.2 - 60 91.2 - 8 % = 60 - 8 91.2 - 8 Multiply by 100 to get % Phases present Composition _______ _______ 8% Ag _______ 91.2% Ag _______

## Ch. 9.9 825 oC, 85% Ag

Figure 9.4

MICROSTRUCTURES

% = 85 - 80 X100 94 - 80 % L = 94 - 85 X 100 94 - 80 Multiply by 100 to get % Phases present Composition L _______ _______ 94% Ag _______ 80% Ag _______ 80 94

## 64.2% 35.7% _______ Amount of Phases _______

Nonequilibrium Cooling

Figure 9.5

## CORED VS EQUILIBRIUM PHASES

C changes as we solidify. Cu-Ni case: First to solidify has C = 46wt%Ni. Fast rate of cooling:
Cored structure
Last to solidify has C = 35wt%Ni.

## Slow rate of cooling:

Equilibrium structure

Cu

Ni

Ch. 9.10

Ch. 9.11

## MECHANICAL PROPERTIES: Cu-Ni System

Effect of solid solution strengthening on:
--Tensile strength (TS) --Ductility (%EL,%AR)

BINARY-EUTECTIC SYSTEMS
has a special composition with a minimum melting Temperature

2 components

Ch. 9.12

Figure 9.11

Figure 9.12

## 2 wt% Sn < Co < 18.3 wt% Sn Result:

- polycrystal with fine crystals.

- polycrystals of grains.

Pb

Sn

Pb

Sn

Figure 9.13

Figure 9.15

## Co = CE Result: Eutectic microstructure

- alternating layers of and

T(C)
3 00

L L+ + L+

## The Iron - Carbon Phase Diagram

Steels <2.1% carbon (0.05 - 1.1% most common) Cast Irons - 2.1 - 4% carbon

2 00 TE

(Pb-Sn System)

1 00

hypoeutectic
0 20 18.3 40

Co

hypereutectic
60 80 100 97.8

Co

Figure 9.17
hypoeutectic: C

C o , wt% Sn

eutectic
61.9

o =50wt%Sn

## hypereutectic: (illustration only)

175 m

eutectic: C o =61.9wt%Sn

Figure 9.17a

160 m eutectic micro-constituent

Figure 9.14

## STEEL PHASE DIAGRAM DEFINITIONS

Te: eutectic temperature (~720OC 730OC) changes with chemistry : (gamma) Austenite, FCC, exists and is stable above Te : (alpha) Ferrite, BCC, soft iron with a low percent carbon (<0.022%) Fe3C: Cementite, hard and brittle compound Pearlite: fine layers of (alpha) and Fe3C, formed at Te Proeutectoid or Fe3C: Formed above Te Hypoeutectoid steel: has LESS than 0.76% carbon content Eutectoid steel: has 0.76% carbon content Hypereutectoid steel: has MORE than 0.76% carbon content

Summary of General Properties (more in Chapter 10) Like composites, the properties of the metal is representative of what it is made of UTS, MPa 1000 35 275 830 Elongation, % 10 ~0 40 20 Brinell Hardness ~110 794 (highest) 80 - 100 coarse - 170 fine - 375

## Austenite, Cementite, Fe3C Ferrite, Pearlite

Figure 9.26

Figure 9.24

6.7% Fe3C

Figure 9.27 Photomicrograph of a eutectoid steel showing the pearlite microstructure consisting of alternating layers of ferrite (the light phase) and Fe3C (thin layers most of which appear dark), 500X

Figure 9.29

For carbon contents below the eutectoid (hypoeutectoid), the reactions involving proeutectoid ferrite can result in several morphologies of the ferrite phase. red regions are proeutectoid ferrite
Figure 9.30

Figure 9.32

For carbon contents above the eutectoid (hypereutectoid), proeutectoid cementite can form during slow cooling as a brittle layer at the original austenite grain boundaries. blue regions are proeutectoid cementite
Figure 9.33

Figure 9.33

brittle

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Figure 9.34

Figure 9.35

## These two regions are listed in the textbook as + Fe3C

800oC, 1.2% C
% Austenite () % Proeutectoid ferrite

750oC, 0.5% C
% Austenite () % Proeutectoid ferrite

## 2.7 % Proeutectoid cementite ______

% Total cementite
same as above

## 0 % Proeutectoid cementite ______

% Total cementite
same as above

2.7 ______

0 ______
0.011 0.62

0 % Pearlite ______ (remaining changes into pearlite at 727OC) % = 6.67 - 1.2 x 100 = 97.3 6.67 - 1.05

1.05

0 % Pearlite ______ ( changes into pearlite at 727OC) % = 0.5 - 0.02 x 100 = 80.0 0.62 - 0.02

## % Proeutectoid cementite = 1.2 - 1.05 x 100 = 2.7 6.67 - 1.05

Total cementite = proeutectoid cementite + cementite amount in pearlite Total alpha = proeutectoid alpha + alpha amount in pearlite

## % Proeutectoid = 0.62 - 0.5 x 100 = 20.0 0.62 - 0.02

Total cementite = proeutectoid cementite + cementite amount in pearlite Total alpha = proeutectoid alpha + alpha amount in pearlite

727oC - T, 0.6% C
% Austenite () % Proeutectoid ferrite

727oC + T, 0.6% C
% Austenite () % Proeutectoid ferrite

## 0 % Proeutectoid cementite ______

% Total cementite

## 0 % Proeutectoid cementite ______

% Total cementite
0.02 0.77

8.7 ______

0 ______ 0 ______
0.02 0.77

77.3 % Pearlite use 727 +T ______ (remaining changes into pearlite at 727OC)

% Pearlite

% Total Fe3C = 0.6 - 0.02 x 100 = 8.7 6.67 - 0.02 % Proeutectoid = 0.77 - 0.6 x 100 = 22.7 0.77 - 0.02 % pearlite = 0.6 - 0.02 x 100 = 77.3 0.77 - 0.02

% = 0.6 - 0.02 x 100 = 77.3 0.77 - 0.02 % Proeutectoid = 0.77 - 0.6 x 100 = 22.7 0.77 - 0.02
Total cementite = proeutectoid cementite + cementite amount in pearlite Total alpha = proeutectoid alpha + alpha amount in pearlite

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727oC - T, 1.1% C
% Austenite () % Proeutectoid ferrite use 727 +T % Total cementite

727oC + T, 1.1% C
% Austenite () % Proeutectoid ferrite

0 ______ 0 ______

0.02 0.77

## 5.6 % Proeutectoid cementite ______

% Total cementite % Pearlite

## 5.6 ______ 0 ______

0.02 0.77

94.4 % Pearlite use 727 +T ______ (remaining changes into pearlite at 727OC)

% Proeutectoid cementite = 1.1 - 0.77 x 100 = 5.6 6.67 - 0.77 % Total Fe3C = 1.1 - 0.02 x 100 = 16.2 6.67 - 0.02 % pearlite = 6.67 - 1.1 x 100 = 94.4 6.67 - 0.77

% = 6.67 - 1.1 x 100 = 94.4 6.67 - 0.77 % Proeutectoid cementite = 1.1 - 0.77 x 100 = 5.6 6.67 - 0.77 % Total Fe3C = Proeutectoid cementite = 5.6%
Total cementite = proeutectoid cementite + cementite amount in pearlite Total alpha = proeutectoid alpha + alpha amount in pearlite

600oC, 0.77% C
% Austenite () % Proeutectoid ferrite

0 ______ 0 ______ 9.28. Explain why, upon solidification, an alloy of eutectic composition forms a microstructure consisting of alternating layers of the two solid phases. Upon solidification, an alloy of eutectic composition forms a microstructure consisting of alternating layers of the two solid phases because during the solidification atomic diffusion must occur, and with this layered configuration the diffusion path length for the atoms is a minimum.

## 0 % Proeutectoid cementite ______

% Total cementite % Pearlite % Total ferrite

## 11.5 ______ 100 ______ 88.5 ______

% Total cementite = 0.77- 0 x 100 = 11.5 6.67 - 0 Total ferrite = 100 11.5 = 88.5% or [(6.67 0.77) / 6.67] x 100
Total cementite = proeutectoid cementite + cementite amount in pearlite Total alpha = proeutectoid alpha + alpha amount in pearlite

9.25. (a) Describe the phenomenon of coring and why it occurs. (b) cite one undesirable consequence of coring. (a) Coring is the phenomenon whereby concentration gradients exist across grains in polycrystalline alloys, with higher concentrations of the component having the lower melting temperature at the grain boundaries. It occurs, during solidification, as a consequence of cooling rates that are too rapid to allow for the maintenance of the equilibrium composition of the solid phase. (b) One undesirable consequence of a cored structure is that, upon heating, the grain boundary regions will melt first and at a temperature below the equilibrium phase boundary from the phase diagram; this melting results in a loss in mechanical integrity of the alloy.

WHAT TO STUDY FOR THE EXAMS -Understand the textbook Summary (p. 302 - 303) and the important terms and concepts (p. 303). -Understand the assigned homework and examples given in class. -Interpretation of phase diagrams (including steel diagrams) phases present, phase compositions, phase amounts -Understand the influence of different alloying elements and that they can change the temperatures and percentages given in the textbook phase diagrams. -Alloying produces a solid solution which usually increases the tensile strength and decreases the ductility. -Understand general microstructures

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