Phase Diagrams

A phase diagram shows what phases are

present at a given temperature, pressure and
composition
Phase = part of material having uniform
structure and composition, can be solid, liquid
or gas

Application story: rocket nozzle cone

1
 Phase Diagram for
Graphite/Diamond

Graphite

1000 K
Diamond

Temperature

14 kBar 34 kBar
300K

Pressure

1 Bar = 105 Pa  1 atm 2

 Making Diamond at Low Pressures

• 1% methane + 99% hydrogen

• Electric (plasma) discharge at 10-1 - 10-3 Torr
• Substrate at 800 - 1000 C
• Simultaneous deposition of graphite and diamond
• Atomic hydrogen in the gas discharge etches graphite
faster than diamond, resulting in net deposition of
diamond
3
 NaCl+H2O:
a common binary system
10

Liquid (brine)
O
Temperature
23.3% NaCl
(oC)
-10
Ice + brine
Salt + brine
-20 21oC
Ice + salt

10 20 30

Pure H2O % NaCl

4
NaCl has negligible solubility in ice
 Cooling Curve for Pure Cu

1085 C
Temperature

Time

5
 Cooling Curve for Cu50Ni50

1320 C
Temperature
1260 C

Time
6
 Phase Diagram for Ni+Cu
(binary isomorphous system)
1

LIQUID (L) 1453

A

Liquidus
Temperature (C) +L
B

2
1085 SOLID ()

Solidus
C2 C1
Pure Cu % Ni Pure Ni
7
 Lever Rule
LIQUID (L)

Temperature

+L

SOLID ()

Pure A wL wo w Pure B

8
 Lever Rule

wL wo w 

L 

w w w w
X   o X  o L
L w w  w w
 L  L

  9
Pb+Sn: binary eutectic system

327C
L
+L 232C
 183C +L

 18.3 61.9 97.8
 +


Pb Sn
C1 C2 C4 C3



  10
 Zone Refining
• Purification of materials through repeated
heat treatments
• Example: obtaining pure silver from a
silver-copper mixture

11
 Zone Refining of Silver
Temperature

1084.5C
961.9C L
+L
+L 780C
 
8.8 28.1 92.1

+

Ag Cu
12
 Lever Rule
LIQUID (L)

Temperature

+L

SOLID ()

Pure A wL wo w Pure B

13
 Lever Rule

wL wo w 

L 

w w w w
X   o X  o L
L w w  w w
 L  L

  14
Application of Phase Diagrams in
Steel-Making
• Production of iron and steels
– First step: reaction between iron ores (iron oxides) with
coke (mainly carbon) --> pig iron (iron with up to 4 wt.
% carbon + other impurities, e.g., P and S)
– Second step: mix pig iron with lime (CaO) + oxygen
(+scrap or recycled steels) --> P and S removed as
CaSO4 and Ca3(PO4)2 (slag), C as CO+CO2
– Third step: introduce alloying elements for improved
properties, e.g., Mn for grain refinement

15
 Fe-C Phase Diagram
 ferrite (BCC)
 austenite (FCC)
Fe3 Ccementite

1147C
2.14
912C


Temperature
+

727C
0.022 0.76
 + Fe3C

w/o carbon 16
 Piano Wire Experiment

Piano wire just above

- transition

Piano wire just below -

 transition

17
Pb+Sn: binary eutectic system

327C
L
+L 232C
 183C +L

 18.3 61.9 97.8
 +


Pb Sn
C1 C2 C4 C3



  18
 Fe-C Phase Diagram
 ferrite (BCC)
 austenite (FCC)
Fe3 Ccementite

1147C
2.14
912C

 + Fe3C
Temperature
+
 eutectoid
727C
0.022 0.76
 + Fe3C

w/o carbon 19
 Influence of Composition on
Microstructure
Cooling Fe+C from > 727 C to ~ 540 C and hold
---> Austenite  ferrite + cementite

Fe3C Fe3C Fe3C

  

eutectoid hypo-eutectoid hyper-eutectoid

20
 Other Microstructures of Fe+C
• When cooled to between ~200 and 540 C,
obtain elongated strips of ferrites and
cementite (Bainite)
• When cooled to less than 200 C rapidly,
obtain martensite --> supersaturated
solution of C in Fe with a body-centered
tetragonal unit cell

21
Martensitic vs Pearlitic Steels

Martensitic steels

iron
Hardness carbon

Pearlitic steels

w/o carbon

22
 TTT Diagram
Tcr

Temperature

Topt

Time for 99% of the phase to transform

23
 Alloying Elements to Improve
Properties of Steels
• Solid-solution strengthening with little loss
of ductility
• Cr and W to form hard carbides --> strength
increase
• Ni to stabilize the FCC phase --> improved
ductility
• Adding >12% Cr to improve oxidation and
corrosion resistance (basis of SS)
24
 Alloying Elements to Improve
Properties of Steels
• Mn for grain refinement
• Fine precipitates to improve strength and
toughness
• Avoid adding elements that destabilize
certain components, e.g. do not add Si in
high-C steels

25
 Classification of Steels
1xxx Carbon steels Low, medium, high

2xxx Nickel steels 5-35% Ni

3xxx Nickel-chromium steels Toughness and wear

resistance
4xxx Molybdenum steels High strength

5xxx Chromium steels High strength and

toughness
86xx, 87xx, Triple alloy steels (Ni, Strength and
93xx, 94xx, Cr, Mo) corrosion resistance
97xx, 98xx 26
 Sample Steels
1040 Plain carbon steel typically used in crankshafts,
nuts and bolts, with 0.40 w/o carbon and
typically 0.45 w/o Mn
4340 Alloy steel used in bushings, and aircraft struts
and tubings, containing 1.71 Ni, 0.77 Cr, 0.3
Mo, 0.75 Mn and 0.40 C
8620 Alloy steel used in gears, containing 0.55 Ni,
0.50 Cr, 0.2 Mo and 0.20 C
52100 Alloy steel used in bearings, containing 1.45
w/o of Cr and 1.0 w/o of C
27
 Shape Memory Alloys
• Two interesting properties: shape memory
and super- or pseudo-elasticity
• First discovered in 1938
• Most common SMA’s: NiTi, CuZnAl, and
CuNiAl
• Due to phase transformation, driven by
temperature or stress

28
 Demonstration of
the Shape Memory Effect
• Start with the high-temperature phase
(austenite) having a specific shape
• Cool below some critical temperature to obtain
the low-temperature phase (martensite)
• Deform it
• Warm the alloy above the critical temperature
• Material returns to original shape
29
Temperature
austenite
stress

austenite

martensite

strain

twinned martensite deformed martensite

Load 30
 Pseudo-Elasticity

temperature

A99

M99

stress
31
 Applications of SMA’s
• Thermostats
• Wire frames for eyeglasses
• Vascular stents
• Self-healing materials
• …..

32
 Lessons learned from
Chapter 5
• How to read a phase diagram
– Melting temperatures and maximum solubility
– Eutectic
– Zone-refining
– Lever rule
• Applications in steelmaking
– From pig iron to steels
– Fe-C phase diagram
– Terminologies: ferrite, austenite, cementite, eutectoid,
martensite, TTT diagram
• Shape memory alloys 33