Transformation and Treatment

Chapter 11

In the last chapter

We looked at some fairly simple 2 component phase diagrams in some detail We explored more complicated phase diagrams We did not examine how the phase change from one solid phase to another or others occurs

Solid State Reactions

The change from one solid to another has a lot in common with the solidification process It does not happen instantly
Need nucleation Need time for growth

Recall
For solidification
DG = 4/3 p r3 DGv +4 p r2 s Volume free energy + surface energy

For one solid phase changing to another

DG = 4/3 p r3 DGv +4 p r2 s + 4/3 p r3 e Volume energy + surface energy + strain energy Because the new solid does not take up the same volume as the old solid

Nucleation
Nucleation usually occurs at grain boundaries Unlike solidification, it isnt too hard to get a nucleus going However, the nucleation rate increases as the temperature goes down

Growth
The nucleus grows as material diffuses to the site Diffusion is a function of temperature If you cool the material off immediately, it is hard for diffusion to occur Supersaturated non-equilibrium structures can occur

Kinetics
Nucleation and growth determine how fast the transformation will occur. Avrami relationship f=1-exp(-ctn)
f is the fraction converted t is time c and n are constants for a given temperature

Avrami Plot
Fraction Converted

Conversion is 50% Complete

t is the time
required for 50% conversion
| Incubation Time |

Time (sec)

Growth Rate
Often expressed as 1/t The growth rate is a function of temperature Often, the higher the temperature, the faster the solid transforms Why? Diffusion dominates in many systems Not always true though for example..

Effect of Temperature on Phase Transformation

Equilibrium transformation temperature
Growth Rate Overall Transformation Rate Nucleation Rate Rate

Temperature

Effect of Temperature on Phase Transformation

Time for 50% Transformation

Minimum Time required for Transformation

Time

C-curve
Typical of many metals, ceramics, glasses and polymers Ex. Iron changes phase this way

What if growth dominates?

For some metals nucleation occurs readily The only factor that changes with temperature then is the growth rate which is diffusion controlled For these metals, the solid to solid phase change always occurs faster at higher temperatures

Effect of Temperature on Copper

Fraction Transformed

135 C
120 C 80 C

Time

Growth rate follows an Arrhenius Relationship

Growth rate = A exp(-Q/RT)
Growth rate is proportional to overall transformation rate

How Does the Solid Form?

Liquid a This is what we would like to happen

L+a

a+b

How Does the Solid Form?

Liquid a This is what typically happens a

L+a

We want to avoid this structure, which is caused by slow cooling

Age hardening or Precipitation Hardening

A treatment used on non optimum alloy structures Produces a uniform dispersion of
Fine Hard Coherent Precipitate

In a softer, more ductile matrix

#1 Solution Treatment
Reheat the alloy up to a temperature where only one solid phase exists (above the solvus) This dissolves the second solid phase (b for example) into the primary phase Dont exceed the eutectic temperature a
a+L a+q L

#2 Quench
Rapidly cool to room temperature or below This results in a supersaturated nonequilibrium structure The second phase does not form, because diffusion is so slow!! L
a
a+L

a+q

# Aging
Reheat to a temperature below the solvus Diffusion is still slow, so the atoms can only diffuse a short distance Results in a fine precipitate There is an optimum aging time
a
a+L a+q L

Types of Precipitates
Coherent Non Coherent

Coherent Precipitates
Form First Eventually grow until they snap out of solution Produce more hardening If you over age the strength goes down because
Precipitate goes from coherent to noncoherent

Aging
See the animations on the CD Artificial aging elevated temperatures Natural aging room temperature Not suitable for use at high temperature
Why?

Problems with welding

Requirements for Age Hardening

Must have a phase diagram that exhibits a change from a single solid phase to two solid phases (a->a + b) Matrix should be soft and ductile Precipitate should be hard and strong Must be quenchable Must have a coherent precipitate

Aluminum - Copper Aging

a
q a
as
s

a+ q

#1 Solution Treatment

#2 Quench

#3 Aging

Eutectoid Reaction
One solid phase transforms to two different solid phases The iron carbon phase diagram has a eutectoid This diagram is the basis for iron and steels

Iron-Iron Carbide Phase Diagram d, ferrite

1600 C

Liquid
1400 C

Eutectic
g, austenite L+g L + cementite

1200 C

1000 C

Eutectoid
a, ferrite

g + Cementite

800 C

600 C

Cementite (Fe3C
2% C 3% C 4% C 5% C 6% C 6.70% C

400 C Fe

1% C

Pure Iron
16 00 C 14 00 C 12 00 C 10 00 C 80 0 C

Solidifies first as d ferrite which is BCC Then, as it cools, it goes through an allotropic phase transformation to g austenite which is FCC Finally, it changes to a ferrite, which is BCC

60 0C
40 F 0C e

1 % C

2% C

3 % C

4% C

5% C

6% C

6.70 %C

Carbon is significantly more soluble in austenite than in ferrite, because of the crystal structure As the austenite cools, the carbon eventually comes out of solution as cementite

16 00 C 14 00 C 12 00 C 10 00 C 8 0 0 C 60 0 C 40 0 F C e 1 % C 2% C 3 % C 4 % C 5% C 6% C 6.70 %C

Dispersion Strengthened Iron

In this region the iron is dispersion strengthened Solid a converts to a + cementite
a a +Cementite

Hypoeutectoid Iron
g

Ductile Continuous Phase

Pearlite

Hypereutectoid Iron
g

Fe3C

Brittle Continuous Phase

Used in Ball Bearings

Fe3C Pearlite

Is it Iron or Steel?
Steel is an iron-carbon alloy that may contain other alloying elements Low , Medium and High Carbon Steel
Usually less than about 1%

Alloy Steels such as Stainless contain other elements such as Chromium

Cast Iron
Cast Iron has more than 2.14% C Usually has 3 or 4% Iron
160 0C 140 0C 12 00 C 100 0C 80 0 C

Note the low melting point, which is an advantage for casting

L g 2.14%C

600 C 400 C F e

1% C

2% C

3% C

4% C

5% C

6% C 6.70 %C

Lever Law Calculations

Performed the same way as in Chapters 9 and 10 Remember A phase diagram represents equilibrium conditions The actual condition may be different, depending on the cooling conditions

Time -Temperature Transformation

The rate of transformation depends on how much you undercool the metal

Time for 50% Transformation

Minimum Time required for Transformation

Time

Iron
The microstructure depends on how much you undercool the iron If transformation occurs at a high temperature (near the equilibrium phase change temperature) the microstructure will be course At cooler temperatures, a finer microstructure is formed

Other Microstructures of Iron

If the transformation temperature of iron is kept above about 550 C, a lamellar microstructure results which we call pearlite At temperatures below 550 C diffusion is very slow. The resulting microstructure changes to round particles of cementite in a ferrite matrix. Its called bainite

Why Does Bainite form?

Extremely thin lamellar layers result in a lot of surface area at the boundary between the cementite and ferrite This results in high total surface energy too high The surface energy is reduced by switching to more rounded particles

Affect of Temperature on Bainite

Transformation temperature affects the bainite microstructure, just like it affects pearlite Lower temperatures result in smaller cementite particles in the ferrite matrix

What happens if you get REALLY COLD

At really low transformation temperatures diffusion basically stops Neither bainite or pearlite can form The crystal trys to change from the FCC austenite phase to the BCC ferrite phase, but it traps the excess C in the matrix The result is a BCT crystal structure called Martensite

Martinsitic Reaction
Diffusionless Not time dependant Not an equilibrium structure Steel Martinsite is very hard and brittle

Tempering Steel Martinsite

If you warm martinsite back up diffusion can occur At least some of the carbon forms cementite By controlling the tempering temperature and time, a wide range of properties can be produced

Can you control the microstructure that forms?

Yes, by controlling the transformation temperature and time You can get pearlite, bainite or martinsite Or.. Combinations of the different microstructures Consider the following TTT diagram for a eutectoid steel (0.77% C)

Time-Temperature-Transformation for a Eutectiod Steel

Equilibrium Phase Change Temperature

700
600 500 400 300 Bs

Ps

Pf Bf

Pearlite

Bainite
Finish Time

Start Time Ms Mf

200
100 0.1 1

Martinsite 10

100

1000

10,000

seconds

Try the quiz

On the CD

Friday
Jominy End Quench Test Each part of the sample of steel is cooled at a different rate What kind of structure do you expect? How does that relate to strength and hardness?