Chapter 10: Phase Transformations in Metals

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10.1 Introduction

The goal is to obtain specific microstructures that will improve the mechanical properties of a metal, in addition to grain-size refinement, solid-solution strengthening, and strain-hardening.

10.2 Basic Concepts

Phase transformations that involve a change in the microstructure can occur through:

  • Diffusion
  • Maintaining the type and number of phases (e.g., solidification of a pure metal, allotropic transformation, recrystallization, grain growth.
  • Alteration of phase composition (e.g., eutectoid reactions, see 10.5)
  • Diffusionless
  • Production of metastable phases (e.g., martensitic transformation, see 10.5)

10.3 The Kinetics of Solid-State Reactions

Change in composition implies atomic rearrangement, which requires diffusion. Atoms are displaced by random walk. The displacement of a given atom, d, is not linear in time t (as would be for a straight trajectory) but is proportional to the square root of time, due to the tortuous path: d = c(Dt) 1/2 where c is a constant and D the diffusion constant. This time-dependence of the rate at which the reaction (phase transformation) occurs is what is meant by the term reaction kinetics.

D is called a constant because it does not depend on time, but it depends on temperature as we have seen in Ch. 5. Diffusion occurs faster at high temperatures.

Phase transformation requires two processes: nucleation and growth. Nucleation involves the formation of very small particles, or nuclei (e.g., grain boundaries, defects). This is similar to rain happening when water molecules condensed around dust particles. During growth, the nuclei grow in size at the expense of the surrounding material.

The kinetic behavior often has the S-shape form of Fig. 10.1, when plotting percent of material transformed vs. the logarithm of time. The nucleation phase is seen as an incubation period, where nothing seems to happen. Usually the transformation rate has the form r = A e-Q/RT (similar to the temperature dependence of the diffusion constant), in which case it is said to be thermally activated.

10.4 Multiphase Transformations

To describe phase transformations that occur during cooling, equilibrium phase diagrams are inadequate if the transformation rate is slow compared to the cooling rate. This is usually the case in practice, so that equilibrium microstructures are seldom obtained. This means that the transformations are delayed (e.g., case of supercooling), and metastable states are formed. We then need to know the effect of time on phase transformations.

      Microstructural and Property Changes in Fe-C Alloys

10.5 Isothermal Transformation Diagrams

We use as an example the cooling of an eutectoid alloy (0.76 wt% C) from the austenite (g- phase) to pearlite, that contains ferrite (a) plus cementite (Fe3C or iron carbide). When cooling proceeds below the eutectoid temperature (727 oC) nucleation of pearlite starts. The S-shaped curves (fraction of pearlite vs. log. time, fig. 10.3) are displaced to longer times at higher temperatures showing that the transformation is dominated by nucleation (the nucleation period is longer at higher temperatures) and not by diffusion (which occurs faster at higher temperatures).

The family of S-shaped curves at different temperatures can be used to construct the TTT (Time-Temperature-Transformation) diagrams (e.g., fig. 10.4.) For these diagrams to apply, one needs to cool the material quickly to a given temperature To before the transformation occurs, and keep it at that temperature over time. The horizontal line that indicates constant temperature To intercepts the TTT curves on the left (beginning of the transformation) and the right (end of the transformation); thus one can read from the diagrams when the transformation occurs. The formation of pearlite shown in fig. 10.4 also indicates that the transformation occurs sooner at low temperatures, which is an indication that it is controlled by the rate of nucleation. At low temperatures, nucleation occurs fast and grain growth is reduced (since it occurs by diffusion, which is hindered at low temperatures). This reduced grain growth leads to fine-grained microstructure (fine pearlite). At higher temperatures, diffusion allows for larger grain growth, thus leading to coarse pearlite.

At lower temperatures nucleation starts to become slower, and a new phase is formed, bainite. Since diffusion is low at low temperatures, this phase has a very fine (microscopic) microstructure.

Spheroidite is a coarse phase that forms at temperatures close to the eutectoid temperature. The relatively high temperatures caused a slow nucleation but enhances the growth of the nuclei leading to large grains.

A very important structure is martensite, which forms when cooling austenite very fast (quenching) to below a maximum temperature that is required for the transformation. It forms nearly instantaneously when the required low temperature is reached; since no thermal activation is needed, this is called an athermal transformation. Martensite is a different phase, a body-centered tetragonal (BCT) structure with interstitial C atoms. Martensite is metastable and decomposes into ferrite and pearlite but this is extremely slow (and not noticeable) at room temperature.

In the examples, we used an eutectoid composition. For hypo- and hypereutectoid alloys, the analysis is the same, but the proeutectoid phase that forms before cooling through the eutectoid temperature is also part of the final microstructure.

10.6 Continuous Cooling Transformation Diagrams - not covered

10.7 Mechanical Behavior of Fe-C Alloys

The strength and hardness of the different microstructures is inversely related to the size of the microstructures. Thus, spheroidite is softest, fine pearlite is stronger than coarse pearlite, bainite is stronger than pearlite and martensite is the strongest of all. The stronger and harder the phase the more brittle it becomes.

10.8 Tempered Martensite

Martensite is so brittle that it needs to be modified in many practical cases. This is done by heating it to 250-650 oC for some time (tempering) which produces tempered martensite, an extremely fine-grained and well dispersed cementite grains in a ferrite matrix.


Alloy steel
Athermal transformation
Coarse pearlite
Fine pearlite
Isothermal transformation diagram
Phase transformation
Plain carbon steel
Tempered martensite
Thermally activated transformation
Transformation rate