Phase Transformations

Chapter 11 Callister, 2001 5th Edition

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Why do we study phase transformations?

The tensile strength of an Fe-C alloy of eutectoid composition can be varied between 700-2000 MPa depending on the heat treatment process adopted. This shows that the desirable mechanical properties of a material can be obtained as a result of phase transformations using the right heat treatment process. In order to design a heat treatment for some alloy with desired RT properties, time and temperature dependencies of some phase transformations can be represented on modified phase diagrams. Based on this, we will learn: a) Phase transformations in metals b) Microstructure and property dependence in Fe-C alloy system c) Precipitation HardeningCrystallization, Melting, and Glass Transition

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Phase Transformation in Metals

Development of microstructure in both single- and two-phase alloys involves phase transformations-which involves the alteration in the number and character of the phases. Phase transformations take time and this allows the definition of transformation rate or kinetics. Phase transformations alter the microstructure and there can be three different classes of phase transformations: a) Diffusion dependent transformations with no change in number of phases and composition ( solidification of a pure metal, allotropic transformations, etc.) b) Diffusion dependent transformations with change in number of phases and composition (eutectoid reaction) c) Diffusionless transformations (martensitic transformation in steel alloys)

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Kinetics of Solid State Reactions: Transformations (formation of a new phase with a different composition and structure) involving diffusion depend on time (Chapter 6). Time is also necessary for the energy increase associated with the phase boundaries between parent and product phases.Moreover, nucleation, growth of the nuclei, formation of grains and grain boundaries and establishment of equilibrium take time. As a result we can say the transformation rate (progress of the transformation) is a function of time. In kinetic investigations, the fraction of reaction completed is measured as a function of time at constant T. Tranformation progress can be measured by microscopic examination or measuring a physical property (e.g., conductivity). The obtained data is plotted as fraction of the transformation versus logarithm of time.

k and n are time independent constants.

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Temperature controls the kinetics of the transformations. For the recrystallization of Cu:

For a specific temperature range, rate increases according to :

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Multiphase transformations: Phase transformations may be accomplished by varying temperature, composition and external pressure. Most of the phase transformations require some finite time to go to completion and the rate of transformation is important in the relationship between heat treatment and microstructure development. The rate of transformation to achieve the equilibrium state is very slow and equilibrium conditions are maintained if the heating/cooling is really slow. This is usually unpractical. In general, transformations are shifted to lower or higher temperatures for cooling and heating respectively. These phenomena are termed supercooling and superheating respectively. The more rapid the cooling or heating, the greater the supercooling or superheating. For example, Fe-C eutectoid reaction is typically displaced 10-20C lower than the equilibrium transformation temperature. For many alloys, the preferred state is metastable state (intermediate between initial and eqm . States )

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Microstructural and Property Changes in Fe-C Alloys

1) Isothermal Transformation Diagrams: Pearlite is a microstructural product of the transformation of

Temperature is important in this transformation:

Each curve is obtained by rapidly cooling the austenite to the temperature indicated.

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The dependance of transformation to temperature and time can be analyzed best using the diagram below:

Data for the construction of isothermal transformation diagram is obtained from a series of plots of the percentage transformation versus logarithm of time investigated over a range of temperatures.

isothermal transformation diagram for Fe-C alloy of eutectoid composition

727C At T just below 727C, very long times (on the order of 105 s) are required for 50% transformation and therefore transformation rate is slow. The transformation rate increases as T decreases, for example, at 540C 3 s is required for 50% completion. This type of diagram is valid for constant T.
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This observation is in clear contradiction with the equation of

This is because in T range of 540C-727C, the transformation rate is mainly controlled by the rate of pearlite nucleation and nucleation rate decreases with T increase. Q in this equation is the activation energy for nucleation and it increases with T increase. It has been found that at lower T, the austenite decomposition is diffusion controlled and the rate behavior can be calculated using Q for diffusion which is independent of T. Isothermal phase diagrams are also called time-temperaturetransformation (T-T-T) plots.

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An actual isothermal heat treatment curve on the isothermal transformation diagram:

rapid cooling

the thickness of the ferrite to cementite layers is about 8 to 1.

isothermal treatment

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The layer thickness depends on temperature at which the isothermal transformation occurs. For example at T just below the eutectoid, relatively thick layers of both ferrite and cementite phases are produced. This structure is called coarse pearlite. At lower T, diffusion rates are slower, which causes formation of thinner layers at the vicinity of 5400C. This structure is called fine pearlite.

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For Fe-C alloys of other compositions, a proeutectoid phase of ferrite or cementite will coexist with pearlite and therefore the isothermal transformation diagram has additional curves:

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Bainite: is another microstructure formed as a result of transformation of austenite. Bainite consists of ferrite and cementite and diffusion processes take place as a result. This structure looks like needles or plates. There is no proeutectoid phase in bainite.

nose 5400C

2150C

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Pearlitic and bainitic transformations are competitive and transformation from to another requires reheating. The kinetics of bainite formation follows the Equation relating the rate to temperature.
If steel alloy with pearlitic or bainitic structure is heated to and left at a temperature below the eutectoid temperature (such as 7000C) for 18 to 24 hours, another microstructure, called spheroidite, forms.

ferrite

cementite

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Another microstructure is formed when austenite is rapidly cooled or quenched to a relatively low temperature (ambient T) called martensite. Martensite is a single phase nonequilibrium structure and produced as a result of diffusionless transformation of austenite. The quenching rate should be very high to prevent carbon diffusion. FCC austenite undergoes a polymorphic transformation to a body centered tetragonal (BCT) martensite.
Fe

carbon Steels can maintain their martensitic structure indefinetely at RT. Since martensitic transformation does not involve diffusion, it is almost instantaneous. Therefore its transformation is independent of time.

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Since martensite is in a nonequilibrium phase, it does not appear on the phase diagram of Fe-Fe3C.

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The austenite to martensite transformation is shown in the isothermal transformation diagram:

Temperatures of these transformations change with the composition of alloy and transformation to martensite only depends on T not time. This type of transformation is called athermal transformation.

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Steels in which C is the prime alloying element are called plain carbon steels, whereas alloy steels containg other elements, such as, Cr, Ni, Mo, W, etc. In the presence of other elements the isothermal transformaion diagrams may be different:
Remarks about the diagram:

1. shifting to longer times the nose of austenite to pearlite transformation (a proeutectoid phase nose if it exists) 2. formation of separate bainite nose

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Mechanical Behavior of Fe-C Alloys: Pearlite: Cementite is much harder but more brittle than ferrite. Therefore increasing the fraction of Fe3C will make the resulting material harder and stronger. Since Fe3C is brittle, increasing its content decreases ductility of the material.

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The layer thickness is also important for the mechanical behavior of the material. Fine pearlite is harder and stronger than coarse pearlite. Coarse pearlite is more ductile than fine pearlite because of greater restriction to plastic deformation of the fine pearlite.

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There is a large adherence between the two phases across a boundary of and Fe3C. The strong and rigid cementite layers restricts the deformation of soft ferrite layers and as the phase boundary area increases per unit volume of the material, the degree of reinforcement is higher. In addition phase boundaries act like barriers for dislocation motions. This is why fine pearlite has a greater strength and hardness. Spheroidite: has lower strength and hardness than pearlitic microstructures. This is becuase of the smaller phase boundary area in spheroiditic microstructures. Of all the steel alloys, those that are softest and weakest have a spheroidite microstructure. The spheroidized steels have higher ductility than coarse pearlite.

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Bainite: Bainitic steels have a finer structure and therefore they are stronger and harder than pearlitic ones. They have a good combination of strength and ductility

Martensite:The hardest and strongest and the most brittle form of the steel alloy. It has a negligibly small ductility. Its hardness is controlled by C content up to 0.6 wt% rather than its microstructure. These properties are the results of effectiveness of the interstitial C atoms in hindering dislocation motion and existence of few slip systems for BCT structure.
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Tempered Martensite: Martensite is hard but also very brittle so that it can not be used in most of the applications. Any internal stress that has been introduced during quenching has a weakining effect. The ductility and toughness of the material can be enhanced by heat treatment called as tempering. This also helps to release any internal stress.

Tempering is performed by heating martensite to a T below eutectoid temperature (2500C-6500C) and keeping at that T for specified period of time. The formation of tempered martensite is by diffusional processes.
very small cementite particles dispersed homogeneously.

ferrite matrix
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Tempered martensite may be nearly as hard and strong as martensite, but with substantially enhanced ductility and toughness. The hardness and strength may be due to large area of phase boundary per unit volume of the material. The phase boundary acts like a barrier for dislocaitons. The continuous ferrite phase in tempered martensite adds ductility and toughness to the material. The size of the cementite particles is important factor determining the mechanical behavior. As the cementite particle size increases, material becomes softer and weaker. The temperature of tempering determines the cementite particle size. Since martensite-tempered martensite transformation involves diffusion, T increase will accelerate the diffusion and rate of cementite particle growth and rate of softening as a result. Heat treatment of martensite has two variables: Temperature and time.

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This type of data is usually provided by the steel manufacturer. For this data, martensite is quenched in oil and tempering time is 1 hour.

This data is obtained for water quenched eutectoid composition. As tempering time increases the hardness decreases. Overtempered martensite is relatively soft and ductile.
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Tempering of some steels may result in decrease in toughness and this is called temper embrittlement. These are the alloys with high concentrations of alloying elements, P, As, Ni, Cr, Sb and Sn. The presence of alloying elements increases the T at which the ductile-to-brittle transition occurs. This has been observed when steel is tempered at a temperature above about 5750C followed by slow cooling to RT or when tempering is carried out b/w 375-5750C. Crack propagation in this type of materials is intergranular, that is the fracture path follows the grain boundaries of the precursor austenite phase. We can avoid the temper embrittlement by 1) compositional control 2) tempering above 5750C or below 3750C followed by quenching to RT.

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Summary of the Phase Transformations for Fe-C Alloy System

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Precipitation Hardening: is the enhancement of the strength and hardness by forming extremely small uniformly dispersed particles of a second phase within the original phase matrix. This can be done by phase tranformations at appropriate temperatures. Small particles in the new phase are called precipitates. For example: Al-Cu, Cu-Be, Cu-Sn, Mg-Al and some ferrous alloys are precitation hardenable. Heat Treatments-Precipitation hardenable alloys usually contain two or more alloying elements. The simplest system is binary system: A-B system.

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There are conditions for the precipitation hardening to be applied: a) considerably high solubility of the elements in each other b) solubility limit should rapidly decrease in concentration of the major element as T decreases. c) The composition of a preipitation hardenable alloy must be less than the maximum solubility.
There are two different types of heat treatment: 1) Solution heat treating: all solute atoms are dissolved to form a single phase solid solution. Consider the alloy with C0 composition, which is heated to T0 -and waiting all phase to dissolve completely. At this point there is only with C0 composition. Then it is quenched to T1, which is usually RT so that any diffusion and formation of phase is prevented. The resulting material is phase solid solution supersaturated with B atoms at T1.

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2) Precipitation heat treating: Supersaturated solid solution is heated to T2 within the + two phase region, at which the diffusion rate is high.The precipitate phase forms as fine particles with a composition of C, which is called sometimes as aging. After aging time, the alloy is cooled to RT.

The behavior of a typical precipitation hardenable alloy. The reduction in strength and hardness after long time periods is called overaging.

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Mechanism of Hardening: Precipitation hardening is commonly used in Al alloys with high strength. For example Al-Cu alloys.

phase is a substitutional solid solution of Cu in Al

phase is intermetallic compound, CuAl2

During the initial hardening stage Cu atoms cluster together in small discs (few atoms thick and about 25 atoms in diameter) at countless positions within phase. The discs are very small that they are not considered as particles. With time and diffusion of Cu atoms, the discs become particles and increase in size. The particles undergoes two transition phases ( and ) before the formation of equilibrium phase.
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The strengthening process is improved by T increase.

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Crystallization, Melting, and Glass Transition in Polymers: Crystallization: is the production of an ordered solid phase upon cooling from a liquid melt having no crystalline structure. The degree of crystallization controls the mechanical properties of the polymers. The crystallization of polymers follows the same steps as: nucleation and growth processes. Time dependence of crystallization can be described by
(Avrami equation)

Since 100 % crystallinity of the polymer is not possible, the vertical axis is scaled as normalized fraction crystallized. Fraction 1.0 is the highest level of crystallization.

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Melting: is the opposite of crystallization and occurs at melting temperature. Melting of a polymer takes place over a range of temperature and behavior of the polymer during melting depends on the history of the material, such as the temperature of crystallization, rate of heating. Glass transition: This occurs in amorphous and semicrystalline polymers. As a result of glass transition, motions of molecular chains are restricted at lower temperatures. As T is decreased, a gradual transformation is observed from a liquid to a rubbery material and finally a rigid solid. The temperature of transition from rubbery to rigid solid phase is called glass transition temperature (Tg). Stiffness, heat capacity and thermal expansion coefficient are the major properties changed during this transition. Melting and glass transition temperatures are important since they define the upper and lower temperature limits of applications.

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The temperature of melting and glass transition can be determined from a plot of specific volume (reciprocal of the density) versus temperature.

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Factors influencing melting temperature: Molecular chemistry and structure, chain stiffness (double bonds and aromatic groups lowers the flexibility), size and type of the side groups, molecular weight, degree of branching. Factors affecting glass transition temperature: Molecular characteristics controlling the chain flexibility or stiffness control Tg to some degree. As chain flexibility is diminished glass transition temperature increases. Molecular weight also affects Tg:

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