Phase Diagrams, Phase Transformation and Heat Treating
Phase Diagrams
Learning Objectives:
- Describe the major features of a phase diagram.
Gibbs Phase Rule:
In a system under a set of conditions, number of phases (P) exist can be related to the number of components (C) and degrees of freedom (F) by Gibbs phase rule.
where,
P = Number of phases making up a system
F = Degrees of freedom
C = Number of components in a system
Degrees of freedom refers to the number of independent variables (e.g.: pressure, temperature) that can be varied individually to effect changes in a system.
Critical Point
Learning Objectives:
- Understand the critical point and the meaning of the terms saturated liquid, saturated vapor and quality of mixture.
The liquid-vapour equilibrium curve has a top limit which is known as the critical point. The temperature and pressure corresponding to this are known as the critical temperature and critical pressure.
Triple Point
Learning Objectives:
- Identify the different points (triple point, normal boiling point, freezing point) and regions (solid, liquid, vapor) of a phase diagram.
Where all three curves, solid, liquid and gas, meet, there is a unique combination of temperature and pressure where all three phases are in equilibrium together. This point is called a triple point.
Maksim, CC BY-SA 3.0, via Wikimedia Commons
Iron-Iron Carbide Diagram
Learning Objectives:
- Introduce students to the basic understanding of the interpretations of iron-carbon diagrams and isothermal transformation diagrams.
- Provide students with the skills needed to determine the temperatures to which steel must be heated to cause it to harden.

There are two iron-carbon equilibrium diagrams:
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Stable iron-graphite Fe-Gr
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Metastable iron-cementite Fe-Fe\(_3\)C
The stable condition usually takes a very long time to develop. The metastable diagram is of more interest. Fe\(_3\)C iron carbide called cementite because it is hard. Following phases exist on Fe-Fe\(_3\)C diagram: - Liquid solution of iron and carbon (L) - Ferrite (\(\alpha\)) – an interstitial solid solution of carbon in Fe \(\alpha\) (BCC). At room temperature ferrite is ductile but not very strong. - Austenite - an interstitial solid solution of carbon in Fe \(\gamma\) (FCC). - Cementite (Fe\(_3\)C) hard and brittle compound with chemical formula Fe\(_3\)C. It has metallic properties. On a base of Fe-Fe\(_3\)C diagram we can divide iron-carbon alloys into:
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Steels,
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Cast steels,
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Cast irons.
Steel is an alloy of carbon and iron and other alloying elements (e.g. Mn, Si) with carbon content up to 2% intended for wrought products or semi products. Cast iron is an alloy of carbon and iron and other alloying elements (e.g. Mn, Si) with carbon content over 2% intended for castings. Now, we consider only a part of Fe-Fe\(_3\)C diagram referring to steel. Perlite is a structure (i.e. consists of two phases) consists of alternate layers of Ferrite and Cementite in the proportion 87:13 by weight. Perlite is formed from Austenite at eutectoid temperature (A\(_1\)) 727\(^\circ\)C upon slow cooling. There are three groups of steels according to carbon content:
- Hypoeutectoid steels containing less than 0.76% C
- Eutectoid steel with carbon content about 0.76%
- Hypereutectoid steels contain more than 0.76% C (up to 2% C).
Important Points in Iron-Iron Carbide Phase Diagram
Learning Objectives:
- Interpret an iron-iron carbide diagram in terms of its key points such as eutectic and eutectoid points.
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Eutectic: Eutectic Point refers to the point in a phase diagram indicating the chemical composition and temperature corresponding to the lowest melting point of a mixture of components. In case of Iron-Iron-carbide diagram, eutectic is at 4.30 wt%C, 1147 deg C.
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Eutectoid: A eutectoid reaction is a three-phase reaction by which, on cooling, a solid transforms into two other solid phases at the same time. If the bottom of a single-phase solid field closes (and provided the adjacent two-phase fields are solid also), it does so with a eutectoid point. In case of Iron-Iron-carbide diagram, eutectoid is at 0.76 wt%C, 727 Deg C.
- A peritectic reaction is a reaction where a solid phase and liquid phase will together form a second solid phase at a particular temperature and composition.
- A peritectoid reaction is the transformation of two solid phases in an alloy system, forming a new phase.
Allotropes of Iron
Learning Objectives:
- Describe important structural forms of steel and iron.
There are three allotropic forms of iron:
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Delta iron (\(\delta\)):
As molten iron cools down, it solidifies at 1,538\(^\circ\)C into its \(\delta\) allotrope, which has a body-centered cubic (BCC) crystal structure. -
Gamma iron (\(\gamma\)) or austenite:
As the iron cools further to 1,394\(^\circ\)C its crystal structure changes to a face centered cubic (FCC) crystalline structure. In this form it is called gamma iron (\(\gamma\)-Fe) or Austenite. \(\gamma\)-iron can dissolve considerably more carbon (as much as 2.04% by mass at 1,146\(^\circ\)C). -
Alpha iron (\(\alpha\)) or ferrite:
At 912\(^\circ\)C the crystal structure again becomes BCC as \(\alpha\)-iron is formed. \(\alpha\)-iron can dissolve only a small concentration of carbon (no more than 0.021% by mass at 910\(^\circ\)C).
Trempe_acier_et_mouvements_atomes.svg: Cdangderivative work: Alu, CC BY-SA 3.0, via Wikimedia Commons
Solved Example: 3453245
The carbon content in cementite (Fe₃C) is approximately:
A. 0.76%
B. 6.67%
C. 2.14%
D. 4.3%
Correct Answer: B
Solved Example: 34534
At what temperature does alpha iron (Ferrite) become gamma iron (Austenite)?
A. 910°C
B. 1400°C
C. 1538°C
D. 770°C
Correct Answer: D
Solved Example: 345345
Which of the following is NOT an allotrope of iron?
A. Alpha iron (Ferrite)
B. Beta iron
C. Gamma iron (Austenite)
D. Delta iron
Correct Answer: B
Lever Rule
Learning Objectives:
- Given a binary phase diagram, the composition of an alloy, its temperature, and assuming that the alloy is at equilibrium, determine:
- What phase(s) is (are) present,
- The composition(s) of the phase(s), and
- The mass fraction(s) of the phase(s)
The Lever Rule is a way in which to calculate the proportions of each phase present on a phase diagram in a two phase field at a given temperature and composition.
The lever rule is a mechanical analogy to the mass balance calculation. The tie line in the two-phase region is analogous to a lever balanced on a fulcrum. Finding the amounts of phases in a two phase region:- Locate composition and temperature in diagram.
- In two phase region draw the tie line or isotherm.
- Fraction of a phase is determined by taking the length of the tie line to the phase boundary for the other phase, and dividing by the total length of tie line.
Wizard191, CC BY-SA 3.0, via Wikimedia Commons
Heat Treatment
Learning Objectives:
- Understand practical applications and procedures of heat treatments of metals and alloys.
- Understand how cooling rate influences steel hardness and gain familiarity with heat treatment regimes for steels and the microstructures that are developed.
- Learn about hardenability and how quench severity, carbon content, grain size and other alloying elements influence it.
Solidification of Pure Metal: Solidification is a phase transition in which a liquid turns into a solid when its temperature is lowered below its freezing point. This process is a first order transformation which involves nucleation and growth. Nucleation is the process whereby nuclei (seeds) act as templates for crystal growth. Solid phase will nucleate till liquid phase is exhausted.
Precipitation Hardening: The strength and hardness of some metal alloys may be improved by the formation of extremely small, uniformly dispersed particles (precipitates) of a second phase within the original phase matrix.
Isothermal Transformation Diagrams or Time-Temperature-Transformation (TTT): Isothermal transformation diagrams are also known as Time-Temperature-Transformation (TTT) diagrams) are plots of temperature versus time (usually on a logarithmic scale). A typical TTT diagram shows what structures can be expected after various rates of cooling. It graphically describes the cooling rate required for the transformation of austenite to pearlite, bainite or martensite. TTT diagram also gives the temperature at which such transformation takes place.
Annealing:
The annealing process is intended to optimize the steel’s machinability and formability. In manufacturing steel products, machining and forming are often employed. Quenched and tempered steel may not machine or bend very easily and annealing is often necessary to manufacture steel components economically. Annealing is used after cold forming operations, since during forming, the deformed areas of the steel may become work-hardened and susceptible to fracture.
Full Annealing:
Steel is heated 50 to 100\(^\circ\)F (10 to 38\(^\circ\)C) above the A3 for hypoeutectoid steels, and above the Acm for hypereutectoid steels, with slow controlled cooling, resulting in soft andductile microstructures that have commercially maximized machinability and formability. In full annealing, cooling must take place very slowly so that a coarse pearlite is formed. When the term annealing is applied to steels it is assumed that full annealing was performed.
georgelade, Public domain, via Wikimedia Commons
Normalizing:
The process of normalizing consists of heating to a temperature 50 to 100\(^\circ\)F (10 to 38\(^\circ\)C) above the A3 and allowing the part to cool in still room temperature air. Normalizing can be described as a homogenizing or grain-refining treatment. Within any piece of steel, the composition is usually not uniform throughout. That is, one area may have more carbon than the area adjacent to it. These compositional differences affect the way in which the steel will respond to heat treatment. If the steel is austenitized, the carbon can readily diffuse throughout, and the result is a reasonably uniform composition from one area to the next. The steel is then more homogeneous and will respond to the heat treatment is a more uniform way.
Tempering:
Tempering is generally applied to hardened or quenched steel to improve mechanical properties, for the most part, tensile strength, ductility and toughness. Tempering, formerly called drawing, is performed by heating a quenched part to some point below the lower critical transformation temperature for sufficient time depending on its size, commonly 2 hours or more. Most steels are tempered between 400 to 1100\(^\circ\)F (205 to 595\(^\circ\)C). As higher temperatures or longer periods of time are employed, toughness and ductility are increased, but at the expense of reduced hardness and tensile strength. The microstructure of quenched and tempered steel is referred to as tempered martensite.
Stress Relieving:
When a metal is heated, expansion occurs which is proportional to the temperature rise. Similarly, upon cooling a metal, contraction occurs. When a steel component is heated at one point more than at another, as in welding or during forging, internal stresses are set up. During heating, expansion of the heated area do not occur uniformly, and the component tends to distort. On cooling, contraction is restricted from occurring by the unyielding cold metal surrounding the heated area, as in a weldment. The forces attempting to contract the metal are not relieved, and when the metal is cold again, the forces remain as internal stresses, also called residual stresses. Stresses also result from volume changes which accompany phase transformations, such as the transformation of austenite to martensite.
Residual stresses are harmful because they may cause distortion of steel parts and/or may render the part susceptible to brittle fracture and stress corrosion cracking mechanisms. To relieve these stresses, plain carbon steel is typically heated to between 940 to 1100\(^\circ\)F (482 to 595\(^\circ\)C), assuring that the entire part is heated uniformly, then slowly cooled back to room temperature. This procedure is called relief annealing or, more commonly, stress relieving.
Steps in Heat Treatment:
The process of heat treatment consists of the following or steps:
- Controlled Heating of Metal/Alloy (Steel) Heating temperature of metal depends upon its grade, grain size, type and shape of a metal or alloy. Generally, the metal is heated upto its upper critical temperature.
- Holding or Soaking period Metal or alloy to be given heat treatment, is held at the specified temperature for a specified period so that there is a uniformity of temperature throughout the mass. The period of heating depends upon the size and shape of the component.
- Controlled Cooling of the Metal (Steel) Main changes in the properties of metal or alloy take place in the cooling process. Change in properties or transformation depends mostly on the rate at which the cooling takes place. Cooling of metal is also known as quenching. Generally five quenching media adopted for quenching are: caustic soda solution, brine, water, oil and air.
Solved Example: 56-8-01
Materials after cold working are subjected to following process to relieve stresses:
A. Hot working
B. Tempering
C. Normalizing
D. Annealing
Correct Answer: D
Solved Example: 56-8-02
__________ is a surface hardening process gives maximum hardness to the surface.
A. Pack hardening
B. Nitriding
C. Cyaniding
D. Induction hardening
Correct Answer: B
Solved Example: 56-8-03
The process of reheating the martensitic steel to reduce its brittleness without any significant loss in its hardness is:
A. Normalising
B. Annealing
C. Quenching
D. Tempering
Correct Answer: D
Solved Example: 56-8-04
During quenching, martensite is produced:
A. With an appropriate cooling rate such that the carbon has time to migrate
B. With low cooling rate
C. Rapid cooling rate
D. Medium cooling rate
Correct Answer: C