Experiment 7: Fe-c Phase Diagrams

AIM
The objectives of this experiment are as follows:
1. To record cooling curves for various iron-carbon alloys and, using these data alongside the iron-
carbon equilibrium phase diagram, determine the chemical composition of each alloy.
2. To experimentally construct the Fe-C equilibrium phase diagram, illustrating phase equilibria in
a binary metallic system.
3. To demonstrate how variations in composition influence microstructure.

INTRODUCTION

Carbon is a crucial alloying element in iron, significantly affecting its hardness, strength, and
ductility (Callister & Rethwisch, 2018). The austenite phase of iron can dissolve more carbon than
the ferrite phase, which is vital for heat treatment and mechanical properties. Iron and carbon can
form cementite (Fe₃C), an intermetallic compound that influences the microstructure and
performance of steels (Smith & Hashemi, 2011). The iron-carbon phase diagram illustrates the
relationship between temperature and carbon concentration, with a focus on compositions up to 2.0%
carbon for steel; beyond this, materials are classified as cast iron (Totten, 2006). During cooling,
molten iron-carbon alloys primarily transition from austenite to ferrite and cementite, with excess
carbon precipitating as cementite when the lattice structure can no longer accommodate it (Porter &
Easterling, 2009). This interplay of carbon content, temperature, and phase transformations is
essential for designing steels for various applications.

THEORY
The microstructural study of steels begins with the metastable iron-carbon (Fe-C) binary phase
diagram, a critical tool for understanding carbon steels, alloy steels, and their heat treatments, such as
hardening and annealing. This diagram shows the equilibrium phases expected for different
combinations of temperature and carbon content, typically focusing on the metastable interaction
between iron, carbon, and cementite (Fe₃C). Modern versions of the diagram are often calculated
using software like Thermo-Calc.
. The Fe-C phase diagram shows which phases are to be expected at metastable equilibrium for
different combinations of carbon content and temperature. The metastable Fe-C phase diagram was
calculated with ThermoCalc, coupled with PBIN thermodynamic database.

At lower carbon contents, ferrite (α-iron) predominates, with a maximum solubility of 0.028 wt.% C
at 738 °C. Austenite (γ-iron), with a much higher solubility of up to 2.08 wt.% C at 1154 °C, plays a
crucial role in the hardening of steels due to this solubility difference. On the carbon-rich side,
cementite (Fe₃C) forms. Delta-ferrite appears at very high temperatures but is mainly relevant to
specialized steels.

BCC ferrite remains stable up to 912 °C, transitioning to FCC austenite, which is stable until 1394
°C, after which delta-ferrite forms until melting at 1538 °C. Between single-phase fields, two-phase
mixtures like ferrite + cementite or austenite + cementite occur. Heat treatment processes typically
avoid the liquid phase region.

The steel region of the Fe-C diagram spans 0 to 2.08 wt.% C, divided into hypoeutectoid (0–0.68 wt.
% C), eutectoid (0.68 wt.% C), and hypereutectoid (0.68–2.08 wt.% C) steels. A major
transformation at 0.68 wt.% C produces pearlite, a lamellar mixture of ferrite and cementite:
gamma-iron (austenite) → alpha-iron (ferrite) + Fe₃C (cementite).

Critical boundaries include A₁ (eutectoid temperature), A₃ (ferrite to austenite transition at low

Alloying elements shift these boundaries. Austenite stabilizers (e.g., Ni, Mn) lower the A₁
temperature, while ferrite stabilizers (e.g., Cr, Si, Al) raise it. The eutectoid composition remains
crucial for steel microstructure control.

Extended cooling near the eutectoid temperature causes pearlite to coarsen, forming spheroidized
structures. Rapid cooling transforms austenite into martensite, defined by the martensite start (Ms)
and finish (Mf) temperatures.

EXPERIMENTAL METHODOLOGY
Cooling curves for iron-carbon alloys of known composition were obtained by controlled
solidification. The temperature was monitored as a function of time, and phase transformation points
were identified by changes in the slope of the cooling curves. These experimental data were
compared with the calculated Fe-C phase diagram, constructed using thermodynamic models such as
the regular solution-sublattice approach and incorporating empirical data for phase boundaries and
carbon activities.

RESULTS AND ANALYSIS

The cooling curves revealed distinct thermal arrests corresponding to phase transformations
predicted by the Fe-C phase diagram. For example, the eutectoid transformation was observed near
727 °C for alloys with approximately 0.8 wt.% C, consistent with literature values. The
experimentally determined phase boundaries closely matched those calculated using thermodynamic
models, with deviations attributable to experimental conditions and kinetic effects.

The solubility limits of carbon in ferrite and austenite, as well as the formation of cementite, were
confirmed by both experimental data and thermodynamic predictions. The presence of
microstructures such as pearlite, bainite, and martensite was inferred based on the alloy composition
and cooling rate, in agreement with established metallurgical principles

DISCUSSIONS
a. What conditions determine equilibrium in binary systems?

For a binary system (two components), the degrees of freedom (F) are defined by F=4-P, where P is
the number of phases. At least one phase must exist, so the maximum F is 3, and the system cannot
have more than four phases at equilibrium. While temperature, pressure, and overall composition can
vary independently, phase diagrams are typically represented in two dimensions as either
temperature-composition plots at a constant pressure or pressure-composition plots at a constant
temperature. A point on these diagrams represents a specific temperature, pressure, and overall
composition, with composition usually displayed on the horizontal axis using mole fraction, mass
fraction, or mass percent.

b. How can phase diagrams be utilized for engineering applications?

Phase diagrams are vital for predicting microsegregation and the formation of inclusions or
secondary phases during alloy solidification. Because solid-state diffusion is slow, modern
approaches use the Scheil equation instead of the lever rule, which assumes complete diffusion. The
Scheil equation, combined with partition coefficients from phase diagrams, estimates liquid and solid
compositions relative to the fraction of solid formed or temperature. This allows for calculating the
solidification path and predicting when secondary phases, inclusions, or eutectics will form, as well
as estimating the volume fraction of phases and concentration gradients in the cast structure. For
macrosegregation, fluid flow is added to the mass balance to forecast the local accumulation or
reduction of secondary phases and shifts in composition, which is used to explain phenomena like
chill zones and centerline segregation. All of this requires data extracted directly from phase
diagrams.

The microstructural study of steels relies on the iron-carbon (Fe-C) binary phase diagram, which
illustrates equilibrium phases at varying temperatures and carbon contents. At low carbon levels,
ferrite (α-iron) predominates, while austenite (γ-iron) can dissolve more carbon, crucial for
hardening. Cementite (Fe₃C) forms at higher carbon concentrations. The diagram classifies steels
into hypoeutectoid (0–0.68 wt.% C), eutectoid (0.68 wt.% C), and hypereutectoid (0.68–2.08 wt.%
C) categories, with eutectoid transformation producing pearlite.

Critical boundaries like A₁ (eutectoid temperature) and A₃ (ferrite to austenite) are influenced by
alloying elements. Extended cooling near A₁ coarsens pearlite, while rapid cooling produces
martensite. The Gibbs phase rule and temperature-composition diagrams aid in understanding phase
stability, and the Scheil equation helps model diffusion during solidification.

Overall, the Fe-C diagram is vital for predicting phase transformations and designing ferrous alloys,
making it essential knowledge for materials engineers and metallurgists.

REFERENCES
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