7/22/2020 Allotropes of iron - Wikipedia

Allotropes of iron
At atmospheric pressure, three allotropic forms of iron exist: alpha
iron (α-Fe), gamma iron (γ-Fe), and delta iron (δ-Fe). At very high
pressure, a fourth form exists, called epsilon iron (ε-Fe). Some
controversial experimental evidence suggests the existence of a fifth
high-pressure form that is stable at very high pressures and
temperatures.[1]

The phases of iron at atmospheric pressure are important because of

the differences in solubility of carbon, forming different types of
steel. The high-pressure phases of iron are important as models for
the solid parts of planetary cores. The inner core of the Earth is
generally assumed to consist essentially of a crystalline iron-nickel Low-pressure phase diagram of
alloy with ε structure.[2][3][4] The outer core surrounding the solid pure iron. BCC is body centered
inner core is believed to be composed of liquid iron mixed with cubic and FCC is face-centered
nickel and trace amounts of lighter elements. cubic.

Contents
Standard pressure allotropes
Alpha iron (α-Fe)
A2 critical temperature and induction heating
Gamma iron (γ-Fe)
Delta iron (δ-Fe)
High pressure allotropes Iron-carbon eutectic phase diagram,
Epsilon iron / Hexaferrum (ε-Fe) showing various forms of FexCy
substances.
Experimental high temperature and pressure
Phase transitions
Melting and boiling points
Structural phase transitions
See also
References

Iron allotropes, showing the

Standard pressure allotropes differences in lattice structure. The
alpha iron (α-Fe) is a body-centered
cubic (BCC) and the gamma iron (γ-
Fe) is a face-centered cubic (FCC).
Alpha iron (α-Fe)

Below 912 °C (1,674 °F), iron has a body-centered cubic structure

and is known as α-iron or ferrite. It is thermodynamically stable and fairly soft metal. α-Fe can be
subjected to pressures up to ca. 15 GPa before transforming into a high-pressure form termed ε-iron,
which crystallizes in a hexagonal close-packed (hcp) structure.
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Magnetically, α-iron is paramagnetic at high temperatures. However, as it cools to 771 °C (1044K or

1420 °F),[5], the Curie temperature (TC or A2), it becomes ferromagnetic. The reverse also occurs: As α-
iron is heated above the Curie temperature, the random thermal agitation of the atoms exceeds the
oriented magnetic moment of the unpaired electron spins and it becomes paramagnetic.[6] In the past,
the paramagnetic form of α-iron was known as Beta iron (β-Fe).[7][8] However, this terminology is
obsolete and misleading, since as iron passes below the Curie temperature, the magnetic domains
become aligned, but no structural change occurs. β-Fe is crystallographically identical to α-Fe, except for
magnetic domains and the expanded body-centered cubic lattice parameter as a function of temperature,
and is therefore of only minor importance in steel heat treating. For this reason, the beta "phase" is not
usually considered a distinct phase but merely the high-temperature end of the alpha phase field. The A2
forms the boundary between the beta iron and alpha fields in the phase diagram in Figure 1.

Similarly, the A2 is of only minor importance compared to the A1 (eutectoid), A3 and Acm critical
temperatures. The Acm, where austenite is in equilibrium with cementite + γ-Fe, is beyond the right edge
in Fig. 1. The α + γ phase field is, technically, the β + γ field above the A2. The beta designation maintains
continuity of the Greek-letter progression of phases in iron and steel: α-Fe, β-Fe, austenite (γ-Fe), high-
temperature δ-Fe, and high-pressure hexaferrum (ε-Fe).

The primary phase of low-carbon or mild steel and most cast irons at
room temperature is ferromagnetic α-Fe.[9][10] It has a hardness of
approximately 80 Brinell.[11][12] The maximum solubility is about 0.02
wt% at 727 °C (1,341 °F) and 0.001% carbon at 0 °C (32 °F).[13] When it
dissolves in iron, carbon atoms occupy interstitial "holes". Being about
twice the diameter of the tetrahedral hole, the carbon introduces a
strong local strain field.

Mild steel (carbon steel with up to about 0.2 wt% C) consist mostly of
Molar volume vs. pressure for α-
α-Fe and increasing amounts of cementite (Fe3C, an iron carbide). The
Fe at room temperature.
mixture adopts a laminar structure called pearlite. Since bainite and
pearlite each contain α-Fe as a component, any iron-carbon alloy will
contain some amount of α-Fe if it is allowed to reach equilibrium at
room temperature. The amount of α-Fe depends on the cooling process.

A2 critical temperature and induction heating

β-Fe and the A2 critical temperature are important in induction

heating of steel, such as for surface-hardening heat treatments. Steel
is typically austenitized at 900–1000 °C before it is quenched and
tempered. The high-frequency alternating magnetic field of
induction heating heats the steel by two mechanisms below the
Curie temperature: resistance or Joule (I2R) heating and
ferromagnetic hysteresis losses. Above the A2, the hysteresis
Figure 1: The beta field and A2
critical temperature on the iron-rich
mechanism disappears and the required amount of energy per
side of the iron-carbon phase
degree of temperature increase is substantially larger than below A2.
diagram.[5] Load-matching circuits may be needed to vary the impedance in the
induction power source to compensate for the change.[14]

Gamma iron (γ-Fe)

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As the iron cools further to 1,394 °C (2,541 °F) its crystal structure changes to a face-centered cubic
(FCC) crystalline structure. In this form it is called gamma iron (γ-Fe) or Austenite. γ-iron can dissolve
considerably more carbon (as much as 2.04% by mass at 1,146 °C). This γ form of carbon saturation is
exhibited in stainless steel.

Delta iron (δ-Fe)

As molten iron cools down, it solidifies at 1,538 °C (2,800 °F) into its δ allotrope, which has a body-
centered cubic (BCC) crystal structure.[15] δ-iron can dissolve as much as 0.08% of carbon by mass at
1,475 °C.

High pressure allotropes

Epsilon iron / Hexaferrum (ε-Fe)

At pressures above approximately 10 GPa and temperatures of a few hundred kelvin or less, α-iron
changes into a hexagonal close-packed (hcp) structure, which is also known as ε-iron or hexaferrum;[16]
the higher-temperature γ-phase also changes into ε-iron, but does so at a higher pressure.
Antiferromagnetism in alloys of epsilon-Fe with Mn, Os and Ru has been observed.[17]

Experimental high temperature and pressure

An alternate stable form, if it exists, may appear at pressures of at least 50 GPa and temperatures of at
least 1,500 K; it has been thought to have an orthorhombic or a double hcp structure.[1] as of December
2011, recent and ongoing experiments are being conducted on high-pressure and Superdense carbon
allotropes.

Phase transitions

Melting and boiling points

The melting point of iron is experimentally well defined for pressures less than 50 GPa.

For greater pressures, published data (as of 2007) put the γ-ε-liquid triple point at pressures that differ
by tens of gigapascals and 1000 K in the melting point. Generally speaking, molecular dynamics
computer simulations of iron melting and shock wave experiments suggest higher melting points and a
much steeper slope of the melting curve than static experiments carried out in diamond anvil cells.[18]

The melting and boiling points of iron, along with its enthalpy of atomization, are lower than those of the
earlier group 3d elements from scandium to chromium, showing the lessened contribution of the 3d
electrons to metallic bonding as they are attracted more and more into the inert core by the nucleus;[19]
however, they are higher than the values for the previous element manganese because that element has a
half-filled 3d subshell and consequently its d-electrons are not easily delocalized. This same trend
appears for ruthenium but not osmium.[20]

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Structural phase transitions

The exact temperatures at which iron will transition from one crystal structure to another depends on
how much and what type of other elements are dissolved in the iron. The phase boundary between the
different solid phases is drawn on a binary phase diagram, usually plotted as temperature versus percent
iron. Adding some elements, such as Chromium, narrows the temperature range for the gamma phase,
while others increase the temperature range of the gamma phase. In elements that reduce the gamma
phase range, the alpha-gamma phase boundary connects with the gamma-delta phase boundary,
forming what is usually called the Gamma loop. Adding Gamma loop additives keeps the iron in a body-
centered cubic structure and prevents the steel from suffering phase transition to other solid states.[21]

See also
Superdense carbon allotropes
Allotropy
Austenite
Curie point
Eutectic system
Tempering (metallurgy)

References
1. Boehler, Reinhard (2000). "High-pressure experiments and the phase diagram of lower mantle and
core materials". Reviews of Geophysics. American Geophysical Union. 38 (2): 221–245.
Bibcode:2000RvGeo..38..221B (https://ui.adsabs.harvard.edu/abs/2000RvGeo..38..221B).
doi:10.1029/1998RG000053 (https://doi.org/10.1029%2F1998RG000053). S2CID 33458168 (https://
api.semanticscholar.org/CorpusID:33458168).
2. Cohen, Ronald; Stixrude, Lars. "Crystal at the Center of the Earth" (https://web.archive.org/web/2007
0205041442/http://www.psc.edu/science/Cohen_Stix/cohen_stix.html). Archived from the original (htt
p://www.psc.edu/science/Cohen_Stix/cohen_stix.html) on 5 February 2007. Retrieved 2007-02-05.
3. Stixrude, Lars; Cohen, R.E. (March 1995). "High-Pressure Elasticity of Iron and Anisotropy of Earth's
Inner Core". Science. 267 (5206): 1972–5. Bibcode:1995Sci...267.1972S (https://ui.adsabs.harvard.e
du/abs/1995Sci...267.1972S). doi:10.1126/science.267.5206.1972 (https://doi.org/10.1126%2Fscienc
e.267.5206.1972). PMID 17770110 (https://pubmed.ncbi.nlm.nih.gov/17770110).
4. "What is at the centre of the Earth?" (https://www.bbc.co.uk/news/uk-14678004). BBC News. 31
August 2011.
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87170-381-1.
6. Cullity, B.D.; Graham, C.D. (2009). Introduction to Magnetic Materials (2nd ed.). IEEE. p. 91.
ISBN 978-0-471-47741-9.
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8. Avner, S.H. (1974). Introduction to physical metallurgy (https://books.google.com/books?id=ZsBTAA
AAMAAJ) (2nd ed.). McGraw-Hill. p. 225. ISBN 978-0-07-002499-1.
9. Maranian, Peter (2009), Reducing Brittle and Fatigue Failures in Steel Structures (https://books.goog
le.com/books?id=qTT2LgLnpMUC&pg=PA81), New York: American Society of Civil Engineers,
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10. Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-
Heinemann. ISBN 978-0-08-037941-8.
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11. Structure of plain steel (http://www.keytometals.com/page.aspx?ID=CheckArticle&site=kts&NM=3),

retrieved 2008-10-21.
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Carbide Morphology and Microstructure on the Kinetics of Superficial Decarburization of C-Mn
Steels". Metall Mater Trans A. 46 (1): 123–133. Bibcode:2015MMTA...46..123A (https://ui.adsabs.har
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1661-014-2600-y).
13. Smith & Hashemi 2006, p. 363.
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ed.). Metals Park, Ohio: ASM International. OCLC 490375371 (https://www.worldcat.org/oclc/490375
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16. Mathon O; Baudelet F; Itié JP; Polian A; d'Astuto M; Chervin JC; Pascarelli S. (14 December 2004).
"Dynamics of the magnetic and structural alpha-epsilon phase transition in iron". Physical Review
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