Crystal Structure and Defects
When a substance freezes from a liquid state, it forms either an amorphous or a crystalline
solid structure. An amorphous structure is essentially random, possessing only short-range
order where small groups of atoms are arranged orderly, but lacking long-range order where
all atoms are arranged uniformly. Examples of amorphous materials include glasses and
most organic compounds. In contrast, metals typically form long-range, orderly
crystalline structures under normal freezing conditions, as do almost all ceramic
materials (except glasses). Therefore, metals and ceramics are generally crystalline, while
glasses and polymers are mostly amorphous.
A crystalline structure is characterized by atoms or molecules arranged in a regular,
repeating three-dimensional pattern with long-range order, and their speci c arrangement
within the crystal determines the type of crystalline structure. A space lattice is a
distribution of points (or atoms) in three dimensions where every point has identical
surroundings. The intersections of the lines in a space lattice are called lattice points,
representing locations with the same type of atom or group of atoms. The geometry of a
space lattice is fully de ned by its lattice constants (a, b, c) and interaxial angles (α, β, γ).
The unit cell is the smallest repeating pattern of arrangement that can be contained within a
parallelepiped, whose edges form the a, b, and c axes of the crystal.
All crystal systems can be grouped into one of seven basic systems, which can be arranged
in 14 different ways, known as Bravais lattices. However, almost all structural metals
crystallize into one of three primary crystalline patterns:
1. Face-centered cubic (fcc).
2. Hexagonal close-packed (hcp).
3. Body-centered cubic (bcc).
Each crystalline substance has unique unit cell edge lengths and axial angles, which are
called lattice parameters.
Crystal imperfections or defects are common in real materials, even though ideal
crystalline lattices are perfectly ordered. These imperfections in uence the physical,
chemical, mechanical, and electronic properties of materials, sometimes positively and
sometimes negatively. They are crucial in processes such as mechanical deformation,
annealing, precipitation, diffusion, and sintering. These defects are classi ed into four main
divisions:
• Point defects (zero-dimensional defects): These occur at any lattice node and
include a vacancy (missing atom), an extra (interstitial) atom, or an impurity
(substitutional) atom. Point defects are inherent to the equilibrium state and are
in uenced by temperature, pressure, and composition.
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• Line defects (one-dimensional defects), also known as dislocations: These defects
lie along an axis (or line) of atoms in a crystalline lattice.
◦ The main type is an edge dislocation, where a partial plane of extra atoms is
present above or below the dislocation line. Edge dislocations can be positive
or negative.
◦ Another type is a screw dislocation, which features a spiral axis connecting
two normally parallel planes.
◦ Most metals contain mixed dislocations, which are combinations of edge and
screw dislocations.
◦ Dislocations are not stationary; they can move through a crystalline
structure when suf cient stress is applied. This movement is the underlying
basis of slip deformation and the mechanism of plastic ow. Slip occurs as
single bonds are broken one at a time, allowing the dislocation to move one
lattice spacing at a time, rather than the entire lattice moving simultaneously.
The presence of dislocations signi cantly lowers the stress required for plastic
deformation compared to a perfect, defect-free structure. Numerous
dislocations provide ample opportunity for motion along slip planes, leading
to macroscopic plastic deformation. Both edge and screw dislocations can
cause slip, and they produce the same unit slip. Line dislocations must
terminate at a surface, such as a grain boundary or the crystal surface.
• Surface or planar defects: These occur when the crystalline structure is
discontinuous across a plane. They extend in two directions over a large surface but
are only one or two lattice parameters thick.
◦ Grain boundaries are common surface disruptions between the crystalline
lattices of individual grains. They are formed during solidi cation due to the
misorientation of grains as they freeze. Grain boundaries are regions with
many irregularly placed atoms, dislocations, and voids, making them high-
energy sites and sinks for vacancies and dislocations. They are typically very
thin, only one or two atoms thick, and can strengthen polycrystalline materials
by impeding dislocation movement (dislocation pile-up). However,
undesirable precipitates along grain boundaries (e.g., phosphorus in
martensitic stainless steels) can substantially weaken a material.
◦ Phase boundaries are also surface defects independent of crystal structure.
◦ Stacking faults occur within crystals when the stacking sequence of planes is
inconsistent in the lattice. The difference in energy between a perfect lattice
and one with a stacking fault is called the stacking fault energy (SFE). SFE
in uences deformation textures and plastic deformation characteristics; metals
with low SFE (wide stacking faults) strain harden more rapidly and twin more
readily than those with high SFE (narrow stacking faults).
◦ Coherent phase boundaries involve small groups of solute atoms tting
within the host lattice, causing some lattice distortion.
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◦ Mechanical twinning is a coordinated movement of large numbers of atoms
that deforms a portion of the crystal via an abrupt shearing motion. During
twinning, atoms on each side of the twinning plane form a mirror image.
▪ Twinning differs from slip: in slip, the orientation above and below the
slip plane remains the same, but in twinning, there's an orientation
change across the twin plane and atoms form a mirror image. Slip
deformation is non-homogeneous and concentrated in bands, while
twinning deformation is homogeneous, with all atoms moving
cooperatively. Slip requires lower stress to initiate but higher stress to
propagate, whereas twinning requires high stress to initiate but very
low stress for propagation. Twin boundaries are generally at and have
lower stored energy than high-angle grain boundaries, making them
less effective as sources and sinks of other defects and less active in
deformation and corrosion than ordinary grain boundaries.
• Volume defects: These include discontinuities such as porosity, inclusions, and
microcracks. They almost always reduce strength and fracture resistance, even when
they constitute a minor volume percentage. Microporosity can result from shrinkage
during solidi cation, being more common in castings than wrought products, as
plastic deformation during wrought production usually heals internal microporosity.
Crystal Structure of Metals
Most metallic materials are polycrystalline, meaning they consist of many small crystalline
grains that form independently during solidi cation. Specialized methods can produce large
single-crystal structures or a preferred grain orientation, which bene ts high-temperature
applications.
Metallic grains generally have one of the following three lattice structures:
1. Face-Centered Cubic (fcc) System:
◦ In addition to corner atoms, there is an atom centrally located on each face.
◦ Each unit cell contains four atoms (eight corner atoms shared by eight cells,
plus six face-centered atoms shared by two cells).
◦ It has an atomic packing factor of 0.74, which is the densest packing
possible, making it a close-packed structure.
◦ Atoms in the fcc structure have 12 nearest neighbours (coordination number,
CN = 12).
◦ Common fcc metals include aluminium, copper, and nickel.
◦ The crystal structure of iron and steels can transform from bcc (ferrite) to fcc
(austenite) with temperature changes or alloying. Austenite (γ) is stable at
relatively high temperatures in steel and is crucial for heat treatment. Alloying
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with suf cient nickel and chromium can make steel maintain an austenitic
(fcc) structure at room temperature.
◦ Fcc systems exhibit good ductility, even at low temperatures. Slip nearly
always occurs along their close-packed planes. The fcc system has four slip
planes, each with three slip directions, resulting in 12 slip systems. This
abundance of slip systems contributes to the good toughness (ductility) of fcc
metals, even at cryogenic temperatures, making materials like aluminium
desirable for such applications.
2. Hexagonal Close-Packed (hcp) System:
◦ Atoms are also packed along close-packed planes, called basal planes, with
the same arrangement as fcc close-packed planes.
◦ The stacking sequence in hcp is ABABAB..., repeating every other layer.
◦ The hcp unit cell contains 6 atoms, and its atomic packing factor is 0.74, the
same as fcc.
◦ The coordination number for hcp is also CN = 12.
◦ Two lattice parameters, c and a, describe the hcp unit cell. In an ideal hcp
structure, the c/a ratio is 1.633. Deviations from this ideal ratio (e.g.,
beryllium's low c/a of 1.57, or zinc and cadmium's high c/a > 1.85) can cause
lattice distortion and affect packing density, but they are still generally
described as hcp.
3. Body-Centered Cubic (bcc) System:
◦ Similar to a simple cubic system but with an additional atom in the center.
◦ The bcc unit cell contains two atoms.
◦ Its coordination number is eight, as the center atom is in contact with eight
corner atoms.
◦ The atomic packing factor for bcc is 0.68, making it less densely packed
than fcc or hcp structures.
◦ Despite less ef cient packing, bcc is the equilibrium structure for 15
metallic elements at room temperature, including important transition
elements like iron, nickel, titanium, and zirconium. This is partly due to
signi cant contributions from second-nearest neighbour bonds and the greater
entropy of the less dense bcc structure, which provides a stability advantage at
high temperatures.
◦ Unlike fcc, bcc is not a close-packed structure, and its slip planes are not
always operative, making its ductility more dependent on temperature and
chemical composition. For example, bcc ferrite in steel can become brittle at
low temperatures, characterized by the ductile-brittle transition
temperature (DBTT), where fewer active slip planes are available for
deformation.
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The microstructure of metals and alloys, including grains and grain boundaries, is
observed using metallography. This involves polishing and lightly etching a metal
specimen to reveal the underlying microstructure, which becomes visible under a
microscope. The photographic image is called a photomicrograph or micrograph.
Grain size signi cantly impacts structural properties. Methods for quantifying average
grain size include counting grains in a known area (grains/area). The ASTM (American
Society for Testing Materials) Standard E112 de nes a grain size number based on the
number of grains per square inch at 100x magni cation; larger ASTM numbers indicate
ner (smaller) grain sizes. The Snyder-Graff technique is used for ne grain structures in
tool and high-speed steels, counting grains intersecting a line at 1000x magni cation; a
higher number indicates ner grain structure. The size, shape, and distribution of grains
have important implications for the strength, ductility, and toughness of alloys.
Metallography is also essential for identifying different phase constituents and their
morphology in an alloy.
Classi cation of Steels
Steels are a complex group of alloys, primarily iron-carbon alloys with carbon contents
ranging from 0.02% to less than 2%. While classi cation by chemical composition is
widely used, steels can be categorized in many other ways.
Broad categories based on chemical composition:
• Plain carbon steels.
• Low-alloy steels.
• High-alloy steels (including stainless steels).
Other classi cation methods:
• Steelmaking method: such as open hearth, basic oxygen process (BOF/LD), or
electric furnace (EAF) methods. EAF accounts for 35-40% of world steel production,
and BOF for 55-60%.
• Deoxidation practice during steelmaking:
◦ Killed steel: Steels deoxidized, usually with aluminium and/or silicon,
resulting in slight gas evolution during solidi cation and less porosity. Almost
all alloy steels, forging steels, and carburizing steels are killed, as are sheet
steels for better formability and aging resistance.
◦ Rimmed steel: No deoxidizing agents added, characterized by signi cant
chemical composition differences across the ingot section, with an outer rim
lower in carbon, phosphorus, and sulfur.
◦ Capped steel: Partially deoxidized, with excess gas entrapped during
solidi cation causing the steel to rise in the ingot mold.
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◦ Rimmed and capped steels have largely been replaced by killed steels,
especially with continuous casting.
• Solidi cation method: such as ingot casting, continuous casting (most steel now), or
component (shape) casting. Shape casting uses foundry processes like green sand
molding, chemically bonded sand molding, and permanent molding.
• Mill product form: such as bar, plate, sheet, strip, tubing, structural shape, wire, or
steel powders produced for powder metallurgy.
• Finishing method: such as hot rolling (removes scale, improves nish) or cold
rolling (allows thinner gauges, better surface nish, and dimensional control).
• Microstructure: such as ferritic, pearlitic, martensitic, bainitic, or austenitic. Most
steels are ferritic (bcc) at room temperature, but alloying (e.g., with nickel and
manganese) can create austenitic (fcc) structures. Some stainless steels have
austenitic or duplex (ferrite-austenite) microstructures.
• Required strength level: For instance, high strength low-alloy (HSLA) steels have
yield strengths greater than 275 MPa (40 ksi) and are designed to meet speci c
mechanical properties. Ultrahigh-strength steels have minimum yield strengths of
1380 MPa (200 ksi), including medium-carbon low-alloy, medium-alloy air-
hardening, and high-alloy hardenable steels.
• Heat treatment: such as annealing, quenching and tempering, and
thermomechanical processing. Steels can achieve high strengths and other property
combinations (ductility, formability, machinability) through heat treatment processes
like annealing, stress relieving, normalizing, spheroidizing, and hardening by
quenching and tempering.
• Quality descriptors: These describe the intended application (e.g., forging quality,
cold extrusion quality, merchant quality) and imply certain mechanical and physical
attributes (internal soundness, chemical uniformity, surface imperfections, testing
extent, inclusion characteristics, hardenability). Most quality requirements are
subjective, though non-metallic inclusion count, chemical composition, austenitic
grain size, and hardenability are quanti ed.
Carbon Steels
Carbon steels are iron-carbon alloys with carbon contents typically between 0.02% and less
than 2%, also containing small amounts of manganese and silicon.
They are further classi ed by carbon content:
• Low-carbon steel (or mild steel): Contains less than 0.30% C.
◦ The largest category is at rolled products (sheet or strip), often cold rolled
and annealed. These high-formability steels have very low carbon (less than
0.10%) and up to 0.4% Mn. Uses include automobile body panels, tin plate,
and wire products. They have relatively low tensile values (205 to 240 MPa or
30 to 35 ksi) and are chosen for enhanced cold formability or drawability.
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◦ For rolled structural plates and sections, carbon content can increase to around
0.30%, with manganese up to 1.5%. This group (0.15 to 0.30% C) is known as
mild steel and is used for stampings, forgings, seamless tubes, and boiler
plate. They are also known as carburizing or case-hardening grades for heat
treatment, where increased carbon and manganese improve core and case
hardenability.
• Medium-carbon steel: Contains between 0.20% and 0.60% C, with manganese from
0.60% to 1.65%.
◦ Increasing carbon to about 0.5% with accompanying manganese allows these
steels to be used in the quenched and tempered condition. Applications
include shafts, couplings, crankshafts, axles, gears, and forgings. Steels in the
0.40% to 0.60% C range are also used for rails, railway wheels, and rail axles.
◦ They are used both with and without heat treatment and are considered good
for normal machining. Welding is possible but requires precautions to avoid
cracking from rapid heating or cooling.
• High-carbon steel: Contains from 0.60% to 1.00% C, with manganese from 0.30%
to 0.90%.
◦ Their microstructure is largely pearlitic. They are used when higher carbon is
needed for improved wear characteristics and higher strength. Applications
include spring materials and high-strength wires. Cold forming is generally
not practical; almost all parts made from these steels are heat treated before
use.
Carbon levels have a pronounced effect on properties. Carbon has limited solubility in
iron, forming a hard carbide compound called cementite (Fe3C). The physical form of
cementite (lamellae, plates, needles, or spheres) can be modi ed by processing. During
quenching, carbon can be retained in a supersaturated condition, forming a very hard
metastable phase called martensite.
Steels also contain fractional amounts of impurities like phosphorus and sulfur, which
originate from raw steelmaking materials. While generally limited (e.g., 0.040% phosphorus
and 0.050% sulfur) to avoid adverse effects on hot forming and mechanical behaviors,
special-purpose steels may have higher sulfur for improved machinability or lower amounts
for speci c applications (e.g., gas/oil pipelines in Arctic regions). Higher phosphorus
amounts can be speci ed to improve strength and atmospheric corrosion resistance.
Currently, commercial steel products typically have sulfur and phosphorus contents around
0.010%.
Free-machining grades of carbon steels contain additives like sulfur and phosphorus
(which can negatively affect weldability, cold forming, and forging) that enhance machining
characteristics and lower costs. Calcium is also used to improve sul de shape, while the use
of lead, bismuth, or selenium has declined due to environmental restrictions.
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