Metallic Materials

S Mridha, University of Strathclyde, Glasgow, UK

r 2016 Elsevier Inc. All rights reserved.

Introduction

Metallic Materials contain metal and having the properties of metal. This group of materials includes elemental metal and
compound or alloy. Of the 118 elements in the periodic table there are 86 metals with distinct characteristic properties, and a
limited number of these metals have engineering importance.
New techniques have been developed over a period of time for producing various materials that had properties superior to
those of the natural materials including gold and copper. Until relatively recent years the scientists came to understand the
relationships between the structural elements of materials and their properties. The ‘properties are related to the microstructures.’
The properties can be changed by altering the relative proportions of the micro-constituents (or phases); phases are identified by
their unique crystal structures, composition, and properties. The ‘equilibrium microstructure can be predicted with the help of
phase diagram.’ The properties influence the performance of a material in service and to change the performance, the micro-
structure has to be modified. The modification of microstructure or transformation of crystalline structures can be done by
infusion of new elements and or by applying mechanical and thermal treatments.
The microstructure and the properties have a close parallel with the crystal structure of the elements and their deformation
behavior. For example, FCC elements such as Au, Ag, Cu, Al have superior ductility because of a multiplicity of slip systems and are
hence, easy to deform when cold, warm, or hot. Another parallel is the relationship between the electron distribution within the
atoms of elements and such physical properties as the electrical and thermal conductivities, magnetic properties, etc. It is now
evident that central to the success of commercial units marketing materials for components is the need to appreciate the
importance of producing an appropriate microstructure within the material. Two essential factors contribute to this. The first is the
role of the material composition that has to be controlled to within close limits. The second is the processing of the material to the
finished product.
The knowledge acquired in the past 70 years or so, has empowered scientists to fashion the characteristics of materials to a large
degree. Thus tens of thousands of different materials have evolved with rather specialized characteristics that meet the various
service requirements of our modern and complex society.
The metallic materials are broadly grouped as ‘ferrous and nonferrous.’ Iron base materials are ferrous and all other materials
are nonferrous families. The ferrous materials constitute more that 50% of the metallic materials section. Depending on the
importance and application in services ferrous materials is divided into several subsections and they are iron and steel, alloy steel,
stainless steel, tool and die steel, cast iron, and thermal treatment to alter properties in steel. The metallurgy and history of metal
extraction processes and hard metals are in two separate subsections.
In ‘nonferrous materials’ family the subdivision is again based on importance and usage. Aluminum, magnesium, and titanium
metals with their alloys are grouped under light metals and alloys and all other nonferrous materials are placed in nonferrous
metals and alloys family. Under this subdivision there are several small groups such as high temperature materials, super alloys,
shape memory alloys, glass metals, solder materials, noble metals, and so on. The intermetallics and refractory materials are placed
in two separate groups because of their distinct characteristics.

Metallurgy and History

The history of metallurgy for extraction of metals can be traced back to 6000 BC. With time, different techniques have been
developed for production of metals from naturally occurring and man-made resources. The extractive metallurgy principles are
applied for separation of metal from gangue materials, which involve physical chemistry. In general, the extraction processes are
classified as pyrometallurgy, hydrometallurgy, and electrometallurgy.
Modern civilization started with the discovery of metals. Without metals it would not have been possible to build railway,
transport, bridges, buildings, cars, generate power or any of the automobile, electrical and electronic industries. As the standard of
living grows and demand for metals also expands. The sheer size of population growth coupled with ongoing requirements in the
developed world has created unprecedented demand for metals. Strong demand growth comes mainly from millions of aspiring
individuals in emerging economies striving for a better standard of living. More metals have been extracted in the twentieth
century than the entire amount produced from the beginning of mankind’s history until 1900 A.D.
Iron was the most popular metal through the introduction of implements, tools, and utensils. It was a ‘democratic material’ in
the early civilizations because its wide spread availability affected the common person in every clan. And this material was also

Reference Module in Materials Science and Materials Engineering doi:10.1016/B978-0-12-803581-8.04097-2 1

2 Metallic Materials

affordable, formable, and of high strength, which caused explosion in its use. Advances now occurred in centuries and decades,
rather than millennia. This acceleration continues to the present day.

Ferrous materials

Ferrous materials containing iron, and steel is the most important material of this family. Because of availability, low cost, high
strength, ease of fabrication into many shapes, and a wide range of properties, steel accounts for 80% of all metallic materials. It is
widely used in manufacturing, building and construction industries. The demand of this material increases steadily with expansion
of industries. In fact, the growth of steel production indicates the overall development of the industrial world.
In 2013, total world crude steel production was 1607.2 million tons (Figure 1). The biggest steel producing country is currently
China, which accounted for 48.5% of world steel production in 2013. In 2008 and 2009, output fell in the majority of steel
producing countries as a result of the global recession, in 2010 started to rise again. In 2014 global output reached 1665 million
tons, an increase of just 1% when compared to last year. This slowdown in growth is driven by the reduction in Chinese growth.
China remains by far the largest producer of steel in the world.

Figure 1 Total crude steel production of the World and China (ISSB 2015).

The allotropic property of iron is responsible for obtaining different microstructures and properties. Below 910 1C iron is
stable as a-phase (ferrite). Between 910–1392 1C, g-phase (austenite) is stable, and above 1392 1C the δ-phase prevails. Iron is also
an excellent solvent for many metals. The additions of the alloying elements to iron, especially carbon, stabilize these phases to a
range of compositions and temperatures, which evolve the phase diagram for each individual system. The Fe-C system in Figure 2
shows how phase changes with variation of carbon content and temperature.
Pure iron is a soft material. By addition of carbon alone makes iron strong. Iron containing up to 2 wt% carbon is called steel.
When carbon content is over 2% carbon, the iron becomes very hard and can only be formed by casting to the required shape. This
variety of iron is called cast iron.
Steels have two broad groups: ‘plain carbon steels and alloy steels.’ Again within the same family there are several divisions
based on composition, application, properties, and phase structure. Plain carbon steels contain C up to 1.7% with Si, Mn, S, P, Al,
and some others elements below a critical limit where they do not affect the properties of the steel. The plain carbon steel is further
divided as low, medium, and high carbon steels. Based on structure it is grouped as hypoeutectoid (ferrite þ pearlite), eutectoid
(pearlite), and hypereutectoid (pearlite þ cementite) steels. These divisions immediately specify the range of properties of the steels
as is demonstrated in Figure 3. However, the major shortcomings of plain carbon steels are low hardenability, loss of hardness on
tempering, low corrosion and oxidation resistance, and low strength at elevated temperatures.
These limitations of plain carbon steel are overcome by alloying with other elements. By definition, the elements which are
deliberately added to achieve desirable properties in a metallic system are called alloying elements, whereas those elements which
are inevitably present in steel without any deliberate intention to serve additional purposes are known as impurities. For example,
 Metallic Materials 3

Figure 2 Fe–Fe3C Phase Diagram (clickable), Materials Science and Metallurgy, 4th ed., Pollack, Prentice-Hall, 1988.

the steel making operation cannot fully remove sulfur and therefore some amount of sulfur is always present in steel. Sulfur in
such situation is called an impurity. Again the same sulfur when present in appreciable amount has the capacity to make chips
brittle during machining. A particular variety of steel, known as free cutting steel contains deliberately added sulfur. In this case
sulfur, is an alloying element, even though in majority of cases sulfur is considered an unwanted element in steel due to its adverse
effect on the properties for example, inducing hot shortness to steel. Steels containing alloying element are called alloy steels. So
long as the total alloying element content is less than 5 wt%, the steels are considered as low alloy steels whereas the steels with
alloying elements in excess of 5 wt% is called high alloy steels. The alloy steels also identified on the basis of the added alloying
element such as nickel steel, chromium steel, nickel–chromium steel, and so on. By structure it is known as martensitic steel,
austenitic steel, ferritic steel, bainitic steel, and duplex steel. Based on application they are further divided as corrosion resistant
steel, heat resistant steel, magnetic steel, tool steel, and electric steel. These groupings identify the range of properties and
applications.
Development of microstructure involves some type of ‘phase transformation.’ The microstructural make up of any steel consists
of transformed product(s) from austenite. Depending on the various parameters, transformed products may be ferrite, pearlite,
bainite, or martensite. Presence of these phases and morphology of these products decide the resultant properties of steel. Several
heat treatment processes are employed to produce these phase structures in steels containing a range of compositions. Heat
treatments change the microstructure and make the materials hard or soft. The ferrite phase alone cannot be strengthened by heat
treatment; cold working and grain size refining are the alternative options. Figure 4 shows such refined ferrite grain structure of hot
rolled mild steel which can be achieved by changing
pffiffiffiffiffiffiffiffi
ffi the finishing temperature in hot rolling operation; according to the Hall Petch
relation, the strength is proportional to D1 , D is grain size.
4 Metallic Materials

Figure 3 (a) Yield strength, tensile strength, hardness versus carbon content for plain carbon steels having microstructures consisting of ferrite–
pearlite, pearlite, and pearlite–cementite; (b) Ductility (%EL and %RA) and impact energy versus carbon concentration. Reproduced from Masseria,
V. (Ed.), 1981. Metal Handbook: Heat Treating, vol. 4, ninth ed. American Society for Metals, p. 9.

Pearlite is an equilibrium structure and it is often known as a phase but it is a combination of ferrite and cementite (Fe3C)
phases. Cementite is very hard, ferrite is soft and ductile while pearlite is very tough and strong. Distribution of these phases along
with grain size and morphology of microstructure determine the level of properties in steels. The graded microstructure in Figure 5,
produced by diffusion transformation treatment of plain carbon steel, demonstrates an increasing concentration of pearlite toward
the surface and ferrite away from the surface. This type of microstructure makes the component tough with high impact loading
capacity. Transformation hardening treatments of this pearlitic structure can produce martensite, a nonequilibrium phase of much
increased hardness, generating high wear resistance properties.
Cast irons, a distinct family of ferrous materials have wide diversity of properties. In the general grade of cast irons (no alloy
addition) carbon is present as combined carbon (Fe3C) or free carbon (graphite). Combined carbon (cementite) makes the
structure very hard, while free carbon, graphite gives excellent machining property. The morphology variations of the free carbon
such as flake, nodule, and small rosettes dramatically change the properties of cast irons. For example, ductile cast iron has unusual
combination of properties because its graphite occurs as nodules rather than flakes. Ductile (nodular) iron has a number of
properties similar to those of steels yet it has advantages of low melting point, good fluidity and castability, excellent machin-
ability, and good wear resistance. Hardening treatment of the nodular iron can produce very high hardness with microstructure
consisting of martensite and graphite nodules (see Figure 6). The austempering treatments of this iron generate both strength and
wear resistance properties comparable to some wrought steels and it has applications particularly for heavy machinery and
transport equipment.

Nonferrous Materials

The family of nonferrous materials has several divisions. Aluminum, magnesium, and titanium metals with their alloys are
grouped as light metals. This group has a wide application in transport industries because they are lightweight materials. All other
nonferrous metals are placed under nonferrous metals and alloys group. The intermetallics and refractory materials are placed in
two separate groups because of their distinct characteristics. In all these divisions there are also several small groups.
Among the nonferrous materials aluminum, titanium, and copper have wide applications after iron. The properties of these
metals compared to iron are shown in Table 1.
 Metallic Materials 5

Figure 4 Effect of finishing temperature on the ferrite grain structure of hot rolled mild steel: (Top) temperature above austenite transformation
line, A1 and (Bottom) temperature closer to A1 line (Dasarathy, 2012).

Figure 5 Graded microstructure produced by carburizing treatment of mild steel showing more pearlite toward the surface X50.

Aluminum
Aluminum is the third most abundant element in the earth's crust but because it is so reactive with other elements it is not found
in the native state. It is one of the lightest metals. Aluminum is ductile and has good electrical and thermal conductivity. It has a
low density of 2.7 g cm3 compared to that of iron (7.9 g cm3) due to its low atomic mass of 27. The ductility and formability of
6 Metallic Materials

Figure 6 Martensitic microstructure of quench-hardened ductile iron; graphite nodules in the matrix structure X200.

Table 1 Comparable properties of aluminum, titanium, copper, and iron

Units Aluminum Titanium Copper Iron

Crystalline structure FCC Hexagonal 882 C ↓BCC

o
FCC BCC 910 oC ↓FCC 1410 oC ↓BCC
3
Density g cm 2.7 4.5 8.9 7.8
o
Melting temperature C 660 1660 1085 1535
Specific heat cal g  1 oC 0.215 0.124 0.092 0.114
Expansion coefficient  106 23.5 8.9 17 12
Thermal conductivity W mK  1 238 17 397 71
Electrical conductivity % 64 4 100 17
Electrochemical potential V  1.7  1.6 þ 0.34  0.4
Corrosion resistance M-R-B-E Good Excellent Good Regular
Young’s modules GPa 70 120 130 200
Tensile strength MPa 700 1400 220 1600
Content in earth’s crust % 8 0.9 0.12 5.8
Relative price 1 5 1 0.1

Source: http://ocw.uc3m.es.

aluminum is due to the high symmetry and thermodynamic stability of the FCC lattice and its high stacking-fault energy. In the
pure form, aluminum has a low stiffness, E, of 70 GPa compared to 211 GPa for iron, and low tensile strength, 80 MPa, compared
to 300 MPa for iron. However, its specific modulus, that is, modulus divided by density, is almost equal to that for iron, titanium,
and magnesium. An advantageous chemical property of aluminum is its reactivity with oxygen, which leads to the formation of a
dense layer of Al2O3 on the surface, which shields the base metal from further environmental interactions. Pure aluminum has less
importance in engineering applications because of its low strength, but its alloys have much improved properties. Because of
lightweight, aluminum alloys are widely used in transport applications. Precipitation treatment is the most common heat treat-
ment applied to aluminum alloys that produces extremely fine particles out of a supersaturated solid solution and they are in
coherence with the matrix phase. These particles are responsible for hardening action.

Titanium
Titanium is a relatively light metal having density of 4.5 g cm3, which is intermediate between that of aluminum and iron. It has
high melting point (1666 1C); the strength is comparable with that of iron and much higher than those of aluminum and copper
(see Table 1). Like iron it has allotropic properties. Because of difficulty in extraction and processing, this material is very expensive
compared to iron, aluminum, and copper. Titanium and its alloys are very attractive in many industries because of high specimen
strength, high temperature properties to about 550 1C, and excellent corrosion resistance, particularly in oxidizing acids, chloride
media, and in most natural environments. This material has wide applications in aerospace, food, biomedical and chemical
industries.
Important commercial groups of titanium materials are (1) a-alloys- weldable, moderate strength, oxidation resistance, good
notch toughness, creep resistance and these alloys may form a2 (Ti3Al) brittle phase and thus lose ductility. (2) Near-a alloys –
contain mostly a and some b phase. This family, particularly Ti–8Al–1Mo–1V is used at high temperature for compressor section
 Metallic Materials 7

of jet engine. (3) a-b alloys – appreciable amount of b present at room temperature resulting an a þ b structure. These alloys can be
solution-heat-treated, quenched, and aged for increased strength. The most popular alloy of this group is Ti–6Al–4V alloy.

Copper
Copper has wide commercial applications as a pure metal and as in alloys with other metals. Pure copper has extraordinary
combination of properties that make it the basic material for electrical industries. Some of these properties being its high electrical
conductivity and corrosion resistance, ease of fabrication, reasonable tensile strength, joining characteristics, and controllable
annealing properties. The common metals alloyed with copper are zinc, tin nickel, and beryllium.
Brass and bronze are very popular alloys, which have applications in marine, transport and automobile, construction, and food
industries. They are also used in fabrication of manufacturing goods and industrial machinery. The tools for explosive mine
applications are made of Cu-1.75–2.5% Be alloy and it does not produce any spark.

References

Dasarathy, C., 2012. Examples of microstructures in metallic materials, February, 2012. Available at: https://upload.wikimedia.org/wikipedia/commons/b/b4/
Examples_of_microstructures_in_metallic_materials.pdf (accessed 26.08.15).

Further Reading

Baradarani, B., Raiszadeh, R., 2011. Materials and Design 32, 935–940.
Cramb A.W., 2007. A Short History of Metals: The E-Sylum, vol 10, Number 32, August 12, 2007.
Gordin, D.M., Ion, R., Vasilescu, C., et al., 2014. Materials Science and Engineering C 44, 362–370.
International Council of Mining and Metals (ICMM), 2012. Trends in the Mining and Metals Industry.
International Steel Statistics Bureau (ISSB), 2015. International Steel Statistics Bureau report. Available at: https://www.worldsteel.org/statistics/crude-steel-production.html
(accessed 15.09.15).
K˛etkowska, B., Dziurka, R., Bala, P., 2015. Archives of Civil and Mechanical Engineering 15, 308–3016.
Lambert-Perlade, A., Gourgues, A.F., Pineau, A., 2004. Acta Materialia 52, 2337–2348.
Melchers, R.E., 2015. Corrosion Science 95, 51–61.
Metallic materials topic Available at: http://ocw.uc3m.es/ciencia-e-oin/materials-science-and-engineering/lecture-notes-1/Chapter_5_3.pdf (accessed 26.08.15).
Mohamed, I.F., Yonenaga, Y., Lee, S., Edalati, K., Horita, Z., 2015. Materials Science & Engineering A 627, 111–118.
Porter, D.A., Easterling, K.E., 1992. Phase Transformations in Metals and Alloys, second ed. New York: Chapman & Hall.
Smith, W.F., 1993. Structure and Properties of Engineering Alloys. New York, NY: McGraw-Hill.
Zhang, H., Pradeep, K.G., Mandal, S., Ponge, D., Raabe, D., 2014. Acta Materialia 80, 296–308.