Chapter 2

Alloys

Chapter Outline
Alloys 7 Effects of Alloying
Effects of Alloying Elements 8 Elements on Carbide 10
Carbon Steels 8 Nickel Steels (2xx Series) 10
Sulfur 8 Nickel-Chromium
Manganese 8 Steels (3xx Series) 10
Phosphorus 9 Manganese Steels
Silicon 9 (31x Series) 10
Alloy Steels 9 Molybdenum Steels
The Effect of Alloying (4xx Series) 11
Elements on Ferrite 9 Chromium Steels
(5xx Series) 11

ALLOYS
An alloy is a substance that has metallic properties and is composed of two or
more chemical elements, of which at least one, the primary one, is a metal. A
binary alloy system is a group of alloys that can be formed by two elements
combined in all possible proportions.
Homogeneous alloys consist of a single phase and mixtures consist of sev-
eral phases. A phase is anything that is homogeneous and physically distinct if
viewed under a microscope. When an allotropic metal undergoes a change in
crystal structure, it undergoes a phase change.
There are three possible phases in the solid state:
l Pure metal
l Intermediate alloy phase or compound
l Solid solution.

Compounds have their own characteristic physical, mechanical, and chemi-

cal properties and exhibit definite melting and freezing points. Intermetallic
compounds are formed between dissimilar metals by chemical valence rules, and
generally have non-metallic properties; Mg2Sn and Cu2Se are examples of these.

Applied Welding Engineering: Processes, Codes and Standards.

Copyright © 2012 Elsevier Inc. All rights reserved. 7
8 SECTION | 1  Introduction to Basic Metallurgy

Interstitial compounds are formed between transition metals such as tita-

nium and iron with hydrogen, oxygen, carbon, boron, and nitrogen. They are
usually metallic, with high melting points and are extremely hard; TiC and
Fe3C are examples of interstitial compounds.
Electron compounds are formed from materials with similar lattice systems
and have a definite ratio of valence electrons to atoms; Cu3Si and FeZn are
examples of electron compounds.
Solid solutions are solutions in the solid state and consist of two kinds of
atoms combined in one kind of space lattice. The solute atoms can be present
in either a substitutional or an interstitial position in the crystal lattice.
There are three possible conditions for solid solutions:
l Unsaturated
l Saturated and
l Supersaturated.

The solute is usually more soluble in the liquid state than in the solid state.
Solid solutions show a wide range of chemistry so they are not expressed as
a chemical formula. Most solid solutions solidify over a temperature range,
rather than having a defined freezing point.
Having gained this basic understanding of alloy formation and type of
alloy, we move forward to learn about a specific alloy – steel – and the effects
of various alloying elements on its properties.

EFFECTS OF ALLOYING ELEMENTS

Carbon Steels
Metals are alloyed for a specific purpose, generally with the aim of improving a
property or a specific set of properties. In order to take full advantages of such
alloying, it is important that the resulting property of alloying elements is known.
In the following discussions we shall learn, with the help of steel metallurgy,
about some of the most common alloying practices and the resulting alloy metals.

Sulfur
Sulfur in steel is generally kept below 0.05% as it combines with iron to form
FeS, which melts at low temperatures and tends to concentrate at grain bounda-
ries. At elevated temperatures, high sulfur steel becomes hot-short due to melting
of the FeS eutectic. In free-machining steels, the sulfur content is increased to
0.08% or 0.35%. The sulfide inclusions act as chip breakers, reducing tool wear.

Manganese
Manganese is present in all commercial carbon steels in the range of 0.03%
to 1.00%. Manganese functions to counteract the effect of sulfur by forming
Chapter | 2  Alloys 9

MnS. Any excess manganese combines with carbon to form Mn3C; the com-
pound associated with cementite. Manganese also acts as a deoxidizer in the
steel melt.

Phosphorus
Phosphorus in steel is kept below 0.04%. The presence of phosphorus at lev-
els over 0.04% reduces the steel’s ductility, resulting in cold-shortness. Higher
levels (from 0.07% to 0.12%) are included in steels that are specifically devel-
oped for machining, to improve cutting properties.

Silicon
Silicon is present in most steels in the 0.05% to 0.3% range. Silicon dissolves
in ferrite, increasing its strength while maintaining ductility. Silicon promotes
deoxidation in the molten steel through the formation of SiO2, hence it is an
especially important addition in castings.

ALLOY STEELS
Plain carbon steel is satisfactory where strength and other property requirements
are not severe, and when high temperatures and corrosive environments are not a
major factor in the selection of a material. Alloy steels have characteristic prop-
erties, due to some element other than carbon being added to them. Alloying ele-
ments are added to obtain several properties including the following:
l Increased hardenability
l Improved strength at ambient temperatures
l Improved mechanical properties at low and high temperatures
l Improved toughness
l Improved wear resistance
l Increased corrosion resistance
l Improved magnetic permeability or magnetic retentivity.
There are two ways in which alloyed elements are distributed in the main
constituents of steel:
l Dissolved in ferrite
l Combined with carbon to form simple or complex carbides.

THE EFFECT OF ALLOYING ELEMENTS ON FERRITE

Nickel, aluminum, silicon, copper, and cobalt are all elements which largely
dissolve in ferrite. They tend to increase the ferrite’s strength by solid solution
hardening.
10 SECTION | 1  Introduction to Basic Metallurgy

Alloying elements change the critical temperature range, eutectoid point

position, and location of the alpha (α) and gamma (γ) fields on the iron-iron
carbide phase diagram. These changes affect the heat-treating requirements
and final properties of alloys.

EFFECTS OF ALLOYING ELEMENTS ON CARBIDE

Carbide-forming elements, including manganese, chromium, tungsten, molyb-
denum, vanadium, and titanium, increase room temperature tensile properties
since all carbides are hard and brittle. The order of increasing effectiveness
is chromium, tungsten, vanadium, molybdenum, manganese, nickel, and sili-
con. Of these, nickel and silicon do not form carbides. Complex carbides are
sluggish and hard to dissolve. They act as inhibitors to grain growth and often
improve high temperature properties. Chromium and vanadium carbides are
exceptionally hard and wear resistant.
Tempering temperatures are raised significantly and in some cases sec-
ondary hardening may occur with higher tempering temperatures due to the
delayed precipitation of fine alloy carbides.
Some of the alloys in general use are discussed briefly here.

Nickel Steels (2xx Series)

Nickel has unlimited solubility in γ-iron and is highly soluble in ferrite. It
widens the range for successful heat treatment, retards the decomposition of
austenite, and does not form carbides.
Nickel promotes the formation of very fine and tough pearlite at lower car-
bon contents, thus, toughness, plasticity, and fatigue resistance are improved.
Nickel alloys are used for high-strength structural steels in the as-rolled condi-
tion and for large forgings that cannot be hardened by heat treatment.

Nickel-Chromium Steels (3xx Series)

The effect of nickel on increasing toughness and ductility is combined with
the effect of chromium on improving hardenability and wear resistance. The
combined effect of these two alloying elements is often greater than the sum of
their individual effects.

Manganese Steels (31x Series)

Manganese is one of the least expensive of the alloying elements and is always
present as a deoxidizer and to reduce hot-shortness. When the manganese
content exceeds 0.8%, it acts as an alloying element to increase strength and
hardness in high carbon steels. Fine-grained manganese steels have excellent
toughness and strength.
Steels with greater than 10% manganese remain austenitic after cooling
and are known as Hadfield manganese steel. After heat treatment, this steel has
Chapter | 2  Alloys 11

excellent toughness and wear resistance as well as high strength and ductility.
Work hardening occurs as the austenite is strain hardened to martensite.

Molybdenum Steels (4xx Series)

Molybdenum has limited solubility in α and γ-iron and is a strong carbide
former. It has a strong effect on hardenability and increases high-temperature
strength and hardness. Molybdenum alloys are less susceptible to temper brit-
tleness. Chromium-molybdenum alloys (AISI 41xx) are relatively cheap and
ductile, have good hardenability, and are weldable.

Chromium Steels (5xx Series)

Chromium forms both simple (Cr7C3 and Cr4C) and complex carbides
[(FeCr)3C]. These carbides have high hardness and resist wear. Chromium is
soluble up to about 13% in γ-iron and has unlimited solubility in ferrite. It
increases the strength and toughness of the ferrite and improves high-tempera-
ture properties and corrosion resistance.