Chapter 2

Classification of Metallic Engineering

Materials

Abstract Materials are classified under the three categories of (i) metals
(ii) non-metals and composites. Of these, metals and its alloys broadly meet all
requirements to be considered as the most suitable engineering material. Amongst
metals, the largest use in the petrochemical industry is of ferrous metals and alloys
like carbon and low alloy steels and stainless steels. Once selected, it is necessary to
finalize the material specification as per requirement and adhere to the same for all
procurements during construction and maintenance. Though limited to some
specific services, non-ferrous metals and alloys are also used in petrochemical
industry. In the first part of the chapter, a brief description and composition of the
commonly used grades of carbon and alloy steels are given, followed by those of
the conventional and high performance austenitic, ferritic and duplex stainless
steels. Compositions of some important non-ferrous alloys have also been included.
In the second part, the importance of standardization and material specification has
been discussed which sets the requirements with regard to chemical analysis,
mechanical properties heat treatment, dimensional tolerance, etc., that a product
should satisfy. In a way, specification is considered as a contract between users and
manufacturers.

Keywords Engineering materials Carbon and alloy steels
Stainless steels



Non-ferrous alloys Material specification

2.1 Introduction

In the early state of civilization, the only known constructional materials were mud,
wood and stone which were used for construction of dwellings, containers and
hunting weapons. This was followed by use of bronze and finally iron and these are
known in archaeological terms as stone, bronze and iron ages. It is difficult to
visualize the past scenario when today different metals and alloys are available and
new developments are taking place in the production of materials having specific
properties. If the non-metallics are also taken into consideration, there appears to be

© Springer Nature Singapore Pte Ltd. 2017 17

A.K. Lahiri, Applied Metallurgy and Corrosion Control,
Indian Institute of Metals Series, DOI 10.1007/978-981-10-4684-1_2
18 2 Classification of Metallic Engineering Materials

ENGINEERING MATERIALS

Metals Non-metals Composites

Ferrous Non- terrous - Ceramics Carbon / Resin

- Steel - Graphite Fiber Glass / Resin
- Alloy Steels - Plastics
- Stainless Steels - Elastomers
- Cast Iron

Fig. 2.1 Classification of engineering materials

no end to the range of materials which are available and will be available in the
coming years.
Figure 2.1 gives some of the important and commonly used groups of materials,
which can be broadly defined into metallic, non-metallic and the composites.
Among these, metals and alloys form the bulk of engineering materials. In the
present book, the emphasis is on metallic materials and their uses in petrochemical
and chemical process industries. As of 2016 out of 118 confirmed elements the
periodic table shows presence of 94 naturally occurring elements (rest of 24 occurs
only when synthesized in the laboratory) and a large number of them fall under the
category of metals. However, only a few of the metals are of practical value as far
as their usability as engineering material is concerned. This is because any metallic
engineering material should meet certain specific properties, viz. strength, ductility,
workability, comparative ease of production and availability. If we consider the
metallic materials, it is found that:
* There are two basic groups, ferrous and non-ferrous, and
* Most of the engineering materials are alloys and only a few are used as
pure metals.
It is interesting to note that though Iron Age followed Bronze Age, finally it is
the ferrous base alloys which occupy the leading position as the ‘most used’
engineering material. The reasons for this are:
* Abundance of iron ore in the earth crust,
* Comparatively easier and cheaper methods of production of iron and its
alloys,
* Some special inherent features of iron which can be utilized by suitable
alloying and heat treatment to obtain a wide range of strength combined
2.1 Introduction 19

with toughness; from soft low strength Armco iron to ultra-high strength
steels,
* Producing materials by suitable alloying, having requisite mechanical
properties, suitable for use at as low as −270 °C or as high as 1150 °C.
* Vast improvement in corrosion and oxidation resistance properties that
can be attained by alloying.
Unlike ferrous materials, which have iron as the base metal, non-ferrous material
includes all other metals. The important practical materials which fall under this
group are copper, nickel, aluminium, titanium, zinc, tin and lead and their alloys.
Metal like chromium, manganese, tungsten, antimony, bismuth, boron, etc., are
used only as alloying elements. On the other hand, metals like zirconium, tantalum,
silver, gold, etc., and their alloys are too expensive and are used for very specific
applications.

2.2 Ferrous Materials

2.2.1 Cast Irons

Cast irons (CI) are Fe-alloys, with carbon varying from 2.5 to 4.5%. Depending on
the composition and cooling rate from the molten state the carbon in CI is present as
either Fe3C (cementite) or free carbon (graphite) or both. The various types of cast
irons have basic variations in the form and morphology of carbon distribution. The
strength and brittleness of cast irons depend on the form in which the carbon is
present and increase with increase in the amount of Fe3C.
The graphite in normal cast iron (grey cast iron) is distributed in flake form in a
ferritic or pearlitic matrix. The poor workability or brittleness of graphitic cast iron
is due to the presence of graphite in flake form. However, by suitable treatment
(during melting and alternately by suitable heat treatment), the shape of graphite
can be modified into nodular form. Nodular and malleable cast iron fall under this
category. The nature of graphite in two irons in shown in Fig. 2.2a [1] and b [2].
These have improved ductility and are less prone to failure under shock loading as
compared to grey cast iron. The white cast irons, on the other hand, are hard and
highly brittle and are used only where wear resistance is required.
Cast irons cannot be worked and easily welded and therefore used only in cast
form, which does not involve any mechanical working. Some of the important
components made of cast irons are: pumps, valves, pipes, gears, cover boxes, pump
base plates, etc. Being brittle in nature, use of CI in hydrocarbon service is gen-
erally avoided.
20 2 Classification of Metallic Engineering Materials

Fig. 2.2 a Graphite flakes seen in unetched grey cast iron [1]. b Nodular graphite observed in
etched SG iron [2] X 100

2.2.1.1 Alloy Cast Irons

Cast irons, like other metals, can be alloyed with nickel, silicon, chromium,
molybdenum, etc., either singly or in combination, to impart resistance to corrosion
in various media and to impart high wear resistance. Ni-hard, austenitic cast irons
(Ni-resist), high silicon iron are some of the commonly used alloyed cast irons.
Ni-resist also possesses better mechanical properties, especially when graphite is in
the nodular form.

2.2.2 Plain Carbon Steels

Plain carbon steels constitute the largest tonnage of ferrous material in use and
cover alloys of iron and carbon, with small amounts of Mn, Si, S, P either added
deliberately or present as impurities. As impurities, P and S are most deleterious and
special care is needed to keep their contents at low levels. Sulphur (and also
selenium) is, however, sometimes deliberately added to improve machinability of
iron and its alloys. For structural, plates for pressure vessels, sheets, rods and pipes,
the carbon content varies from 0.1 to 0.35%. For higher strength and wear resis-
tance and for components requiring heat treatment, higher carbon, normally up to
1.0%, are used for specific end uses, e.g. files, saws, cutting tools, rails, shafts etc.
For deep drawing purposes, for making components like cans and car bodies the
low carbon steel (<0.1%C) is specified.
Carbon is the most important element to impart strength. Higher the carbon
content higher is the strength. However, higher carbon adversely affects toughness
and weldability. Thus to retain the strength and also good weldability, carbon steels
containing lower carbon (0.2–0.30%) are used for pressure vessels. The carbon
2.2 Ferrous Materials 21

Table 2.1 Typical composition of some plain carbon steels

AISI/SAE %C %Mn %P max %S max UNS No.
1010 0.08–0.13 0.30–0.60 0.04 0.05 G10100
1015 0.13–0.18 0.30–0.60 0.04 0.05 G10150
1020 0.18–0.23 0.30–0.60 0.04 0.05 G10200
1025 0.22–0.28 0.30–0.60 0.04 0.05 G10250
1030 0.28–0.34 0.60–0.90 0.04 0.05 G10300
1040 0.37–0.44 0.60–0.90 0.04 0.05 G10400
1055 0.50–0.60 0.60–0.90 0.04 0.05 G10550
1080 0.75–0.88 0.60–0.90 0.04 0.05 G12250
1522 0.18–0.24 1.30–1.60 0.04 0.05 G15220

steels generally have adequate impact strength at low temperatures (−29 °C), but
for still lower temperature fine-grained impact tested steels are used up to a tem-
perature of −48 °C. For high temperature use (above creep limit), creep rupture
strength and resistance to oxidation are the two important criteria. Almost all codes
allow use of carbon steel up to 480 °C, though in earlier times it is used to be
prescribed for temperatures as high as 520 °C (ASME Section VIII Div. 1 gives
design stress of carbon steel up to 527 °C). The present-day accepted practice is to
limit its use to a maximum temperature of 450 °C. Composition of some commonly
used carbon steel containing different carbon is given in Table 2.1 [3].

2.2.3 Low and Medium Alloy Steels

Innumerable grades of steels containing comparatively small amounts of alloying

elements, e.g. chromium, molybdenum, nickel, vanadium, boron, etc., in different
combinations are in commercial use. The total alloying content in these steels may
vary from 0.5 to 9.0%. The alloying elements are added to increase strength; to
lower UTS/YS ratio; improve ductility, fracture toughness, heat treatment and
carburizing properties; corrosion resistance in specific environments; high tem-
perature creep strength and resistance to oxidation. Excluding carbon, the alloys of
iron containing <5% and 5 to <10% alloying elements are broadly classified as low
and medium alloy steels, respectively. The carbon and low and medium alloy steels
are available both in wrought and cast forms and designated by numbering systems
in different national and international specifications like SAE, AISI, DIN, BS, EN,
etc. To have an idea of the range of different alloys available, composition of some
of the low and medium alloy steels (AISI/SAE designation) are given in Table 2.2
[4]. The trend during the last 20 years has been to produce steels with high degree
of cleanliness and low UTS/YS ratio, by micro-alloying and giving greater attention
 22

Table 2.2 Typical composition of some alloy steels

AISI/SAE %C %Mn %Ni %Cr %Mo %V UNS No. Type
1330 0.28–0.33 1.60–1.90 – – – – G13300 Mn steel
1340 0.38–0.43 1.60–1.70 – – – – G13400
2317 0.15–0.20 0.40–0.60 3.25–3.75 – – – G23150 3% Ni steel
2330 0.38–0.43 0.70–0.90 3.25–3.75 – – – G23300
3115 0.13–0.18 0.40–0.60 1.10–1.40 0.55–0.75 – – G31150 Ni–Cr steel
3140 0.38–0.43 0.70–0.90 1.10–1.40 0.65–0.95 – – G31400
4023 0.20–0.25 0.75–0.90 – – 0.20–0.30 – G40230 Mo steel
4037 0.35–0.4 0.70–0.90 – – 0.20–0.30 – G44190
4130 0.28–0.33 0.75–1.00 – 0.80–1.00 0.15–0.25 – G41300 Cr–Mo steel
4140 0.38–0.43 0.75–1.00 – 0.80–1.10 0.15–0.25 – G41400
4340 0.38–0.43 0.60–0.80 1.65–2.00 0.70–0.90 0.20–0.30 – G43400 Ni–Cr–Mo steel
5120 0.17–0.22 0.70–0.90 – 0.70–0.90 – – G51200 Cr steel
5140 0.38–0.43 0.70–0.90 – 0.70–0.90 – – G51400
N.B Significance of the digits: The first two digits represent the major alloying elements (Types) and the last two digits the carbon content
2 Classification of Metallic Engineering Materials
2.2 Ferrous Materials 23

to production and working techniques like quenched and tempered and thermo
mechanical treatment. Line pipe steels (API 5LX) having YS up to 584 Mpa
(85 ksi) are presently in use. In the recent years, line pipe material of X 120 grade
has been developed specially for transport of gas [5].

2.2.4 High Alloy Steels

High alloy steels are mainly those which contain high amounts (>10%) of alloying
elements. Stainless steels constitute the major material of construction among the
high alloy steels in petrochemical industry.

2.2.4.1 Wrought Austenitic, Ferritic and Martensitic Stainless Steels

Stainless steels are alloys with a minimum of 10.5%Cr. In addition, these can also
have nickel, and comparatively smaller amounts of molybdenum, titanium, niobium
and nitrogen. It is chromium which imparts the resistance to corrosion by forming a
thin (*2 nm) passive layer of chromium oxide on the surface [2]. Many metals and
alloys form a thin oxide film when exposed to air, but these are not stable and get
easily destroyed when exposed to corrosive environments. However, for the film to
impart protection it should form easily, be stable and most importantly re-form
quickly once damaged. These requirements are fulfilled by chromium when added
to iron as an alloying element. A number of commercial alloys are available, having
high resistance to corrosion and oxidation and improved creep rupture properties.
Some alloys, in addition, also possess much higher strength. Stainless steels are
classified mainly into three categories based on their crystal structure, i.e. Fe–Cr
martensitic, Fe–Cr ferritic (4XX series) and Fe–Cr–Ni austenitic (3XX series).
While the first two are magnetic, the latter is non-magnetic. It is important to
remember that numbers 4XX and 3XX refer to stainless steels shaped by working,
such as rolling, forging, etc. Both these categories of alloys were developed in early
twentieth century. The credit for discovery of the corrosion resistance stainless steel
goes to P. Monnartz in Germany in 1911 when the first detailed data on the
corrosion of stainless steel as a function of composition were published. In 1912,
Eduard Maurer at Germany’s Krupp Iron Works patented the first austenitic
stainless steel. In 1913, Harry Brearly of Sheffield, England, discovered and
patented the first martensitic stainless steel. For these achievements, Maurer and
Brearly are given the distinction as co-discoverers of the industrial usefulness of
stainless steel [6].
24 2 Classification of Metallic Engineering Materials

Stainless steels can be broadly divided into four groups

• Straight chromium ferritic/martensitic stainless steels
• Austenitic Stainless Steels:
– Chromium–nickel
– Chromium–nickel–molybdenum
– High performance
– Heat resistant
• Duplex Stainless Steel
• PH steels
Of these most commonly used stainless steels in process industry are of auste-
nitic chromium–nickel–molybdenum grades. Austenitic steels are more ductile and
can be formed and welded with comparatively greater ease than the ferritic grades.
They have good creep rupture strength and oxidation resistance up to 1100 °C.
They are also suitable for cryogenic use up to almost 0° absolute (−270 °C). Many
of the austenitic stainless steels are also available in low carbon (with suffix L) or
stabilized grades (e.g. 321 and 347). Alloys meant for high temperature service
wrought alloys are given a suffix of H, e.g. 304H, 347H, 316H, 321H etc., which
specifies minimum carbon content of 0.04%, the amount of other elements
remaining the same. Fe–Cr or Fe–Cr–Ni alloys are also used in cast form for
number of services. Austenitic stainless steels of cheaper varieties are also avail-
able, where nickel has been partly or fully replaced by manganese + nitrogen to get
a stable austenite phase (2XX series). This is possible because like nickel both
manganese and nitrogen is austenite stabilizer. These alloys have better strength,
but lower resistance to corrosion compared to Fe–Cr–Ni alloys and not very much
in use as engineering material. Table 2.3 gives the nominal composition of various
grades of 300 and 400 series of stainless steels [7].
Ferritic stainless steels are mainly Fe–Cr alloys with chromium content of 10.5%
and above. As mentioned earlier, these are available in hardenable (martensitic) or
non-hardenable (ferritic) grades. The former, with suitable heat treatment can
develop high strength and hardness. The hardenable grades contain 12–15%
chromium with carbon above 0.1%. Alloys containing still higher chromium are
non-hardenable. In higher chromium containing alloys sometimes titanium is added
in small amounts (1.5%) to improve corrosion resistance.
Ferritic stainless steels have very good resistance to high temperature oxidation
but their use is limited because of their susceptibility to 475 °C embrittlement.
Thus, the use of ferritic stainless steels is limited to *300 °C.
2.2 Ferrous Materials 25

Table 2.3 Some typical wrought austenitic and ferritic stainless steels
Designation Type %C max %Cr %Ni % Others
AISI (UNS NO)
304 (S30400) Austenitic 0.08 18–20 8–12
304L (S30403) Austenitic 0.03 18–20 8–12
321 (S32100) Austenitic 0.08 17–19 9–12 Ti, 5X(C + N); 0.7 max
347 (S34700) Austenitic 0.08 17–19 9–12 Nb, 10XC; 1.0 max
304H Austenitic 0.10 17–19 9–12 C-0.04 min
(S30409)
316 (S31600) Austenitic 0.08 16–18 10– 2–3 Mo
14
316L (S31603) Austenitic 0.03 16–18 10– 2–3 Mo
14
317 (S31700) Austenitic 0.08 18–20 11– 3–4 Mo
15
317L (S31703) Austenitic 0.03 18–20 11– 3–4 Mo
15
309 (S30900) Austenitic 0.08 22–24 12–
15
310 (S31000) Austenitic 0.08 24–26 19–
22
304LN 0.03 18–20 8–12 N 0.10–0.16
(S30451)
316LN 0.03 16–18 10– N 0.10–0.16
(S31653) 14
201(S20100) Austenitic 0.15 16–18 3.5– Mn 5.5–7.5; N 0.25
5.5
405 (S40500) Martensitic 0.08 11.5–14.5 –
410S Martensitic 0.08 11.5–13.5 –
410 (S41008) Martensitic 0.15 11.5–13.5
430 (S43000) Ferritic 0.12 16–18
444 (S44400) Ferritic 0.025 17.5–19.5 Mo 1.75–2.5; (Ti + Nb)
[0.2 + 4(C + N)] to 0.80 max

2.2.4.2 Cast Stainless Steels

Many stainless steel components, like other metals and alloys, are available in both
wrought and cast forms, such as, pumps, valves, bends, reformer tubes, etc. On the
other hand, some of the alloys are available only in cast form because they cannot
be worked into various shapes. However, wrought and cast alloys are designated
separately even in case of those having similar composition. Cast stainless steels are
usually specified on the basis of composition by using the alloy designation system
established by the Alloy Casting Institute (ACI). The ACI designations of corrosion
resistant castings have been adopted by ASTM International and are preferred for
cast alloys over the American Iron and Steel Institute (AISI) designation for similar
26 2 Classification of Metallic Engineering Materials

Table 2.4 Some typical cast stainless steels

Designation Type %C max %Cr %Ni % Others
a
ACI/UNS No.
CA-15 (J91150) Ferritic 0.15 11.5–14 1 max
CC-50 (J92615) Ferritic 0.50 26–30 4 max
CF-8 (J92600) Austenitic 0.08 18–21 8–11
CF-8M (J92999) Austenitic 0.08 18–21 9–12 2–3 Mo
CF-8C (J92710) Austenitic 0.08 18–21 9–12 Nb (8xC)
CH-20 (J93402) Austenitic 0.20 22–26 12–15
b
ACI/UNS No.
HC (J92605) Ferritic 0.50 26–30 1 max 2.0 Si
HH (J93503) Austenitic 0.2–0.5 24–28 11–14 2.0 Si
HI (J94003) Austenitic 0.2–0.5 26–30 14–18 2.0 Si
HK (J92224) Austenitic 0.2–0.6 24–28 18–22 2.0 Si
HT (J94605) Austenitic 0.35–0.75 13–17 33–37 2.5 Si
HX Austenitic 0.35–0.37 15–19 64–68 2.5 Si
HPJ95705 Austenitic 0.25–0.5 24–27 33–37 2.0 Si; Nb, Ti, W
a
Cast corrosion resistant alloys
b
Cast heat resistant alloys

wrought steels. Table 2.4 gives some of the typical cast stainless steels used for
corrosive and high temperature services [8].
The alloys are identified by the letters and numbers assigned. The terms C and H
indicate use of alloy for corrosive and heat resistant service, respectively. The
second term indicates nominal Cr–Ni type as per ASTM E527 [9]. Increasing nickel
content of the alloy is indicated by adding A–Z to the ACI designation. Number
following this letter denotes carbon content of the alloy. In case of any additional
element in the alloy, the same is indicated by adding a letter to the designation. For
example Alloy CF8M would mean “cast corrosion resistant alloy containing 19Cr–
9Ni (location F in the ASTM E527) containing max 0.08C with addition of Mo”.
Cast alloys are classified as corrosion resistant when used in corrosive and vapour
environment below 650 °C and heat resistant above this temperature. Cast stainless
steel is considered to have corrosion rates equivalent to wrought grade but this may
also be lower because of cast structure’s inhomogeneity or micro segregation [10].

2.2.4.3 Duplex Stainless Steel (DSS)

First developed and introduced in mid 1970s duplex stainless steels (DSS) ideally
consist of a mixture of about equal proportion of ferrite and austenite. The mixed
phase (Fig. 2.3) [11] is obtained by using a balanced composition of chromium,
nickel, molybdenum and nitrogen, with nickel reduced in the range of 5–7%,
depending on the chromium content. To compensate the reduction in nickel small
2.2 Ferrous Materials 27

Fig. 2.3 Duplex stainless

steel micro structure of
austenite and ferrite [11]

amounts of nitrogen is added, which as stated earlier is an austenite stabilizer. In

practice, it is not possible to get equal proportion of austenite and ferrite and
variations in the same primarily affect corrosion rate (decreasing austenite) and
impact energy (increasing ferrite). Optimal results are obtained in ferrite range
between 35 and 60%. Though first produced in 1930s [12], use of DSS was limited.
The first-generation DSS provided good performance in non-welded conditions in
some service but had limited use in as-welded condition. Presence of excessive
ferrite in weld and HAZ drastically affected toughness and corrosion resistance of
welds. It was only in early 1970s that a new grade (18Cr grade), with good
properties was added to the first-generation DSS which was accepted by the
industry for its resistance to chloride SCC and used primarily for coolers and
condensers where the service involved water or processing medium containing high
level of chloride. Subsequently, a number of DSS alloys have been produced based
on 22Cr, 23Cr and 25Cr grades [12–14] with different amounts of nickel, molyb-
denum and nitrogen; the 25Cr grade being called Super DSS. In addition to good
corrosion resistance, these have much higher strength than the 300 series of alloys.
Charles [15] has published an excellent review on the development and importance
of DSS.
Considerable work is still going on in the development and studies on DSS.
During the last few years DSS having high PRE of minimum 48, called Hyper DSS
[16], has been developed for use under highly corrosive conditions. Of all the
alloying elements in stainless steels, nickel is not only costliest but its price also
fluctuates considerably. Therefore cheaper varieties of DSS, where nickel has been
replaced with manganese and nitrogen, called lean DSS [17] have been developed.
It is claimed to be suitable for use in place of 304L and 316L for many services.
These alloys also have the advantage of higher strength and resistance to chloride
stress corrosion cracking.
DSS is not as easy to weld as austenitic stainless steels but has better weldability
than ferritic and martensitic stainless steels. Initial problems experienced in welding
28 2 Classification of Metallic Engineering Materials

Table 2.5 Nominal composition of major grades of duplex stainless steels (wt%)
Steel Name/UNS No. C Si Mn Cr Ni Mo Cu N
LDX 2101a S32101 0.03 0.6 5.0 21.5 1.5 0.3 0.3 0.22
LDX 2404™ S82441 0.02 – 3.0 24.0 3.6 1.6 – 0.27
2304b S32304 0.02 0.4 1.5 23.0 4.8 0.3 0.3 0.10
2205c S32205 0.02 0.4 1.5 22.0 5.7 3.1 0.2 0.17
2507d S32750 0.02 0.2 0.7 25.0 7.0 4.0 0.3 0.27
2707e S32707 0.03 – – 27.0 6.5 5.0 0.4
a
Recent development—low Ni, high Mn Lean DSS
b
Recent development—low Ni, high Mn Conventional DSS
c
Present-day Lean DSS
d
Present-day DSS (conventional)
e
Present-day DSS (Super DSS)
f
Recent development, Hyper DSS

DSS have now been overcome. Table 2.5 gives composition of some of the typical
DSS compiled from data of reputed manufacturers [13, 14, 16, 17].
Another important group of stainless steels falls under the category of precipi-
tation hardening (PH) stainless steels used primarily where wear resistance is an
important requirement.

2.2.4.4 High Performance Ferritic and Austenitic Stainless Steels

Number of highly alloyed materials have been developed and are under develop-
ment to meet the requirements of highly corrosive services in oil and gas, chemical,
petrochemical and other industries. Under some of the conditions encountered in
these services conventional stainless steels and nickel alloys fail to give satisfactory
service. These alloys fall under the category of super austenitic, super ferritic, super
duplex and nickel base alloys; last two having been discussed separately. While
super austenitic stainless steels are used for fabrication of different equipment,
ferritic stainless steels have been developed to be used primarily as heat exchanger
tubing in seawater service where resistance to pitting and chloride stress corrosion
cracking is an important requirement. Moreover, these have the advantage of lower
cost compared to high nickel containing super austenitic stainless steels. Table 2.6
gives the composition of some of the high performance stainless steels [18].

2.2.4.5 Comparison of Different Stainless Steels

It will be apparent from the above discussion that number of alloys have been
developed falling in the category of stainless steels. Table 2.7 summarizes the
comparative properties of the various grades of stainless steels. These varying
physical, mechanical and corrosion resistant properties enable their use under varying
conditions which will be discussed in detail at appropriate sections in the book.
 2.2 Ferrous Materials

Table 2.6 Composition of wrought high performance ferritic and austenitic stainless steels showing major alloying elements
Name UNS No. C N Cr Ni Mo Others PRE No.
Super austenitic
904L N08904 0.02 – 19.0–23.0 23.0–28.0 4.0–5.0 Cu 1.0–2.0 32
Alloy 28 N08028 0.02 – 26.0–28.0 29.5–32.5 3.0–4.0 Cu 0.6–1.4 36
254 SMO S31254 0.02 0.18–0.22 19.5–20.5 17.5–18.5 6.0–6.5 – 42
Al-6XN N08367 0.03 0.18–0.25 20.0–22.0 23.5–25.5 6.0–7.0 0.76 43
654 SMO S32654 0.02 0.45–0.55 24.0–28.0 21.0–23.0 7.0–8.0 Mn 2.0–4.0 54
Super ferritic
E-BRITE 26-1 S44627 0.01 0.015 25.0–27.0 0.5 0.75–1.5 Nb 27
SEA-CURE S44660 0.03 0.040 25.0–28.0 1.0–3.5 3.0–4.0 Ti; Nb 35
AL-29-42 S44800 0.01 0.020 28.0–30.0 2.0–2.5 3.5–4.2 40
29
30 2 Classification of Metallic Engineering Materials

Table 2.7 Comparison of properties of different types of stainless steels

Characteristics Austenitic Ferritic Duplex
Basic composition Cr. 18–25, Ni 8–40 Cr 10–27 Cr. 18–25; Ni 5–27
Phases Austenite Ferrite 50 Austenite + 50 Ferrite
Magnetic properties Non-magnetic Strongly magnetic Magnetic
R.T. strength Fair Good Very good
H.T. strength Very good Poor (>300 °C) Poor (>300 °C)
Cryogenic property Very good Poor Poor
Weldability Very good Poor Fair
Corrosion/Oxidation Very good Fair/Good (>300 °C) Good (>300 °C)

2.3 Non-ferrous Materials

2.3.1 Aluminium and Aluminium Alloys

Of the non-ferrous metals, tonnage-wise aluminium occupies the highest position. It

is soft, has low strength and comparatively low melting point (about 660 °C). In
spite of this, its lightness (about 1/3rd of that of iron), good resistance to corrosion,
good electrical conductivity and comparatively lower cost make these as attractive
alternative in many structural, decorative, electrical and corrosion resistance ser-
vice. Aluminium and its alloys are extensively used in aerospace industry. An
important property of aluminium is its ability to develop considerable strength by
suitable alloying and in some cases by subsequent heat treatment, known as age
hardening. The aluminium and its alloys on cold working retain good ductility with
increase in strength and therefore, are available in various degrees of cold working,
known as tempers that are mentioned in alloys specifications.

2.3.2 Copper and Copper Alloys

Copper is the second most important non-ferrous metal after aluminium. Its largest
use is as electric conductor but is also extensively used in producing various alloys
having good resistance to corrosion, especially in fresh and sea water service.
Copper and its alloys are highly ductile and can be easily cast and worked to
produce various components. The largest use of copper alloys in process industries
is in tubing and piping. Where resistance to some specific corrosive media is
required, the preferred method of using copper and its alloys is to use as lining over
steel base for fabrication of pressure vessels, tanks, etc.
The most important copper alloys are brasses (Cu–Zn, Cu–Zn–Sn; Cu–Zn–Al),
bronzes (Cu–Al, Cu–P, Cu–Zn–Si), cupronickels (Cu–Ni), etc. Some of the
2.3 Non-ferrous Materials 31

Table 2.8 Composition of some copper alloys used in process industries

UNS No. Copper Aluminium Nickel Zinc Iron Others
C28000 59.0–63.0 – – Balance
C44300 72.0 – – Balance SN 0.9–1.2; AS 0.04
C44400 70.0–73.0 – – Balance SN 0.9–1.2;
SB 0.02–0.10
C44500 70.0–73.0 – – Balance SN 0.9–1.2;
P 0.02–0.10
C60800 Balance 5.0–6.5 – 0.02–0.35
C68700 76.0–79.0 1.8–2.5 – Balance 0.02–0.10
C70400 Balance – 4.8–6.2 1.0 max 1.3–1.7
C70600 Balance – 9.0–11.0 1.0 max 1.0–1.8
C71000 Balance – 19.0–23.0 1.0 max 0.5–1.0
C71500 Balance – 29.0–33.0 1.0 max 0.40–1.0
C71600 Balance 31.0 1.7–2.3

important uses of copper alloys used in process industries are heat exchanger
tubing, piping and fittings for handling sea water, fasteners and other hardware, etc.
Table 2.8 lists some important copper alloys [19].

2.3.3 Nickel and Nickel Alloys

Compared to aluminium and copper, nickel is costlier but in spite of this it is

extensively used both as pure nickel or mainly its alloy both for corrosion and high
temperature services. Some of the important nickel base alloys are Monel® (Ni–
Cu), Inconels® (Ni–Cr–Fe), Hastelloys® (Ni–Cr–Mo,). Use of nickel and its alloys
is specially made where resistance to specific highly corrosive environment is
needed as in strong caustic or hydrofluoric acid service. Table 2.9 lists some
important nickel alloys [20].

2.3.4 Lead and Lead Alloys

Lead and its alloys as engineering material have limited but important uses. Lead
alloys are used for soldering (Pb–Sn, Pb–Sn–Sb) and bearings (Pb–Sn–Sb, Cu–Pb,
Cu–Sn–Pb). Pure lead and Pb–Sb (hard lead) sheets and pipes are used in specific
corrosive environment, e.g. dilute sulphuric acid service. Lead has low melting
point (327 °C) and low strength. Its creep resistance is poor and creep failure occurs
at normal temperature under self-load. By alloying, its strength, both normal and
32 2 Classification of Metallic Engineering Materials

Table 2.9 Nominal composition of typical nickel alloys

UNS No. Nickel Copper Iron Aluminium Chromium Molybdenum Others
Monel (N04400) 66.5 31.5 1.0 1.0Mn
Monel K 500 (N05500) 64.0 30.0 2.8 0.60Ti
Incoloy 600 (N06600) 75.0 8.0 15.5 0.15C
Alloy 825 (N08825) 42.0 29.5 21.5 3.0 1.3Cu;
1.0Ti
Alloy G2 (N06985) 44.0 19.5 22.0 7.0 1.5W;
2.0Cu
Hastelloy C276 Balance 57.0 5.5 15.0 16.0 3.8W
(N10276)
Hastelloy C22 (N06022) Balance 3.0 22.0 13.0 3.0W

creep, can be increased, e.g. Pb–Sb (hard lead) has better stability as lining. Because
of its low strength it is more commonly used as a lining (sheet or homogenous).

2.3.5 Titanium and Titanium Alloys

In process industry unalloyed titanium (also known as commercially pure or CP

titanium) is commonly used. Titanium is selected for its excellent corrosion resis-
tance properties in large varieties of environments, especially in applications where
high strength is not required. However, because of high cost its use is limited to
exchanger tubes using sea water as coolant and for some specific corrosive
chemicals. CP grade titanium is available in four ASTM grades, i.e. 1, 2, 3 and 4
where strength of the material increases progressively from 240 MPa (35 ksi) to
640 MPa (93 ksi). The chemical composition and strength for the four CP grades
are given in Table 2.10 [21]. It will be evident from the table that, the variations in
mechanical properties are dependent on interstitial solid solution (oxygen, hydro-
gen, nitrogen) and impurity (iron) levels.
Titanium is light compared to iron (about 50%) and therefore it has the
advantages of having lower weight to strength ratio. Ti6 Al–4V alloy is widely used
titanium alloy where strength and toughness are required.

Table 2.10 Variations in composition (by wt%) and strength of unalloyed titanium
ASTM B265/UNS Fe max O max N max C max H max Elongation % Y.S. MPa UTS MPa
Gr. 1/R50250 0.2 0.18 0.3 0.1 0.015 24.0 170–310 240
Gr. 2/R50400 0.3 0.25 0.3 0.1 0.015 20.0 275–450 345–480
Gr. 3/R50550 0.25 0.3 0.5 0.1 0.015 18.0 360–480 480–700
Gr. 4/R50700 0.5 0.4 0.5 0.1 0.015 15.0 500–530 600–680
2.3 Non-ferrous Materials 33

2.3.6 Other Non-ferrous Metals

The other non-ferrous metals have either no utility in process industries (zinc,
silver, tin, etc.) or have limited use under special conditions (tantalum, zirconium,
magnesium, cobalt, etc.). Others like silicon, antimony, barium, etc., are used in
small quantities as minor or micro-alloying elements. For example, magnesium is
used for handling hydrofluoric acid, zirconium for its resistance to carbamate
solution, tantalum for its resistance to many highly corrosive solutions.

2.4 Unified Numbering System

Originally alloys were classified independently by producers and users of metals

and alloys and societies and trade associations concerned for identification. Ferrous
materials in USA were classified by AISI, SAE, and Foundry Societies, etc. With
increasing number of alloys being developed, numerous uncoordinated designation
systems created a lot of confusion. To overcome this, the Unified Numbering
System (UNS) was developed in 1977 [22] jointly by Society of Automotive
Engineering (SAE) and ASTM to unify the different systems in vogue over the
years. In this system, the metals and alloys are divided into 18 series with desig-
nations starting with a letter followed by five numbers. The letter identifies the
family of material such as, S for stainless steels, C for copper alloys G for carbon
and alloy steels. The following five numbers represent as far as possible the
commonly designated user friendly numbers. For example, stainless steel type 316
would be designated as S31600 and carbon steel containing 0.2%C as G10200.
Thus, it also provides the uniformity necessary for efficient indexing, record
keeping, data storage and retrieval and cross referencing. Some of the important
items of UNS system are listed in Table 2.11.
Two important aspects of UNS are that (1) arbitrary assignment of UNS numbers
derived unofficially from former members is avoided and proper trade association
contacted and (2) a UNS number is not a specification in itself but is only for
identifying metals and alloys specified elsewhere. A UNS number therefore should
not be considered as a specification as it does not set any requirements but identifies
groups of metals and alloys whose controlling limits have been established in
specifications published elsewhere. The UNS numbers identify metals and alloys
that are generally in regular production and use. According to ASTM E 527, UNS
number will not ordinarily be issued for a material that has just been conceived or
that is still in only experimental trial.
34 2 Classification of Metallic Engineering Materials

Table 2.11 Unified alloying number system (UNS)

Ferrous metals and alloys
D00001–D99999 Specified mechanical properties steels
F00001–F99999 Cast irons and cast steels
G0000–G99999 AISI and SAE carbon and alloy steels
H00001–H99999 AISI H steels
K00001–K99999 Miscellaneous steels and ferrous alloys
S00001–S99999 Heat and corrosion resistance stainless steels
T00001–T99999 Tool steels
Non-ferrous metals and alloys
A00001–A99999 Aluminium and aluminium alloys
L00001–L99999 Low melting metals and alloys
M00001–M99999 Miscellaneous non-ferrous metals and alloys
N00001–N99999 Nickel and nickel alloys
P00001–P99999 Precious metals and alloys
T00001–T99999 Reactive and refractory metals and alloys
Examples
Alloy description Former designation System No. UNS designation No.
Al–1.2Mn AA 3003 A93006
Copper electrolytic (Tough Pitch) CDA 110 C11000
Carbon steel (0.2%C) AISI 1020 G10200
Stainless steel (18Cr–8Ni) AISI 304 S30400

2.5 Material Specification

2.5.1 Material Standard

It is a document that contains a technical specification or other precise criteria

designed to be used consistently as a rule, guideline or definition and thus increase
reliability and the effectiveness of many goods and services. Standards are created
by bringing together the experience and expertise of all interested parties such as
the producers, sellers, buyers, users and regulators of a particular material, product,
process or service. Standards are designed for voluntary use and do not impose any
regulations. However, laws and regulations may refer to certain standards and make
compliance with them mandatory.

2.5.2 Purpose of Specification

In the previous sections, the classification of metallic materials on the basis

of composition, e.g. C-steel, C–0.5Mo, 2.25Cr–1.0Mo, 18Cr–8Ni, 90Cu–10Ni,
2.5 Material Specification 35

70Ni–30Cu, etc. has been briefly presented. Composition forms the first step in the
selection of material under certain conditions. However, during design or pro-
curement simply mentioning the general composition does not suffice because
metals and alloys of the same composition may be required to have different shapes
to fulfil some specific purpose, which in turn can depend on purpose, requiring
different
1. Manufacturing processes
2. Working and shaping of metals
3. Heat treatment
4. Mechanical properties
5. Workability, ductility and toughness
6. Weldability
To facilitate and ensure the right material having required properties, there is
need to have some definite guidelines which can be used by both the users and
manufacturers. The need for this has resulted in the development of material
standards. Almost all countries have National Standards and follow the same or
internationally well-recognized standards for metallic materials and codes like
ASTM, ASME and API, of USA. Other important standards such as BS of U.K.,
DIN of Germany, JIS of Japan and GOST of Russia. International Standard
Organization (ISO) and European standards (EN) are also slowly getting accepted.
Presently all EU nations have adopted the EN Standard.
For familiarity with original designations and trade names these, instead of UNS
numbers, have been mostly used in this book. Readers can get the equivalent UNS
number by referring to relevant ASTM/ASME standards.

2.5.3 Preparation of Standards

Preparation for standards involves various steps, such as (a) repeatability of com-
position and property data submitted by the manufacturer (b) existence of any
standards of similar material in other accepted standards (c) and extensive trial and
its feedback from fabricators, designers and actual users. Standards do not include
products having company trade names but only requirements of a particular
material, which any manufacturer is free to produce and market under the relevant
specifications. All data submitted/collected are reviewed by a panel of experts and,
if the result is found to be satisfactory, the standard is prepared and issued. Some of
the organizations bring out an interim specification and make it a permanent one
only after the performance is found to be satisfactory. If not, the standard is either
withdrawn or modified.
When a new alloy is developed, the manufacturers are required to submit room,
low or high temperature properties, depending on the proposed service, welding
procedure and weldability, feedback on field performance and other necessary
36 2 Classification of Metallic Engineering Materials

details. Once the committee is convinced that the material will meet the require-
ments of safe pressurized components, then only it is accepted. ASME first pub-
lishes these as Code Cases and then subsequently issued as standard. It may be
mentioned that such standards exist not only for metals and alloys but also for all
products, including various testing and analytical procedures.

2.5.3.1 Broad Coverage Under Specifications

Standards are prepared with a view to specifying minimum requirements for the
material to be certified as usable. It is natural that the specification cannot include
special requirements under all types of uses. For example, all pressure vessel quality
carbon steels can be used up to sub-zero temperatures of −29 °C as per ASME. For
use at still lower temperatures, additional requirement of impact test is included
only in those specifications of carbon steels, where the design/operating tempera-
tures are in the sub-zero range of −29 to −46 °C. In addition, there are some
service-related specific requirements, which are not covered in specifications. For
example, many ferrous and non-ferrous metals and alloys used in sour service (in
oil and gas production/refineries) fail if the composition, strength and or hardness
are not controlled within required limits. In such cases, it is the responsibility of the
users to specify these, where necessary, as an additional requirement.
For metallic material of interest to the process industry, separate specifications
cover the different forms in which the material of the same group, such as, low and
medium alloy Cr–Mo steel, stainless steels, etc., are produced. These are
• Plates
• Tubes/Pipes
• Forgings
• Casting, etc.
In addition, some specifications are also made for specific services. For example,
there are separate specifications for superheater tubes, high temperature castings,
steel plates for use at medium and low temperatures, and so on. It may be men-
tioned that, unless specially required, the standards give only room temperature
mechanical properties, which form the basis for both production and acceptance of
a material.
Some of the important contents of material specifications are:
Shaping Process
The metals and alloys come in various forms like plates, pipe, tube, wire, valve,
etc. The methods used are rolling, extrusion, drawing, forgoing, casting, etc. While
composition may be the same, properties may vary depending on the process need.
Thus for each of these processes there are different specifications.
Manufacturing Process
The material properties will also vary with the presence of small amounts of
additional elements, which may be deliberately added or present as impurities. The
2.5 Material Specification 37

various grades of carbon and low alloy ferritic steel can be produced in rimmed,
semi-killed and killed conditions which form part of a specification. Each of these
have advantages and disadvantage and the user has to decide under what condition
the material will meet his requirements.
Chemical Composition
Any metal or alloy does not have a fixed composition because it is never
possible to ensure the same for all the heats (molten metal/alloy) during manu-
facturing. In other words, there will always be some range within which different
elements can vary without affecting the basic characteristic of the alloy. In addition,
there is likely to be other elements, either added or present as impurities. For
example, in any iron base alloys there is presence of manganese and silicon, which
are to be added during production. On the other hand, sulphur and phosphorous are
always present as impurities. Thus it is necessary that the composition remains
within limits to be designated as a particular metal or alloy. Normally the maximum
content of each element is specified, except in some cases where the range is
mentioned.
Mechanical Properties
Mechanical properties like, strength, elongations, toughness, etc., are very
important parameters to judge the suitability of an alloy for a particular service.
Again the mechanical properties will depend on heat treatment to which the
material is subjected. So the specification also states the heat treatments to be used.
For example, the properties of carbon steel will vary with heat treatments like
annealing or normalizing and tempering. Thus heat treatment becomes an important
step for both manufacturer and users. For example, the user can ask for the product
to be provided in normalized and tempered condition to have optimum properties.
On the other hand, the manufacturer can attain the desired properties by adjusting
the composition (mainly carbon and manganese) and heat treatment.
Specification gives the minimum mechanical properties like UTS, Y.S (0.2%
Proof stress), % elongation, and reduction in area (% RA). The minimum value is
given because while manufacturing one can never attain repeatedly the some preset
fixed properties. So within a reasonable range, changes in mechanical properties, as
in case of chemical analysis, are permitted. If the user asks for say carbon steel
plates of Gr. 60 (min UTS of 410 MPa (60 ksi)), the manufacturer guarantees that it
would meet the minimum requirement of all properties specified. However, the
actual properties of plates supplied may be more and vary from plate to plate but in
no case it will be less than the minimum specified values.
Quality
The quality of the finished material is also important. Presence of inclusions or
lamination will have an adverse effect on performance. In case of cladding, only
limited amount of disbonded area can be permitted to avoid in-service failure.
Similarly, dimensional variations of any product or component should be within
limits. For example, tolerance limits in plate thickness and size, inner diameter and
outer diameter of tubes/pipes, flanges, rods, etc., are to be set. All these
38 2 Classification of Metallic Engineering Materials

requirements are covered under specification. Thus in the use of material, it is

always essential to procure the material based on recognized specifications along
with any requirements specially required for a particular service.

2.5.4 Dual Certification

Presently available in market are stainless steel products which have dual or mul-
tiple certifications, often involving both standard and low carbon variants of the
grade being certified together. Dual or multiple certifications means the issue of two
separate inspection certificate for the same inspected/tested or delivered batch of
steel. Since 1980s, it has become a practice and acceptable by stainless steel sup-
plier to provide dual certificate for the same batch of steel. According to the British
Steel Association, [23, 24] to reduce inventory the suppliers certify together if the
chemical composition and mechanical properties match the grades, such as,
304/304L or 316/316L or 304/304H. Full compliance with all the requirements of
the first (primary) standard is assured and for the others only the cast chemical
composition and room temperature mechanical properties of the products are cer-
tified, Dual certification can be used for other materials also provided they meet all
the requirements of the identified material specification and grade [25]. For
example, steel plates of SA-516 come in five grades, that is, 55, 60, 65 and 70 with
composition and mechanical properties (tensile and yield stress) as given in
Table 2.12.
If we examine the table above, we find that a material with maximum carbon of
0.18%, manganese content of 0.9%, having a tensile strength of 476 MPa (70 ksi)
and a yield strength of 239 MPa (35 ksi) will satisfy for all four grades of SA-516.
In that case, it can be dual stamped for all four grades provided it also meets other
requirements stipulated in the specification. The designer can therefore consider its
use for any of the four grades.
Once the material is selected and the specification decided, the equipment is to
be designed and fabricated using applicable Codes. Codes are systematically
arranged comprehensive collection of laws or procedure to attain desired objective
of safety. However, unlike specifications, Codes have got statutory status binding
on parties concerned.

Table 2.12 Chemical and mechanical properties of A-516 plate with respect to different grades
Requirement Gr. 55 Gr. 60 Gr. 65 Gr. 70
Carbon max—  ½ in. 0.18% 0.21% 0.24% 0.27%
Manganese—  ½ in. 0.60–0.90% 0.60–0.90% 0.85–1.20% 0.85–1.20%
Tensile strength—ksi 55–75 60–80 65–85 70–90
Yield strength, min—ksi 30 32 35 38
References 39

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