Dr.

Md Shahinoor Islam
Associate Professor
Department of Chemical Engineering
BUET, Dhaka-1000
 Introduction
 Selection of materials of construction combined with the
appropriate techniques of fabrication can play a vital role in
the success or failure of a new chemical plant or in the
improvement of an existing facility.
 Chemical process plants turn to higher temperatures and flow
rates to boost yields and throughputs.
 More severe operating conditions forces the chemical engineer
to search for more dependable, more corrosion-resistant
materials of construction for these process plants, because all
these severe conditions intensify corrosive action.
 A broad range of materials is now available for corrosive
service.
 Choosing the “best material”.
 Sound economic analysis of competing materials.
Galvanic Action between Two Dissimilar Metals

 Table 10-1 shows the galvanic series of various metals.

 The resulting galvanic action can cause one of the

metals to dissolve into the conducting fluid and
deposit on the other metal.

 As an example, if a piece of copper equipment

containing a solution of sodium chloride in water is
connected to an iron pipe, electrolysis can occur
between the iron and copper, causing high rates of
corrosion.
Factors contributing to corrosion
 Corrosion: chemical or electrochemical attack
 Corrosive action can also be initiated by galvanic
action, impingement, cavitation, or hydrogen attack.
 Major factors affecting the corrosion rate are:
 pH: 4-10
 Air/oxygen
 Galvanic action-structural corrosion
 Biological activity
 Minimization of corrosion
 Change in the operating environment: pH
 Use of an inhibitor (chromates, phosphates, and silicates)
 Cathodic protection-underground pipes and storage tanks
 Anodic protection
 Substitution of less corrosive materials
 Use of nonmetallic castings and lining materials with steel
and iron
 Cladding of steel with an alloy
 the use of a permissible corrosion rate in the design of
certain equipment if the corrosion is anticipated and
properly allowed for in the thickness calculation.
 Materials of Construction
 Divided into the two general classifications: metals and
nonmetals.
 The American Iron and Steel Institute (AISI) has set up a series of
standards for steel products.

Metals-Ferrous metals and alloys

Carbon steel is the most commonly used material in the chemical
process industry.
Because of its availability, low cost, and ease of fabrication,
carbon steel is used even in situations with corrosion rates of
0.13 to 0.5 mm/yr by specifying an added thickness to ensure
achievement of the desired service life.
 Metals-Ferrous metals and alloys

 Low-alloy steels contain one or more alloying components

to improve the mechanical and corrosion-resistant
properties over those of carbon steel.
 Nickel increases toughness and improves low-
temperature properties and corrosion resistance.
 Chromium and silicon improve hardness, abrasion
resistance, corrosion resistance, and resistance to
oxidation.
 Molybdenum provides added strength for higher-
temperature operation.
Stainless Steels
 Contain high chromium or high nickel-chromium alloys of
iron with small amounts of other essential constituents.

Characteristics
Higher work hardening rate
Higher ductility
Higher strength and hardness
Higher hot strength
Higher corrosion resistance
Higher cryogenic toughness
Lower magnetic response (austenitic only)
Must retain corrosion resistant surface in the finished product
The Martensitic alloys:

 Contain 12 to 20 percent chromium with controlled

amounts of carbon and other alloys.
 These alloys can be hardened by heat treatment
 Can increase the tensile strength from 550 to 1380 MPa.
 Corrosion resistance is poor relative to that for austenitic
stainless steels.
Ferritic stainless steels:
 Contain 15 to 30 percent chromium with 0.1 percent or
less carbon content.
 The strength of ferritic stainless can be increased by
cold working but not by heat treatment.
 Corrosion resistance is good, although ferritic alloys
experience considerable corrosion with reducing acids
such as HCl.
 However, mildly corrosive solutions and oxidizing
media are handled with minimum damage.
Austenitic stainless steels:
 are the most corrosion-resistant of the three groups of stainless
steels.
 These steels contain 16 to 26 percent chromium and 6 to 22
percent nickel.
 Carbon content is maintained below 0.08 percent to minimize
carbide precipitation.
 These alloys can be work-hardened, but heat treatment will not
cause hardening.
 Tensile strength in the annealed condition is about 585 MPa, but
work-hardening can increase this to 2000 MPa.
 The addition of molybdenum to the austenitic alloy, as in type
316, increases the corrosion resistance and improves high-
temperature strength.
 Most Common stainless Steels:
 Type 304, contain approximately 18-20 percent chromium and
8-12 percent nickel and 0.08% C, and are designated as 18-8
stainless steels.
 The addition of molybdenum to the alloy, as in type 316,
increases the corrosion resistance and high-temperature
strength.
 If nickel is not included, the low-temperature brittleness of the
material is increased and the ductility and pit-type corrosion
resistance are reduced.
 The presence of chromium in the alloy gives resistance to
oxidizing agents. Thus, type 430, which contains chromium but
no nickel or molybdenum, exhibits excellent corrosion
resistance to nitric acid and other oxidizing agents.
Compositions of 316 SS
Element Type 316 (%) Type 316L (%)
Carbon 0.08 max. 0.03 max.
Manganese 2.00 max. 2.00 max.
Phosphorus 0.045 max. 0.045 max.
Sulfur 0.03 max. 0.03 max.
Silicon 0.75 max. 0.75 max.
Chromium 16.00-18.00 16.00-18.00
Nickel 10.00-14.00 10.00-14.00
Molybdenum 2.00-3.00 2.00-3.00
Nitrogen 0.10 max. 0.10 max.
Iron Balance Balance
 The properties of types 430F, 416,410, 310, 309, and 303
make these materials particularly well suited for machining
or other fabricating operations.
 In general, machinability is improved if small quantities of
phosphorus, selenium, or sulfur are present in the alloy.

Table 10-3 outlines the information according to the classes of

stainless steels—austenitic, martensitic, and ferritic.
Table 10-4 presents characteristics and typical applications of
various types of stainless steel while
Table 10-5 indicates resistance of stainless steels to oxidation in
air.
 Hastelloy C
 A typical analysis of this alloy shows 56 percent nickel, 17
percent molybdenum, 16 percent chromium, 5 percent iron,
and 4 percent tungsten, with manganese, silicon, carbon,
phosphorus, and sulfur making up the balance.
 Hastelloy C is used where structural strength and good
corrosion resistance are necessary under conditions of high
temperatures.
 The material can be machined and is readily fabricated.
 It is used in the form of valves, piping, heat exchangers, and
various types of vessels.
 Hastelloy B
 Contains 61 percent nickel and 28 percent
molybdenum.
 Oxidizing acids and salts rapidly corrode this alloy, but
it provides unusually high resistance to all
concentrations of hydrochloric acid at all temperatures
in the absence of oxidizing agents.
 Copper and its Alloys
 Copper is relatively inexpensive, possesses fair
mechanical strength, and can be fabricated easily
into a wide variety of shapes.
 Copper is resistant to atmospheric moisture or oxygen
because a protective coating composed primarily of
copper oxide is formed on the surface.
 The oxide is soluble in most acids, and thus copper is
not a suitable material of construction when it must
contact any acid in the presence of oxygen or
oxidizing agents.
 Copper exhibits good corrosion resistance to strong
alkalies, with the exception of ammonium hydroxide.

 At room temperature it can handle sodium and
potassium hydroxide of all concentrations.
 It resists most organic solvents and aqueous solutions
of organic acids
 Copper alloys, such as brass, bronze, admiralty, and
Muntz metals, can exhibit better corrosion resistance
and better mechanical properties than pure copper.
 High-zinc alloys should not be used with acids or
alkalies owing to the possibility of dezincification.
 Most of the low-zinc alloys are resistant to hot dilute
alkalies
Nickel and its Alloys
 Nickel exhibits high corrosion resistance to most alkalies.
 Nickel-clad steel is used extensively for equipment in the
production of caustic soda and alkalies.
 The strength and hardness of nickel is almost as great as
that of carbon steel, and the metal can be fabricated easily.
 Oxidizing conditions promote the corrosion of nickel, and
reducing conditions retard it.
 Monel, an alloy of nickel containing 67 percent nickel and
30 percent copper, is often used in the food industries.
 Inconel (77 percent nickel and 15 percent chromium). The
presence of chromium in this alloy increases its resistance
to oxidizing conditions.
 Aluminum

 The lightness and relative ease of fabrication of aluminum

and its alloys are factors favoring the use of these materials.

 Aluminum resists attack by acids because a surface film of

inert hydrated aluminum oxide is formed.

 However the film is not suitable for halogen acids or

alkalies, are present.
 Lead

 Pure lead has low creep and fatigue resistance, but its physical
properties can be improved by the addition of small amounts of
silver, copper, antimony, or tellurium.
 Lead-clad equipment is in common use in many chemical
plants.
 The excellent corrosion-resistance properties of lead are caused
by the formation of protective surface coatings. If the coating is
one of the highly insoluble lead salts, such as sulfate, carbonate,
or phosphate, good corrosion resistance is obtained.
 Little protection is offered, if the coating is a soluble salt, such as
nitrate, acetate, or chloride.
 Lead shows good resistance to sufuric acid and phosphoric acid,
but it is susceptible to attack by acetic acid and nitric acid.
 Nonmetals
 Glass, carbon, stoneware, brick, rubber, plastics, and
wood are common examples of nonmetals used as
materials of construction. Many of the nonmetals
have low structural strength.

 Consequently, they are often used in the form of

linings or coatings bonded to metal supports.

 For example, glass-lined or rubber-lined equipment

has many applications in the chemical industries.
 Glass and Glassed Steel
 Glass has excellent resistance and is subject to attack only by
hydrofluoric acid and hot alkaline solutions.

 A chief drawback is its brittleness and damage by thermal

shock.

 Nucerite is a ceramic-metal composite made in a similar

manner to glassed steel and resists corrosive hydrogen-
chloride gas, chlorine, or sulfur dioxide at 650°C. Its impact
strength is 18 times that of safety glass and the abrasion
resistance is superior to porcelain enamel.
 Rubber and Elastomers
 Natural and synthetic rubbers are used as linings or as
structural components for equipment in the chemical
industries.
 Hard rubbers are chemically saturated with sulfur. The
vulcanized products are rigid and exhibit excellent
resistance to chemical attack by dilute sulfuric acid and
dilute hydrochloric acid.
 Natural rubber is resistant to dilute mineral acids, alkalies,
and salts, but oxidizing media, oils, benzene, and ketones
will attack it.
 Chloroprene or neoprene rubber is resistant to attack by
ozone, sunlight, oils, gasoline, and aromatic or halogenated
solvents.
 Styrene rubber has chemical resistance similar to natural.
Nitrile rubber is known for resistance to oils and solvents.
 Butyl rubber’s resistance to dilute mineral acids and
alkalies is exceptional; resistance to concentrated acids,
except nitric and sulfuric, is good.
 Silicone rubbers, also known as polysiloxanes, have
outstanding resistance to high and low temperatures as
well as against aliphatic solvents, oils, and greases.
 Chlorosulfonated polyethylene, known as hypalon, has
outstanding resistance to ozone and oxidizing agents
except fuming nitric and sulfuric acids. Oil resistance is
good.
 Polyvinyl chloride elastomer (Koroseal) has excellent
resistance to mineral acids and petroleum oils.
 Plastics
 The use of plastics is limited to relatively moderate
temperatures and pressures (230°C is considered high
for plastics).

 Generally, plastics have excellent resistance to weak

mineral acids and are unaffected by inorganic salt
solutions-areas where metals are not entirely suitable.
 Plastics
 Since plastics do not corrode in the electrochemical sense,
they offer another advantage over metals: most metals are
affected by slight changes in pH, or minor impurities, or
oxygen content, while plastics will remain resistant to these
same changes.

 One of the most chemical-resistant plastics commercially

available today is tetrafluoroethylene or TFE (Teflon). This
thermoplastic is practically unaffected by all alkalies and
acids except fluorine and chlorine gas at elevated
temperatures and molten metals. It retains its properties up
to 260°C.
 Plastics
 Chlorotrifluoroethylene or CFE (Kel-F) also possesses excellent
corrosion resistance to almost all acids and alkalies up to 175°C.
 FEP, a copolymer of tetrafluoroethylene and hexafluoropropylene, has
similar properties to TFE except that it is not recommended for
continuous exposures at temperatures above 200°C.
 Polyvinylidene floride, or PVF2 (Kynar), has excellent resistance to
alkalies and acids to 150°C .
 Perfloroalkoxy , or PFA, on the other hand, can tolerate temperatures
up to 300°C while exhibiting the general properties and chemical
resistance of FEP.
 Polyethylene is the lowest-cost plastic commercially available.
Mechanical properties are generally poor, particularly above 50°C and
pipe must be fully supported.
 Plastics
 Polyester resins, reinforced with fiberglass, have good
strength and good chemical resistance, except to alkalies.
Bisphenol is more alkali-resistant. Temperature limit for
polyesters is 95C.
 The general area of fiberglass-reinforced plastic (FRP)
represents a rapidly expanding application of plastics for
processing equipment, but fabrication standards still
need to be formalized.
 Epoxies reinforced with fiberglass have very high
strengths and resistance to heat
 Chemical resistance of the epoxy resin is excellent in
nonoxidizing and weak acids but poor with strong acids.
Alkaline resistance is excellent in weak solutions.
 Low- and high temperature materials

 The extremes of low and high temperatures used in

many recent chemical processes has created some
unusual problems in fabrication of equipment.

 For example, some metals lose their ductility and

impact strength at low temperatures, although in
many cases yield and tensile strengths increase as the
temperature is decreased.
 Gasket materials
 Metallic and nonmetallic gaskets of many different
forms and compositions are used in industrial
equipment.

 The choice of a gasket material depends on the

corrosive action of the chemicals that may contact
the gasket, the location of the gasket, and the type of
gasket construction.

 Other factors of importance are the cost of the

materials, pressure and temperature involved, and
frequency of opening the joint.
 SELECTION OF MATERIALS

 The chemical engineer responsible for the selection

of materials of construction must have a thorough
understanding of all the basic process information
available.

 This knowledge of the process can then be used to

select materials of construction in a logical manner.
A brief plan for studying materials of construction is
as follows:
 Fabrication of Equipment
 design and fabrication details for equipment are
governed by various codes, such as the ASME Codes.
 Layout
 The first step in the fabrication is to establish the layout of
the various components on the basis of detailed
instructions prepared by the fabricator.
 Flat pieces of the metal or other constructional material
involved are marked to indicate where cutting and forming
are required.
 Allowances must be made for losses caused by cutting,
shrinkage due to welding, or deformation caused by the
various forming operations.
 Cutting
 Several methods can be used for cutting the laid-out
materials to the correct size. Shearing is the cheapest
method and is satisfactory for relatively thin sheets.
 The edge resulting from a shearing operation may not be
usable for welding, and the sheared edges may require an
additional grinding or machining treatment.
 Burning is often used for cutting metals. This method can
be employed to cut and, simultaneously, prepare a beveled
edge suitable for welding. Carbon steel is easily cut by an
oxyacetylene flame.
 An oxyacetylene flame is used, and powdered iron is
introduced into the cut to increase the amount of heat
and improve the cutting characteristics.

 Sawing can be used to cut metals that are in the form

of flat sheets. However, sawing is expensive, and it is
used only when the heat effects from burning would be
detrimental.
 Forming

 Is accomplished by rolling, bending, pressing,

bumping (i.e., pounding), or spinning on a die.

 When the shaping operations are finished, the

different parts are assembled and fitted for fastening.
 Fastening
 Riveting can be used for fastening operations, but electric
welding is far more common and gives superior results.

 The quality of a weld is very important, because the ability

of equipment to withstand pressure or corrosive
conditions is often limited by the conditions along the
welds.

 Although good welds may be stronger than the metal that

is fastened together, design engineers usually assume a
weld is not perfect and employ weld efficiencies of 80 to 95
percent in the design of pressure vessels.
 Testing

 All welded joints can be tested for concealed

imperfections by X rays, and code specifications usually
require X-ray examination of main seams.

 Hydrostatic tests can be conducted to locate leaks.

Sometimes, delicate tests, such as a helium probe test,
are used to check for very small leaks.
 Heat-treating
 After the preliminary testing and necessary repairs are
completed, it may be necessary to heat-treat the equipment
to remove forming and welding stresses, restore corrosion-
resistance properties to heat-affected materials, and prevent
stress-corrosion conditions.

 A low-temperature treatment may be adequate, or the

particular conditions may require a full anneal followed by a
rapid quench.
 Finishing

 The finishing operation involves preparing the

equipment for final shipment. Sandblasting,
polishing, and painting may be necessary.
 Final pressure tests at 1/1.5 to 2 or more times the
design pressure are conducted together with other
tests as demanded by the specified code or requested
by the inspector.