Chapter 7: Materials of Construction ChE 515 Chemical Process Equipment Design

Material Properties Corrosion Resistance

1. Mechanical Properties 1. Uniform Corrosion (General Wastage of

a. Strength: tensile strength – maximum strength Material)
in which a material can withstand before ♦ Corrosion Rates – penetration rate in inches
fracture (Ultimate Tensile Strength) per year (ipy, mpy mill = 10-3), measured by
b. Stiffness: Elastic Modulus (Young’s) the reduction in weight of a specimen of
c. Toughness: fracture resistance, resists crack known area over a fixed period of time
propagates at on, impact loading 12𝑤
𝑖𝑝𝑦 =
d. Hardness: wear resistance, ability to resist 𝑡𝐴𝜌
abrasion Where w = mass loss in time
e. Fatigue Resistance; cyclic loading, torture, t = time
most common form of mechanical failure A = surface area
f. Creep Resistance – plastic deformation of a Ρ = density of material
material which occurs as a function of time ♦ 1 ipy – 25 mm per year
♦ The corrosion rate will depend on the
2. The effect of high temperature, low temperature temperature and concentration of the
and thermal cycling on the mechanical corrosive fluid.
properties. ♦ An increase in temperature usually results in
3. Corrosion Resistance – chemical compatibility increased rate of corrosion.
4. Any special properties required: thermal ♦ Oxygen solubility
conductivity, electrical resistance, magnetic
properties. 2. Galvanic Corrosion
5. Ease of fabrication: forming, welding, casting
♦ Due to the fusion of two metals from different
6. Availability in standard sizes: plates, sections,
galvanic series.
tubes
♦ The corrosion rate will depend on the relative
7. Cost
areas of the anodic and cathodic metals.
• Ductility – amount of plastic deformation that a
♦ A high cathode to anode area should be
material can withstand without fracture.
avoided.
Mechanical Properties ♦ Sacrificial anodes are used to protect
underground steel pipes.
1. Tensile Strength (Tensile Stress)
♦ Proof Stress – stress to cause a specified 3. Pitting – highly localized corrosion that forms
permanent extension pits in the metal surface.
2. Stiffness – ability to resist bending and buckling. ♦ Can occur if the composition of the metal is
3. Toughness not uniform.
♦Crystal structure of steel, aluminum, copper ♦ The impingement of bubbles during
♦ Brittle – strong in compression cavitation in pumps (erosion – corrosion)
4. Hardness ♦ A good surface finish will reduce attack.
♦ Brinell Hardness Test
5. Fatigue 4. Intergranular Corrosion – preferential
6. Creep – gradual extension of a material under a corrosion of material at the grain (crystal
steady tensile stress boundaries).
7. Effect of Temperature on the Mechanical ♦ Common form of attack on alloys.
Properties ♦ Usually caused by a differential couple
being set up between impurities existing at
♦ Tensile strength and elastic modulus of metals the grain boundary.
decrease with increasing temperature. ♦ Example: Weld decay of not stabilized
♦ Creep resistance will be important if the stainless steel: annealing
material is subjected to high stresses at elevated
temperatures. 5. Stress Corrosion
♦ At low temperatures, metal that are normally ♦ Stress Corrosion Cracking – combination of
ductile can fail in a brittle manner. metal, corrosive media and temperature. A
form of attack in which cracks are produced
that grow rapidly, and can cause premature,
brittle failure of the metal.

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Chapter 7: Materials of Construction ChE 515 Chemical Process Equipment Design
♦ Conditions for Stress Cracking:
a. Simultaneous Stress and Corrosion Factors to Consider:
b. A specific corrosive substance in the 1. Temperature: affects corrosion rate and mechanical
particular presence of Cl-, OH-, NO3-, NH4+ properties

♦ Mild stress from fabrication and welding 2. Pressure

♦ Seasonal cracking of brass catridge cases
♦ Caustic embrittlement of steel boilers
♦ Stress corrosion cracking of stainless steels in
the presence of chloride ions.
♦ Select materials not susceptible in the
specific corrosion environment + post weld
heat treatment
6. Erosion – Corrosion – describes the increased
rate of attack caused by a combination of
erosion and corrosion.
♦ Usually happens when there is turbulent /
jet flow of particulates.
3. Ph
4. Presence of trace impurities: stress corrosion
5. The amount of aeration: differential oxidation cells
6. Stream velocity and agitation: erosion – corrosion
7. Heat transfer rates: differential temperatures
Material Costs
♦ The quantity of material used will depend on the
material density and strength.
♦ Cost Rating Factor (Moore, 1970)

𝐶 × 𝜌
7. Corrosion Fatigue – describes the premature 𝐶𝑜𝑠𝑡 𝑟𝑎𝑡𝑖𝑛𝑔 =
𝜎𝑑
failure of materials in corrosive environments
caused by cyclic stresses. Where:
C = cost per unit mass, $/kg
8. High Temperature Oxidation and Sulfidation ρ = density, kg/m3
♦ Chromium is the most effective alloying σd = maximum allowable stress, N/mm2
element to give resistance to oxidation
forming a tenacious oxide film. ♦ The relative cost of equipment made from different
♦ Sulfur – very common corrosive materials will depend on the cost of fabrication.
contaminant, present in reducing ♦ The annual cost will depend on the predicted life,
environments calculated from the corrosion rate and the purchased
cost of the equipment.
9. Hydrogen Embrittlement – the loss of ductility
caused by absorption and reaction of Contamination
hydrogen in a metal. ♦ avoid poisoning of catalysts
♦ Alloy steels have greater resistance to ♦ explosive acetylides
hydrogen embrittlement. ♦ mercury – copper amalgam
♦ Metallic Corrosion is essentially an electrochemical ♦ zinc contamination
process.

Components necessary to set up an electrochemical Surface Finish

cell: ♦ to avoid contamination
1. Anode: the corroding electrode ♦ Stainless steel is widely used + abrasive blasting and
2. Cathode: the passive, non-corroding electrode mechanical polishing
3. The conducting medium: the electrolyte, the ♦ prevent material adhering to the surface
corroding fluid ♦ aid in cleaning and sterilization
4. Completion of the electrical circuit

Selection for Corrosion Resistance

♦ The process environment to which the material will be
exposed must be clearly defined.
♦ Conditions may arise during abnormal operation, such
as start-up and shut down.

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Chapter 7: Materials of Construction ChE 515 Chemical Process Equipment Design
General Classification of Materials
◊ Cast Iron
I. Metals
- Generally malleable, fusible and ductile - a ferrous alloy which has been heated until it liquefies,
and is the poured into a mold to solidify.
▲Alloying - Carbon content ranges from 2.1- 4 %wt. and silicon 1-
The properties of alloys can be manipulated by varying 3%wt.
composition. For example, steel formed from iron and - White cast iron has carbide impurities
carbon can vary in hardness depending on the amount - Grey cast iron has graphite flakes
of carbon added and the way in which it was processed. - Tends to be brittle, except for the malleable cast irons.
When a second element is added, two basically different - Relatively low melting point, good fluidity, castability,
structural changes are possible: excellent machineability, resistance to deformation and
1. Solid solution strengthening occurs when the atoms of wear resistance.
the new element form a solid solution with the original - Resistance to destruction and weakening by oxidation
element, but there is still only one phase. (rust)
- Used in pipes, machine and automotive industry pipes
2. The atoms of the new elements form a new second
phase. The entire microstructure may change to this new ◊ Pig Iron
phase or two phases may be present. - smelting iron ores with a high – carbon fuel
- 3.5 – 4.5% carbon content silica and other constituents
of dross
Alloy Composition
Brass Copper, Zinc - Some are suitable for producing ductile iron
Bronze Copper, Zinc, Tin
Pewter Tin, Copper, Bismuth, Antimony ◊ Wrought Iron
Cast Iron Iron, Mg, Carbon, Silicon
- has a fibrous “slag” inclusion
Steel Iron, Carbon +
- very low carbon content (0.1 to 0.25%)
Stainless Steel Iron, Chromium, Nickel
- tough, malleable, ductile and easily welded

▲ Heat Treatment *Slag – usually a mixture of metal oxides and silicon

The major objectives of the different kinds of thermal dioxide. They are generally used to remove waste in
treatments are: metal smelting but they can also serve as assisting in the
temperature control of smelting, minimizing any re-
1. Soften the material for improved workability. oxidation of the final liquid metal product before the
2. Increase the strength or hardness of the material. molten metal is removed from the furnace and used to
3. Increase the toughness or resistance to fracture of the make solid metal.
material.
4. Stabilize mechanical or physical properties against Other Iron Alloys
changes that might occur during exposure to service Fernico
environments. Elinavar
5. Insure part dimensional stability. Invar
6. Relieve undesirable residual stresses induced during Kovar
part fabrication. Spiegeleisen

2. Steel

Carbon is the primary alloying element and its content in

▲ Ferrous Metals and Alloys
steel is between 0.002% and 2.1% by wt. Additional
alloying elements have been intentionally added to
1. Iron Alloys modify the characteristics of steel.

An increase in the carbon content of the iron ill initially
cause a significant corresponding increase in the iron’s
hardness and tensile strength.
◊ Manganese and Nickel – add to its tensile strength and
make the austenite form more stable
◊ Chromium – increase hardness and melting
temperature,
◊ Nickel and Chromium – inhibits corrosion
◊ Molybdenum – improve the hardenability of thick
sections; resistance to chloride pitting
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Chapter 7: Materials of Construction
◊ Cobalt – used in the preparation of magnetic, wear –
resistant and high strength alloys
◊ Vanadium – increases hardness while reducing the
effects of metal fatigue
◊ Tungsten – adding it may result to high speed steel
◊ S, N and P – make steel more brittle; removed during
processing
◊ Carbon – increases hardness
◊ Dross – impurities that needs to be removed during
smelting
Carbon steel is steel in which the main interstitial alloying
constituent is carbon in the range of 0.12 -2.0%. Stainless
steel is a steel alloy with a minimum of 10.5% chromium
content by mass. Stainless steel does not readily corrode,
rust or stain with water as ordinary steel does, but despite
the name it is not fully stain-proof, most notably under low
oxygen, high salinity and poor circulation environments. +
oxide film: resistance to corrosion
♦ Austenitic
- contains a maximum of 0.15% C, a minimum of 16% Cr
and sufficient Ni and or Mn to retain an austenitic
structure
- non-magnetic allotrope of iron
- Type 315: Marine Grade Stainless; Type 202: General
purpose Stainless Steel
♦ Ferritic
- Contains between 10.5% and 27% Cr, and very little Ni, if
any, but some types can contain Pb.
- Most compositions include Mo, some Al or It
♦ Martensitic
- Not as corrosion-resistant as the other 2 class but are
extremely strong and tough, as well as highly,
machinable, and can be hardened by heat treatment.
Martensitic stainless steel contains Cr 12-14%, Mo 0.2-1%,
Ni < 2%, C 0.1-1%
- It is quenched and its magnetic
♦ Duplex
- Mixed microstructure of Austenite and Ferrite
- Have roughly twice the strength compared to austenitic
ss
- Improve resistance to localized corrosion, pitting,
crevice corrosion and stress corrosion cracking.
- characterized by high Cr (19-32%) and Mo (up to 5%)
and lower nickel contents
ChE 515 Chemical Process Equipment Design
♦ Precipitation Hardening
- Chromium – nickel ss which contain alloying conditions
such as Al, Cu, Titanium that allow them to be hardened
by a solution and aging heat treatment. They can be
either austenitic or martensitic in the aged condition.
Pitting Resistance Equivalent Number (PREN)
- a measurement of the corrosion resistance of SS
containing Ni. Exact testing procedures are specified in
the ASTM G48 Standard.
- The higher PREN – values are, the more corrosion
resistant the steel is. Steels with PREN – values above 32
are considered seawater corrosion resistant.
𝑃𝑅𝐸𝑁 = (1 × %𝐶𝑟) + (3.3 × %𝑀𝑜) + (16 × %𝑁)
- A PREN – value ≥ 40 for duplex steels is called for in the
DIN EN ISO 15156 as well as the American NACE – a
standard for use in hydrogen sulfide environments known
in the oil and gas extraction industries.
Exception: stainless steels with Mo content ≥ 1.5% may
have PREN - value ≥ 30.
Non – Ferrous Metals and Alloys
1. Aluminum
- very lightweight but with alloying an become very
strong
- excellent thermal conductor
- excellent electrical conductor (on a weight for mass
basis, Al will conduct more than twice as much electricity
as Cu)
- corrosion resistance due to the formation of a thin oxide
film
- highly reflective to radiant energy in the
electromagnetic spectrum
- highly corrosion resistant in air and water (including sea
water)
- highly workable and can be formed into almost any
structural shape
- non – magnetic and non – toxic
- used in construction, electrical products, packaging
and containers, cooking utensils, aeronautics and
sporting goods
- for storage and distribution of demineralized water
Al + metal : reduced modulus of elasticity and hardness
strength
Al + Mg : less flammable
Al + Mg + Si : good in extrusion
- pure: lacks mechanical strength, higher resistance to
corrosion
- Duralumin (Dural) – main structural alloys
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Chapter 7: Materials of Construction
2. Titanium
- Low density and high strength
- Highly resistant to corrosion in sea water, aqua regia,
chlorine
- can be alloyed with Fe, Al, V, Mo for strength
- not very flexible but returns to its original shape after
bending
- non – magnetic and biocompatible (non – toxic, non –
allergenic) : increase use in Medicine
- Aerospace, military, industrial processes, automotive,
Agri food, medical prosthesis, sporting goods
- Nuclear Waste storage – containers lasting over 100, 00
years are possible under proper manufacturing conditions
to reduce defects in the process.
- A Ti “drip shield” could be placed over other types of
containers to further contain the waste.
3. Copper
- one of the best electrical conductors, good thermal
conductor, tough, ductile and malleable
- disagreeable taste and a peculiar smell
- corrosion resistance in most atmospheres, ease of
forming, joining, color
- corroded by oxidizing acids, halogens, sulfides, and
ammonia based solutions
- resistant to caustic alkalis, except ammonia
- weak metal with a tensile strength about half of mild
carbon steel but has a high degree of toughness
- Heat exchanges tubes for condensers in steam power
stations and chemical plants
- Irrigation and agricultural sprinkler systems
- Piping at distillation plants, Seawater feed lines
- Cement pumps for drill water supply
- Tubes for distribution of natural and liquefied petroleum
- Fuel gas distribution piping
4. Lead
- most impervious of all common metals to X- rays and
gamma radiation
- it resists attack by many corrosive chemicals, most types
of soil and marine and industrial environments
- low melting temperature, ease of casting and forming
- high density, good sound and vibration absorption, ease
of salvaging from scrap
- natural lubricity and wear resistance of lead make the
metal suitable, in alloys, for heavy – duty bearing
applications
- anti – knock agent
5. Tin
- low melting point, fluidity when molten
- readiness to form alloys with other metals, relative
softness and good formability
- non – toxic, solderable, high boiling point
- used as a constituent of solder and as coating for steel
(tinplate or terneplate)
ChE 515 Chemical Process Equipment Design
- used in bronze, pewter and bearing alloys
6. Gold
- extremely inert, soft, ductile metal, that undergoes very
little work hardening
- it is used chiefly for linings or electrodeposits and is often
alloyed with other metals such as copper or nickel to
increase strength or hardness
- conductor
- resistant to dilute nitric acid and hot concentrated
sulfuric acid
7. Silver
- very malleable, ductile, corrosion resistant metal
- has the highest thermal an electrical conductivity of all
metals
- least costly of all the precious metals
- alloyed with Cu, Zn, used in high – melting temperature
solders
- used for equipment handling HCl
8. Platinum
- extremely malleable, ductile, corrosion resistant silver
white metal
- when heated to redness, it softens and is easily worked
- nearly non – oxidizable and is soluble only in liquids that
generate free chlorine such as aqua regia
- inert and stable even at high temperatures: for high –
temperature handling of high – purity chemicals and
laboratory materials
- applications: electrical contacts, resistance wire,
thermocouples, standard weights
9. Nickel
- good mechanical properties, easily worked
- Main use: for equipment handling caustic alkalis at
temperatures above that at which carbon steel could be
used
- not subject to corrosion cracking
- alloys ≥ pure metal usage
10. Monel
- the classic Nickel – Copper alloy 2:
- most commonly used alloy for chemical plants
- good resistance to dilute mineral acids and can be
used in reducing conditions
- may be used for equipment handling alkalis, organic
acids, salts and seawater
11. Inconel and Incoloy
- 76% Ni, 7% Fe, 15% Cr
- Ni alloys with higher Cr content: better oxidation
resistance at higher temperatures
- for acid resistance at high temperatures
- maintains strength at elevated temperatures
- resistant to furnace gases
- not suitable for use in sulphiding environments
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Chapter 7: Materials of Construction
12. Hastelloys
- range of Ni, Cr, Mo, Fe alloys
- developed for corrosion resistance to strong mineral
acids, HCL
13. Tantalum
- metallic glass (corrosion resistance like glass)
- expensive
- used to repair glass – lined equipment
14. Zirconium
- low neutron absorption cross – section and resistance to
hot water at high pressures
- used as resistance to hot and boiling acids
II. Ceramics
- Inorganic, nonmetallic solid that is prepared from
powdered materials
- Fabricated into products through application of
heat
- Hardness, strength, low electrical conductivity,
brittleness
- From “keramikos” means “pottery”
- Typically, crystalline in nature and are
compounds formed between metallic and
nonmetallic elements such as Al and O (alumina
Al2O3), Ca and O (calcia CaO), Si and N (silicon
nitride Si3N4)
- Magnetic properties
- More resistant to high temperatures and harsh
environments than metals and polymers
a. Structural Clay Products – brick, sewer pipe,
roofing, wall tile, flue linings
b. Whitewares – dinnerware, electrical porcelain
c. Refractories – brick and monolithic products used
in metal, glass, cements, ceramic, energy
conversion, petroleum, chemical industries
d. Glass – flat glass (windows), container glass,
pressed and blown glass, glass fibers (home
insulation) and advanced/specialty glass (optical
fibers)
e. Abrasives – used for grinding, cutting, polishing,
pressure blasting, natural (garnet, diamond) and
synthetic (silicon carbide, diamond, fused
alumina)
f. Cement – roads, bridges, dams, buildings
Advanced Applications
1. Structural – wear parts, bio ceramics, cutting tools
and engine components
2. Electrical – capacitors, insulators, substrates,
integrated circuit packages, piezoelectric,
magnets and superconductors
3. Coatings – engine components, cutting tools,
industrial wear parts
ChE 515 Chemical Process Equipment Design
4. Chemical and environmental – filters,
membranes, catalysts and catalyst support
Boron – gives silica – based glasses and ceramics
resistance to thermal shock; boron polymers and
ceramics play specializes roles as high – strength
lightweight structural and refractory materials.
Borosilicate Glass
- Pyrex
III. Polymers
Polymeric Solid
- material that contains many chemically bonded parts
or units which themselves are bonded together to form a
solid
Polymer Properties
- less dense than metals or ceramics
- resist atmospheric and other forms of corrosion
- offer good compatibility with human tissue
- exhibit excellent resistance to the conduction of
electrical current
Elastomers
- rubbers, can be elastically deformed when a force is
applied to them and can return to their original shape
when force Is released
Plastics
- large group of synthetic materials which are processed
by forming or molding into shape
- mechanical strength and operating temperature: low
- good resistance to dilute acids and inorganic salts
- degradation in organic solvents
- can absorb solvents: swelling and softening
A. Thermoplastic Materials
- soften with increasing temperature; PVC, polyethylene
B. Thermosetting Materials
- rigid, cross – linked structure; Polyester and epoxy resins
1. Poly – Vinyl Chloride
- most commonly used
- resistant to most inorganic acids and salt
solutions
- max operating temperature @ 60C
2. Polyolefins
- Cheap, tough, flexible
- low softening point
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Chapter 7: Materials of Construction ChE 515 Chemical Process Equipment Design
3. Polytetrafluorethylene PTFE
- Teflon and Fluon
- resistant to all chemicals except molten alkalis
and Fl
- max operating temperature @ 250C
- expensive, difficult to fabricate
- used in gaskets, gland packing, demister pads
- used as coating for non – stick properties
- liner for vessels

4. Polyvinylidene Fluoride PVDF

- easier to fabricate than PTFE
- good resistance to inorganic acids, alkalis and
organic solvents
- max operating temperature @ 140C

5. Glass – Fiber Reinforced Plastics GRP

- polyester resins, reinforced with glass fiber
- most common thermosetting plastic
- forms complex shapes
- relative strong

6. Rubber
- lining for tanks and pipes
- good resistance to acids
- Hypalon: good resistance to strongly oxidizing
chemicals, unsuitable with chlorinated solvents
- Viton: better resistance to solvents

IV. Composites
- combination of two or more distinct
materials, each of which retains its own
distinctive properties to create a new
material

Concrete – Portland cement + aggregate

Fiberglass Sheet – glass fibers imbedded in a polymer

Reinforcing Phase
- fibers, sheets, particles that are embedded in the
matrix phase. (Metal, Ceramic, Polymer)
Reinforcing materials
- low densities, strong
Matrix Material
- ductile, tough

Matrix phase: bulk materials such as:

Metals, Ceramics, Polymers

Reinforcement: fibers and particulates such as

Glass, Silicon Carbide, Ceramic
Carbon, Boron, Metallic
Kevlar, Ceramic, Aggregate