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Materials

General Properties





 Elastic behaviour – bond stretching (reversible)

 Plastic behaviour – ductile, irreversible movement of

dislocations









 Perfect metal: ~ TS 1 million psi

 Perfect metal + dislocations TS ~ 100000 psi

Ductile v/s Brittle Fracture





 Ductile – plastic deformation, starts at voids (high stress

area @ centre of metal)

 Ductile – withstand heavy impacts, absorbs lot of energy

 Brittle – fracture starts @ surface, fine cracks

Ductile-Brittle Transition





 Ductility = f(temperature)









 Y strength increases as loading rate increases (dislocations

can only move so fast). Hence transition temperature

increases

Alloys





 Most materials

 Minor elements in small concentrations

 C + Fe produces carbon steel (higher strength), Cu is

added to aluminum to increase strength.

 Allow properties depend upon phase diagram and heat

treatment

Alloys: Phase diagram and TTT

Cast Iron

C is good cathode

but improves mech

 Grey

properties





 White









 When cast white on exterior and grey on interior.

– Problems when machining

 Mg sometimes added for strength

 1 –2 % Si may be added for strength

Cast Iron: Mechanical Properties





 Tensile strength: 50000 psi

 Fatigue limit: 20000 psi

 Max working temperature: 400 – 500 oC

 Brittle at low temperature

 Welding: Possible but difficult

 Machining: Good

 Elongation: 3 to 18 %

Cast Iron: Corrosion





 Similar to Fe but modified by carbon (similar PD)

 Silicon oxides produce a protective film

 Acids:

– Passivation in 70 % sulphuric acid

– Nitric acid – passivation is unreliable (water production

when nitric acid is reduced)

– Nitric + sulphuric (10 % to 96 %) OK

– Do not use with HCL

Cast Iron Corrosion





 Neutral:

– High corrosion rates (but alloy is cheap)

– Hard water (scaling reduces corrosion rate)

– Sea water 0.004 to 0.008 ipy

 Alkaline Solutions

– NaOH (30 %) OK

– NaOH (70 % if temperature less than 80 oC)

Cast Iron – Applications and Cost





 Complex cast shapes

 Sulphuric acid plant > 70 %

 Water, seawater lines

 Neutral salt solutions

 Alkaline solutions

 Nitrating vessels





 Cheapest (5 – 30 cents per pound fabricated)

Carbon Steel - General





 Brittle at temperature less than 50 oC.

 Tensile strength ~ 60000 psi

 Ductile (elongation ~ 30 %)

 Carbon content ~ 2 %

 Can be hot rolled and extruded: Suitable for chemical plant

construction on or off-site

 Killed steel add Al

Carbon Steel – Corrosion in Acids





 Do not use with dilute acids (no passivation)

 OK for cold conc sulphuric acid (65 %)

 OK with oleum

 Do not use with HCl

 OK for HF > 60 %

 Nitric acid passivation is unreliable

 Phosphoric acid will pit

 OK with dry chlorine and fluorine but not bromine or

iodine

Carbon Steel – Corrosion in Neutral, Alkaline,

organics



 Neutral – see cast iron

 Alkaline – see cast iron

 Organics

– OK for atmospheric towers (careful if chloride,

sulphide present)

– Do not use with acetic acid

Carbon Steel – Applications





 Cheapest mech reliable steel

 Corrosion is often accepted

 Use wherever possible

 At temperature greater than 500 oC, oxidation of the metal

and strength decrease.

Silicon Steel





 14 – 16 % Si or higher if appreciable corrosion rates









 Very brittle – thus impact resistance very low

 Fresh castings – stress relieved@ 750 to 850 oC

Silicon Steel





 High thermoductility (thermal shock not a problem)

 Welding – difficult

– Heat to 750 oC, use oxidizing flame

 Excellent acid resistance

 Applications

– Considered metallic glass or stoneware

• Use: nitric, sulphuric, dil. hydrochloric acid lines

Stainless Steels





 Alloys of Fe-Cr-Ni







Passivity Uniformity

Promotes formation of a phase in which

CrxCy’s are more soluble



 Weld decay

– Alloy with Titanium (4 x C)

– Use low carbon stainless steel (eg 304 L)

 Alloying with Mo improves corrosion resistance to non

oxidizing acids (316)

Stainless Steel Properties (304 L)





 Tensile strength: 80000 psi

 Good at high temperature. Has 2 x allowable stress than

mild steel @ 500 oC

 Brittle at low temperature

 Welding: Good – electric arc. Can be welded to mild steel

with special welding rods

 Can be used to clad mild steel

 Elongation: 55 % (v. ductile)

 Good impact resistance

Stainless Steels – Corrosion Resistance Acids





 Protection based on Cr2O3 passive film. Polish?

 Generally poor resistance in reducing acids. Add Mo.

 O.K. for sulphuric acid if oxygen present

 No – No HCl

 Phosphoric: Use 18/8 + Mo

 OK. For oxidizing acids up to 95 %. After 95 % metal goes

transpassive

Stainless Steels – Corrosion Resistance Neutral

+ Alkaline + Organics

 Neutral

– Add oxidizing agents to maintain passivity

– Chlorides – Bad Karma

 Alkaline Solutions

– Not much better than mild steel

 Organic Solutions

– Acetic acid – 18/8 + Mo

– Petroleum

• Same as mild steel except wider temperature range

 Cost ~ $3 per pound fabricated (several times CS)

Nickel Alloys – General Properties

 Major use of Ni is alloying element

 BEST METAL for high conc, high temp alkaline (passive)

 TS: 60000 psi

 Good high and low temperature properties

 Add NI to Steel changes min working temperature

– 3.5 % = - 100 oC, 9 % = -200 oC.

 High thermoductility

 Good machining properties

 Expensive (~$4 – 7 per pound fabricated)

 Acid Solutions: Corrosion based on nobility, alkaline

based on passivity. If chlorides will pit.

 Used in industries where Fe will cause discoloration

Monel

 70/30 Ni/Cu

 Important in chemical industry

 Mechanically reliable over a wide range of temperatures

– TS: 75000 psi @ room temp. 30000 psi @ 750 oC.

– Reasonable thermoductility

– Good impact resistance down to – 180 oC.

 Easy to machine and gas weld

K-Monel





 K-Monel: Addition of 3 % Al

 K-Monel designed as a high temp, high acid alloy

 TS: 80000 psi @ room temp. 30000 psi @ 800 oC.

 Corrosion resistance better than Cu or Ni except in

Alkaline solutions. Nobility of Cu and Passivity of Ni (not

attacked by acid and Cu will no longer complex)

K-Monel





 Acids

– Sulphuric: OK to 60 %

– HCl: OK to 10 % (hot)

– Nitric: If conc. > 5 % rapid attack

– HF: OK

– Cl, Br, I: OK

 Alkaline: OK up to 50 % then cracking

 Neutral: OK for NaCl

Ni-Mo Alloys





 Hastelloy B: 28 % Mo, 5 % Fe, TS: 130000 psi, elongation

50 %

 Hastelloy C: 15 % Mo, 17 % Cr, - excellent resistance to

acids.

 10 % Si casting alloy: 8.5 % Ni, 10 % Si, 3 % Cu, TS

115000 psi.

 All have outstanding corrosion resistance including

concentrated HCl (dilute HCl use monel)

Copper Alloys





 Excellent thermal conductivity

 Welding used deoxidized rods (0.02 – 0.08 % P) as oxygen

will segregate around the grains and cause cracking.

 Ductile at low temperatures

 Max Temp:









 Cost approx same as stainless steel.

 Easily worked.

Copper Alloys





 Corrosion resistance based on nobility

 Does not evolve hydrogen: Thus oxygen usually present

 Do not use with oxidizing acids

 OK in alkaline

 Neutral: Low corrosion rate due to film production

 Complexing agents…Arrggghhh

 Fine for acetic, lactic and formic acids

 Major Problem with Cu: Erosion-Corrosion

 Also discolours

Copper Alloys: Brass + Bronze





 Contain at least 50 % Cu. Developed to overcome softness,

low strength and high casting temp of Cu.

 Brass = Cu-Zn: High thermoductility

– Admiralty brass 70/30 Cu/Zn. Not as corrosion resistant

as Cu and subject to dezincification (add 0.1 % As to

prevent this). Add 2 % Al for better resistance to E-C.

 Bronze = Cu-Sn (5-10 % Sn)

– Phosphor bronze (phosphorous) increases hardness as

does addition of 5 % Zn (Gunmetal Bronze).

– Aluminum-Bronze (93 % Cu, 7 % Al) good high temp

properties

Aluminum





 Corrosion resistance is based on “passivity.”

 Poor mech properties (10000 – 20000 psi TS)

– Ad 3 % Mg (TS 30000 psi). But reduces the corrosion

resistance.

 Light weight, high thermoductility

 Fusion welding (tungsten metal arc + inert gas)

 Cost ~$1.50 per pound fabrication

 Corrosion resistance is better than indicated by P-D

 Can be coupled with stainless steel

Aluminum – Corrosion Resistance





 Nitric









 Sulphuric









 HCL – No – No – No.

Aluminum – Corrosion





 Neutral

– Do not use if chloride or sulphur compounds present

– Do not use in high temp water

– OK for H2O2 up to 90 %

 Alkaline Solutions

– Rapid attack

 Organics

– Fair corrosion resistance with organic acids (low temp)

– Does not discolour

Lead

 Used to be standby in chemical plants with difficult

corrosion problems. Now Monel, Al, polymer etc.

 Uses diffusion barrier approach for protection

 TS: 20000 psi

 Low creep stress 100’s psi

 Add Cu. Ag, Al to harden

 Max Working temp is only 200 oC.

 Melts easily on the stove top (327 oC)

 Welding use pure Pb wire, no flux

 Cost $500 per ton, high scrap value

 Softest and most easily worked

 Fine grains, susceptible to intergranular attack.

Lead – Corrosion Resistance









 Not shown is formation of salts.

 Sulphuric acid forms lead sulphate

 Nitric acid – steady attack

 Neutral: Very good.

 Alkaline: DNUse

Titanium





 Strong like Arnold, with excellent corrosion resistance

based on passivity. TS: 44000 to 100000 psi

 Very light weight (4.5 g/cm3 v/s 7.9 g/cm3 for CS)

 Expensive. Often used as lining

 Thermoductility is OK – use in thin sections



Can be passivated

by hydrogen

evolution reaction Add Pt or Pd

and make

passivation

easier

Corrosion resistance





 Good for boiling 5 % sulphuric acid

 Great for all concentrations of nitric acid

 Outstanding resistance to seawater, brines and other

neutral chlorides.

 Better resistance to SCC than stainless steel

Tantalum





 Corrosion resistance of GLASS!!!

– OK for all solutions except HF

 Excellent thermal properties

 Ten times as expensive as Ti

Zirconium





 Similar mechanical properties to C-S but almost

transparent to neutrons.

 Corrosion rate is based upon passivity

 Good for all concentrations of HCL at temperature less

than bpt.

 No good with HF

 OK with medium concs of sulphuric and nitric acid up to

200 oC.

 Cost $50 per pound fabricated

Non-Metals





 In many cases superior corrosion resistance but inferior

mechanical and thermal properties

 Silicates: Stoneware, glass, acid resistant bricks, enamel

– Corrosion resistant in all except HF, hot conc

phosphoric acid, alkali > 10 %.

– Use in acidic environments and under tension (brittle)

– Stoneware adsorption columns, acid resitant brick

lining, glass reaction vessel, HX, enamelled C-S

reactors.

Non-Metals





 Carbon (graphite)

– Acid resistant linings

– HX

– Good for acids and alkalis at all concentrations up to

the bpt.

– Graphite bonded with resin has max working temp of

around 250 oC.

– Brittle, but can be used in thick sections because of

high thermal conductivity

Non-Metals





 Plastics

– In general low working temperature, low strength and

low thermal conductivity.

– DNU with oxidizing acids, aromatics and chlorinated

hydrocarbons (swelling + dissolution)

– Uses: Pipes/Valves/Fittings/Linings

– Construction: Hot gas or solvent welding

Non-Metals





 Thermosetting Phenolics, Epoxyresins

– Laminated structures/tanks etc.

– Expensive but can compete with stainless steel

– Max working temp ~ 200 oC

 Vulcanized rubber

– Linings, cured in situ

– Excellent abrasion resistance (mining)

• Max working temp ~ 100 oC

High Temperatures

Creep

High Temperature Oxidation



Temperature below

which oxidation

is negligible



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