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SELECTION ALTERATION OF ENVIRONMENT PROPER DESIGN CATHODIC PROTECTION ANODIC PROTECTION COATINGS & WRAPPING
MATERIAL
(1) MATERIAL SELECTION (selection of proper material for a particular corrosive service)
Metallic [metal and alloy]
Nonmetallic [rubbers (natural and synthetic), plastics, ceramics, carbon and graphite, and wood]
1
2 3 4
Nitric acid
Caustic Hydrofluoric acid Hot hydrochloric acid
Stainless steels
Nickel and nickel alloys Monel (Ni-Cu) Hastelloys (Ni-Cr-Mo) (Chlorimets)
Lead
No 6 7 8 9
Environment Nonstaining atmospheric exposure Distilled water Hot strong oxidizing solution Ultimate resistance
10
Steel
wt.% Cr
Other than Ni, Cr and C, the following alloying elements may also present in stainless steel: Mo, N, Si, Mn, Cu, Ti, Nb, Ta and/or W. Main alloying elements (Cr, Ni and C):
1. Chromium Minimum concentration of Cr in a stainless steel is 12-14wt.% Structure : BCC (ferrite forming element)
* Note that the affinity of Cr to form Cr-carbides is very high. Chromium carbide formation along grain boundaries may induce intergranular corrosion.
2. Nickel Structure: FCC (austenite forming element/stabilize austenitic structure) Added to produce austenitic or duplex stainless steels. These materials possess excellent ductility, formability and toughness as well as weld-ability. Nickel improves mechanical properties of stainless steels servicing at high temperatures. Nickel increases aqueous corrosion resistance of materials.
3. Carbon Very strong austenite forming element (30x more effective than Ni). I.e. if austenitic stainless steel 18Cr-8Ni contains 0.007%C, its structure will convert to ferritic structure. However the concentration of carbon is usually limited to 0.08%C (normal stainless steels) and 0.03%C (low carbon stainless steels to avoid sensitization during welding).
Manganese Austenitic forming element. When necessary can be used to substitute Ni. Concentration of Mn in stainless steel is usually 23%. Molybdenum Ferritic forming element. Added to increase pitting corrosion resistance of stainless steel (2-4%). Molybdenum addition has to be followed by decreasing chromium concentration (i.e. in 18-8SS has to be decreased down to 1618%) and increasing nickel concentration (i.e. has to be increased up to 10-14%). Improves mechanical properties of stainless steel at high temperature. Increase aqueous corrosion resistance of material exposed in reducing acid.
Tungsten Is added to increase the strength and toughness of martensitic stainless steel.
Nitrogen (up to 0.25%) Stabilize austenitic structure. Increases strength and corrosion resistance. Increases weld ability of duplex SS.
Titanium, Niobium and Tantalum To stabilize stainless steel by reducing susceptibility of the material to intergranular corrosion. Ti addition > 5x%C. Ta+Nb addition > 10x%C.
Copper Is added to increase corrosion resistance of stainless steel exposed in environment containing sulfuric acid.
Austenitic - Susceptible to SCC. Can be hardened by only by cold working. Good toughness and formability, easily to be welded and high corrosion resistance. Nonmagnetic except after excess cold working due to martensitic formation. Martensitic - Application: when high mechanical strength and wear resistance combined with some degree of corrosion resistance are required. Typical application include steam turbine blades, valves body and seats, bolts and screws, springs, knives, surgical instruments, and chemical engineering equipment. Ferritic - Higher resistance to SCC than austenitic SS. Tend to be notch sensitive and are susceptible to embrittlement during welding. Not recommended for service above 3000C because they will loss their room temperature ductility.
Duplex (austenitic + ferritic) has enhanced resistance to SCC with corrosion resistance performance similar to AISI 316 SS. Has higher tensile strengths than the austenitic type, are slightly less easy to form and have weld ability similar to the austenitic stainless steel. Can be considered as combining many of the best features of both the austenitic and ferritic types. Suffer a loss impact strength if held for extended periods at high temperatures above 3000C. Precipitation hardening - Have the highest strength but require proper heat-treatment to develop the correct combination of strength and corrosion resistance. To be used for specialized application where high strength together with good corrosion resistance is required.
Stress corrosion cracking (SCC) is defined as crack nucleation and propagation in stainless steel caused by synergistic action of tensile stress, either constant or slightly changing with time, together with crack tip chemical reactions or other environment-induced crack tip effect. SCC failure is a brittle failure at relatively low constant tensile stress of an alloy exposed in a specific corrosive environment.
However the final fracture because of overload of remaining load-bearing section is no longer SCC.
Three conditions must be present simultaneously to produce SCC: - a critical environment - a susceptible alloy - some component of tensile stress
Pure metals are more resistance to SCC but not immune and susceptibility increases with strength
Susceptible material
Corrosive environment
Surface morphology
Example of crack propagation during transgranular stress corrosion cracking (TGSCC) brass
Example of crack propagation during intergranular stress corrosion cracking (IGSCC) ASTM A245 carbon steel
Fracture surface of transgranular SCC on austenitic stainless steel in hot chloride solution
Fracture surface due to local stress has reached its tensile strength value on the remaining section
Electrochemical effect
Usual region for TGSCC, mostly is initiated by pitting corrosion (transgranular cracking propagation needs higher energy)
pitting
Zone 1
cracking zones
Zone 2
passive
active
Usual region for IGSCC, SCC usually occurs where the passive film is relatively weak
Note that non-susceptible alloy-environment combinations, will not crack the alloy even if held in one of the potential zones. Temperature and solution composition (including pH, dissolved oxidizers, aggressive ions and inhibitors or passivators) can modify the anodic polarization behavior to permit SCC. Susceptibility to SCC cannot be predicted solely from the anodic polarization curve.
Slip step dissolution model Discontinuous intergranular crack growth Crack nucleation by rows of corrosion microtunnels Absorption induced cleavage Surface mobility (atoms migrate out of the crack tips) Hydrogen embrittlementHIC
Control/prevention :
Reduce applied stress level Remove residual tensile stress (internal stress) Lowering oxidizing agent and/or critical species from the environment Add inhibitor Use more resistant alloys Cathodic protection
Alteration of Environment
Typical changes in medium are : Lowering temperature but there are cases where
increasing T decreases attack. E.g hot, fresh or salt water is raised to boiling T and result in decreasing O2 solubility with T.
Dust particles and man-made pollution CO, NO, methane, etc. Temperature high T & high humidity accelerates corrosion. Rainfall excess washes corrosive materials and debris but scarce may leave water droplets. Proximity to sea Air pollution NaCl, SO2, sulfurous acid, etc. Humidity cause condensation.
Wall thickness allowance to accommodate for corrosion effect. Avoid excessive mechanical stresses and stress concentrations in components exposed to corrosive mediums. Esp when using materials susceptible to SCC. Avoid galvanic contact / electrical contact between dissimilar metals to prevent galvanic corrosion. Avoid sharp bends in piping systems when high velocities and/or solid in suspension are involved erosion corrosion. Avoid crevices e.g weld rather than rivet tanks and other containers, proper trimming of gasket, etc.
Avoid sharp corners paint tends to be thinner at sharp corners and often starts to fail. Provide for easy drainage (esp tanks) avoid remaining liquids collect at bottom. E.g steel is resistant against concentrated sulfuric acid. But if remaining liquid is exposed to air, acid tend to absorb moisture, resulting in dilution and rapid attack occurs. Avoid hot spots during heat transfer operations localized heating and high corrosion rates. Hot spots also tend to produce stresses SCC failures. Design to exclude air except for active-passive metals and alloys coz they require O2 for protective films. Most general rule : AVOID HETEROGENEITY!!!
Provide barrier between metal and environment. Coatings may act as sacrificial anode or release substance that inhibit corrosive attack on substrate. Metal coatings : Noble silver, copper, nickel, Cr, Sn, Pb on steel. Should be free of pores/discontinuity coz creates small anode-large cathode leading to rapid attack at the damaged areas. Sacrificial Zn, Al, Cd on steel. Exposed substrate will be cathodic & will be protected. Application hot dipping, flame spraying, cladding, electroplating, vapor deposition, etc.
Surface modification to structure or composition by use of directed energy or particle beams. E.g ion implantation and laser processing. Inorganic coating : cement coatings, glass coatings, ceramic coatings, chemical conversion coatings. Chemical conversion anodizing, phosphatizing, oxide coating, chromate. Organic coating : paints, lacquers, varnishes. Coating liquid generally consists of solvent, resin and pigment. The resin provides chemical and corrosion resistance, and pigments may also have corrosion inhibition functions.