Corrosion is the degradation of materials (esp. metals) by its combination bi ti with ith a non-metal t l such h as oxygen , sulfur lf etc.

Corrosion Steel making

Man sees ore in lowest energy state. Man transforms ore in useful object. bj Nature wants her dirt back. Nature N t transforms t f the th object bj t back to dirt.

Ene ergy

Smelted, heated and beated, f forged, d ground, d drilled and machined

Useful life!

Left out in the rain

Ore Time

Rusted away

Country England USA U.S.A. Japan Australia Germany

Year
1969~1 970 1975 1976~ 1977 1973 1968~1 1968 1 969

Corrosion cost
(% of GNP)

(sum)

Ref. 1 23 2,3 4 5 6

3.5 49 4.9 1.8 1.5 3.0

$3.2 bil. $82 0 bil. $82.0 bil $9.2 bil.* $0.6 bil.* $6.0 bil.

Thefigureof4%GNPisprobablyreasonablyresponsibleforother developedcountries (L.L.Shereir)

Corrosion is electrochemical Anode (Oxidizing losing electrons) Electrode Cathode C th d (Reducing (R d i gaining i i electrons) l t ) El Electrode t d Need Short circuit for electrons between terminals And need a medium for ion transport Electricity and chemicals are main drivers Influenced by other factors

Most corrosion is electrochemical G l i cell Galvanic ll iis necessary

electrical connection anode cathode th d

No corrosion if one of these is missing: anode cathode electrolyte electrical connection

electrolyte

Usual Textbook Equations q

Chemical: Zn + 2HCl = ZnCl2 + 2H Electrical: El i l Z Zn
2 + 2e Zn Z +2 2 - (anode) ( d ) 2H+ + 2e2H (cathode)

Note: hydrogen is atomic, not diatomic

This Thi can come b back kt to get t you

Generally, y, the electrical p part is not shown Oxygen reaction can be inserted as well.

Note that atomic hydrogen forms on surface and becomes diatomic in solution. Hydrogen atoms can be absorbed into materials (Ti and carbon steel couple) Figure 2.6 Electrochemical reactions occurring during the corrosion of zinc in air-free hydrochloric acid.
Used by permission, NACE, Corrosion Basics An Introduction, NACE, 1984, pg 28.

Corrosion rates are almost initially very high Polarization something to slow down reactions

Areas of reaction (anode to cathode) Oxygen Content (cathodic depolarizer) Temperature every 10C = 2 x corrosion rate Velocity effects moving species to & fro

Cathodic and anodic surface polarization Film thickness of corrosion product Rate of hydrogen or oxygen diffusion to and from surfaces Rate of corrodant ion diffusion away

General Pitting Crevice Underdeposit Dealloying Galvanic

Enviromental Cracking
Stress Corrosion Hydrogen Embrittlement Liquid Li id metal t l embrittlement b ittl t

Corrosion Fatigue Ca itation Cavitation Erosion

1.5 Forms of Corrosion Factors affecting forms of corrosion : Microstructure

Environment

Stress

Geometry

Time

more cathodic

Result: the galvanic series

electricalconnection anode cathode electricalconnection Zn Cu

electrolyte electrolyte

more anodic

What constitutes an anode/cathode pair? Dissimilar metals Different electrolytes y Ex: 1 contains little di dissolved l d oxygen 2 contains t i much h dissolved oxygen

What constitutes an anode/cathode pair? Dissimilar metals Different electrolytes y Practical example: crevice corrosion

What constitutes an anode/cathode pair? Dissimilar metals Different electrolytes Deformation > non-homogeneous residual stress

What constitutes an anode/cathode pair? Dissimilar metals Different electrolytes Deformation > non-homogeneous residual id l stress Non-passivated Non passivated vs. vs passivated metal or alloy
1 2

What constitutes an anode/cathode pair? In summary Anything that makes two halff cells different gives anode & cathode th d > corrosion We can call these types macro cells

Then what about micro cells? anode & cathode within single material operating ti on a micro i scale l Grain boundary - high energy regionanodic wrt bulk of grain

Differently oriented grains - some planes of atoms dissolve faster than others

Segregation (coring)

Then what about micro cells? anode & cathode within single material operating ti on a micro i scale l

Segregation (coring)

The even removal of metal. Allows great planning

Monitoring M it i Replacement p and scheduling g

Unfortunately, rare in the real world.

What general corrosion might look like!

Most common form of localized attack Break down of protective scale Localized attack in break Pit sets up its own environment Draws in chlorides and sulfates Can form caps over pits Low corrosion rates are deceitful

Pitting corrosion small and large

Much like a large g area p pit. Occurs in cracks or crevices Think of flanged connections such as
Piping p g flanges g Column body flanges Trays T on t tray rings i Car or truck doors

It will also set up its own environment

Crevice attack on titanium from fluorinated o-ring

Severe crevice attack as well as general

2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning is a trademark used herein under license.

Figure22.11Alternativemethodsforjoiningtwopiecesofsteel:(a)Fasteners mayproduceaconcentrationcell,(b)brazingorsolderingmayproducea p cell, ,and(c) ( )welding gwithafillermetalthatmatchesthebasemetal composition mayavoidtheformationofgalvaniccells(forExample22.8)

26

Very y similar to crevice corrosion but a larger g Usually an unplanned occurrence

Tools T l left l ft on fl floor River water silt buildup p in bottoms

Sometimes called poultice corrosion Sometimes called oxygen concentration cell

Copper pp alloys y Brasses with >30% zinc (bath sink tap screws) Copper C nickel i k l alloys ll ( (nickel i k l removed) d) Cast iron (graphitization) Almost any alloy can have the problem Two Theories One element is leached from solution Both B th elements l t corroded d d but b t more noble bl plates l t back. b k

Brass River Water Impellor suffering from dealloying and cavitation

Think dry y cell battery y

Carbon center cathode Zinc jacket anode MnOH (manganese hydroxide paste) Switch short circuit provided by your flashlight

Galvanized water pipe to your house Powerhouse soot blower of SS nozzle and steel pipe Over the road trailers with Al sides and steel rivets Your water heater with aluminum sacrificial anode

CSTL Pipe SS Nozzle

S t blower Soot bl metallographic t ll hi sample l

Stress Corrosion Cracking g

Chlorides (aluminum, 300 series SS) Caustic C i (cstl, ( l 300 series i SS, SS nickel i k l alloys) ll ) Ammonia (brass drain)

Hydrogen Embrittlement Liquid Metal Embrittlement

Copper pp on stainless steel p pipe p Zinc on stainless steel pipe

Weld metal

Knife line attack Transgranular chloride SCC in 316 stainless steel

Intergranular caustic SCC in 304L stainless steel finned tube.

If your sink at home is a nice shiny chromium plated brass, do not pour your ammonia down this drain and let it sit overnight. It will stress corrosion crack! PVC/galvanized steel trap drains go ahead no problem with ammonia.

Starts with an alternating g stress state Protective oxide breaks open Corrosive species attack and form products Next cycle y repeats:
crack growth more corrosion i product d t accelerated fatigue g failure

Seen in rotating shafts

Corrosion fatigue, g cracks can be oriented the other direction depending p g on stress state of shaft.

Mostly y found at
Pump impellor tips Boat propellers Constriction in fast fluids

Caused by formation of low pressure bubble Bubble is a vacuum C ll Collapse of fb bubble bbl slams l th the metal t l
Breaking protective oxide Causing great mechanical damage

Pieceofpumpimpellorwithtip cavitation

Valvetrimdiffuserwith cavitation

Centrifugefeednozzle

Can be from
Gaseous vapor (steam cuts on flanges) Liquid Li id Solids (Coal slurry)

Removes the protective oxide layer faster than it can heal

Lookforcomettails!Waterwasflowing fromrighttoleftincopperwaterpipe.

Visual examination for leaks Lab testing Field testing (Corrosion racks with coupons) C Corrosion i probes b
ER (electrical resistance) LPR (linear polarization resistance) New technology

Metals analysis in process fluids

All kinds of materials and shapes

Homemade or store bought coupons Welds Heat treatments

Metals Plastics Fiber reinforced plastics Ceramics Elastomers Glass

Coupons Lab testing at many temps but low pressure Heat flux testing to simulate exchangers High pressure labs Ingenious bench scale or pilot plant testing Key question - What do you want to know?

Agitator blades as corrosion coupons

Weld wires as coupons p

Corrosion racks Electrical resistance probes Linear polarization resistance probes New technology
Using electrical noise LPRs ERs

M t l analysis Metals l i iin solutions l ti

Typical yp field corrosion rack for insertion through a nozzle.

V = I*R

Electrical resistance probe

R = *l/A

Gives instantaneous corrosion rates Only used in conductive solutions Based on the current flow between two or more electrodes Requires the surface to become passivated (or polarized) and current t resistance i t iis measured. d Sometimes p probe has a reference electrode as well.

Electron Microscopy Elemental analysis Surface features FTIR for identification X-ray X ray Diffraction X-ray Fluorescence
Metals in fluids Fluids in plastics Corrosion products

Looking for clues by

Occlude electrolyte - coatings

asphalt greases, oils paints polymers ceramic coatings "noble" metals

Occlude electrolyte - coatings

"noble" noble metals: unless scratch heals, a galvanic cell is set up

Cathodic protection

galvanizing: Zn coating applied by hot dipping hot-dipping electroplating

Cathodic protection

galvanizing: presence of scratch does not promote corrosion of protected metal but steel helps Zn corrode

Cathodic protection

set up cell by adding metal which is more anodic than metal or alloy to be protected

Cathodic protection

example: protecting ship plate

Oxidation
Fl Flux Inert environment

Stress Build-up
Choose appropriate pp p material for welding g rod to reduce mechanical

stress

Weld Decay
De-zincification Grain Boundary y Chromium Depletion p Knifeline Attack

W ld Weldment tC Corrosion i

Weldments have a high sensitivity to environmentally induced corrosion. i Residual stresses can cause Stress Corrosion Cracking (SCC) Stress risers and inclusions due to welding can increase the sensitivity to Corrosion Fatigue Cracking (CFC) Welding g in the p presence of water or organic g molecules can trap p hydrogen in the weld, leading to Hydrogen Induced Cracking (HIC) Misoriented welding geometry can cause crevice corrosion/pitting corrosion. i

Susceptibility to environmentally i t ll iinduced d d corrosion is increased by improper welding technique. technique Defects include:

Stress risers Inclusions I Incomplete l t welding ldi Improper filler metal or flux used

Causes:
Residual tensile stresses Stress risers caused by improper

welding ldi

Prevention:
Use a metal that is resistant to

SCC in environment Specify post welding heat treatment Ensure smooth weld bead

One of the most common and best understood types of environmental i t l cracking ki often ft results lt iin white hit crystalline t lli external t l deposits near leaks Cracks often wide-open, wide-open easy to see see, but can be fine/tight Typically in non-PWHT weldments and other areas of high residual stresses Some common causes:

steaming out and carry-over into non-PWHT equipment Inadequately designed caustic injection nozzles Inadequate PWHT and non-PWHT repair welds Heat tracing in direct contact with caustic containing equipment Operators and maintenance people that dont understand the issue

64

Possible when weld is subjected to variable loads Stress risers at the weld will increase the sensitivity to CFC Prevention:
Smooth weld area Minimization of inclusions

Hydrogen present in water or organic molecules is released at high temperatures Monatomic Hydrogen is infused in the weld pool Hydrogen combines within metal and causes HIC Prevention:
Store welding g rods in dry y environment Use low-hydrogen electrodes (non-organic binders and flux) Local heat treatment before & after welding g

Arc Welding g
Atmosphere Surface contaminants W ldi rod Welding d
H2O

WELD

Heat breaks down Water.

H2O O2 H

WELD

Hydrogen y g causes cracking g Oxygen creates crevice

O2

WELD

Mechanism
Environment High Hi h P P, hi high hTh hydrogen d environment i t
Petrochemical plants Hydrocarbon H d b processing i at t 21 MP MPa, 540C

Stress level, exposure time, steel composition

Mechanism Hydrogen reacts with carbides to form methane Methane bubbles form at grain boundaries Bubbles merge to create fissures

Characteristics
Symptoms Unexpected U t d failure f il Microstructure Decarburization along grain boundaries Fissuring along grain boundaries Embedded methane bubbles

Case Study
Hydrogen attack at the ID weld

in a high pressure carbon steel boiler tube

Case Study
Cracking due to hydrogen attack

at the ID weld in a high pressure carbon steel boiler tube

Transgranular Cleavage

During welding, the weld bead and the metal on either side pass through the temperature range for sensitization. Temperature AND time are crucial for carbide precipitation: sensitized areas are on either side of the bead.

Tablecloth analogy of heat flow and temperatures during welding. The rise and fall of each stripe represents the rise and fall of temperature in a welded plate.

80

Actual measurements made with thermocouples at points ABCD. Fontana says metal at and between points B and C within sensitizing range for some time.

Temperatures during electric-arc welding of type 304 stainless steel..

81

Fe-Cr alloy in boiling 50% H2SO4 with Fe2(SO4)3 83

In the Heat Affected Zone of the weld, chromium may precipitate out of solution as a carbide. bid Prevention:

Pre- or post- heat treatments Use low carbon content alloys

(304L Stainless) Use Niobium or Titanium stabilized alloys

Fig : Intergrannular corrosion i of f a 310 310stainless-steel welded tube after exposure to a caustic solution. The weld line is at the center of the photograph. Scanning electron micrographs at 20X. 20X

(1) Heat Treatment Quench-Annealing or ... Solution-Annealing o So ut o ea g or .... Solution-Quenching g to above Cr carbide p precipitation p temperature p to dissolve carbides, Involves heating then water-quenching to cool through sensitization range rapidly. Most austenitic SS supplied in solution-quenching condition; if welded during f b i ti must fabrication, tb be quench-annealed h l dt to avoid id weld ld d decay during d i subsequent b t exposure to corrosive environments. Solution-quenching of large components can be a problem.

86

(2) Alloy Stabilization Elements that are strong carbide formers are added: Nb (or Nb+Ta) type 347 SS Ti type 327 SS Important to ensure that Nb (for example) carbide has precipitated precipitated, so that Cr Carbide cannot precipitate and reduce corrosion resistance at grain boundaries It is the Cr that p provides the corrosion resistance, not the stabilizer). )
Melting point, F Cr + Nb carbides dissolve 2250 1450 950 No reactions 70 Cr carbide dissolves Nb carbide precipitates Cr carbide precipitates 1230 790 510 20 C

Schematic S h ti chart h t showing h i solution l ti and precipitation reactions in types 304 and 347 SS.

87

Knife-Line-Attack (KLA) may now occur in narrow band next to weld if exposed to corrosive environment.

Knife-line attack on type 347 stainless steel.

Should have been heat-treated between 790 & 1230 C (Nb carbide precipitates, Cr dissolves).
88

(3) Use Low-Carbon (< 0.03%) Alloy. At concentrations < 0.03%, not enough C can precipitate as Cr carbide to sensitize. y e.g., g , type yp 304L. Get L-Grade or ELC alloys
Elimination of weld decay by type 304ELC. weld e d bead at bac back

N.B. N B Must take care to avoid C contamination during casting, casting welding welding, etc etc. Other Alloys and IGA Alloy with precipitated phases may also show IGA: Duralumin(um) Al Al-Cu Cu can precipitate CuAl2 and deplete Cu locally; Die-cast Zn alloys containing Al... IGA in steam, marine environments; Minor IGA effects in many Al alloys.

89

PRACTICE A B S Streicher C Huey y

TEST Oxalic acid etch Screening test Fe2(SO4)3 50% % H2SO4 65% HNO3

TEMP. Ambient Boiling Boiling 70C

TIME 1.5 m 120 h 240 h 4h

APPLICABILITY Chromium carbide sensitization Only (1.5A/cm2) Chromium carbide Chromium carbide and phase Chronium carbide in 316, 316 L, 317 and 317 L

EVALUATION Microscopic: classification of etch Structure (screening test) Weight loss corrosion rate Weight loss corrosion rate Corrosion ratio compared to solution annealed specimen

D 10% HNO3 Mod. Strau 3% HF 6% CuSO4 10% H2SO4 Metallic copper CuSO4 50% H2SO4 Metallic copper

E Strau

Boiling

24 h

Chromium carbide

Examination for fissures after bending

Boiling

120 h

Chromium carbide in cast 316 and 316 L

Weight loss corrosion rate

91

92

Source: http://www.sandvik.com

93

The filler metal is usually y of a different composition p than the base metal. Making the filler metal noble to the base metal will cathodically protect the weld. Oxidation and diffusion will lower the alloy. alloy concentration in weld, so filler metal should also h have higher hi h amounts t of f alloying ll i elements l t th than th the base metal.

In the Unmixed Zone, non-equilibrium cooling can cause potential problems:

Grain boundary segregation Primary phase structures Precipitation p of alloying y g elements

Prevention:
Pre and post heating avoids unequilibrium cooling

Stress Corrosion Cracking g Hydrogen Induced Cracking Crevice corrosion Intergranular g Cracking g
Sensitization from welding heat & stress Carbide C bid precipitation i it ti

Offshore Structure Weld Decay y Solar Power Plant Chloride Corrosion Gas Pipeline SCC Pipes Crevice Corrosion Chloride Stress Corrosion Cracking

Welded Steels Stress from sea and Corrosive Environment Problems

Weld decay Weld cracking Pitting

Painting Structure Better choice of weld material Cathodic Protection Zinc bar B tt welding Better ldi of f steels t l Better weld geometry

Material Selection: Ni Superalloy vs. vs Stainless Steel Aeration during Maintenance

Corrosion along pipe walls at welds due to Ch i d Chromium depletion l ti and d De-zincification

Stress Corrosion Cracking g

Caused by tough environment Operation O i of f lload d and d stresses Stress are either mechanical or chemical Mechanical Stresses: scratches, rivets, residual stresses Chemical Stresses: cracks cracks, corrosion in the media

Stress Corrosion Cracking g in weld

Stress cracks under operation. operation Cracking is longitudinal along the weld

Crevice Corrosion in Duplex p Steel Corrosion due to Heating Internal oxide layer created Crevice
Caused p pipe p to corrode and burst

Aggressive media increased corrosion

Crevice corrosion of socket weld at gap formed between type 304L pipe and type 316L valve

Use an oxygen-free yg backing gg gas to p prevent scale formation during welding Annealing Use specific filler metals
Increase in Ni increases resistance to SCC, but also

becomes brittle Find stability between heat and nickel concentration

34cm

810cm

Intergranular g crack p propagation p g in welded region g Stressed region Unprotected region to environment. Chlorine accumulation

High g chloride concentration found If compared to other parts of the sample there is no cracking Chloride enhances cracking mechanisms

Molten lead is held in thick steel pots during refining. In this case, the molten lead has attacked a weld in a steel plate and cracks have p Eventually, y the cracks p propagate p g through g the steel, and developed. molten lead leaks from the pot.
113

Materials Selection Weld Geometry

Effective Eff ti welding ldi mechanisms h i (h (heat t input, i t cooling li rate) t ) Cathodic Protection

Annealing De sensitizing stainless steel De-sensitizing

Supplementary technical requirements for the supply of components in 6% Mo Austenitic, 22% Cr Duplex and 25% Cr Super Duplex Stainless Steel Requires

Impact testing Hardness testing g Microstructure examination and ferrite phase balance (not 6Mo) Pitting corrosion testing (additionally, stress corrosion cracking for 25Cr if specified)
Base Metal: ASTM G48 method A test required for each lot. Test temperature shall be 122F (50C) and the exposure time 24 hours. hours Corrosion test specimens shall be at same location as those for tension tests. The test shall expose the external and internal surfaces in the as delivered condition (including pickling) and a cross section surface in full wall thickness. Weld Corrosion test shall be performed on one sample from each of the 3 and 6 oclock welding locations in accordance with ASTM G48 method A. A sample including the root shall be taken and be exposed to the solution. Test temperature shall be 104F (40C) and exposure time 24 hours. hours

No pitting at 20X magnification & weight loss shall be less than 4.0 g/m2.
115

Metallurgical g effects Geometrical effects

Preferential corrosion of HAZ Stress concentration at weld toe Creation of crevice due to joint design Temperature, conductivity, etc. SCC

Environmental effects

Metallurgical + Geometrical effects

More common in carbon and C-Mn steel than in higher-alloy higher alloy steels Tramline corrosion High conductive aqueous solution l ti pH below 7 and 8 (acidic mine water)

Seawater Higher tensile residual stresses allow corrosion to proceed slightly faster than in the less highly stressed t d steel. t l

Galvanic Corrosion

Occurs in ERW/HFI pipe Att k of Attack f seam weld ld line li in i aqueous environment i t or when h exposed to the water phase in a mixed-phase system due to fl conditions flow diti or water t d dropout t iin llow points. i t Unstable Inclusion (MnS) produced during the welding cycle. L S content, Low t t alloying ll i element l t such h as C Cu, REM
Galvanic corrosion (1 to 10 mm/y) Potential difference between 30 to 70mV, but high C/A area ratio

Highest g corrosion rate Shielded metal are electrodes using a basic coating In seawater, seawater a weld made using a basic basic-flux-coated flux coated consumable has a higher g corrosion rate.

In boilers and other vessels producing water at high temperature together with free alkalis (usually NaOH)
50 80oC Residual stress Local evaporation of water

can lead to high conc. of NaOH

PWHT Selection of appropriate materials or welding procedure d Alloying

When PWHT is impractical p Base metal (grooving corrosion) Make weld more cathodic to the adjacent base metal Residual stress relieving Reducing HAZ attack

Which is better, , a steel bolt in a brass structure, , or a brass bolt in a steel structure?
Steelboltinabrassstructure

Brassboltinasteelstructure

Smallbrasscathodewillcause smallincreaseincorrosionofsteel structure.Boltwillbeprotected fromcorrosionbycouplingtosteel. steel

Smallsteelanodewillsuffer largeincreaseincorrosiondue tocouplingwithbrassstructure.

 How to Select an Optimum Filler Metal Welding of stainless steel can cause sensitization and hence intergranular corrosion in heat affected zone (HAZ) As a filler metal, Select more resistive one to corrosion than base metal. (i.e., With higher Ecorr) (Small cathode large anode)

filler metal 308L SS (20Cr-11Ni) (20Cr 11Ni) 347 SS (18Cr-11Ni-Nb)

base metal 304L SS (18Cr-8Ni)

Premature weld failures in a 4 ASTM A53 pipe transfering a mixture of chlorinated h d hydrocarbons b and d water. t Welding electrode: E7010-Al

2 3 1 4 5 6 7

The most widespread p type yp is hydrogen y g induced SCC when H2S is present, particularly in acidic solutions (oil & gas industry) Sulfide Stress Cracking g( (SSC) ) Risk of cracking increases with the max. hardness.
Max 22 HRC (~ ( 248 HV) Alloy steel need to be PWHTed at a temp. exceeding

620oC.

Absorbent to remove acid gases containing t i i H2S and d CO2 in refinery (Amine gas treating) At all MEA conc. & below 55oC Tank, absorbers, carbon treater drums, skimming d drums and d piping i i SCC in vessels in age from 2 to 25 y. y No SCC in vessels PWHT stress relieved

Cross sections of pipe-to-elbow welds showing stress-corrosion cracks originating from the inside surface of the weld metal and the base metal

Boiler feedwater storage g tank made of CS Feedwater chemistry

Total hardness < 0.5ppm as

CaCO3 5 ppm filming amine corrosion inhibitor Chloride: 7 to 8 ppm Oxygen scavenger: NaHCO3 to storage tanks

No fault with the steel chemical composition or welding consumables No evidence of caustic SCC (branched IGSCC) Stress assisted localized corrosion Residual weld shrinkage stress (sometimes of YS magnitude) W ld iin deaerator Welds d t vessels l t typically i ll have h not tb been postweld t ld stress t relieved. li d

Cycling of heating and cooling during welding results:

Microosegragation g g Precipitation of secondary phases Formation of unmixed zones Recrystalization and grain growth in the weld heat affected zone (HAZ) Volatilization of alloying elements from the molten weld pool Contamination of the solidifying y g weld p pool

Corrosion resistance maintenance

Balancing alloy compositions to inhibit certain precipitation reactions Shielding molten and hot metal surfaces from reactive gases in the weld

environment Removing R i chromium-enriched h i i h d oxides id and d chromium-depleted h i d l t db base metal t lf from thermally discolored ( (heat tinted) ) surfaces Choosing the proper welding parameters

Main problem p
Precipitation effect Chemical Ch i l segregation i

Remedy
Control C t l of fb base metal t l metallurgy t ll Control of welding gp practice Selection of proper filler metal

Preferential attack associated with weld metal precipitates i it t (C (Cr- and d MoM rich i h phases). h )
-ferrite (transforms to brittle intermetallics to and )
500-850C & 650-950C

-phase (including and laves () phases) M23C6 carbides Small amount of M6C carbide Continuous intergranular phase networks of a phase reduce

th t the toughness, h d ductility, tilit and d corrosion i resistance i t of f ASS ASS.

Depletion of crucial alloying element concentration in the surrounding matrix. matrix

Voids where ferrite Has been attacked.

Preferential weld ferrite attack & less severe attack in the sensitized HAZ Acid cleaning of 304SS and 316SS black liquor evaporators in the pulp and paper industry with poorly inhibited HCl can lead to weld metal -ferrite attack.

In alloy depleted regions of weld metal austenite Moderately oxidizing environments Microsegragation or coring of weld metal dendrites Most likely:
In autogenous (no filler) GTA welding In 4 to 6% Mo alloys When the recommended filler metal has the same composition as

the base metal When higher-heat-input welding leaves a coarse microstructure with surface-lying dendrites. Such a microstructure is avoided by use of a suitably alloyed filler metal. metal

CPT vs. %Mo in 10% FeCl3.

Pitting of underalloyed (relative to the base metal) type 308L weld metal. The type 316L stainless steel base metal is unaffected ff t d Tap water environment

Defects such as:

Residual R id l welding ldi fl flux Microfissures, etc.

Especially p y in chloride-containing g environments Example

Slags from the basic- coated electrodes for out-of-position welding can be b diffi difficult lt t to remov

Crevice corrosion under residual slag (S) in IN-135 weld metal after bleach plant exposure.

Microfissure caused by thermal contraction stress during weld solidification When P & S content are higher (>0.015%) Hi h h t i t welding High-heat-input ldi

Microfissure corrosion on IN-135 weld metal on an alloy 904L test coupon after bleach plant exposure

Weld spatter is most troublesome when it is loose or poorly adherent.

Weld decay and methods for its prevention. The four different panels were joined by welding and then exposed to a hot solution of HNO3/HF. Weld decay decay, such as that shown for the type 304 steel (bottom right) right), is prevented by reduction of the carbon content (type 304L, top left) or by stabilizing with titanium (type 321, bottom left) or niobium (type 347, top right)

Selective attack of a type 317L stainless steel weldment and chloride stress-corrosion cracking of the adjacent 317L base metal. The environment was a bleaching solution (7 g/L Cl2) at 70oC

Chloride stress-corrosion cracking of type 304 stainless steel base metal and type 308 weld metal in an aqueous chloride environment at 95oC. Cracks are branching and intergranular

Welds in ASS (except for 310 and 310Mo) contain a small amount t of f -ferrite f it (usually ( ll lless th than 10%) to t prevent th hot t cracking during weld solidification. In hot, hot aqueous chloride environments environments, these duplex weldments generally show a marked resistance to cracking, while their counterparts crack readily. readily The generally accepted explanation for this behavior is that the ferrite phase is resistant to chloride SCC and impedes crack propagation through the austenite phase. Electrochemical effects may also play a part; however, however under sufficient tensile stress, temperature, and chloride conc., these duplex weldments will readily crack. crack

When the caustic concentration exceeds approximately 25% and temperatures are above 100 C Cracking occurs most often in the weld HAZ. 316L reactor vessel failed repeatedly by caustic SCC in 50% sodium hydroxide (NaOH) at 105 C (220 F). Failure was restricted to the weld HAZ adjacent to bracket attachment welds used to hold a steam coil. The stresses caused by y the thermal expansion p of the Nickel 200 steam coil at 1034 kPa (150 psig) aggravated the problem. It was recommended that the vessel be weld overlayed with nickel or that the existing vessel be scrapped and a replacement fabricated from Nickel 200 200.

Caustic SCC in the HAZ of 316L SSNaOH reactor vessel. Cracks are branching and intergranular

Found at
Cooling water system Aqueous waste treatment Groundwater left in new equipment or piping after hydrotest

Characteristics
Underdeposit corrosion (discrete mound) Subsurface cavities with minute pinhole penetration at the surface Natural, untreated water containing one or more culprit species of

microorganisms.

MIC of butt weld in water tanks

304L or 316L to resist HNO3 organic acid and to maintain p product p purity y Hydrotest with water containing 200 ppm chlrodie. No N drain d i of f piping i i after ft hydrotest h d t t Reddish brown deposit p and corrosion ( (& leakage) after 1 to 4 months a tiny mouth at the surface and a thin shell of metal t l covering i a bottle-shape b ttl h pit it that th t h had d consumed both weld and base metal.

Moundlike microbiological deposits along a weld seam in the bottom of f a type 304L stainless steel tank after several months of exposure to well water at ambient temperature

Moundlike microbiological deposits along a weld seam in the bottom of f a type 304L stainless steel tank after several months of exposure to well water at ambient temperature

Close-up of a wet deposit Deposit was slimy and gelatinous

Cross section through a pitted weld seam from a type 304L tank showing a typical subsurface cavity

Radiograph of a pitted weld seam in a type 304L stainless steel tank bottom

Well water: high g count of

Iron bacteria (Gallionella) Iron-manganese bacteria (Siderocapsa) No SRB & SOB

Corrosion products contain large amount of

Fe, Mn, Cl

Nearly all biodeposits and pits were found at the edges of, or very close l to, weld ld seams

Susceptible p to IGC and to embrittlement in the aswelded condition. Corrosion in the weld metal and HAZ together. together Initial attempts to avoid problems
Use of ASS filler metals Corrosion of HAZ

As welded type 430 stainless steel saturator tank used in the As-welded manufacture of carbonated water that failed after two months of service. The tank was shielded metal arc welded using type 308 stainless steel filler metal.

Micrograph Mi h of f the th outside t id surface f of f th the saturator t t t tank k showing intergranular corrosion at the fusion line.

PWHT at 785C for 4h restores weld area ductility y and corrosion resistance equal to that of unwelded metal. metal

Weldability Improvement Superferritic p SS

430- or 309 type filler metal High Cr-Mo-Fe Good mechanical condition Resistance to general, pitting corrosion and SCC
F Formation ti of f martensite t it eliminated li i t d either ith b by ultra lt purity it or b by stabilization with Ti or Nb.
Ultrapurity: (C+N) intrestitial < 150 ppm

Weld: corrosion-resistant, tough, ductile Immund to Cl Cl-SCC SCC

Chemical Comp. p
Cr: 25-28%, > 3% Mo, Ni 4% max. Ultrapurity: Ul i (C+N) (C N) intrestitial i i i l < 150 1 0 ppm

Proper welding procedure required.

Top view of a longitudinal weld in 6.4 mm ( in.) E-Brite ferritic Intergranular corrosion of a contaminated E-Brite ferritic stainless steel plate showing intergranular corrosion. The stainless steel weld weld was made with matching filler metal.

The distribution of austenite and ferrite in the weld and HAZ is known to affect the corrosion properties and the mechanical properties of d l stainless duplex t i l steels. t l
Low carbon content

Effect ff of ff ferrite-austenite balance on pitting resistance of f Fe22Cr-5.5Ni-3.0Mo-0.12N SS GTA welds

For balanced weld microstructure

Low carbon content (~0.02%) to minimize sensitization Addition of nitrogen (0.1 (0.1-0.2%) 0.2%) to slow the precipitation

Avg. ferrite content of weld should not exceed 60%.

Minimizing weld dilution dilution, especially in the root pass pass.

kinetics of Cr- Mo- segregate during welding and to enhance the reformation of austenite in the HAZ

Weld metal with a lower Ni content will have a higher ferrite content
Use enriched filler metal containing more Ni than base metal.

Good resistance to IGC

Effect Eff t of f welding ldi heat h t input i t on the th corrosion i resistance i t of f autogenous t gas tungsten arc welds in Ferralium alloy 255 (UNS S32550) in 10% FeCl3 at 10 C (40 F). The base metal was 25 mm (1 in.) thick.

High g arc energy: gy beneficial to p pitting g resistance

The presence of chromium nitride (Cr2N) in the ferrite

phase lowers the resistance to pitting of the weld metal and the HAZ in DSS

Microstructure of bead bead-on-tube on tube weld made by autogenous gas tungsten arc welding with an arc energy of 0.5 kJ/mm (13 kJ/in.). Note the abundance of chromium nitrides in the ferrite phase

Microstructure of bead bead-on-tube on tube weld made by autogenous gas tungsten arc welding with an arc energy of 3 kJ/mm (76 kJ/in.). Virtually no chromium nitrides are present, which results in adequate pitting resistance.

The SCC resistance of alloy y 2205 in aerated, concentrated chloride solutions is very good. The effect of welding on the SCC resistance is negligible from a practical point of view. In environments containing both hydrogen sulfide (H2S) and chlorides, the resistance of welds is almost l t as high hi h as f for th the parent t metal. t l I In thi this t type of environment. However, it is important to avoid too high a ferrite content in weld metal and the HAZ. HAZ

To improve p crevice and p pitting g corrosion resistance

1. 2. 3. 4. 5 5. 6. 7. 8. 9. 10. 11. 12.

R. Fernandez, E. Rege and M. Beatty, Weldment Corrosion. University of Berkeley D.H. Lister and W.G. Cook, Reactor Chemistry and Corrosion, Department of Chemical Engineering, University of New Brunswick. Brunswick R.J. Sinko, Corrosion Basics, AIChE, Jan. 21, 2009, http://www.tnengineering.net. D.R. Askeland and P.P. Phule, W H Weber W.H. Weber, Guided Wave Ultrasonics (GWUT) An Effective Screening Tool, Tool 40th Annual SIEO/NACE Winter Symposium 2005. N. Bailey, Weldability of Ferritic Steels, Abington Publishing, 1994. , , , 1997. C.G. Arnold, Galvanic Corrosion of Weldment, CORROSION/80, NACE Internatial, 1980. P.R. Roberge, g , Handbook of Corrosion Engineering, g g, McGraw-Hill, , NY, , 1999. T.G. Gooch and P.H.M. Hartt, Review of Welding Practices for Carbon Steel Deaerator Vessels, Paper no. 303, CORROSION/86, NACE International. http://en.wikipedia.org/wiki/Deaerator M.A. Streicher, Theory and Application of Evaluation Tests for Detecting Susceptibility to Intergranular Attack in Stainless Steels and Related AlloysProblems and Opportunities, Intergranulur Corrosion of Stainless Alloys, STP 656, American Society for Testing and Materials, 1978, p 70.

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