Pitting resistance Hastelloy

Ti
5 Intergranular Corrosion
Localized attack at and adjacent to grain boundaries with relatively little
corrosion of grains.
5.1 Characteristics
- caused by impurities at grain boundaries, enrichment of one of alloying
elements or depletion of one of these elements in grain boundary areas.
- ound in !l alloys containing e, "u, #g $ #n, some #g $ "u base
alloys, die cast %n alloys containing !l $ stainless alloys.
5.2 Mechanism
&n the case of s. s. ' impoverishment of "r in grain boundary areas.
(hen s. s. containing ) *.*+, " heated in temp. -**./**
*
", "r combines
with " forming "r
+0
"
1
.
- precipitates at grain boundaries.
- 2egions near 34s ' depleted in "r
- 4ecome anodic w. r. t. matri5
- 6ndesirable area ratio ' galvanic corrosion
7ensitization ' during welding. "orrosion ' weld decay. 2egion of weld decay
away from welded region ' temp. ' within pptn of "r
+0
"
1
range.
&3 corrosion ' also in stabilized s. s. ' containing 8b 90:;< or Ti 90+=<. 3reater
affinity for " ' form carbides ' preventing formation of "r
+0
"
1
. (hen heated in
sensitization range, "r
+0
"
1
forms. Happen during heat treatment or annealing of
welded structures. "orrosion ' thin line very near to welded zone. >nown as
>nife Line !ttack 9>L!<.
>L! is similar to weld decay ' both result from &3 corrosion ' both associated
with welding.
?ifferences are@
=.=>L! occurs in narrow band in parent metal immediately adjacent to
weld whereas weld decay ' appreciable distance from weld.
=.+>L! ' in stabilized steels
=.0Thermal history ' different
5.3 Prevention
0 #ethods ' to control &3 corrosion of austenitic s. s.
=. Amploying high temp. solution treatment ' Buench annealing or
solution Buenching
+. !dding elements ' strong carbide formers ' stabilizers ' 8b, Ti, etc.
0. Lowering " content to below *.*0, . 0*:L
To prevent >L! ' heat to about =*-*
*
" ' "r
+0
"
1
dissolves ' 8b" forms. 2ate of
cooling unimportant.
Ppt formed in !l based alloys ' "u!l
+
9duralumin ' !l."u<, e!l
0
, #g
-
!l
/
, #g
+
7i,
#g%n
+
, $ #n!l
1
7. Erosion Corrosion
!cceleration in the rate of deterioration on a metal because of relative movement
between a corrosive fluid and metal surface
7.1 Characteristics
"haracterized by appearance ' grooves $ waves ' e5hibits directional pattern
#any metals depend on a surface film for corrosion resistance ' !l, Pb, $ 7.7.
A.". ' when surface films are damaged or worn
#any types of corrosive media could cause e. c. ' gases, aBueous solutions,
organic systems $ liBuid metals.
7olids in suspension ' particularly destructive
!ll types of eBuipment e5posed to moving fluids subjected e. c. ' piping systems '
bends, elbows $ TsC valvesC pumpsC blowersC centrifugalsC propellersC impellersC
agitatorsC agitated vesselsC heat e5changer tubesC orificesC turbines bladesC nozzlesC
ductsC scrapersC cuttersC wear platesC grindersC millsC bafflesC and eBuipment
subjected to spray.
7.2 Factors
;.+.= 7urface films. 8ature and properties important
!bility to protect ' depends ' speed with which they form
. resistance to mechanical damage or
wear
. rate of reforming when damaged
8ature of protective film depends on environment
Tests on "u $ brass ' 8a"l ' with $ without D
+
"u ' attacked more than brass in D
+
saturated solution
"u ' covered with "u"l
+
4rass . covered with "uD ' greater stability
Ti 'reactive ' but resistant to e. c. ' stability of TiD
+
film
7teel tubes handling oils at high temperatures in petroleum refineries depend on
sulphide films.
(hen film . erodes, rapid attack
. becomes porous when cyanides are present.
Affective use of inhibitors ' depends on ' nature of films formed
7.2.2 Velocity. #echanical wear at high values ' particularly ' when solids
in suspension
Affect ' nil or increase slowly until critical velocity is reached and then increase at
a rapid rate.
&ncreased velocity ' increase or decrease attack ' depending on effect on corrosion
mechanism.
&ncrease attack on steel ' increasing supply of D
+
, "D
+
or H
+
7 or increase diffusion
by reducing thickness of stagnant film.
Eelocity can decrease attack and increase effectiveness of inhibitors by supplying
chemical to metal surface at a higher rate. 8a8D
+
is needed at high velocity to
protect steel in tap water.
Higher velocity ' decrease attack ' preventing deposition of silt o dirt ' crevice
corrosion.
7olids in suspension moving at high velocity ' scouring effect ' destroy surface
protection.
A.". studies of !l $ 7.7. in fuming H8D
0
. interesting results. !ttack on !l
increased $ attack on type 0:; 77 decreased as velocity was increased ' different
corrosion mechanisms.
ig. 0.:0 ' increasing attack on !l
&ncreasing velocity ' removes nitrate and o5ide films.
ig. 0.:/ shows decrease in attack on type 0:; 77.
6nder stagnant conditions, this steel attacked auto.catalytically because of
formation of formation of H8D
+
as a cathodic reaction product. &ncreasing velocity
sweeps away H8D
+
' thus, removes corrosive agent.
#any 77 ' strong tendency to pit and suffer crevice corrosion in seawater and
other chlorides. 7ome used successfully in seawater provided seawater is kept
moving at substantial velocity. This motion prevents formation of deposits and
retards initiation of pits.
7.2.3 ur!ulence
#any e. c. failures because of turbulence. Turbulence results in greater
agitation. #ore intimate contact. #ost freBuent e5ample ' inlet ends of tubing in
condensers and shell and tube heat e5changers. ?esignated as inlet.tube corrosion.
Type of flow depends on rate and Buantity of fluid handled and also geometry or
design of eBuipment. &n addition to high velocities, ledges, crevices, deposits,
sharp changes in cross sections and other obstructions, that disturb laminar flow,
may result in e. c. &mpellers and propellers ' operating under turbulent conditions.
;.+.: &mpingement
#any failures ' attributed to impingement.
A5amples ' elbow in steam condensate line
7team turbine blades
Antrainment separators
4ends, Ts, e5ternal components of aircraft, parts in front of inlet pipes
in tanks, cyclones.
7olids and sometimes bubbles in liBuid increase impingement effect.
;.+.- 3alvanic effect
3alvanic corrosion can influence e. c.
ig. 0.:/ ' attack on 0=1 ' nil in high velocity H
+
7D
:
' increased to very high
values ' when ' contact with Pb.
Eelocity changes can produce surprising galvanic effects. &n seawater at low
velocity, corrosion of steel not appreciably affected by coupling with 7. 7., "u, 8i,
or Ti. !t high velocities, attack is much less when coupled to 7.7. $ Ti, than when
coupled to "u or 8i. !ttributed to more effective cathodic polarization of 7.7. and
Ti at high velocities.
;.+.1 8ature of metal or alloy
"hemical composition, corrosion resistance, hardness and metallurgical
history ' influence ' performance under e. c. conditions.
"omposition largely determines corrosion resistance
&f active metal ' corrosion resistance ' ability to form and maintain protective film.
#aterial with better inherent resistance ' e5pected to show better performance.
A.g. /*, 8i'+*, "r superior to /*, e.+*,"r
8i."u better than %n."u
!ddition of third element ' often increases resistance ' produces more stable
protective film.
Thus, addition of e to cupronickel and #o to =/./ 9type 0=1<
7oft metals ' more susceptible ' subjected to wear
7ure method for good e. c. resistance ' solid solution strengthening. A.g. high 7i
9=:.-, 7i< iron ' most universally corrosion resistant of non.precious metal.
Hardening by heat treatment ' changes in microstructure ' heterogeneity '
decreases resistance to corrosion. Heterogeneity ' galvanic effect.
"ast iron ' better than steel ' in hot strong H
+
7D
:
. e ' corroded ' graphitized
layer ' graphite network and corrosion product ' protection.
7.3 Preventive measures
ive methods
=. material with better resistance
+. design
0. alteration of environment
:. coatings
-. cathodic protection
;.0.= 4etter materials
- represents an economical solution
;.0.+ ?esign
Life . e5tended or attack eliminated.
A.g.
=< &ncrease pipe diameter ' decreases velocity ' laminar flow
+< &ncrease thickness ' strengthens
0< &nlets and outlets ' stream lined
:< 2eadily replaceable impingement plates or baffles
-< &nlet pipes directed towards center instead of near its wall.
1< Tubes should be designed to e5tend several cms beyond tube sheet at
inlet end.
;< ABuipment should be designed so parts can be replaced readily.
/< #isalignment from one pipe section to ne5t can cause e. c.
;.0.: "oatings
- 2esilient barrier
- Hard facings
- 2epair attacked areas by welding
;.0.- "athodic protection
- reduces attack
" #tress Corrosion Crac$ing
- "racking caused by simultaneous presence of tensile stress and specific
corrosive medium.
#etal or alloy virtually unattacked ' fine cracks progress through surface
#etal or alloy virtually unattacked ' fine cracks progress through surface
"racking ' within range of typical design stress
A.g. 0*: 77 to boiling #g"l
+
' ig. 0.-:
"lassic cases ' season cracking of brass . ig. 0.--
. caustic embrittlement
of steel ' ig. 0.-1
8ot all metal.environment combinations susceptible ' Table 0.=+.
8o. of different environment in which a metal crack is small
&mportant variables ' temp., solution composition, metal composition, stress, and
metal structure.
".1 Crac$ mor%hology
. appearance of brittle mechanical fracture ' result of local corrosion
processes
. both intergranular and transgranular 9ig.0.-0< 7""
. 4oth ' in same alloy, depending on environment or structure
. 7uch transitions ' high nickel alloys, iron.chromium alloys and brasses
. cracking proceeds generally perpendicular to applied stress
. depending on metal structure and composition and environment
composition, crack morphology ' single crack to e5treme branching
".2 #tress e&&ects
. &ncreasing stress decreases time before cracking ' ig. 0.-F
. #inimum stress reBuired to prevent cracking depends on temperature,
alloy composition and environment composition
. !s low as =*, y.s. ' as high as ;*,
. #ostly tensile of sufficient magnitude
. ?ue to applied, residual, thermal or welding and corrosion products
".3 ime to crac$ing
#ajor physical damage occurs during later stages
!s cracks penetrate, cross sectional area reduced and final failure results
from mechanical action
igs. 0.1= and 0.1+
".' Environmental &actors
&n various aBueous media, liBuid metals, fused salts, and non.aBueous inorganic
liBuids
Presence of o5idizers ' influence
Presence of dissolved o5ygen or o5idizing species is critical ' cracking of
austenitic s. s. in chloride solutions
"haracteristic of crack producing environment ' alloy negligibly attacked in non.
stressed condition
7"" accelerated by increasing temperature
&n some systems, such as #g alloys, cracking occurs readily at 2T
&n others, boiling temperatures reBuired.
#ost alloys 'will begin cracking ' as low as =**
*
"
Affect of temperature ' cracking of austenitic s. steels ' ig. 0.1:
Physical state of environment also important
!lloys e5posed to single phase aBueous environment ' less severely attacked than
metals ' e5posed to alternate wetting and drying conditions
".5 Metallurgical &actors
7usceptibility affected b chemical composition, preferential orientation of grains,
composition and distribution of precipitates, dislocation interactions and progress
of phase transformation 9or degree of metastability<.
These factors further interact with environmental composition and stress to affect
time to cracking
"ommon observation ' for a specific composition ' minimum time to cracking
High strength !l alloys ' much greater susceptibility to 7"" in directions
transverse to rolling direction than in those parallel to longitudinal direction
?ue to distribution of precipitates ' from rolling
Pools of ferrite in austenitic matri5 tend to block progress of cracks
2esistance to 7"" ' increased by increasing amount of ferrite
".( Mechanism
"omple5 interplay of metal interface and environment properties
Possible processes@
"orrosion ' important part ' initiation of cracks
Pit, trench or other discontinuity ' stress raiser
7tress concentration at tip of notch increases as radius of notch radius of notch
decreases
7tress corrosion cracks ' start at base of pit
Dnce started, tip ' small radius ' stress concentration great
&f corrosion is also taking place ' reBuirement of high stress minimized ' crack
propagates ' faster rate
Plastic deformation ' occur ' region immediately preceding crack tip ' high
stresses
&f alloy metastable ' phase transformation 9austenite to martensite<
8ewly formed phase ' different strength, susceptibility to hydrogen or reactivity
&f alloy not metastable ' cold worked 9plastically deformed< region ' less corrosion
resistant than matri5 because of continuous emergence of slip steps
2ole of tensile stress ' rupturing protective films during initiation and propagation
of cracks
4reaks in passive film ' more rapid corrosion ' initiates cracks
2apid local dissolution without stifling ' for rapid propagation
&ntergranular cracking ' grain boundary regions ' more anodic ' precipitated
phases, depletion, enrichment or adsorption ' susceptible path for crack
!nother e5ample for local dissolution ' mild steel in nitrate solutions
&ron carbide is cathodic to ferrite
".7 Preventive measures
=< Lowering stress ' below threshold value. !nnealing ' residual stresses,
thickening the section, or reducing load
+< Aliminating critical environment species. ?egasification, demineralization or
distillation
0< "hanging the alloy. &f neither environment nor stress ' changed
:< !pplying cathodic protection. &mpressed current or sacrificial anode method
-< !dding inhibitor.
3 C)**)#I)+ *,E ME,#-*EME+#
"orrosion of metals in aBueous environments proceeds by electrochemical
processes
Alectrochemical measurements ' to measure corrosion rate
3.1 Potential Measurements
Alectrode potential recorded as a function of time
To interpret corrosion phenomenon
"onclusions@
=. &nitial shift in anodic direction ' start of anodic reactions as solution penetrates
pores or cracks in o5ide film
+. Passage of metal cations into solution at anodic points soon e5ceeds solubility
product of metal o5ide or hydro5ide within pores and results in precipitation within
pores
"auses general shift of corrosion potential in cathodic direction
0. Precipitation of hydro5ide is accompanied by a decrease in pH in the pores and
unless pores become completely sealed, metal starts to dissolve with the formation
of soluble products.
ilm breakdown and pitting attack follow and corrosion potential shifts in anodic
direction, then levels off
:. (ith stressed specimen, sharp anodic shift in potential corresponds to the
propagation of stress corrosion cracks through the specimen resulting in its failure
3.2 Potential an. Current /istri!ution Measurements
A5ploring solution in vicinity of cell with a pair of reference electrodes 9one
stationery< and a potentiometer
?isadvantages@
=. Laborious
:. 8eeds solutions of low conductivity
-. "an be applied to corrosion cells having distinct cathodic and anodic areas.
3.3Corrosion Current Measurement using *otating Electro.e Metho.
2otating specimen at a constant speed past a stationary reference electrode
held close to it
7tandard electrode probe is alternatively being closer to anodic area and
cathodic area producing a slight variation of potential in the lead wire
This variation is amplified and used to activate the vertical plates of
oscilloscope
Horizontal sweep of oscilloscope is synchronized with rotation speed of
specimen
(hen inhibitor concentration * ppm, several peaks indicating several anodic
areas
!t =+* ppm, attack at two points increased, at other places eliminated
Level trace at -** ppm
!lso used to determine intensity and distribution of corrosion attack by
scanning as it rotates
3.1 Polari0ation Measurements
(ith ' e5ternal circuit, . accelerate anodic reactions by shifting potential in
cathodic direction or accelerate cathodic reactions by shifting potential in
anodic direction
Plot between electrode potential and current density ' anodic polarization
curve ' former case and cathodic polarization curve in latter
Polarization behaviour ' studied either by galvanostatic or potentiostatic
method