8

4591
office of
Pipe 1 ine
Safetv
Techni cal Repor t No. OPS- TR- 71- 001 Oct ober 1971
n w s f f PG a ~ r o s 6 / , ~ ~
FERROUS PI PELI NE CORROSI ON PROCESSES,
DETkCTI ON, AND MI TI GATI ON
Pr epar ed f or
Of f i ce of Pi pel i ne Saf et y
Depar t ment of Tr anspor t at i on
Under Cont r act DOT- Ok- A9- 108 by
Mechani cs Resear ch, I nc.
9841 Ai r por t Boul evar d
Los A r r gel es, Cal i f or ni a 90045
Cont ent s of t hi s r epor t r ef l ect t he vi ews
of t he cont r act or , who i s r esponsi bl e f or
t he accur acy of t he dat a pr esent ed, and
do not necessar i l y r ef l ect t he of f i ci al
vi ews or pol i cy of t he Depar t ment of
Tr anspor t at i on. Thi s r epor t does not
const i t ut e a st andar d, speci f i cat i on, or
r egul at i on.
CONTENTS
CONTENTS
LI ST OF I LLUSTRATI ONS
LI ST OF TABLES
LI ST OF SYMBOLS
I . I NTRODUCTI ON
1. Pr ogr amObj ect i ves
2. Li t er at ur e Sur vey
3. Quest i onnai r e Met hods and Responses
4. Per sonal Cont act s
5. Out l i ne of Repor t
11. SUPWRY
1. Fact or s I nf l uenci ng Cor r osi on
2. Cor r osi on Cont r ol
3 . Const r uct i on, I nspect i on, and Mai nt enance
111. FORMS OF CORROSI ON
1. Basi c Cor r osi on Mechani sms
2. I nt er nal and Ext er nal Pi pel i ne Cor r osi on
3. Uni f or mCor r osi on
4. Pi t t i ng
5. Cr evi ce Cor r osi on
6. Gal vani c Cor r osi on
7. Cor r osi on by St r ay Cur r ent s and Hi gh Vol t age
Di r ect Cur r ent
8. Mechani cal St r ess Ef f ect s
Page
1
V
vi
i x
1
1
1
3
7
7
9
9
13
17
18
21
25
29
30
4 2
43
45
49
i
9.
10.
11.
12.
13.
14.
15.
16.
I ntergranul ar Corrosi on
I nfl uence of Temperature, Vel oci ty, and Ti me
Ef f ect of Sol utes
Underground Corrosi on
G as and Petroleum Corrosi on Ef f ects
Corrosi on i n Natural Waters
Bi ol ogi cal Ef f ects
Atmospheric Corrosi on
I V . CORROSI ON CONTROL
1.
2.
3 .
4.
5.
6 .
7.
8.
9.
10.
11.
12.
13.
Materi al Sel ecti on and Treatment
I nhi bi tors
Coati ngs: General Pri nci pl es and Surface
Preparati on
Pai nts
Metal Coatings
Organic Coatings
C er ami c and Concrete Coatings
Anodic and Cathodic Protecti on
Cathodic Protecti on of Coated Pi pel i nes
Standard C el l s and Potenti al s i n Cathodic
Protecti on
Measurements on Pi pel i nes under Cathodic
Protecti on
Protecti on Cri teri a Reported by Companies
Surveyed
Di scussi on of Cathodic Protecti on Cri teri a
V. CONSTRUCTION, MAI NTENANCE, AND I NSPECTI ON
1. Constructi on
Page
56
57
59
62
66
67
69
72
74
74
82
85
91
93
94
97
98
110
114
123
127
129
135
135
ii
. -
2 . Mai nt enance
3 . I nspect i on
VI . ECONOMI CS
VI I . OTHER PROBLEMS ASSOCI ATED WI TH CORROSI OI \ I OF PI PELI NES
1. Tr ai ni ng of Cor r osi on Engi neer s and Techni ci ans
2. I nt er f er ence wi t h Smal l Pi pi ng Syst ems
VI I I .
3 . Gr oundi ng of El ect r i cal Ci r cui t s on Wat er Pi pe
4. Mechani cal Damage t o Pi pi ng
5. I mpr oper U se of Cat hodi c Pr ot ect i on
GAPS I N THE TECHNOLOGY AND CONCLUSI ONS
Page
140
144
154
158
158
160
160
161
161
16 2
APP END I X
I . Exampl e Abst r act Ret r i eval Run
11. Quest i onnai r e
111. Al phabet i cal Li st i ng of El ect r ol ysi s or
Cor r osi on I nt er f er ence Commi t t ees
I V. Al phabet i cal Li st i ng of Or gani zat i ons and
Soci et i es wi t h I nt er est s i n Cor r osi on
and Cor r osi on Cont r ol
173
176
200
205
216 REFERENCES
i i i
L I ST OF ILLUSTRATIONS
Figure
1
5
6
7
Mixed Potential Diagram for Corrosion of Iron
(Schematic)
Cathodic Polarization Curve
Anodic Polarization Curve
Schematic Representation of the Underground
Corrosion Process
Mixed Potential Curve for Galvanic Corrosion of
More Noble Metal M Having Higher Rate of Cathodic
Reaction
Effectiveness of Cathodic Protection
Nomogram of Some Oxidation Potentials at 25OC
Page
23
25
26
34
4 4
112
120
V
LI ST OF TABLES
Tab l e Page
1 Key Wor d Code f or Comput er Ret r i eval of Cor r osi on
Li t er at ur e 4
Oper at i ng Responses 6
Most Pr eval ent Causes f or Cor r osi on Leaks 18
Measur ement s That Have Been Used f or I dent i f i cat i on
of Causes of Cor r osi on Leaks 19,
5 Most Pr eval ent Ci r cumst ances Under Whi ch Cor r osi on
Leaks of Coat ed Pi pe Have Been Found Dur i ng t he
Last 5 Year s 28
6 Number of Cor r osi on Leaks Occur r i ng i n 1969 at
J oi nt s and Wel ds 29
7 Some Oxi des, Sul f i des, and Sal t s of I r on Appear i ng
i n Cor r osi on Pr oduct s 35
8 Number of Cor r osi on Leaks That Have Been Caused
by Hydr ogen Bl i st er s and Cr acks 51
9 Mat er i al s Tr anspor t ed Whi ch Cause I nt er nal Cor r osi on
i n t he Pr esence of Fr ee Moi st ur e 66
10
11
12
Composi t i on of Seawat er 68
Compani es Exper i enci ng Bact er i al Cor r osi on 71
Maj or Ar eas of Cor r osi on Resear ch Engaged i n or
Sponsor ed by t he Oper at i ng Compani es 75
13 Met al Tr eat ment s I mpr ovi ng Resi st ance t o Gener al
Cor r osi on 78
14 Met al Tr eat ment s I mpr ovi ng Resi st ance t o Pi t t i ng
and Cr evi ce Cor r osi on 79
15 Met al Tr eat ment s I mpr ovi ng Resi st ance t o St r ess
Cor r osi on Cr acki ng 80
16 Met al Tr eat ment s I mpr ovi ng Resi st ance t o Hydr ogen
Ef f ect s 80
17 Met al Tr eat ment s I mpr ovi ng Resi st ance t o Sul f i de
St r ess Cr acki ng 81
vi
Page
Metal Treatments Improving Resi stance to I nter-
granul ar Corrosi on 81
Tab l e
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
Values of Material Parameters i n Equati on 11
from NBS Underground T est Data 81
Major Types of Protecti ve Coatings Used by Companies
During the L ast 5 Years by Order of U se 87
Factors Considered i n Sel ecti ng Coati ng Materi al s
and Wrappings f or Speci f i c Appl i cati on 88
Materi al s Currentl y Used to Coat Fi el d J oi nts
and Appurtenances 89
Number of Companies Favoring Di f f erent Gal vani c
Anodes 102
Performance of Galvanic Anodes 10 3
Types of Recti f i ers Used 10 4
Number of Generators i n U s e per Company 104
I mpressed Current Anodes According to Performance 107
Major Sources of I nformati on About the Presence
of I nterf erence Currents 108
Cri teri a Used to Determine When I nterf erence H as
Been Mi ti gated 10 8
Number of Corrosi on Leaks per Li near M i l e Occurring
i n 1969 f or Steel Pi pe 113
MaximumPi pe Potenti al or I nstantaneous Open
Ci rcui t Potenti al at the Recti f i er Locati on
Hydrogen and Oxygen El ectrode Potenti al s
115
117
Vol tage Values at Which the Companies Consider
Protecti on Has Been Achieved 127
Other Cathodic Protecti on Cri teri a Used by the
Companies 128
Normal Placement of Reference El ectrode 128
Condi ti ons Under Which Pl ant Applied Coatings
A r e Preferred 137
Page Tabl e
37
38
39
40
41
42
43
44
45
46
47
48
49
50
Condi ti ons Under Which Over-the-Ditch Applied
Coatings A r e Preferred
Standards and Speci f i cati ons f or Coatings
Fi el d Practices Used to Ensure Good Coatings
Methods Currentl y Used f or Attachi ng Conductor
to Pi pe
Methods Used to Repai r Corrosi on Leaks
Factors Taken I nto Consi derati on i n the Replace-
ment or Abandonment of Corroded Pi pe
Cri teri a f or Replacement of 12-I nch and Smal l er
Mains
Frequenci es of Survei l l ance Methods
Supplemental Observati ons on the I nspecti on of
Corrosi on Leaks
Underground Pi pe I nspecti on Report
Leak Repair Report
Publ i cati ons and I nformati on Sources Which Have
Been Found to Contri bute Most to Corrosi on
Control Programs
El ectrol ysi s or Corrosi on I nterf erence Committees
Organi zati ons and Soci eti es wi th I nterests i n
Corrosi on and Corrosi on Control
138
139
138
.
140
141
142
143
145
150
152
153
159
201
20 7
.
vi . i i
LIST OF SYMBOLS
Capi tal Letters
A =Amperes
A242 =ASTM standard f or hi gh strength, l ow al l oy
structural steel
A285 = ASTM standard f or l ow to i ntermedi ate strength,
low al l oy steel f or pressure vessel s
A517 =ASTM standard f or hi gh strength, low al l ay
steel s f or pressure vessel s
A = Exposed area i n square feet
AC =Al ternati ng current
Ag = Si l ver
AGA =American Gas Associ ati on
AI ME =American I nsti tute of Mining, Metal l urgi cal , and
Petroleum Engi neers
A I S1 = American I ron and Steel I nsti tute
A 1 = Aluminum
ApI =American Petroleum I nsti tute
A s = Arseni c
As203 =A rseni c tri oxi de
ASTM = American Soci ety f or Testi ng Materials
AWWA = American Water Works Associ ati on
B = Boron
BaS04 = Barium Sul phate
Br- = Bromide i on
C = Carbon
OC = Degrees centri grade
Ca = Aggressor concentrati on
Ca++ =Cal ci um i on
CaC03 = Calcium carbonate
Ca (HC03) = Cal ci um bi carbonate
Ca(N03) =Cal ci um ni trate
CaS04 = Cal ci um sul phate
Cd = Cadmi um
C1 = Chl ori ne
C1- = Chl ori de i on
C02 = Carbon di oxi de
CO, = Carbonate i on
-
C = Passi vator concentrati on
C r = Chromium
2-
Cr 04 = Chromate i on
Cu = Copper
P
CuS04 = Copper sul phate
DC = Direct current
DOT = Department of Transportati on
E = Potenti al (vol ts)
Eo = Standard hal f - cel l potenti al for uni t acti vi ti es of
reactants and products: functi on of temperature
= Corrosi on potenti al (vol ts)
Ecorr
EMF = El ectromoti ve f orce
F =Faraday's constant (96,500 coulombs/g. equi v. reacti on)
O F = Degrees Fahrenhei t
F = Fl uori de i on
. -
Fe =I ron
Fe ,Fe2+ = Ferrous i on
++
c
3+
Fe = Ferri c i on
FeC12 = Ferrous chl ori de (Lawrenci te)
Fe(OH)3 = Ferri c hydroxide
Fe203 = I ron oxi de (hematite)
Fe304 = I ron oxi de (magneti te)
Fe P = I ron phosphide
2
H = Hydrogen
H+ = Hydrogen i on
HC1 =Hydrogen chl ori de (hydrochl ori c aci d)
HCO; =Bi carbonate i on
-
HCr04 = Bi chromate i on
Hg =Mercury
HN03 =N i t r i c aci d
HS- = Bi sul fi de i on
HVDC = High vol tage di rect current
H2 = Hydrogen molecule (gas)
H2C03 = Carbonic aci d
H 0 = Water
H S = Hydrogen sul f i de
2
2
H2S04 = Sul phuri c aci d
H3B03 = Bori c aci d
I = I odi de i on
-
I -E Curves : = Current-potenti al plots
13 = Indium
= Current t i mes resiszance
J -55 =Al l oy tubi ng speci f i cati ons
K+ =Potassium i on
x a
Xa = Constant dependent on met al type
Kn =Constant dependent on aerati on of soi l
L i Cl =Lithium chl ori de
M =Metal
Mn+ =Metal i on wi th a posi ti ve charge of n.
Mg =Magnesium
Mg2+=Magnesium i on
MgC12 =Magnesium chl ori de
Mg(OH) =Magnesium hydroxide (Bruei te)
Mn =Manganese
Mo =Molybdenum
N =Normality of a SOlUtiOn
N =Ni trogen
N-80 = Alloy tubi ng speci f i cati ons
+
N a = Sodium i on
NaBr = Sodium bromide
NACE = Nati onal Associ ati on of Corrosi on Engi neers
NaCl = Sodium chl ori de (common sal t)
NaF = Sodium f l uori de
NaI = SQdium i odi de
NAPCA = Nati onal Associ ati on of Pi pe Coating Appl i cator7-
NBS =Nati onal Bureau of Standards
NH3 =Ammonia
NH4 =Ammonium i on
NH4N03 =Ammoniumni trate
+
NH40H =Ammoniumhydroxide
N i =Ni ckel
.
NO; =N i t r i t e i on
NO; = Ni trate i on
N2 = Ni trogen molecule (gas)
O2 =Oxygen mol ecul e (gas)
OD = Outsi de di ameter
OPS = Offi ce of Pi pel i ne Safety
OH- = Hydroxide
P = Phosphorous
Pb = Lead
P t = Platinum
R = Li near corrosi on rate (e.g., mpy)
R = Gas constant
Re = Rhenium
R = Pi tti ng rate
P
S = Sulphur
S+ = Sulphide i on
SCE = Saturated calomel el ectrode
SHE = Standard hydrogen el ectrode
Si = Si l i con
Sn = Tin
SO2 = Sulphur di oxi de
2-
SO4 = Sul phate i on
Sr++ = Stronti um i on
T = Absolute temperature
Ti -- Titanium
TB = Alloy tubi ng speci f i cati ons
U = Uranium
UK = United Kingdom
v = V o l t s
X i L i
Vm = Molar volume of the metal
Zn = Zinc
Zn++= Zinc i on
Small Letters
a =Acti vi ty, equal s concentrati on f or i deal mi xture
a = Equation constant dependent on al l oy
a4 - =Fourth power of the acti vi ty of the hydroxide i on
OH
a = Oxygen acti vi ti es
O2
aH =Hydrogen i on acti vi ty
b = Constant
cm2 = Square centi meters
cu = Cubic
-
e = El ectron
exp =e (base of natural l ogari thms) rai sed to the power
i n the parentheses
f t =Length i n feet
g = Gr ams
i = Current
i = Corrosi on current, amperes
corr
k = Equation constant
lb/A year = Pounds per ampere year
l og = Common l ogari thm (base 10)
2
m = Square met er
mA or ma =Mi l l i amperes
mi l s = Thousandths of an i nch
mm =M i l l i met er s
.
t
mpy = Thousandths of an i nch per year
mV = Mi l l i vol ts
n = Equati on constant dependent on aerati on of soi l
n = Number of el ectrons exchanged i n the anodi c corrosi on
reacti on
ohm cm = Resi sti vi ty - el ectri cal resi stance of a 1 cm-cube
of materi al
p = P i t depth
pH = Negative l ogari thm (base 10) of the hydrogen i on
pOH = Negative l ogari thm (base 10) of hydroxide i on
concentrati on
ppm= Parts per mi l l i on
psi = Pounds per square i nch
Greek L etters
a = Value of rl at current i = 1
u = Proporti onal to
3 = "Beta constant," Tafel constant, or Taf el sl ope
y-Fe 0 OH 0 = Gamma f erri c oxi de monohydrate
2 3 2
rl = Overpotenti al (devi ati on of potenti al from the
reversi bl e val ue)
8 = Ti me i n years
p = Soi l resi sti vi ty i n ohm-cm
SECTION I
INTRODUCTION
1. Pr ogr amObj ect i ves
The pur pose of t hi s pr ogr amwas t o det er mi ne t he cur r ent
st at e of t he ar t of cor r osi on of f er r ous pi pel i nes. Thi s i n-
cl uded cor r osi on mechani sms, f r equency and causes of cor r osi on
f ai l ur e, cor r osi on mi t i gat i on, cor r osi on det ect i on, and i nspect i on
and st andar ds. The pr ogr amgoal was achi eved by t hr ee separ at e
but i nt er act i ng pat hs: ( 1) a l i t er at ur e sur vey, ( 2 ) a quest i on-
nai r e, and ( 3 ) per sonal cont act s.
2. Li t er at ur e Sur vev
Emphasi s was pl aced on cor r osi on l i t er at ur e publ i shed bet ween
1945 and J ul y 1970. Onl y except i onal publ i cat i ons out si de of t hi s
per i od wer e ut i l i zed. The maj or sour ces of t he cor r osi on l i t er a-
t ur e wer e Bi bl i ogr aphi c Sur veys of Cor r osi on, Cor r osi on Abst r act s,
and Suppl ement s t o Cor r osi on Abst r act s, al l publ i shed by NACE
( Nat i , mal Associ at i on of Cor r osi on Engi neer s, Houst on) . Ot her
sour ces wer e sever al hundr ed books, t r ade and pr of essi onal
j our nal s, symposi a and r esear ch publ i cat i ons, and Cor r osi on Cont r ol
Abst r act s ( publ i shed by Sci ent i f i c I nf or mat i on Consul t ant s Li mi t ed,
London) .
Cor r osi on Abst r act s compr ehensi vel y cover 88 dom?st i c,
f or ei gn, and gover r . ment sour ces. Ti l e Cor r osi on Cont r ol Abst r act s
ar e a t r ansl at i on of t he Russi an abst r act j our nal Ref er at i vnyy
Zhur nal w' l i ch cover s about 800 wor l dwi de publ i cat i ons.
Appr oxi mat el y 90 per cent of t he wor l d' s cor r osi on l i t er at ur e
F rom 1945 t hr ough 1970 was cover ed i n t hese ser i es. Thi s amou. nt ed
to sorti ng through over 80,000 general cosmsi on abstracts and
papers. Approximately 32,000 of these wer e from forei gn sources.
Each abstract that was perti nent to thi s program was mounted on
separate sheets of paper, edi ted, and key word coded f or computer
retri eval . Thi s came to a total of 1826 abstracts. Approximately
35 percent of these appeared suf f i ci entl y i nteresti ng to warrant
detai l ed study of the ori gi nal works. I n those cases the abstracts
wer e f urther edi ted or enti rel y rewri tten, and subj ecti ve comments
wer e made i n the abstract and/or as part of the di scussi on i n the
body of thi s report.
.
The 1826 abstracts mentioned above were pl aced on magnetic
tape. Thirty-one percent of these wer e from forei gn j ournal s,
whi l e the remainder wer e from domestic sources. L i sti ngs of the
abstracts grouped by key words and i n numerical order are on f i l e
at OPS-DOT (Offi ce of Pi pel i ne Safety-Department of Transportati on).
Table 1 shows the key words (or key phrases) used! t o code or
cl assi f y the abstracts. The key word code, followed by the authors'
names, the l i terature reference and the abstract i tsel f , was then
keypunched on Hol l eri th cards. A l l of thi s i nformati on may be
recal l ed on command. Thus one may, f or example, recal l al l ab-
stracts deal i ng wi th anaerobi c-bacteri al -corrosi on of carbon-steel s
underground by aski ng the computer f or those key phrases. The
search f or these three key phrases i s found i n Appendix I . Any
si ngl e key word or combinations of keg words may be searched. I n
addi ti on, al l the papers wri tten by an author or groups of authors
can be recal l ed; f or example, al l the abstracts or papers wri tten
by Peabody can be recal l ed and pri nted out. Other key words
2
deal i ng wi th pi pel i ne corrosi on but not l i sted i n Table 1 may
al so be used to search f or abstracts.
The abstracts wer e numbered sequenti al l y as recei ved. The
ref erences i n thi s report use the same abstract numbers as the
l i terature search, e.g., (552) i s Reference 552 i n the l i st of
references.
A wide range of l i terature was uncovered. The l evel of pre-
sentati on vari ed the f ul l range from very el ementary to very ad-
vanced. Many, i f not most , of the papers wer e merely restate-
ments of what was al ready known. Numerous papers wer e cl earl y
sal es promotions f or one company's products or servi ces. Never-
thel ess, much new i nformati on has been uncovered which does not
yet appear i n any book. Thi s rej?ort emphasizes the new informa-
%i on that was consi dered i mportant.
3 . Questi onnai re Methods and Responses
The development and response of the corrosi on questi onnai re
was a si gni f i cant cooperati ve achievement of the operati ng i n-
dustry and the Offi ce of Pi pel i ne Safety.
I n the development phase, the enti re f i el d of underground
and underwater f errous pi pel i ne corrasi on knowledge was outl i ned.
From thi s was drawn a seri es of questi ons on i nspecti on, causes,
coati ngs, cathodi c protecti on, cathodi c protecti on cri teri a,
survei l l ance, control , maintenance, i nterf erence, and research.
The questi ons were chosen to supplement and. expand on the know-
,edge avai l abl e from the l i terature search. The questi onnai re
was then reviewed and expanded by a nvinber of i ndustry and govern-
Tental corrosi on committees and speci zl i sts. The reviews of the
TABLE 1
KEY WORD* CODE FOR COMPUTER RETRI EVAL OF CORROSION LITERATURE
-
CORROSION MECHANISMS HEMI CAL ENVIRONMENT ROTECT I ON YPE OF ARTI CLE
Corrosi on Mechani sms(gen)
Uniform Corrosi on oi l Resi sti vi ty
Gal vani c Corrosi on
Crevice Corrosi on
Pi tti ng Corrosi on
I ntergranul ar Corrosi on
Sel ecti ve Leachi ng
Stress Corrosi on ci ds - Low pH ( <7)
Corrosi on Fati gue l kal i es - High pH
Erosi on Corrosi on rgani cs, Petrol eum
Hydrogen Ef f ects
Bi ol ogi cal Attack (gen)
Anaerobi c Bacteri al nhvdrous Ammonia
dA
'7 1
rotecti on Methods (gen) Experi ment
athodi c Protecti on Seneral Revi ew or Book
ater i al s Sel ecti on Speci f i c Revi ew
oati ngs (gen) Theory
sphal t Coati ngs Acci dents
oal Tar Coati ngs Fi el d Experi ence
ax Coati ngs Rul es, L aws, Standards
l asti c and Other News Arti cl es
Organi c Coati ngs
Lhi n F i l m Coati ngs LOY BEI NG STUDIED
arbon Steel s
ast I rons
i l i con I rons
ure I rons
tai nl ess Steel s
Corrosi on
Aerobi c Bacteri al
Corrosi on
Fungal ani! Other
Mi crobi ol ogi cal l ogi cal Agents
Co r r o s i on
xternal Current
tray Currents
nodi c Protecti on
Testi ng
Data
Basi c El ectrochemi cal
f f ect of Vel oci ty
f f ect of Ti me
oi l Stress
*
Key words other than those l i sted may be Used to dcf l 2- ?.::e retri eval search area.
questi onnai re were constructi ve, and the cooperati on was excel l ent.
More than 92 i ndi vi dual s contri buted to the questi onnai re. A copy
of the 21-page questi onnai re i s contai ned i n Appendix 11.
The response of the operati ng i ndustry to the vol untary
questi onnai re was unprecedented for a nati onwi de survey. Si x
hundred questi onnai res wer e sent to the operati ng i ndustry. From
thi s 62. 1 percent, or 373 operati ng companies, responded. Ten
and seven-tenths percent of the corrosi on research organi zati ons
and 9. 6 percent of the corrosi on consul tants responded to the
questi onnai re. A total of 404 questi onnai re responses were
recei ved. Ei ghty-ei ght percent of the petrol eum companies, 59
percent of the gas operati ng companies, and 53 percent of the
water companies responded. The maj ori ty of the companies that
di d not respond wer e s mal l companies wi t?- a l i mi ted techni cal
staf f who f el t that they coul d not j usti f y the t i me and expense
to respond or that they di d rlot have the necessary corrosi on
knowledge.
The 373 operati ng responses wer e di vi ded as shown Ln Table 2.
The questi onnai re had two types of enswers, numeri cal and
essay. The numeri cal answers were coded and pl aced cn Hol l eri th
cards f or computerized anal ysi s. The computer tabul ated the
responses and pri nted a copy of the questi onnai re wi th answers.
A separate report Wac made f or:
e The 373 Operati ng Companies
e Consul tants
e Research Organi zati ons
e Other I nterested GroEps
C
TABLE 2
OPERATING RESPONSES
Operati ng Companies -
Gas Gatheri ng
Gas Storage A r ea Gatheri ng
Gas Transmission
Gas Di stri buti on
O i l Gatheri ng
O i l Transmission
Petroleum Product Transmission
Petroleum Product Di stri buti on
Water
Total
Number of Companies
32
18
63
159 .
13
28
31
1
28
373
-
0 Gas Gatheri ng
0 Gas Storage A r ea Gatheri ng
0 G as Transmission
0 G as Di stri buti on
0 O i l Gatheri ng
0 O i l Transmission
0 Petroleum Product Traxsmission
0 Petroleum Product Di stri buti Qn
0 Water
These reports are on f i l e at OPS-DOT. Except f or the expected
di f f erences related. to ,he materials transported, there wer e no
si gni f i cant vari ati ons i n the numerical responses of the separate
reports l i sted above. Therefore, the numeri cal resul ts of the
.
6
questi onnai re contai ned i n thi s report are the combined resul ts
of the 373 operati ng compani es. The occasi onal di f f erences i n
response of gas, oi l , water, gatheri ng, transmi ssi on, or di str i -
buti on compani es are noted.
All of the responses to each parti cul ar essay questi on wer e
pl aced together. Thi s permi tted a rapi d overvi ew of the responses
t o each questi on. Where appl i cabl e, the resul ts of the essay
questi ons were pl aced i n tabl es f or easy anal ysi s. Many of these
tabl es appear i n thi s report. Other i nteresti ng comments wer e
al so i ncl uded and are ref erenced by questi onnai re number, e.g.,
(QlOO). The combined essay questi ons and the questi onnai re
responses are on f i l e at OPS-DOT.
The 404 responses represent the experi ence and knowledge of
corrosi on control associ ated wi th 1,369,947 mi l e s of pi pe.
4. Personal Contacts
More than 96 corrosi on sci enti sts and engi neers from al l
over the Uni ted States wer e i ntervi ewed f or both f act and opi ni on.
L ocal and nati onal meeti ngs of WACE, El ectrochemi cal Soci ety, and
the Metal l urgi cal Soci ety 05 AI ME wer e attended.
5. Outl i ne of Report
The r esul ts of the l i ter atur e s i rvey, the questi onnai re, and
- - . he personal i ntervi ews wer e combined i nsof ar as possi bl e. The
stat? of the art of corrosi on of f errous pi pi p.g i s summarized anti
concl usi ons are gi ven i n Secti on I T. Hence, an overvi ew of t hi s
study can be obtai ned. by readi ng Secti on I and Secti on 11.
Current knowledge of the basi c forms of corrosi on i s outl i ned
i n Secti on I I I . Thi s starts wi th the basi c Isubrne-ged corrosi on
mechanisms, which lays the groundwork and expl ai ns the nomencl ature
f or understandi ng the vari ous forms and compl exi ti es of corrosi on.
The forms of corrosi on (uni form, pi tti ng, stray current, crevi ce,
etc.) are then di scussed i n some detai l . Next, corrosi on control
i s di scussed i n Secti on IV. Thi s i ncl udes material sel ecti on, i n-
hi bi tors, coati ngs, and cathodi c protecti on. Thi s and the fol l ow-
i ng secti ons are more appl i cati on ori ented and shoul d be under-
standabl e t o the begi nni ng corrosi on student.
Secti on V presents data on constructi on, mai ntenance, and i n-
specti on from the questi onnai re and the l i terature. The s mal l
amount of publ i shed i nformati on found on economics i s di scussed
i n Secti on V I . Secti cn V I 1 summarizes other probl ems di rectl y
rel ated t o corrosi on. These i ncl ude th.e trai ni ng of corrosi on
personnel , the use of yi pi ng as an el ectri cal grou.nd, mechani cal
damage t o coati ngs, and i nterf erence. Gaps i n the technol ogy
and the concl usi ons are l i sted i n Secti on V I I I .
Appendi ces I through I V , respecti vel y, present an abstract
retri eval run, the questi onnai re, a l i st of el ectrol ysi s or
corrosi on i nterf erence commi ttees, and: a l i st of organi zati ons
and soci eti es wi t h i nterest i n. corrosi on and corrosi on control .
SECTI ON I1
SUMMARY
1. Factors I nf l uenci ng Corrosi on
Under normal condi ti ons, metal l i c i ron i s unstabl e wi th
respect to formati on of i ts compounds. Thus f errous metals
corrode underground, i n the atmosphere, and i n natural waters.
Thi s does not necessari l y mean, however, that al l corrosi on i s
i ntol erabl y destructi ve. I t i s possi bl e f or corrosi on to take
pl ace at such a sl ow r ate that l eaks never devel op over the
usef ul l i f e of a pi pe secti on.
Real soi l and r eal engi nezri ng metal s are not homogeneous.
I f they were, corrosi on would general l y be uni form and negl i -
gi bl y sl ow. I n real si tuati ons, i nhomogenei ti es exi st and cause
di f f erences i n el ectri cal potenti al to devel op al ong the surf ace
ef a pi pe.
I ron di ssol ves at anodi c areas and l i berates el ectrons,
which fl ow through the pi pe and parti ci pate i n cathodi c re-
acti ons el sewhere. Such gal vani c cel l s ar i se parti cul arl y when
di f f erent metals are i n contact. For example, new steel pi pe
i s anodi c wi th respect to nl d rzsted pi pe and di ssol ves pre-
f erenti al l y. Contact wi th a nobl e met al suc5 as copper causes
steel t o corrode rap!-dly. Gal vani c concentrati on cel l s may al so
ari se from vari ati ons i n aci di ty, oxygen concentrati on, bacteri al
acti vi ty, etc., al ong a pi pe trench..
Seventy-si x percent of the companies surveyed rated gal vani c
cel l s as the most preval ent cciuse of corrosi on l eaks.
Steel pi pe sel dom f ai l s by uni form corrosj-c'?. I t f ai l s pre-
domi nantl y by l ocal i zed attack i n the form of pi ts. The pi ts are
i ni ti ated by some sort of i nhomogenei ty, as di scussed above.
Chl ori de i on seems to be parti cul arl y i mpl i cated as a causati ve
agent f or pi tti ng, as wel l as f or crevi ce corrosi on. Once
i ni ti ated, a pi t rapi dl y evol ves t o a f ai r l y stabl e confi gura-
ti on. Wi thi n the pi t, i ron di ssol ves to form f errous i ons,
xhi ch mi grate away and react wi th oxygen and water to form
vari ous hydrated oxi des i n the f or m of a sol i d crust. Cathodi c
reacti ons, such as reducti on of oxygen gas to hydroxi de i on or
reducti on of hydrogen i on to hydrogen gas, occur el sewhere on
the pi pe. The rusty scal e l i mi t s access of oxygen to the pi t,
whi l e negati ve i ons such as chl ori de are attracted by the l arge
number of posi ti ve f errous i ons l i berated. Such condi ti ons are
conduci ve f or f urther di ssol uti on, and so the pi t conti nues i ts
sel f - sti mul ated but control l ed growth.
The surveyed companies bel i eve stray current i s thei r second
most preval ent cause of corrosi on. Current fl ows through a pi pe-
lirre when in an el ectri c f i el d which i s present i n the soi l .
Metal di ssol ves rapi dl y where posi t:-ve current leaves the pi pe.
El ectri c rai l ways ~5 sti l l a major wourcp of di rect current Fn
the soi l . Al ternati rq current i r! power l i nes i nduces current
i n a paral l el pi pel i ne and, when recki f i ed, causes Corrosi on.
Cathodi c protecti an of nearby underground strcctures car.
cause current i nterf erence. Many measures can be taken t o
reduce thi s i nterf erence probl em, but there are sti l l i nstances
when the hi gh densi ty and
structures make avoi dance
arrangement OP underground met al
of i nterf erence nearl y i mpcssi bl e.
10
A major threat may be the use of hi gh vol tage, di rect current
power transmi ssi on. I t i s l i kel y that very l arge currents w i l l
at l east occasi onal l y be rel eased i nto the soi l . Research i s
under way to determi ne the magni tude of the hazard to pi pel i nes
and measures which can be taken to reduce corrosi on from thi s
source. The ef f ects can be appreci abl e and may, i n some cases,
requi re use of automati c cathodi c protecti on systems.
When hi gh strength steel s are subj ected si mul taneousl y to
mechani cal stress and to a corrosi ve envi ronment, cracks can
devel op very rapi dl y. The survey di d not show that thi s i s
a maj or cause of corrosi on, but it i s si gni f i cant i n that f ai l ure
i s apt t o be catastrophi c. The vari ous stress corrosi on cracki ng
mechanisms and phemmena are not w e l l understcod and are under
acti ve i nvesti gati on. A t thi s t i me the onl y reasonabl y sure
method f or preventi ng stress corrosi on cracki ng i s to avoi d
use 05 hi gh strength steel s. Hard wel ds shoul d a!.so be avoi ded
for thi s reason.
Twenty-two leaks wer e attri buked to hydrogen bl i steri ng by
the surveyed conpani es. Hydroqen i s generated bct h by corrosi on
i n an aci d envi ronment .and by cathodi c protecti Q9, especi al l y at
hi gh Foeenti al s. Metal s wi th voi ds and i ncl usi ons ar e parti cu-
l arl y suscepti bl e. I n-zeryranul ar corrosi on cf mar.y stai nl ess
steel s can be rapi d when the thermal cycl e cf wel di ng senerates
certai n types of i nhomogenei ti es.
Temperature i nf l uences corrosi on i r several ways; the net
ecf ect i s general l y f or corrosion -to acceL erat3 a.s temperatrre
i ncreases. A l so, stress corrosi on cracki ny has bee? fourld! to be
more common i n pi pe l eadi ng from compressor stati ons, presumabl y
because of the el evated gas temperatures generated by compressi on.
Corrosi on of steel buri ed i n permafrost soils, on the other hand,
has been found to be negl i gi bl e.
Uniform corrosi on tends to decrease wi t h t i me because of , the
i
presence of corrosi on products bl ocki ng access of corrodents. a
Pi tti ng and stress cracki ng, however, i ncrease wi t h t i me. The
corrosi on f ai l ure rate of unprotected pi pel i nes tends to i n-
crease exponenti al l y wi th t i me.
-
I n general , the most corrosi ve soi l s contai n l arge concen-
trati ons of sol ubl e sal ts and, consequentl y, have rel ati vel y l ow
resi sti vi ti es. On the other hand, the l east corrosi ve soi l s
usual l y have hi gh r esi sti vi ti es, i ndi cati ng l ow concentrati ons
of soluble sal ts. Soiis wi t h r esi sti vi ti es greater than about
5,000 ohm-cn can general l y be expected to be mi l dl y to non-
corrosi ve. I t shoul d be real i zed, however, that because many
other f actors may affect the corrosi on rate of metal , certai n
hi gh resi sti vi ty soi l s may be mor e corrosi ve than soi l s of
lower resi sti vi ty .
The pi tti ng rats cf netal buri ed i n soil >as beer, found to
i ncrease exponenti al l y as a f uncti on of soi l ;.erati on. The
Lower the amount of aerati on, the f aster ,he pi tti ng rate i n-
creased wi t h t i me.
Chl ori de i on i s known to accel erate cozrcsi on. Eydrogen
sul f i de accel erates corrosi on, and cag cause sul f i de stress
cracki ng. Carbon di oxi de pressures over 30 psi i n wet oi l and
gas cause corrosi on. The spl ash and ti dal zones i n E eawat er ere
12
the most corrosi ve mari ne envi ronment. Furthermore, cathodi c
protecti on i s i nef f ecti ve there.
I t i s known that products of mi crobi ol ogi cal metabol i sm
can accel erate corrosi on. Sul f ate reduci ng bacteri a cause IJ2S
formati on under anaerobi c condi ti ons and accel erate corrosi on.
The extent t o which mi cro-organi sms contri bute to pi pel i ne
corrosi on i s uncertai n. Very l i ttl e good f i el d data are
avai l abl e. There tends t o be a si gni f i cant pol ari zati on of
opi ni on on thi s subj ect.
I n the atmosphere, corrosi on i s accel erated by moi sture,
wind-blown sea sal t, sul f ur di oxi de, and to some extent, ozone.
The combined effect of di l ute sul f uri c aci d and ozone i s worse
than the sum of thei r i ndi vi dual effects.
2. Corrosi on Cont r ol
I t i s rarel y f easi bl e to compl etel y el i mi nate al l corrosi on
i n practi cal si tuati ons.
to an acceptabl e l evel f or the lowest cost.
The goal i s rather to bri ng corrosi on
Nearl y 3. 11 of the
companies surveyed had a corrosi on control program.
Al though no f errous metal i s untouched by corrosi on, the
extent of corrosi on i s si gni f i cackl y i nfl uenced by the exact
composi ti on of the met al and. by thermal and mechani cal trez-L-
ments. Welds ar e noted to be parti cul arl y suscepti bl e to
corrosi on. L nf Qrtunatel y, most of the addi ti ves which markedly
improve corrcsFon resi stance are probabl-y too expensi ve f or use
i n larce Fl pel i ne systems.
Al*:qougb most ccrrosi on occurs externaL l y, i nternal corrosi on
i s zl so a pr05l e~n wken m.oi sture and chl ori de i on, hydrogen sul -
13
f i de, or carbon di oxi de are present. Thi s has been control l ed
by removing moi sture (dryi ng the gas and oi l streams) , addi ng
i nhi bi tors, or coati ng. Proper i nhi bi tors are sel ected empi ri -
cal l y. I t i s i mportant to note that many i nhi bi tors accelerate
corrosi on if thei r concentrati on i s too l ow.
A wi del y used method of corrosi on control i s the appl i cati on
of coati ngs. Al though met al coati ngs are ef f ecti ve under some
condi ti ons, thi ck organi c coati ngs are general l y favored f or
underground use where protecti on i s requi red f or l ong peri ods.
.
These coati ngs are i deal l y wat er i mpervi ous, el ectri cal l y i n-
sul ati ng, and tough. General l y, ti ght adhesi on to the pi pe i s
al so requi red, al thol i yh good resul ts have been reported wi th
l oose f i tti ng pl asti c sheaths. The requi remeet for wat er
i mpermeabi l i ty i s probabl y even more severe when the coati ng
i s not bonded to the pi pe. 1.: shoul d be noted that no perf ect
coati ng materi al exi sts.
The most common ci rcumstance f or l eaks i n coated. pi pe was
physi cal damage cf the coati ng. The secord. most common ci r-
cumstance was corrosi o?. at i mproperl y appl i ed castings. M i c r s -
organi sms attac'c mosC,, i f not al l , organi c coati ngs. Theref ore,
one cannot assume f , F ~, t once 7 pi pe i s coated it yemains effec-.
ti vel y coated f orever. I nspcti on and repai r i s necessary LO':
onl y when l ayi ng p i p , but al so peri odi cal l y thereaf ter.
mai ntenance requi reyents are probabl y parti cul arl y severe when
cathodi c protecti on i s not employed si mul taneousl y.
The
Al though sel dom used f or pi pes carryi ng gas and oi l , concrete
coati -ngs can provi de ef f ectii-e corrosi on control . Cmcrete ' s
14
ef f ecti veness i s l argel y due to i ts hi gh pH. Agai n, proper
appl i cati on i s requi rec?, i ncl u?.i ng choosi ng the proper concrete
mix.
I n cathodi c protecti on, corrosi on i s reduce2 by making the
Bi pe negati ve wi th respect to the adj acent soi l . I t i s not a
panacea f or al l corrosi on probl ems. Nei ther i s the proper
appl i cati on of cathodi c protecti on a tri vi al mat t er . I ncreased
corrosi on due t o cathodi c protecti on has actual l y been observed
when steel was conti nuousl y or i ntermi ttentl y heated and i nter-
mi ttentl y wetted.
j ust downstream from compressor stati ons i n areas where the
soi l i s i ntermi ttentl y dry and wet . Cathodi c protecti on can
i ncrease the l eak r ate at f i r st , when appl i ed t o ol d pi pe, by
l ooseni ng the adherent rust scal e which previ ousl y covered
s3al l hol es.
externzl l y appl i ed DC power or by attachment of sacr i f i ci al
anodes, such as Yg, Zn, or A l , which are sl owl y consumed.
E i t ?er rnethod i s ef f ecti ve when properl y i nstal l ed and main-
tai ned.
Such condi ti ons would be expected on pi pes
Cathodi c protecti on may be accompl i shed ei ther by
I t may be possi bl e t o mai ntai n coati ngs to the extent that
adequate protecti on i s achi eved wi thout other measures.
the Zi f f i cul ty i n achi evi ng thi s l evel of mai ntenance has caused
many conpani es to suppl ement coati ngs wi th cathodi c protecti on.
O n the other hand, cathozi c protecti on used al one can general l y
provi de adequate protecti on, except that l arge currents are
requi red and i nterf erence wi th other structures that may be
near by i s l i kel y. Khen used wi th coati ngs, onl y enough current
Ilowever,
15
i s requi red t o protect areas where hol es have devel oped i n the
coati ngs. Thus, coati ngs and cathodi c protecti on are of ten used
i n c.onj uncti on. Even though the data from the surveyed companies
i ndi cated a lower corrosi on l eak rate w i t h coated and cathodi c-
al l y protected pi pe than wi t h unprotected pi pe, some l eaks di d
devel op on protected pi pes. Thus the control measures do not A
appear to be total l y ef f ecti ve. I n many cases, thi s may refl ect
i mproper use of ei ther coati ngs or cathodi c protecti on, or both.
U se of cathodi c protecti on and coati ngs together i s not
.
wi thout probl ems. Cathodi c protecti on may cause di sbondi ng of
the cocti ng. Cavi ti es under di sbonded coati ng are i deal f or
crevi ce corrosi on and mi crobi ol ogi cal corrosi on. To a l arge
extent, cathodi c protecti on i s i nef f ecti ve i n disbDnded areas.
Cathodi c protecti on i ncreases t5e pH i n the surroundi ng electro-
l yte, which damages many coati ng materi al s.
Cathodi c protecti on has bee? found to cause cal ci um carbon-
ate and magnesium hydroxi de deposi ts to form on steel i n sal t
wat er . These not onl y hel p protect the metal , but gradual l y
reduce the cathodi c pro5ecti on current as wel l . The best coat-
i ngs w~xe found to be formed at l ower current depsi ti es (.: 150
mA/sq f t ) ard t o consi st pri mari l y of calc:-um carbonate. One
can cause s i mi l ar i kposi ts to form on buri ed 2i pe by addi ng
calcium bi carbonaks to the backf il-1 and appSyi,:g cathodi c pro-
tecti on.
There appears to $e n- enti re- - y sati sf actory cri teri on f5r
veri f yi ng that cathcdic pr3z 2ctlor hi 2S been achieved. 2otei i ti al s
cannot be made too negaL ve D?- cr\z.-:ings are di sbonded. Most of
the companies surveyed used a pi pe potenti al of 0.85 volt rela-
ti ve to the copper sul f ate el ectrode as thei r cri teri on f or
cathodi c protecti on.
a 300-mV di f f erence between the energi zed and the ori gi nal
open ci rcui t potenti al s.
more than one cathodi c protecti on cri teri on.
The second most common cri teri on used was
Most of the companies surveyed used
Pi pel i nes passi ng under roadways are f requentl y encased i n
outsi de met al casi ngs. There i s evi dence to the ef f ect that
such casi ngs are unnecessary f or structural saf ety. Further-
more, when the metal casi ng becomes shorted t o the pi pe, cathodi c
protecti on is i nef f ecti ve. The companies surveyed had a total of
22, 669 casi ngs shorted to the carrier pi pe, Over 300 leaks wer e
reported i nsi de casi ngs f or 1969.
3. Constructi on, I nspecti on, and Mai ntenance
To ensure good corrosi on control , one must not onl y desi gn
the control systems properl y, but al so draw up detai l ed speci -
f i cati ons, i nspect the work, and peri odi cal l y mai ntai n the
system.
clamps to repai r at l east some of thei r l eaksp whi l e 5 4 percent
repl aced porti ons c+ the pi pe.
pi pe was the l eak hi story. The nost common annual survei l l ance
I rethod was a pi pe- to- soi l potc5nti al survey, whi l e the second
rest cc.mmon was l i ne cur r mt measurement. The 373 operati ng
companies reported 252,552 corrosi on .',eaks 6uri ncj 1969 f or
1, 369, 947 mi l e s of pi pe.
Si xty-one percent of the surveyed companies used
The Rai n cri teri orl f or repl aci ng
SECTION I11
FORMS OF CORROSION
1st 2nd 3rd 4th 5th 6th
Two hundred and f i f ty- three of the surveyed operati ng com-
pani es i ndi cated i n the questi onnai re that they determi ne the
probabl e type of corrosi on wi th regard t o corrosi on l eaks.
3 summarizes opi ni ons as to the most preval ent causes i n each
company.
Tabl e
*
i
7th 1 8th
MOST PREVALENT
0 :
(A) Gal vani c C el l
(B) Stray Current
i nterf erence)
(i ncl udi ng cathodi c
('C) Stress Corrosi on
Cracki ng
(D) Corrosi on Fatig1J .e
(E) Hydrogen Embri ttl e-
ment
(F: Causti c Embri ttl e-
w n t
( G) Mi crobi ol ogi cal
Corrosi on
(HI Other
*Unlessh otherwi se speci f i e
284"
19
3
4
2
0
7
11
3 7
I
18
lS0
17
1 -
-.. 3
0
3
3 2
2
num
--
unbe
?
4 b
-
21
17
3
3
33
12
z r s
--
of Conpani es
I I
0
4
I
l5 I
4
3
1
_-
l o
c
c.
--
onca
0
2
1
@
2
4
0
0 0
-
ned i n t
o i
0
0
0
4
1
2
0
0
0
1
7
1-
.
2
0
0
.
! tabi es
are the number of operati ng companies 3ut of the total 373 com-
pani es t hat responc?.e$ to t bat pax-titular cyuestion i n the questi orl -
nai re.
18
. ... .
Gal vani c cel l corrosi on was the mo s t preval ent cause accord-
i ng to 284 companies. Stray current was the second most preval -
ent cause f or 150 companies. For 19 companies stray current was
the major problem. Mi crobi ol ogi cal metabolism was apparentl y
a si gni f i cant cause f or corrosi on f or 30 percent of the companies
pol l ed. Many companies apparentl y f el t that stress corrosi on
cracki ng and corrosi on f ati gue wer e a preval ent cause, but onl y a
few l eaks due to stress corrosi on cracki ng and corrosi on f ati gue
have been reported.
Table 4 gi ves the suppl emental measurements that companies
heve used to i denti f y causes of corrosi on l eaks.
TABLE 4
MEASUREMENTS THAT qAVE BEEN USED FOR I DENTI FI CATI ON
OF CAUSES OF CORROSION LEAKS
--
Number of
C omp ani e s
(A) Coati ng Thi ckness 137
(E) Chemi cal Anal ysi s of Soi l 47
(C) Pi pe Potenti al 275
(D) Maximum P i t Depths at Adj zcent Corroded A r eas
Wi tbi n the Excava,",ion 187
(E) Metal l -urgi cal Ana.l yri s 46
(F) Redox Potenti al 9
(G) Soi l pF; 88
( H) Soi l Resi sti vi ty 2 3 0
:I) Qual i tati ve Fi el d Tes.1 f or Sul f i de I on 5c
;J > Potenti al or Current wi th Tespeet to Forei gn
Structure 219
19
There are two compel l i ng reasons f or studyi ng the under-
ground corrosi on processes. These are: (1) To def i ne the con-
di ti ons and consti tuents i n the soil whi ch contri bute to the soi l s
corrosi veness, and ( 2) To def i ne the reacti ons at and near the
met al surf ace so as t o provi de a theoreti cal basi s f or cathodi c
protecti on cri teri a to suppl ant the empi ri cal methods i n present
use.
-
Def i ni ti on of the soi l condi ti ons whi ch contri bute to corro-
si veness would make the soi l corrosi vi ty survey more posi ti ve i n
resul ts and of great economic val ue to i ndustry. However, onl y
a f ew of the operati ng companies i n the Uni ted States stri ve for
thi s obj ecti ve as shown by Tabl e 4 .
Many operators rel y upon soil resi sti vi ty as a measure of the
soi l s corrosi veness. Thi s i ndi cator i s i nadequate to compl etel y
def i ne corrosi vi ty. A neutral carbonate soi l would be rel ati vel y
l nnocuous compared to one cofi.taining sol ubl e chl ori des and sul -
fates at the same resi sti vi ty. Many s i mi l ar compari sons can be
made where r esi sti vi ty al one i s seen i;o be i nsuf f i ci ent i nforma-
ti on f or predi cti ng corrosi vi ty.
The pi pe potenti al ( Part C of Tabl e 4 ) , i ncl udi ng that wi t h
respect to nei ghbori ng pi pel i nes ( Par t J of Tabl e 4 ) , i s used ex-
tensi vel y t o f i nd the cause of corrosi on leaks. The nagni tude of
a steady potenti al can of ten detect lack of cathodi c protecti on,
*
sverprotecti on, gal vani z acti vi :y and cathodi c i nterf erence, .
Fl uctuati ng currents are hel pf ul i n di scoveri ng the source of
i nterf erence current.
1. B asi c Corrosi on Mechanisms
Corrosi on i s an el ectrochemi cal process wi th an anodi c re-
acti on as
Fe Fe2+ f 2e-
and such cathodi c reacti ons as
2H + 2e- H2, or (Eq. 2)
(Eq. 3 )
-b
O2 + 2H20 + 4e- +40H-
Once formed, the Fe2+ i s not normal l y stabl e, but reacts wi th oxy-
gen and water to form magneti te, Fe304, or hemati te, Fe203*3H2.
Thi s l atter compoundl both dehydrated and vari ousl y hydrated, i s
cal l ed rust. The equi l i bri um exi sti ng between i ron and i ts corro-
si on products may be found by thermodynamic cal cul ati ons. The
resul ts are presented i n the form of phase di agrams, of ten ref er-
red to i n corrosi on theory as Pol xbai x pl ots.
I t i s general l y thought that l ertai n regi ons on a gi ven pi ece
of steel are anodes whi l e other parts are cathodes. These regi ons
pay be mi croscopi cal l y near one another or very f ar apart. Micro-
el ectrode experi ments have confi rmed that some regi ons are pri mar-
i l y anodi c and. others are cathodi c ( 779) .
I n recent years, mclch attenti on has been devoted to uncover-
i n.5 the reacti or. nechani sns at the el ectrodes, si nce the above re-
acticrls are merel y what i s external l y observed and tel l nothi ng
zbout the vari ous steps i wol vec! (758, 760, 761, 766-768). Even
WithoLt thi s detai l ed cnowledgc, howeiwr, one can prof i tabl y make
use ;f the concepts of el ectrci e ki neti cs. I n corrosio:, thi s
takc.c; the form of mixed potenti al th2ory (763). Consi der the re-
ac:!-on of Equati on 1 taki nc pl ace 3.t an el ectrode. El ectroas are
21
bei ng l i berated at the metal surf ace whi l e posi ti ve i oni c current
flows i nto the el ectrol yte. As the el ectrode i s made more posi ti ve,
the rc:acti on r ate i ncreases as shown i n Fi gure 1. Soon, however,
i ron passi vates and the reacti on rate decreases.
tenti al s agai n cause the current to i ncrease. Passi vati on resul ts
from the formati on of a sol i d f i l m at the metal surf ace which
i nterf eres wi t h i on and el ectron f l ow.
Very hi gh po-
On the other hand, the i ron can al so serve as an el ectrode
f or a cathodi c reacti on, such as Equati on 3 . For t hi s reacti on,
the rate i ncreases as the surf ace i s made more negati ve. I f , as
i s usual , the metal surf ace has both anodi c and cathodi c regi ons,
then both reacti ons proceed si mul taneousl y. I f no external source
or si nk of el ectrons
must be equal at the
The l i near corrosi on
i V
corr m
nFA
R =
i s avai l abl e, then the rate of both reacti ons
poi nt where the curves i n Fi gure 1 cross.
ri te, R, is rel ated to thi s i ntersecti on by
where icorr i s the corrosi on current, (gLvep by the i ntersecti on
of curves i n Fi gure 1), Vm is the molar volume of the met al , n i s
the number of el ectrons zxchanged i n tho anodi c corrosi on reacti on
( two i n Equati on 11, F is Faraday's constant and A i s the surf ace
area of the met al . I n the case of several si mul taneous anodi c
reac-ci ons, the I-E curves for each are added and the system agai n
3perates at the i ntersect:-on of the curves.
The ori gi ns of the anodi c a d cati i odi c curves ?.re the poi nts
at whi ch fqrward and reverse reacti ons are taki ng pl ace at equal
vel oci ti es !-.e., equi l i bri um for that parti cul ar reacti on. The
22
I
I
i corr
LOG CURRENT
Fi gure 1. Mixed Fotenti -a1 Diagram f or Corrosi on of I ron
(Schemzti.,-)
potenti al s at those poi nts are gi ven by the hal f - cel l potenti al ,
whi ch, usi ng Equati on 3 as an exampl e,
may be gi ven by the fami l -
i ar Nernst Equati on of ckerni czl thermodym.mics,
where Eo i s the standard hal f-cel l potenti al f or uni t acti vi ti es
of reactants and products, R i s the gas constant, T i s absol ute
temyj erature, n i s the number of el ectrons i n the reacti on
(f our
f or thi s exampl e), F i s Faraday's constant, and the a' s are acti v-
i ti es, which equal concentrati ons f or i deal mi xtures. Note the
concentrati on of reactants i nf l uences the potenti al at the ori gi ns.
The mixed potenti al theory i s not onl y usef ul conceptual l y,
but al so provi des the basis for i nstantaneousl y measuri ng corro-
*
si on rates and studyi ng electrode reacti on mechanisms. An exter-
nal potenti al i s appl i ed and the current measured. The current
observed w i l l actual l y be the di f f erence between the two curves
of Fi gure 1 at some speci f i ed potenti al . Thus, potenti al and
current measurements of the system shown i n Fi gure 1 would yi el d
the cathodi c pol ari zati on cur-J e of Fi gure 2 and the anodi c pol ar-
i zati on curve of Fi gure 3 .
K i neti c studi es ha.ve shown that severa.1 steps are i nvol ved i n
net cathodi c an2 net anodi c reacti ons, Theoreti cal l y, when one
step control s the rate of an el ectrode process,
the ki neti cs
follow the T af el equatj -on (766, 765),
T- I = a - + @ I n i (Eq* 6)
where q i s the over:potectia?- I deviatio,? of potenti al f r om the
reversible val ue), 3 i s <;he val ue of q at current i = 1, and f3 i s
the "beta constant, "Tzfe.?.. constan", ' I or "Tafel sl ope. T hi s
equati m i mpl i es a s'xai gh+ l i np v i sFnilogarithmic pl ots as i r
porti ons of the curves of Fi gure 1.
effects of varyi ng sol ute concentrati ons permi t deducti ons about
Measurements of 6 and the
mechanisms of reacti ons at electrodes.
24
-.I
a
I-
Z E
W cor r
I-
O
a
-
I
I
icorr
LOG CURRENT
Fi gure 2. Cathodic Pol ari zati on Curve
Corrosi on engi neeri ng and sci ence now uti l i ze a wide vari ety
of experi nental techni ques i n addi ti on to pol ari zati on studi es.
These range from simple pi t depth, l oss i n wei ght, and thi ckness
measurements to very sophi sti cated methods such as el l i psometry,
el ectron di ffracti c.!n, radi otracers, and the use of the el ectron
microscope (688).
2. I nternal and External Pi pel i ne Corrosi on
The bz-i c mechanisms f or corrosi on are the same f or i nternal
and extes, 11 cor;ITasion, al though t i l e _ environments are qui te
di f f erent. I n nost i nstances, the exteri or environment i s much
more corrosi ve Clan the i nteri or, which i s f ortunate because
corrosi on mi ti gati on i s much si mpl er on the outsi de.
Roughly 75 percent of the gas transmi ssi on l i nes i n the United
States wer e surveyed duri ng the peri od from 1 J ul y 1967 to 30 J une
2 5
' c on
LOG CURRENT
Fi gure 3 . Anodic Pol ari zati on Curve.
1968 50 determi ne causes of pi pel i ne f ai l ures; the survey covered
30th preservi ce tests and i nservi ce operati onal f ai l ures (586).
The pri mary cause of test f ai l ures was the l ongi tudi nal weld,
:..-hereas external dar.?.;e (bul l dozer, di tcher, etc .) was the pr i me
cau.se i n operati onal f ai l ures, wi t h corrosi on and the l ongi tudi nal
weld as the next most frequent causes. A number of f ai l ures i n
ol der, uncoated l i nes or poorl y coated l i nes wer e found to have
occnrred as a resul t of external corrosi on. I n these f ai l ures,
c
t
- r
r >- -
the wal l thi ckness i s gradual l y reduced t o the poi nt at which
f ai l ure resul ts. Hydrogen cracki ng i n hard spots i n the pi pe
w al l wer e found t o have caused f ai l ures af ter the pi pe had been
i n servi ce f or 2 t o 15 years. Hard spots are l ocal i zed hard re-
gi ons, usual l y wi th hardnesses i n the range of Rockwell C 39 t o
51, that have ranged f r om about 2 to 10 i nches i n di ameter i n the
base metal. Stress- corrosi on cracks i n mo s t i nstances wer e found
i n areas that wer e essenti al l y f ree from both pi tti ng corrosi on
and general corrosi on. A few f ai l ures from hydrogen bl i ster s
wer e found i n gatheri ng l i nes contai ni ng sour gas. Fai l ure can
occur from formati on of a bl i ster on ei ther the i nsi de or outsi de
sarf ace of the pi pe resul ti ng from generati on of atomic hydrogen
i n the attack of the steel by the H2S and moi sture i n the sour
gas. L ongi tudi nal weld f ai l ures i n servi ce pi pe were found t o
have resui ted frcm sel ecti ve corrcsi on and hydrogen cracks i n hard
regi ons.
Tabl e 5 i ndi cates the most preval ent ci rcumstances under which
corrosi on l eaks of coated pi pe have been found by the 373 operat-
i ng companies duri ng the l ast Si ve years. A s may be seen, the
most preval ent causes of l zaks are at l ocati ons of external damage
and i mproperl y appl i ed coati ng, i rregardl ess of whether the pi pe
i s cathodi cal l y protected or - ot.
Tabl e 6 l i sts the nurnbe.: 02 l eaks i n .'369 that occurre2 at
j oi nts and wel ds. For ex3mple. ei ght companies had one cr two
compressi on coupl i ~z~ l eaks whereas 20 companies had over 1-5 .'_eaks.
The companies wi th over 15 l eaks general l y hsd B def i ci ent pi pi ng
system wi th many l eaks at the j oi nts. W i t ? t'?e 2xrl epti on of a
2 '7
TABLE 5
MOST PREVALENT CIRCUMSTANCES UNDER WHI CH CORROSION LEAKS OF COATED
PIPE HAVE BEEN FOUND DYJ KING THE LAST 5 YEARS
II_ .-
Order of Frequency
--1_1_
Cathodi cal l y Protected
1st 2nd 3rd 4th 5th 6th
Number of Companies
(A) Corrosi on at I mproperl y Appl i ed Coati ng 55 56 20 4 4 1
Constructi on or Subsequentl y Abraded by Others 81 35 15 5 5 0
N Root Growth 4 22 23 15 13 2
(D) Corrosi on Beneath Unbonded Coati ng 13 22 28 16 6 1
(E) Fai l ure of the Coati ng Material 12 13 13 11 12 1
(B) Corrosi on Where Coati ng H as Cl earl y Been Damaged During
(C) Corrosi on Where Coati ng I s Ruptured by Soil Stress or
0)
N o t Cathodi cal l y Protected
1st 2nd 3rd 4th 5th 6th
Number of ComDani es
(A) Corrosi on at I mproperl y Appl i ed Coati ng 43 65 28 6 2 1
(B) Corrosi on Where Coating H as Cl earl y Been Damaged During
Constructi on or Subsequentl y Abraded by Others 108 42 17 2 0 0
(cj corrosi on Where Coatirig 1s Ruptured by Soi l Stress or
Root Growth 8 19 18 21 15 1
(Dj Corrosi on Beneath Unbonded Coati ng 5 -10 36 23 11 1
(E) Fai l ure of the Coati ng Material 11 18 15 12 11 1
TABLE 6
NUMBER OF CORROSI ON LEAKS OCCURRING I N 1969 AT J OI NTS AND WELDS
J OI NTS
Number of Leaks
1- 2 3-4 5-6 7-15 over 15
( A) Compression Coupl i ngs 8 6 12 11 20
(B) Threaded Coupl i ngs & Fl anged J oi nts 19 11 3 26 33
(C) Other 5 4 2 3 15
WELDS
Number of Leaks
( A) L ongi tudi nal Factory Welds
8 4 4 2 12
(B) Spi ral Factory Welds
0 0 0 0 2
(C) Fi el d Welds
6 9 3 0 27
few exi sti nq pi pi ng systems, the l eaks at. j oi nts and wel ds are
i nsi gni f i cant when compared to $he total number of l eaks.
3. Uniform Corrosi on
Uniform removal of met al i s the l east troubl esome of the
vari ous forms of corrosi on. However, it i s the easi est form of
corrosi on to study, and as a resul t much of our fundamental know-
l edge of corrosi on comes from reFearch on uni form corrosi on
processes. For exampl e, the uni form corrosi on rate i s what one
determi nes di rectl y from pcl ari mt:-on studi es ( 7, 537) Errors
can ari se, however, i f another e.-odic reacti m i s of conparabl e
magni tude t o the met al rernovE1 reactl or.. Thi s has ari sen, for
exampl e, Zrom the oxi dati on c.5 hydrogen under pressure (hydrogen
exchange! ?wi ng corrosi on i n a seal ed actocl ave (547). Corrosi on
current \&73s 9.8 t i mes the actual zorrosi on rate. Cathodi c pol ar-
2 3
i zati on studi es of i ron i n one normal hal ogen aci d showed the
hydrogen coverage t o be near one monol ayer at the corrosi on poten-
ti al (153). Thi s seems to i ndi cate that nearl y the enti re i ron
surf ace f uncti ons as a cathode duri ng corrosi on and that onl y a
s mal l part of the surf ace undergoes di ssol uti on at any gi ven t i me.
Radi otracer studi es of i ron i n water reveal ed that no corrosi on
takes pl ace i f oxygen i s excl uded and that negl i gi bl e exchange
of i ron atoms wi th the sol uti on takes pl ace (265).
Af ter a f i l m was formed on i ron i n wat er contai ni ng oxygen,
the Taf el porti on of the pol ari zati on curve was found to change
i n sl ope ( 6 decreased) as the f i l m thi ckness i ncreased (235).
For thi n f i l ms it was concl uded that the charge passed was used
FYI the formati on of i ron-i on vacancy-el ectron pai rs and f or
transf er of oxygen frorn the sol uti on to the outer l ayer of the
oxi de. The f i el d dri ves i ons through the l ayer ( 4 7 8 ) . I n the
transi ent state there i s a nonzero charge di stri buti on i n the
l ayer which sl owl y decays when steady state current i s restored.
(Thi s may be rel ated to the ef f ect of AC on corrosi on.)
been suqgested that the f i l m conti nuousl y di ssol ves and so must be
regenerated to mai ntai n passi vi ty ( 692) . The ef f ects of compl exi ng
agents, potenti al s, i nhi bi tors, and doubl e l ayer on corrosi on wer e
I t has
expl ai ned by thei r i nf l uence on di ssol uti on of the f i l m.
4 . Pi tti ng
(.
Steel pi pe general l y does not f ai l by uni form corrosi on. I t .
f ai l s predomi natel y by l ocal i zed zttack i n the form of pi ts.
P i t s appear to be i ni ti ated wheP l ocal penetrati on of the surf ace
f i l m occu.rs on steel general l y prDtected by the f i l m. That i s,
it i s a form of attack i ntermedi ate between general attack and
compl ete passi vati on. When the f l ui d i n a pi pe i s under pressure,
a pi pe may possi bl y f ai l by f racture before the pi t compl etel y
penetrates the wal l (598).
Most pi tti ng appears to be associ ated wi t h chl ori de i ons.
Bromi de and hypochl ori tes cause pi tti ng, whi l e f l uori des and
i odi des have l i ttl e ef f ect. Cathodi c reacti ons occur on the sur-
face of the steel , whi l e anodi c di ssol uti on takes pl ace i n the
pi t. Thus, an excess of posi ti ve charge i s produced i n the pi t ,
which attracts the negati ve chl ori de i ons ( 769) . I t has been
cl ai med that pi tti ng i s more severe on the top si de of pi pe than
on the bottom because the sol uti on i n the pi t s i s heavi er thar!
the surrcmndi ng el ectrol yte ( 769) ; however, anal yses of extensi ve
f i el d experi ence on buri ed pi pel Fnes have shown that pi ts occur
more of ten on the bottom of pi pes. T hi s As attri butabl e to
several factors -- a hi gher sal t concentreti on and moi sture con-
tent at the bottom because of drai nage and- because the soi l i s
packed more ti ghtl y there, and a l ower oxygen concentrati on be-
cause of the greater di stance f r om the sci l surf ace. T hi s offers
one expl anati on :or pi t i ni ti ati on on pol ycrystal l i ne steel sur-
faces. Commonly, pi t s appear to be pref erenti al i n l ocati on and
di recti on, probabl y fol l owi ng vei c? of hi gh i mpuri ty content i ntro-
dxee duri ng casti ng, rol l i ng, etc. Skce pi tti ng i s a stati sti -
cal phenomenon, %he maximum pi, Cepth ircrpases as the surf ace
ares of .?he sample i ncreases, of ten bel -9 Dzoporti onal t o the 0.15
pwe r ~f the area ( 657) .
I t has been found i n pol ari zati on studi es that when potenti al s
on passi ve surf aces are l owered, a poi nt i s reached where the
current rapi dl y i ncreases. T hi s has been i nterpreted as due to
i ni ti ati on and autocatal yti c growth of pi ts. The breakdown po-
tenti al has been cal l ed the "cri ti cal " or "pi tti ng" potenti al ,
wi th the suggesti on that pi tti ng does not occur at more acti ve
(negati ve) potenti al s. Thus, measurements of pi tti ng potenti al
have been employed to compare pi tti ng tendenci es of metals and
el ectrol ytes (e.g., 154, 772, 285). However, thi s procedure, and
i n fact the whole concept, has recentl y been severel y cri ti ci zed.
I n one paper it was concl uded that pi tti ng potenti al i s rel ated
to pi tti ng, but questi oned that it i s a basi c characteri sti c of
t3e al l oy (770). I t was found that the rate of potenti odynami c
scanni ng and t i me of hcl di ng Zuri ng potecti ostati c pol ari zati on
have a marked effect on the measured val ue of cri ti cal potenti al .
It has been found thak the rates and types of corrosi on of stai n-
less steel i n chl ori de media were qui te di f f erent f or control l ed
potenti al corrosi on tests than wi t h conventi onal corrosi on tests
under i denti cal condi ti ons of concentrati on, temperature, and
potenti a?. (771). The electrochemical tests more of ten produced
pi tti ng. These resul ts wer e attri buted to the mi grati on and
surZace accumul ati on of C1- duri ng potenti al measurements.
Consi derabl e evi dence has been accumul ated to show that
chl ari de i on causes breakdown of the passi ve f i l m. I n pol ari za-
ti m studi es wi t h C1- added to a sol uti on contacti ng passi ve i ron,
it wz s foun6 that an :xducti on peri od i s necessary before the
anodtc current i ncreases (773). "he i n2ucti on peri od was i n-
.
. ,
.
32
versel y proporti onal to the C1- concentrati on, wi th a minimum
concentrati on requi red f or attack (328). A f reshl y passi vated
surf ace was less resi stant t o C1- than one at steady state.
These resul ts have been expl ai ned by mi grati on of C1- through the
f i l m. A second i nducti on peri od has al so been observed, beyond
which porous y-Fe203*H20 grows on the surf ace, al l owi ng easy l ocal
di ssol uti on l eadi ng to pi tti ng (773).
Once i ni ti ated a pi t rapi dl y devel ops i nto the conf i gurati on
diagrammed i n Fi gure 4 . A l l of the f actors i nf l uenci ng the pro-
gress and devel opment of a pi t duri ng underground corrosi on coul d
not conveni entl y be i ncl uded i n a si ngl e di agram. However, thi s
di agram, suppl emented by Tabl e 7, suf f i ces f or descri pti on of the
more evi dent characteri sti cs.
Thu.s ref erri ng to Fi gure 4:
(1) The l i qui d-gas i nterf ace shown at the top ranges from the
l i qui d boundary of a parti al l y or f ul l y submerged pi pel i ne t o the
thi n f i l m of moi sture ei ther on the pi pe surf ace or bri dgi ng a
soi l parti cl e and the pi pe. The avai l abi l i ty of gases at the pi pe
may Se severel y l i mi ted i n the f i r st case, whereas i n an 3pen
textwee. soi l the gas may be abundantl y avai l abl e through. a thi n
moi stxre f i l m and i s qui ckl y repl aced i f consamed.
(2) Four gases are shown i n equi l i bri um wi th the l i qui d
phase. Oxygen and hydrogen sul f i de are sol ubl e i n water, whi l e
carbon di oxi de and ammoni?. react wi th water t o form new i oni c
qeci es:
(a) Oxygen., compri si ng one- f i f th of the earth s atmosphere,
i s wel.- di spersed i n open textured soil; it is al so produced by
f V
: Oi f H'
.=
+ I
NH, O H Z N H i t OH-
.. W J 1
HCO;, C O , " , ~ S ~ S ~ ~ L V E D
AS cot OR ncs OR PRE-
Cl PrATEO AS IflON
CARBONA TS +SULFIDES
--
Figure 4. Schematic Representation of the Underground Corrosion' Process
TABLE 7
SOME OXI DES, SUL FI DES, AND SALTS OF I RON APPEARI NG
Substance
Ferrous hydroxi de
Ferri c hydroxi de
Ferrosof erri c oxi de
Ferrous sul f i de
Ferri c sul f i de
Ferrous chl ori de
Ferrous sul f ate
(a) Not normal l y WI
I N CORROSI ON PRODUCTS
Formula
(a)
Fe(0H) 2; F eO- H20
Fe2O3*3H20;Fe (OH) (b
Fe 0 ;Fe203*Fe0 ( C)
3 4
FeS
Fe2S3
F eCl 2- 4H20 (d)
FeS04-7H20 (d)
tten as the hydratec
Sol ubi l i ty
-
Col or, Form
White ,
crystal l i ne
Red-yellow t o
brown
Bl ack ,
granul ar
Bl ack t o
brown
Y ellow-green
Bl ue -green
Bl ue -green
oxi de si nce FeO i s bl ack
(b) Rarel y wri tgen as the hydroxi de
(c) The oxi de i s magneti c and has an af f i ni ty f or wat er , i .e.,
Fe3C4'H20
(d) These sal ts preci pi tate wi th f i xe2 proporti ons of ws. ter
(1) Hi ghl y i nsol ubl e
(2) Sol ubl e i n aci d
( 3 ) Sol ubl e i n. aci d i n the presence of oxygen
( 4) Hi ghl y sol ubl e
(5) Sol ubl e i n al kal i
pl ant l i f e wnich may cause the concentrati on i x soi l moi sture to
read- val ues wel l above the normal 9 to 10 ;arts per mi l l i on. The
oxygen ccncentrati on i s probabl y near the equi l i bri um val ue at al -
mo s t every poi nt i n backf i l l ed soi l .
I b) Hydrogen sul f i de i s an end product of the reducti on
of sul f ate i on by anaerobi c bacteri a 2nd i s, unl i ke oxygen, pro-
ducec! i n mi l and of ten at the ~i p e surf ace,
(c) Carbon di oxi de, i mportant i n the l i f e cycl e, reacts
wi th water to form the di proti c aci d which di ssoci ates as shown.
I t i s of ei ther atmospheri c or bi ol ogi cal ori gi n.
i ni ti ati ng f actor.
I t i s an
(d) Ammonia, f requentl y i ntroduced i nto the soi l as a
f er ti l i zer , reacts wi th water to form ammonium and hydroxi de i ons.
( 3 ) The product of the concentrati ons of the components of
.
di ssoci ated water and the consequent rel ati on between the pH and
pOH are appropri atel y shown i n the central porti on of the di agram.
The hydrati on of hydrogen i ons and the equi l i bri um constant are
al so shown there.
-
(The unhydrated proton, H', i s evi dentl y non-
exi stent. However, it i s used i n the f i gure f or si mpl i ci ty. I t
is to be read as the hydronium i on, H30 . )
+
(4) A pi t is shown i n the pi pe wal l at the bottom of the
page al ong wi th the uncorroded area to the l ef t , i n order t o
i l l ustr ate the wel l establ i shed el ectrochemi cal theory of corro-
si on. I n the i deal case a l arge cathodi c area i s concentri c
wi th the anodi c pi t where i ron goes i nto sol uti on and gi ves
el ectrons to the met al . These el ectrons move to the cathodi c
areas where they parti ci pate i n a reducti on process such as
i l l ustrated by Equati ons 2 and 3 .
sol uti on carryi ng two posi ti ve charges wi thout negati vel y charged
i ons bei ng avai l abl e to bal ance the charge. Ei ther one doubl y
charged ani on such as sul f ate or a pai r of si ngl e charged i ons
such as OH-, Cl-, Qr HS- must be provi ded. I f the el ectrol yte
at the poi nt of corrosi on i s al kal i ne, f errous hydroxi de pre-
The i ron atom cannot go i nto
-
I
ci pi tateF,
36
A s corrosi on proceeds, the ani ons move through the
el ectrol yte (soi l , water) al ong an arc toward the anode, whi l e
the cati ons f ol l ow si mi l ar paths t o the cathode. The l arger arc
shows the di recti on of f l o w of the i ons usual l y found i n soi l .
The sol uti on through which sol ubl e sal ts are transf erred from one
area to another under the el ectri c gradi ent establ i shed between
anode and cathode i s the el ectrol yte and, l ogi cal l y, . the el ectro-
l yte at the anode i s the anol yte and that at the cathode, the
cathol yte.
I f the transport arcs are i magi ned to be shortened, to
the poi nt that the adj acent reacti ng surf aces are of atomi c dimen-
si ons, then the process i s ref erred t o as chemi cal corrosi on and
a more general attack of the corrodi ng surf aces resul ts.
Accordi ng to cl assi cal theory, the reacti on at the anode
i s confi ned t o the formati on OX f errous i on. But there i s evi -
dence that other reacti ons can somet i mes occur there. Thi s w i l l
be di scussed l ater.
Shown toward the l ef t i n the f i gure are f our reducti on
reacti ons. Two reacti ons account f or the di sposi ti on of the same
number of el ectrons as rel eased at the anode. Two show di sposi -
ti on of monatomic (nascent) hydrogen (a) by evol uti on of hydrogen
.. gas, and (b) by reacti on wi th oxygen to form water. I n el ectro-
l ytes low i n pH the f orrnati m of mol ecul ar hydrogen i s favored.
On the other hand, abundant oxyqen i s known to depol ari ze
cathodes in el ectrol ytes 'n.j-gh i n pH. A f i f t h reacti on i n the
f i gure emphasi zes the tendency of the csthol yte t o i ncrease i n
pH as corrosi on proceeds.
37
(5) Overl ayi ng the pi t are zones of a corrosi on product
mantl e i l l ustrated i n the form of a rai nbow. The oxi dati on state
of the i ron i n the oxi des i ncreases outwardl y from f errous through
f errosof erri c to ferri c. The order of appearance of these oxi des
i s i nvari ant. Some properti es of the oxi des are shown i n the
di agram and are suppl emented i n Table 7. Ferrous and ferri c hy-
droxi de have each been found al one i n the f i el d -- the former
.
under anaerobi c condi ti ons and the l atter under strongl y aerobic
exposures. Ferrous hydroxi de i s found, f or exampl e, i n wet cl ays
al ong the banks of "bayous" i n Texas. The whi t e oxi de changes
on exposure t o ai r t o the f ami l i ar red-brown ferri c oxi de. Pure
whi te f errous hydroxi de has been observed i n pi t s beneath a bi -
tumi nous coati ng on pi pe under cathodi c protecti on, which produces
a reduci ng envi ronment. Pure ferri c hydroxi de has been produced
under a hi gh potenti al i n the preser?ce of oxygen and has been
observed i n the f i el d under si mi l ar condi ti ons. All three oxi des
have been reported i n coexi stence i n nature and al l three can
easi l y be produced i n "rai nbow" order i n the l aboratory.
Magneti te has been found nei ther al one nor i n combi nati on wi t h
f errous hydroxi de. The overwhel mi ngl y preval ent combi nati on i s
magneti c oxi de overl ai n wi t h ferri c oxi de. Even i n dri ed sampl es
of these oxi de scales removed f r om pi pe and i ron structures above
ground there al ways remai ns an underl ayer of magneti te. The
oxi dati on never seems compl ete even upon prol onged exposure to
ai r. Ferrous and ferri c oxi de hslve not been observed together
wi thout the i ntermedi ate oxi de.
.
.
38
There are two i nteresti ng characteri sti cs of the corro-
si on product mantl e. F i r st, consi derabl e quanti ti es of wat er
are consumed i n the preci pi tati on of the oxi des. Second, the
release of hydrogen i on tends t o carry water away from the corro-
di ng area due to hydrati on. T est s on sampl es of r ust taken i n
the f i el d show that the pH of Zone I11 i s of the order of 3.5,
whereas the pH of the anol yte i s onl y sl i ghtl y aci di c, as i ndi -
cated i n the f i gure.
The orderl y fl ow of ani ons i s i nterrupted i n Zone I11 by
reacti on of i ncomi ng sul f i des and carbonates wi th hydrogen i ons
and consequent evol uti on of hydrogen sul f i de and carbon di oxi de
and neutral i zati on of hydroxi de i ons. I ron sul f i des have not
been found i n Zone 111. Ni trate i ons, general l y rare i n soi l ,
presumabl y oxi di ze the i ron oxi des to the f er r i c state. These
reacti ons thus al l ow onl y the chl ori de and sul f ate i ons, and
possi bl y bi sul f i de, t o reach the anol yte. On the other hand,
the orderl y fl ow of cati ons i s uni nterrupted t o the me t a l sur-
face, where magnesium and cal ci um i ons preci pi tate as hydroxi des
and carbonates. There hydrogen i ons, i f any, are al so neutral i zed.
Sgdium and potassi um i ons accumul ate at the surf ace, and the pH
tends t o i ncrease.
Two f acts of i nterest i n the movement of the i ons are:
(a) that whi l e the current densi ty i n the cathodi c area i s a
maximum near the pi t , i t attenuates rapi dl y wi th i ncrease i n the
radi us of the transport arc; and ( b) that di f f usi on, predomi nates
over the mi grati on of the i ons due t o the i nf l uence of the el ec-
tri c f i el d establ i shed by the corrosi on processes.
39
(6) The corrosi on product mantl e i s never as i deal l y con-
sti tuted as depi cted i n the f i gure. The magneti c oxi de f i l l s and
overl ays the pi t i n the absence of f errous hydroxi de. I t i s
porous and essenti al l y f ree of condensed moi sture. The parti ci -
pati on of water i n the formati on of the several oxi des has been
menti oned. Added to thi s dryi ng effect i s the repul si on of hydro- .
nium i ons by the el ectri c f i el d. However, the voi ds are saturated
wi t h water vapor.
the anol yte i s barel y aci d and the bl ack oxi de may exhi bi t a
greeni sh cast i ndi cati ng i ts saturati on wi t h f errous chl ori de.
Pal e green crystal s of thi s sal t have been pi cked from the bl ack
granul ar mass. They devel op a thi n browni sh coat on exposure to
ai r. Water of crystal l i zati on f urther depl etes the anol yte of
f ree water.
-
I n accord wi th thermodynamic consi derati ons,
Chemi cal anal ysi s of materi al i n pi ts has been more exten-
si ve i n pi pe coated wi t h cement mortar than wi t h pi pe ei ther bare
or coated wi t h organi c materi al s. I n these anal yses the rati o of
i ron to chl ori ne i s al ways i n good agreement wi th f errous chl or-
i de stoi chi ometry. Sul f ate and other i ons appear i n the anol yte
i n traces only, The mortar reacts wi th sul f ate i on and i nhi bi ts
i ts transport to the pi t.
(7) The mechanism f or the formati on of magneti te i s obscure.
The probl emati cal equati ons i n the mantl e are i ntended pri mari l y
to show the end products and to gi ve a reasonabl e account of thei r
formati on i n accord wi t h observati on. A nurqber of other equati ons
coul d be wri tten but these would be equal l y specul ati ve. However,
there i s evi dence that magneti te forms spontaneousl y f r om f errous
.
40
hydroxi de wi th evol uti on of hydrogen.
expl ai n the formati on of magneti te i n boi l er tubes.
i s thermodynami cal l y possi bl e.
formed the f errosof erri c oxi de seeds i ts conti nued producti on.
On the other hand, mounting evi dence shows that under hi gh aera-
ti on ferri c i on forms di rectl y from the metal.
of the Fe,Fe3+ coupl e would f avor thi s reacti on i n a sol uti on
saturated wi t h f errous chl ori de combined wi t h a hi ghl y aerated
cathode provi ded, of course, that the acti vi ty of the f er r i c
i on i s mai ntai ned essenti al l y at zero by preci pi tati on of the
T hi s reacti on i s used to
The reacti on
I t has been suggested that once
Thus the potenti al
-
magneti c oxi de.
(8) The overal l potenti al of the goi ng cel l may be approxi -
mated by thermodynamic cal cul ati ons.
equi l i bri um wi t h i ts sal ts FeC12- 4H20 and FeS04-7H 2 0 as requi red
by the schematic, are readi l y computed (Tabl e 7) . The potenti al s
of the hydrogen and oxygen el ectrodes present problems rel ati ng
to the absorpti on of hydrogen by i ron and l ack of i nformati on
on the reacti ons at the el ectrode surf aces. Further compl i cati ng
the approxi mati ons, the substanti al redox potenti al between Zones
I1 and I11 must be taken i nto account. I t would appear easy to
measure the actual potenti al i n the anol yte and the redox poten-
ti al i n Zone I11 and the cathode potenti al i n a case approachi ng
the i deal . Some such measurements have beer! made i n the f i el d.
The mixed potenti al taken remotel y, as on the surf ace of the
earth over the pi pe, i s poorl y i nf ormati ve except w i t h respect
to the order of the reacti on on the met a l surf ace. T hi s i s
general l y found to be bi f aradai c (two el -ectroxs exchanged), i n
The potenti al of i ron i n
,.
41
accord wi th cl assi cal theory. As a practi cal matter, opportuni -
ti es f or test are few. Excavati ons are general l y made f or repai r
of pi pe, and i n such cases the corrosi on cel l s are destroyed by
escapi ng oi l , gas, or water.
As a matter of i nterest, it is noted at thi s poi nt that oxy-
gen may pl ay three rol es i n the corrosi on process, namely, (a)
removal of adsorbed and absorbed hydrogen, (b) i ts di r ect reduc-
ti on at the cathode, and (c) i ts reducti on wi thi n the mantl e to -
form f er r i c oxi de. Perhaps the reacti on
4Fe2+ + O2 + 2H20 =4Fe3+ + 40H- (Eq. 7)
shoul d be i ncl uded i n di scussi ons of basic mechanisms.
The i nf l uence of bacteri a and sul f i des on pi tti ng w i l l be
di scussed l ater.
5. Crevice Corrosi on
I ntense l ocal i zed corrosi on f requentl y occurs wi thi n shi el ded
areas exposed to certai n envi ronments. Shi el ded areas are ex-
pected when porous gaskets are employed, when l arge dense rocks
contact bare pi pes, under f ractured or di sbonded coati ngs, etc.
The mechanism of attack i s thought to be si mi l ar to that for pi t-
ti ng, except that there i s no necessi ty f or i ni ti al l y formi ng a
shi el ded area.
i on hydrol ysi s, di f f erenti al aerati on contri butes to crevi ce corro-
si on (and al so to pi tti ng) , especi al l y i n the earl y stages. Si nce
oxygen has di f f i cul ty moving i nto a crevi ce, the concentrati on
of oxygen wi thi n the crevi ce soon f a l l s below that at the ex-
ternal surf ace. Equati on 5 i ndi cates di f f erent potenti al s
I n addi ti on to chl ori de i on mi grati on and f errous
.
.
4 2
between the exteri or and crevi ce, making them cathodi c and anodi c,
respecti vel y.
Crevice corrosi on of mi l d steel i n NH NO sol uti ons was found
4 3
to be maximum under condi ti ons of weak passi vati on (485). I n
- crevice corrosi on of stai nl ess steel i n seawater, it was found
that the entrapped corrodent had a pH below t wo and contai ned
f errous but not f er r i c i ons (584). Eydrol ysi s of chromi c i ons
was thought to occur wi th stai nl ess steel i n addi ti on to hydrol -
ysi s of f errous i ons to l ower pH.
Crevi ce corrosi on of stai nl ess steel onl y occurred below a
Chl ori de i ons f aci l i tated cri ti cal potenti al i n di l ute H2S04.
spreadi ng of attack (487).
6. Gal vani c Corrosi on
I t i s wel l known that, when a more nobl e met al i s i n contact
wi th i ron the corrosi on rate of the i ron i s accel erated because
i t has a l ower potenti al . Comparison of gal vani c corrosi on re-
sul ts wi th standard EMF val ues shows that thi s i s not preci sel y
tr ue. Gal vani c corrosi on can onl y be wel l understood by study-
i ng mixed potenti al behavi or, as i l l ustrated by Fi gure 5. The
main reason the corrosi on rate i s accel erated i s that the cathodi c
reacti on i s f aster, so that the net anodi c di ssol uti on reacti on i s
f aster. I f the other metal 's cathodi c reacti on i s suf f i ci entl y
f ast and i ts anodi c reacti on i s sl ow, then it can accel erate the
corrosi on of i ron even though it has a lower standard potenti al .
The magni tude of the ef f ect depends on the rel ati ve si z e of the
metal s. The i ron nezxest the f orei gn metal i s af f ected mo s t
severel y.
icorr
LOO CURRENT
Fi gure 5. Mixed Potenti al Curve f or Gal vani c Corrpsi on of More
Noble Metal M Having Hi gher Rate of
Cathodi c Reacti on
h
Even two di f f erent steel al l oys i n contact create a gal vani c
coupl e and accel erate corrosi on of one of them. Thus, stai nl ess
$
doubl ed the corrosi on r ate of carbon steel i n aerated 3.5-percent
NaCl when the areas wer e equal and i ncreased the rate by ei ght to
ni ne t i mes when the stai nl ess had an area ei ght t i mes as l arge
( 7 8 4 ) . Certai n corrosi on products can be cathodi c wi t h respect
.
t o steel . Thus, f or example, new pi pe i n a rusted l i ne w i l l be *
anodi c and corrode pref erenti al i y. A recent survey of pi pel i ne
corrosi on at 23 U. S . Navy l ocati ons reveal ed that many f ai l ures
wer e caused by use of di ssi mi l ar netal a.
44
Gal vani c cel l s wer e named as the most preval ent cause f or
corrosi on by mor e companies (76 percent) surveyed than any other
cause.
7 . Corrosi on by Stray Currents and High Vol tage D i r e c t Current
Equati on 1 shows that anodi c di ssol uti on takes pl ace where
(posi ti ve) current l eaves the pi pe. I f el ectri c f i el ds are
present i n the soi l , current w i l l fl ow i n the pi pe. Where the
current exi sts, corrosi on w i l l take pl ace accordi ng to Equati on 4 .
Thi s amounts to 0.55 mi l s per year f or a current densi ty of 1
mA/square f t . I f a coati ng of l ow el ectri cal conducti vi ty i s
appl i ed t o the pi pe, the corrosi on w i l l be even more rapi d at
the hol i days because the current i s then concentrated i n smal l
spots.
Stray currents wer e second onl y to gal vani c cel l s i n causi ng
corrosi on l eaks accordi ng to the companies surveyed (Tabl e 3) .
A maj or source of stray current i s el ectri c rai l ways (333).
Thi s can be minimized by usi ng a w el l i nsul ated roadbed and 100-
percent rai l return f or the DC.
Cathodi c protecti on of one underground structure can i nduce
stray currents and corrosi on i n nearby structures and i s known
as "i nterf erence." Thi s may be al l evi ated by j oi ni ng nearby
structures wi th el ectri cal cabl e and provi di ng protecti on j oi ntl y.
A total of 12,408 drai nage bonds between the compani es' pi pi ng and
other structures was reported by the surveyed compani es. Many of
the bonds contai ned resi stors and di odes t o control the magni tude
and the di recti on of the current flow between structures. The
l argest current was 150 A wi th. the zverage f or many companies
45
around 7 A per maj or bond. The maj ori ty of the bonds carri ed
0.5 to 5 A. Thi s i mpl i es a minimum of 12, 000 amperes bei ng ex-
changed by the companies parti ci pati ng i n the questi onnai re survey.
The ef f ect of stray currents on pi pes can be i sol ated by
i nterrupti ng the el ectri cal conti nui ty of the pi pe at i nterval s
wi t h i nsul ati ng f l anges. I ndi scri mi nate use of i nsul ati ng 4
f l anges may cause probl ems due to di f f erences of potenti al be-
tween the t wo secti ons of pi pe. Cathodi c protecti on i s very hel p-
-
f ul but must be coordi nated wi t h other nearby cathodi c protecti on
ventures, as di scussed l ater. A source of stray current may be
determi ned by usi ng two or more copper sul f ate el ectrodes to
f i nd the potenti al gradi ent. The vector sum of two such measure-
ments i n perpendi cul ar di recti ons poi nts toward the source of
stray current (568). I t has been poi nted out that vol tages are
i nduced i n pi pel i nes paral l el t o overhead hi gh vol tage AC power
l i nes (701). When cathodi c protecti on wi t h recti fi ers i s used
i n addi ti on to the i nduced AC, a net DC current resul ts. Corro-
si on can be avoi ded by arrangi ng the recti fi ers so that i nduced
current i s drai ned of f i nto the ground bed. AC i tsel f has been
found to accelerate corrosi on sl i ghtl y -- less than 1 percent of
that f r om equi val ent DC (354, 683). Others have quoted a f i gure
of 0. 1 percent i ndependent of current densi ty ( 405) .
-
High vol tage DC (HVDC) power transmi ssi on l i nes are pl anned
for the near f uture. Power companies have claimed that earth .
currents w i l l nei ther be l arge nor f requent, and that i n any
event, the currents w i l l l argel y fol l ow deep strata i n the earth.
The pi pel i ne i ndustry and some corrosi on consul tants di sagree
46
(253, 336). I f the pi pel i ne companies f ears are real i zed, l i ti ga-
ti on f or damage i s l i kel y. N o t onl y coul d l arge currents of even
a few mi nutes durati on cause si gni f i cant corrosi on where the
current l eaves the pi pes, but coati ngs can be damaged where
current enters the pi pes. Si nce the power companies onl y expect
to i nduce stray currents several hours per year, a possi bl e sol u-
ti on wi th respect to corrosi on i s f or the HVDC system to shut
down, rather than di vert current i nto the earth and create a
di f f i cul t, random stray current si tuati on.
Several tests have been conducted to determi ne HVDC ef f ects.
Currents of 300 A near L os Angel es had l i ttl e ef f ect on pi pes i n
Los Angel es, presumabl y because of the hi gh densi ty of pi pel i nes.
Fi f ty mi l e s from Los Angel es 50 mV changes wer e observed. How-
*
ever, on some pi pel i nes current was pi cked up i n damaging amounts
( 260, 523, 252, 727) . One surpri si ng r esul t of the L os Angeles
measurements i s the random tel l ur i c currents that wer e found.
These are thought to be due to such sources as s mal l shi f ts i n
the earth' s magneti c f i el d and f l uctuati ons i n cosmi c rays. A
study on tel l uri c ef f ects concl uded that corrosi on i s i nsi gni f i -
cant f or coated, protected l i nes and bare l i nes ( 794) .
U s e of HVDC deep wel l el ectrodes does not necessari l y l i mi t
the ri sks of stray current (252). The l ocati on of the el ectrodes
i n rel ati on to pi pel i nes was found to be cri ti cal . L ocati on of
el ectrodes i n the sea was found to be best. More tests are needed
and are under way ( 727) .
*
September 1969 meeti ng of Los Angel es Cathodi c Protecti on
Committee.
47
A computer study showed that currents do not pl unge to the
core of the earth. Depth of buri al , soi l resi sti vi ty, and pi pe
were found to have l i ttl e ef f ect on i nterf erence ef f ects. Larger
di ameter pi pe showed l arger effects. The di stance of the pi pel i ne
from the HVDC el ectrode was found to be the maj or f actor i n deter-
mi ni ng the ef f ects on a pi pel i ne (488). 4
Al though cathodi c protecti on i s usef ul agai nst normal i nter-
.
f erence, the HVDC currents are expected to change so rapi dl y that
ordi nary manual l y adj usted systems cannot compensate f or them.
Large current sources wi t h automati c control w i l l be requi red --
and w i l l be expensi ve ( 3 3 5 ) . Automati c control may be requi red
onl y f or up to 150 mi l e s from the HVDC el ectrode ( 795) .
A study was made of a hypotheti cal pi pel i ne 36 i nches i n
diameter and 250 mi l e s l ong, wi t h 50,000 ohms-square f oot coati ng
resi stance ( 796) . The pi pel i ne was assumed to be i n the el ectri c-
al f i el d establ i shed by HVDC earth currents and separated 20 mi l e s
f r o m the el ectrode. Under these ci rcumstances, a probl em of corro-
si on and disbanding would exi st. The study concl uded that: (1)
HVDC ef f ects can at best onl y be mi ti gated at consi derabl e expense:
(2) because of the wi de f l uctuati on i n the amperage of HVDC cur-
rent, automati c regul ati on of protecti ve currents would be neces-
sary over the l ength of the buri ed structures; ( 3 ) f or the hypo-
theti cal pi pel i ne studi ed, ni ne control l ed recti fi er i nstal l a-
ti ons would be requi red at an esti mated capi tal cost of about
$200,000.
I n another study (797), the l i ter atur e and "off-the-shel f"
equi pment wer e reviewed to determi ne the best arrangement for
4 8
correl ati ng HVDC currents wi th earth currents and cathodi c pro-
tecti on currents. For about $5,000 per assembl y, equi pment can
be put together from avai l abl e commercial components. Requi red
would be a hi gh impedance di gi tal vol tmeter, a paper tape punch,
and appropri ate swi tchi ng and mul ti pl exi ng equi pment t o measure
several potenti al s at one t i me. The package coul d operate un-
attended f or an extended peri od of t i me on AC power ( 797) .
8. Mechani cal Stress Ef f ects
Steel can be made t o f ai l both by corrosi on and by appl i cati on
of suf f i ci ent mechani cal stress. When both stress and a corrosi ve
envi ronment are appl i ed si mul taneousl y, f ai l ure occurs at l ower
l evel s of stress and/or sooner than when ei ther act al one. Severe
cracki ng somet i mes resul ts from the acti on of certai n corrodents
on certai n metals when a tensi l e stress i s appl i ed.
Tabl e 3 shows that a s mal l but si gni f i cant f racti on of the
companies surveyed consi der mechani cal l y ai ded corrosi on to be a
preval ent cause of l eaks.
Some corrosi on engi neers di sti ngui sh between t wo types of
cracki ng -- stress corrosi on cracki ng and hydrogen embri ttl ement
or hydrogen stress cracki ng -- whi l e others do not. I t i s
thought by some that stress corrosi on cracki ng i s due t o stress-
accelerated di ssol uti on at the t i p of the crack and that cathodi c
pol ari zati on can el i mi nate the phenomenon. On the other hand,
hydrogen stress cracki ng i s attri buted by some t o hydrogen atoms
di f f usi ng i nto the i ron and embri ttl i ng it so that it cracks
easi l y. Cathodi c pol ari zati on would worsen t hi s phenomenon,
whi l e anodi c pol ari zati on would rel i eve it. Causti c embri ttl ement
49
i s thought t o be hydrogen embri ttl ement engendered by a hi gh pH
envi ronment.
Related to other hydrogen ef f ects i s hydrogen bl i steri ng i n
which bl i sters are formed i n the met al . Bl i sters general l y occur
at el evated temperatures. W e t hydrogen sul f i de can cause stress
cracki ng cal l ed sul f i de stress corrosi on cracki ng (337, 338).
6
One i mportant di f f erence between thi s and other forms of stress
cracki ng i s that the envi ronment i n sul f i de processes i s usual l y
1
i nsi de the pi pe rather than external , as wi th most other corro-
dents. Hydrogen sul f i de i s found i n sour gas, crude oi l , swamps,
marshes, and open sewage di sposal areas.
Corrosi on f ati gue ref ers to accel erated f ai l ure caused by
stress cycl i ng due to the presence of a corrosi ve envi ronment.
The exact mechanisms responsi bl e f or these phenomena are uncertai n
and may not al ways be the same. These phenomena are under very
acti ve i nvesti gati on, partl y because so many unanswered questi ons
remai n and partl y because f ai l ure can be catastrophi c.
I n pi pel i nes stresses ari se f r o m i nternal hydrostati c pres-
sure, bendi ng i n i rregul ar trenches, backf i l l , etc. Resi dual
stresses are al so present from pl asti c deformati on i n manufacture
and pi pel ayi ng. Even the thermal stresses of wel di ng produce
resi dual stresses. I n 1965 a 24-i nch natural gas pi pel i ne f ai l ed
f r o m stress corrosi on cracki ng and 17 peopl e wer e ki l l ed ( 694) .
A recent survey showed that stress corrosi on cracki ng was observed
i n a vari ety of pi pel i nes (586). Fai l ures and nearby secondary
cracks wer e axi al and not associ ated wi th wel ds, pi tti ng, general
corrosi on, or any other defect. Cracks fol l owed grai n boundari es
50
and contai ned bl ack Fe30q crystal s.
bare and coated pi pes, al though di sbonded coati ngs were of ten
Fai l ures occurred on both
associ ated wi th cracki ng. Di f f erences i n the amount of cracki ng
were noted between di f f erent l ots of pi pe steel but coul d not be
expl ai ned. I n general the tendency to crack i ncreases wi th yi el d
strength. Hydrogen stress cracki ng was found not t o be a.probl em
unl ess yi el d strength exceeded 130,000 psi (587). The few servi ce
f ai l ures i n gas transmi ssi on l i nes due t o hydrogen stress crack-
i ng wer e i ni ti ated at i nadvertent hard spots or hard wel d zones
wi th ul ti mate strengths over 175,000 psi . Hard spots i n pi pe are
usual l y detectabl e as f l at regi ons i n the pi pe. Sul f i de cracki ng
al so i ncreases as yi el d strength i ncreases (337). Hard el ectri c
resi stance wel ds have been known t o crack f or hundreds of f eet
i n the presence of i nternal hydrogen sul f i de (338).
Tabl e 8 i ndi cates the total number of l eaks caused by hydro-
gen bl i sters and cracks that the 373 operati ng companies have ex-
peri enced. The questi onnai re asked the respondants t o expl ai n
the exi sti ng exposure condi ti ons f or each l eak or crack, such as
tenperature of pi pe, vi brati on, pressure, pi pe potenti al , presence
of ni cks or scratches, hard spots, anal ysi s of cause of crack,
TABLE 8
NUMBER OF CORROSI ON LEAKS THAT HAVE BEEN CAUSED
BY HYDROGEN BLI STERS AND CRACKS
Number of Leaks
1 2 3 4 6 17 100
Number of Companies
(A) Hydrogen B l i s t er s
(B) Cracks
3 1 0 0 0 1 0
8 1 1 0 1 0 1
51
such as hydrogen stress cracki ng or stress corrosi on cracki ng,
etc.
The fol l owi ng quotati ons are some of the more i nteresti ng
expl anati ons:
(1) "The two hydrogen bl i ster l eaks occurred i n areas of hi gh
C02 and H2S content co- exi sti ng wi t h free water i n the gas
stream upstream of a process pl ant. I t was determi ned by an
i ndependent l aboratory that hydrogen atoms penetrated vast
l ami nati ons i n the pi pe and resul ted i n pressure bui l d-up
wi thi n the l ami nati ons. I n thi s respect, corrosi on was a
contri buti ng factor to the l eaks. I t was esti mated that up-
wards of 25 percent of the pi pe area was l ami nated i n the
af f ected area. The enti re systems i nvol ved wer e taken out of
servi ce, hydrostati cal l y tested, and ul ti matel y the enti re
.
-
systems wer e returned t o service. Dehydrati on equi pment was
then i nstal l ed at wel l -heads t o dry the gas streams. I n-
hi bi tors were used duri ng the i nteri m peri od and conti nue to
be used as a saf ety f actor. " (Q533)
( 2) "I n 1951 and 1952, we had 17 f ai l ures i n the gatheri ng
*
system due to hydrogen bl i sters ori gi nati ng from generati on
of hydrogen f r o m the corrosi on processes of the aci d gas
(C02 and H2S content) bei ng gathered." (4636)
(3) "One leak i nci dent has been attri buted to stress corro-
si on cracki ng based on the characteri sti cs of the observed
secondary cracks, f racture i n the f i el d and i n the l aboratory.
The i nformati on on thi s i nvesti gati on has been i ncl uded i n
*
Numbers i n parentheses preceded by I 'Q" refer to i nformati on f r om
speci f i c questi onnai res.
52
t he NG-18 Pi pel i ne Resear ch on St r ess Cor r osi on Cr acki ng.
The envi r onment al f act or whi ch pr omot ed t he cr acki ng has not
been i dent i f i ed. Har dness, t ensi l e pr oper t i es, and chemi cal
pr oper t i es of t he st eel wer e nor mal . The oper at i ng st r ess was
wel l bel ow t he yi el d st r engt h of t he st eel . The pi pe was bar e
( except f or mi l l pr i mer ) and cat hodi c pr ot ect i on had been i n-
st al l ed one year pr evi ousl y. The act ual pi pe- t o- soi l pot en-
t i al at t hat t i me i s not known. Chemi cal anal ysi s of t he
soi l di d not r eveal any unusual const i t uent s. " (Q663)
( 4 ) "Bot h cr acks occur r ed i n a har d spot whi ch had an ar ea
somewhat equal t o t hi s sheet . The mass har dness was Br i nnel l
4 7 7 . 'I (Q341)
(5) "One cr ack wi t h t he f ol l owi ng exposur e condi t i ons:
Pr essur e 960 psi
Temper at ur e 110F t o 115F
I nst al l ed i n 1959
Pi pel i ne Coat i ng - Pol yken Tape #900
Type Pi pe - X- 52
Cat hodi c pr ot ect i on i nst al l ed 1959
Cat hodi c pr ot ect i on pot ent i al - 1.8 t o -2.0 voAt s" (Q388 )
(6) "TWO cases of st r ess cor r osi on cr acki ng wi t h t he f ol l ow-
i ng exposur e condi t i ons:
Temper at ur e - 45" - 60F
Pr essur e - 500 l bs/ i n
No vi br at i on, ni cks or scr at ches, or har d spot s
Pi pe- t o- soi l pot ent i al 2 vol t s" (Q439)
2
53
(7) "On 100 cast i ron l eaks, the pi pe was cracked. We do not
know whether the corrosi on caused the cracks or the cracks
caused the corrosi on. 'I (Ql44)
(8) "One crack due t o selective corrosi on i n a l ongi tudi nal
seam of el ectri c resi stance welded pi pe." (4580)
Some recent research resul ts on stress- corrosi on phenomena
are revi ewed bri ef l y i n the fol l owi ng paragraphs.
Pi pel i ne steel was heat treated to obtai n yi el d strengths
rangi ng from 110, 000 to 150,000 psi . Cracki ng occurred at stress
and cathodi c protecti on condi ti ons l i ke those that mi ght be used
w i t h hi gh strength steel s. Suscepti bi l i ty to hydrogen stress
cracki ng depended on the rate at which hydrogen atoms entered the
steel , which i n turn was general l y l arger at hi gh pH (356).
Ducti l i ty and tensi l e strength of stai nl ess steel f oi l s wer e re-
duced by atomic hydrogen absorpti on duri ng cathodi c chargi ng (332).
I n si ngl e crystal i ron the hydrogen atom penetrati on rate de-
creased as the packi ng densi ty of the pl ane paral l el to the sur-
face i ncreased ( 199) . I t was found that hydrogen sol ubi l i ty i n
i ron and steel was i ncreased by tensi l e stress and decreased by
compressi ve stress ( 3 8 7 ) . Di f f usi vi ty was unaf f ected. Beyond a
cri ti cal concentrati on, which depended on temperature, hydrogen
produced structural damage and embri ttl ed the metal . I ron sul -
f i de f i l ms retarded hydrogen penetrati on (385).
The suscepti bi l i ty to f ai l ure of 9-4-45 hi gh strength steel
.I
was observed to i ncrease wi th both anodi c and cathodi c pol ari za-
ti on ( 407) . I t was suggested that hydrogen embri ttl ement may be
I
I
54
i nvol ved i n al l stress corrosi on cracki ng. The pI-1 at the t i p of
a crack as a f uncti on of potenti al i n sal t water was measured, and
it appeared that condi ti ons wer e al ways f avorabl e f or hydrogen
reducti on ( 400) . El ectron mi croscopy reveal ed no di f f erence i n
f racture f eatures at di f f erent potenti al s. A model has been pro-
posed which requi res H2 l i berati on at the crack t i p (548).
I t has been suggested that pl asti c deformati on at the t i p of
the crack i ncreases the rate of di ssol uti on at the ti p. However,
col d work has been found to have no ef f ect on the corrosi on rate
of pure i ron (756, 759). Carbon addi ti ons caused the rate to i n-
crease wi th col d worki ng, especi al l y at normal l y passi ve poten-
ti al s (756, 316). High temperature anneal i ng reduced the rate,
suggesti ng that l atti ce i mperf ecti ons by themsel ves do not cause
i ncreased corrosi on but that composi ti onal i nhomogenei ti es do.
Studi es of structural changes i n AI S 1 4340 hi gh strength
carbon steel suggested that the ef f ect of hydrogen i s t o reduce
the austeni ti c grai n boundary energy ( 800) . Hydrogen i n hi gh
puri ty i ron causes surf ace bl i steri ng and some i nternal f i ssures
at grai n boundari es (681). The yi el d stress was l owered, even
after hydrogen removal . Thi s suggests that embri ttl ement i s due
to di sl ocati on creati on and not to di sl ocati on l ocki ng.
Measurements of l ocal el ectri cal potenti al s showed that
stresses do not lower the potenti al at the poi nts of stress con-
centrati on i n corrosi on f ati gue experi ments ( 629) . When a crack
forms, then the potenti al decreases. Cathodi c pol ari zati on was
deduced t o protect not by suppressi on of l ocal currents but by
formati on of an al kal i ne envi ronment causi ng passi vati on. On the
other hand tensi l e stress e.t(i fted the cathodi c pol ari zati on
55
curve of AIS1 4340 steel i n 3 percent NaCl i n the more nobl e
di recti on (484).
I ni ti ati on of cracks has been rel ated to def ects i n the
surf ace f i l m, somewhat s i mi l ar t o pi t i ni ti ati on (288, 485).
U s e of radi otracer C1 showed i ndi cati ons of charged areas on
the surf ace of the steel , possi bl y due to sul f i de i ncl usi ons .
(306).
ci ent to start corrosi on and subsequent surf ace cracks.
Seven micrograms of C1- on one charged area wer e suf f i -
.
A consi derabl e i ncrease i n aci di ty was found at the t i p
of an advanci ng crack i n seawater, i ndi cati ng a mechanism
aki n t o that f or pi tti ng and crevice corrosi on (596, 774).
Fe but no Fe was detected i n the crack (774).
9. I ntergranul ar Corrosi on
2+ 3+
Grai n boundari es i n metals tend to be parti cul arl y sensi -
ti ve to corrosi on because the energy of the met al i s greater
there and because i mpuri ti es tend to concentrate between crys-
tal l i tes. When attack i s strongl y pref erenti al f or grai n
boundari es, it i s known as "i ntergranul ar corrosi on" and l eads
to rapi d f ai l ure. Austeni ti c stai nl ess steel s are parti cul arl y
suscepti bl e. Heati ng i n certai n temperature ranges causes
sensi ti zati on, whereas anneal i ng i n other temperature ranges
can el i mi nate the problem. Unfortunatel y, sensi ti zati on of ten
occurs duri ng wel di ng. Corrosi on f ai l ure i s then known as
" wel d decay." Addi ti on or subtracti on of certai n el ements
can reduce or el i mi nate the probl em.
One proposed mechanism f or i ntergranul ar corrosi on of
austeni ti c stai nl ess i nvol ves chromium carbi de preci pi tati on at
56
grai n boundari es wi th depl eti on of the nei ghbori ng steel i n chro-
miurn ( 769) . The chromium depl eted areas are then anodi c wi t h
respect to the remai nder of the steel and di ssol ve rapi dl y.
everyone agrees wi th thi s mechanism.
Not
I ntergranul ar corrosi on was
found t o occur onl y when the carbi des formed a conti nuous path and
not when they formed as i sol ated crystal s ( 5 3 4 ) . I t al so occurred
when hi gh temperature treatment removed preci pi tates but l ef t hi gh
sol ute concentrati ons al ong the grai n boundari es.
Other workers
observed i ntergranul ar corrosi on onl y when preci pi tates were
present (535).
10. I nf l uence of Temperature, Vel oci ty, and Ti me
Temperature i nf l uences el ectrochemi cal reacti ons i n several
ways, al though the net ef f ect i s general l y f or corrosi on to accel -
erate as temperature i ncreases.
Thus, i n H2S, low al l oy steel s
corrode accordi ng to an Arrheni us rel ati onshi p; i .e., the corro-
si on rate was proporti onal t o exp (-10,72O/T) where T i s i n degrees
Ranki ne. A maximum rate i s of ten observed i n neutral el ectrol yte
sol uti ons at about 70C ( 776) . The tendency of austeni ti c stai n-
l ess t o stress crack i ncreases wi th temperature
( 691) .
The equi l i bri um potenti al f or an el ectrcci ,z;ni cal reacti on
changes wi th temperature, dependent on the entropy of the reacti on.
I n Equati on 5, E i s a f uncti on of temperature. The dependence of
E on concentrati on i ncreases as temperature i ncreases by vi rtue of
the l ast t e r m i n Equati on 5.
0
Another ef f ect of temperature i s to
acceler.;.te al l cnemi cal reacti ons.
di f f usi on rates, both i n the sol uti on next to the metal and
through any f i l m coveri ng the surface.
A thi rd ef f ect i s t o i ncrease
The sol ubi l i ty of oxygen
57
decreases as temperature i ncreases, which tends to reduce the
corrosi on rate.
Stress corrosi on cracki ng has been reported to be a problem
i n pi pe l eadi ng from compressor stati ons, presumabl y because of
the el evated gas temperatures generated by compressi on.
Underground corrosi on of steel has been found to be negl i gi bl e a
i n permafrost soi l s ( 550) . I n soi l s subj ected to hi gh tempera-
.
tures, corrosi on i s i ncreased unl ess rai nf al l i s so sparse that
the water content of the soi l i s low because of evaporati on. A
pi pel i ne carryi ng hot spri ng water exhi bi ted unusual l y rapi d
corrosi on ( 149) .
I ncreases i n sol uti on vel oci ty near the metal l owers the
resi stance f or mas s transf er, both f or transport of reactants
to the met al surf ace and f or removal of corrosi on products (1).
Whether t hi s i ncreases or decreases the corrosi on r ate depends
on what i s control l i ng the rate. I f the steel i s near the passi ve
state, then i ncreased vel oci ty coul d i ncrease oxygen concentrati on
at the surf ace, cause passi vati on, and reduce corrosi on. Fl ow of th,
sol uti on w i l l al so tend t o remove the concentrated sol uti ons necessa
f or pi tti ng and crevi ce corrosi on. I n the l aboratory, fl owi ng sea-
water was found to be more corrosi ve than qui escent seawater f or
304 stai nl ess ( 584) . On the other hand, stai nl ess corrodes more
sl owl y near the susf zce of the ocean than i n deep qui escent sea-
wat er , which i s much l ower i n oxygen content. Sti rri ng reduced -
deposi ti on of f errous hydroxi de f i l m i n 0. 1 N borax ( 327) . I f
parti cl es are present i n the f l ui d, passi ve f i l ms can be damaged
and corrosi on greatl y accel erated as vel oci ty i ncreases. Thi s
58
i s known as "erosi on corrosi on." With hi gh puri ty water fl owi ng
i n mi l d steel tubes, corrosi on i ncreased wi th vel oci ty up t o a
certai n val ue and then decreased ( 309) . T hi s i ndi cates di f f erent
rate control l i ng steps i n the t wo regi mes.
Uniform corrosi on tends to decrease wi th t i me because of the
presence of corrosi on products bl ocki ng access of corrodents.
On the other hand, pi tti ng and stress cracki ng i ncrease wi th
t i me. Chl ori de-i nduced breakdown of passi ve f i l ms requi res an
i nducti on t i me, which decreases as temperature i ncreases ( 773) .
From an empi ri cal standpoi nt the corrosi on f ai l ure r ate of unpro-
tected pi pel i nes tends t o i ncrease i n an exponenti al manner wi t h
t i me.
11. Ef f ect of Sol utes
The rol e of vari ous i ons i n corrosi on of i ron and steel was
recentl y revi ewed i n Reference 777. The si tuati on i s complex
because so many f actors are i nvol ved i n determi ni ng the corrosi on
rate. There are al so an i nf i ni te vari ety of combi nati ons of
di f f erent sol utes and condi ti ons. Neverthel ess, it i s possi bl e
to state a few general pri nci pl es and summarize the observati ons.
One can see from the cathocl i c reacti ons, Equati ons 2-3, that
corrosi on shoul d be accel erated by low pH and by hi gher oxygen
concentrati ons at the surf ace. Al though i ncreasi ng H concentra-
+
ti on i ncreases corrosi on, the anodi c pol ari zati on curve of Fi gure
, 2 i s actual l y shi f ted to the l ef t , wi th current densi ty change
2 +
H 1
proporti cnal t o l / a +, where a + i s the acti vi ty of H ( 389) . I t
has been suggested both that OH- catal yzes the anodi c reacti on
(Equati on 1) and that H i nhi bi ts tne anodi c reactl on. The
+
59
i nf l uence of oxygen on r ate was of ten i gnored i n earl y experi -
ments, and so contradi ctory resul ts wer e of ten obtai ned for the
i nf l uence of el ectrol ytes on corrosi on.
the corrosi on rate i s of ten found to be proporti onal t o the square
root of concentrati on ( 776, 777) . T hi s probabl y refl ects the
i nf l uence of the conductance of the sol uti on, si nce corrosi on i n-
vol ves novement of el ectri c charge through the sol uti on and w i l l
A t l ow concentrati ons
-
i ncrease as conductance i ncreases. Typi cal l y, corrosi on rate i n-
creases wi t h concentrati on onl y to a certai n poi nt and then di mi n-
i shes as concentrati on i s increased f urther. For "aggressi ve"
ani ons such as C1- the maximum occurs at about 0.5 normal . For
"passi vati ng" ani ons it occurs at a lower concentrati on i n the
nei ghborhood of 1-10 ppm.
centrati on of aggressi ve i ons apparentl y are (1) reduced oxygen
sol ubi l i ty, and ( 2) changes i n corrosi on product f i l ms . Corro-
si on i s reduced wi t h hi gher concentrati ons of i nhi bi tor i ons be-
cause of surf ace adsorption.
The reason f or f al l of f w i t h hi gher con-
The type and. stabi l i ty of any f i l m formed on the surf ace of
steel has a very l arge effect on corrosi on.
depend i n turn on the sol utes present. Thus, sol ubl e cati ons have
onl y a s mal l i nf l uence on corrosi on rate, whi l e cati ons such a s
Zn form an i nsol ubl e product at cathodi c areas and greatl y re-
duce corrosi on. I f the reacti on products are sol ubl e, corrosi on
stays at a hi gh rate, whi l e the rate decreases i f i nsol ubl e prod-
ucts are formed.
The f i l m properti es
++
1
I
Corrosi on i s accelerated by i ons whi ch pass easi l y f r om one
val ence stare to another, such as
60
- 2+
Fe3+ + e = Fe (Eq. 8)
Thi s reacti on acts as an addi ti onal cathodi c reacti on.
Fe 2+ i s
3+
reoxi di zed to Fe by oxygen. Cati ons of nobl e met al s such as
Cu are di spl acement pl ated onto steel and accel erate corrosi on by
gal vani c acti on. The presence of other met al s i n the general
nei ghborhood of the pi pe can i nf l uence corrosi on by changi ng the
composi ti on of the soi l (786).
Resul ts are di f f i cul t to predi ct f or mixed sol utes. Neutral
+
sal ts wer e found to i ncrease H acti vi ty and so t o reduce the
anodi c reacti on rate (389). I n sul f uri c aci d, NaI , NaBr, and
NaCl i nhi bi ted, whi l e NaF accel erated corrosi on. Ten percent HC1,
NaC1, and L i C l accel erated corrosi on, whi l e FeC12 i nhi bi ted.
Chl ori de i ons al tered the structure of f i l ms formed i n NO;. Break-
down of previ ousl y formed passi vi ty occurred onl y above a "break-
through" potenti al i n borax-chl ori de sol uti ons, which became more
negati ve wi th i ncreases i n C1- and more posi ti ve wi th i ncreases i n
borax concentrati on (329) . Bel ow the "pi tti ng" potenti al , C1-
produced no changes i n passi ve f i l ms ( 401) .
i nhi bi ted corrosi on, the amount requi red i ncreased as C1- and SO;
concentrati ons i ncreased (775, 776). To produce a gi ven corrosi on
rate, passi vator concentrati on C was found to be rel ated t o ag-
P
gressor concentrati on C by
P
While NO; and C r Oi
a
l og c = a + b l og Ca (Eq. 9 )
Thi s i ndi cates a competi ti ve adsorpti on mechanism. Corrosi on r ate
remai ned l ow as pH was decreased t o 2.8 i f HCrOI was employed to
l ower pH, whi l e it i ncreased below pH 5 i f H2S04 was used to re-
duce pY (776) On the other hand, hal i des enhanced organi c
61
ami nes' i nhi bi tor ef f i ci ency, most notabl y wi th I- (343). Both
H2S and C1- accel erated corrosi on at 15OoC, but thei r ef f ects wer e
not addi ti ve (706).
Sol utes can al so pl ay a si gni f i cant rol e i n hydrogen absorp-
ti on phenomena such as embri ttl ement, stress cracki ng, and bl i s-
teri ng. For exampl e, oxi di zed arseni c compounds i ncreased Lydro-
gen absorpti on (399). Thi s was thought to ari se from hi ndrance of
the combi nati on of l i berated hydrogen to form mol ecul ar hydrogen,
which i s competi ti ve wi th absorpti on.
12. Underaround Corrosi on
Many studi es have been made on corrosi on of bare unprotected
f errous metal s buri ed i n vari ous types of soi l f or peri ods of up
to 45 years (282, 429, 525, 539, 550, 551, 552, 639, 678, 687,
778, 788-790). Fi el d tests wer e shown to be necessary from the
observati on that pi tti ng was many t i me s greater i n the f i el d than
f or the same soi l i n the l aboratory. Vari ous soi l parameters,
such as pH, el ectrol yte concentrati on, moi sture content, resis-
ti vi ty, etc., wer e determi ned and attempts made to correl ate
corrosi on rate wi th such parameters. Moi sture, which i s general l y
mor e abundant i n poorl y aerated soi l s, provi des the el ectrol yte
f or the corrosi on process. The el ectrol yte i s composed of hydro-
gen and hydroxyl i ons f r o m the wat er i t sel f , and a vari ety of
cati ons and ani ons that depend upon the sol ubl e sal ts di ssol ved
i n the soi l . These i ons determi ne the el ectri cal conducti vi ty,
or r esi sti vi ty, of the soi l and the chemi cal properti es such as
aci di ty and al kal i ni ty.
62
I
I
The ki nd and concent r at i on of sol ubl e sal t s i n soi l s seemt o
af f ect t he i ni t i al r at e of cor r osi on and t he pr ogr ess of cor r osi on
wi t h t i me. I n gener al , t he most cor r osi ve soi l s cont ai n l ar ge
concent r at i ons of sol ubl e sal t s, especi al l y i n t he f or mof sul -
f at es, chl or i des and bi car bonat es, and may have ver y aci d or
hi ghl y al kal i ne pH val ues.
conduct i vi t i es, or l ow r esi st i vi t i es. The l east cor r osi ve soi l s,
as a gr oup, have hi gh r esi st i vi t y val ues, whi ch i ndi cat e l ow con-
cent r at i ons of sol ubl e sal t s. Si nce r esi st i vi t y measur ement s
pr ovi de as much i nf or mat i on as any ot her si ngl e soi l pr oper t y
r egar di ng t he cor r osi ve char act er i st i cs of a soi l , and si nce i t
can be r eadi l y measur ed, i t i s of t en used t o pr ovi de appr oxi ma-
t i ons of t he cor r osi vi t y of soi l s. Resi st i vi t y measur ement s have
st i l l gr eat er val ue when suppl ement ed by obser vat i ons of soi l
dr ai nage and/ or measur ement s of pH. I n gener al , soi l s wi t h r e-
si st i vi t i es gr eat er t han 5, 000 ohm- cmar e f ound t o be mi l dl y
cor r osi ve t o noncor r osi ve. I t shoul d be r eal i zed, however , t hat
because many ot her f act or s may af f ect t he cor r osi on r at e of met al ,
cer t ai n hi gh r esi st i vi t y soi l s nay be mor e cor r osi ve t han soi l s of
l ower r esi st i vi t y (552). I nst ances have occur r ed wher e change i n
soi l r esi st i vi t y, r at her t han t he absol ut e val ue, has been f ound
t o be t he maj or cause of cor r osi on.
Such soi l s al so have r el at i vel y hi gh
I t has been f ound t nat t he r esi st i vi t i es of most soi l s exhi bi t
a l ogar i t hmi c nor mal di st r i but i on, i . e. , t hat t he cumul at i ve di s-
t r i but i on of t he l ogar i t hms of many r esi st i vi t y measur ement s al ong
a pi pel i ne r i ght - of - way f al l s 07 a st r ai ght l i ne on pr obabi l i t y
paper . Such a soi l i s def i ned 2s "st at i st i cal l y uni f or m. "
63
I n one study, pi ts were found onl y at poi nts where r esi sti vi ty
was below about 1200 ohm-cm, wi th i ncreasi ng frequency below
tnat (763).
Rates appeared to i ncrease as pH i ncreased, al though pH al so
tended to i ncrease wi th decreasi ng resi sti vi ty. Another study
reveal ed no correl ati on wi th pH, water hol di ng capaci ty, or sal t
concentrati ons f or vari ous i rons and steel s ( 639) . Tests of ni ck-
.
el cast i ron sampl es reveal ed no correl ati on wi th moi sture, re-
si sti vi ty, pH, or C1- content (525).
Oxygen avai l abi l i ty has a l arge i nf l uence on corrosi on rate.
I t has been found that undi sturbed soi l s are so def i ci ent i n oxy-
gen a few f eet below the ground l i ne or below the wat er tabl e
zone, that steel pi l i ngs were not appreci abl y af f ected by corro-
si on, regardl ess of the soil types or properti es (539). Unfortu-
natel y, pi pel i nes are al most i nvari abl y found i n trenches, where
the soi l has been di sturbed.
Temperature can have a si gni f i cant ef f ect. Thus, steel pi l es
i n Al aska showed no corrosi on when buri ed i n permaf rost (below
5 feet) f or 6 to 11years (550). A few pi t s were found i n the
acti ve thaw regi on (about 5 f eet) and ranged up to 0.7 mm i n
depth. (I t shoul d not be concl u6d from thi s that oi l pi pel i nes
i n permafrost iy.ii-1 not corrodep si nce they w i l l be warmed to pre- L
vent sol i di f i cati on of the oi l ) . Conversel y, seri ous probl ems
-2ere encountered wi th heat di stri buti on l i nes below the wat er
-,able but not wi th those above the water tabl e ( 479) .
I
-
Iri an extensi ve NBS program, it was found that the i ni t i al
pi tti ng rate decreased i n w el l drai ned, hj gh r esi sti vi ty soi l s,
64
but i s mai ntai ned i n poorl y drai ned, low resi sti vi ty soi l s (552).
The pi tti ng rate R changed wi th t i me 0 accordi ng to
P
l og R = log k + n l og 0 (Eq. 10)
P
where n = 0.19 f or w el l aerated and n = 0.68 f or poorl y aerated
soi l s.
The fol l owi ng equati on was deri ved f or maximum pi t depth i n
mi l s (754):
p = K K (10 - ~H P ( e/ pI n (Eq. 11)
n a
where pH i s the soi l pH, p i s the soi l r esi sti vi ty i n ohm-cm, 0
i s t i me i n years, and A i s the exposed area i n square f eet. I(.
and "a1' are dependent on the al l oy used, as shown i n Tabl e 19.
Theoreti cal val ues f or n wer e deri ved by consi deri ng the probabl e
a
r ate l i mi ti ng step. They compare w el l wi th the NBS empi ri cal
val ues i n Equati on 10. Thus, i n w e l l aerated soi l s n = 1/6
f or Taco3 f i l m formati on on cathodi c areas bei ng r ate l i mi ti ng.
For f ai rl y aerated soi l s n = 1/3 f or formati on of f er r i c corro-
si on products over the pi t. For poorl y aerated soi l s n = 1/ 2,
which i s an area ef f ect wi th constant corrosi on current. I n
very poorl y aerated soi l s the corrosi on products are sol ubl e
and lower the resi sti vi ty of the soi l el ectrol yte, l eadi ng to
n = 2/3. Comparison wi th NBS f i el d experi ence gave val ues of
Kn
= 170, 222, and 355 f or good, f ai r , and poor soi l aerati on,.
A Sovi et study i ndi cated that the -:umber and depth of pi tti ng
of gas pi pel i nes i ncreased wi th :-.,zcreas'.?g frequency of changes
i n soi l properti es wi th di stance ( 7 3 C ; . Changes i n el evati on,
soi l type, and resi yti vi ty- wer e consi dered. Greatest pi t depths
were caused by a?.:ernating from cl ays to sandy soi_'s.
65
13. Gas and Petrol eum Corrosi on Ef f ects
Seventy-three of the oi l and gas operati ng companies respond-
i ng to the questi onnai re transport materi al s whi ch, i n the pre-
sence of f ree moi sture, may cause i nternal corrosi on. Tabl e 9
l i sts the materi al s transported by these compani es.
Corrosi on i n oi l and gas w el l equi pment was revi ewed i n
Reference 553. Corrosi on was pri mari l y i nternal . Sour oi l and
gas contai n H2S, whi l e sweet oi l contai ns onl y C02 and f atty aci ds.
Sweet corrosi on i s associ ated wi th hi gh sal twater producti on,
TABLE 9
MATERIALS TRANSPORTED WHI CH CAUSE INTERNAL CORROSION
I N THE PRESENCE OF FREE MOISTURE
Mater i a1 Number of Companies
7 7,
Sour Crude ( H2S) -~_.
Sweet Crude (C02) 14
Crude oi l 7
ivater 6
Sal twater 5
Sul phur
LPG
Refi ned Petrol eum Products
Casi ng head, gas, & f racki ng sol uti on
Causti cs
c12
s04
Gdsol i nes
6 6
i .e., 40 to 50 percent.
caused corrosi on, whi l e pressures below 7 psi wer e noncorrosi ve.
A C02 pressure of over 30 psi usual l y
The general corrosi on rate of l ow al l oy steel s i n aqueous
H S sol uti ons i ncreases as the H2S concentrati on i ncreases.
Hydrogen sul f i de i n sour wel l s caused corrosi on by produci ng
cathodi c i ron sul f i de and by hydrogen cracks and bl i ster s (553).
2
I t has been noted previ ousl y that H2S can i nduce stress corrosi on
cracki ng. On the other hand, i ron sul f i de f i l ms produced on i r on
by H2S-C02-H20 corrosi on were protecti ve ( 3 7 4 ) . Studi es of pH
effect showed that f i l m was l east protecti ve i n pH range 6.5 t o
8.8 and essenti al l y contai ned kansi te (Fe S ) . The niost protec-
ti ve f i l m al so contai ned pyri te (FeS ) and t r oi l i t e ( FeS) .
3 4
2
The corrosi vi ty of petrol eum i ncreases as i ts water content
i ncreases. I n f act, there i s very l i ttl e or no corrosi on unl ess
moi sture i s present ( 706) . A 1953 survey showed requi red main-
tenance of 348 sweet wel l s i n Cal i f orni a i ncreased i rregul arl y as
the percentage of produced water i ncreased (6183). Water i n l ow
spots i n pi pes i s especi al l y del eteri ous parti cul arl y wi th sour
oi l and gas. Such water i s el i mi nated or reduced by proper desi gn
and by peri odi cal l y pi ggi ng the l i ne. The determi nati on of saf e
l i mi t s f or H2S, C 0 2 , and H 0 contents i n rel ati on t o pi pe grade,
2
operati ng pressure, stress l evel , etc., are needed (4126).
14. Corrosi on i n Natural Waters
--
Offshore oi l producti on has i ncreased dramati cal l y i n recent
years. Accompanyi??g thi s has been an i ncreased publ i c sensi ti vi ty
to mari ne oi l l eakages. Pi pel i nes al so cross ri vers, harbors,
bays, etc. Some of these envi ronments are very corrosi ve.
67
Al though seawater i s approxi matel y equi val ent i n strength
t o 3.5 percent NaCl ( 0. 6 normal ), many other components are
present, as shown i n Tabl e 10. The pH vari es from 8. 1 t o 8.3.
The corrosi on behavi or of seawater i s al so appreci abl y di f f erent
from 3 . 5 percent NaC1. A cri ti cal f actor i n corrosi vi ty i s the
oxygen content, which decreases wi th i ncreasi ng temperature, i n-
creasi ng depth, and i ncreased stagnance ( 779) . Attack of mi l d
steel i s l ess at great depths, whi l e stai nl ess steel i s corroded
l ess at hi gh oxygen concentrati ons. The spl ash and ti dal zones
are most corrosi ve f or ordi nary steel s (784). Coastal and harbor
waters are more vari abl e i n composi ti on and more corrosi ve. Forty-
seven percent of steel pi l i ngs submerged f or 37 years i n San Fran-
ci sco Bay had severe corrosi on wi th broad pi ts of an average depth
of 0. 1 i nch (138).
TABLE 10
COMPOSITION OF SEAWATER
ppm
c11- 18,980
- -
s04
HCO-
3
Br-
-
F
2, 649
140
65
1
H BO 26
10,556
N a
Mg++ 1,272
Ca++ 400
K+ 380
Sr++ 13
3+
68
Fresh waters vary i n corrosi vi ty. Sof t waters are more
corrosi ve than hard waters, probabl y because of preci pi tati on of
calcium sal ts from hard waters.
corrosi on by preventi ng preci pi tati on of protecti ve carbonate
Excess C02 and l ow pH enhance
f i l ms. Pol l uted waters sometimes contai n NH H2S, or SO al l
3 ' 2'
of which may i ncrease attack.
Marine pi pel i nes may pass through di f f erent zones of soi l
condi ti ons, aerati on, etc. Concentrati on cel l s formed between
two zones cause "macro-corrosi on," which i s more seri ous than
the "mi cro-corrosi on" caused by condi ti ons wi thi n a si ngl e zone
( 241, 160) . The macro-corrosi on rate has been found t o i ncrease
rapi dl y as the r ati o of cathodi c area t o anodi c area i ncreased.
15. Bi ol ogi cal Ef f ects
L i vi ng organi sms can have l arge i nf l uences on corrosi on of
f errous met al s. The del eteri ous i nf l uence of some mari ne organ-
i s ms i s readi l y apparent. For example: Purpl e sea urchi ns remove
r ust coati ngs, and thus accel erate corrosi on; pi tti ng i s favored
under barnacl es. Such f oul i ng i s much less severe at 5500 f t than
at the surf ace (254).
The effect of mi cro-orTani sms i s di f f i cul t t o i sol ate and t o
determi ne. I t i s known that they are present under ?round, i n
natural waters, i n sewage, and probabl y also i n soiie petrol eum
prodl zcts. Si gh popul ati ons have been found adj acent to pi pel i nes
(5025). Green a:.gae can create oxygen supersati .xati on which
accel2rates cathodi c reacti ons and forms concen7rati on cel i s.
Bacteri a consuxe oxygen and generate cel l s when orgaEi c food i s
present, such as Eound i n some coati ngs ( 174) . Al ternate bznds
69
of aerobi c-anaerobi c zones are found i n sedi ments contai ni ng,
di f f erent amounts of organi c materi al s. Thi s i s very corrosi ve.
Sul f .i ri c aci d i s generated from sul f ur and sul f i des (780). pH
l evel s of 5 and 6 have been produced by generati on of humic aci ds
i n the soi l . C02 i s a uni versal metabol i c product of al l sapro-
phyti c mi crobes. Ammonia can be produced by bacteri al hydrol ysi s
of urea.
The mo s t studi ed mi cro-organi sms from a corrosi on standpoi nt
are the sul f ate reduci ng bacteri a (780, 538, 549, 524, 375).
-
These anaerobi c bacteri a reduce SO, to H2S, which i s i n i tsel f
corrosi ve. I ron sul f i de- i ron cel l s are al so formed. However,
the main i nf l uence seems t o be di r ect depol ari zati on or accel era-
ti on of the cathodi c reacti on.
The schemati c of Fi gure 4 obvi ousl y does not appl y to corro-
si on which resul ts from bacteri al reducti on of sul f ate i ons.
L i t t l e has been publ i shed on the composi ti on of the consequent
corrosi on product. However, si nce the reducti on occurs under
anaerobi c condi ti ons, f errous sul f i de would be expected as the
preval ent form. But both it and the l i ght col ored f er r i c sul -
f i de, both comparabl e i n formul a t o the correspondi ng oxi des, are
hi ghl y i nsol ubl e. The mantl e of ten takes the form of a sl ab
def i ni ng, no doubt, the extent of the bacteri al prol i f erati on.
The sl ab i s used by some as an i t e m Df i denti f i cati on of hydrogen
*
sul f i de corrosi on.
Sul f ate reducers (desul f ovi bri o) produced Fe2P and a vol ati l e
phosphorous compound when growing i n contact wi th steel and phos-
phates (538, 549). Soi l bacteri a i.: s..J ntact- wi th bare steel
70
generated potenti al di f f erences i n the l ab (5025, 5023) . L i ght
i ncreased the corrosi on rate. Methane-generati ng bacteri a al so
i ncrease the corrosi on rate ( 4) .
The i mportance and preval ence of thi s type of corrosi on have
One extensi ve random i nspecti on of coat-
l ong been i n questi on.
i ngs on a pi pel i ne from the southwest to the eastern seaboard
f ai l ed to di scover sul f i des i n the soi l . Tabl e 3 shows that 24
percent of the compani es surveyed consi der mi crobi ol ogi cal corro-
si on to be a si gni f i cant cause of l eaks. Tabl e 11exempl i f i es the
uncertai nty i n extent of bacteri ai corrosi on.
The uncertai nty can al so be shown by quoti ng from respondents
t o the questi onnai re:
(1) "One of our consul tants (cl ai ms) t hi s as a maj or cause
of corrosi on. Other consul tants have si nce expressed doubts
as t o the val i di ty of hi s assumpti on." (Q625)
( 2) " We f i nd . . . that anaerobi c sul f ate reduci ng bacteri a
are the maj or cause of corrosi on." (Q357)
(3) " We bel i eve that maj ori ty of al l corrosi on leaks on steel
pi pes (i s) caused by sul f ate reduci ng bacteri a." (4500)
TABLE 11
COMPANI ES EXPERI ENCI NG BACTERI AL CORROSI ON
Do N o t
Y e s No Know Rarel y
(A) Anaerobi c 37 120 158 33
17 3 16
(B) Aerobic 9 134
( 4) " We do not consi der that it ever has been demonstrated
that bacteri a cause corrosi on on pi pel i nes." (Q585)
Aany of those who attri bute corrosi on to bacteri al acti on base
thei r concl usi on on the presence of sul f i de i on i n the soi l , not
on a detai l ed exami nati on of the corrosi on product mantl e. Thi s
si mpl e and prof i tabl e way t o determi ne the l ocal cause of corro-
si on has been negl ected.
16. Atmospheri c Corrosi on
Porti ons of every pi pi ng system are above ground at pumping
stati ons, end poi nts, etc. Al though corrosi on i s not as great a
probl em aboveground as underground, i t i s present nonethel ess.
A t low pressures of dry oxygen, an i ron oxi de f i l m f i r st
forms at a l i near rate and then approaches a l i mi ti ng thi ckness
of 26 Angstroms. Traces of water vapor lower the l i mi ti ng thi ck-
ness to 18 Angstroms ( 102) . Under real atmospheri c condi ti ons
corrosi on i s si mi l ar to that found underground. Water i s, of
course, necessary f or these corrosi on processes. Rai nf al l suppl i es
occasi onal moi sture. A t a tropi cal mari ne si te corrosi on was more
rapi d i n peri ods of hi gh r ai nf al l and hi gh humi di ty (234). Once
corrosi on products have formed, they can store wat er by shi el di ng
it from evaporati on, by formi ng sol uti ons wi th lower vapor pres-
sures, etc. I t was found that corrosi on was negl i gi bl e when the
rel ati ve humi di ty was hel d below 40 percent wi th the steel bei ng
1
covered by syntheti c rusts contai ni ng sul phates and chl ori des
(781). Hygroscopi c sal ts and aci ds from the atmosphere can settl e
on the steel surf ace and keep it mo.d,st. I t was suggested that
f errous sul f ate hydrate cap. suppl y water by dehy?.rati on (782).
7 2
Many f i el d tests of atmospheri c corrosi on have been made
(e.g., Refs. 189, 4 3 , 169, 234). Corrosi vi ty vari es wi th the
met al bei ng tested (189). Sea sal t and SO2 accel erated corro-
si on ( 4 3 ) . Corrosi on of a vari ety of steel s was found t o be i n-
f l uenced t o the greatest extent by SO2 content ( 169) . Specimens
exposed i n the wi nter have a much hi gher S content at the metal
surf ace than those exposed i n the summer (173). S02-f orms hygro-
scopi c and corrosi ve H2S04 i n the atmosphere and al so on the i ron
surf ace, which may, i n f act, accel erate the reacti on.
The i nf l uence of ai rborne sal t was i l l ustr ated by the obser-
vati on that the corrosi on rate of i ron was an order of magni tude
greater at 80 f eet'f rom the ocean than at 800 f eet away (784).
Ozolle, a component of smog, caused pi tti ng of steel i r, dei oni zed
water but reduced pi tti ng i n sea water ( 785) . Ozone al so accel -
erated corrosi on of steel i n di l ute H2S04.
73