SECTI ON IT'

CORROSI OE CONT3OL
I t has been seen that corrosi on ari ses from a vari ety of
sources and that it can be very destructi ve. I n hi qh resi s-
ti vi ty soi l s corrosi on may be very low, but excepti ons are
known.
vari ety of corrosi on mi ti gati on techni ques. Previ ous di s-
cussi on shows that certai n obvi ous mi stakes, such as pl aci ng
di ssi mi l ar metal s i n contact, must be avoi ded.
avai l abl e f or corrosi on control are di scussed i n thi s secti on.
I t i s Frobabl y saf e to say that no one method of corrosi on
mi ti gati on answers al l probl ems.
Pi pel i ne operators are making i ncreasi ng use of a
Speci al methods
Out of 373 operati ng companies 330 sai d thev have a corrosi on
control program.
.'.ected and are on f i l e at OPS-DOT.
2rcsess of setti ng ap a corrosi on control program, wr i i l e others
use consul tants. The reasons gi ven f or not havi ng a corrosi on
control program wer e to the ef f ect that corrosi on was not of
suf f i ci ent magni tude to j usti f y such a program.
The descri pti ons of these programs were col -
A few companies are i n the
The number of operati ng companies that have sponsored or
engaged i n corrosi on control research are shown i n Tabl e 12.
1. Materi al Sel ecti on and Treatment
Al though no f errous metal i s untouched by corrosi on, the
extent of corrosi on i s si gni f i cantl y i nf l uenced by the exact
composi ti on of the metal and i ts thermal and mezhani cal treat-
ment. Tabl es 13-18 summarize recent resul ts on var'ous treat-
ments al teri nc; resi stance to corrosi on of vari outi types Q
7 4
TABLE 12
MAJ OR AREAS OF CORROSI ON RESEARCH ENGAGED I N OR SPOYSORED
BY THE OPERATI NG COMPANI ES
Resear ch Ar ea Numbe r of Comp an i e s
HVDC 45
Coat i ngs 42
Cor r osi on r esi st ance of pi pi ng and
or gani c coat i ngs i n var i ous envi r onment s 20
Anode composi t i on & gr oundbeds
St r ess cor r osi on
I nt er nal cor r osi on, i nhi bi t or s
Cat hodi c pr ot ect i on
Al t er nat i ng cur r ent cor r osi on
Fi el d t est met hods
Over - t he- l i ne sur veys
St r ay cur r ent s
Hydr ogen embr i t t l ement
Pul se r ect i f i cat i on
De- i ci ng sal t ef f ect s
Pol ar i zat i on
Under gr ound cor r osi on
Bact er i al cor r osi on
Cat hodi c pr ot ect i on cr i t er i a
Cor r osi on r at e st udi es
Li ght ni ng ef f ect s
15
13
12
7
5
5
Sour gas cor r osi on 2
St at i st i cal anal ysi s of l eak f r equency, pi t t i ng 2
Tel l ur i c ear t h cur r ent s
Casi ngs at r ai l r oad cr ossi ngs and r oads
2
1
Copper pi pe 1
Fi ber gl ass pi pe 1
I nsul at ed f i t t i nqs 1
St ai nl ess st eel t ubi ng f or gas di st r i but i on 1
75
met al s. A s noted previ ousl y, suscepti bi l i ty to stress corrosi on
cracki ng, hydrogen embri ttl ement, sul f i de cracki ng, etc., i n-
creases as the yi el d strength of steel i ncreases.
Many addi ti ves improve corrosi on resi stance by i ncreasi ng the
tendency to form passi vati ng f i l ms. Thus, chromium addi ti ons
( stai nl ess steel ) i ncrease resi stance to mo s t forms of corrosi on, .
but i ncrease suscepti bi l i ty to rapi d i ntergranul ar corrosi on
ari si ng from certai n heati ng cycl es -- especi al l y duri ng weld-
i ng. Other addi ti ves can be used t o avoi d these probl ems.
I t has been cl ai med that cast i ron pi pe has a good record
f or resi stance to underground corrosi on by vi rtue of i ts l arge
wal l thi ckness and the graphi te parti cl es remai ni ng t o form a
sol i d graphi te- rust coati ng (788, 789, 142) . These resi dues
pl ug hol es i n pi pe due to pi tti ng and prevent l eakage at sub-
stanti al hydrostati c pressures (788). However, the ol d gray
cast i ron was br i t t l e and weak because of the f l aky morphology
of the graphi te. Thus, f or example, cast i ron gas mains wer e
prone t o break i n hi gh shri nk-swel l cl ays and wer e repl aced by
steel pi pe (543). Al so, catastrophi c mechani cal fai 2.ure of
graphi ti zed cast i ron pi pe has been observed. I n ducti l e cast
i ron, speci al heat treatments are used to produce nearl y
spheroi dal graphi te parti cl es. Accordhg t o one manufacturer,
the resul t i s a ducti l e met al wi th t wi c e the i ni t i al strength,
less strength loss upon pi tti ng, and a sl i ghtl y lower corrosi on
rate ( 142) . I n seawater, however, gra.y cast i ron corroded t wi c e
as f ast as mi l d steel and f i ve t i mes as f ast as 18 percent K i
cast Fe.
76
Equati on 11 gi ves pi tti ng rate as a f uncti on of several var-
i abl es. The parameters K and a i n Equati on 11 were determi ned
empi ri cal l y from NBS data and are gi ven i n Tabl e 19. From thi s
it would appear that cast i ron corrodes more rapi dl y than steel
a
f or l arge exposed areas and slower f or s mal l areas.
Cu addi ti ons have been found to practi cal l y suppress bac-
teri al acti vi ty ( 165) . I ncl usi ons of second phase materi al can
of ten accel erate corrosi on by formi ng l ocal gal vani c cel l s. Sul -
c
f i de i ncl usi ons i n stai nl ess steel caused pi t i ni ti ati on (331).
Heat treatment can greatl y i nf l uence corrosi on resi stance,
as i ndi cated i n the tabl es. Unf ortunatel y, the ef f ect of weld-
i ng i s general l y del eteri ous. The kni f e- l i ne i ntergranul ar
corrosi on i n some stai nl ess steel s has been menti oned previ ousl y.
Hardness i s of ten i ncreased al ong wel ds, which i ncreases crack-
i ng. Thus, hard el ectri c resi stance wel ds have cracked f or
hundreds of f eet i n sul f i de envi ronments (338), Post-wel d heat
treatment has proved benef i ci al i n preventi ng cracki ng (337).
Oxi dati on duri ng anneal i ng, heat treati ng, and wel di ng prod.uced
Cr-ri ch scal e and Cr-depl eted metal surf ace on stai nl ess steel
( 536) . Scal e and a thi n l ayer of the surf ace had to be remove?
to restore corrosi on resi stance.
I n Tabl e 6 it was shown that l eaks have been observed much
*
more of ten on l ongi tudi nal f actory and f i el d wel ds than on
spi r al f actory wel ds.
L,er.gthy tests are necessary to determi ne true di f f erences
i n underground corrosi on. The corrosi on rate of cast i rons
decreases rapi dl y because of the graphi te- rust coati ng formati on.
77
TABLE 13
METAL TREATMENTS IMPROVING RESISTANCE TO GENERAL CORROSION
Al l oy Types Environment Factors I mproving Resi stance Ref.
- - Underground C r , Cu + N i addi ti ons 526
Underground Gray cast i ron >> steel and 282
ducti l e cast i ron
a
Steel s Seawater, 18% N i cast i ron > mi l d 330
Steel s Spl ash and 0.5% N i , 0.5% Cu, O.l2%P 784 .I
Steel s Marine 2. 6 Cr-0.5 M o 10 X C steel 784
Stai nl ess 3% NaC l C r addi ti on >11% 4 7 3
16 years Steel > grey cast i ron
ti dal seawater 2X C steel
18-8 Austeni ti c Seawater -Mo addi ti ons --
18-8 >Cr f er r i t i c and
martensi ti c steel s
677
Steel s Atmosphere - A517 grade F > A 242 Type 1 784
Marine > Cu steel > C steel
H S i n H20 C r addi ti ons
2
Low al l oy
steel s
0.007 - O2 f ree, Avoid col d work
0.15% C 0.12 N HC1
787
756
0 f ree, Don't col e work & anneal 756 0. 01 -
Pure i ron Aerated 0.12N Avoid i mpuri ti es, i n order of 280
Fe-Cr-C al l oys 0. 1N borax Decrease pearl i te/ f erri te 327
Pure i ron 1N H2S04 Anneal i ng at 9 0 0 Cf l hr. 783
2
0.02% N2 0.12 N HC1
HC1 i mportance P, S, C f A s, N, B
r ati o, prevent cementi te
vacuum, and i mpuri ti es
Pure Fe - - S removal or Mn & Cu
addi ti on
319
430 Stai nl ess - - 0.1-0.5% U addi ti ons 279
Stai nl ess
. .
- - Smooth surf ace ratb.er than 536
r0ug.h
78
TABLE 14
METAL TREATMENTS I MPROVI NG mSISTANCE TO PI TTI NG
AND CREVI CE CORROSION
Al l oy Types Environment Factors I mproving Resi stance Ref.
C as t i ron Underground 15% N i 525
C as t i ron Underground Ducti l e sl i ghtl y better 788
Fe crystal Di sti l l ed (111) *> (100) *> (110) * 492
Steel s S e awater N i reducti ons, 330
than grey
* water Puri f i cati on
mi l d steel > hi gh strength
steel
Stai nl ess c1- N i addi ti ons 179
Stai nl ess Marine 316,316-6, 20-Cd, 17 Cr- 7Ni 254
steel s
steel s -0.7Ti -0.2 A1 not corroded:
405, 410, 430, 301, 304, pi t
18-8 Stai nl ess 0. 1N NaC1, Re reducti ons 772
18-8 Stai nl ess 0.lN NaC1, Re addi ti ons 772
Stai nl ess - - E l ec tropassi vati on 536
Cr-Fe c1- C r addi ti ons, N i had no 326
Cr-Fe 0. 1N N aC l I ncreasi ng C r 154
15% Cr-Fe 0.1M NaCl N i addi ti ons 154
Stai nl ess C1- i n di l 316 > 321 > 302 > 304 487
I ron + C r c1- i n IN C r addi ti ons 328
487 Stai nl ess Di l . , H2S04 321 > 316 > 304 > 302
Vari ous CaS04 or TK-2>3% N i > J -55 6184
ooc
25OC
(anodi zi ng)
ef f ect
steel s H2S04
H2S04
steel s
BaSO paske = N-80
scal 8
Steels Atmospheri c 0.3% Cu 165
*?4i l l er i ndi ces
79
TABLE 15
MEXAL TREATMENTS I MPROVI NG RESISTANCE TO STRESS
CORROSION CRACKI NG
Al l oy Type Envi ronment Factor I mproving Resi stance Ref.
Steel s C a (NO3) 2+ T i addi ti on of 4 X C 175
NH 4"3
l 0O0C A
-- Decrease N i ncrease C 301
2'
(at constant strength)
Steel s
Steel s -- U s e hi gh puri ty Fe, C r , N i 694 .
4340 Steel -- Addi ti ons of Si > 1.5%, 530
18-8 Stai n- MgCl sol n., F er r i ti c >> austeni ti c 272
reducti ons of S & P
l ess 154O8
Annealed austen- Boi l i ng 42% C & N i addi ti ons
Cold-worked Boi l i ng 42% C & S i addi ti ons
i te stai nl ess !1gCl2 N2 reducti ons
austeni te MgC12 P & Mo reducti ons
stai nl ess
321
321
-- -- Puri ty, br i t t l e al l oys 691
TABLE 16
METAL TREATMENTS I MPROVI NG RESISTANCE
TO HYDROGEN EFFECTS
Alloy Type Environment Factor I mproving Resi stance Ref.
18-8 Stai n- D i l . H,SO, + austeni ti c >> f er r i t i c 272
less
L 4
As203.
301 I 17-7 D i l . H2S04 + anneal ed >> col d reduced 272
As203.
Steel s Y i el d strengths <130,00@ psi r 587
avoi d hard wel ds
80
TABLE 17
bETAL TREATMENTS I MPROVI NG RESI STANCE TO SUL FI DE
STRESS CRACKING
Alloy Type Factors I mproving R es i s t anc e Ref .
Low al l oy steel s T emper to el i mi nate martensi te 408
Steels L ow yi el d strength, A285 337
immune, 365 very suscepti bl e
-
TABLE 18
METAL TREATMENTS I MPROVI NG RESI STANCE
TO INTERGRANULAR CORROSI ON
A l l oy T ype E nvi r onment Factor I mprovi ng R es i s t anc e Ref .
Steel - - low N i , C; T i addi ti on 535
O.l%C, 20%Cr,
3-6% N i
- - 0.4% TI ( someti mes) 289
A us t eni t e 304 B o i l i ng HN03 Smal l addi ti ons of Cb+B
stai nl ess
528
304, 316 stai n- - -
less
M o addi ti on 654
TABLE 19
VALUES OF MATERI AL PARAMETERS I N EQUATION 11 FROM NBS
UNDERGROUND TEST DATA (754)
Parameters Wrought I ron Steel C as t I ron
-
1. oc 1.06 1.40 K
a 0.13 3.16 e.22
2.
. - . .-
81
Steel s wi th 3- 5 percent C r i n seawater had lower wei ght l osses
for two years, but l arger losses af ter f our years.
Even surf ace preparati on can i nf l uence corrosi on rates.
Rough surf aces were found to corrode faster than smooth sur-
faces on stai nl ess steel (536). Cold work di d not change the
corrosi on r ate of pure i ron but did. i ncrease the corrosi on rate
when some C was present ( 756) . Anneal i ng above 2 O O O C decreased
the rate, suggesti ng that pl asti c deformati on i ncreases corro-
si on by produci ng composi ti onal i nhomogenei ti es.
Sel ecti on of a parti cul ar al l oy depends not onl y on corrosi on
resi stance but on mechani cal properti es and l argel y on economic
consi derati ons, whi ch i ncl ude cost of the metal and f abri cati on,
protecti on necessary, requi red l i f eti me, mai ntenance and repai r,
damage due t o l eaks, etc.
2. I nhi bi tors
An i nhi bi tor i s a chemi cal whi ch si gni f i cantl y reduces corro-
si on when present i n s mal l amounts. General l y, there is a con-
centrati on below whi ch the i nhi bi tor accel erates corrosi on.
On
the other hand, it i s not economi cal t o use more i nhi bi tor than
requi red.
must be determi ned experi mental l y.
coupons or hydrogen probes whi ch control automati c i nj ecti on
equi pment.
Thus, there is an optimum concentrati on range -- which
T hi s can be accompl i shed by
I nhi bi tors have proven to be c7 practi cal means of control l i ng I
i nternal corrosi on of pi pel i nes carryi ng petrol eum products.
a 1950 survey of 8215 sour crude wel l s i n the mi d-southwest, 4 4
percent wer e found to be economi cal l y affected by c2rrosl on
I n
82
(6185). Of those af f ected, 26 percent were bei ng treated by
corrosi on i nhi bi tors. I n a 1953 survey of 348 s weet crude oi l
wells i n Cal i f orni a, it was found t hat i nhi bi tors caused an 80
percent reducti on i n i ron content of the oi l produced
Pul l i ng j obs were reduced 51 percent; rod j obs, 46 percent; tub-
i ng j obs, 71 percent; and pump repl acements, 36 percent. I n-
hi bi tors have been found to be ef f ecti ve not onl y f or control l i ng
pi tti ng but al so f or reduci ng sul f i de cracki ng,
al though some
cracki ng of wel d-suscepti bl e steel sti l l occurred (337).
(6183).
I
Fi fty-seven of the 373 operati ng companies surveyed i n
thi s study used i nhi bi ti on to control i nternal corrosi on.
Fi f ty- ei ght used dehydrati on.
A wi de vari ety of chemi cal s has been found to i nhi bi t corro-
si on. I n 1955, NACE commFttee T-3A publ i shed a ref erence l i st
of 68 i nhi bi tors and cl asses of i nhi bi tors ( 6186) . The com-
posi ti on of many i nhi bi tors i s, of course, propri etary and/or
secret.
I nhi bi tors may be di vi ded i nto organi c and i norgani c.
I n the 1953 Cal i f orni a oi l w e l l survey, 65 percent wer e i norgani c
and 35 percent organi c (6183).
Apparentl y, several di f f erent mechanisms can be i nvol ved i n
i nhi bi ti on. Strongl y oxi di zi ng addi ti ves, such as chromate, can
cause formati on of passi vati ng oxi de f i l ms. Other addi ti ves
merel y al ter the corrosi vi ty of the el ectrol yte by changi ng pH
or by removing corrosi ve sol utes.
The pol ar organi c i nhi bi tor2
are general l y thought t o act by formi ng an adsorbed l ayer on the
metal surf ace to bl ock reacti cns there. Radi otracers showed
that monol ayers were formed and gave protecti on (693).
83
Obvi ousl y, bl ockage of any step i n the corrosi on sequence
w i l l be ef f ecti ve and i s probabl y found i n the acti on of some
i nhi bi tor. Thus, the f uncti on of strong oxi di zi ng agents, such
as l ead suberate an6 l ead azel ate, i s to convert Fe 2+ t o Fe 3+ i n
2+
f i l ms (36). Fe was thought to he responsi bl e f or breakdown of
the f i l ms . Amines were chemi sorbed on Fe and i nhi bi ted corrosi on
onl y when the surf ace was not dry ( 226) . The amount of chromate
A
or ni t r i t e requi red to i nhi bi t corrosi on was found to i ncrease -
as the amount of chl ori de and sul f ate i ncreased (775). A com-
peti ti ve adsorpti on mechanism between i nhi bi ti ng i ons and aggres-
si ve i ons was thought to be i nvol ved.
The i nhi bi ti ng acti on of neutral benzoate was si mi l arl y
attri buted to reducti on i n breakdown of the f i l m ( 220) . I t was
hypothesi zed that hexamethyl enei mi ne 3, 5-di ni trobenzoate i n-
hi bi ts by depol ari zi ng the cathodi c reacti on, whi ch changes the
potenti al to the posi ti ve si de and causes passi vati on ( 396) .
Ammonium i on was found to be an i nhi bi tor i ndependent of pH,
A certai n amount of corrosi on
H2S and C1- concentrati ons ( 706) .
occurred bef ore protecti on was obtai ned,
even i f sampl es were
presoaked i n the i nhi bi tor. Thi s suggests that i nhi bi ti on
resul ts from i nteracti on of NH4
wi th the metal surf ace i tsel f .
have been used i n conj uncti on to provi de grea.ter i nhi bi ti on -- a
synergi sti c ef f ect. Of several si mpl e ani ons, I- was observed
+
wi th f i l m or scal e and not
Organi c and i norgani c compounds
c
t
to yi el d the greatest improvement i n corrosi on mi ti gati on of
organi c ami nes.
Only some of the basi c experi mental and theoreti cal research
84
done on the i nhi bi ti on mechanism i s menti oned above. Reference
690 gi ves a l engthy review of these resul ts. One research goal
i s to enabl e mol ecul ar desi gni ng of organi c corrosi on i nhi bi tors.
I t would appear that di scovery and use of i nhi bi tors i s sti l l
pri mari l y an empi ri cal art, al though eventual l y rati onal sci en-
t i f i c approaches may be possi bl e. I n other words, f urther quan-
ti tati ve i nvesti gati on of i nhi bi tor ef f ecti veness and. i nhi bi ti on
procedures i s needed (Q126).
3 . Coati ngs: General Pri nci pl es and Surf ace Preparati on
An i mportant method of corrosi on mi ti gati on i s the del i berate
appl i cati on of a coati ng to ei ther the i nteri or or the exteri or
of the pi pe. I nteri or coati ng i s general l y confi ned to rel a-
ti vel y short l engths of metal , as ir. oi l wel l s , and to l arge
di ameter pi pes. Only 17 companies surveyed used i nternal
coati ngs. Coati ng of the exteri or of the pi pe on the other
hand i s very wi del y employed.
one must take care to di sti ngui sh between the i ntact coati ngs
and degraded coati ngs which are no l onger protecti ve. I n other
words, i t i s not saf e to assume that "once coated -- al ways
coated." A l l coati ngs have f i ni te l i f eti mes, al though these
may i n some cases exceed the usef ul l i f e of the pi pel i ne. The
preval ent ci rcumstances under which coazed pi pes have devel oped
l eaks wer e summarized i n Tabl e 5. Tne qval i ty of nonconducti ve
coati ngs -an be conveni entl y j udged ei ther by thei r average
conductance or by what i s equi val ent, the average current den-
*
I n consi deri ng pi pe coati ngs
si ty requi red f or cathodi c protecti on.
"Coati ngs formed by the zorrosi on process i tsel f , such as the
graphi te- rust scal e formed on cast i rons, are excl uded.
Coati ngs reduce corrosi on by many di f f erent mechanisms.
A
gi ven coati ng may f uncti on by more than one mechanism, ei th,er
si ni ul taneousl y or sequenti al l y at di f f erent stages i n i ts l i f e.
Metal coati ngs may act as sacri f i ci al anodes; as barri ers t o
contact wi th the el ectrol yte; as sources of a passi ve f i l m; by
al ternati on of the surroundi ng envi ronment; and/or as a source
of i nhi bi ti ng i ons. Nonmetal coati ngs may act as barri ers to
contact of water and el ectrol ytes wi th the surf ace, as i nsul ators
to fl ow of el ectri cal current, and as sources of i nhi bi tors and
bi oci des. The ef f ecti ve l i f e of protecti ve coati ngs can be con-
si derabl y extended by qual i ty control of surf ace preparati on,
coati ng sel ecti on, and appl i cati on procedure ( 82) .
Many cl ai ms have been made as
to the superi ori ty of vari ous
coati ngs. I t i s true that some coati ngs have advantages, al -
though which coati ngs are best depends 3n a vari ety of f actors
i ncl udi ng economics, envi ronment, requi red l i f eti me, etc. N o
one coati ng i s best under al l condi ti ons, and no coati ng i s
absol utel y perf ect under any gi ven condi ti on (682). Therefore,
conti nued research f or the "perf ect" coati ng i s worthwhi l e
(Ql O9, Q436). I mprovement i n the ef f ecti veness and appl i cati on
(hol i day detecti ng, f i el d j oi nts, bond agi ng, etc.) of thi n f i l m
coati ngs i s needed (Q274, Q256, Q323, 4812). Of equal i mportance .
to the type of coati ng i s the method cf appl i cati on.
cati on can negate the protecti ve qual i ti es and coul d concei vabl y
i ncrease corrosi on by pr0vi di r.g shi el ded areas f or bacteri al
acti on, produce concentrati on cel l s, augment densi ty of di s-
charge of i nterf erence current, and reduce ef f ecti veness of
Poor appl i -
.
86
cathodi c protecti on. I n fact i nstances have been noted i n which
pi tti ng i s more severe wi t h coated than wi th uncoated met al (131,
682). Tabl e 5 shows that the second mo s t f requent ci rcumstance
for l eaks i n coated pi pes was i mproperl y appl i ed coati ngs.
(Damage of the coati ng was the mo s t f requent ci rcumstance.)
The maj or types of protecti ve coati ngs used by the companies
Coal tar ename-1 was used by 205 surveyed are shown i n Tabl e 20.
companies as f i r st choi ce. Forty-ei ght of these companies wer e
oi l companies and 144 wer e gas companies. Asphal t was the f i r st
choi ce of 34 companies.
companies.
-
Ten wer e oi l companies and 19 wer e gas
TABLE 20
MAJ OR TYPES OF PROTECTI VE COATI NGS USED BY COMPANI ES
DURI Y G THE LAST 5 Y EARS BY ORDER OF USE
Protecti ve Coati ng 1st 2nd 3rd 4th 5th 6th
(A) Asphal t
34 37 14 1 3 0
(B) Coal tar
205 72 30 1 0 0
(C) Masti c
20 42 50 22 6 1
( D) Pref abri cated f i l m
55 71 53 11 6 0
(E) Wax
3 11 13 i1 1 0
(F) Other
49 70 24 13 0 0
Tabl e 21 l i sts the maj or f actors consi dered by the surveyed
companies i n sel ecti ng coati ng materi al s and wrappi ngs.
87
TABLE 21
FACTORS CONSIDERED I N SELECTI NG COATI NG MATERIALS
AND WRAPPINGS FOR SPECIFIC APPLICATION
Factor Number of Companies
Exp e r i en ce 187
Resi stance to Deteri orati on 164
Economics 159
El ectri cal Properti es 154
Soi l Stress Resi stance 135
Permeabi l i ty 92
Temperature Stabi l i ty 76
Ease of Appl i cati on 54
Compati bi l i ty 16
Mechani cal Properti es 12
Geography and Geology 11
Manufacturer's Speci f i cati ons LO
Storage 10
Saf ety of Personnel 1
The materi al s currentl y used by the companies to coat f i el d
Pl asti c tapes j oi nts and appurtenances are l i sted i n Tabl e 22,
i n vari ous forms and modes of appl i cati on are by f ar the mo s t
wi del y used.
The f i r st step i n proper coati ng appl i cati on i s surf ace
preparati on, as thoroughl y revi ewed i n a NACE report C6171).
For good coati ng adherence a cl ean surf aqe sl i oul d be produced
by removal of such thi ngs as oil, qrease, c5rt, wel di ng f l ux,
88
TABLE 22
MATERIALS CURRENTLY USED TO COAT FI ELD
J OI NT S AND APPURTENANCES
Coati ng System Number of Companies
Tapes; pl asti c, rubber or bi tumen
m adhesi ves, col d or hot appl i ed 318
Asphal t Mastic 111
Bi tumi nous Materials, hot appl i ed
Coal tar
Asphal t
88
65
Bi tumi nous Materials, col d appl i ed 5
Mi scel l aneous Materials
Cement Mortar
EPOXY
Gl ass tape
Pol yurethane f oam
Sand
Sheet pl asti c
3
18
6
1
1
48
sl ag, mi l l scale, rust, etc. For mo s t coati ngs the surf ace
shoul d be rough, as measured by the surf ace prof i l e or "anchor"
pattern. The rul e of thumb has been that anchor depth (bi te)
shoul d not exceed one-thi rd of the total thi ckness of the coat-
i ng system. I nstruments have been devi sed to assess the surf ace
prof i l e (791). Rough corners or bumps, as mi ght resul t from
wel di ng, shoul d be removed.
Surf ace treatments may be roughl y di vi ded i nto chemi cal
and mechani cal . Grease and oi l must general l y be removed bef ore
other treatments. T hi s may be accompl i shed wi th organi c sol -
vents, al kal i ne sol uti ons, emul si ons, or hot watar pl us deter-
gents. Scale and rust can be removed by aci 6 pi ckl i ng and
89
el ectrol yti c pi ckl i ng.
ousl y by treatment wi t h sol uti ons of phosphori c aci d and organi c
sol vent or al kal i phosphate pl us detergents. Scale and heavy
r ust can be popped of f by fl ame condi ti oni ng or i nducti on heat-
i ng. Heati ng can al so be usef ul f or removing hydrogen from the
metal i nteri or.
O i l and scal e may be removed si mul tane-
Mechani cal methods i ncl ude wi r e brushi ng, i mpact tool ,
gri ndi ng, bl asti ng wi th abrasi ve, and wheel bl asti ng. These
operati ons may be ei ther carri ed out by hand or by equi pment of
vari ous degrees of automati on. Bl asti ng has been j udged by
appearance accordi ng to the Swedish standards, wi th a "whi te"
surf ace the best (731). Normal l y, it has not been consi dered
economi cal or necessary to go to a whi t e surf ace.
Weatheri ng or treatment wi th phosphori c aci d mi xtures i s
requi red f or coati ngs to adhere to gal vani zed steel . A cet i c
and hydrochl ori c acids have not been recommended.
Appl i cati on of pri mer shoul d f ol i ow surf ace cl eani ng as
soon as possi bl e, bef ore oxi dati on and contami nati on occur.
I f it i s not possi bl e to pri me i mmedi atel y then several pre-
treatments are avai l abl e. Vi nyl metal condi ti oner, or wash
pri mer, consi sts of a resi n-chromate-phosphate mi xture pro-
vi di ng seal i ng and i nhi bi ti ng acti on. O i l s of vari ous types
can al so be employed.
Red l ead pai nt has been found to be an ef f ecti ve pri mer i n
many i nstances. C as t i ron and steel sampl es wi th a si ngl e coat
of red l ed pai nt suf f ered practi cai l y RO corrosi on under f i el d
condi ti ons f or one year in tests co;?ducted i n I ndi a ( 6 3 9 ) . A
.
90
10-year underground test showed that zi nc chromate and baked-on
red l ead pri mers adhered wel l and retarded corrosi on, but that
they provi ded i nsuf f i ci ent protecti on when used al one (682). I n
the atmosphere, three coats Of red-l ead pri mer showed no si gns
of rusti ng af ter f i ve years i n a South Af ri can test program (83).
. . Zi nc chromate-epoxy resi n pri mers gave si mi l ar resul ts and wer e
pref erred f or mari ne envi ronments. Lead si l i co-chromate was
al so good but kept better i n prol onged storage. I t was cl ai med
that the passi vati ng acti on of pri mers can be determi ned by
measuri ng the potenti al of the met al (283).
Organi c coati ngs are commonly used f or pi pel i nes. Except
f or sacr i f i ci al anode coati ngs such as zi nc, it i s i mportant to
mi ni mi ze the number of hol es or "hol i days" i n the coati ng. Water
and el ectrol yte can reach the metal surf ace through hol i days and
cause rusti ng. Thi s resul ts i n peel i ng and. bl i steri ng of the
coati ng, greatl y reduci ng i ts ef f ecti veness. General l y, the
hol i day probl em di mi ni shes as the number of coats and the total
coati ng thi ckness i ncrease. A total of 263 of the companies
surveyed used hol i day detectors to check the ef f ecti veness of
coati ngs appl i ed to f i el d j oi nts, main l i ne val ves, f l anges,
and taps.
4 . Pai nts
Pai nts consi st of f i nel y di vi ded i norgani c pi gments and
organi c bi nders of vari ous types. They may be appl i ed by
brush, rol l er, spray, di ppi ng, el ectrostati c spray, etc.
Apparentl y, pai nts have seldom been used f or underground
pi pel i nes,.al though they 3ave al most al ways been employed f or
91
aboveground porti ons and of ten on mari ne pi pel i nes.
The pi gments i n rust-proof pai nts are not selected f or the
sake of appearance but f or ef f ecti veness i n the control of corro-
si on. Zn, A l , or Mn dusts have someti mes been used and act as
sacr i f i ci al anodes (246, 144) . Other pi gments serve as i n-
hi bi tors or form protecti ve f i l ms by reacti ng wi th the sur-
roundi ng and/or corrosi on products to yi el d new compounds. Red
l ead, zi nc chromate, zi nc si l i cate, zi nc oxi de, and phdsphates
have al l found favor.
The stabi l i ty, f l exi bi l i ty, adhesi veness, and permeabi l i ty
of the organi c consti tuents are equal l y i mportant. I n a 14-year
study of pai nts i n potabl e-water tanks, vi nyl s wer e found t o
perform better than phenol i cs ( 166) . Thermosetti ng acryl i cs
have been found to adhere better than melamine al kyds. Mul ti -
l ayer coati ngs have of ten been favored. Another study con-
cl uded that 0.2 nun Zn-ri ch pai nt covered wi th 0.15 mm of bi tumi n-
ous coati ng was best f or water-immersed structural steel (256).
When a coati ng i s subj ected to dai l y temperature f l uctua-
ti ons, it must mai ntai n i ts f l exi bi l i ty under the thermal
stresses generated.
general l y accepted speci f i ceti ons have been found to l ose much
of thei r ori gi nal bond under dai l y temperature f l uctuati ons.
The same study found syntheti c pri med coati ngs to have cl ear
adhesi on superi ori ty over coal tar pri med coati ngs ( 722) .
Some coati ng-pri mer combi nati ons meeti ng
B es t protecti on agai nst sea ai r has been reported obtai ned
wi th pure zi nc-dust pai nt and a syptheti c impermeable and
mechani cal l y hard bi nder ( 246) . Marine pai nts qui te of ten
92
contai n bi oci dal agents and are known as "anti f oul i ng." Toxi c
mercury and copper pai nts have been found to retard f oul i ng f or
t wo t o three years. I n the use of copper based pai nts, it i s
absol utel y essenti al that the undercoati ng be hol i day-f ree.
Thi s i s because copper sal ts can di spl acement-pl ate copper metal
onto steel and cause rapi d gal vani c corrosi on ( 2 5 4 ) .
5. Metal Coati ngs
Metal coati ngs can be appl i ed by vari ous methods i ncl udi ng
hot di ppi ng, el ectropl ati ng, flame sprayi ng, and vacuum evapo-
rati on, as revi ewed, f or example, i n Reference 546. Heati ng
af ter coati ng t o permi t some di f f usi on i nto the i ron general l y
i mproves adhesi on. Metal coati ngs can be di vi ded i nto t wo
categori es - anodi c and cathodi c -- accordi ng to thei r posi ti on
i n the gal vani c series rel ati ve to steel . A l l metal coati ngs
protect steel by denyi ng access of water, oxygen, and el ectro-
l ytes to the steel surf ace. The anodi c coati ngs, i n addi ti on,
act as a sacri f i ci al anode, di ssol vi ng pref erenti al l y i n pl ace
of the steel . The oxi dati on/corrosi on products of the coati ng
may al so pl ay an i mportant rol e i n protecti on.
The ol dest of the anodi c coati ngs i s zi nc, or "gal vani zi ng."
Two ounces per square f oot of zi nc was found to protect steel
f or 10-15 years i n the most corrosi ve soi l tested (603). The
corrosi on r ate of Zn i n di f f erent atmospheres can vary f r om
0. 01 to 2.9 mpy (679). H eat treatment at 500C f or 10-15 mi nutes
i ncreased the corrosi on resi stance and pl asti ci ty of a Zn coati ng
( 201) . Protecti on of Zn by pai nt i s recommended f or mari ne envi -
ronments (156).
93
A mor e r ecent and pr omi si ng anodi c coat i ng mat er i al is
al umi num. I n a r ef i ner y at mospher e a Zn coat i ng was r emoved
comj j l et el y i n t hr ee year s whi l e t en year s was r equi r ed t o r enove
94 per cent of an equi val ent A1 coat i ng (546). Al umi numcoat i ngs
l ast ed al most f i ve t i nes as l ong as Zn i n i ndust r i al at mospher es
( 679) . A mar i ne at mospher e at t acked bot h sl i ght l y ( 546) . Al u-
mi numcoat i ngs 0.25 t o 0.375 mm t hi ck wer e r ecommended f or bur i ed
condi t i ons ( 497) . I n f r esh wat er t he at t ack of A1 decr eased
.r
par abol i cal l y wi t h t i me, i ndi cat i ng bui l dup of a passi vat i ng.
al umi numoxi de f i l m. Advant ages of bot h A1 and Zn wer e obt ai ned
by vapor - deposi t i ng A1 over gal vani zed st eel ( 219) .
The mor e nobl e cat hodi c coat i ngs of t en st and up t o degr ada-
t i on of t hemsel ves bet t er t han t he anodi c coat i ngs. Chr omi zed
st eel was f ound t o be mor e r esi st ant t o seawat er t han al umi ni zed
and gal vani zed st eel ( 499) . However , any di scont i nui t i es i n t he
coat i ng l ead t o r api d l ocal i zed at t ack of t he exposed st eel due
t o gal vani c act i on. Thus t hi ck, dense coat i ngs ar e essent i al .
Chr omi umpl at i ngs bel ow 8 mi cr ons t hi ckness had poor cor r osi on
r esi st ance whi l e t hose above 18 mi cr ons t hi ck wer e consi der abl y
bet t er ( 680) .
Anodi c and cat hodi c coat i ngs have occasi onal l y been com-
par ed. Zi nc coat i ngs wer e f ound t o per f or mbet t er t han Cd i n
at mospher es r i ch i n SO2 ( 222) . Ef f ect i veness i n r educi ng st r ess
.
cor r osi on cr acki ng of 302 aust eni t i c st ai nl ess i n boi l i ng 42
per cent MgC12 was i n or der Ni t Cu, Al , Zn, Pb (477).
6. Or gani c Coat i ngs
Or gani c coat i ngs may be cl assi f i ed i n many ways: by t hei r
94
method of hardeni ng, by composi ti on, by thi ckness, by properti es,
etc. Organi cs such as coal tar enamel , asphal t, and pol yethyl ene
are thermopl asti c -- they sof ten and fl ow when heated and harden
when cool ed. These are of ten appl i ed hot. Others are thermo-
setti ng -- they harden i rreversi bl y by chemi cal reacti on when
heated. Some harden at room temperature by chemi cal reacti on
whi l e others harden by sol vent evaporati on. I n a 1962 survey
by the American Soci ety of Ci vi l Engi neers about hal f of 178
f i rms wer e not sati sf i ed wi th the coati ngs they wer e usi ng and
wer e seeki ng better means of control l i ng corrosi on ( 7 7 ) .
Appl i cati on techni ques i ncl ude pai nti ng, pouri ng, sprayi ng,
fl ame sprayi ng, el ectrostati c sprayi ng, f l ui di zed bed coati ng,
di spersi on coati ng, f l ock, and sol uti on coati ng. Machines exi st
f or coati ng l arge pi pel i nes f ai r l y automati cal l y. Strengtheni ng
agents such as f i bergl ass, cl oth, asbestos, j ute, paper, etc.,
are f requentl y added to organi c coati ngs -- of ten by al ternate
wrappi ng and coati ng.
Organi c coati ngs f uncti on pri mari l y by excl udi ng water and
el ectrol ytes from contact wi th the pi pe. They al so resi st the
fl ow of el ectri ci ty and the passage of oxygen and other gases.
A seri ous probl em wi th organi c coati ngs i s attack of the
coati ngs by mi cro-organi sms. Organi cs are food f or many mi cro-
organi sms and the necessary oxygen and water f or metabol i sm are
present i n mo s t pi pe trenches. Large popul ati ons of bacteri a
wer e found adj acent to al l pi pel i nes i nvesti gated i n one study
(5025). Asphal ts and pl asti c. tape wer e found attacked and di s-
bonded (5000). Another stxdy. i nvesti gated the resi stance of
95
several types of coati ngs t o oceani c bacteri al attack and found
that the rate of attack f or al l coati ngs was so l ow that hal f -
i nch thi ck coati ng was expected to protect a pi pel i ne f or many
years ( 4 7 1 ) . Evi dence of bacteri al attack of pol yvi nyl chl ori de
l i ni ng of sewer pi pe has been found (780). I ncl usi on of bio-
ci dal chemi cal s such as arseni c oxi de i n coati ngs to prevent
bi ol ogi cal deteri orati on has been suggested but has not been
adequatel y tested.
natural resi stance. Also i mportant i n organi c coati ngs i s thei r
resi stance to water and el ectrol yte absorpti on, soi l stress, and
f l ow under depressi on f orces (e.g., rocks). Thei r adhesi ve
strength to the pi pe shoul d be about the same as the tensi l e
strength of the coati ng.
Some organi c coati ngs appear to have some
Bituminous coati ngs have a l ong hi story of use i n protecti ng
underground structures. These i ncl ude nati ve asphal ts, oi l s,
and resi ns of both ani mal and vegetabl e ori gi n; products deri ved
f r om these; ref i ned and chemi cal l y treated petrol eum asphal ts
and coal tar products; and pi tches and resi dues from treatment
and processi ng of resi ns and oi l s.
C oal tar enamel has shown good resi stance t o water permeati on
and to f l ow of el ectri cal current. I t adheres and resists abra-
si on wel l . However, at temperatures below 40F i t loses i ts
ducti l i ty and cracks easi l y ( 7 0 3 ) . Dock gates at the Panama
Cane1 wer e coated wi th hot coal tar pi tch up to 3/16 i nch thi ck
and found to be i n f i rst- cl ass condi ti on af ter 20 years ( 501) .
Apparentl y, not al l coati ngs must be ti ghtl y adherent. Good
resul ts are claimed f or loose pol yethyl ene sl eevi ng over cast
96
i ron pi pe (789, 788, 572, 790) . Al though not stated, one sus-
pects that care must be taken to excl ude moi sture, otherwi se
bacteri a coul d f l ouri sh. Pol yethyl ene and pol yvi nyl chl ori de
tapes have been devel oped f or wrappi ng pi pel i nes ( 726) . Pi pe
i s al so coated i n the mi l l , wi th 750 mi l l i on f eet of pl asti c
coated pi pe produced from 1957 to 1966 (556). J oi nt protecti on
i n the f i el d then becomes cr i ti cal . Mel ti ng on of powdered
-
pol yethyl ene under hi gh pressure produced a coati ng so resis-
tant to abrasi on that pi pe coul d be f orced through roads, di kes,
and soi l embankments wi thout damage (566).
Many tests have been devi sed to j udge the qual i ty of an
organi c coati ng. For example, adhesi on can be tested by re-
si stance to di sbondi ng by cathodi c protecti on currents (557).
Measurement of el ectri cal conductance has been suggested as a
method f or determi ni ng the i nservi ce condi ti on of coati ngs ( 4 8 ) .
El ectri cal resi stance and capaci tance measurements have al so
been proposed f or moni tori ng coati ng performance ( 747) .
7. C er ami c and Concrete Coati ngs
Fused coati ngs are nonporous, nonconducti ng, and nonreacti ve.
They are, unf ortunatel y, br i ttl e. Gl ass-l i ned steel has been
used i n very corrosi ve chemi cal envi ronments (163). Vi treous
enamel coated thermal pi pel i nes have been very successf ul i n
the Sovi et Union (195). These coati ngs wer e reported to be
practi cal l y wear-free and the most l ong l asti ng and rel i abl e
protecti on f or thermal networks.
L
Concrete has been shown to be potenti al l y usef ul f or corro-
si on control . W e t Portl and cement has a pH of about 12.4,
97
normal l y causi ng passi vati on of steel (165, 792). I ni ti ati on
of corrosi on requi res f ree oxygen at the steel surf aces and a
rati o of chl ori de to hydroxyl i on acti vi ty of at l east 0.6 ( 172) .
Chl ori de i ons i n the mi xi ng wat er are ef f ecti ve i n destroyi ng
passi vati on, onl y 1 percent bei ng requi red. Adding i nhi bi tors
such as ni tr i te, chromate, and phosphate to the mi xi ng wat er
was found to be benef i ci al (312). Sal t can di f f use i n through
concrete but i s hi ndered by hi gh qual i ty, l ow permeabi l i ty,
..
l ow water-cement r ati o concrete (281). With good concrete,
di f f i cul ty i s encountered onl y i f the NaCl concentrati on exceeds
about 4 percent.
Stress corrosi on can occur i n prestressed concrete ( 165) .
Stray current fl ow i n concrete coated steel can l ower the pH
where current l eaves the steel and eventual l y cause corrosi on.
Gal vani zed steel l asts better than bl ack steel . When corrosi on
of steel i n concrete does occur, the corrosi on products can
expand wi th enough f orce to crack the concrete. Usual l y, how-
ever, corrosi on occurs onl y where the concrete i s f i r st cracked.
Calcium carbonate coati ngs may be preci pi tated by appl i ca-
ti on of cathodi c protecti on when the backf i l l has been treated
wi th calcium bi carbonate. Thi s process reduced the cathodi c
protecti on current by 80 percent i n a 6-month t r i al (131).
8. Anodic and Cathodi c Protecti on
The di ssol uti on rate of i ron depends on potenti al , as
i l l ustrated by Fi gure 1. With no external current suppl y
attached, the met al potenti al becomes the corrosi on potenti al
at which anodi c and cathodi c reacti on rates are equal . One can
.
98
see from Fi gure 1, however, that the anodi c reacti on rate can be
decreased ei ther by l oweri ng the potenti al or by i ncreasi ng the
potenti al i nto the passi ve regi on.
potenti al i n the mor e nobl e di recti on by an external power source
i s cal l ed anodi c protecti on. I t i s parti cul arl y usef ul f or very
corrosi ve envi ronments. The current drawn i s very nearl y equal
to the corrosi on current. Unfortunatel y, the potenti al must be
The method of shi f ti ng the
control l ed so that it l i es i n the passi ve regi on. Potenti al
excursi ons outsi de the passi ve regi on can cause drasti c i ncreases
i n corrosi on. Thus, expensi ve i nstrumentati on i s requi red, which
probabl y expl ai ns why the method has not been used f or control
of pi pel i ne corrosi on.
Lowering the potenti al al so reduces the corrosi on rate.
T hi s i s cal l ed cathodi c protecti on and i s wi del y appl i ed f or
control of underground corrosi on. I t has al so been used f or
protecti on agai nst i nternal corrosi on ( 202) . Cathodi c protec-
ti on i s so wi del y appl i ed, i n f act, that it i s wel l to cauti on
at the outset that correct uti l i zati on i s not tr i vi al nor wi t h-
out probl ems. Although 213 of the companies surveyed desi gned
thei r own cathodi c protecti on i nstal l ati ons, 95 companies em-
pl oyed consul tants.
I t i s di f f i cul t to achi eve adequate cathodi c protecti on i n
hi gh resi sti vi ty soi l s. Cathodi c protecti on i s i nef f ecti ve i n
the spl ash zone of seawater (which i s usual l y the most rapi dl y
corroded area) ( 128) . When the peri od of pl anned usage i s smal l ,
it may be uneconomi cal to protect pi pe even i n corrosi ve soi l s
(158). Cathodi c protecti on i s not very ef f ecti ve i n hol es,
99
crevices, and i nternal corners ( 69) . Unwanted contami nants can
be i ntroduced i nto the soi l at the anode (e.g., Pb). Adequate
cathodi c protecti on under congested ci ty streets i s very di f f i -
cul t to achi eve wi thout causi ng i nterf erence.
Cathodi c protecti on can actual l y i ncrease corrosi on rates
under certai n condi ti ons. When i t i s appl i ed to an ol d and
l eaky pi pel i ne, several months must be al l owed f or a noti ceabl e
reducti on i n the f ai l ure rate. Cathodi c protecti on of ol d pi pe-
l i nes may, i n f act, i ncrease the l eak r ate duri ng the f i r st year
because l i berated hydrogen can l oosen adherent r ust scale which
had previ ousl y covered s mal l hol es ( 490) . Cathodi c protecti on
can al so i ncrease the pH to the poi nt where r ust di ssol ves.
Several i nstances have been reported where appl i cati on of
cathodi c protecti on apparentl y had del eteri ous ef f ects under
speci al ci rcumstances (257, 264, 334).
The current densi ty requi red f or cathodi c protecti on vari es
wi del y under di f f erent condi ti ons; representati ve examples are
summarized below. More current was requi red to stop crevi ce
corrosi on of 304 stai nl ess i n fl owi ng seawater than was re-
qui red f or qui escent seawater (584). When sul f ate reduci ng
bacteri a wer e present, 50 percent more current was requi red
i n i ndi rect sunl i ght than i n the dark (538). I n aerated sol u-
ti ons the minimum current was found to be equal to the corrosi on
I
current, whi l e it was t wi c e the corrosi on current i n deaerated
sol uti ons ( 729) . I n 3 percent N aC l the current requi red to
protect steel was reduced by a short prel i mi nary peri od of
exposure wi thout protecti on (531). I n hi gh r esi sti vi ty soi l ,
100
three t i mes the corrosi on current (i ntersecti on i n Fi gure 1) was
requi red f or protecti on (532). Current requi red to stop stress
corrosi on cracki ng of stai nl ess i ncreased rapi dl y wi th the depth
of the crack (579).
One study ( 7 2 9 ) found that cathodi c protecti on i n seawater
* caused protecti ve l ayers of CaC03 and Mg(OH)2 t o form roughl y
i n proporti on to the current densi ty. A t lower current den-
si ti es ( < 150 mA/sq f t ) , the formati ons were predomi nantl y
CaC03; at hi gher current densi ti es, Mg(0H) was more preval ent.
The CaC03 l ayers wer e found t o be l ess porous and to provi de
more protecti on.
Many f actors must be taken i nto account i n desi gn of a
cathodi c protecti on system. A soi l conducti vi ty survey i s
advi sed bef ore l ayi ng the pi pe so that cathodi c protecti on
can be centered i n areas of hi gher conducti vi ty ( 7 6 3 ) . Thi s
would ensure maximum ef f i ci ency and minimum damage to coati ngs,
i f used. There are basi cal l y two methods of appl yi ng cathodi c
protecti on (482). One i s t o use sacri f i ci al anodes and the
other i s to use external l y appl i ed i mpressed current.
Sacri f i ci al anodes typi cal l y consi st of Mg, Zn, or A l .
These may be connected by i nsul ated w i r e to the pi pe, i n the
form of bracelets attached at pi pe j oi nts ( 728) , or as coati ngs.
Al l oy addi ti ons can markedly af f ect the performance of sacri-
f i ci al anodes. Aluminum contai ni ng 0.01-0.02 percent I ndium
and 0.5-5 percent Zn was found t o be parti cul arl y ef f ecti ve,
yi el di ng a potenti al of about 1.1 V and a current ef f i ci ency
greater than 80 percent at current densi ti es about 1 mA/cm
2
( 21, 95). Smal l amounts of Fe and Si improved performance,
whi l e 0.01 percent Cu markedl y degraded it. Aluminum contai n-
i ng 0.45 percent Zn and 0.045 percent Hg was found to be pro-
mi si ng from an economic standpoi nt for mari ne appl i cati ons (529).
Zn al l oys are al so usef ul i n seawater. The zi nc shoul d contai n
less than 0.0014 percent Fe (105). Addi ti on of 0.5 percent A 1
to Zn was found to reduce the del eteri ous ef f ect of Fe (150).
Zn wi th 0.3 percent A 1 pl us 0.05 percent Cd, or 0.3 percent
A 1 pl us 0.5 percent Cd and 0. 1 percent Si exhi bi ted superi or
performance (388). Depl eted urani um has al so been successf ul l y
used as a sacr i f i ci al anode (85). One di f f i cul ty i n the use
of many sacr i f i ci al anodes over a l ength of pi pe i s that they
w i l l expi re over a wi de range of t i me, making opti mal repl ace-
ment di f f i cul t.
Tabl e 23 i ndi cates the choi ce of materi al s f or anodes among
the companies surveyed, and Tabl e 24 summarizes the anode per-
formance experi ence reported i n thi s survey.
TABLE 23
NUMBER OF COMPANIES FAVORI NG DIFFERENT GALVANI C ANODES
1st Choi ce 2nd Choi ce 3rd Choi ce
Aluminum 9 9 10
Magnesium 30 8 8 3
Zi nc 14 79 2
Other 1 4 0
102
TABLE 24
PERFOFWANCE OF GALVANI C ANODES
Earth Exposure
B es t 2nd B es t 3rd B es t
Aluminum l o* 8 45
Magnesium 282 5 2
Zinc 6 106 8
Other 1 0 . o
Aluminum 7 18 7
Magne s i um 28 16 15
Zinc 32 13 0
Other 4 2 1
*Number of companies reporti ng best performance.
The second, and mos t popul ar, means of appl yi ng cathodi c pro-
tecti on i s by i mpressed current, external l y appl i ed. Di rect
current i s requi red and may be suppl i ed by a vari ety of means,
i ncl udi ng step-down and recti f i cati on of commercial AC power,
sol ar cel l s pl us batteri es, thermoel ectri c cel l s usi ng f uel from
the pi pel i ne, f uel cel l s, and nucl ear generators (278, 335).
Generators wi th moving parts, e.g., wi ndmi l l s, general l y requi re
too much mai ntenance to be ef f i ci ent.
I n the si mpl est case, currents are peri odi cal l y set manual l y
t o provi de the requi red potenti al . I ncreasi ng use w i l l be made
of automati c control l ers, especi al l y i f HVDC presents the pro-
blems that are f eared (335, 357, 296, 120, 76, 576) . Automati c
103
control i s al so desi rabl e i n mari ne i nstal l ati ons where current
requi rements change wi th t i me because of vari ati ons i n vel oci ty,
aerati on, etc. (384). Recent i nnovati ons i ncl ude si l i con con-
trol l ed recti f i ers, constant-current recti f i ers, permanent pi pe
potenti al i ndi cati ng meters, and tel emeteri ng potenti al s down
the pi pe i tsel f (335).
Tabl e 25 l i sts the types of r ecti f i er s used by the companies
surveyed. The numbers and types of generators reported- i n use
by these companies are summarized i n Tabl e 26.
TABLE 25
TYPES OF RECTIFIERS USED
.
Number of U s e r Companies
(A) Sel eni um 289
(B) Si l i con 148
(C) Copper Oxide 19
(D) Other 9
TABLE 26
NUMBER OF GENERATORS I N USE PER COMPANY
Number of Generators
1-5 6-10 11-25 26-50 Over 50
(A) Fuel powered 20 4 0 2 0
(B) Pul se 5 0 2 0 0
(C) Sol ar 1 0 0 0 0
(D) Thermoel ectri c 21 10 7 1 1
(E) Other 6 0 1 1 0
104
I f pi pe i s t o be cathodi cal l y protected, an anode must be
pl aced i n the ground t o compl ete the el ectrol yti c ci rcui t. The
anode must be of suf f i ci ent si z e to operate at reasonabl e current
densi ti es and to l ast a l ong peri od of t i me. Si l i con i ron ( 146) ,
T i pl ated wi th a very thi n f i l m of pl ati num (3571, Pb al l oys f or
seawater ( 3 8 8 ) , Pb wi th embedded P t pi ns (391, 491) , Pb-Ag al l oys
(75), graphi te and carbon (542), Si - Cr i ron (541), and steel
(540) have all been employed as anodes. I n ari d or semi ari d
soi l s, el ectro-osmosi s can si gni f i cantl y i ncrease the soi l re-
si sti vi ty around an anode ground bed by reduci ng the moi sture
content (405). To avoi d t hi s ef f ect, current densi ti es shoul d
be kept l ow.
I n soi l , anodes are general l y surrounded wi t h coke or graph-
i te ''breeze" which transmi ts the current to the soi l . The
f uncti on of the coke breeze i s both t o extend the l i f e of the
anode (si nce it reacts mi ni mal l y wi th el ectrol ysi s products),
and to lower the current densi ty. The anode must al so be l ocated
so as to provi de good current di stri buti on on the pi pe to sati sf y
the potenti al cri teri on everywhere. One devel opment devi sed to
achi eve thi s i s the deep ground bed anode. The deep ground bed
i s l ocated beneath the pi pel i ne and so requi res no addi ti onal
ri ght of way (540). Geol ogi cal formati ons, however, can con-
cei vabl y cause an unfavorabl e potenti al di stri buti on. Si nce
gases are usual l y generated at the anode, a standpi pe to the
surf ace i s requi red f or thei r escape. Steel standpi pes have been
noted to be attacked by the cathodi c protecti on current (542).
For thi s reason, perf orated pl asti c pi pe i s of ten used. The
105
performance of i mpressed current anodes reported by the companies
surveyed i s outl i ned i n Tabl e 27.
A phenomenon of wi de concern i n cathodi c protecti on i s i nter-
f erence (e.g., 267). Si nce cathodi c protecti on generates an
el ectri c f i el d i n the soi l , current tends to fl ow i n any con-
ductor pl aced i n the soi l . Where thi s (posi ti ve) current l eaves
4
the pi pe, corrosi on i s rapi d. I n London an anode 460 f eet deep
was used i n an unsuccessf ul attempt to avoi d i nterf erence ( 146) .
%
The best method to avoi d i nterf erence has proved to be
hol di ng a11 buri ed metal structures and pi pes at or near the
same potenti al .
l i nes i n crowded areas can be very di f f i cul t. Owners of di f f er-
Avoidance of i nterf erence from exi sti ng pi pe-
ent pi pel i nes and structures i n the same area must coordi nate
cathodi c protecti on ef f orts. Coordi nati on i s carri ed out by
i nformal l ocal cathodi c protecti on groups which mai ntai n maps
showing underground metal , hol d meeti ngs to di scuss probl ems,
advi se l ocal governmental uni ts, etc. Sacri f i ci al (e.g., Mg)
anodes are bel i eved to produce minimum i nterf erence wi th bare
l i nes (592).
Tabl e 28 l i sts the major sources of i nformati on that the
surveyed companies used. t o determi ne the presence of i nter-
f erence currents. (An al phabeti cal l i sti ng of El ectrol ysi s
or Corrosi on I nterf erence Committees compi l ed duri ng the sur-
vey i s i ncl uded as Tabl e 4 9 , Appendix 111.) Cri teri a uti l i zed
by the companies surveyed t o determi ne whether i nterf erence has
been mi ti gated are summarized i n Tabl e 29.
106
TABLE 27
IMPRESSED CURRENT ANODES ACCORDI NG TO PERFOWANCE
Earth Exposure
Anode Materi al B es t 2nd 3rd 4th 5th E*
Graphi te i n coke breeze 152 70 19 3 2 4
0 15 5 10 2 1
Graphi te
Lead 0 0 0 0 0 3
L ead-si l ver al l oy 1 0 0 0 0 3
High si l i con cast i ron i n
coke breeze 104 85 3 4 0 1
High si l i con cast i ron 13 19 29 21 0 3
Scrap i ron i n coke breeze 1 6 23 5 3 0
Scrap i ron
Pl ati ni zed ti tani um
11 11 46 15 4 3
0 3 0 0 0 0
0 0 0 2 Pl ati ni zed tantal um 2 0
0 0 0 Other 6 2 6
Marine Exposure
Anode Material B es t 2nd 3rd E*
Graphi te i n coke breeze 2 0 0 1
Graphi te 7 3 3 1
Lead 0 0 0 0
L ead-si l ver al l oy 8 0 3 3
High si l i con cast i ron i n
coke breeze
I ligh si l i con cast i ron
Scrap i ron i n coke breeze
3 2 0 0
36 4 1 0
0 5 0 0
Scrap i ron
2 6 1 0
Pl ati ni zed ti tani um
2 1 0 0
Pl ati ni zed tantal um
1 0 0 0
Other 1 0 2 0
*Experiment a 1
107
TABLE 28
MAJ OR SOURCES OF I NFORMATI ON ABOUT THE PRESENCE
OF I NTERFERENCE CURRENTS
1st 2nd 3rd 4th
Number of Companies
(A) El ectrol ysi s or Corrosi on
I nterf erence Committees
(B) Di rect Communication from
Other Companies
85 53 64 0
85 174 35 0
(C) Current and Voltage Measurements 143 61 88 0
(D) Other 1 2 7 9
Tabl e 29
CRI TERI A USED TO DETERMINE WHEN INTERFERENCE
HAS BEEN MI TI GATED
C r i t er i a Number of U s er Companies
No Change i n Pi pe Potenti al wi th
Recti f i er On and Off
L i ne Current Measurements or When al l
Current Flow on Pi pe i s Toward the
Drai n Bond
74
34
Restorati on of Ori gi nal Pi pe Potenti al t o
Those Val ues Which Exi sted Pri or to
I nterf erence 84
Earth Current Techni que 10
Pi pe-to-soi l Potenti al i s -0.85 V o l t s or more 10
Adj ustment of the Sl ope of the B et a Curve
at Locati on of Maxi mum Exposure None
Other 25
I t was once common practi ce, and of ten
or muni ci pal code, to pl ace a metab casi ng
requi red by state
around a pi pel i ne
where it passed under a roadway. Unf ortunatel y, thi s procedure
can reduce or negate the benef i ci al ef f ects of cathodi c protec-
ti on (561). I n addi ti on, corrosi on of the i nner surf ace of the
casi ng can be accel erated by the currents passi ng through it
(563). Accel erated corrosi on of the casi ng can be prevented
by el ectri cal l y connecti ng the pi pe and the casi ng, but thi s
compl etel y negates the cathodi c protecti on of the pi pe. One
suggesti on i s t o grout the annul us (594) or to dry and f i l l it
wi th grease (561) i f the pi pe and the casi ng are shorted. An-
other approach i s t o swage down the ends of the casi ng, wel d them
t o the pi pe at each end, and fill the annul us wi th saturated l i me
sol uti on (563). Si mi l ar ef f ects can be obtai ned wi th wi r e mesh
rei nf orced mortar coati ng. Connecti on of mesh to pi pe i s re-
commended. Si mi l arl y, pi pe clamps shoul d be bonded t o the pi pe
and the pi pe surf ace coated wi th i nsul ati ng materi al (594). When
possi bl e nonconducti ve rei nf orci ng materi al s are recommended t o
avoi d screeni ng ef f ects. The companies surveyed had a total of
22,669 casi ngs shorted to the carri er pi pe. Three hundred and
t wo l eaks wer e reported i nsi de pi pel i ne casi ngs.
Some pi pel i nes contai n nonconducti ve j oi nts. When cathodi c
protecti on i s appl i ed to such a pi pel i ne, it i s essenti al t o use
bond strap el ectri cal coupl i ngs across these j oi nts. I t has been
esti mated that wi th up to 150 j oi nts per mi l e one shoul d expect
one mi ssed j oi nt every 50 mi l e s (575). Thi s mi ssed j oi nt may be
l ocated by appl yi ng cathodi c protecti on and making a pi pe t o
soi l potenti al survey. One must al so consi der el ectri cal di s-
conti nui ti es i n ol d underground. structures when seeki ng t o avoi d
i nterf erence from cathodi c protecti on of a new pi pel i ne (267).
I n such cases a si mpl e bond from the pi pel i ne to the structure
w i l l not sol ve the i nterf erence problem.
Vari ous techni ques have been devel oped f or desi gni ng cathodi c
protecti on systems. Analog models consi sti ng of wi r es immersed
i n an el ectrol yte have been suggested f or sol uti on of complell
i nterf erence probl ems ( 4 9 4 ) . Mathemati cal anal ysi s has been used
f or desi gn of i mpressed current protecti on of i nternal pi pe sur-
faces (569). Computers have al so been employed f or cal cul ati ons
of current and potenti al di stri buti ons under di f f erent condi -
ti ons. General l y, the mathemati cal models i gnore pol ari zati on,
which may have a control l i ng i nf l uence.
9. Cathodi c Protecti on of Coated Pi pel i nes
Nonconducti ve coati ngs and cathodi c protecti on are qui te
of ten used together f or protecti on of pi pel i nes from corrosi on.
Coati ngs and cathodi c protecti on complement each other ni cel y.
Coati ngs are usual l y not perf ect -- some hol i days remai n, at
which corrosi on can occur. Cathodi c protecti on serves to pro-
tect the pi pe at the hol i days, and may be consi derabl y cheaper
than ef f orts to produce a perf ect coati ng. On the other hand,
the coati ng drasti cal l y reduces the current requi red to protect
the pi pe -- so much so, i n f act, that the requi red current i s
of ten taken as a measure of the qual i ty and i ntegri ty of the
coati ng. Coati ngs and cathodi c protecti on may economi cal l y
be a good i nvestment si nce wel l preserved pi pe i s wor t h more
after i ts usef ul l i f e i n a parti cul ar appl i cati on. The pi pe
may then be recoated and reused.
110
Fi gure 6 i s a graph of the l eak hi story on an aqueduct, whi ch
shows the ef f ecti veness of coati ng combined wi th cathodi c protec-
ti on. The aqueduct was a 65-i nch di ameter, 90- mi l e, wel ded steel
pi pe coated wi th a bi tumi nous mastic. Cathodi c protecti on was
i nterrupted t wi c e as t wo addi ti onal aqueducts wer e i nstal l ed i n
the same 100-foot ri ght-of-way (6114).
The performance of pi pe wi th and wi thout protecti on reported
by the companies surveyed i s shown i n Tabl e 30. A s may be seen,
the number of l eaks per mi l e was much l ess wi th any type of pro-
tecti on than wi t h bare unprotected pi pe. The l eaks per mi l e for
cathodi cal l y protected and coated steel pi pe were wi del y di stri -
buted over the age groups, whereas bare pi pe wi th and wi thout
cathodi c protecti on or coated pi pe wi thout cathodi c protecti on
had si gni f i cant l eak rates f or pi pe i nstal l ed over 10 years.
Cathodi c protecti on can damage coati ng materi al s under cer-
tai n condi ti ons. Water can be dri ven by el ectro-osmosi s through
smal l hol i days to form bl i sters under the coati ng. Cathodi c pro-
tecti on generates hydrogen when the potenti al exceeds the hydro-
gen overvol tage of steel and can cai xe di sbondi ng of coati ngs to
di f f erent degrees. I n f azt, cathodi c pol ari zati on i s one test
f or bondi ng of coati ngs. Di sbondi ng i ncreases as the potenti al
becomes more negati ve, as temperature i ncreases, and as external
pressure decreases, and i s greater i n seawater than i n 3 percent
NaC1. The temperature ef f ect vari es wi del y from coati ng t o coat-
i ng, however (684). I f the coati ng i s di sbonded, corrosi on can
occur under the coati ng even wi th cathodi c protecti on ( 570) .
I t was found that cathodi c protecti on may f ai l to st op mi cro-
111
50
40
rn
Y
W
Q 30
P J
P
W
N
10
0
TOTAL LEAKS
m
f- LEAKS PER YEAR
c
L.
I n n n I n n I nfl nl
I I I I
1940 I945 4950 1955 1960 1965 I970
1930 1935
YEAR
Fi gure 6. Ef f ecti veness of Cat hodi c Prott-,cti.on.
I k
Age Groups Number of Companies
Bare Steel Pi pe, Not Cathodi cal l y Protected
Over 30 years 0 3 1 1 3 12 46 22
21-30 years 1 4 1 12 14 37 9
11- 20 years 0 4 0 19 10 19 10
6-10 years I 4 2 2 7 7 2
0-5 years 2 3 1 3 1 5 1
Over 30 years 0 4 2 13 10 9 4
21- 30 years 0 4 1 11 3 6 4
P 11-20 years 1 2 1 4 5 4 1
W 6-10 years 0 1 2 0 1 2 1
0-5 years 0 0 0 0 0 0 0
Bare Steel Pi pe, Cathodi cal l y Protected
P
Coated Steel Pi pe, Not Cathodi cal l y Protected
Over 30 years 0 3 1 6 3 18 9
21-30 years 1 6 1 7 14 14 2
11-20 years 1 8 3 10 11 15 5
6-10 years 1 6 1 11 8 5 4
0-5 years 0 2 2 3 7 4 3
I
TABLE 30
1 1
2 2
2 0
0 0
0 0
0 0
1 1
0 1
0 0
0 0
0 0
0 0
0 0
0 0
0 0
WMBEf? OF CORROSI ON LEAKS PER LI NEAR PULE OCCURRI NG I N 1969 FOR STEEL PI PE
Coated Steel Pi pe, C
Over 30 years 4 5 3
21-30 years 6 8 3
11-20 years 7 15 7
6-10 years 8 5 3
0-5 years 4 2 3
thodi cal l y Protected
11 2 6
4 2 5
5 5 3
7 4 2
1 1 0
0 0 0
0 0 0
2 0 0
2 0 0
0 0 0
bi ol ogi cal corrosi on i n moi sture pockets under di sbonded coati ngs
(5024).
Loss of adhesi on and bl i steri ng of vi nyl coati ngs on cathod-
i cal l y protected shi ps has been attri buted to devel opment af
l ocal i zed al kal i ni ty at hol i days ( 3 6 4 ) . Na' and K di f f used
through the f i l m under the appl i ed potenti al . L i t t l e bl i steri ng
+
and peel i ng of vi nyl pai nt has been found to occur i f less nobl e
potenti al s wer e employed, which l owered the &rent densi ty t o
about 3 mA/m . Zi nc anodes are reportedl y gai ni ng f avor over
2
Mg f or the hul l s of shi ps, partl y because they make it possi bl e
t o avoi d overprotecti on harmful to pai nt ( 99) .
I t has been reported that the normal cathodi c protecti on
potenti al of -0.85 V to CuS04 el ectrode causes red-l ead pai nt
to bl i ster, does not af f ect coal t ar enamel , and af f ects other
coati ngs to i ntermedi ate extents. Another study (259) found
*
pai nts based on l i nseed/tungsten oi l phenol i c varni sh, aluminum
bi tumi ni zed oi l and metal l i c pi gmented epoxy good t o -0.85 V;
aluminum vi nyl pri mer wi th cuprous
oxi de pai nt good to -1.0 V;
and coal tar epoxi es to -1.25 V.
Tabl e 31 shows the maximum pi pe potenti al or i nstantaneous
open ci r cui t potenti al at the r ecti f i er l ocati on that best des-
cri bes the surveyed compani es' practi ce of l i mi ti ng potenti al .
10. Standard C el l s and Potenti al s i n Cathodi c Protecti on
A major probl em i n cathodi c protecti on i s the establ i shment
of cri teri a whereby under any gi ven set of ci rcumstances it may
be mani fested by test that the pi pe i s protected agai nst corro-
*J anuary 1970 Meeti ng of Los Angel es Secti on of NACE.
TABLE 31
MAXI MUM PI PE POTENTI AL OR INSTANTANEOUS OPEN CI RCUI T
POTENTIAL AT THE RECTI FI ER LOCATI ON
Pi pe-to-Soi l Potenti al ( V ol t s) Number of Companies
up to 1.5 83
1.6 t o 2.5 164
2.6 to 3.5 59
3.6 t o 5.0 16
Other 23
I nstantaneous Open Ci rcui t Potenti al Number of Companies
( V ol t s)
up t o 1. 00 45
1. 01 to 1.05 36
1. 06 t o 1. 20 4 4
Other 7
si on and that thi s protecti on i s not attai ned at the expense of
other components of the underground pi pe, e.g., the coati ng.
Such cri teri a, i ncl udi ng those di rected more parti cul arl y toward
desi gn than to adequacy, depend i n most i nstances upon measure-
ment of the el ectri c potenti al of the pi pe, pi l e, shi p, tank or
other structure, wi th respect to some ref erence potenti al .
Several possi bl e ref erence potenti al s are descri bed bri ef l y i n
f ol l owi ng paragraphs.
I n el ectrochemi stry the uni versal ref erence i s the standard
hydrogen el ectrode (SHE), the potenti al of which i s arbi trari l y
taken as zero. The physi cal and chemi cal characteri sti cs of %hi s
115
hal f cel l are represented as fol l ows:
+
P t I
gas, 1 atm) 1 H (a = 1); E O =o
P t i ndi cates the chemi cal l y i ner t pl ati num el ectrode, about which
equi l i bri um i s establ i shed between hydrogen gas at 1 atmosphere
pressure and the proton at uni t acti vi ty.
Thi s equi l i bri um was earl i er presented as one reacti on basi c
.
to corrosi on and was shown at the cathode i n the schemati c re-
presentati on of the underground corrosi on process, Fi gure 4.
I t i s al so of paramount i mportance i n cathodi c protecti on si nce
-
the protected structure i s, i n essence, a hydrogen el ectrode.
Accordi ng to the Nernst equati on of chemi cal thermodynamics
(e.g., Equati on 5) the potenti al E of any metal M of uni t acti v-
i t y i n equi l i bri um wi th Mn+ i ons at acti vi ty aMn+ may be wr i tten
i n the form
E = Eo + (0.05916/n) l og aMn+ (Eq. 12)
f or room temperature, where the standard potenti al Eo for the
metal i s experi mental l y determi ned f or uni t acti vi ty of met al
i on wi th ref erence to the SHE and n represents the number of
f aradays of el ectri ci ty enteri ng i nto the reacti on. For the
hydrogen/hydrogen i on hal f - cel l reacti on at uni t hydrogen
pressure, Eo equal s zero by conventi on and Equati on 12, i n
mi l l i vol ts, reduces t o
+
E = 0 + 59.16 l og (H ) = -59.16 pH
+
assumi ng the hydrogen i on acti vi ty equal s i ts concentrati on (H I
and, by def i ni ti on, -l og (H ) = pH.
+
The reacti on f or oxygen at uni t pressure i n equi l i bri um wi t h
hydroxi de i on (Equati on 3) i s al so monofaradai c (n = l), and
Equati on 5 i s appl i cabl e wi th Eo = +1.229 vol ts wi th respect t o
the SHE at zero pH.
The hydrogen and oxygen cel l potenti al s are gi ven i n Tabl e 32
f or several val ues of pH.
TABLE 32
HYDROGEN AND OXYGEN ELECTRODE POTENTI ALS
z
pH E (Hydrogen El ectrode) E (Oxygen El ectrode) pOH
0 0 +1229 mv 1 4
7 - 414 mv +815 7
9.33 -551.9
12.45 -736.5
1 4 -828 +401 0
- -
- -
The SHE i s f ar too cumbersome f or use i n the f i el d. The
saturated copper sul f ate el ectrode on the other hand i s sturdy,
rel i abl e, and almost uni versal l y used a-id understood by corro-
si on engi neers. Thi s si mpl e el ectrode and i ts potenti al at
room temperature are as fol l ows:
Cu (sol i d) 1 CuS04 (saturated sol uti on) I E' = 0.441
E = 4 4 1 - 29.58 l og acU++ mV (Eq. 14)
*
When the acti vi ty of the cupri c i on acU++ i s that of a sol u-
ti on of copper sul f ate i n equi l i bri um wi th the hydrated sal t,
CuSC,*5H20, the potenti al to the SHE i s +298.1 mV.
i s never used at any other cupri c i on concentrati on, so that it
i s suf f i ci ent and unambiguous t o ref er to thi s ref erence elec-
trode si mpl y as "the copper sul f ate el ectrode." I t i s rel ati vel y
l
The el ectrode
117
i nsensi ti ve to contami nati on.
The saturated calomel electrode, SCE, i s an even more rel i a-
bl e -:eference el ectrode and consi sts of Hg 1 Hg2C12 (saturated
sol uti on). I t i s used extensi vel y i n the l aboratory but i s less
conveni ent i n the f i el d than the copper sul f ate el ectrode.
Neverthel ess, it i s used i n the f i el d by some corrosi on engi -
neers t o check the potenti al of the copper sul f ate electrode.
The si l ver chl ori de el ectrode i s enti rel y di f f er ent- i n
performance, i n that the el ectrode i s responsi ve to the chl ori de
i on concentrati on of the sol uti on i nto which it i s di pped.
el ectrode i s formed by "pl ati ng" si l ver chl ori de onto a si l ver
rod or button. I t i s parti cul arl y usef ul i n mari ne envi ronments,
and i ts potenti al on the hydrogen scal e i n average seawater i s
computed to be 195.5 mV. The el ectrode i s al so responsi ve to
hydroxi de i on concentrati on, and to avoi d contami nati on from
OH- a rej uvenati ng ci r cui t i s somet i mes used i n seawater which
i ntermi ttentl y appl i es a posi ti ve potenti al to the el ectrode t o
nudge it i nto i ts equi l i bri um val ue. The si l ver chl ori de elec-
trode i s destroyed by the sul f i de i on. I ts use below the mud
l i ne i n mari ne i nstal l ati ons may, theref ore, be i nadvi sabl e.
The
The potenti al of the si l ver chl ori de el ectrode can be f i xed
by r.ai ntai ni ng the chl ori de i on concentrati on constant. I n
one commercial! uni t the el ectrode i s surrounded by a si l ver
chl ori de- saturated 4N K C1 sol uti on. The potenti al i s then
+243.7 mV. Thi s si l ver chl ori de electrode has been successf ul l y
used to measure the chl ori de i ons i n soi l and &he i nf i l tr ati on
of the i ons i n soi l i nto concrete.
A conventi onal pH meter i s
118
used wi th the aci di f i ed sampl e and resul ts reported as pC1-
(-l og (C1-)) . Si mi l ar el ectrodes, which are sensi ti ve to sul -
f ate i on cencentrati on, have been devi sed. These el ectrodes,
however, have not yet been used to measure the i mportant sul -
f ate i on concentrati ons i n the soi l .
Ref erri ng to the potenti al s gi ven i n Tabl e 32, it i s now
evi dent that the pH 9.33 corresponds to the potenti al -850 mV
wi th respect to the copper sul f ate el ectrode (which i s of ten
/
used as a cri teri on i n cathodi c protecti on). The potenti al
-736.5 + (-298.1) = -1034.6 mV wi th respect to the copper sul -
f ate el ectrode i s the potenti al of the hydrogen el ectrode at
the pH of saturated cal ci um hydroxi de sol uti on. Thi s potenti al ,
of ten encountered i n practi ce, l ends support to the contenti on
that a cathodi cal l y protected pi pel i ne i s, i n essence, a hydro-
gen el ectrode.
The several potenti al s descri bed above are shown on a nomo-
gram i n Fi gure 7. These are usef ul f or an understandi ng of (a)
the si gn of el ectrode potenti al s, (h) the rel ati onshi p between
the several ref erence electrodes, (c) the powerful rol e that
oxygen must surel y pl ay i n the underground corrosi on process,
and (d) the potenti al s of certai n sal ts of i ron which are impor-
tant i n cathodi c protecti on. The corrosi on engi neer would do
w el l to commit a few potenti al s to pemory f or ori entati on wi th
- respect to nobi l i ty and si gn.
I
The si gn of the potenti al i s to some extent arbi trary, and
depends on one's vi ewpoi nt. The si gn conventi on used here i s
that which appears on the i nstrument. termi nal s; i .e., the
119
Y i l l i vol ts Mi l l i vol ts
to SHE -~ to cuso4- H al f C el l
NOSLE
+1000.0
+930.9 . . . . . . Oxygen, pH 0 ( 1)
' +1300.0
+1229.0
( 1)
+102.9 . . . . . . Oxyqen, pH 14
0. 0 . . . . . . Copper sul f ate (saturated)
101.5 . . . . . . Si l ver chl ori de (seawater)
- 54.4 . . . . . . Si l ver chl ori de ( 4N K c 1)
-
~ 57.1 . . . . . . Cal omel SCE
C401.0
'298.1
&243.7 -
+243.1 ,
+196.0
/
0.0
i
298.1 . . . . . . Hyd-rogen (2) , PH 0, SHE
( 2)
414. 0 .- 712.1 . . . . . . Hydrogen, pH 7
414.5 -
468.0 -
- 712.6 . . . . . . Ferrous chl ori de (saturated)
..- 766.1 . . . . . . Ferrous sul f ate (saturated)
850.0 . . . . . . One protecti on cri teri on
(3)
(2)
. . . . . . / 1034. 6 Hydrogen, pH 12.45
. . . . . .
(3)
. . . . . .
. . . . . .
(3)
i
1268.2 Ferrous sul f i de, pH 14
I
551.9
736.5 '-r
777.8 - 1075.9 Ferrous sul f i de, pH 7
822.2, ,1120.3 Ferrous sul f i de, pH 8.5
828.0 - - 1126.1 Hydrogen, pH 14
970.1 i . . . . . .
BASE
(1) A t oxygen pressure of 1 atmosphere
(2) A t hydroqen pressure of 1 atmosphere
( 3 ) A t hydrogen bi sul f i de i on (HS ) acti vi ty = 1
Fi gure 7. Nomogram of Some Oxi dati on P ot ent i al s at 25OC
120
potenti al between the SHE and the copper sul f ate el ectrode i s
- 298.1 mi l l i vol ts wi th the posi ti ve i nstrument termi nal connected
to the copper sul f ate el ectrode. The reverse si gn conventi on has
al so appeared i n the l i terature.
The SCE i s negati ve wi th respect to the copper sul f ate elec-
trode, but posi ti ve wi th respect t o the SHE. To avoi d confusi on
-
it i s hel pf ul to consi der the metals si l ver, copper and mercury
as more nobl e, and hydrogen and i ron as more basi c as shown i n
Fi gure 7. To obtai n the si gn of a reacti on between any two of
the hal f cel l s, the more nobl e potenti al i s subtracted from the
more basi c. Thus, on the hydrogen scal e
+
++
H2 = 2H
Cu = Cu + 2e-, E = 298.1
++ +
+ 2e- , E = 0.0
subtracti ng, H2 + Cu
Thus, the negati ve si gn above i ndi cates that i n measuri ng the
= Cu + 2H , E = -298.1
potenti al of the SHE to the copper sul f ate el ectrode the el ectron
fl ow w i l l be from the baser hal f cel l , through the i nstrument, to
the more nobl e hal f cel l . A hal f cel l w i l l gi ve up el ectrons t o
a reacti on toward the more nobl e end of the scale.
A gl ance at the al i gnment chart w i l l show that the pi pe
potenti al w i l l al so al ways be, accordi ng to the conventi on
adopted, negati ve to the copper sul f ate el ectrode. Therefore,
to avoi d repeated use of the negati ve si gn, i n practi ce the
absol ute val ues nay be reported and the posi ti ve si gp used when
and onl y when the neasured potenti al i s posi ti ve wi th respect
to the ref erence. The nomogram and the fol l owi ng text i s i n
accord wi th thi s suggesti on.
121
Most of the el ectrodes i n common use are cl ustered wi thi n
a narrow range of 100 mV. Thei r rel ati onshi p has been di scussed
on p::evious pages and f urther ampl i f i ed i n the paragraph immed-
i atel y above.
On certai n rare occasi ons aluminum, a base met al , may be
observed corrodi ng wi th rel ease of hydrogen gas which bubbl es
through voluminous whi te creamy hydroxi de. A fl ame i gni tes the
gas showing it to be hydrogen. Si mi l ar corrosi on has not been
reported f or i ron. I f the underground corrosi on of i ron i s
substanti al l y that portrayed i n Fi gure 4 and the anol yte i n the
pi t i s saturated wi th f errous chl ori de, then, i n the absence of
oxygen, evol uti on of hydrogen and corrosi on cannot conti nue if
the pH i s greater than 7 or 8, as i s evi dent i n the nomogram.
The argument i s more apparent i f we consi der a pi t i n the metal
beneath a crack i n a concrete coati ng, the pH of which i s that
of a saturated l i me sol uti on, i .e., pH = 12.45. Taki ng the
potenti al s from the nomogram and fol l owi ng the rul e
+
++
Base: H2 = 2H (Ca(OH)2) + 2e- E = -736.5mV (Eq. 16)
Noble: Fe = Fe (FeC1,*4H,O) + 2e- E = -414.5
++ +
H2 + Fe = Fe + 2H E = -322.0
Thus, the reacti on tends t o proceed from l ef t t o ri ght so that
corrosi on of i ron cannot occur. I nstea?., i ron w i l l tend to
pl ate out under a potenti al of about one-thi rd of a vol t. Using
any one of the oxygen potenti al s wi th the same i ron potenti al
would show that corrosi on would certai nl y proceed.
Si nce, i n f act, corrosi on does occur under the condi ti ons
stated, ei ther (a) there i s some mechanism f or the l i berati on
122
of hydrogen on an i ron surf ace not understood, or (b) the energy
f or the oxi dati on of i ron i s deri ved f r om the reducti on of oxy-
gen. There i s abundant experi mental evi dence for the second
al ternati ve.
Unfortunatel y, many of the computed potenti al s l i sted i n
the nomogram are di f f i cul t to confi rm i n the f i ei d. The causes
of these di f f i cul ti es resul t f r om i rreversi bi l i ty of the ''oxygen
-
el ectrode" and the sti l l mysteri ous metal oxi de f i l ms and other
ef f ects. Neverthel ess, many of these potenti al s have been ob-
served, i ncl udi ng the ref erence cel l s, the i ron-f errous chl ori de
equi l i bri um potenti al , and i n general al l of the hydrogen poten-
ti al s when hydrogen i s evol ved duri ng cathodi c protecti on. The
potenti al s correl ate wi th the pH at the metal surf ace.
11. Measurements on Pi pel i nes Under Cathodi c Protecti on
Properti es of a pi pel i ne under cathodi c protecti on open to
measurement by the corrosi on engi neer i ncl ude (a) the el ectri c
potenti al of the pi pe, (b) the transaxi al and radi al current
fl ow between pi pe and soi l , (c) the current fl ow i n the pi pe
i tsel f, and (d) the very practi cal measure of the reducti on i n
rate of l eaks w i t h t i me. These are di sc- xsed f urther below.
a. Pi pe Potenti al
The pi pe potenti al l ends i tsel f to a vari ety of measure-
-
ments, many of which are rel ated to speci f i c properti es of the
system. I n i ts most general . appl i cati on to buri ed pi pel i nes,
the ref erence el ectrode i s posi ti oned on the ground surf ace i n
the verti cal pl ane thrmgh the pi pe's hori zontal axi s. Thi s i s
the poi nt on the earth's surf ace cl osest to the pi pel i ne.
123
The potenti al Eh i s def i ned as the natural or base poten-
ti al i n the absence of cathodi c protecti on. I t i s stabl e and
i nvari ant wi th respect t o the ref erence el ectrode al though the
potenti al w i l l move sl owl y i n the more nobl e di recti on wi th
t i me. The i nteracti on of the pi pe wi th the ref erence electrode
suppl i es the energy to operate the measuri ng i nstrument. For
.d
example, the reacti on
Fe + Cu++= Fe ++ +Cu
(Eq. 17)
i ndi cates that a quanti ty of i ron corrodes
t o gi ve up a stream
of el ectrodes which pass through the i nstrument and pl ate out
cupri c i ons on the copper el ectrode of the ref erence cel l . Thi s
tri vi al example can be extended to the natural potenti al which
may be a resul tant of potenti al s of t wo i nterconnected coupl es
reacti ng natural l y underground.
I f the pi pel i ne i s coated and under cathodi c protecti on,
several new f actors become i nvol ved.
through (1) the coati ng: (2) the coati ng- soi l i nterf ace, attri -
butabl e i n the absence of total submergence to i mperf ect contact
between pi pe and soi l : and ( 3 ) the soi l between the coated pi pe
surf ace and the l ocati on of the ref erence el ectrode. An addi -
These i ncl ude I R drops
ti onal potenti al drop i s due to the p9l zri zati on necessary to
dri ve the formati on of new chemi cal speci es
at the pi pe surf ace.
Thus, summari zi ng, the potenti al measured at hei ght h over the
pi pe i s
-
Eh =E + AEc + AEs I Eq. 18)
i s the new or pol ari zed potenti al , AEc i s the potenti al .
P
where E
di f f erence between the pi pe surf ace and the coati ng exteri or
P
124
c
( I R drop) combined, and AEs i s the I R drop through the soi l .
Fortunatel y, the three potenti al s on the ri ght of Equa-
ti on 18 can be determi ned wi th suf f i ci ent accuracy f or practi cal
purposes. The potenti al i ncrement AE may be measured i n two
ways which have i n general been found to agree wel l . One i s by
di rect measurement wi th an auxi l i ary probe el ectrode at the
pi pe surf ace. Thi s i ncrement i s obtai ned by i nterrupti on of
the energi zi ng ci r cui t which el i mi nates the resi dual I R drop
attri butabl e to natural soi l currents or pol ari zati on. The
second method i s to measure the I R drop wi th two el ectrodes
pl aced al ong the earth' s surf ace i n the pl ane perpendi cul ar to
the verti cal pl ane through the pi pe's axi s at a poi nt x. The
span x-h i s f i xed by the geometry exi sti ng such that the poten-
t i al between x and h measures the i ncrement AEs.
AEc, may si mi l arl y be esti mated by measuri ng the di f f erence
between the probe el ectrode and the pi pe wi th and wi thout the
ci r cui t energi zed.
s -
The potenti al ,
I f the cathodi c protecti on ci r cui t i s opened, there
resul ts the potenti al E which i s reasonabl y i ndependent of
the el ectrode l ocati on and qui te reproduci bl e. I t nay under
some ci rcumstance be remarkabl y stabl e. However, wi th the
ci r cui t open, the potenti al may move sl owl y i n the nobl e di rec-
ti on; i .e., the pi pe w i l l depol ari ze.
P
Rewri ti ng the equati on
Eh (pi pe potenti al ) = E (pol ari zati on potenti al )
P
+ AEch ( total I R 6rop) (Eq. 19)
The easi l y measured pol ari zati on potenti al i s of great i mportance
1 2 5
i n connecti on wi t h Fi gure 4 and the nomogram, Fi gure 7. The
total I R drop through the soi l i s used to esti mate the current
den:,ity wi t h the ai d of the soi l resi sti vi ty at the poi nt of
test. The I R drop through the coati ng, together wi t h current
densi ty, yi el ds the coati ng conductance. Thus, i f f or example,
too much current has been appl i ed to the pi pe at the poi nt of
drai nage, then it may be expected that the coati ng i s di si nte-
grated and the conductance serves as a measure to compare the
coati ng conductance wi t h the current densi ty elsewhere al ong
the pi pel i ne.
b. Current Flow Between Pi pe and Soi l
The densi ty of current enteri ng the pi pe f r om the soi l
i n the transaxi al pl ane can be measured i n three ways: (1) by
measurement of transaxi al gradi ent as expl ai ned above, (2) by
determi nati on of vol tage and current attenuati on al ong a pi pe,
and ( 3 ) by use of the McCollum earth current met er . Methods
1 and 2 are l i mi ted t o bare or poorl y coated pi pel i nes. Method
1 i s i nappl i cabl e to mul ti pl e paral l el pi pel i nes. Attenuati on
theory leads to average val ues over l arge l engths of pi pe. An
excavati on i s requi red for the earth current meter which can
then be used to expl ore the radi al current densi ti es as at
the hours on the f ace of the clock. The method i s appl i cabl e
in streets congested wi t h pi pel i nes where other methods may be
i mpracti cabl e.
c. Current Fl ow i n Pi pe
The current fl owi ng i n the pi pel i ne i s easi l y measured.
c
126
I t i s attentuated i n excel l ent conformi ty wi th theory under a
vari ety of boundary condi ti ons i ncl udi ng pi pel i nes which termi n-
ate at wel l s wi th near zero resi stance or at i sol ati ng f l anges
wi th near i nf i ni te resi stance and any i ntermedi ate termi nal
boundary condi ti on.
d. Cumul ati ve Leaks
A pl ot of cumul ati ve l eaks attri butabl e to corrosi on
versus t i me may be used f or corrosi on control . A pl ot of l eaks
on an area chart can be used to i ndi cate where cathodi c protec-
ti on has been ef f ecti ve i n di stri buti on systems.
12. Protecti on Cri teri a Reported by Companies Surveyed
Cathodi c protecti on cri teri a uti l i zed by the companies sur-
veyed are summarized i n Tabl es 33 and 34.
TABLE 33
VOLTAGE VALUES AT WHI CH THE COMPANIES CONSI DER
PROTECTI ON HAS BEEN ACHI EVED
Cri teri on Used Protected Vol tage or Del ta E Shi f t (Vol ts)
f or Bar e Pi pe 0.1- 0.31- 0.51- 0.86- Over
0.85 0.30 0.10 0 . 3 0.5 0. 84 1.0 1 Vol t
Pi pe Potenti al 104* 3 3 1 4 29 4 0
Vol tage Shi f t 1 114 20 35 4 0 4 0
Pol ari zati on
Vol tage Shi f t 6 7 43 16 0 0 0 0
Cri teri on Used Protected Vol tase or D e l t a E Shi f t (Vol ts)
f or Coated Pi pe 0:l- 0.31- 0.51- 0.86- Over
0.85 0. 30 0.10 0.3 0 . 5 13.84 1.0 1 V o l t
Pi pe Potenti al 268 5 4 0 1 6 28 3
Vol tage Shi f t 5 106 3 15 13 A 0 0
Pol ari zati on
V ol t ase Shi f t 0 1 2 42 12 2 2 1 0
*Number of compmi es
127
. - . -. , . .
TABLE 34
OTHER CATHODI C PROTECTI ON CRI TERI A USED BY THE COIWANIES
Cri teri a Number of Companies
Current Loss and Gain on the Structure 34
Current Traci ng i n the El ectrol yte
Perpendi cul ar to the Pi pel i ne 13
Pol ari zati on Potenti al 6
Smal l I nterval or Conti nuous Pi pe
Potenti al Surveys
Other
11
i a
c
The cathodi c protecti on cri teri a l i sted under "Other" i n
Tabl e 34 i ncl uded pH measurement, decrease i n l eak rate, corro-
si on coupons, corrosometer probes, anal ysi s of cal careous de-
posi t i n pi ts, rusty i ron ref erence el ectrodes, correl ati on wi t h
soi l resi sti vi ty, etc. Most of the companies surveyed used sev-
eral cr i ter i a to determi ne i f the pi pi ng i s protected. Tabl e 35
shows where the companies normal l y pl aced thei r ref erence elec-
trode when determi ni ng i f the cri teri a of cathodi c protecti on
has been achi eved.
TABLE 35
NORMAL PLACEMENT OF REFERENCE ELECTRODE
Number of Companies
El ectrode Posi ti on Bare Coated -
On Surf ace Over Pi pe
Remote from Pi pe
I mmedi atel y A6-j acent to Pi pe
Other
202
50
34
6
29 2
52
57
14
128
13. Di scussi on of Cathodi c Protecti on Cri teri a
a. Fi xed Pi pe Potenti al
The pi pe potenti al ( ci rcui t energi zed) i s the si mpl est
measure used t o gage the ef f ecti veness of cathodi c protecti on.
The general l y used val ue i s 0.850 vol t to the copper sul f ate
el ectrode. I t i s, accordi ng to the conventi on stated ear l i er ,
negati ve wi th respect t o the ref erence. The cri teri on i s a
minimum i n that the pi pe potenti al everywhere i s numeri cal l y
equal to or greater than the sel ected val ue (commonly 0.85 V).
I ts wi despread use attests to i ts popul ari ty and success i n the
f i el d.
and stori ng peri odi c readi ngs. The magni tude of such ef f or t
may be envi si oned on a 350-mile l ong, w e l l coated pi pel i ne wi t h
test stati ons at mi l e i nterval s. The cri teri on i s i ndependent
of sequenti al l y adj acent cathodi c protecti on uni ts on the same
pi pel i ne.
Further advantages i ncl ude the l ow cost of col l ecti ng
A di sadvantage i s that a f i xed pi pe potenti al cri teri on
contai ns acknowledged but unknown I R drops through soi l and coat-
i ng, as di scussed previ ousl y. These mi ght wel l permi t i nsuf f i -
ci ent current f or protecti on. A seri ous break i n an otherwi se
perf ect coati ng remote from the poi nt of test coul d w e l l r ef l ect
an apparent sati sf actory potenti al , a l arge component of which
i s, i n f act, an I R drop i n the soi l . To avoi d I R drops i n the
soi l , some observers iise an el ectrode at the pi pe surf ace.
el ectrode can be pl aced there upon excavati on.
trodes can be f orced to the pi pe surf ace. Permanent di rect
buri al el ectrodes can be l ai d on the pi pe upon cgnstructi on
-
The
Probe type elec-
129
as a component of the test stati on.
Another shortcomi ng i n a f i xed pi pe potenti al cri teri on
i s that there i s no provi si on f or taki ng account of unusual con-
di ti ons. For example, potenti al readi ngs can vary wi t h the tem-
perature of the ref erence el ectrode. A l so, reacti on potenti al s
may vary wi th the temperature of protected structures such as
hot oi l l i nes, hot f uel oi l tank bottoms, etc. Accordi ngl y,
unusual condi ti ons whi ch may be present shoul d be taken i nto
account i n uti l i zi ng a f i xed pi pe potenti al protecti on cri teri on.
b. Pol ari zati on Potenti al
The requi rements to arrest corrosi on i n the typi cal case
as depi cted i n Fi gure 4 may be examined bef ore descri bi ng other
si mpl e potenti al cri teri a. One possi bi l i ty would be to reverse
the current fl ow from the pi t. I t would be hel pf ul toward thi s
end to el i mi nate oxygen as a contri butor to the cel l 's overal l
potenti al . T hi s coul d be done by suppl yi ng suf f i ci ent el ectrons
t o the pi pe surf ace t o tax the incoming oxygen's abi l i ty to re-
act wi th the surf ace l ayer of monatomic hydrogen -- i n short,
to render the pi pe surf ace negati ve. On new pi pe a potenti al
j ust suf f i ci ent t o repel the chl ori de or sul f ate i ons would pre-
vent the devel opment of a corrosi on cel l .
A cri teri op. advanced by Brown and Mears states that
cathodi c protecti on of a metal w i l l be achi eved at any i nstant
i f the cathode i n a corrosi on cel l i s brought to the potenti al
of the most anodi c potenti al exi sti ng on the metal at that i n-
stant. T hi s condi ti on, pl us the experi mental f act that the i ron
i n the corrodi ng pi t as earl i er di scussed i s i n equi l i bri um wi th
130
i ts saturated sal t, l eads to a promi si ng theoreti cal l y based
cri teri on. To achi eve cathodi c protecti on, then, it would be
necessary, accordi ng to the nomogram, onl y t o bri ng the cathode
to a potenti al of 712.6 or 766.1 mV dependi ng upon the chemi stry
of the el ectrol yte i .e., if the predomi nant sal t i s, respec-
.
ti vel y, f errous chl ori de or f errous sul f ate. I f the cathode
i s brought to ei ther of these val ues, it shoul d assure that at
l east the depol ari zi ng ef f ect of oxygen has been overcome.
The obj ecti ve potenti al i s the pol ari zati on potenti al
of the cathode. I t shoul d be measured by el i mi nati ng al l the
I R drops i n the cathol yte as previ ousl y di scussed. I t coul d
be mos t si mpl y and cl osel y approxi mated by readi ng the pi pe
potenti al i mmedi atel y upon i nterrupti on of the appl i ed current.
c. Depol ari zati on I ncrement
Condi ti ons i n the f i el d are extraordi nari l y vari ed.
Accordi ngl y, speci al measures or techni ques have appeared as
cri teri a f or cathodi c protecti on. Among these i s a depol ari za-
ti on i ncrement of potenti al of at l east 100 mi l l i vol ts measured
from the i nstantaneous open ci r cui t potenti al (the pol ari zati on
potenti al ) to the potenti al at some unspeci f i ed l ater t i me.
A di sadvantage of the cri teri on i s that there i s no apparent
techni cal basi s f or it other than experi ence. Further, under
some ci rcumstances, i ncl udi ng hi gh current densi ti es, the de-
pol ari zati on essenti al l y vani shes.
-
d. The E-log I Curve
The cri ti cal potenti al representi :?g the cri teri on f or
protecti on i s read at the i ntersecti on of the extrapol ated l i near
131
porti ons of the curves obtai ned f or a series of associ ated val ues
of E and I when pl otted on semi l ogari thmi c coordi nates (Fi gures
2 ar.d 3 and Equati on 6) . However, a l i near connecti on between
the vari abl es, consi deri ng the f aul ts of measurement, coul d be
i nterpreted on the l ogari thmi c pl ot as di sti nct l i near curves
havi ng the sought i ntersecti on upon extrapol ati on. A change i n
reacti on at the metal surf ace may cause a proporti onate change
i n E as the current i s i ncreased. For example, when i ron be-
comes saturated wi t h monotomic hydrogen and mol ecul ar hydrogen
begi ns to form, a proporti onate change i n E resul ts as the
current i s f urther i ncreased. Other such changes coul d come
about when suf f i ci ent hydrogen i s formed to react w i t h avai l -
abl e oxygen or when the anode of a corrosi on cel l becomes a
cathode. The method, thus, has consi derabl e me r i t both as a
desi gn and a protecti on cri teri on.
Di sadvantages i ncl ude l ocati ng anodi c poi nts on the
system to be tested. The most desi rabl e poi nt to test would
be the most anodi c poi nt i f it coul d be found. To base pro-
tecti on on measurements at a cathodi c poi nt would l ead t o f ai l -
ure or a f orced eval uati on of a purel y l ogari thmi c curve. Fur-
ther f or reasons of i nstrumentati on, onl y a si ngl e poi nt i n a
system can be tested at a t i me because once tested the system
i s so pol ari zed that a repeated test would not dupl i cate the
-
ori gi nal test. Thus an E-log I test on a cat5odi cal l y protected
pipe1iT.e wocld not be concl usi ve because there would be no change
I
i n chemi cal reacti on at the metal surf ace al ready cath.odi cal l y
pol ari zed. However, on a l ong pi pel i ne the me"3od can be
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modi fi ed advantageousl y i n such a way that the poi nt at which
f urther i ncrease i n current would not be prof i tabl e (no i ncreased
pol ari zati on) can be determi ned by pl otti ng the dri vi ng vol tage
(current densi ty) agai nst the pol ari zati on. Appl i ed i n thi s
manner the method becomes a desi gn cri teri on and can be exceed-
* i ngl y usef ul .
e. Radi al Earth Current
I f i n an excavati on it i s determi ned by test that a
pi pe i s recei vi ng current through the soi l al ong every radi us,
then it i s assured that the pi pe i s protected at that parti c-
ul ar l ocati on. L i ke the E-log I method, however, the deter-
mi nati on i s l i mi ted t o the poi nt of test. I t has a great
advantage i n that it can be used under condi ti ons of crowded
pi pel i nes. Further determi nati ons are preci se f or each radi us
and any marked vari ati ons i n current strength about the ci r-
cumference w i l l be evi dent and can possi bl y be correl ated wi th
nei ghbori ng structures. I t i s, theref ore, especi al l y usef ul
i n cathodi c i nterf erence probl ems. A di sadvantage i s the hi gh
cost of excavati on.
f . Pi pe Potenti al Probabi l i ty Curve
A stati sti cal method has been devel oped t o establ i sh a
cri teri on of protecti on, uni que f or the system under test. The
method has been appl i ed to copper pi pi ng under ground, but i ts
-
usef ul ness wi th steel i s i mpai red because of the redox potenti al
exi sti ng i n the corrosi on product mantl e bptween pi pe and soi l .
The methcd has not been publ i shed and w i l l , tl zerefore, xot be
f urther el aborated here.
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g. Summary
I t has probabl y become apparent that there i s no one.
cri teri on for cathodi c protecti on that w i l l be appl i cabl e under
al l condi ti ons. On the other hand, the cr i ter i a menti oned abovr,
plus several other standards and methods not menti oned, can be
qui te sati sf actory when appl i ed wi thi n the constrai nts governi ng
thei r use. Often a combi nati on of cr i ter i a i s necessary to pro-
perl y eval ute the ef f ecti veness of cathodi c protecti on of a par-
ti cul ar structure or system.
*
134