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Corrosion Science, 1968, Vol. 8, pp, 173 to 193. Pergamon press.

Printed in Great Britain

STEEL PIPE CORROSION U N D E R FLOW CONDITIONS--I. AN ISOTHERMAL CORRELATION FOR A MASS TRANSFER MODEL*
B. K . MAHATO, S. K . VOORA a n d L. W . SHEMILT Department of Chemical Engineering, University of New Brunswick, Fredericton, New Brunswick, Canada Abstraet--A critical review of the existing literature on the effect of velocity on the corrosion of Fe and steel in water has been made. Based on a double resistance model with one resistance significantly time-dependent, the analytical form required to portray the corrosion amount-time relationship for the steel pipe-water system has been established. A modified mass transfer coefficient with determinable relationship to the Re number for flow conditions has been obtained. An adequate semi-empirical correlation for corrosion rate, either in usual units or in a dimensionless form, as a function of Re number and a dimensionless diffusion group has been obtained for isothermal flow conditions. This correlation, based on corrosion as an unsteady state mass transfer process, adequately represents new data on corrosion of steel pipe at 150F in natural water, as well as available data from other laboratories. R6sum6----On a fait une revue critique de ce qui a 6t6 publi6 sur l'effet de la vitesse d'6coulement d'eau sur la corrosion du fer et de l'acier. A partir d'un mod~le b. double rdsistance dent une est'fonction du temps, on a r6alisd l'6quation qui donne la valeur du montant de la corrosion en fonction du temps pour le syst/~me d'un conduit d'eau en acier. On a obtenu un coefficient modifid d'6change de masse en fonction du nombre de Reynolds et des conditions de l'&:oulement. Une relation semi-empirique qui ddtermine le taux de corrosion en fonction du hombre de Reynolds et d'un nombre de diffusion (non-dimensionelle) a dt6 obtenu pour condition isotherme. Cette dquation, bas6e sur un mod~le qui voit la corrosion comme 6tant un proc6dd de transfer de masse variable avec le temps, d6termine suffisamment bien les valeurs expdrimentales obtenues pour la corrosion d'un tuyau d'acier par eau naturelle ~ 150F, et aussi autres valeurs obtenues par divers chercheurs. Zusammenfassung--Es wird ein kritischer 0berbliek iiber die vorhandene Literatur gegeben, die den Einflug der Str6mungsgeschwindigkeit auf die Korrosion von Eisen und Stahl in Wasser behandelt. Auf der Grundlage eines Zwei-Widerstand-Modells, bei dem ein Widerstand deutlich zeitabh,~ngig ist, wird die analytische Form des Korrosionszeitablaufs fi.ir den Angriff yon Stahlrohren dutch Wasser aufgestellt. Ein abgewandelter Stoffiibergangskoeflizient, der in de3nierter Weise yon der Reynolds-Zahl abhiingt, wird fiir unterschiedliche Str6mungsbedingungen erhalten. Ein angemessener, halb empirischer Zusammenhang zwischen der Korrosionsgeschwindigkeit und der Reynolds-Zahl sowie einer dimensionslosen Diffusionszahl wird fiir isotherme Str6mungsbedingungen angegeben sowohl in den iiblichen Einheiten als auch in dimensionsloser Form. Dieser Zusammenhang, der die Korrosion als einen instation~ren Stoffiibergang darstellt, entspricht gut Messungen der Korrosion von Stahlrohren in natiirlichen W/issern bei 150F und auch den Ergebnissen, die in anderen Laboratorien erhalten wurden.

The Russian abstract for this Manuscript will appear as a loose insert in the next issue of this Volume.

*Manuscript received 28 July 1967. 173

174

B.K. MAHATO,S. K. VOORAand L. W. SHEMILT

INTRODUCTION Tim practical importance of the corrosion of Fe has led to a vast literature in the field. In the case of corrosion in aqueous environment the important variables recognized have been the amount of dissolved O, temperature, flow conditions, pH, metal composition, duration of exposure, and composition of water. 1 While many investigations of these important factors have been carried out, the correlation of some or all of them has not been adequately achieved. This investigation reports on an initial effort to correlate the factors of amount of dissolved O, flow rates, and duration of exposure. The addition of the temperature parameter is also contemplated, as is variation in water composition. At this stage it is assumed that metal composition and water composition are maintained constant and this paper reports an isothermal investigation. It is widely recognized that the corrosion of Fe may be accounted for by an anodic reaction, equation 1 and a cathodic reaction equation 2, illustrating the basic electrochemical nature of the corrosion phenomena. 2 Fe --->Fe ++ + 2e 2H + + 2e --->H2. (1) (2)

In the presence of O, depolarization of the cathodic products takes place according to equation 3. 02 + H~O + 2e --> 2OH-.

(3)

In most situations it is the cathodic reaction and the subsequent depolarization by oxygen that tend to control the rate at which Fe corrodes. However, equation 3 is generally so rapid that O concentration at the cathodic surface approaches zero. It is therefore accepted that the rate of O depolarization depends on the rate of the diffusion of O through the resistant films at the surface of the metal. One of the diffusion barriers is due to the corrosion product, often largely consisting of Fe(OH)2 accounted for by combining equations 1 and 3 : Fe + H20 + 02 --->Fe(OH)2 Fe(OH)2 + H~O + O2 --~ Fe(OHh

(4) (5)

Ferrous ion is converted to the ferric state by further oxidation as in equation 5 and

Steel pipe corrosion under flow conditions

175

most ordinary rust is comprised of the hydrated ferric oxide. Frequently a black layer of magnetic hydrous ferrous ferrite (FeaO4. n H20) forms between Fe~O3 and FeO. Hence it is considered that rust films normally consist of three layers, of iron oxide in different states of oxidation, x Examination of the corrosion process can be made from one or more of four types of measurements. Firstly, the weight loss of metal itself will be a complete indication of the amount of corrosion, while secondly the growth of corrosion product fi'.m will give an indirect indication of the amount of corrosion. This latter can be related directly to amount of corrosion only if there is no loss of corrosion product into the aqueous environment, and provided that its chemical composition is completely and accurately known. Electrochemical methods include measurements of corrosion current and corrosion potential. The fourth approach is in terms of measurement of the transfer of the cathode reactant, i.e. dissolved O in water, and hence essentially a mass transfer measurement. The equivalence of weight loss, amount of corrosion product formed, and O transfer or uptake is direct and obvious. Numerous investigations have been made of the relationship between these and the electrochemical measurement of corrosion current s and of polarization, a-9 although little success has apparently been achieved in achieving quantitative correlation with overall specimen or corrosion potential. Irrespective of the measurement method, the results of corrosion tests are usually expressed in relation to the time of exposure. The growth of corrosion product film with time, for example, has been represented by many mathematical expressions, and Evans 1 has provided a theoretical basis for these laws of film growth with a general set of curves representing the various equations where the amount of corrosion is equated to the O uptake. The added parameter selected for special consideration in this investigation is that of the velocity or flow situation in the aqueous environment. A review of literature dealing with the corrosion of Fe when velocity and fluid flow is a variable shows many apparent contradictions. Friend u-aa observed the corrosion rate of Fe in a natural water to decrease with increasing velocity until above 8 ft]s it was almost zero, while Speller and Kendall 14 found the rate low under laminar flow conditions, rapidly increasing in the transition range, and more slowly increasing under turbulent flow conditions. Whitman 15 stated that the corrosion rates should increase at higher flow rates due to an increase in O diffusion and breaking down of the protective films on the metal surfaces. Wilson 18 emphasized the effect of velocity as an important factor in governing the thickness of the film through which O must diffuse in the corrosion process. Evans 1 indicated that greater turbulence due to high velocities results in more uniform O concentration and most likely delays the initiation of corrosion on a previously uncorroded surface. Cox and Roetheli x7 obtained data for steel specimens in aerated natural water (Cambridge, Mass., U.S.A.) by varying the rotational speed of the specimen and the O content in the water, and found that corrosion rate increased with the increased O content (up to 6 ppm) and increased peripheral velocity (up to 1.2 ft/s). Roetheli and Brown as further reported that the corrosion rates increased to a maximum, as the rotational velocities of their steel specimens, in oxygenated water,

176

B. K. M.AHATO,S. K. VOORAand L. W. SI-IF, MILT

increased, then decreased to a very low value and increased again to a somewhat higher value at very high velocities. Frese 19 showed that Fe tends to become passive with high O concentration and the corrosion rates may drop to low values. Speller2 observed that the effect of velocity was to bring O into more intimate contact with the cathodic surfaces. This resulted in active oxidation and formation of protective Fe(OH)3 film nearer to the reaction points, thus stifling the corrosion reaction. Wormwel121 reported that corrosion rates were determined largely by the rate of O supply to the metal surfaces. H a t : h and Rice 2z observed that the change in the O concentration gradient near the metal surface was due to the effect of velocity. In spite of very high velocities the O concentration at the metal surface was only slightly greater than at moderate velocities, and thus the corrosion rate was increased but a small amount. Cohen ~3 showed that in natural water (Ottawa, Ont., Canada) pipe corrosion increased with velocity up to 4.5 ft/s and then decreased with the further increase of
flOW.

Copson u found that corrosion, in general, increased with increase in velocity, but the effect was sometimes the opposite. Streicherz5 explained the drop in corrosion rates of steel at higher velocities as due to passivation brought about by the increased O supply. Uhlig 2 has reported extensively on the effect of O passivation at high O concentration. Eliassen e t al. 2e,27 presented fundamental hydraulic concepts as applied to corrosion and the rate of transfer of interacting chemicals in flow over plates, rotating disks and through pipes. He indicated that the velocity of the water, degree of turbulence, geometry of pipes, and other physical factors have a direct influence on the movement of dissolved O and ions throughout the fluid. These factors in turn exert effezts on the formation of corrosion products, and on depolarization and thus on the corrosion reaction itself. Dey 28 observed the lowest amount of corrosion in black Fe pipe specimens, carrying Vancouver (Canada) city water, for the highest level of flow rates (i.e. 4.5 compared to 0.75, 1.5 and 3.0 ft/s) at 90F and 130F, irrespective of test duration. He attributed this to the passivating effect of O. Butler and Ison "9 investigated corrosion of mild steel pipe specimens in flowing water of Teddington (England) mains and presented data for different flow rates and different temperatures. They found that the corrosivity of water is largely governed by its scale-forming properties and an increase in both speed of flow and temperature promotes the deposition of a protective scale. Ross and Hitchen a showed the importance of water velocity in the depolarization of cathodic processes by a study on the short-term electrochemical behaviour of Fe, Cu and C arranged in annular couples and exposed to distilled water. An explanation of the results in terms of the liquid boundary layer at the metal surface was suggested but not evaluated. Butler and Stroud a~ studied the corrosion rate of mild steel tubes by high purity water and observed that the corrosion rate increased with increasing speed of flow to a maximum value at about 3.3 ft/s; any further increase resulted in a decreased corrosion rate.

Steel pipe corrosion under flow conditions

177

A complete summary tabulation of the conditions for corrosion tests of steel or iron in natural or synthetic water under flow or forced convection is shown in Tables 1-3 for three different experimental methods: (a) flow of fluid past plates or small specimens, (b) rotation of specimens in a mass of liquid and (c) flow'of fluid through pipe specimens. It is clear that in the first two methods it is impossible to obtain a definitive value of the hydrodynamic situation that pertains and it is therefore impossible to analyse these results in the form of dynamic similarity for comparative or correlation purposes. The investigations based on flow of fluids through a pipe specimen in such a way that the hydrodynamics are clearly defined has only been used in any extensive way by Elliasen, 26,27 Dey 2s and Butler and [son. 2 The lack of agreement amongst the other investigators is certainly related, and probably almost entirely due, to the impossibility of making adequate hydrodynamic comparisons between the various experiments recorded. In the work reported here, the flow-in-pipe method was therefore used, corrosion amounts were obtained by weight loss, and potentials of individual specimens relative to a reference electrode, measured. The method of analysis of the system took into account the factors stressed above, i.e. mass diffusion of O, a corrosion product layer, and a definable fluid flow.

SIMPLIFIED MASS TRANSFER MODEL The corrosion situation specified is an heterogeneous reaction between a" solid and a fluid in which there is a continual growth of a product layer, and in which the transfer of the cathode reactant, dissolved O, to the solid surface may be assumed to be the controlling factor. In addition, the aqueous medium is flowing past the reacting solid. Any mechanism proposed for this mass transfer situation must include the presence of any forced convection and of any unsteady state or time-dependent factors. The model proposed is therefore based on two series resistances to diffusion. Dissolved O in the flowing turbulent test water must diffuse through some form of fluid film and then through a porous corrosion product to reach the reaction zone. All of the current theories replacing the classic boundary layer theory would give a reasonable mechanism for the transport process in a turbulent fluid adjacent to a solid. Since only a total equivalent resistance is to be used, the recent hypothesis of a damped turbulence layer4 will present an adequate picture of the turbulent flow past a very rough porous solid interface. The second resistance is this porous solid layer filled with inert fluid through which the dissolved O must pass by molecular diffusion. The cathode reaction which takes place at the pipe wall surface has such a low activation energy that it proceeds rapidly and irreversibly.4s The O concentration at the pipe wall surface can thus safely be assumed to be zero or negligibly small when compared to its bulk concentration. For turbulent flow, the bulk concentration of O can be considered uniform at all times, except in the region immediately adjacent to the solid corrosion product, and will be very close to the saturation value at the temperature of operation for an aerated liquid supply. Figure 1 presents the very simple model thus described. The mass flux of O through the fluid film is given by equation 6 and through the corrosion product layer by equation 7.

178

B . K . MAHATO, S. K. VOORA and L. W. SHEMILT

Y
/ / / /
2 I ( 02

t"
/

Y2 Yl

/
water
flow

I.damped turbulence layer 2. corrosion product layer


I I

, I
I I

Cb " ' " "

o" ci ~ ; 8 "-' % ,
>
distance from w a l l

PIG. I.

Physical model for transfer of dissolved 0 for F corrosion process.

dn _ (D, 4- ~) (Cb -- Ci) dt (In dt Yx Dv (Ci -- Cw) Y2

(6)

(7)

The resistance, Y2 offered by the corrosion product layer is given by equation 8, assuming it to vary as the amount of corrosion product (or amount of O transferred) and with a resistance coefficient which is independent of time.
t

[ - k ~ dt = kn. Y~ = d dt
0

(8)

The total mass flux is then obtained as in equation 9, which on integration gives a parabolic form, equation 10.
tin dt D, Cb D, Yl kn 4 - -

Dv+~
t.

(9)
(10)

a n2 +

{3 n =

The mass transfer rate in terms of the coefficients a and [3 is given by equation 11 with coefficients defined in equations 12 and 13.

Steel pipe corrosion under flow conditions dn dt


1

179

2 a n + f~ k a -- - 2 D~Cb
_ yx

(11)
"(12)

Cb ( Dv + ~)

(13)

The conventional overall mass transfer coefficient Ko (equation 14) may then be reliated to the coefficients ct and ~3 as in equation 15.
--

dn dt

KoAC

K o Cb

(14)

Ko =

C b ( 2 u n q- ~)

(15)

Considering the two mass transfer coefficients in series (equation I6), and with the corrosion product layer providing the greater resistance (equation 17), the significant mass transfer coefficient K~ may then be found in terms of system properties (equation 18). 1 _ 1 + /('1 1 =Cbf~-{-Cb2ctn (16)

Ko = K 2 w h e n K 2 < < K t
_ 1 1 _ D~ I

(17)
(18)

K2

2Cb(~

, - - - -

. - -

In this form, however, it depends on the total amount of O transferred, and is better defined as a modified time-independent mass transfer coefficient K 2.
K~ - - Dv (19)

k In this fashion, measurement of corrosion amounts, related to time as in equation 10, can be used to provide a mass transfer coefficient. APPARATUS AND PROCEDURE FOR CORROSION MEASUREMENTS The re-circulating flow apparatus (Fig. 2) consisted of a beating tank, pump distributor and collecting reservoirs, with the necessary valves and flow meters. The distributor and collecting reservoirs could accommodate several test sections simultaneously. All materials used were either polyethylene or neoprene, with the exception

180

B.K.

MAHATO, S. K . VOORA a n d L. W. SHErmLr

'

I
7

I0

r'

T
9 I
I I

14 8 II
12 -'.. -

iJ

FIG. 2. Schematic diagram of the recirculating corrosion test apparatus. I. Distributor tank. 2. Flow stabilizer. 3. Test section. 4. Silver-silver chloride electrode. 5. Collecting tank. 6. Thermometer. 7. Supply tank. 8. Level indicator. 9. Air bubbler. 10. Feedback line. 11. Compressed air line. 12. Feed water line. 13. Sampling point. 14. Sample cooler. 15. Bypass line. 16. Leading to drain. 17. Flow meter.

of valves and pump which were lined with Heresite. Each test section was preceded with a flow stabilizer and a diaphragm valve for manual control. The water temperature was controlled to within 0.5F. About 12 per cent of the volume of the system water was replaced daily by fresh water. The test sections were composed of six or twelve ~ in. dia. (schedule 40) black Fe pipe specimens, each 3 in. long. The specimens were connected with couplings and separated by acrylic washers. They were carefully mounted, and specially reamed to prevent any disturbance of the flow pattern. About half of the specimens were connected electrically to a potentiometer. A Ag-AgCI electrode for reference purposes was inserted in the collecting reservoir. During the test runs, the potentials were recorded potentiometrically at frequent intervals. The water used was Fredericton city tap-water, which is well water with a total alkalinity, as CaCOs, o f about 80 ppm, a total dissolved solids of 100--150 ppm, and p H ,-, 7.2. Daily samples of water were taken during the test run and analysed for Fe content, O content, and pH. All specimens were carefully marked as to location and were carefully cleaned and weighed before use. At the end of a definite test period the specimens were removed, dried and reweighed. The corrosion products were then removed, the specimen cathodically cleaned ~9 and weighed. Most tests were performed on twelve specimens although in some cases only six were used. All results were averaged and standard

Steel pipe corrosion under flow conditions

181

deviations obtained. Flow rates were corrected to pipe Re numbers (Re = DtUp/[.t) based on initial pipe diameters. This report covers tests carried out at 150F at a series of four flow rates and for varied test durations up to 25 days.
RESULTS AND DISCUSSION

The standard deviations obtained for the weight loss measurements were never greater than 8 per cent and usually less than 5 per cent. No consistent variation relative to the specimen position was noted. No appreciable build-up of Fe in the water and no significant change in pH were found, and the dissolved O content was close to saturated conditions throughout the test durations. Blank tests on the method of cathodic cleaning indicated an insignificant weight loss. Visual and microscopic inspection of the corrosion products showed a porous, rust-coloured precipitate underlaid by a fine, dense, granular, black film in agreement with usual observations under similar situations. The surface roughness characteristic of the corrosion product varied with each flow rate and each test period. In almost all cases corrosion was quite uniform over the specimen surface. The corrosion product surface was wavy in appearance with significant peaks and valleys, the peaks projecting in the direction of flow. Figures 3 and 4 give some indication of the effect of flow rate and of test duration on the exterior form of the corrosion product.
7000

-Q

0 = a: a.

o o

o
~n

o o

(.1

200~ Z

OW 0

I 1000

I 2000

I 3000

| 4 ooo

AMOUNT

OF C O R R O S I O N ,

md

F[o. 5.

Relationship between the amount of corrosion product and the amount of corrosion.

.trc af the corrosion product layer. mperaturc 150 F IO; (c) Rc 26,210: (cl) Re 26,210.

Test

period

182

B . K . MAHATO, S. K . VOORA a n d L. W. SHEMILT


I I I I I I

600C
0 -

450C

3000

1500

Re
0 0 I 4 1 8 I 12 I 16

26210
I 20 I 24

TIME, DAYS
FIG. 6. Effect o f d u r a t i o n o n the a m o u n t o f corrosion at 150F.
1 i I 1 (~1 i I (~

4000

Z o 3000 ~) e. o J
,, o 2000

qD

~Z
o '5 1000

Re
39320

.~
0 I I I I

o
I

13110
6550
I I

6 TIME,

8 DAYS

I0

12

14

FIG. 7.

Effect o f duration on the a m o u n t o f corrosion for different flow rates at 150F.

The corrosion product had a composition that closely approximated to hydrated ferric oxide. In Fig. 5, the reference lines indicate the stoichiometric relationship between pure Fe and the theoretical corrosion product of hydrated ferric oxide FeOOH and of ferrous oxide, FeO. The experimental data agree very closely with the former. The average weight losses as MD (mg/dm2) are shown as function of time in Figs 6 and 7, with the Re number corresponding to the fluid velocity as a parameter;

Steel pipe corrosion under flow conditions


l ! 1 !

183

o.

teo

l
I
J ! !

12Q

6O

;~

16

2'0

' 24

TIME,days
FIG. 8, Effect of duration on the speci~qccorrosion rate at 150F.

the solid lines correspond to the parabolic corrosion equation (equation 10). The best values of the coefficients ct and ~ were obtained from the experimental data by the method of least squares. The corrosion rates as MDD (rag/drug/day) v~ere then obtained using equation 11, and the results plotted as specific corrosion rates, i.e. MDD/ppm of dissolved O, are shown in Fig. 8. The corrosion rates fall rapidly in the initial periods and then gradually level off until they decrease slowly and regularly with time. Within the range investigated, the velocity increases the corrosion rates for the same corresponding test duration. These results are qualitatively consistent with the model proposed above, in that higher Re numbers should decrease the resistance factor in the so-called damped turbulence zone, thus increasing the rate of O transfer to the cathodic areas. The lack of agreement noted amongst earlier workers is understandable from two standpoints. In the first instance the hydrodynamics were mixed and ill-defined. Secondly a simple relationship between corrosion rate and velocity does not exist; the crossover of the curves shown in Figs 6 and 7 is evidence of this. Some clarification ensues when a specific corrosion rate plot (Fig. 8) is used. Examples of the measured potentials relative to the Ag/AgCI electrode, as a function of time are shown in Fig. 9. The data plotted are average values of from three to six specimen potentials belonging to the same test section. Average deviations from the average however are quite high. The sudden change in potential shown part way through the test period is due to the disturbance of the test section when half of the specimens were replaced. This same disturbance did not occur in undisturbed test sections and is similar to results noted by others. 39,3o The general relationship between the potentials and the corrosion rates is clear. The rapid change of potential in the anodic direction corresponds to the high initial corrosion rate. The potentials then become gradually more cathodic with time and approach a constant value. This latter tends to be higher (more positive) at higher values of Re numbers. The correspondence between corrosion potentials and corrosion

184

B.K. MAHATO,S. K. VOOP.Aand L. W. SHEMILT

600 70( ~j
~.

800
900

Re

13110

d
:> u
~E

50C 600
i i i I i i i i i i , i , ,

"7
t/) _1
m

12

I-Z LU I-0 n

6oo
c)
700

9-----I. /

.r.t-_..O-~"JC,

aoo
| i i i i i

ORe 26210
0 6
T I M E

i 12

18 DAYS

24

FIG.

9.

Average specimen. Potential w.r.t, silver-silver chloride electrode (ACE)


curv~.

rates is exemplified when both are plotted on the same time scale. From the time when the potentials reach their maximum anodic value for the duration of the test, very similar curves result. This indicates the self-adjusting nature of the anodic and cathodic area potentials so as to produce a corrosion current exactly sufficient to consume the O as it becomes available at the metal surface. 1o A clear portrayal of this may be shown by replotting the data in an alternative form. Since the time-dependent equation for the amount of corrosion is ct W 2 -F [3 W = t, then the reciprocal of the square of the corrosion rate will be linear with time. Figure 10 shows both this reciprocal square and the reciprocal square of the potentials (average potentials but weighted for the number of specimens involved) on a time base. The potential results show a fairly uniform scattering about the corrosion rate line. The potentials of individual specimens relative to the Ag-AgC1 show large differences and therefore the average potential is of limited value. Nonetheless the correspondence here with corrosion rate is considered significant. Values for the modified mass transfer coefficient K' were calculated from the smooth experimental data and plotted against Re number (Fig. 11). The relation may be expressed exponentially and has been thus evalu&ted as
K~ = 6"31 . 106 R e TM.

(20)

The model proposed above, which assists in relating the modified mass transfer coefficient to the actual corrosion measurements, is based on an unsteady-state mass

Steel pipe corrosion underflow conditions

185

325 IDrate t potential .... ]OSf


.~

/ ~
()

t
2400

i
FIG. 10.

1,.

,,5~

TIME,days.

'

'

,o

Relationship between corrosion potential and corrosion rate.

30 20

10 S
o x

|0

20 number

30
x 10 . 3

40

50

Reynolds
FIG.

11.

Effect of Ke on the modified mass transfer coet~cient.

transfer process. The rate of 0 transfer is basically a function of temperature, time and flow rate. Using the physical properties of this system, these basic variables may be transformed into related dimensionless groups

B K. .

-O T,

S K. VOORAand L W. SHEMILT . .

T I M E , days.

FIG.12. Effect of exposure time on the overall mass transfer coefficient for different flow rates.

The left-hand side of the equation gives the ratio of chemical reaction rate to molecular diffusion rate, and the independent variable groups are respectively Re number, an unsteady-state diffusion group representing the ratio of diffusive mass transport to bulk mass transport, Schmidt number, porosity of corrosion product (which is essentially a function of the Re number and the reaction rate group) and a dimensionless temperature group. For an isothermal system this reduces to two dependent variable groupings as in equation 22. This may be rewritten showing a functional dependence (equation 23). By substitution of the overall mass transfer coefficient KOfrom equationl24, the final dimensionless relationship is obtained (equation 25).

Steel pipe corrosion under flow conditions

187

R--

dW ---dt

dn dt

--KoCh

(24)

D, =a.f(Re).q~' KoDJ \ D~ /

(25)

The functional relationship of the unsteady-state diffusion group with the reciprocal of the square of the mass transfer coefficient can be obtained by plotting the latter against time, t. This is shown in Fig. 12 and indicates a strong dependence on Re number. A plot of a f(Re) against the Re number itself could indicate the probable relationship of the Re number function with lIKe, and Fig. 13 shows a reasonable straight line relationship. In Fig. 12 the plot of 1/K~ vs. t gives a straight line relationship for each Re number indicating the linear nature of the unsteady state diffusion group. As a result, equation 25 may be rewritten, with the introduction of a term r to indicate the straight line relationship. i.

K~I __ \D,/(D'~za f ( R e ) The slope is then equal to


,

\(tD~D' + r )

(26)

a "f(Re)/Dv,
| , i

and the intercept is


| I

a .f(Re).(Da/D,)Z.r.

40

20

o -x ~

'10 8

i 4

I 6

I 8

I 10

I0 2

I 40 X I0 " s

Reynolds
FIG. 13.

number

Determination of the functional relationship of R.e number (equation 27).

188

B . K . MAHATO, S. K. VOORA and L. W. SHEMILT

From the slope and intercept values it was possible to obtain an average value of 0-13 for r for the range of Re numbers studied. The straight line relationship from Fig. 13 is a .f(Re) = P Rea. (27)

Substitution then puts this in the form of equation 28 which involves the rate as a differential (R= dW/dt).
R

D, __

D,Cb
dW
- -

p Req/t D,

(28)
1

or

-~-

D~Cb. Dt

dt

Re7 , D , , +

(29)

Integrating equation 29 gives equation 30 for the total amount of corrosion, IV, as a function of time.

6000

1;

:E

o
n

o R,

8:
o u
u= 3000

o iz -.i o q[

Re

Q) 26210 39320
T= lSoF

95S0 13110

O 0

5OO

IOO0

1500

Do
Fxo. 14.

Correlation between the amount of corrosion and ~ (Re,

D v t / D t 2)

at 150F.

Steel pipe corrosion under flow conditions

189

,,,,: ~ <~o,,,<o-o.,,r,', o, r) - ,-} o~,, o,

(30)

Under isothermal conditions the constancy of a number of the properties in equation 30 leads to

,+._-.,.,<:-.,,re,,>.DI L\

,)o.~ ,o.q"
-

(31)

The values of the constants which pertain for a particular tube diameter and temperature can then be obtained from the smoothed experimental data and substituted. The resultant equation 32 gives corrosion amount as a function of Re number and time. W = 5.21 Re '535 [(0-96t + 0.31)'5-0.56]

(32)

This is plotted as a straight line in Fig. 14 and the actual experimental values for W agree fairly well with this straight line correlation. Similar calculations on recent work by Eliassen 28.~7 at a much lower temperature are presented in Fig. 15. Considerably better agreement is shown apparently because

IS'~

Re

S.O00 ~

6"370 lt.740

! 9"! 00
25'470

T =
E - 4.000 z O (/) O ~. 3000,! O U

68F

Z 0

0 0 I

(b,-~t)

FIG. 15. Correlation between the amount of corrosion and the q)(Re, Dvt/D,') at 150F.

190

B. K. MAHATO, S. K. VOORA and L. W. SHEM1LT


TABLE 1. CORROSION OF F e IN NATURAL WATER

Environment Natural water Natural water (Cambridge, Mass., U.S.A.) Natural water (Cambridge, Mass., U.S.A.) Natural water (Iowa City, U.S.A.) Natural water (Middletown, Ohio, U.S.A.) Distilled water

Suspended specimen apparatus Method of Variables investigated Specimen measurement Temp. F Flow rate Duration Fe foil Coldrolled steel Mild steel coupon Fe coupon Fe rods Coldrolled steel Mild steel Steel Mild steel Black iron Mild steel Cast Fe Pure Fe Wt. loss Wt. loss R.T. 72-104 0"028 ft/s --12 d

Reference 13 32

Wt. loss

70

0.047"05 ft/s -100-500 cm/min --

2-14 d

33

Wt. loss Wt. loss Wt. Joss

R.T. R.T. 95

24 h 1-60 d 24 h

34 35 36

Distilled water Distilled water (CO2-r 02) Natural water (Pittsburgh, P.A., U.S.A.) Colorado River water Natural water (Great Lakes) Natural water (Great Lakes) Distilled water

Wt. loss Wt. loss Wt. loss Wt. loss Wt. loss and potential Wt. loss Wt. loss

77 140, 194 82 51--60 R.T.

--0-240
cm/s

8d 5h 10 d 14 d 2-16 d

19 37 22 25 38

1-15 ft/s 0.0850-14 ft/s 0.2-2 ft/s --

R.T. 122-567

-163 d

39 40

TABLE 2.

CORROSION OF E e IN NATURAL WATER

Environment Distilled water Natural water (Cambridge, Mass.,

Rotating specimen apparatus Method of Variables investigated Specimen measurement Temp. F Flow rate Duration Mild steel coupon Chrome steel Wt. loss Water 70 R.T. 0-7-6 ft/s 230 rpm 2-14 d 40 rain

Reference 33 41

U.S.A.)
Natural water (Cambridge, Mass., U.S.A.) Natural water (Cambridge, Mass., U.S.A.) Distilled water Artificial sea-water Low-carbon annealed steel Mild steel coupon Mild steel Mild steel Water R.T. 0-342 rpm 29 h 18

Wt. loss

73

0-1.2 ft/s

5-7 d

17

Wt. loss Wt. loss and potential

R.T. 77

13-260 rpm 1500 rpm

-100 d

21 42

FIG. 3. Transmission electron micrograph of the thorn-shaped the surface by plastic replica.

deposits stripped from

FIG. 4. Electron diffraction

pattern carresponding to Wile obtained from the thornshaped crystals of Fig. 3

FIG.

I.

Transmission

elcctrnn Cl

micrograph of oxide Tim wt. ;> H,SO, for 24 II.

fOrmed

on Ti

in hoiking

FIG.

2.

Electron

diffraction

patterns film

of rutile and of Fig, I.

anatase

obtained

from

the

oxide

Steel pipe corrosion under flow conditions TABLE3. CORROSION Fe IN NATURALWATER OF

191

Environment Natural water (Pittsburgh, Pa., U.S.A.) Natural water (Washington, D.C., U.S.A.) Natural water (Ottawa, Canada) Synthetic water (Mass., U.S.A.) Synthetic water Natural water (Vancouver, Canada) Natural water (Teddington, England) Distilled water Natural water (Fredericton, N.B. Canada) Natural water (Fredericton, N.B., Canada) High purity water Natural water (Fredericton, N.B., Canada)

Pipe specimen apparatus Method of Variables investigated Specimen measureReference ment Temp. F Flow rate Duration Mild steel (, , ~-dia.) Wrought Fe (2" dia.) Mild steel Mild steel Mild steel Mild steel Water analysis Wt. loss Wt. loss Wt. loss Wt. loss 60-170 R.T. 68-100 68 68 0.1-8 ft/s 30 ft/s 0-12 ft/s
0.125-

25-50 10 y 5d 42 d 42 d 25 d 70 d -25 d 40 d 70 d 210 d

14 43 23 26 27 28 29 30 44 45 31 46

4 ft/s
0,125-

Wt. loss 90-130 and potential Mild steel Wt. loss 72-131 and potential Fe--Cu couple Potential 68 Mild steel Wt. loss 150 and potential Mild steel Mild steel Mild steel Wt. loss 125-170 and potential Wt. loss Wt. loss and potential 72-131 100

4 ft/s 0.754"5 ft/s 5~140 It/ min Re =4050 0-452"7 ft/s 0"452'7 ft/s 2'4400 ft/s 0"45 2'7 ft/s

only the s m o o t h e d d a t a were used, the a c t u a l experimental results n o t being reported. The constants in the c o r r e s p o n d i n g e q u a t i o n for Eliassen's d a t a o f course are considerably different because o f the difference in t e m p e r a t u r e a n d physical p r o p e r t i e s o f the system. O f the experimental w o r k carried out u n d e r h y d r o d y n a m i c a l l y definable c o n d i t i o n s (Table 3), t h a t o f Speller a n d K e n d a l l 14 gave initial c o r r o s i o n rates only, a n d t h a t o f Ellinger a n d W a l d r o n 4s only final c o r r o s i o n a m o u n t s . Similarly the w o r k o f C o h e n 2s a n d o f D e y 28 d i d n o t provide sufficient d a t a for the type o f analysis carried out here. T h e latter w o r k 2s as well as other results f r o m this l a b o r a t o r y 45,46 can be applied, however, if the analysis is b r o a d e n e d to include t e m p e r a t u r e as a variable, a n d this will be d e a l t with in a later paper. T h e w o r k o f Butler a n d I s o n ~9 was based on a w a t e r with a n exceedingly high dissolved solids c o n t e n t which o f course negated the basic a s s u m p t i o n s o f the chemical reactions f o r m i n g the c o r r o s i o n p r o d u c t (equations 4 a n d 5). Nonetheless p r e l i m i n a r y calculations on their d a t a indicate t h a t a similar c o r r e l a t i o n to t h a t r e p o r t e d here will be valid. This type o f c o r r e l a t i o n can therefore be considered as having c o n s i d e r a b l e experimental justification, a n d can be used to predict c o r r o s i o n a m o u n t s o f steel p i p e in water over a considerable range o f flow rates.

192

B . K . MAHATO,S. K. VOORAand L. W. SHEMILT

Acknowledgements--The authors wish to thank Dr. F. R. Steward for most helpful discussions on the correlations presented here, and the Steel Company of Canada who supplied the pipe used for the tests. The financial assistance of the National Research Council of Canada is gratefully acknowledged.

REFERENCES 1. H. H. UHUG, Corrosion and corrosion control. John Wiley, New York (1963). 2. H. H. UHUG, The corrosion handbook. John Wiley, New York (1948). 3. U. R. EVANSand T. P. HOAR, Proc. R. Soc., Lond. (Series A) 137, 343 (1932). 4. W. R. WnrrNEx,, d. Am. chem. Soc. 25, 394 (1903). 5. R. B. MEA~ and R. H. BROWN, Trans. electrochem. Soc. 74, 495 (1938). 6. R. H. BROWN and R. B. MEA~, Trans. electrochem. Soc. 81, 455 (1942). 7. M. A. STREICHER,J. electrochem. Soc. 96, 170 (1949). 8. R. B. MEmaS and R. H. BROWN, J. electrochem. Soc. 97, 75 (1950). 9. T. P. HOAR and J. G. H ~ r s , J. Iron Steel Inst. 182, 124 (1956). 10. U. R. EVANS, The corrosion and oxidation o f metals. Edward Arnold, London (1960). 11. J. N. FmEND, J. chem. Soc. 119, 932 (1921). 12. J. N. FRIEND, Trans. Am. electrochem. Soc. 40, 63 (1921). 13. J. N. FmErCa, J. Iron Steel Inst. 11, 62, 128 (1922). 14. F. N. SPELLERand V. V. Krr~ALL, Ind. Engng Chem. 15, 134 (1923). 15. W. G. WHrrMAN, Chem. Rev. 2, 419 (1925). 16. R. E. Wmsos, Ind. Engng Chem. 15, 127 (1923). , 17. C. L. Cox and B. E. Ro~rHEta, Ind. Engng Chem. 23, 1012 (1931). 18. B. E. RO~rlEU and R. H. BROWN, Ind. Engng Chem. 23, 1010 (1931). 19. F. G. FRESE, Ind. Engng Chem. 30, 83 (1938). 20. F. N. SPELLER,J. New Engl. War. Wks. Ass. 52, 231 (1938). 21. F. J. WOmW~VELL,J. Iron Steel Inst. 154, 219 (1946). 22. G. B. HATCH and O. RICE, Ind. Engng Chem. 37, 752 (1945). 23. M. CoaEN, J. electrochem. Soc. 93, 26 (1948). 24. H. R. CoPsoN, Ind. Engng Chem. 44, 1745 (1952). 25. L. STREICHER,J. Am. War. Wks Ass. 48, 219 (1956). 26. R. ELIASSErq,C. PEREDA,A. J. ROMEOand 1L T. Sr,.~atcoE, J. Am. Wat. 14"ks Ass. 48, 1005 (1956). 27. A. J. ROMEO,R. T. SKmt,a~. and R. EtaASSErq,Proc. Am. Soc. Cir. Engrs Paper 1702, July (1958). 28. W. R. DEY, M.A.Sc. Thesis, University of British Columbia, 1959. 29. G. BtrrLER and H. C. K. ISON,J. appl. Chem. 10, 80 (1960). 30. T. K. Ross and B. P. L. HrrCHEN, Corros. Sci. 1, 65 (1961). 31. G. BtrrLER and E. G. STROUD,J. appl. Chem. 15, 325 (1965). 32. G. E. WmTMAN, R. P. RUSSELand V. J. AL~ERY, Ind. Engng Chem. 16, 665 (1924). 33. R. P. RUSSEL,E. L. CrtAPPEL and A. WroTE, Ind. Engng Chem. 19, 65 (1927). 34. W. L. DENMANand E. BARLOW, Ind. Engng Chem. 22, 36 (1930). 35. R. F. PASSANOand F. R. NAt3LEY, Proc. Am. Soc. Test. Mater. 33, 387 (1933). 36. C. S. BORGMAN,Ind. Engng Chem. 29, 815 (1937). 37. G. T. S~'.APE~AS and H. H. UrILm, Ind. Engng Chem. 24, 748 (1942). 38. R. V. SKOL~ and T. E. LA~ON, Corrosion 13, 139t (1957). 39. E. L. LARSONand R. V. SKOLD, J. Am. War. Wks. Ass. 50, 1429 (1958). 40. W. E. RUTHERand R. K. HART, Corrosion 19, 127t (1963). 41. H. O. FOR~T, B. E. RoF.rasu and R. H. BrtowN, Incl. Engng Chem. 22, 1197 (1930). 42. F. W O ~ W L L , 3". appl. Chem. 3, 164 (1953). 43. G. A. ELUNGER and L. J. WALDRON,Paper Trade J. 127, 27 (1948). 44. S. K. VOORA, M.Sc. Thesis, University of New Brunswick, Fredericton, 1964. 45. B. K. MAHATO, M.Sc. Thesis, University of New Brunswick, Fredericton, 1964. 46. B. K. MArlArO, Ph.D. Thesis, University of New Brunswick, Fredericton, 1967. 47. V. G. LEXqCH,Physicochemical Hydrodynamics. Prentice-Hall, Inc., New York (1962). 48. G. S. GARDNER, Corrosion 19, 81t-90t (1963). NOTATION Concentration of O in the main stream, ppm or g mole/l. Concentration of O at the interface at the solid wall and damped turbulence layer, ppm or g mole/l. Concentration of O at the metal wall surface, ppm or g mole]l. Pipe diameter, era.

C,:
C~"
D~:

Steel pipe corrosion under flow conditions Diffusion coefficient of O in water, cml/s. Functions. As defined in equations 15-19. Resistance coefficient, cm3/g mole. Moles of O transferred unit area, g moles/cm 2. Porosity. Coefficient, equation 27. Exponent, equation 27. Reaction rate, g mole/cm-~/s -1. Re number based on initial pipe diameter. As equation 26. Temperature, F. Time, day. Velocity, cm/s. Amount of corrosion, mg/dm z. Resistance to the transfer of O through the damped turbulent layer, era. Resistance to the transfer of O through the corrosion product layer, cm. As defined in equation 12. As defined in equation 13. Absolute viscosity, g c m -1 s -x. Fluid density, g/cm 3. Eddy diffusion coefficient, cml/s. Functions.

193

K,, K1, K2, K l- :


k: n: P: p: q: R:

Re: r" T:
t:

U: W: Ya:
Ys:

8:
~.: p: p, p':