Experimental pH Potential Diagram of Aluminum for Sea Water*

Ph. G/MENEZ, * J. J. RAMEAU, * and M. C. REBOUL * *

Abstract
The theoretical Pourbaix diagram for the aluminum-water system does not take into account pitting corrosion, the usual form of corrosion for aluminum in chloride containing environments. To obtain a practical representation of aluminum corrosion usable in sea water, pitting potentials, protection potentials, and uniform attack potentials have been measured with 5086 AA specimens in 3% NaCI solutions buffered within the 4 to 9 pH range. These potentials limit passivity, pitting corrosion, and uniform corrosion areas in the potential-pH diagram. The passivity area of 5086 AA in 3% NaCI solution is bordered by pitting areas both in the most noble direction (anodic polarization) where crystallographic pits are formed, and in the most active direction (cathodic polarization) where semi-spherical pits are formed. The results are interpreted on the basis of local pH evolutions during polarization of the specimens. This experimental diagram has been extended both to more acidic and more alkaline environments.

Introduction
Aluminum is an oxidizable metal, the standard potential of the AI 3 +/AI system is 1.66 V/NHE. However, it is very resistant to uniform corrosion. This fact can be explained by the presence of an oxide layer which insulates the metal from its corrosive environment. This resistance is limited, however, to an environment where this oxide is only slightly soluble between pH 4 and 9 (Figure 1). In this pH range, aluminum is passive and like all passive metals, it is prone to pitting corrosion. This is generally explained by the localized acidification of the solution within the pits formed at anodic sites in chloride containing solutions. The corrosion resistance of metals can be anticipated on thermodynamic "potential-pH" diagrams on which the thermodynamic metal-water reactions are represented. This diagram shows: (1) The corrosion areas of the metal by the formation of soluble compounds; (2) the passivity areas by the formation of solid phases; and (3) the immunity areas where the metal is thermodynamically stable. The cathodic protection of metals is a remarkable practical application of the E-pH diagrams: these indicate the potential limit that must be reached to prevent corrosion. As far as aluminum is concerned, there exists a theoretical E-pH diagram' (Figure 2) which unfortunately does not give any useful information on pitting corrosion, the most common form of corrosion for aluminum in chloride containing environments. Pitting corrosion occurs within the theoretical passivity area. It is also well known that aluminum corrodes in its theoretical immunity area. Therefore, this theoretical diagram is practically useless. *Submitted for publication September, 1980; revised June, 1981. *Laboratoire d'Energkique Electrochimique, L.A. au C. N. R. S. 265, E. N. S. d'Electrochimie et d'Electrometallurgie de Grenoble, Domaine Universitaire, 38401 Saint-MartinD'Heres, France. * *Aluminum Pechiney, Centre de Recherches et de Developpement, B.P. 24 38340 Voreppe, France.

As M. Pourbaix did for iron ,2 it is necessary to complete this theoretical diagram with an experimental E-pH diagram relying on kinetic data. The aim of this study is to draw that of aluminum, applicable in sea water. For these tests, the 5086 aluminum alloy is used because this alloy is usually recommended for marine applications. The tests were carried out in a 3% NaCI solution between pH 7 and 9, which is the simplest electrolyte for stimulating sea water.

Methods and Experimental Devices

Measuring Methods
The areas of passivity, pitting corrosion, and uniform corrosion are limited by the characteristic potentials of the metal, and by the particular type of environment and, for certain metals, by the experimental conditions. We determine: The Corrosion Potential Eo. This is a mixed metal-water potential measure in both aerated and deaerated NaCI solutions: Firstly in an aerated solution: according to a standard ASTM project (third draft September 27, 1971). The NaCI 1M electrolyte also contains hydrogen peroxide. This allows us to obtain stable and reproducible potentials. The potential is noted as soon as the sample is immersed and every five minutes after that for one hour. The corrosion potential is the average of the values noted during the last 30 minutes. Secondly in a deaerated solution: the sample is placed in contact with the deaerated solution. The potential is registered until it reaches a steady value. This condition usually occurs after four days. 3 The Pitting Potential Ec (or critical pitting potential). Potential above which corrosion pits will initiate and propagate. Two different testing methods are used. The samples used to measure the corrosion potential in the deaerated solution are then polarized anodically by the quasistationary galvanokinetic method. For each value of impressed current, the corresponding potential is recorded two minutes after each step.

Vol. 37, No. 12, December, 1981 1981, National Association of Corrosion Engineers

0010-9312/81 /000207/$3.00/0

673

19

11

12

14 IS

_1
_2 -
-4

-1
A"DH)3
AI203O

-2 3
-4

0 O

Q rn 0 c

HMITE Al 2 03 ,H 20 _ 5

BAYERITE Al 203,3H20 -6
i-I YDRARGIWTE

-7

Aj3+
AIOz

-9
1 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16
- 10

pH

FIGURE 1 pH influence on the solubility of Al 2 0 3 and its hydrates at 25 C (according to Pourbaixt).

14

-2 -1 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16

1A
4- i -6 4 -2 0 1.2

=12

W 1 1
0,8 ;

Al
0,6 0,4

^^--

0,8

From these curves, Ec and Eo and possibly the io corrosion current are determined. The pitting potential is determined on the same sample by the scraping method proposed by Pessal and Liu . 4 The potential of the sample is imposed in steps of 10 mV then of 5 mV beginning at 70 mV below the pitting potential determined by

' ,
AI:01.3H:0

0,6 0.4
0. 2

the galvanokinetic method. At each potential value, the sample is scraped with the Pyrex Luggin Haber capillary probe.
This provokes a violent increase in the current. If the current

02

;hydrargillite

0
-0,2 -0,4 --

Jo; 0
-0.2 -0,4

goes back to a very low value, then the metal is once again passive and the imposed potential is more negative than the
Ec. If it remains at a high value, then the metal corrodes by pitting and so the potential is therefore higher than the Ec. In this

way, a framework can be obtained for the pitting potential.

The Protection Potential Ep. This is the potential below which corrosion pits do not propagate. Although studies carried out over the last 10 years have shown that there is no difference between the Ep and the Ec if the induction time of pitting^t is taken into account, more recent studies have

-0,6 -0,8
1 t.2 -1.4 is -1,8 0 _s _a -s I

;
I

-0,8
-1 -1,2 -14 -t,6

shown that an aluminum chloride saturated solution is formed

within the pits, 11 and the Ep is the pitting potential in this solution. In this paper, Ep is determined by the scraping method in aluminum chloride saturated solution. The Anodic Uniform Attack Potential Eg. This is the potential from which anodic pitting corrosion can become so exten-

- 2

-2
-2,2

2,2 AI
I

sive that it invades the whole surface and in this way creates a more or less uniform attack. Because it is impossible to use a potentiostatic method (metals are impolarizable above the pitting potential), tests are carried out by an intentiostatic

2'62 -1 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 2,6

pH

FIGURE 2 Diagram of the voltage-pH balance of aluminum-water system at 25 C (according to Pourbaixl).

method which gives fairly steady potentials. Polarization time is one hour. Increasing anodic currents are impressed until a uniform attack of the surface is obtained. Different samples
are used for each polarization step. Ecc Cathodic Corrosion Potential. With cathodic polarization, there is no reduction of the AI 3 + (or AIO 2- or AI(OH) 3 ) but rather a reduction of water with hydrogen evolved. The following reactions are involved:

Current increments used for the anodic curves E = f(log

1
0.01 <i< 0.1AAcm -2 Ai =0.01AAcm -2 0.1 <i< 1Acm -2 Di=0.1AA cm -2 1 <i<10Acm -2 Ai=1AAcm-2 in an acidic environment: H+ + e - H 2 2

1
in a basic environment: H 2 O + e H 2 + OH 2

674

CORROSION-NACE

TABLE 1 - Composition of the Solutions Used

pH 4 Composition for 1 Liter of Solution NaOH 0.1 M 85 ml KH Phtalate 0.1M 500 ml NaCI 30 g Citric acid 0.1 N 493 ml NaOH N/3 409 ml NaCI 30 g tris 0.1 M 500 ml HCI 0.1M 440 ml NaCI 27.43 g tris 0.1M 513 ml HCI 0.1 M 307 ml NaCI 28.20 g NaOH 0.1M 275 ml Boric acid 0.1M 500 ml NaCI 30 g ion citrate C6 H5 O7 Comments

5.5

7.5

8.2

This is madeup to 1000 ml by adding distilled water

molecule tris (CH2OH)3C(NH2)

TABLE 2 - Composition of the 5086 Samples Used

Element Plate No. 1 Plate No. 2 Si <0.15 0.18 Fe <0.30 0.32 Cu <0.02 0.08 Mn 0.40 0.42 Mg 4.30 4.26 Cr 0.15 0.15 Zn 0.10 0.04 Ti 0.05 0.02

Therefore, as well as hydrogen being released, the solution also becomes alkaline in the vicinity of the cathode. The layer of oxide is brought into a pH range where it is more soluble (Figure 1). The metal, being no longer protected, then oxidizes in order to form another oxide film. The Ecc corresponds to the potential value from which this corrosion occurs. As for the anodic polarization, there is also a potential from which the corrosion, which is at first localized in the form of pits, covers the whole surface. It is called the Egc cathodic uniform attack potential. The Holtan and Nisancioglu methods 12 ' 13 are used; that is to say, a potentiostatic study method. Polarization time is 1000 minutes for each test (a comparison is made at pH = 8.2 with the potentiodynamic method 100 mV/mn).

the potentials of the diagram at different pH's, it is necessary to buffer the solutions, so that variations in the pH can be avoided in the bulk solution during the course of each test. By proceeding in this manner, we are afraid of inhibiting corrosion at least partially. Electrochemical tests are used to check that the buffers have no noticeable inhibiting effect on the corrosion. The composition of the solutions used in these tests is given in Table 1 after Bates. 15 The molar concentration of the buffer is about one tenth of the concentration of chlorides. The power of the buffer of different solutions is of the same order. In these conditions, the pH variations between the beginning and the end of a test does not exceed 0.1 unit. Except for corrosion potential measurements, the solutions are deaerated prior to introduction into the cell.

Apparatus
The apparatus used for the electrochemical readings are made by Taccussel (France): Potentiostats PRT 20-2 and PRT 10-05 L, recorder apparatus TU 116 and TI 206, millivoltmeter Aries 10,000, Servovit pilot and pH meter TS 60 N. The polarization cell is of type CRV, 3 constructed by following Greene's advicet 4 for flat samples. Its originality lies in the conical Teflon gasket which accurately defines the active surface (5 cm 2 ), a limited sealed area on a very small surface thus avoiding crevice corrosion under the gasket. The reference electrode is the saturated calomel in a saturated KCI solution (SCE) (all the potentials quoted are versus the SCE unless otherwise stated). The auxiliary electrodes are in platinum. The working electrode is a 60 x 40 x 1 mm sheet specimen. The solutions are not thermostated but the laboratory is airconditioned at 20 C.

Preparation of Samples
The composition of the two 5086 aluminum sheets used for the tests is given in Table 2. Samples were cut from laminated sheet thick. The specimens are cleaned by soaking them in alcohol for several hours and then for a few minutes in acetone; then they are rinsed in distilled water and dried.

Micrographic Tests
After each test, the samples are examined with an optical microscope, then with a scanning microscope, and finally in micrographic cross section.

Results
Corrosion Potential
The corrosion potentials are given at each pH value in Table 3 for aerated solutions, and in Table 4 for dearated solu-

Preparation of Solutions
The solutions are chosen in order to simulate sea water with an average NaCI content of 30 g/l. In order to determine

Vol. 37, No. 12, December, 1981

675

tions. Also indicated are standard duration potentials, number

of tests carried out in the 5.5 to 8.2 pH range and the i o corrosion current.

Test 1the aluminum sheet is soaked for two days (pH = 0.5); Test 2idem; and Test 3the aluminum sheet is soaked for 5 days (pH = 1).

Anodic Corrosion
Figure 3 shows the curve E = f (log i) obtained by the

The 5086 alloy has no passivity range in an aluminum

chloride saturated solution. This is why the pitting potential is at the same level as the corrosion potential.

quasistationary galvanokinetic method at pH = 8.2. Table 5

recapitulates the pitting potentials obtained. The protection potential is the critical pitting potential

Table 6 shows that there is no significant differences

between the two solutions prepared for these tests. The pro-

measured in a saturated AICI 3 solution. Commercial aluminum

chloride contains an excess of acid. In order to eliminate this

tection potential can be taken at: Ep = 863 mV; Standard

deviation = 9 mV.

acid, a high purity aluminum sheet is soaked at 20 C in the

solution. So two types of solution are prepared and three tests are carried out:

The anodic uniform attack potential Ega is given in Table 7 at different pH's as well as the corresponding anodic current. These pits are of the crystallographic type (Figures 4 and

TABLE 3 Corrosion Potentials in an Aerated Solution

pH Eo (mV) 4 -743 5.5 -741 7.5 -749 8.2 -751 9 -754

Standard
deviation (mV) Number of tests 6 4 3 3 6 3 4 4 7 4

TABLE 4 Corrosion Potentials in a Deaerated Solution

pH
Eo (mV) Number of tests

4
irreproducible 2

5.5
-890 4

7.5

8.2

9
-1120 2

irreproducible 4 2

Standard
deviation (mV) iO (AA/cm z)
-

10 0.25

0.07

0.16

23

E V ,v 3 ,

sce

,o'

^,

p
0.7

0.7

-^$

7S^l.FU-1

oe

os

PH: BR

^n oQ

test, os n test 2

't

,o

1.

TR

FIGURE 3 Curve E = f (log I) obtained by the quasistationary galvanokinetic at pH = 8.2 (NaCI 30 gll).

676

CORROSION-NACE

TABLE 5 Pitting Potentials

Number of Tests Carried Out 2 5 4 5 4 7 2 5 2 3

Method Used Galvanokinetic Scraping potential Galvanokinetic Scraping potential Galvanokinetic Scraping potential Galvanokinetic Scraping potential Galvanokinetic Scraping potential

pH 4 4 5.5 5.5 7.5 7.5 8.2 8.2 9 9

Ec (mV) 714 724 727 745 762 768 704 764 707 718

Standard Deviation 27 3 15 8 11 5 2 8 50 6

TABLE 6 Corrosion Potentials and Scraping Potentials in an Environment of Saturated AIC1 3

Test Eo (mV) E scraping (mV) 1 868 868 2 847 853 3 868 868

TABLE 7 Anodic Uniform Attack Potential

pH Ega (mV) i mA/cm 2 4 707 30 5.5 693 30 7.6 715 28 8.2 720 40 9 718 28

5). The depths of the pits are measured with the micrometric screw of an optical microscope. They are between 20 and 30 m inclusive. They are spread in a uniform manner over the whole surface of the sample. However, when the specimen is scratched, the scratch becomes a favorite point of attack. We have not noticed any pH influence. The pits density increases with the current density. There is no obvious morphological difference between the pits obtained in a 30 g/I NaCI solution and those obtained in an AICI 3 saturated environment. By using the scanning microscope, we observe some very geometric facets (Figures 4 and 5). This can be explained by the fact that the attack occurs according to well defined crystallographic directions. Previous studies have shown that it is the <100> direction.

Cathodic Corrosion
For each pH, the network of potentiostatic curves is traced, an example of which is given at pH 8.2 (Figures 6 and 7). The log i in function with log t curves shows that a return to passivity takes place "in a short time" (Figure 6). The log i in function with t (Figure 7) shows that a stationary current is usually reached within 1000 minutes. On each curve, two particular currents are tabulated: (1) The density of the current at 1000 minutes (i at 1000 mn), and (2) the density of the maximum current during the course of the 1000 mn of polarization (i max).

FIGURE 4 Photograph with scanning electron microscope. Anodic pitting obtained by a potentiodynamic test NaCI 30 g /l, pH = 7.5, 224X. FIGURE 5 Same specimen as in Figure 4 but at 2240X.

Vol. 37, No. 12, December, 1981

677

I5

'

1E

^ ^ l\
S

.-ate

n`y- n ^ n ^ n ^

r `rte /

10

*-*

i K fj-:

pH: e,2

E:

-1,1

o-

E:-115

SCE

102

XE42
V E:43

E; -1,45 ^^^ \^ / / K E:o E: -1,35 103

,o

,o

FIGURE 6 Cathodic potentiostatic curves log i = f (log t) - NaCI 30 gll pH = 8.2.

qw

^ uu

70
V

N ^--^ ^

E..1,1 VSC n E:.11S *; ,4

jE
O

-- O
QOO

^^^
mo

^^-

pHQ E:.145 .. 011,55 E1,6 (:1 , 65 . Innn

K R:1,5

Ann

enn

FIGURE 7 Cathodic potentiostatic curves log I = f (t) - NaCI 30 g/l pH = 8.2.

On each pH, two polarization curves are drawn. Figure 8 is an example for pH 8.2: (1) E as a function of log (i max), and (2) E as a function of log (i to 1000 mn). A comparison has been done between this method and the potentiodynamic method 100 mV/mn. Microscopic observation of the samples enables to distinguish the two potentials Ecc and Egc. Table 8 gives the

from localized corrosion to uniform attack is quite sudden. An examination through the scanning microscope shows (Figure

9) that each pit is a crater, the bottom of which is carpeted

cavities. Examinations in micrographic cross section show the existence of small deep holes of 3 to 4m in width opening up

into the main crater of a pit. On the other hand, the presence of
intermetallic compounds containing the elements Fe, Si, Mn, and Mg were observed inside the anodic pits. The matrix is

Ecc and the Egc for each pH as well as the corresponding currents icc max and icc at 1000 mn, igc max and igc at 1000 mn.
The cathodic pits are of the hemispherical type. From a macroscopic point of view, they follow the milling lines. For a given potential, their size grows when the pH increases. In order to make this point clearer, if we consider a pH of 7.5, the

worn away by corrosion and not the emerged precipitates.

However, there are quite a large number of empty pits.

Extending the Graph

Two series of tests were carried out to obtain information on the development of the graph for pH's of less than 4 and more than 9. Acidic solution (250 ml KCI, 0.2M; 670 ml HCI, 0.2M; and 19.23 g NaCI) diluted to 1000 ml with distilled water,

depth and diameters of the pits vary between 20 and 30 m.

For a given pH, the density of pitting increases when the potential becomes more negative. Moreover, the transition

678

CORROSION-NACE

1 11 , n

10

10'

10'

10'

E`
SCE 11

n
'12

pIt 8,2
12
,I max n i at 1000 min

*potentiokinetic0 V mm a

1,a

*\
# n

*^

le

10

10

10'

10

i uAcm - '

FIGURE 8 Drawing of cathodic potentlostatic tests E = f (log 1)1 indicates: either i after 1000 mn of polarization (i to 1000 mn) or i maximum during these 1000 mn of polarization, pH = 8.2 - NaCI 30 g/l.

TABLE 8 Ecc Cathodic Corrosion Potentials (Appearance of Pitting) and Egc Uniform Cathodic Attack Potential
icc pH 4 5.5 7.5 8.2 9 at Ecc Egc 1000 mn icc max mV A cm -2 A cm -2 mV -1375 -1325 -1300 -1175 -1075 4 30 2 1.3 0.5 7 30 4 16 0.7 -1475 -1450 -1600 -1650 -1625 igc at 1000 mn igc max A cm -2 A cm -2 9000 1200 1100 1500 1500 12000 1200 3600 5500 6000

It is possible to limit the Ecc of this pH at: -1065 mV < Ecc < -945 mV Alkaline solution (3 g Ca(OH) 2 , 30 g NaCI) diluted to 1000 ml with distilled water. A lime saturated solution pH = 11.6 is obtained; therefore, a good buffer. A 5086 aluminum alloy sample is immersed in this solution exposed to the air for one week. Its corrosion potential fluctuates from between -1200 to -1400 mV. The corrosion observed is identical to the type of uniform cathodic attack (Figure 10). We also observe that this type of corrosion increases in the form of hemispherical shaped pits.

In the deaerated solution, a sample is cathodically

polarized for 100 mn under a current of 1A cm -2 . The potential increases from -1365 to -1250 mV. At the end of the test, a large number of localized pits appears. From these two tests, one can limit Ecc and Egc: Ecc > -1250 my and Egc > -1400 mV. To take into account the length of time for each test, it must be noted that these values

FIGURE 9 Cathodic pitting which took place at E _ -1550 mVISCE NaCI 30 gll pH = 7.5.

are, without a doubt, much more negative than the real values. a pH of 0.9 is obtained. The solution is deaerated, two intentiostatic tests which last one and a half hours each in cathodic
polarization: (1) i impressed = -1 mA cm -2 . The potential increases from -945 to -900 mV. There is no pitting corrosion discernable. (2) i impressed = - 10 mA cm -2 . The potential increases from - 1065 to -965 mV, cathodic pits appears.

Discussion of the Results

In this section, the validity and the choice of the poten-

tials measured to draw an experimental pH-potential diagram of the 5086 aluminum alloy usable in sea water (Figure 11)
are discussed.

Vol. 37, No. 12, December, 1981

679

FIGURE 10 Scanning electron microscope: cathodic pitting obtained by immersion in a lime saturated solution. NaCl 30 gll - pH = 11.6.

Corrosion Potential in Aerated Solution (Figure 11)

The values obtained are reproducible. They show a very slight decrease in the corrosion potential when the pH increases. It is important to notice that the corrosion potential is within the pitting area of the diagram. This is an agreement with practical observations: aluminum alloy is liable to pitting corrosion in sea water. Groover, Lennox, and Peterson 16 found a more negative corrosion potential with different experimental conditions.

FIGURE 11 Experimental E-pH diagram of the 5086 aluminum alloy in a chloride environment (Thermodynamic E-pH graph in mixed lines).

Anodic Corrosion (Figure 11)

Concerning the Ec pitting potential, the scraping method gives the most negative results which are characteristic of the metal and not of the oxide layer. As far as the pH influence is concerned, it is very weak, and varies from between - 720 to - 750 mV/SCE and is minimum in the 7 to 8 pH range. Turcotte and Heidersbach 17 observed similar results after tests on the 6351 aluminum alloy. Hung N'Guyen and Foley 18 explain the influence of the pH by the stoichiometry of the soluble compound formed (AICI 4 - in an acidic environment; Al (OH) 2 Cl 4 in a neutral environment). In any case, all the authors are in agreement over the fact that the pH does not determine the pitting potential and this point of view also matches the present observations. Concerning the Ep protection potential (Figure 11), the hypothesis that Ep is the pitting potential in an AICI 3 saturated solution is made and so Ep is independent of the pH. In this hypothesis, Ep = -863 mV/SCE. This value is exactly the same as observed by de Michell'' when working in the same electrolyte conditions but with pure aluminum. Holtan and Nisancioglu 9 summarized the bibliography on this topic. This information meets the values obtained here. The Ep position creates an imperfect passivity area which reduces the passivity one. Results concerning the Ega uniform anodic attack potential are given in Figure 11. When anodic currents of increasing intensity are applied, localized corrosion is observed which becomes worse and worse; then etching takes place and finally above a density of about 30 mA/cm 2 , a general attack occurs in the form of uniform corrosion and thus the sample appears to be covered with fine granules. Ega is only different from Ec in the pH range where the oxide is highly insoluble. Three areas are defined on the graph: (1) Above Ega, range general anodic attack; (2) between Ega and Ec, anodic pitting corrosion ranges which only exist for the pH's where the oxide is insoluble; and (3) between Ep and Ec, the imperfect passivity

range in Pourbaix's terminology. 2 In this range, the pitting which has already begun is able to increase. It can be estimated that -863 mV/SCE is the maximum potential that can be reached for protecting the 5086 aluminum alloy. The position of the Ega potential varies according to the polarization time for the intentiostatic tests (one hour). Consequently, we can presume that the range of localized corrosion would doubtless be smaller, had the polarization time been longer.

Cathodic Corrosion (Figure 11)

Ecc increases with the pH, especially from pH 7.5. The development of the Egc is more difficult to understand. The general attack is expected to appear much more quickly with very high pH's. This is also suggested by the rise of the curve above pH 9 and by the tests carried out in lime (Figure 10). General cathodic attack is a disastrous form of corrosion because it consumes 1/10 mm of the sample within 1000 minutes of polarization. Moreover, the transition from general attack to localized corrosion is very sudden (about 50 mV). The theory of local alkalinization seems to have been universally accepted. This can be confirmed by studying the tests carried out in an environment with a lime buffer. These tests seem to show that uniform corrosion at a high pH increases in the form of hemispherical pits. The works of Holtan and Nisancioglu 13 defined two types of patterns: (1) Localized corrosion in an environment with no buffer, and (2) no pitting in an environment with an acetate buffer (pH 4.8). According to these results, there should exist a range of pitting corrosion at pH = 4.8. This difference can perhaps be explained quite simply by the different patterns of the 5086 and pure aluminum. Moreover, the range is smaller, relatively speaking, at pH = 4.8 (100 mV). Cerny 19 carried out tests over a period of several weeks, during his research on cathodic protection. He found a connection of the Am = Aiatb type. Where Om is the weight loss, A = a constant of proportionality, i = the density

680

CORROSION-NACE

ErvS ^Q6 _-_ -_-_-_ general

- - - -
B

attack I-_ - * 't - --.

and (2) a range of uniform attack. The Ecc and Egc positions also vary according to the polarization time (1000 mn) and
probably according to whether or not the solution is renewed.

-_-^!s situp felt ^siri j s * ^A;^-_- -

Extending the Graph (Figure 12)

Hypothesis can be made on the acidic and alkaline ph's
on the extension of the graph by using the results obtained at

ssivity AEga - __ :: ----_ + Ec Ep ttio9'--_ *E gc ----_-_- - -general -- -- -_-_- - - - - _attack -- - - _

pH = 0.9 and 11.6, and taking the following considerations into account: 1. Aluminum is only passive in a neutral environment where it is coated with a layer of protective oxide. 2. Pitting corrosion is connected with the solubility of this oxide and therefore with the passivity of the metal. So, it

disappears in very acidic and very alkaline environments but

the uniform attack which takes over, increases in the pits which rapidly extend over the whole surface. 3. The hypothesis concerning the formation of aluminum

,6 ------------------- ------- -_ zO - - ----- ----------^_-_-_-_-_

-

chloride, with acidification taking place at the bottom of the

pit, becomes more difficult to reach in a very alkaline environment: the Ec potential is very positive and it is probable that between -860 mV and the Ec, there exists a general hemi-

spherical attack connected to the alkaline content of the enQ4----------------------------

1 O 1 2 3 4 5 6 7 9

10 'N 12 1:

pH

vironment. 4. Theoretical immunity (graph with mixed lines) cannot be reached because with these very negative potentials, the destruction of the water is such that it is impossible to talk of neutral solutions. Therefore, if the graph is extended in this way, it shows the importance of the solubility of the oxide layer on the corro-

FIGURE 12 Experimental EpH diagram of the 5086 aluminum alloy in chloride environment with extrapolation of pH less than 4 and more than 9. Thermodynamic graph In dotted lines.

sion of the 5086 aluminum alloy. In particular, it proves the importance of the acidification and alkalinization reactions at
the time of anodic and cathodic pitting.

Conclusions
An experimental E-pH diagram has been drawn for the

of cathodic current, t = the polarization time, and a and b are constants around one. The weight loss would be approximately proportional to the polarization time and to the current density. Moreover, the density would be a more significant factor than the potential for expressing the cathodic corrosion. The works of Lennox and Peterson, 20 carried out over a period of 50 days, show that current densities of 100 to 1000 14A/cm 2 cause disastrous corrosion. Likewise, the present

5086 aluminum alloy in 30 g/I NaCI solutions. This diagram shows different corrosion areas, at the sea water pH (8.2); they are:
1. A passivity area lies between -863 and -1175 mV

SCE. It is limited by anodic and cathodic corrosion areas. The

passivity area only exists within the pH zone where the oxide is slightly soluble. With the experimental conditions used in

this paper, the passivity takes place in the 1 to 9 pH range.

2. An imperfect passivity area lies between -863 and -764 mV SCE. The pits which already existed continue to grow but, on the other hand, new ones do not form. 3. An anodic pitting corrosion area lies between -764

paper also shows that uniform attack begins to appear with

densities of around 1000,uAlcm 2 . In order to interpret the information from the Ecc and the Egc curves, two criteria must be taken into account: (1) The tendency of the environment to become alkalinethis is as high as the pH in the bulk solution is strong; and (2) the release of hydrogen which occurs at potentials which are as high as the pH is low. These two criteria vary and in so doing contradict one another. It would seem that the first criteria is connected with the appearance of pitting and so with the Ecc position. Therefore, the second criteria would be the determining factor for the Egc uniform attack. The power and concentration of the electrolyte's buffer also influence these potentials: the electrochemical reaction

and - 720 mV SCE, and crystallographic pits are formed. 4. A uniform anodic attack range above -720 mV SCE. 5. A cathodic corrosion area range below -1175 mV SCE. First semi-spherical pits are formed, then a uniform attack is
produced with higher cathodic polarization. These corrosion areas may be understood by pH evolutions produced by polarization near the specimens: (1)

acidification generated by anodic polarization, and (2) alkalinization produced by cathodic polarization.

References
1. M. Pourbaix. Atlas d'equilibres electrochimiques a 25 C. Ed. Gauthier Villars, p. 171 (1963). 2. M. Pourbaix. Rapports techniques du Cebelcor RT 179, July, 1970. 3. M. Reboul. Methodes de mesure de la corrosion general-

of the release of hydrogen is affected by the chemical reactions of the proton. 21 Finally, the different behavior patterns of the precipitates of intermetallic phases contained in the matrix were observed. This dissolves under the effect of

cathodic polarization whereas the intermediate compounds are not affected. As far as localizing the spot where pitting
begins is concerned, a great number of these holes are "lived in" by these precipitates. This, however, does not definitively establish a connection between the two. The matter could be solved by carrying out tests of the same kind, but for a previous surface treatment. It is possible to define two fields of cathodic corrosion: (1) A pitting corrosion range which extends towards high pH's,

isee de ('aluminum et de ses alliages. Revue de I'aluminium, p. 339 (1973) June.

4. N. Pessal and C. Liu. Electrochimica Acta, Vol. 16, p. 1987

(1971). 5. A. Broli and H. Holtan. Corrosion Science, Vol. 13, p. 237 (1973). 6. A. Broli and H. Holtan. Corrosion Science, Vol. 17, p. 59 (1977).

Vol. 37, No.12, December, 1981

681

7. H. Holtan and Nisancioglu. Corrosion Science, Vol. 18, p. 235 (1978). 8. A. Broli, H. Holtan, and H. Sigurdson. Werkstoffe and Korrosion, Vol. 26, p. 629 (1975). 9. H. Holtan and K. Nisancioglu. Werkstoffe and Korrosion, Vol. 30, p. 105 (1979). 10. A. Broli, H. Holtan, and K. L. Prestrud. Corrosion, Vol. 30, No. 12, p. 427 (1974). 11. S. De Micheli. Corrosion Science, Vol. 18, p. 605 (1978). 12. H. Holtan and K. Nisancioglu. Electrochimica Acta, Vol. 24, p. 1229 (1979) December. 13. H. Holtan and K. Nisancioglu. Proceedings of the 8th Scandinavian Congress. Theory and Praxis of Corrosion Prevention, Helsinki, Vol. 1, p. 90 (1978). 14. N. D. Greene. Experimental Electrode Kinetics. Rensselaer Polytechnique Institute, Troy, New York 12181 (1965).

15. R. G. Bates. Determination of pH Theory and Practice. J. Wiley and Sons, Inc., N.Y., p. 156-162 (1964). 16. R. E. Groover, T. J. Lennox, and M. H. Peterson. Materials Protection, Vol. 8, No. 11, p. 25 (1969). 17. R. Turcotte and R. Heidersbach. Corrosion/78, Paper No. 165, Houston, March 6-10, 1978. 18. T. H. Nguyen and R. T. Foley. Technical Report No. 9, January, 1979. 19. M. Cerny. Zaschita Metallov., Vol. 11, No. 6, p. 687 (1975), Nov. Dec. 20. T. J. Lennox and M. H. Peterson. Naval Engineers Journal, p. 73 (1977) August. 21. K. J. Vetter. Electrochemical kinetics. Theoretical Aspects. Academic Press, New YorkLondon, p. 433 (1967).

Effect of Steam Impurities on Corrosion Fatigue Crack Growth Rates of a Turbine Disc Steel*
R. RUNGTA, * J. A. BEGLEY, * * and R. W. STAEHLE* * * Abstract
Corrosion fatigue crack growth studies have been conducted on a Ni-Cr-Mo-V turbine disc steel in saturated sodium chloride and sodium sulfate environments at 100C.Theresults show that crack growth rate is accelerated in both the environments at open circuit potential, compared to the rate in air environment. Crack growth rate is further accelerated in both environments with the application of a large cathodic potential. Anodic potential has no effect on crack growth rate relative to that at open circiut potential. Cracking occurred transgranularly around the open circuit potential and intergranularly under severe cathodic charging conditions. The amount of intergranular cracking increased with decreasing frequency in the CI environment and occurred predominantly at lowAK levels. It is suggested thatthematerial cracks by two mechanisms: hydrogen embrittlement at very cathodic potentials, and film rupture and anodic dissolution at relatively noble potentials around the open circuit potential. Finally, comparison of the results with those for concentrated sodium hydroxide (100 C) and double distilled water (97 C) shows that although sodium hydroxide (which is another impurity present in the steam) is the most aggressive specie, distilled water inhances cracking as well. It is recommended that further work be done in high purity water.
-

Introduction
An investigation has been conducted on the effect of steam impurities Cl - and SO 4 = on the fatigue crack growth rate properties of an ASTM A-471 trubine disc steel. These impurities have been found in the deposits on the turbines and occur in very large concentrations. 1 2 The steam picks up impurities from a variety of sources, such as demineralizer breakdown, condenser leaks, and boiler water treatment chemicals. Dry steam carries these impurities to the turbines and deposition occurs whenever the solubility of the impurity in the steam is exceeded. This c ondensation occurs anywhere on the low
'

*Presented during Corrosion/81 (Paper 8), April 1981, Toronto, Ontario, revised June, 1981. *Structural Materials and Tribology, Battelle's Columbus Laboratories, 505 King Ave, Columbus, Ohio. **Westinghouse Electric Corporation, R&D Center, Pittsburgh, Pennsylvania. ***Institute of Technology, University of Minnesota, Minneapolis, Minnesota.

pressure (LP) turbines depending on whether the turbine is running at full load or part load. According to Jonas, 3 the most critical region in a turbine set is in the LP turbine just before the moisture region. Concentrated solutions form ahead of the Wilson line because of their thermodynamic stability in this region. Beyond the Wilson line, the droplets are diluted and the deposits are washed away. Chloride and sulfate are both strong pitting agents. Not only do these pits act as stress raisers (and possibly as crack initiation sites), but the aggressive environment further contributes to increasing the crack growth rates under appropriate conditions of static as well as cyclic loading. Although pitting was found to be of no consequence in this test program, it can exert influence on crack initiation life in service. Since cyclic stresses may, in general, produce much faster crack growth rates compared to static loads, it is important that cyclic stresses be given closer attention in estimating design life or inspection intervals for a turbine.

682

0010-9312/81/000209/$3.00/0 1981, National Association of Corrosion Engineers

CORROSION-NACE