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Abstract
In hot strong nitric acid solutions, stainless steels exhibit intergranular corrosion. Corrosion rates
are often measured from immersion testing of specimens manufactured from the relevant material
(e.g. plate or pipe). The corrosion rates, measured from weight loss, are found to increase with
time prior to reaching steady state, which can take thousands of hours to achieve. The apparent
increase in corrosion rate as a function of time was found to be an artefact due to the surface area
of the specimen’s being used in the corrosion rate calculations, rather than that of the true area
undergoing active corrosion i.e. the grain boundaries. The steady state corrosion rate coincided
with the onset of stable grain dropping, where the use of the surface area of the specimen to
convert the weight loss measurements to corrosion rates was found to be appropriate. This was
confirmed by sectioning of the specimens and measuring the penetration depths. The rate of
penetration was found to be independent of time and no induction period was observed. A method
was developed to shorten considerably the testing time to reach the steady state corrosion rate by
use of a pre-treatment that induces grain dropping. The long-term corrosion rates from specimens
which were pre-treated was similar to that achieved after prolonged testing of untreated (i.e.
initially ground) specimens.
The presence of cut surfaces is generally unavoidable in the simple immersion testing of
specimens in test solutions. However, inaccuracy in the results may occur as the measured
corrosion rate is often influenced by the orientation of the microstructure, the highest rates
typically being observed on the cut surfaces. Two methods are presented which allow
deconvolution of the corrosion rates from immersion testing of specimens containing cut surfaces,
thus allowing reliable prediction of the long-term corrosion rate of plate surfaces.
Introduction
Stainless steels generally exhibit good passivity in many nitric acid (HNO3) solutions and are
accordingly routinely specified for this duty. In sufficiently oxidising conditions, however,
generated either in strong aqueous solutions of nitric acid at or close to boiling or in weaker
solutions incorporating powerful oxidants such as Ce4+ or chromates (CrO42- or Cr2O72-), stainless
steels suffer intergranular attack and the corrosion rate can become appreciable. Intergranular
attack occurs owing to the fact that grain boundaries dissolve much faster than the metal matrix
due to metallurgical effects associated with impurities present in the steel [1-16]. The intensity of
intergranular attack depends on the oxidising power of the solution and the exposure time; it may
range from light etching of grain boundaries to intense penetration accompanied by grain
dropping. In the latter case, the result is uniform metal loss even though the underlying
mechanism is highly localised.
There are a number of difficulties
Side
which can seriously affect the
measured corrosion rates [24].
Immersion testing of coupons HQG
containing cut surfaces and hence 50 µm
18/13/Nb, NAG 18/10L and Uranus 65. The composition of these is given in Table 1. All were
used in the solution annealed condition. The test solutions used were made from Analar grade
reagents and deionized water and were selected to be representative (in terms of corrosivity) of
various process streams encountered in nuclear reprocessing. As described later, test coupons
were prepared either by wet grinding with successively finer SiC paper to 800 grit finish, or were
pre-corroded in boiling 8M nitric acid containing 1 g/L Cr added as CrO3. Full experimental
details are given elsewhere [30,31].
Penetration measurements
A number of 18/13/Nb stainless steel
coupons (initially ground to 800 grit on all SODWH
VLGH
faces) were tested in 8M HNO3 containing
25 g/L Fe at 100 °C. At various intervals, P
coupons were removed and measured to K
W
S
H
determine any thickness loss; macroscopic G
[
Figure 1).
Figures 4 and 5 shows the progression of
intergranular corrosion revealed by the
above measurements. For penetration into
the plate and side faces, the data can be
fitted reasonably well to linear
relationships, indicating a constant rate of
penetration into either surface for the entire 7LPHK
period of testing. This is in marked
contrast to the corrosion rate calculated Figure 5 Intergranular penetration of the end
from weight loss (see Figure 1), which face of 18/13/Nb ss in 8M HNO3 + 25 g/L Fe at
increased linearly until the onset of stable 100 °C.
grain dropping, thereafter becoming
constant. Linear regression of the data presented in Figure 4 gives average penetration rates of
0.78 and 1.27 mm/y for plate and side faces respectively. For penetration into the end grain, the
data are more difficult to interpret owing to the presence of deeper pit-like penetrations extending
beyond the broad corrosion front. Figure 5 shows that the maximum penetrations associated with
the broad front can be fitted reasonably well to a linear relationship, giving an average rate of 1.49
mm/y. However, the pit-like penetrations, which became more pronounced with increased test
time, show considerably more variation. Notwithstanding this, fitting a line to the data using linear
regression gives an average rate for pit-like penetration of 2.82 mm/y.
Back
Since the plate, side and end surfaces respectively contributed 60%, 24% and 16% of the whole
nominal surface area of the test coupons, the average penetration rate is accordingly calculated as
1.01 mm/y or 1.22 mm/y, depending on whether the rate for broad-front penetration or pit-like
penetration is used for the end grain. Figure 1 shows that the steady state corrosion rate of this
stainless steel, obtained by weight loss normalised with respect to nominal surface area, was 1.18
mm/y. It is thus evident that measurement of the intergranular corrosion rate by weight loss is
correct, but only if the metal is undergoing stable grain dropping. The above results also suggest
that end grain pitting, for this steel at least (which has a high susceptibility), contributes
significantly to weight loss. Prior to steady-state grain dropping, the apparent initial increase in
corrosion rate obtained gravimetrically (Figure 1) is clearly an artefact; this is most probably due
to normalisation of the weight loss with respect to the nominal surface area of the test specimen,
which is clearly incorrect owing to the localised nature of the attack. This, in our view, accounts
for the continuously increasing corrosion rate reported by others in relatively short-term tests
carried out in nitric acid solutions [1,3,24,32-35]. Since the penetration rate is constant, it is
clearly the case that the actual area of the metal undergoing corrosion must increase with time, but
reaches a constant value after the onset of stable grain dropping. This explains the constant
corrosion rate observed gravimetrically after the onset of stable grain dropping. In addition, there
is clearly a weight loss contribution due to the loss of grains which will increase with time,
becoming constant once steady state conditions are achieved. However, in our experience, the
grain dropping contribution amounts to at most 30% of the corrosion rate, and hence is
insufficient to account for the totality of the observed effect.
7LP HK
those measured directly by the penetration method, for 18/13/Nb tested in an different liquor (8M
HNO3 + 25 g/L Fe at 100 °C). The agreement is very close. Where two values are given in Table
3, this relates to the difference between broad-front and pit-like attack of the end grain.
For exposed end grain, Table 2 shows that proportionally more attack occurred at 80 °C than at
100 °C (ie. at lower overall corrosivity). It is considered that this may be due to relatively facile
dissolution of exposed inclusion stringers or bands of material containing more highly-segregated
grain boundaries, not greatly affected by increase in solution corrosivity. Thus, at lower
temperature and hence lower corrosivity, a proportionally larger end-grain effect might be
expected owing to the lower corrosion rate of the remaining end grain surface.
The deconvolution method described above is labour intensive involving the preparation of a
complex series of test coupons. In order to overcome that, a second deconvolution method was
devised which uses entirely pre-corroded coupons.
The corrosion rate (W), of a coupon for which the area fractions of plate, side and end faces are
denoted by p, s and e respectively is given by:
W = Pp + Ss + Ee (1)
where P, S and E are the corrosion rates of the plate, side and end faces respectively. It follows
then that P, S and E can be determined unequivocally by measuring W for three coupons selected
to have different values of p, s and e and then solving the three simultaneous equations generated.
It is of course required that the test conditions are such that it can reasonably be assumed that P, S
and E are constant; in practice, this requires all three specimens to be taken from the same plate
(and from adjacent areas) and to be tested simultaneously in the same test vessel in order to ensure
exposure to identical conditions. In order to ensure that measurement of weight loss accurately
reflects the intergranular penetration rate, stable grain dropping is required, as explained above.
Although not strictly required, we have found that this method works best if the three coupons are
sized such that one contains a large proportion of plate surface, the next is predominantly side
surface and the last is mainly end surface. Table 4 illustrates the results obtained for NAG 18/10L
tested in 8M HNO3 + 0.7g/L Ru + 3g/L Fe at 103 °C.
Within the scatter, which is considered to be largely a consequence of grain dropping, but may
also be influenced by the variable
period times (ie. by variable Table 4 Deconvoluted faces rates obtained from testing
corrosion product build-up), the 3 coupons, each consisting primarily of end, side and plate
periodic rates are time independent. faces respectively.
This is consistent with expectation
for material undergoing stable grain- W (mm/y) Face rates (mm/y)
dropping, demonstrating the efficacy t (h) ‘End’ ‘Side’ ‘Plate’ E S P
of the pre-corrosion treatment. Using
71 1.74 1.30 0.96 1.89 1.31 0.86
an identical method, the corrosion
rate of Uranus 65 stainless steel in 144 2.22 1.76 1.48 2.36 1.76 1.38
the same liquor was deconvoluted. 236 1.74 1.30 1.22 1.84 1.28 1.16
Figure 8 compares the results 313 2.16 1.58 1.45 2.30 1.57 1.37
obtained for the two steels. The 408 1.72 1.25 1.15 1.83 1.24 1.08
individual face rates for Uranus 65 476 1.47 1.01 0.87 1.59 1.01 0.80
are all lower than for the 567 1.78 1.51 1.08 1.91 1.54 0.98
corresponding NAG 18/10L faces,
Mean 1.83 1.39 1.17 1.96 1.39 1.09
indicating improved corrosion
resistance. This is most probably due Std dev 0.27 0.25 0.23 0.27 0.25 0.23
Back
2
to the increased chromium content and the
15
convenient coupon design for which a correction
factor can be calculated to covert the coupon rate 10
directly into the contribution provided by the
5
plate or tube surfaces. This of course provides
more realistic data with which to assess plant 0
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 1.1 1.2 1.3
lifetimes. Once a particular batch of material is
deconvoluted, the results from testing in a wide Depth (mm)
interpreted. 8UDQXV
6
Number
pit depths appears broadly similar for either stainless steel, although clearly many more pits
occurred in the NAG 18/10L. Comparison between Figures 9(a) and 9(b) indicates that
considerable end grain pit growth occurred in the test solution for both metals. The high incidence
of pits < 0.1 mm in depth in NAG 18/10L following the pre-corrosion treatment may possibly be
over-estimated (ie. it was difficult to distinguish which features were very small pits and which
were just general intergranular penetration). Including the broad-front corrosion loss given by the
deconvoluted end grain rates found previously (Figure 8), the maximum pit penetrations found
were 1.6 mm for NAG 18/10L and 1.4 mm for Uranus 65. The maximum end grain pitting rates
observed in the test solution were thus 7.0 mm/y and 4.5 mm/y respectively. These results are not
considered significantly different and it is noted that it is unlikely that the maximum extent of
penetration was actually found (systematic, repetitive, sectioning would be required, which was
not done). Hence, it is considered that no significant difference has been found in the end grain
pitting rate, but that NAG 18/10L gives a much larger number of end grain pits compared with
Uranus 65. The underlying cause of this behaviour is not known unequivocally to us, although it
is likely to be due to more extensive segregation (probably positive phosphorus) in NAG 18/10L
than is the case in Uranus 65 (probably negative chromium segregation) [28,29]. In comparison
with the broad-front intergranular corrosion rate (Figure 8), the maximum observed end grain
pitting rates are ~3.6 times larger for NAG 18/10L and ~4.3 times larger for Uranus 65. It is clear
that the weight loss deconvolution method does not predict the end grain pitting rate. No reliable
method, other than careful sectioning or radiography, is presently known to us for measuring the
end grain pitting rate.
Conclusions
1. The intergranular corrosion rate of stainless steels in nitric acid solutions is time-independent;
the apparent initial increase in rate, as measured by weight loss, is an artefact due to incorrect
use of a constant nominal area in calculating the corrosion rate.
2. Sectioning to determine the penetration rate directly works well, but is laborious.
3. Weight loss gives the corrosion rate correctly if the metal being tested is at steady state (ie.
undergoing stable grain dropping). The time required to achieve this can be long for initially
ground coupons.
4. The test time can be considerably shortened by the use of a more aggressive pre-corrosion
treatment, appropriately selected for the stainless steel being tested, which induces stable grain
dropping.
5. The deconvolution method described can be used to determine the corrosion rates of
individual faces of test coupons, thus eliminating variability due to the use of different coupon
geometries by different workers.
6. End grain pitting can be measured at present only by careful sectioning or radiography.
References
1. M.A. Streicher, J. Electrochem. Soc.,106 (1959) 161.
2. S. Abe, M. Kaneko, H. Komatsu and F. Kurosawa, J. Iron Steel Inst. Jpn, 79 (1993) 713.
3. J.S. Armijo, Corrosion, 21 (1965) 235.
4. C.L. Briant, Surface and Interface Analysis, 13 (1988) 209.
5. O.V. Kasparova, Prot. Met., 24 (1989) 709.
6. K.T. Aust, J.S. Armijo and J.H. Westbrook, Trans. of the ASM, 59 (1966) 544.
7. Y.M. Kolotyrkin, O.V. Kasparova, S.D. Bogolyubski, “Role of Segregation of Impurities at Grain
Boundaries in the Intergranular Corrosion of Stainless Steels”, in: Proc. Int. Cong. on Metallic
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