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Anti-Corrosion Methods and Materials

STAINLESS-STEEL CORROSION BY DILUTE NITRIC ACID: at Elevated Temperatures and Pressures


M.L. Pearce V.S. Griffiths
Article information:
To cite this document:
M.L. Pearce V.S. Griffiths, (1960),"STAINLESS-STEEL CORROSION BY DILUTE NITRIC ACID: at Elevated Temperatures
and Pressures", Anti-Corrosion Methods and Materials, Vol. 7 Iss 5 pp. 142 - 162
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STAINLESS-STEEL CORROSION BY DILUTE NITRIC ACID
at Elevated Temperatures and Pressures
By M. L. Pearce, Ph.D., and V. S. Griffiths,Ph.D.,F.R.I.C.*

Stainless steel has been found to exhibit passivity in dilute nitric acid at
300C. The rate of corrosion for passive conditions is unaffected by
increase in temperature or small quantities of oxidising ions, but is
increased in the presence of 10 g./I. of uranium. Corrosion in the vapour
phase was found to be insignificant, though severe corrosion occurs at the
vapour-liquid interface. A weight-loss technique has been used for the
bulk of the determinations, but an alternative electrochemical method of
investigating the corrosion has been studied with encouraging results.

CORROSION resistance of stainless can be obtained, although in some


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steels towards mineral acids has re- cases the graph was markedly curved
ceived considerable attention.1-6 Past and extrapolation of the linear portions
investigations have, with few excep- was necessary.
tions,1 been made at temperatures up The results obtained using the
to the boiling points of the acids con- weight-loss technique exhibited such
cerned and usually at relatively high a high degree of scatter that a large
acid concentrations. Modern industry number of determinations was re-
now needs materials capable of con- quired. An investigation at one acid
taining fairly concentrated solutions of concentration for corrosion times up
heavy metal salts plus the dilute acid to 600 to 700 hr. involved a total
required to prevent their hydrolysis. experimental time of the order of
This is of particular current interest 5,000 hr. It was considered that the
in connection with the proposed design scatter may to some extent be due to
of homogeneous aqueous nuclear re- galvanic effects caused by the contact
actors. Moreover, such solutions are occurring between the test specimen
frequently at temperatures greatly in and platinum container. However,
excess of their boiling points and are experiments were made in which the
accompanied by the corresponding most stringent precautions were taken
steam pressures. to prevent such contact and no.
An investigation has been made of improvement in the reproducibility
the corrosion resistance of 18-8 stain- was observed. Two alternative tech-
less steel to nitric acid over the con- niques were tried in an effort to obtain
were generated without diluting the more reliable results more quickly.
centration range 0.01 to 1.4% at 300C. acid.
and 350C. A corroded specimen was dark The first, which proved unsuccess-
brown in colour and its surface rough ful, involved measuring the change in
EXPERIMENTAL to the touch. It had suffered no loss high-frequency conductance of a very
Initial experiments were carried out in weight, and the corrosion product fine wire of the material. Similar
using a weight-loss method. This was insoluble in either concentrated methods have been used successfully
involved the corrosion of small, rect- phosphoric acid or sulphuric acid at lower temperatures and higher acid
angular, stainless-steel specimens hav- inhibited with paratoluylthiourea. concentrations. An autoclave having
ing areas of approximately 3 sq. cm., Moreover, it could not be removed electrically insulated internal elec-
which were suspended in acid con- satisfactorily by the standard cathodic trodes which projected via pressure
tained in a cylindrical platinum beaker defilming method using inhibited seals through the lid was employed.
of 22-ml. capacity. A tight-fitting 5% sulphuric acid. It was not brittle Using this autoclave, which main-
platinum cap enclosed each beaker, a and was unaffected by wire brushes, tained a temperature of 3002C,
hole 0.5 mm. in diam. being drilled but could be removed by abrasion and a megacycle transformer ratio
through each cap to ensure pressure using a polishing machine and a arm bridge the conductivity of a fine
equilibrium. The beakers were placed domestic metal polish. Fig. 1 shows stainless-steel wire immersed in 1.4%
in a 1-in. autoclave which in turn was the variation in weight of a cor- nitric acid was examined. However,
connected to a high-pressure apparatus roded and an uncorroded stainless- the conductivity varied very little
equipped with a gauge, bursting disc steel specimen on polishing. It is with time and apparently in a random
and valve. Each autoclave was heated evident that a fairly reliable value for manner, so that this method was
by a 1.2-kw. nichrome resistance wind- the weight of the uncorroded residue finally abandoned in favour of the
ing, a small quantity of water being technique described below.
included in the body of the autoclave * Battersea College of Technology, Young7 has successfully estimated
in order to ensure that steam pressures London. the growth of oxide films on metal

142 CORROSION TECHNOLOGY May 1960


ally longer than the corrosion time.
The electrodes were corroded, and
at intervals of approximately 60 hr.
were removed from the high-pressure
apparatus, cleaned with alcohol and
distilled water, washed with the stock
solution and assembled into the cell.
Care was taken on each occasion to
ensure that the electrolyte level coin-
cided with the top of the nylon spacer.
It was found that, whereas the specific
conductance values showed a small
but random variation, the capacitance
values exhibited a definite trend which
is illustrated graphically in Fig. 6.
TABLE
Results: Figs. 1 to 6. Corrosion rates
and weight loss for passivity for 18-8
stainless steel i n dilute nitric acid
Weight loss/
Acid unit area Rate of corrosion
concen- before passivity after passivity
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tration (mg./sq.cm) (mg.lsq.cm.lyr.)


1.41 0.95 1.0
0.366 0.37 0.9
0.074 0.27 1.6
0.010 0.24 1.7
DISCUSSION
Corrosion by pure nitric acid
Despite the high degree of scatter
exhibited by the results obtained
using the weight-loss technique, the
reproducibility was reasonably good
except for corrosion times of short
duration. It was observed during the
course of this investigation that the
physical and possibly chemical nature
of the corrosion product is dependent
on the duration of the corrosion, and
that the removal of the surface film is
relatively easy for short corrosion
times. This leads to an ambiguous
end point in the graph shown in Fig. 1,
and may to some extent account for
the large scatter of the results for runs
of short duration.
It is probable that one of the prin-
cipal reasons for the variation in the
results is the difficulty in obtaining
reproducible surfaces. During the
preparation of a fresh surface on a
stainless-steel specimen, by means of
prolonged abrasion with emery cloth,
the subsequent polishing to obtain a
surfaces by measuring the change in 300C., and then reassembled into uniform surface may in some cases
capacitance of a parallel plate con- the cell. The specific conductivity have been inadequate, with the result
denser constructed of the metal in and capacitance of this cell when that the discrepancy between the real
question, as the oxidation proceeded. immersed in a stock solution of and apparent areas was greater than
Since it would be impractical to approximately 10 -4N KC1 were usual. This possibility is indicated by
attempt to measure the capacity of measured before and after the corro- the fact that an unpolished specimen
a cell contained within an autoclave sion interval, each specimen being exhibited a weight loss three times
at 300C., a capacitance cell was con- thoroughly washed with conductivity greater than that obtained using a
structed which could be dismantled water before it was returned to the polished specimen. Streicher8 has
and reassembled without appreciably acid. One of the principal advantages investigated the effect of surface finish,
changing its cell constant. In this of this method is that an investigation including electropolishing, on the cor-
way, the electrodes or condenser plates at one acid concentration over a rosion of 18-12 stainless steels by 65%
could be detached from a nylon cell period of 700 to 800 hr. involves an nitric acid and concluded that it was
spacer unit, corroded in the acid at experimental time which is not materi- largely a function of the absolute area

May 1960 CORROSION TECHNOLOGY 143


produced by the various finishes.
The best slopes of the linear por
tions of the curves for pure nitric
acid shown in Figs. 2, 3 and 4 do not
differ by as much as a factor of two.
Since they fail to exhibit any kind of
dependence on the acid concentration,
it is reasonable to conclude that the
rate of corrosion for passive con
ditions is 1.51.0 mg./sq.cm./yr., and
is constant for all acid concentrations
over the range studied. Insufficient
determinations have been made to
rule out the possibility that the
assumed linear portions of the curves
may in fact be asymptotic to lines
parallel to the abscissa.
The time needed for the develop
ment of passivity would appear to be
dependent on the acid concentration,
being longer for the more dilute acid.
Despite the fact that for the more
concentrated acid passive conditions
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are reached more quickly, the rate of


corrosion is greater in the initial stages
and this leads to a greater weight loss
for passivity. The table and Fig. 5
are consistent with a linear relation
ship.
Fig. 2 shows the effect of tempera
ture on the corrosion by 1.41% nitric
acid. The initial rate of corrosion is According to Mcintosh, the mech rate of corrosion is considerably in
increased and passive conditions are anism of the corrosion is the oxidation creased and the level of corrosion
reached more rapidly with increasing of Cr2O3 in the protective oxide film corresponding to passivity is raised.
temperature, whereas the rate of cor to Cr 2 O 7 -. This anodic reaction is The rate of corrosion corresponding
rosion after passive conditions have polarised in the absence of the species to passive conditions, however, does
been reached is unaffected. already mentioned as is the cathodic not appear to be affected to an extent
A comparison of photomicrographs reaction occurring 3
in solution, viz. detectable by the method used.
of a specimen taken before and after Cr 2 O 7 - go Cr + and Ce4+ to Ce3+.
Nitric acid containing 10 g./l. of
corrosion revealed that small pits and However, if the species are present,
uranium
scratches present in the uncorroded these reactions become depolarised
steel surface are greatly enlarged and and the corrosion proceeds freely. Uranium, thorium and plutonium
extended during the course of cor Fig. 3 shows the effect of a 100- salts are obviously particular examples
rosion, as was found to be the case for p.p.m. chromium impurity, in the of heavy metal salts which are of
boiling concentrated acid by Shirley form of chromic sulphate, on the current interest in view of the pros
and Truman 9 and Streicher.8 corrosion by 0.01% acid, and Fig. 2 pective design of homogeneous nuclear
shows the effect of a similar cerium reactors. Consequently, corrosion by
Nitric acid containing chromic impurity on the corrosion by 1.4% a solution of uranyl nitrate in 0.01%
and ceric ions acid. The effect of the two impurities nitric acid has been studied and the
were qualitatively similar. The initial results shown graphically in Fig. 3.
It is known that the corrosion of
stainless steel by strong nitric acid is
enhanced by the inclusion of small FRANAIS DEUTSCH
quantities of oxidising salts in the cor La Corrosion de l'Acier Inoxydable
10
roding medium. Mcintosh observed par l'Acide Nitrique Dilu des Korrosion von rostfreiem Stahl in
that, for fairly concentrated acid, the T e m p r a t u r e s Eleves et sous Hautes verdnnter Salpetersure bei
Pressions crhhtem Druck und erhhter
corrosion of stainless steel is accele
Il a t rvl que l'acier inoxydable fait Temperatur
rated by several ions which are the preuve de passivit dans l'acide nitrique dilu
oxidised members of redox couples, 300C. Le taux de corrosion pour des Rostfreier Stahl verhalt sich in verdnnter
Salpetersaure bei 300C passiv. Die
e.g. Cr, Ru, V, Au and I. Apparently conditions passives n'est affect, ni par la Korrosionsgeschviindigkeit fur den passiven
Y activity inhibits corrosion due to hausse de temprature, ni par de faibles Zustand wird durch Temperatursteigerung
the radiochemical decomposition of quantits d'ions oxydants, mais, par contre, oder geringe Mengen oxydierender Ionen
il est accru par la prsence de 10 g./l. nicht beeinflusst, steigt jedoch bei Anwesen-
nitric acid which effectively maintains d'uranium. La corrosion dans la phase heit von 10 Uranionen pro Liter. lm
the oxidation potential below that at vapeur s'est prouve insignificante, quoiqu'une Dampfraum ist der Angriff unbedeutend, an
which the species responsible for corrosion importante se produise au point de der Grenzflache Dampf/Flssigkeit tritt
accelerated corrosion are stable. This sparation vapeur/liquide. Un procd bas jedoch starke Korrosion auf. Die meisten
may be important in those cases sur la perte de poids a t utilis pour la Versuche wurden gravimetrisch durchgefhrt,
where the acid is used as a medium for plupart des valuations, mais, pour tudier
la corrosion, une mthode alternative electro-
daneben wurde jedoch auch eine elektro-
chemische Methode benutzt, deren Ergebnisse
containing radioactive salts. chimique a donn des rsultats encourageants. aussichtsreich scheinen.

144 CORROSION TECHNOLOGY May 1960


The rate of corrosion after the Vapour phase corrosion
passivity level in the region of a weight The corrosion of stainless steel by
loss of 0.5 mg./sq.cm. has been the vapour of nitric acid of two con-
reached, is 4.4 mg./sq.cm./yr. as com- centration's (1.4% and 0.074%) was
pared with a passivity level of 0.24 examined by supporting the specimen
mg./sq.cm. and a corrosion rate of above the acid using a platinum
1.7 mg./sq.cm./yr. for pure acid of pedestal.
the same concentration. This shows Six runs of duration varying from
a marked change in the passivity level 100 to 800 hr. were completed for each
and indicates that the rate of corrosion acid concentration. The corrosion was
after passivity is also affected. In extremely slight and was barely detect-
view of the inaccuracies which have able by the weight-loss technique, so
already been discussed, it is difficult that the quantitative results obtained
to be sure that the change in the rate are of little significance. Some
of corrosion after passivity is signifi- interesting qualitative and semi-quan-
cant. The unusually good linearity of titative observations were made, how-
the graph, however, suggests that in ever.
this case the errors were smaller than
usual and hence it appears probable The only detectable difference in
that the rate of corrosion is increased the appearance of uncorroded and
by the new cations present in the acid. vapour-phase corroded specimens was
a very fainty yellow colour in the
Two interesting observations were latter. This surface film was very
made in connection with the nitric easily and rapidly removed by polish-
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ing, with the result that the weight


loss observed was very small and
therefore the results undoubtedly
attended by large errors. Despite this
fact, it is possible to say with certainty
that there was very little difference in
the weight loss for 100 and 800-hr.
runs for either acid concentration.
Moreover, no appreciable difference
could be detected between the corro-
sion for the two different acid concen-
trations. The weight loss for both
concentrations was of the order of 0.01
mg./sq.cm.
Specimens which were partly im-
mersed in the acid exhibited corrosion
at the vapour/liquid interface which
was greatly in excess of that due to
either of the separate phases. A line
was etched so deeply into the steel
that it could only be removed by
using a file. It is possible that this
preferential attack may be due to
higher ionic concentrations at the
acid-uranyl nitrate solution. Whereas uranyl nitrate. Colani11 has reported, interface.
for all specimens corroded in pure however, that '. . . uranyl nitrate will
acid the surface film was dark brown, Electrochemical method
recrystallise from nitric acid solutions
specimens corroded in the uranium- to give lemon-yellow prisms . . .', and The variation of capacitance of the
bearing acid appeared at first sight to it would appear from this that, due to stainless-steel cell with corrosion time
be uncorroded. Closer examination the slight reduction in volume which shown in Fig. 6 is remarkably similar
revealed that the surface was bright always occurs at the close of an to the weight loss/corrosion time
silvery-yellow and very little polishing experimental run as water vapour con- graph for the same (0.074%) acid
was required to remove this upper denses in the body of the autoclave, concentration.
layer and expose the normal brown uranyl nitrate crystallises out. This Fig. 6 indicates that passivity occurs
oxide. It was also found that for is not consistent, however, with the after a corrosion time of approximately
rather more than half the experimental fact that the solution only contains 200 hr., which confirms the value
runs completed using this solution, 16 g./l. of uranyl nitrate, which is obtained using the weight-loss tech-
the specimen had a mottled appear- considerably below the figure for a nique. Although the slope of Fig. 6
ance after corrosion but that this saturated solution. It is possible that cannot be directly related to a rate of
could be removed simply by wiping. the electrolyte becomes concentrated corrosion, it is valid to compare the
On examining a 'mottled' speci- at the steel surface and that, during ratio
men under a microscope it was found the slow cooling under static con- Slope
to be liberally covered with very small ditions, crystallisation occurs because
pale-yellow prismatic crystals. This is the solubility is exceeded in the surface Change in ordinate for passivity
not the normal crystal structure of regions. (Concluded on page 162)

May 1960 CORROSION TECHNOLOGY 145


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Stainless-steel Corrosion by REFERENCES


1
Dilute Nitric Acid Miller, Treseder and Wachter, Corrosion,
(Concluded from page 145) 2
1954, 10 (7).
Niedrach, Glamm, Brennan and Dearing,
for the capacitance and weight-loss 3
Ind. & Eng. Chem., 1958, 50, 763.
graphs corresponding to 0.074% nitric Edeleanu, CORROSION TECHNOLOGY,
1955, 2, 204.
acid. The figures are 0.007 and 0.005 4
Uhlig and O'Connor, J. Electrochem.
hr. - 1 respectively. The similarity is 5
Soc., 1955, 102, 562.
particularly striking when the large Shirley and Nicholson, J. Iron & Steel
errors inherent in the weight-loss 5
Inst., 1952, 170, 111.
O1dfield and Sheppard, CORROSION
technique are borne in mind. Hence TECHNOLOGY, 1958, 5, 187.
it appears that the capacitance of the 7
8
Young, Acta Metallurgica, 1957, 5, 711.
condenser system varies linearly with Streicher, J. Electrochem. Soc., 1959,
the physical properties of the corrosion 9
106, 161.
film and it seems likely that the most Shirley and Truman, J. Iron & Steel
Inst., 1952, 172, 377.
important parameter involved is thick- 10
Mcintosh, Chem. & Ind., 1957, 687.
11
ness. The method confirms the Colani, Bull. Soc. Chim., 1926, 39, 1243.
qualitative nature of the corrosion
indicated by the weight-loss technique
and lends considerable support to the
quantitative results reported above.

Materials
The stainless steel was supplied in
rod form by Messrs. Firth Brown's
research laboratories in Sheffield, Eng-
land. Spectrographic analysis showed
the presence of trace quantities of
aluminium, copper and manganese.
The acid used was prepared by
diluting Harrington's ' p u r e ' reagent
and standardising against sodium car-
bonate.
All salts used were B.D.H. AnalaR
reagent grade.
Acknowledgment
Thanks are extended to the United
Kingdom Atomic Energy Authority
for a grant and the provision of most
of the apparatus used in this investi-
gation.

162 CORROSION TECHNOLOGY May 1960

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