Corrosion Behavior of AISI 316

Stainless Steel in Formic and Acetic Acid

Solutions*
SEKINE, * A. MASUKO, * K. SENOO*

Abstract
The corrosion behavior of AISI 316 stainless steel (SS) in formic and acetic acids was investigated by
measuring the corrosion weight loss, the polarization curve, the impedance at the steel/solution
interface, and the variation of natural electrode potential (NEP) with time. It was found that the corrosion
rate of AISI 316 SS in formic and acetic acids was markedly dependent on the concentration of the acid
and temperature. The corrosion rate in aqueous solution of these acids was larger than in nonaqueous
solution, and the corrosion behavior in nonaqueous solution was quite different from that in aqueous
solution. It was believed that Cr and Mo mainly contribute to the corrosion resistance of AISI 316 SS
in aqueous solution, while Ni contributes slightly. In nonaqueous solution of formic acid, Cr mainly
contributes to corrosion resistance, and Mo and Fe contribute slightly; in nonaqueous solution of acetic
acid, Cr mainly contributes to corrosion resistance, while Mo contributes slightly. To obtain information
for the passive film on AISI 316 SS after immersion in formic acid, the distribution of the main
compositional elements was analyzed by Auger electron spectroscopy (AES). From these results, it was
found that the amount of Mo distributed on the surface of steel was larger, while the amount of Fe was
smaller than that before immersion. It was also found that the amount of Cu in an aqueous system and
Ni in a nonaqueous one was larger than that before immersion. In the case of formic acid, surface
analysis of steel after immersion in acetic acid was conducted by ion micro analysis (IMA). In 50 and
100% acetic acids, some Cr was present on the steel surface. In 90% acetic acid, it was believed that
selective corrosion did not occur because the distribution of the main compositional elements of the
specimen surface after immersion did not change.

Introduction
AISI 316 stainless steel (SS) has a high corrosion resistance
and is widely used in various corrosive environments. However, the
corrosion behavior of the steel in organic acids has not yet been
the test materials are shown in Table 1. AISI 316 SS was annealed
in a vacuum at 1050 C for 40 min and then quenched in water. Each
test electrode was composed of a cross section whose lateral surface
was covered by Teflon.' Before the test, all of the test electrodes
)

completely clarified. In previous papers, the corrosion behaviors of
AISI 304 SS and SS 41 steel (C - 0.08, Si - trace, Mn - 0.35, P - 0.014,
S - 0.018, and Fe - Bal, similar to mild steel) in formic and acetic acid
solutions have been investigated in detail.' -4
were abraded with emery paper to 1500 grit and then degreased with
acetone in a supersonic washer.
The reagent grade formic acid (98 to 99%) and acetic acid
(99.5%) were purified as described in the previous papers." 4 The
-

In this paper, for the purpose of elucidating the corrosion
behavior of AISI 316 SS in formic and acetic acid solutions, it was
investigated in detail by measuring the corrosion weight loss, the
polarization curve, the impedance at the steel/organic acid interface,
and the variation of natural electrode potential (NEP) with time. In the
concentrations of formic and acetic acids used were in the range of
1 to 100 vol%. The trace amount of water in the nominally 100 vol%
acid solution was determined by the method of Karl Fischer. This
method is an electrochemical measurement of the peculiar reaction
between water and the Karl Fischer reagent, which consists of 1 2 ,

weight loss test, the measurement was conducted at room temper- S0 2 pyridine, and CH 3 OH. In formic acid, the amount of water
,

ature (RT) and at the boiling point. Since the system of the
steel-organic acid at the boiling point was unstable, electrochemical
measurements could not be conducted. Therefore, a surface analy-
sis was conducted to provide information on the steel at boiling point.
Experimental
Materials
The test electrode for AISI 316 SS and pure Mo consisted of a
wire with a cross section of 3.14 mm 2 . The chemical components of
*Submitted for publication August 1985; revised October 1986.
*Dept. of Industrial Chemistry, Faculty of Science and Technology,
Science University of Tokyo, Noda, Chiba 278, Japan.
indicated by titration was 0.3% for weight loss measurements and
0.5% for electrochemical measurements. In acetic acid, it was
0.008% for weight loss measurements and 0.04% for electrochem-
ical measurements. The solution was deaerated with purified nitro-
gen gas for more than 2 h. For electrochemical measurements,
potassium formate (0.5 M) and potassium acetate (0.5 M) as a
supporting electrolyte were dissolved in each solution. The potential
was measured with reference to an SCE.
Weight Loss Measurements
Before the test, the specimen (20 x 50 x 0.8 mm) was abraded
with emery paper from 240 to 1200 grit in the case of formic acid, and
( ' Registered trade name.
)

0010-9312/87/00277/$3.00/0
Vol. 43, September 1987 © 1987, National Association of Corrosion Engineers 553
 TABLE 1 — Chemical Composition of AISI 316 SS

C SI Mn P S Ni Cr Mo Cu

For weight loss 0.06 0.56 1.77 0.03 0.007 11.5 16.9 2.31 0.28
For electrochemical 0.053 0.31 2.56 0.023 0.003 11.91 19.2 2.22 0.13

TABLE 2 — Reduction Time for AISI 316 SS in CH 3 í000H

CH 3 000H/voi% 1 10 20 30 40 50 60 70 80 90 99.96
Reduction time/min 60 50 50 50 45 40 40 40 45 50 50

TABLE 3 — Corrosion Weight Loss in HCOOH at RT

HCOOH/vol% 1 5 20 50 90 99.7

mg 0 0.2 0 - 0.1 0.3 0 - 0.1 0

mdd 0 0.020 0 - 0.014 0.034 0 - 0.013 0

from 800 to 1200 grit in the case of acetic acid. It was then degreased
with methanol and acetone in a supersonic washer. The specimens
in the formic acid solution were examined at the boiling point for 24
h and at RT for 35 days. In acetic acid solution, they were examined
at the boiling point for 7 days and at RT for 70 days. 121 5

Polarization Measurements
The counter electrode was a platinum sheet with dimensions of E E
30 x 40 x 0.5 mm. Prior to measurement, the working electrode of
AISI 316 SS in formic acid was cathodically polarized at -10 mA/cm 2 Q $1 4 Q
for 40 min and was cathodically polarized at -10 mA/cm 2 in acetic
acid for the time shown in Table 2. The solution was then exchanged. z
0 0
The polarization measurements were immediately performed by a CO CD
potentiodynamic method with a scan rate of 50 mV/min. 0 0

To investigate the effect of immersion time on the polarization C>

0 0
U
behavior of AISI $16 SS in formic acid, the polarization curves were "41
measured after standing for 24 h from the end of a cathodic
polarization.

NEP-Immersion Time Curves

Following the cathodic polarization, the NEP of AISI 316 SS was
monitored by an automatic recorder for 24 h.

Impedance Measurements
The counter electrode was in the form of a platinum spiral wire
in formic acid and was in the form of a platinum sheet for polarization
measurements in acetic acid. In formic acid, the time necessary to
stabilize the corrosion potential (E core ) of AISI 316 SS was 5 h after
cathodic polarization at a constant current. The impedance of the
electrode was measured as described in previous papers. 1 3
Surface Analysis
The Auger electron spectroscopy (AES) was conducted using a
Perkin-Elmer Model EDL5 (2 The ion microanalysis (IMA) was
conducted using a Hitachi (3 Model IIA. Specimen surfaces were
sputtered with O 2 + at 2 x 10 -7 torr pressure. The depth reached was
- 500 A after sputtering 15 times.
Resuits and Discussion
Corrosion Weight Loss
The corrosion rate at various concentrations of formic acid at RT
(2),(3)
Registered trade names.
CONCENTRATION / vol,%
FIGURE 1 - Corrosion weight loss In HCOOH and
CH 3 000H.
o: HCOOH at boiling point
A: CH 3 000H at bolling point
• : CH 3 000H at RT.
is shown in Table 3. The weight loss was barely measurable in all
concentrations of formic acid. The highest value of the corrosion rate
was 0.034 mdd at a concentration of 50%. The appearance of the
specimen after the test was scarcely altered from that before
immersion and maintained a silvery metallic luster.
The results of the weight loss test in formic acid at its boiling
point and in acetic acid at its boiling point and RT are shown in Figure
1. In acetic acid at RT, the highest corrosion rate value was 0.044
mdd at a concentration of 30%; peaks were observed at concentra-

554 CORROSION—NACE

FIGURE 2 — Surfaces of test pleces for varlous concen-
trations of HCOOH.
TABLE 4 — Distribution Amounts of Elements on the
Surface of AISI 316 SS in HCOOH by AES
Element (at%) Fe Ni Cr Mo Cu C 0
Before 22.3 2.1 5.1 0 0 33.4 37.2
immersion
50% HCOOH
8.1 0 7.3 10.1 11.9 27.4 38.8
(106.3 C)
99.5% HCOOH
3.4 10.5 4.8 11.1 0.6 31.2 38.5
(101.9 C)
tions of 30 and 80%. The specimen after the test maintained a silvery
metallic luster, as in the case of formic acid. In the lower concentra-
tion range (0 to 50 vol%), the corrosion rate was considered as
dependent on the conductivity of the solution. In the higher concen-
tration range, it is believed that the corrosion rate increases because
the proton of the aggressive species can be as stable as the
hydronium ion up to a concentration of 80%, and the corrosion rate
then decreases because of the Jack of water to stabilize the
hydronium ion and because the dissociation of acetic acid is difficult.
In formic acid at its boiling point, the corrosiort rate increases with
increasing concentration of formic acid up to a maximum value of 137
mdd at 50% and then decreases. The corrosion rates in concentra-
tion of 90 and 100% were both 70 mdd.
Figure 2 shows the surfaces of test pieces after weight loss
measurement in formic acid at its boiling point. While this photograph
is fogged because uniform light was not irradiated onto the speci-
mens, the appearance of the specimens in concentrations other than
nominally 100% formic acid was scarcely altered from that before
immersion and retained a silvery metallic luster. The surface of the
test piece in nominally 100% formic acid showed a greenish-black
color, but a metallic luster was stil) maintained. In a previous paper,
such a black film was not observed on the surface of AISI 304 SS in
nonaqueous formic acid. 2 AISI 304 SS did not contain Mo. However,
since AISI 316 SS contains Mo, the black film that formed in formic
acid was presumed to be the insoluble formate [Mo(HCOO)„].
In acetic acid at its boiling point, the corrosion rate increases
with increasing concentration up to a maximum value of 20.8 mdd at
90% and steeply decreases in 100% concentration (Figure 1). The
specimens in other concentrations except 40 to 80% acetic acid were
scarcely altered from those before immersion. The surface of the
specimens was covered by a black film in 40 to 80% acetic acid.
When the film was removed, the surface retained a silvery metallic
luster. It is believed that the film in this case is the hydrate of
magnetite (Fe 304 H 2 O) because it is eásily dissolved in dilute nitric
acid.
To qualitatively analyze this film, the surface of steel before and
after immersion was examined in formic acid by AES and in acetic
acid by IMA. The results of the surface analysis by AES are shown
in Table 4. A large quantity of Mo distributed on the surface after
immersion was observed. The Fe and Cu contents became smaller,
Vol. 43, September 1987 555
10 (a) (b) (c) (d)
Fe
á, Cr
+ 10 -1
oyN"'
10 -2
10-- 1 15 1 15 1 15 1 15
NUMBER OF SPUTTERING
FIGURE 3 — Surface analysis of AISI 316 SS in CH 3 000H
by IMA: (a) before immersion (b) 50% (c) 90% (d) non-
aqueous.
especially on the surface after immersion in 50% formic acid, and the
Ni content on that in nonaqueous formic acid was seen to be
distributed at a greater level than that before immersion. Ni was
present at Oat% in 50% acetic acid. It might be that the Auger peak
of Ni could not be detected because of the adjacency of the Cu Auger
peaks. At any rate, Ni was considered to be distributed after
immersion as much as before immersion in 50% formic acid. The
greenish-black film could be formed by nickel formate rather than
only molybdenum formate, on the basis of its color, because the
distribution of surface Mo present in the nonaqueous solution is equal
to that in aqueous solution (Figure 2). However, such an explanation
is inconsistent with the fact that the greenish-black film was not
produced on the surface of Ni-containing AISI 304 SS in nonaqueous
formic acid. Therefore, Mo does not independently form passive films
on the surface of AISI 316 SS but coexists with other elements to
produce the film. The coexisting atom is considered to be Cu in the
aqueous solution system and Ni in the nonaqueous solution system.
The results of surface analysis by IMA are shown in Figure 3 for
AISI 316 SS in acetic acid. In a concentration of 50% acetic acid in
which the black film was formed, the amount of Cr compared with Fe
in the surface region increases more after immersion than before.
Therefore, it is considered that Cr is an important part of the film. This
film is easily dissolved in nitric acid as described above, but the film
containing Cr as chromium oxide, chromium hydrate, and chromium
acetate is not easily dissolved. According to the above statement, it
is considered that the black film formed is one containing Fe and Cr,
and that the Fe exists as a hydrate of magnetite. In 90% acetic acid,
although the weight loss was the highest, the surface state did not
change after immersion. Consequently, it is believed that selective
corrosion did not occur in this concentration. In a nonaqueous
solution, Cr can be seen to present somewhat more after immersion
than before.
Polarization Characteristics
Polarization curves of AISI 316 SS in formic and acetic acids
measured immediately after cathodic polarization are shown in
Figure 4. In all the acid concentrations, active and passive regions
were observed, which led to transpassive dissolution. On the anodic
side, the current density (CD) in nonaqueous acids was lower than
that in aqueous solution, which was similar to that of AISI 304 SS in
acids. These polarization curves were compared with anodic polar-
ization curves of Fe, Cr, and Ni in formic and acetic acids presented
previously 2 • 4 and with those of Mo. The results are shown in Figures
5(a), (b) and 6(a), (b). Figures 5(a) and (b) show the curves in the
concentrations of 20 and 100% formic acid, respectively. Figures 6(a)
and (b) show the curves in the concentrations of 80 and 100% acetic
acid, respectively.
According to the potential and passivity of CD, it is considered
that in 20% formic acid, Mo in the region from E corr to 0 V and Cr in
the more noble potential region than 0 V contribute to the corrosion
 103
102
Fe
10 2
10
Mof j
N
10
U 1 N
EE
E N 1 ,I I^\T
10 - 1 E 1

10 --
I r
' 316SS

10 -2

10 -3
- 1,U - U,7 U U,7 l,U 1,7 L,U
10 ' -
I I Ik!
^' ^/504SS

a E / V vs,SCE
10 -,
-1.0 -0.5 0 0.5 1,0 1,5
10 a E / V vs.SCE

• i f/ 10

1 • 80 30
90 f; 1
N 99,96%
i
É 10 -1 10 -1
I ^^ 316SS
304SS
10 -2

10 -2 'i
10 -3

10 -3
-0,5 0 0.5 1.0 1,5
b E / V vs.SCE
FIGURE 4 — Polarization curves of AISI 316 SS in
deaerated acids: (a) HCOOH + 0.5 M HCOOK (b) CH 3 000H
+ 0.5 M CH 3 COOK.
resistance of AISI 316 SS. In 100% formic acid, Mo near
and Fe in the more noble potential region than +0.45 V contribute to
the corrosion resistance.
On the other hand, in 80% acetic acid Mo near E corr, (from E corr
to 0 V, as in the formic acid), Cr in the potential region from 0 V to
+1.0 V, and Ni in the more noble potential region than +1.0 V would
be contributing to the corrosion resistance. In 100% acetic acid, the
anodic polarization curve of AISI 316 SS is almost the same as that
of Cr, so Cr would be contributing strongly to the corrosion resis-
tance. Mo in the potential region from E corr to +0.1 V is also
considered to contribute to the establishment of passivity.
The peak of active dissolution for AISI 316 SS is comparatively
lower than that of AISI 304 SS. This differentie could be attributed to
the effect of Mo, which is not present in AISI 304 SS. Mo promotes
passivity near the E., of AISI 316 SS in formic and acetic acids.
Since the steel is easily passivated by the presence of Mo, the peak
of active dissolution of AISI 316 SS becomes low.
Polarization curves after 24 h from the end of cathodic polar-
ization are shown in Figure 7. The peak of active dissolution was not
observed, unlike the polarization curve immediately after cathodic
l
10 -2 I
10 - 1
V
2.0
-0.5 0 0,5 1,0 1,5
b E / V vs.SCE
FIGURE 5 — Anodic polarization curves of AISI 316 SS,
AISI 304 SS, Fe, Cr, NI, and Mo in deaerated HCOOH + 0.5
M HCOOK: (a) 20% (b) nonaqueous.
Ecorr and Cr
polarization [Figure 4(a)]. This phenomenon is caused by the
crossover of local anodic and cathodic polarization curves.
The relationship between the concentration of formic and acetic
acids and the value of i crr obtained from polarization curves is shown
in Figure 8. The i cor , in formic acid, after 24 h from the end of cathodic
polarization, is one order of magnitude smaller than that immediately
after cathodic polarization; therefore, the corrosion rate decreases
with time. As described above, this would be attributed to the
production of a passive film on the surface of AISI 316 SS. The value
of i corr immediately after cathodic polarization showed a maximum in
a concentration of 90% formic acid and, after 24 h from the end of
cathodic polarization, showed a maximum in 50% formic acid.
Therefore, the peak of the corrosion rate shifts with time because the
film produced on the steel in aqueous formic acid solution of low
concentration is different from that of high concentration. The
production rate of the film depends on time. After 24 h from the end
of cathodic polarization, the corrosion rate was almost the same in all

556 CORROSION—NACE
 ^ Cr ; J
10 Fe í
L _4 _ -r
Mo l,
•^.
1 /^► cut
304SS E
U ! Ír6SS É
10-2 •
F .

10 -4

10 -3 I i 10 -

.5 0 0.5 1,0 1.5 2.0

E / V vs.SCE
10 -2
FIGURE 7 — Polarization curves of AISI 316 SS after 24 h
— 1.0 — U.) V U.J L.
from the end of reduction in deaerated HCOOH + 0.5 M
a E / V vs.SCE HCOOK.

1 Fe/ ,7(^ am
/ ' Mo 1 J/7'
,
/_ .,T304SS—'
M
N
É 10-1 •, E O
U 0.

' ' Cr E
E
L
10 -2 j
( ? . L.ai6ss
0.

10 -3
l
4( 0 20 40 60 80 100
10 -4 CONCENTRATION / vol.%
-0.5 0 0.5 1.0 1.5
FIGURE 8 — Corrosion CD vs acid concentrations:
b E / V vs, SCE o: HCOOH
FIGURE 6 — Anodic polarization curves of AISI 316 SS, A: HCOOH, after 24 h from the end of reduction
AISI 304 SS, Fe, Cr, NI, and Mo In deaerated CH 3 000H + ❑ : CH 3 000H.
0.5 M CH 3 COOK: (a) 80% (b) nonaqueous.

obtained by extrapolation of the cathodic Tafel slope to Ewrr•

concentrations because the steel surface was almost covered with a
film. In 50% formic acid, the film was incomplete, so the corrosion rate
would be increased because of the presence of aggressive H+ Tons.
On the other hand, the shape of i cor; acetic acid concentration curve
was similar to that of corrosion weight loss in acetic acid (Figure 1).
Consequently, the peak in 30% acetic acid could be ascribed to the
electrical conductivity of acetic acid solution. Another small peak can
also be seen in 80% acetic acid. The appearance of this small peak
could be based on an arbitrariness in the value of i^, r . Since the Tafel
linear region was not observed on anodic side, the value of i vo „ was
Therefore, it is impossible to determine absolutely that the peak is
observed in 80% acetic acid.
The relationship between E corr obtained from polarization curves
and the concentration of formic and acetic acids is shown in Figure
9. In all cases, E coar can be seen to shift toward noble potentials with
increasing acid concentration. Such a shift of E cor , has been
described for the corrosion of AISI 304 SS in formic acid in a previous
paper.'
Since the linear Tafel region was observed on the cathodic side
of the polarization curve, an analysis of cathodic reaction was

Vol. 43, September 1987 557

 -0.1 -0.2

-0.3
w -0,2
U
cn
N
-0.4
L
0
O
-0.3 W
L

O
-0,5
U

`iJ -0.4

pH
FIGURE 11 - Corrosion potential vs pH of solution:
-0.5 o: HCOOH
0: CH 3 000H.
1 1 1 :1 :1 O
CONCENTRATION / vo1,% pH deviated slightly from a straight line. If a linear relationship is
assumed , the slope of the line is 0.60. From these results, it was
FIGURE 9 - Corrosion tential vs acids concentration: found that the form of the cathodic reaction does not change with
o: HCOOH time. In acetic acid, the relationship between 11,1 and pH shows a
0: HCOOH, after 24 h from the end of reduction good linearity, the slope of the line being 0.47. It is not easy to explain
❑ : CH 3 000H. on what processes the 0.6 order reaction in formic acid and 0.5 order
reaction in acetic acid are based, since the cathodic reaction is
extremely complex and the imposition of a linear Tafel region of the
polarization curve is arbitrary.
Figure 11 shows the relationship between solution pH and E., r
10 of AISI 316 SS in formic and acetic acids measured immediately after
cathodic polarization. The relationship between E corr and pH shows
a good linearity, as for SS 41 and AISI 304 SS in the previous
papers,'• 3 • 4 and is given by the following equations:

E cor ,/H000H= -0.062 pH -0.251 (V vs SCE) (1)

N 1
E c .„/CH 3 000H = -0.032 pH -0.319 (V vs SCE) (2)
E
E
However, the E corr value after 24 h from the end of cathodic
polarization was not a linear function of the pH of the solution. As
10-1 described in a previous paper, when the meta) behaves under
activation control, the relationship between E corr and pH is linear. 3
According to Pourbaix et al, the occluded cell corrosion (OCC) is the
base of pitting corrosion and intergranular corrosion (IGC) and
depends strongly on solution pH. 6 Therefore, Equations (1) and (2)
are considered to be the standards in the protection and control of
10 -2 corrosion of AISI 316 SS.

pH
FIGURE 10 - Cathodic CD vs pH of solution.
-o-: HCOOH, E=-0.500 V vs SCE
-s-: HCOOH, after 24 h from the end of reduction,
E=-0.525V vs SCE
- ❑ -: CH 3 000H, E=-0.500 V vs SCE.
attempted as in previous papers.' 35 According to the polarization
curves of AISI 316 SS in formic and acetic acids, the relationship
between the absolute value of the cathodic CD, li,l, at constant
potential and the value of solution pH is shown in Figure 10. In formic
acid, li,l at -0.500 V immediately after cathodic polarization linearly
decreases with increasing solution pH and the slope of the straight
line is 0.62. The polarization curve after 24 h from the end of cathodic
polarization was similarly analyzed. In this case, the plot of I i,l against
NEP-Immersion Time
The variation of NEP of AISI 316 SS with the immersion time in
formic and acetic acids is shown in Figures 12(a) and (b), respec-
tively. In all the concentrations of formic acid, NEP shifted to noble
potentials from - 0.3 to 0.5 V -- 1 h after immersion, and NEP was
almost stable after 5 h. In acetic acid, NEP was completely stable at
+0.15 V after 18 h. Such a remarkable shift of NEP toward noble
potentials is indicative of the formation of passive film. When the
potential after the shift is compared to Figures 4(a) through 6 (b), the
potential corresponds to the one in the passive region where Cr is
mainly participating in passivity. Consequently, AISI 316 SS would
become passive in a comparatively short time. The time to shift to the
stable potential is shorter in formic acid than in acetic acid because
the shift to the passive region is faster in the former than in the laffer.
Impedance Measurements
A complex impedance plane plot of AISI 316 SS/HCOOH
measured at E er , at RT in 90% formic acid is shown in Figure 13(a).
Other measurements were also conducted in 20 and 100% formic
acid, and these loci were much the same as in 90% formic acid, so

558 CORROSION—NACE


100
99.5%
0.2 80
w
U
0.
i
50 60
> 0

a 40
w ^` o
-0, 2 0.3
20

0-0,4
r• `

0 5 10 15 20 25 0 20 40 60 80 100 120 140

a Rs/Kn
a Time / h
100

x 5h
80 0.005
17 o
w
L)
60 24 -^-
^í
L)
40
-0,i
a 0.06
w 0.3
20 2

-0.k
0
0 20 40 60 80 100 120 140
b Rs/Kn
-0.E
FIGURE 13 — Complex impedance plane plot of AISI 316
SS/HCOOH + 0.5 M HCOOK (frequencies in Hz): (a) 90%
b Time / h
(b) change by immersion time in 20%.

FIGURE 12 — NEP of AISI 316 SS vs immersion time: (a)

HCOOH + 0.5 M HCOOK (b) CH 3 000H + 0.5 M CH 3 COOK.
TABLE 5 — Resistance of the Electric Charge Transfer and
Double Layer Capacity in AISI 316 SS/HCOOH + 0.5M HCOOK
and AISI 316 SS/CH 3 i000H + 0.5 M CH 3 iCOOK
they are not shown. In the high-frequency region, the locus of the
circular arc is seen to be part of a semicircle whose center is shifted HCOOH CH3000H
under the real axis. This part of the semicircle corresponds to the
process of electric charge transfer, and the resistance of corrosion Concentration vol% 20 90 99.5 30 80 99.96
0/K 44.0 44.0 51.0 17.5 114 355
reaction, 0, was obtained from the diameter. In the lower-frequency C d ,/µF cm ` 115 115 49.7 289 44.4 14.3
region, the locus is seen to show the existence of an adsorptive
intermediate, [M(HCOO) R ,] ad or [M(OH) n ] ad , on the surface of AISI
316 SS.
Figure 13(b) shows the variation of impedance with immersion
Table 5 shows the values of 0 and the electric double layer
time in 20% formic acid. Although 5, 17, and 24 h had passed, no
capacitance,C di , obtained from Figures 13 (a), (b), and 14 for each
change was observed in the high-frequency region, but the semicir-
concentration of formic and acetic acids as was done previously. 2
cle showing the capacitive arc in the lower-frequency region became
Comparing aqueous and nonaqueous solutions, 0 values in the
gradually smaller, which shows that the state of adsorptive interme-
nonaqueous system were larger than those for the aqueous system.
diate changes with time, probably resulting from the formation of
However, the C d , values were smaller. Consequently, it is considered
meta) formate. From the fact that the arc did not change in the
that the corrosion rate in nonaqueous solution is smaller than in
high-frequency region, it is assumed that the corrosion rate of AISI
aqueous solution and the surface roughness of steel also decreases.
316 SS hardly changes after 5 h of immersion in 20% formic acid.
However, in the case of formic acid, since all the values of 0 are
Figure 14 shows the complex impedance plane plot AISI 316
similar, the corrosion rate of AISI 316 SS in nonaqueous solution is
SS/CH 3 000H measured after 24 h from the end of cathodic
not much different from that in aqueous solution in 5 h after
polarization at RT and after a stable NEP. The same locus as that for
immersion. This is consistent with the fact that the values of i corr ,
formic acid appeared. It is, therefore, considered that the part of the
obtained from polarization curves after 24 h from the end of cathodic
semicircle in the high-frequency region corresponds to the process of
polarization are almost the same in all concentrations of formic acid
electric charge transfer, and the locus in the, lower-frequency region
(Figure 8).
shows the existence of an adsorptive intermediate, [M(CH 3 000) m] ad
Thus, from the corrosion rate standpoint, AISI 316 SS generally
or [M(OH)„] ad , on the surface of AISI 316 SS. The resistance of the
corroded more easily in formic acid than in acetic acid, as reported in
corrosion reaction, 0, obtained from the diameter of the semicircle in
previous papers.' -4 This is considered to result from the strength of
the high-frequency region was compared with the weight loss value
the acid. However, in the corrosion weight loss test at RT, the
and i rr The value of 0 is 17.5 k (Z at 30%, 114 k f at 80% and 355
corrosion rate is higher in acetic acid than in formic acid. It is also
k fl at 100%, and these values agree with the trend in the values of
considered that the difference of immersion time is important and that
corrosion weight loss and i corr .

Vol. 43, September 1987 559

 50
S 0.01
U) 0.5
0 depended on acid concentration and temperature.
0 50 100
Rs / Kn
100 .01 80%
C
0.4
50
L)
3 6. According to the variation of NEP with time and the anodic
60
n material was easily passivated by the Mo present, and the effect was
0 50 100 150 200
Rs / Kn
500
0.04 99,96%
C
Y 7. E co, r of AISI 316 SS immediately after cathodic polarization
0.3
U
ru
0 500 1000
Rs / Kn
FIGURE 14 - Complex impedance plane plot of AISI 316
SS/CH 3000H + 0.5 M CH 3 COOK (frequencies in Hz).
passivation is easier in formic acid, as seen from the variation of NEP
with time. However, since the weight loss at RT is very small, ^-
10 -4 g, the error in measurement is large. Therefore, these data are
useful in following the trends of corrosion in each solution rather than
to rigorously compare the behavior in formic and acetic acids.
From the corrosion mechanism standpoint, the polarization
curves in formic and acetic acids show that Cr mainly contributes to
the corrosion resistance in conjunction with Mo. The results of the
surface analysis show that the ratio of Cr is larger on the surface of
steel in acetic acid as in the case of the polarization curve, but in
formic acid, the ratio of Mo and Ni is much larger than that of Cr which
is not consistent with the polarization results. Since the polarization
measurements were conducted at RT and the surface analysis was
performed on specimens after immersion in boiling solution, the
difference between the results of polarization and surface analyses in
formic acid could be caused by the difference in temperature. Hence,
it is assumed that the polarization behavior at the boiling point is
similar to that at RT in acetic acid, but that the polarization behavior
in formic acid changes at the boiling point. Further study is required
to clarify the polarization behavior at the boiling point.
560 CORROSION—NACE
Conclusions
Corrosion behavior of AISI 316 SS in formic and acetic acids
was investigated and the following conclusions were obtained:
1. The corrosion rate of AISI 316 SS depended on immersion
time in formic acid.
2. The corrosion rate of AISI 316 SS in formic and acetic acids
was larger in aqueous solution than in nonaqueous solution, and the
corrosion behavior was different.
3. The corrosion rate of AISI 316 SS in formic and acetic acids
4. It was found that AISI 316 SS had sufficient corrosion
resistance at RT in each acid, and it had resistance, except in 50%
formic acid at the boiling point.
5. As for the corrosion behavior of AISI 316 SS in low
concentration of acetic acid, the trend of corrosion weight loss vs
concentration was similar to that of i corr vs concentration from
polarization measurement and 0 vs concentration from impedance
measurements. These trends were also similar to that of conductivity
vs concentration of acetic acid solution.
polarization characteristics of AISI 316 SS, it was found that this
more apparent in formic acid than in acetic acid. In addition, it was
recognized that in each aqueous solution, primarily Cr, Mo, and some
Ni contributed to the corrosion resistance; in nonaqueous formic acid,
mainly Cr, Mo, and Fe contributed to the corrosion resistance; in
nonaqueous acetic acid, primarily Cr and some Mo contributed to
passivity.
was linearly related to solution pH, and the equations below were
obtained:
E co „/HCOOH = -0.062 pH -0.251 (V vs SCE) E co „/CH 3 000H =
-0.032 pH -0.319 (V vs SCE)
8. In impedance measurements of AISI 316 SS, capacitive loci
were obtained in the lower-frequency region, and these loci showed
the existence of an adsorptive intermediate, [M(HCOO)m]ad or
[M(OH)„] ad in formic acid and [M(CH 3 000) m l ad or [M(OH„)] ad in
acetic acid.
9. From the results of surface analysis, the passive film of AISI
316 SS was supposed to be formed by the coexistence of Mo and Cu
in aqueous formic acid, the coexistence of Mo and Ni in nonaqueous
formic acid and the coexistence of Cr and Fe in 50% acetic acid. In
90% acetic acid, it was considered that selective corrosion did not
occur.
Acknowledgment
The authors wish to thank Mr. T. Takeuchi of Nisshin Steel Co.
for the surface analyses.
References
1. I. Sekine, A. Chinda, Boshoku Gijutsu (Corrosion Engineer-
ing), Vol. 31, p. 313, 1982.
2. I. Sekine, A. Chinda, Corrosion, Vol. 40, No. 3, p. 95, 1984.
3. I. Sekine, K. Senoo, Corros. Sci., Vol. 24, p. 439, 1984.
4. I. Sekine, M. Koeda, Boshoku Gijutsu (Corrosion Engineering),
Vol. 33, p. 500, 1984.
5. E.J. Kelly, J. Electrochem. Soc., Vol. 112, p. 124, 1965.
6. W. Yang, R. Ni, H. Hua, A. Pourbaix, Corros. Sci., Vol. 24, p.
691, 1984.