Corrosion

Pergamon

Science, Vol. 37, No. 6, pp. 1005-1019, 1995

Copyright 0 1995 Elsevier Science Ltd
Printed in Great Britain. All rights reserved
001@938X/95 $9.50+0.00

0010-938x(95)00010-0

THE ROLE OF METAL CATIONS IN IMPROVING

THE
INHIBITIVE
PERFORMANCE
OF HEXAMINE
ON THE
CORROSION
OF STEEL IN HYDROCHLORIC
ACID
SOLUTION
D. D. N. SINGH,
Corrosion

Protection

Division,

National

T. B. SINGH
Metallurgical

and B. GAUR

Laboratory,

Jamshedpur

- 831007, India

Abstract-Hexamethylenetctramine
(HA) or hexamine (or urotropin)
have a moderate inhibitive effect
on the corrosion of mild steel in concentrated
acid solution (3N) but have a negligible effect in very dilute
solutions
(N/200) of the acid. Incorporation
of Cu*, As3+, Sd
and Sn*+ with HA improves
its
performance,
which is synergistic
in nature.
These additives
(except As),
however,
exhibit an
effect in
antagonistic
effect when tested in dilute acid solutions. Cu* and As3 have the most pronounced
3N acid solution. In N/200 HCI solution, the antagonistic
effect is a maximum in the case of St? followed
by Sn*+ and CU*+ cations. Weight-loss, electrochemical
polarization
and zeta potential measurements
are
performed
to understand
the mechanism
of action of these inhibitors.
The positive role played by the
cations on the inhibitive performance
of HA is due to the formation of anionic complexes with the chloride
ions of the acid solution. These anions replace the adsorbed
chloride ion from the metal-electrolyte
interface owing to their higher affinity toward the interface and help the protonized molecule of HA to bc
adsorbed more strongly at the interface. Accumulation
of FeCI, in concentrated
acid solution lowers the
performance
of HA to a greater extent (about 100 times) than HA blended with Cu*+. The latter
composition
also has a substantially
stronger inhibitive role on hydrogen absorption
by the steel than the
former one.

INTRODUCTION
It is now well established
that the use of hydrochloric
acid in pickling of metals,
acidization
of oil wells and in cleaning of scales is more economical,
efficient and
trouble-free,
compared to other mineral acids. ~4 The great advantage of this acid
over the other acids in cleaning and pickling operations lies in its ability to form metal
chlorides
which are extremely
soluble in aqueous
phase, compared
to sulfate,
nitrate, phosphate,
etc. This higher rate of solubility of chloride salts causes the least
polarizing effect and does not hamper the rate of reaction. Some salts, e.g. FeCl,,
produced as a result of the reaction of scales and acid, have a depolarizing
effect on
the reaction rate and make the acid solution extremely aggressive towards the base
metal. To control this depolarizing
effect of metal salts and also the attack of the acid
on the base metal surface, the use of efficient inhibitors in hydrochloric
acid solutions
during the above operations is essential. In acid solutions, the iron surface acquires a
positive charge (the zero charge potential of iron in aqueous acid solutions varies
from -0.4 V to -0.7 V).5.6 This indicates that an inhibitor
capable of providing
anionic species in the solution should be a good inhibitor for the system. The chloride
ion of hydrochloric
acid is adsorbed strongly on the metal surface and makes a
Manuscript

received

18 October

1994.
1005

1006

D. D. N. Singh, T. B. Singh and B.

Gaur

negatively-charged
double layer. Cationic types of species in the solution have a
tendency
to interact with this double layer and provide corrosion inhibition
as a
result of the formation of a compact film on the surface. A literature survey reveals
that inhibitors having an amino group perform very well for the HCI-iron
system,
due to the formation of cationic species in the acid solutions:.
R-NH2

+ H+ +

R-NH,:.

Amongst the different types of amines, hexamine

is the most widely studied
compound
for the dissolution
of iron and iron-based
alloys in acid solutions.-
Its
molecule acquires a positive charge in acid solutions and has a moderate inhibitive
effect on the corrosion of steel in hydrochloric
acid. The theory of synergism on
corrosion inhibition
indicates that the performance
of hexamine can be improved if
surfactants
having an anionic effect at the interface are introduced
with the former
one in the acid solutions. Organic anionic surfactants are quite effective in improving
the performance
of inhibitors.
but owing to their higher costs, a higher degree of
concentrations
is required
(to achieve satisfactory
inhibition),
and their other
effects, which complicate further processing of either metal surface or the electrolyte, have necessitated
a search for inorganic cations which can produce anionic
species in the acid solutions and could achieve synergism with the amines. These ions
are less expensive and produce appreciable
effects on corrosion inhibition
even if
used at very low concentrations.
This paper describes the use of copper, arsenic,
antimony
and tin, in their chloride forms, as sources of anionic species, in combination with hexamine to control the dissolution of steels in hydrochloric
acid under
the influence of different parameters.
The same compositions
have also been studied
for their inhibitive performance
in a very dilute solution of HCI (N/200) to explore
the possibilities
of their use in acidic water. which can be used in recirculating
industrial cooling systems. The low pH water (pH = 3.54) can be used in place of
plain water. which can minimize scale formation in pipelines, and its corrosive action
can be controlled by the incorporation
of highly effective inhibitors.

EXPERIMENTAL

METHOD

Hot rolled mild steel strips were taken from a single lot and small coupons of six 7.5 x 2.5 x 0.2 cm
wcrc cut from it. These wcrc then wet ground on polishing wheel to remove the mill scale. Final polishing
was carried out at 60 grit silicon carbide abrasive paper. The samples were degreascd with acctone before
exposure to the test clcctrolytcs.
A water bath, having a tcmperaturc
sensitivity of 2 1C. was used for
weight-loss studies. Electrochemical
studies wcrc performed
using coupons, of circular arca 1 .O cm. of
the same steel. A saturated calomel electrode (SCE) and a couple of graphite rods were used as reference
and auxiliary electrodes,
rcspcctivcly.
Polarization
experiments
were performed
by using a potentiodyne
analyzer supplied by M/S Petrolyte Instruments
Co.. U.S.A.
Hydrogen absorbed by the steel during its dissolution in acid solution was dctermincd
on samples ol
size I .O x 0.5 x 0.2 cm of the same material as used for the weight-loss and elcctrochcmical
tests. The
technical details of the experimental
method arc described in earlier publications.3.
Zeta potential
measurcmcnts
wcrc performed
on iron powder (particle size 200 mesh) produced
electrochemically.
Lazer Zcc Meter Model SO1 supplied by M/S Pen Kcm, Inc., NY. U.S.A. was used for
this purpose.
AR grade HCI acid was used for the preparation
of the test electrolytes.
Dilution was made with
double distilled water. Hexaminc
and metal salts. taken in their chloride forms, were also of the AR
grade.

Improving

the inhibitive

performance

EXPERIMENTAL

of hexamine

on corrosion

1007

RESULTS

Inhibition studies in concentrated acid solutions

Determining the optimum concentration of inhibitors. Figure

1 shows the performance of HA on the corrosion of steel in 3N HCl at its different concentrations
and temperatures.
Here, it is noted that the inhibitor performs quite well at 22C and
the corrosion rate comes down to ~750 mdd when used at and above concentrations
of 300 ppm. At the elevated temperatures,
however, the inhibitive performance
of
HA deteriorates
and attains values of 2500 and 5000 mdd at 40 and 55C, respectively. At all the three temperatures
studied,
the optimum
performance
of the
inhibitor is achieved at a concentration
of 300 ppm.
To enhance the performance
of inhibitor
at its optimum concentration,
some
metal cations, i.e. Cu2+, As3+, Sb+ and Sn2+, were added with the inhibitor during
the corrosion of steel in acid solution. The results are shown in Figs 2-5. It is evident
from these figures that the copper and arsenic cations achieve a synergistic effect with
hexamine
in inhibiting
the corrosion
rate. This is more pronounced
at elevated
temperatures
(40 and 55C) than at lower temperatures.
These cations perform best
at a concentration
of 10 ppm. The effect of antimony
and tin cations is nominal
compared to copper and arsenic cations and improvement
in the inhibition efficiency
of hexamine takes place between 2.5 and 5.0 ppm of these cations.
In order to test whether the optimum concentration
determined
for the performance of hexamine changes in the presence of metal cations or not, experiments
were
performed taking different concentrations
of hexamine and a fixed concentration
(10
ppm) of cations at 55C only. The results are shown in Fig. 6. The optimum
performance
of hexamine
is still observed at a concentration
of 300 ppm. In the
presence of copper and arsenic ions, the trend is slightly accelerated,
with an increase
in hexamine
concentration
above 300 ppm. As3+ retards corrosion
rate more
of
effectively
(about 2.5 times) than Cu2+, at all the studied concentrations
hexamine.
The effect of the passage of time on the performance
of optimized (300 ppm HA

Fig. 1.

The variation

i100
200
300
400
HA concentration (ppm)

in corrosion

rate of steel in 3N HCI with concentration

of HA

1008

D. D. N. Singh, T. B. Singh and B. Gaur

300ppmHA

I
2.5

*0

I
5.0

Concentration
Fig. 2.

I
1.5

10.0

of Cu*+ (ppm)

The effect of Cu*+ on the corrosion rate of steel in 3N HCI in the presence
ppm of HA

of 300

300ppmHA

.-.3oc._

2.5
5.0
Concentration
Fig. 3.

I.5

10.0

of As3+ (ppm)

The effect of As+ on the corrosion rate of steel in 3N HCI in the presence
ppm of HA.

of 300

Improving

the inhibitive

performance

of hexamine

on corrosion

1009

300ppmHA

l-

OO
Fig. 4.

._.E._

.-.
I

5.0
2.5
Concentration

7.5
10.0
of Sb3+ (ppm)

12.5

The effect of Sb3+ on the corrosion rate of steel in 3N HCI in the presence
ppm of HA.

of 300

300ppmHA

Concentration
Fig. 5.

of Sn*+ (ppm)

The effect of Sn2+ on the corrosion rate of steel in 3N HCI in the presence
ppm of HA.

of 300

lOI

D. D. N. Singh, T. B. Singh and B. tiaur

oi
0

Fig. 6.

300
200
HA concentration (ppm)

loo

400

500

The effect of metal cations on the corrosion rate of steel in 3N HCI in the prescncc
of different concentrations
of HA.

23 C

I - 300ppmHA
2 300ppmHA
3 - 300ppmHA
4 - 300ppmHA
5 - 300ppmHA

0.25

+
+
+
+

I Oppm Cu2+
1Oppm As3+
1Oppm Sb3+
IOppm Sn2+

Time (h)
Fig. 7.

The cffcct

of time on the corrosion

rate of steel in 3N HCI in the prcscnce
optimized concentration
of the inhibitor.

of

+ 10 ppm cations) concentration

of inhibitors is shown in Fig. 7. In all the cases,
observed that the inhibitive performance
of the compositions
increases for times
to 2 h and then becomes almost constant.
A considerable
degree of change in
performance
of the inhibitors
is noted at longer durations
of the exposure

it is
up
the
for

Improving

the inhibitive

performance

of hexamine

on corrosion

1011

I-

I-

, -

'0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

FeCI, (M)
Fig. 8.

The effect of ferric chloride on the corrosion rate and hydrogen

in 3N HCI in the presence of 300 ppm HA.

absorption

of steel

inhibitor having cations and in their absence. At and above the exposure period of
1 h, for example, the inhibitor having cations inhibits the reaction rate about twice as
much as in their absence. This same factor is about 1.3 times when tested at 15 and 30
min.
The effect of ferric chloride on the performance of inhibitors. Accumulation
of
iron salt (FeCls) in acid solution takes place due to the dissolution of scale. This salt
depolarizes
the corrosion
reaction to a considerable
extent. Experiments
were,
therefore, performed to study the effect of FeCls on the corrosion rate and hydrogen
absorption
by the steel during its corrosion in the presence of the inhibitors (300 ppm
HA and 300 ppm HA + 10 ppm Cu+). Only one cation, i.e. Cu*+ , was taken up for
the study with 300 ppm of HA and the results are compared with the performance
of
HA. The observed data is plotted in Figs 8 and 9. A linear relationship
has been
noted between the molar concentration
of FeC13 and the corrosion
rate in plain
hexamine, as well as in hexamine having Cu 2+ . The rate of increase in corrosion rate
(CR) with molar concentration
of FeCl,, i.e. dcR/dlFecI~l, is markedly lower in the
case of the inhibitor fortified with Cu2+ than in the plain inhibitor (in the former case
dcnJdlreci,l = 5.24 X lo* mdd M-l, whereas for the latter, the value is 350 x lo* mdd
M-l). The hydrogen absorption
values are also considerably
less in the case of the
inhibitor boosted with Cu2+.
Adsorption characteristics of the inhibitors. In order to test the adsorption
characteristics
of the studied inhibitors,
their surface coverage at different concentrations was fitted in different adsorption isotherms. It is observed that the inhibitors
obey the Langmuir adsorption isotherm equation. Values of log 19/(1 - 13)vs log Care

1012

D. D. N. Singh, T. B. Singh and B. Gaur

0.35

0.30

_ Inhibitor: 300ppmHA

+ 1Oppm Cu*+

0.8

0.2

0.5

I
0.1

I
0.2

I
0.3

0.4

0.5

0.6

0.7

FeCI, (M)
Fig. 9.

The effect of ferric chloride

in 3N HCI in the presence

IO _

Fig. IO.

on the corrosion rate and hydrogen absorption

of optimized concentration
of the inhibitor.

of steel

HA
10% HCl

Plots of adsorption

isotherm

for HA in 3N HCI at different

studied tcmperaturcs.

plotted in Figs 10-12. Here, 8 is the fraction of surface covered by the inhibitor,
whereas (1 - 0) is the bare surface which acts as a site for corrosion reactions to
proceed and C is the molar concentration
of inhibitors.
Electrochemicalstudies.
The polarization
studies were performed in the presence
of different combinations
of the inhibitors in 3N HCI solution and the plots are shown
in Figs 13 and 14. It is noted from these figures that the presence
of HA in
concentrated
HCI solution has no greater appreciable
effect on the anodic and

Improving

the inhibitive

performance

of hexamine

on corrosion

1013

IO-

.^

log 0
Fig. 11.

Plots of adsorption

isotherm

for cations

having 300 ppm HA in 3N HCI at 23C

for cations

having 300 ppm HA in 3N HCI at 40C

100

Temperature

40 C

300ppmHA
S
L
2
5

Fig. 12.

Plots of adsorption

isotherm

cathodic slopes than on the control plot. The presence of Cu2+, As3+, Sb3+ and
affected the plots. Amongst the additives studied,
Sn2+, however, has considerably
the presence of CL?+ with HA has the maximum influence on the anodic curve,
followed by Sb3+ and Sn+. The cathodic curve in the presence of Cu*+, however, is
not changed at all. The cathodic plots in the presence of Sb3+, Sn*+ and As3 are
considerably
polarized.
Inhibition studies in dilute acid solution
Weight-loss studies. Weight-loss corrosion data of steel exposed in N/200 HCl in
the presence of different inhibitors are shown in Table 1. Due to the very slow rate of

1014

D. D. N. Singh, T. B. Singh and B. Gaur

0

-075 -

10-3

10-2

10-l

IO

102

IO

c.d. (mA cm-*)

Fig. 13.

Electrochemical

polarization
plots of steel in BN HCI in the prcscncc
300 ppm HA with control (in blank).

of 100 and

-0.25 -

-0.50 E
9
4
-0.75 -

-l.Oo-

10-S

10-J

10-3

10-2

10-I

IO

102

c-d. (mA cm-)

Fig. 14.

Electrochemical

polarization
plots of steel in 3N HCI in the prescncc
HA having different cations.

of 300 ppm

Improving

the inhibitive

performance

of hexamine

on corrosion

1015

Table 1. The corrosion rate of mild steel and the zeta potential of the iron
particles in N/200 HCI solution in the absence and presence of different
inhibitors at 29C

S. No.

Solution
composition

1
2
3
4
5
6
7

Blank (b)
b + 100 ppm HA
b + 300 ppm HA (c)
c + 10 ppm Cu2+
c + 10 ppm As+
c + 10 ppm Sn2+
c + 10 ppm Sb+
:Derived

from a 72 h exposure

Corrosion rate?
(mdd x 102)

Zeta potential

10.6
9.6
9.2
11.3
7.2
16.6
42.8

-10
-35
-40
-16
-35
-35
-35

(mv)

test.

attack of the electrolyte on the steel surface, the experiments

were performed for an
exposure period of 72 h. In contrast to its role in concentrated
acid solution, HA
exhibits very poor inhibition
in this case. HA, in combinations
of all the cations
except As?, has a rather accelerating
effect on the corrosion of steel. Amongst the
cations studied, Sb+ has the highest rate of acceleration,
followed by Sn2+ and
cu2+.

Zetapotential measurement. The peculiar results observed for the performance of

different inhibitors on the corrosion of steel in dilute HCI solution led to a study of
their inhibitive nature in detail. The zeta potential studies, which are generally useful
for study of the surface charges on the minerals suspended in a fluid, were performed
for the particles of iron (iron powder of 200 mesh) suspended in N/200 HCI having
different inhibitors. In these studies, since the experiments
were performed within l2 min of exposure of the iron particle in acid solution and also due to an extremely
slow rate of attack of electrolyte on the metal surface, the shapes of the iron particles
were taken as unchanged
during the experimentation.
The measured values of zeta
potential are summarized
in Table 1. It is seen from this table that the values of zeta
potential on the iron particle exposed to N/200 HCI solution (pH = 3.5) is negative
(- 10 mV). A negative value of zeta potential is expected for this system owing to the
strong adsorption of chloride ion in the ionic sphere of the particle in the solution. On
the addition of 100 ppm HA in the bath, the zeta potential jumps to a more negative
value (-35 mV). On increasing the concentration
of HA (300 ppm), the value shifted
towards the negative direction.
The addition of Cu2+ with HA, however, brings
down the potential
to a lower negative value (-16 mV), very close to the blank
solution where no inhibitor was present. A similar trend is noted for Sn2+ and Sb3+
also and the values are very close to that observed for Cu+. In the case of As3+,
however, the particles retain their potential to a more negative value as noted for HA
alone.
Electrochemical studies. The open circuit potential-time
plot for the steel
exposed in different compositions
of inhibitors and in their absence are shown in Fig.
15. In all the cases, it is noted that the potentials shift in the active direction with the

1016

D. D. N. Singh, T. B. Singh and B. Gaur

Time (minj3
Fig. 15.

Potential-time

plots for steel in N/200 HCI in the presence

sitions of inhibitors.

.--------_._-_-0.25

. --

-0.75

3WppmHA+

10ppmAs3+

300ppmHA

+ 1Oppm Cu2+

300ppmHA

+ 1Oppm Sb

300ppmHA

+ 1Oppm Sn2+

of different

compo

100 and 300ppmHA

---

Control

10-I

10

cd. (mA cm-)

Fig. 16.

Electrochemical

polarization
behaviour
of steel in N/200 HCI solution
different inhibitors.

having

passage of time. HA shows the highest negative value of stabilized potential followed
by Cu2+, control and A?+.
The cathodic and anodic polarization
curves in the presence of different compositions of the inhibitors
are shown in Fig. 16. The plots for Sb3+ and Sn2+ are not

Improving

the inhibitive

performance

of hexamine

on

corrosion

1017

included here to avoid crowding. Their trends were also observed to be similar to
Cu2+. In the presence of HA, the cathodic curves are polarized to a greater extent
than the controlled
one, especially
near to the corrosion
potential.
The anodic
curves, on the other hand, in the presence of HA, are depolarized
near the corrosion
potential. The overall corrosion, however, is found to be decreased although not to a
considerable
extent.
the attack and is manifested
with
The addition of Cu2+ with HA accelerates
anodic as well as with cathodic curves. The presence of As3+, on the other hand, has
a strong polarizing effect on anodic reactions.

DISCUSSION
An iron surface attains a positive charge in aqueous acid solutions as its potential
of zero charge varies between
-0.4 and -0.7 V (SCE).5*6 Owing to the strong
anionic component
of HCl, the double layer acquires the negative charge and
cationic type of inhibitors are, therefore, found to provide good inhibition for iron in
acid solutions.
HA forms a quaternary
type of compound when added in the acid solution:
+

I
N

\
I&

CH2
\

CH,
\
N-CH2-NH

C/H,

[W

:.H2

Due to the formation of a cationic surfactant in the solution, HA is expected to

inhibit
the corrosion
cathodically.
This is indeed
reported
by many other
investigators.9--2
To understand
the role of different inhibitors in inhibiting the corrosion of steel in
HCl solution, the following scheme is considered for the adsorption
of HA:

ElElElElEl-

protonized

ooooo+++++t---

chloride

HA
ion adsorbed

steel surface

Adsorbed
chloride ion on the positively charged steel surface acts as a bridge
between the metal surface and the electrolyte
for the adsorption
of the protonized
HA molecule.
The presence of a more densely populated
interface with anionic
species is expected to provide a higher degree of inhibition
to HA according to the
above scheme. This has indeed been observed in the study where an increase in the

1018

D. D. N. Singh, T. B. Singh and B. Gaur

-x_ -.-

HA + NaCl

J___L__-l-_-L2.5
5.0
1.5
NaCl in 3N HCl (%)

I
---

Fig. 17. The variation

HAalone
-

0.3

2.0

4.0
6.0
8.0
Concentration of HCI (N)

in the performance
of inhibitors
trations of HCI and NaCI.

10.0

10.0

for steels

.O

at different

conccn-

concentration
of HCI enhances the inhibitive performance
of HA (Fig. 17). Incorporation of NaCl in 3N HCl having 300 ppm hexamine also enhances its performance. This theory is further supported by the observation
on the performance
of the
inhibitor
in extremely
dilute HCl solution
(N/200), where an almost negligible
inhibitive effect has been noted (Table 1).
The enhanced inhibitive effect of HA in the presence of metal cations (in 3N HCI)
can be explained
by considering
the ionic species formed in concentrated
acid
solutions. In strongly acidic chloride environments,
the copper cation forms species
of the type CuCl, 2- . Such types of anionic species are more surface active and can
cover more surface area on the interface compared to the chloride ion alone. Such
types of adsorbed species are also expected to facilitate the adsorption of protonized
HA to a greater extent on the metal/electrolyte
interface than the chloride ion.
Though there is no reference available in the literature on the combined effect of
metal cations with HA on the corrosion of steel, some authors have reported an
improvement
in the inhibitive
performance
of HA in combination
with certain
anions, such as Cl-, Br , I-, CNS and sulfonates, on the corrosion of steel in acidic
solutions.6.7
The improved performance
of HA in combination
with Asa+ may be
ascribed to the formation of anionic species AsO; in the acidic solution. This anion,
like CuClzP, is expected to enhance the adsorption
of HA+ at the interface of the
corroding
metal. Sb+ and Sn 2+ in the acid solution also enhance the protection
properties of HA and their beneficial effects can also be explained as described above
for Cu2+ and Asa+.
The adverse effect of the studied metal cations on the inhibitive performance
of
HA in dilute acid solution is quite an interesting
phenomenon.
HA has a negligible
effect in diluted acid solution (Table 1). This is probably owing to the inability of HA
to form cationic species in dilute acid solution.
Due to the presence of a weak
negatively
charged interface,
the HA molecule adsorbs on the metal-electrolyte
interface though the lone pair of unshared electrons available at the nitrogen atom of

Improving

the inhibitive

performance

of hexamine

1019

on corrosion

HA and, thus, increases the negative charge of the interface. This is also manifested
by the zeta potential value. In the absence of any additive, the zeta potential value of
the iron particle is -10 mV, which jumps to -35 mV on the addition of HA in the
electrolyte.
The addition of copper cation in the presence of HA replaces the latter
from the interface and may deposit at the metal surface on cathodic sites. This brings
down the zeta potential value (- 16 mV) of the particle. In the case of Sn2+ and Sb3+,
no change in zeta potential takes place, indicating that they are not reduced at the
metal surface and remain in the solution to act as strong depolarizers
of the reaction.
Unlike the other three cations, As3+ shows an inhibitive effect with HA in dilute acid
solution. This is probably owing to the amphoteric nature of arsenious acid (HAs02)
which provides AsO+ and AsO; in the acidic solutions.
AsO+ is reduced at the
cathode to deposit as a neutral arsenic atom on the surface:
AsO+

+ 2Hf

+ 3e- +

As + H,O

Deposited arsenic on the surface increases the cathodic overvoltage and provides
the inhibition
effect. Deposition
of neutral arsenic metal on the surface is further
manifested
from the zeta potential
value. The value of zeta potential of the iron
particle exposed in solution having 300 ppm HA does not change after the addition of
As3+ in the solution (in both cases the value is -35 mV). It is to be noted here that the
inhibition caused due to the As3+ in dilute acid solution is solely due to the deposition
of arsenic metal on the surface and HA has neither an additive nor synergistic effect
on it.
Acknowledgemenr-The
National Metallurgical

authors
Laboratory,

express their thanks to Prof. P. Ramchandra

Rao,
for granting the permission to publish this work.

the

Director,

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Zashch. Me&l. 16, 735 (1980).
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Metallurgiya. Moscow (1971).
R. M. Hudson and C. J. Warning, Sheet Metal Industries 44, 544 (1967).
E. 0. Ayazyan, Dokl. Akad. Nank SSSR, 100,473 (1955).
V. V. Batrakov and N. I. Nanmova,
Electrokhim 15.551 (1979).
A. H. Roebuck and T. R. Pritchett, Mafer. Prof. 5, 16 (1966).
Z. A. lofa and F. L. Kam, Zashch. Merull. 10, 17 (1974).
L. B. Kirilyuk, 1. U. Titakova,
I. L. Korsunskay
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