Materials Science. Vol. 33, No.

3, 1997

EFFECT OF PYROPHOSPHATE-POLYPHOSPHATE INHIBITORS ON THE

PROCESSES OF CORROSION AND SALT DEPOSITION IN AQUEOUS SYSTEMS

H. M. Nykyforchyn, Z. V. Slobodyan, and D.M. Zaverbnyi UDC620.197.3

The efficiency and mechanisms of the protective action of a new modification of the KORSOL-l M inhi-
bitor are studied for 20 and KhI8NIOT steels in water with different values of hardness at different tem-
peratures. It is shown that, as a result of the formation of a quasiamorphous film, the inhibiting compo-
sition suppresses both the cathode and anode reactions and, therefore, is characterized by the complex
mechanism of protection. At elevated temperatures, the protective properties of the inhibitor become
somewhat weaker but remain satisfactory for practical applications. In distilled water, the rate of corro-
sion of 20 steel increases in the presence of the composition. At the same time, for Kh 18N10T steel, the
rate of corrosion decreases due to the formation of the passivating f'tlm. In water with medium hardness,
the protective properties of the inhibitor for stainless steel become weaker. The action of inhibiting
composition is characterized by the presence of the aftereffect.

An increasing demand for relatively inexpensive fresh water requires the intensification o f the use o f water-re-
circulation systems and circuits with restricted losses for blowing and additional feeding. However, under these
conditions, the salt content of the heat carrier readily increases, which makes it more aggressive and intensifies the
process of salt deposition, which, in turn, deteriorates the heat-exchange characteristics of equipment. As one of the
most promising approaches to the solution of this problem, one can mention the application of inhibitors with com-
plex action which suppress both corrosion processes and the process of salt deposition. In the collection of inhibi-
tors of this sort, special attention should be paid to organophosphorus compounds such as derivatives of phosphates,
pyrophosphates, phosphonates, and polyphosphates. Thus, in particular, phosphonates are, probably, the best inhibi-
tors of salt deposition but their efficiency as inhibitors of corrosion is weak [ I, 2]. The compositions based on poly-
phosphates are sufficiently effective inhibitors of the corrosion o f steel and the process of salt deposition. Indeed,
the KORSOL inhibitor based on pyro- and polyphosphates and developed somewhat earlier is now extensively used
for the protection of water-recirculation systems [3, 4]. However, at elevated temperatures (60-80~ its protec-
tive abilities become much weaker. Moreover, it exhibits good protective abilities only within a fairly narrow range
of concentrations of calcium ions (below 1.5 g/m3). We expect that admixtures introduced in a new modification of
this inhibitor (KORSOL-IM) would improve its quality and guarantee the efficient protection o f structural steels
against corrosion and salt deposition in water with various values of hardness.
In the present work, we investigate the mechanism and efficiency of the action of the KORSOL-1M inhibitor in
distilled water as well as in model and natural versatile hardness water ( H ) at temperatures T = 20, 60, and 80~
for 20 and K h I 8 N 1 0 T steels. The total rate of corrosion W and the rates of deposition of corrosion products P and
salts S were measured gravimetrically [5]. The mechanism of the protective action of the inhibiting composition
was studied by using the potentiodynamic and impedance methods with a P2857M potentiostat and a R5021 ac bri-
dge in the four-electrode scheme. For 20 steel, we averaged the results of three measurements and, for Khl 8N 10T
steel, the number of measurements was equal to six because, in the last case, the polarization currents are weaker.
The structure of protective films was studied on a URS-55 roentgenograph. Their chemical compositions were stu-
died with a P2S-3 diffraction spectrograph equipped with an LMAI microanalyzer.

I n h i b i t o r Protection of 20 Steel

It was discovered that the protective efficiency of the composition in water with various concentrations of salts
is maximum if the concentration of the composition C is equal to 200 g / m 3 As C increases further, the efficiency

Karpenko Physicomechanical Institute, Ukrainian Academy of Sciences, L'viv. Translated from Fizyko-Khimichna Mekhanika Materialiv.
Vol. 33, No. 3, pp. 87-96, May-June, 1997. Original article submitted February 3, 1997.

346 1068-820X/97/3303-0346 $18.00 9 1998 PlenumPublishing Corporation

 EFFECT OF PYROPHOSPIIATE-POLYPHOSPHATE INHIBITORS ON THE PROCESSES OF CORROSION AND SALT DEPOSITION 347

of protection remains practically constant. In soft water (H = 0.6 g-eq/m3), the degrees of protection against cor-
rosion Z and salt deposition K for the maximum concentration of the composition of 200g/m 3 are not higher
than 68.0% and 58.0%, respectively.

Table 1. Rates of Corrosion and Salt Deposition for 20 Steel in Water with and without Inhibitors
(for a Concentration of the Inhibitor of 200 g/m 3)

W, mg/(m2-h) S, mg/(m 2- day)

H,
T, ~ Z,% K,%
g-eq/m 3 without with without with
inhibitor inhibitor inhibitor inhibitor

3.6 20 780 90 89.0 210 22 87.0

60 1700 310 82.0 280 40 85.0

80 3700 780 81.0 300 52 82.0

5.6 20 7800 800 90.0 260 30 87.1

60 1700 310 81.4 310 42 86.2

80 3600 700 80.0 350 60 83.3

9.0 20 300 30 92.4 350 30 91.4

60 700 110 84.5 250 30 88.1

80 900 150 83.1 470 70 85.1

In water with medium and high hardness (H --- 5.6 and 9.0 g-eq/m3), for the same concentration of the com-
position, the degree of protection against corrosion Z was equal to 90.0 and 92.4% and the degree of protection
against salt deposition K was equal to 87.l and 91.4%, respectively (T = 20~ see Table 1). As the tempera-
ture of water with medium hardness increases to 80~ the value of Z decreases by 9% and the value of K de-
creases by 4%. In hard water, under the same conditions, this effect is even stronger, namely, 11% for Z and 6%
for K. Thus, as the temperature of heat cartier increases, the protective abilities of the composition become weaker
and this effect is more pronounced in hard water. However, it should be noted that the absolute values of these
quantities for hard water remain higher than for water of medium hardness. For the optimal concentration of the in-
hibiting composition, the protective abilities are preserved if reduce the salt content of water to a total hardness H
of 3.6 g-eq/m 3. As compared with water of higher hardness, the corrosion rate practically does not increase, al-
though the rate of salt deposition decreases.
On the surface of steel held in versatile hardness water without inhibitors, we observe the formation of a tWO-
layer film formed by corrosion products and salt deposits. (The upper layer of this film can easily be scraped off
with a scalpel, whereas the lower one is more dense and it is much more difficult to remove it.) In the external and
internal layers, we observe strips of different nature and crystalline structures embedded in these strips. The acid so-
lution formed in the process of etching of this film was analyzed for anions by the method of qualitative reactions.
We revealed the presence of CO32- and SiO]-ions and traces of pO34- and S O ] - i o n s .
The laser microspectral analysis of the film demonstrates that its main components are calcium and iron. The
amounts of magnesium, manganese, silicon, and aluminum are lower by an order of magnitude.
 348 It. M. NYKYFORCHYN, Z. V. SLOBODYAN, AND D. M. ZAVERBNY!

10 2

to' "::::'/ J

10 -I
!:?
9, it, .! / ,.,

10 .2
-800 -400 0 E, mV + 4 0 0

Fig. I. Potentiodynamic polarization curves of 20 steel in medium-hardness water (H = 5.6g-eq/m 3, T = 20~(1) without inhibitors,
(2) on holding in water for 24h, and in the presence of the KORSOL-IM inhibitor with (3) C = 4 0 g / m 3, (4) 100g/m 3,
(5) 200g/m 3.

Table 2. Rates of Corrosion and Deposition of Corrosion Products for 20 Steel in Distilled Water
(for a Concentration of the Inhibitor of 200 g/m 3)

W, mg/(m 2- h) P, mg/(mZ-h)
T, ~
without inhibitor I with inhibitor without inhibitor with inhibitor

20 490 1300 150 47

60 1900 2800 76 120

80 3700 3300 170 180

In inhibited water [with the optimal concentration of the inhibitor (C = 200 g/m3)], we observe the formation
of a transparent film (similar to annealing colors). As temperature increases, this film becomes opaque and the cor-
rosion rate decreases by an order of magnitude.
The X-ray diffraction analysis of protective films formed on the steel surface as a result of the action of the in-
hibiting composition did not reveal any lines which may serve as an indication of the crystalline structure. This en-
ables us to conclude that the structure of protective films formed in inhibited water is quasiamorphous. The laser
microspectral analysis detects the presence of calcium and iron in these films.
For all selected temperatures, in the range of concentrations 40-200 g / m 3, the inhibiting composition KOR-
SOL-IM increases the rate of corrosion of 20 steel in distilled water (Table 2).
EFFECT OF PYROPHOSPHATE-POLYPHOSPIIATE I N H I B I T O R S ON T H E PROCESSES OF CORROSION AND S A L T D E P O S I T I O N 349

60 " S g--4

50
\

~ 40

l/l/
20 : k.-A-~-~.

10

1 9 .t m i ....

-500 0 +500 ~ mV

Fig. 2. Dependence of the capacitance of electric double layer Cd, on the potential of 20 steel in water (H = 5.6 g-eq/m 3, T = 20~
(1) without inhibitor, (2) on holding for 24h in water, and in the presence of the KORSOL-IM inhibitor with (3) C = 4 0 g / m 3,
(4) 100g/m 3, (5) 2 0 0 g / m 3.

1 02 ~..__-1

i01 -
t

,o o ] _

10 q -

I 0 .2 ' ' '

-800 -400 0 +400
E, mV

Fig. 3. Potentiodynamic polarization curves of 20 steel in distilled and medium-hardness waters ( H = 3.6g-eq/m 3, T = 20~
(1) dis-
tilled water. (2)KORSOL-IM inhibitor with C = 4 0 g / m 3, (3) 200g/m 3, (4)medium-hardness water, (5) KORSOL-IM inhibi-
tor with C = 200 g / m 3.
350 H . M . NYKYFORCHYN, Z. W. SLOBODYAN, AND D. M. ZAVERBNYI

1.4 - 1 J 140"
F 1 2 314 5

r
1.2

1.0 ~
/,///,
. ;/ ! !

i
I ..

~ ~"--"--'--'-
12 120

10 100

/127
0.4 4

0.2 - ~ - - , - ~ - - ' / - ] ~ 2 20

0.0 ' ' ' 0

-500 0 + 5 0 0 k~ mV

Fig. 4. Dependences of the capacitance of electric double layer C,a on the potential of the electrode in distilled water and in medium-
hardness water (H = 3.6g--eq/m 3, T = 20~ in the presence of the inhibiting composition: (1) distilled water, (2) KORSOL-IM
inhibitor with C = 4 0 g / m 3, (3) 200g/m 3, (4)medium-hardness water, (5) KORSOL-IM inhibitor with C = 2 0 0 g / m 3. Right-
hand scales: (*) normal arrow and (**) double arrows.

As the concentration of the composition decreases, we observe an insignificant deceleration of the processes of
corrosion and deposition of corrosion products. A quasiamorphous film of corrosion products is formed on the sur-
face of the specimen and becomes thicker as temperature increases.
The polarization characteristics were measured from the stationary potential Est. The period of time required
for the establishment of this potential is 30 min. The stationary potential of an electrode made of 20 steel does not
change on holding in medium-hardness water (H = 5.6 g-eq/m 3) for 24 h. Moreover, the polarization curves
plotted for these two cases almost coincide (.Fig. I, curves 1 and 2), which means that the conditions under which the
corrosion processes run in these cases are similar. The inhibition of water decreases the corrosion current which at-
tains its minimum icor = 320 m A i m 2 at 200 g / m 3 (Fig. 1, curve 5). In this case, the stationary potential of the elec-
trode Est shifts to the positive side but the dependence of this shift on the concentration of the composition is not
monotonic. This type of behavior of the stationary potential as a function of the concentration indicates that the in-
fluence of the composition on the cathodic and anodic processes is ambiguous. At the same time, it is clear that the
anodic process is inhibited stronger than the cathodic process. This conclusion can readily be made "y analyzing the
variation of slopes of the polarization curves and is explained by changes in the mechanisms of electrode reactions.
The ultimate values of the saturation diffusion currents io~ d begin to decrease as soon as the concentration C at-
tains the value 100 g / m 3 (Fig. 1, curves 4, 5). Hence, the composition is an inhibitor of complex action and the pre-
dominance of its effect on the cathodic or anodic process depends on the concentration of the inhibitor. For C =
40 g / m 3, the capacitance of the double layer Cdl formed on the electrode in the anodic region is lower than in wa-
ter without inhibitors (Fig. 2, curve 3). As the concentration of the inhibiting composition increases to 100 g / m 3,
the capacitance Cdl slightly increases (Fig. 2, curve 4). For the optimal concentration (C = 200g/m3), the value
of Cdl is about 1.5-2 times higher than in water without inhibitors (Fig.2, curve 5).
In distilled water, the stationary potential Est in the presence of the composition (C = 2 0 0 g / m 3) shifts to-
ward negative values (Fig. 3, curves 2, 3), the corrosion currents become stronger in agreement with the gravimetric
data, and the capacitance of the double layer increases by an order of magnitude (Fig. 4, curves 2, 3).
 EFFECT OF PYROPHOSPHATE-POLYPHOSPHATEINIIIBITORSON THE PROCESSES OF CORROSION AND SALT DEPOSITION 35 I

l O: ....

,o,

L.
1 0 "z
-800 -400 0 mV +400

F i g . 5. Potentiodynamic polarization curves of 20 steel in high-hardness water (H = 9.0g-eq/m 3, T = 20~ (1) without inhibitors,
(2) KORSOL-IM inhibitor with C = 4 0 g / m 3, (3) 80g/m 3, (4) 120g/m 3, (5) 200g/m 3.

In water with a total hardness of 3.6g-eq/m 3 for C = 2 0 0 g / m 3, the stationary potential is shifted toward
positive values and attains the value - 2 0 0 mV (in water without inhibitors, Est = - 4 9 0 mV). The slopes of the
cathodic and anodic curves also change (see Fig. 3, curve 5). Due to the presence of dissolved salts, the capacitance
of the double layer is higher than that in distilled water by two orders of magnitude (Fig. 4, curve 4). In the range of
cathodic potentials from - 500 to - I000 mV, the values of Cdl in inhibited and noninhibited water coincide and do
not depend on the potential (Fig. 4, curves 4, 5).
For water without inhibitors, in the region of anodic potentials Ea varying from - 490 to - 100 mV, the capa-
citance of the double layer increases and, for more positive potentials, stabilizes. In the presence of the composition,
the capacitance of the layer under the conditions of cathodic polarization, from the stationary potential to Ec >
- 500 mV, is less pronounced than in water without inhibitors. In the case of anodic polarization, it is constant and
also less pronounced than in water without inhibitors.
In water with high content of salts (H = 9.0 g-eq/m3), the effect of the composition on the cathodic and anod-
ic polarization is pronounced only for its optimal concentration (Fig. 5, curve 5). In noninhibited and inhibited wa-
ter, the capacitance Cdl decreases in the case of cathodic polarization and increases in the case of anodic polariza-
tion (Fig. 6).
In the presence of the composition, the capacitance of the double electric layer decreases as compared with Cdl
for water without inhibitors. The minimum capacitance is attained for a concentration of the composition of
200 g / m 3. In the cathodic region, from - 4 0 0 to - 1000 mV, it is constant (Fig. 6, curve 5), in the anodic region,
from - I00 to +700 mV, it increases and then also stabilizes as in water without inhibitors.
Thus, the maximum effect of the composition on the polarization of cathodic and anodic processes (especially
anodic) is attained for its optimal concentration C = 200 g / m 3. The dependence of the electrode potential on the
concentration of the composition is not monotonic but its values are more positive than in water without inhibitors.
It is worth noting that, in versatile-hardness waters, the presence of the inhibiting composition may shift the value of
the capacitance Cdl recorded at the stationary potential in both directions. Indeed, if the hardness of water is equal
to 3.6 or 9 . 0 g - e q / m 3, then the capacitance of the double layer decreases and, for a hardness of 5.6 g-eq/m 3 it in-
creases as compared with water without inhibitors. As the time of holding in the latter increases from 30 to 80 min,
the values of the capacitance of the double layer Cd~ become smaller than in water without inhibitors.
 352 H.M. NYKYFORCHYN, Z. V. SLOBODYAN, AND D. M. ZAVERUNYI

100

80 , ,

60

40

20

I . . . . . i I I

-500 0 +500 s mV
Fig. 6. Dependences of the capacitanceof electric double layer Cdt on the electrode potential in high-hardness water (H = 9.0g-eq/m 3,
T = 20~ and on the concentrationof the inhibiting composition: (1) water without inhibitors, (2) KORSOL-I M inhibitor with
C = 40g/m 3, (3) 80g/m 3, (4) 120 g/m 3, (5) 200 g/m 3.

It is well known that the process of anodic dissolution of the metal runs not on the entire surface but is localized
at certain active places, which are now called Lewis centers [6]. The initial stage of the process of corrosion of tran-
sition metals is connected with the adsorption of water and formation of surface complexes with charge transfer
(SCCT), which play the role of an intermediate stage in the multistage reaction of anodic dissolution and largely de-
termine its rate [7]. Therefore, the processes of dissolution, depassivation, and inhibition are regarded as a result of
the nucleophilic substitution of ligands in surface complexes [8]. In other words, anions An-, as active nucleophilic
agents, displace passivating oxygen-containing groups such as OH- or water molecules, namely,

[Fe(OH)k(H20)/]~ds k + H3P20 7 ---) [Fe(OH)k_l(H20)l_nH3P207]Zla k + OH- + n H 2 0 + ( Z l - z ) e ,

-k
[Fe(OH)k_l (H20)/_n H3 P2OT]Z lads ~ [Fe(OH)k_t (H 3 P 2 0 7 ) / _ n ]z l;k + (l -- n ) H 2 0 .

If this complex is sufficiently stable and difficultly soluble in corrosive media, the dissolution of the metal de-
celerates. At the same time, the other properties of the complex may accelerate the process of active dissolution and
promote the formation of pits.
Thus, in the initial stage of the formation of protective films, the evolution of the capacitance Cdt may have
certain specific features but, in the final stage of the process (the stage of SCCT), the capacitance of the double layer
formed on the electrode decreases. This is explained by the fact that the number of water molecules substantially
exceed the number of the other components of the solution and, hence, they form a layer of adsorbed water mole-
cules H2Oads on the metal surface immersed in water. The capacitance of the electric double layer Cdl is largely
determined by the adsorbed molecules of water playing the role of the dielectric layer of the capacitor. If a medium
contains the inhibiting composition, then the latter affects the process of adsorption of water and its amount in SCCT
and, hence, the capacitance of the double layer. Most likely, local maxima of the capacitance Cdl are explained by
EFFECT OF PYROPHOSPHATE--POLYPHOSPHATE INHIBITORS ON THE PROCESSES OF CORROSION AND SALT DEPOSITION 353

the kinetics of the electrode processes, namely, by the local intensification of the process of adsorption of water ob-
served despite the fact that the anodic process is suppressed. In the case of prolonged holding, we detect a decrease
in Cdl. The decrease in the capacitance of electric double layer means that the number of adsorbed water molecules
also decreases. This phenomenon can be regarded as an additional factor contributing to the inhibition of the cath-
odic and anodic processes. Changes in Cdl observed in the process of polarization of the electrode in water with
high content of salts can be explained by the increasing influence of salts dissolved in water on the adsorption of
water molecules as well as by the deformation of hydrated surface complexes.
The effect of inhibition of the cathodic process in waters with medium and high hardness is caused by the for-
mation of insoluble calcium, magnesium, and iron hydrates in some parts of the cathode accompanied by the deposi-
tion of insoluble phosphates of these metals [9]. Anodic polarization is caused by the formation, on the surface of
the anode, of the compounds of calcium, magnesium, and iron with aquo-ions of phosphates which may then form
oxide-salt films or films with more complicated structures and compositions. The fact that the mechanism of elec-
trochemical reactions changes can be explained by changes in the reactivity of ions in the solution (including the
components of the inhibiting composition) and active centers of SCCT on the basis of Pearson's principle of hard
and soft acids and bases according to which the properties of these acids and bases depend on the salt content of the
solution and the electrode potential [ 10, 11 ]. This enables us to conclude that the mechanism of protective action of
the KORSOL-IM composition can be described as the formation, on the metal surface (via SCCT), of finely divided
quasiamorphous films of iron and calcium hydroxides which are then enriched with iron and calcium phosphates,
different types of substituted pyrophosphates, and oxides (which are formed somewhat later). Being structureless,
the film suppresses the growth of salt deposits.

Table 3. Dependences of icor and Cdi at Various Stationary Potentials Est on Temperature for
20 Steel in Water with H = 3.6 g-eq/m 3

,oc I ,mV ! /co,mm2 I ,,mF,m2

20 -490 500 22

60 -530 2500 76

80 -510 2000 97

in the presence of the inhibitor, C = 200 g/m 3

20 -200 30 19

60 -400 700 36

80 -460 400 41

Effect of Temperature on the Inhibitor Protection of 20 Steel

Since a hardness of 3.6 g-eq/m 3 is the lower limit guaranteeing the required efficiency of the inhibiting com-
position in water, we studied the effect of temperature just for this value of hardness. As the temperature of water
increases, the capacitance of the electric double layer formed on the electrode also increases, both in inhibited water
and in water without inhibitors. However, in the presence of the composition, the values of capacitance are lower
than without it (Table 3).
354 H . M . NYKYFORCHYN, Z, V. SLOBODYAN, AND D. M. ZAVERI3Nu

10 2

l0 t t:://f//
10 ~ -j ; r

0-I t .. i I
-800 -400 0 E,, mV + 4 0 0

Fig. 7. Potentiodynamic polarization curves of KhI8N 10T steel in distilled and medium-hardness water ( H = 3.6g-eq/m 3, T = 20~
(I) distilled water, ( 2 ) K O R S O L - I M inhibitor with C = 2 0 0 g / m 3, (3)medium-hardness water, (4) KORSOL-IM inhibitor with
C = 200 g / m 3.

It is well known [12] that the dielectric constant of water decreases as temperature increases. Thus, for T =
20, 60, and 80~ it is equal to 80.8, 66.5, and 60.5, respectively. Therefore, Cdi must decrease as temperature
increases [13]. This contradiction is explained by the specific behavior of adsorbed water in the near-electrode layer
whose behavior is similar to that of ligands surrounding the central ion in a complex. As temperature increases, the
forces of attraction between water molecules and complex-forming ions become weaker, the degree of their polari-
zation decreases, the process of desorption intensifies, and, hence, the capacitance of the double layer formed on the
electrode increases.
As temperature increases, the corrosion currents (at stationary potentials) in steel placed in water without inhi-
bitors first increase but then slightly decrease due to a decrease in the concentration of 02 which plays the role of
depolarizer. In the presence of the inhibiting composition, at the same temperatures, they decrease by an order of
magnitude. After recalculation, the results of gravimetrie investigation give the following values of corrosion cur-
rents: 3t0 and 230 mA/m 2 at 60~ and 80~ respectively. This disagreement is explained by the fact that, in the
course of these tests, the specimen was held for a longer period of time and by the formation of corrosion-resistant
protective films. A decrease in the capacitance Cdl and corrosion currents demonstrates that the inhibiting compo-
sition suppresses the corrosion processes by decreasing the amount of adsorbed water and preserving the stability of
SCCT at elevated temperatures.

Inhibitor Protection of Khl8N10T Steel

The fact that the corrosion resistance of chromium-nickel steels is high is explained by their ability to form pas-
sivating films. However, the long-term action of neutral aqueous media on stainless steels may lead to corrosion
damage, more precisely, to local depassivation, which depends on the anionic composition and pH value of water as
EFFECT OF PYROPIIOSPHATE--PoI.YPHOSPHATE I[NHIBITORS ON TIlE PROCESSES OF CORROSION AND SALT DEPOSITION 355

well as on the properties of passivating films. This type of corrosion damage is typical of pipes of KhI8NIOT steel
operating in heat exchangers of nuclear power plants. For this reason, it is necessary to analyze the effect of the in-
hibitor composition on the electrochemical characteristics of corrosion processes in heat carriers.

Table 4. Dependences of icor and Cdl at Various Stationary Potentials on Temperature for Khl8N10T Steel

T, ~ Distilled water Water ( H = 3.6 g-eq/m 3)

Est, mV i icor,mA1m2 [ Cdl,mFIm2 Est, mV ieor, mA/m2 Cdl, m F t m 2

20 - 160 2.1 0.6 - 200 2.0 1.7

60 - 190 7.0 2.1 - 220 5.0 24.0

80 - 20 1.5 1.2 - 200 1.8 27.0

in the presence of the inhibitor, C = 200 g / m 3

20 - 40 0.8 0.7 - 190 1.8 1.0

60 - 120 3.5 1.5 - 160 4.5 23.0

80 - 10 1.0 5.0 - 140 1.5 25.0

The electrode processes running on the surface of the passivating film include stages similar to the reactions of
nucleophilic substitution but the process of formation of SCCT on the passivating films (whose role in the process of
inhibition is predominant) is, to a large extent, governed by the presence of alloying components in stainless steel
[8]. The stationary potential of stainless steel Est in distilled water at room temperature is equal to - 160 mV and,
under the action of the inhibiting composition ( C = 200 g/m3), undergoes a substantial shift in the positive direc-
tion and becomes equal to - 4 0 mV (Fig. 7, curves 1, 2). In water with medium hardness ( H = 3.6 g-eq/m3), under
the same conditions, we have Est = - 200 mV, and an admixture of the composition with the same concentration
shifts the stationary potential in the positive direction by only 10 inV. The presence of the composition in distilled
water leads to the changes in the slopes of polarization curves. This shows that the composition affects the dissolu-
tion of the passivating film. The significant shift of the stationary potential in inhibited distilled water is caused by
an additional passivation of the surface under action of the inhibitor. As temperature increases to 60~ the poten-
tial shifts in the negative direction both in inhibited water and in water without inhibitors (Table 4). At the same
time, at 80~ the potential shifts in the positive direction.
The influence of temperature on the corrosion currents and differential capacitance is also ambiguous. Thus, in
distilled water, both with and without inhibitors, the quantities icor and C01 attain their maximum values at 60~
As temperature increases to 80~ the growth of these quantities is less pronounced. An increase in the temperature
of medium-hardness water weakly affects the value of stationary potential in water without inhibitors and shifts it in
the positive direction in inhibited water. The differential capacitance increases in both cases. The value of Cdl is
always lower in inhibited water than in water without inhibitors. The corrosion current slightly decreases in the pre-
sence of the inhibiting composition.
The data presented above demonstrate that, as a result of the adsorption of anions that can be encountered in
water (CI-, S O ] - , etc.), the protective parameters of the passivating film on the surface of Khl 8NIOT steel in wa-
ter with a hardness of 3.6 g - e q / m 3 are worse than in distilled water, The inhibiting composition is adsorbed on the
356 H.M. N Y K Y F O R C H Y N , Z . V. SLOBODYAN, AND D . M . Z A V E R B N Y I

surface of stainless steel in distilled water and, thus, enhances the protective ability of passivating films. In medi-
um-hardness water, the process of adsorption competes with the adsorption of anions and, hence, its influence on the
corrosion resistance of stainless steel is insignificant.
It is worth noting that the anodic polarization in inhibited water at potentials of up to + 1500 mV does not lead
to the formation of pits on the surface of stainless steel. We did not also discover any oscillations of the anodic
curves. Actually, this means that the inhibiting composition does not promote the formation of pits.

/' ?
2130
,IP A A L

g
100

/
1
!
I ! t 9 ~ 9 I '" 0

0 2 4 6 8 10 t, days

Fig. 8. Dependences of the corrosion rate Ip of 20 steel on the time of holding in medium-hardnesswater(H = 3.5 g--eqlm3, T = 20~
(l) without inhibitor, (2) KORSOL-IM inhibitorwith C= 200 g/m 3, (3) aftereffect (a specimen with protective film immersed
in water without inhibitors).

Aftereffect of the Inhibitor

It was discovered that the procedure of holding of specimens of 20 steel in inhibited water (C = 200 g / m 3) for
three days (this time is sufficient for the formation of protective films) with subsequent immersion in water without
inhibitors guarantees their reliable protection for 9 - 12 days. The degree of protection against corrosion was as high
as 90%. The evaluation of the indicated aftereffect on a UK-2 corrosion meter demonstrated (Fig. 8) that the corro-
sion rate is higher than in inhibited water by a factor of 1.4 but lower than in water without inhibitors by an order of
magnitude.

CONCLUSIONS

The protective effect of the KORSOL-1M inhibiting composition is pronounced in waters of medium (not less
than 3.6 g-eq/m 3) and, especially, high hardness. In distilled water, this composition facilitates the process of cor-
rosion in 20 steel.
The mechanism of protective action of the composition is complex, with predominant inhibition of the anodic
reaction due to the formation of a phase quasiamorphous film with aftereffect (for 9 - 1 2 days).
EFFECT OF PYROPllOSPHATE-POLYPHOSPHATEINHIBITORSON THE PROCESSES OF CORROSION AND SALT DEPOSITION 357

In distilled water, the inhibiting composition improves the protective properties of the passivating films on
Khl 8N 10T steel. In this case, the indicated protective properties are better than in medium-hardness water.
As temperature increases to 80~ the efficiency of the inhibitor protection somewhat decreases but remains
satisfactory for the application of this composition in industrial water-recirculation systems.

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