1.

Introduction
During the last decade the development and
characterization of coatings with enhanced protective
properties against corrosion has been demanded
by the increased industrial requirements for longer
service life combined with reduced thickness of the
layers. For example, zinc and its alloys obtained by
the electrodeposition method, hot dip technique etc.
are practically some of the widely used materials for
preventing the damage of iron and steel [1]. In general,
the interest concerning zinc alloys is grounded on their
very good resistance against corrosion which ensures
reliable prolonged protection of the substrate. Another
reason is to seek alternatives for some toxic layers like
cadmium which has been banned since 2007 in the EU.
The quality of the coatings depends mainly on the
deposition technology, bath composition as well as
surface morphology and crystallographic orientation
[2-6]. It is well known that the protective properties of the
zinc electrodeposits can be also signifcantly improved by
their additional treatment in tri-valence based (chromite)
solutions, obtaining of nanocrystalline deposits,
nanocomposite coatings, alloying with other metals [7-11].
For example, the presence of relatively small amounts of
nickel in the zinc electrodeposits increases the corrosion
resistance of the newly received alloy. In addition, the
mechanical properties like strength, hardness, ductility
etc. also show better qualitative indices. Neutral salt
spray investigations confrm the better protective ability
of the Zn-Ni alloy compared to the pure zinc coatings.
Therefore, the alloying of Zn with metals from the
Fe-group, e.g. Ni, Co, Fe is one possible way to realize
enhanced corrosion resistance and improved protective
ability toward the substrate [12,13]. These positive
infuences are better expressed in the co-deposition
of the abovementioned metals with non-metals, e.g.
phosphorus [14-18]. Some investigations clearly
show that the presence of phosphorus in the metal or
alloy matrix increase the corrosion resistance of the
electrodeposited coatings [19-23]. This element also
leads to some changes in the microstructure, residual
stresses and adhesion strength between the coating and
the substrate.
Central European Journal of Chemistry
Corrosion properties of Zn-Ni-P
alloys in neutral model medium
* E-mail: NBoshkov@ipc.bas.bg
Received 8 October 2013; Accepted 9 March 2014
Abstract:
Versita Sp. z o.o.
Keywords: Zinc alloy Phosphorus Corrosion X-ray diffraction Protective ability
Institute of Physical Chemistry, Bulgarian Academy of Sciences
Sofa 1113, Bulgaria
Vassil D. Bachvarov, Miglena T. Peshova,
Stefana D. Vitkova, Nikolai S. Boshkov
*
Research Article
The presented work reports on the peculiarities of the anodic behavior, corrosion resistance and protective ability of electrodeposited
Zn-Ni-P alloys with a different composition in a model corrosion medium of 5% NaCl. Three characteristic coating types have been
investigated using experimental methods such as potentiodynamic polarization (PD) technique and polarization resistance (Rp)
measurements. In addition, X-ray diffraction (XRD) analysis as well as scanning electron microscopy (SEM) coupled with an Energy-
dispersive X-ray (EDAX) device were applied to determine the differences in the chemical composition and surface morphology which
appeared as a result of the corrosion treatment. The data obtained are compared to those of electrodeposited pure Zn coatings with
identical experimental conditions demonstrating the enhanced protective characteristics of the ternary alloys during the test period in the
model medium. The infuence of the chemical and phase composition of the alloys on its corrosion resistance and protective ability is
also commented and discussed.
Cent. Eur. J. Chem. 12(11) 2014 1183-1193
DOI: 10.2478/s11532-014-0564-9
1183
Corrosion properties of Zn-Ni-P
alloys in neutral model medium
Additionally, the electrolytic co-deposition of Zn-Ni
alloys isan anomalous process. This means that the
deposition of the nickel being the relatively noble metal,
is partially impeded while the deposition of the zinc
takes place.
The present work will determine the protective
characteristics of electrodeposited Zn-Ni-P alloys in a
model test medium containing chloride ions as corrosion
activators. Another point of interest is the investigation of
the anodic behavior in terms of the electrode processes
involved as well as the role of the chemical and phase
composition. The role of the newly appeared corrosion
products for the enhanced corrosion resistance of the
alloys is also discussed.
2. Experimental procedure
2.1. Galvanic coatings
2.1.1. Zn-Ni-P alloy coatings
The composition of the starting electrolyte (SE) differs
from the other electrolytes reported in the literature.
It contains the following components: NiSO
4
7H
2
O
(100 g L
-1
), NiCl
2
6H
2
O (100 g L
-1
), ZnCl
2
(30 g L
-1
),
beta()-alanine (10 g L
-1
) as well as two phosphorus
containing additives: NaH
2
PO
2
H
2
O and H
3
PO
2
(50%). Both latter compounds simultaneously act as
very strong buffers at the operating pH values of the
electrolyte. The total phosphorous amount in the bath
is 4.4 g L
-1
. The electrolytic bath is corrected at regular
intervals relating to the zinc content and is targeted at
a constant concentration of this metal in the solution as
well as at a constant correlation between Zn
2+
and Ni
2+

ions in the electrolyte.
Some preliminary investigations [20] showed that
Zn-Ni-P alloys can be obtained with different elemental
and phase composition as well as with specifc surface
morphology. The alloys with high amounts of Ni and
P have predominantly an amorphous structure. It
has been determined that they could not successfully
fulfll the role of sacrifcial coating for the iron or steel
substrate. These alloys were not suffciently of interest
from a corrosion point of view.
As a result, alloys with relative low Ni and P
contents have been selected for these investigations.
The coatings are electrodeposited galvanostatically at
cathodic current density of 2 or 5 A dm
-2
respectively,
an operating temperature of 40
o
C, values 3 or
4, respectively and non-soluble Ti-Pt meshes as
anodes.
The time for the electrodeposition of the samples
varies between 8 and 30 minutes and to coat with almost
equal thickness since this parameter is very important
for the characterization of their protective properties.
The thermostatic double-chamber electrolytic cell with a
volume of 400 mL and a circulation of the bath solution
(700 rpm) are applied for the electrodeposition of the
Zn-Ni- alloys [20].
Alloy samples with following composition (in wt.%)
have been selected for the following investigation:
- Zn
86
Ni
11
P
3
- Zn 86.3, Ni 10.7, P 3.0;
- Zn
76
Ni
18
P
6
- Zn 76.3, Ni 17.7, P 6.0;
- Zn
90
Ni
10
P
0
- Zn 89.6, Ni 10.4, P 0.0.
This coating is a binary Zn-Ni alloy which is
electrodeposited from SE described above but no
traces of the phosphorous have been detected via EDX
analysis after the electrodeposition process. However,
the presence of this element in the electrolyte leads
to layers with a tighter and more compact surface
morphology compared to the usual Zn-Ni alloys obtained
from electrolytic bath which does not contain P-based
compounds or additives [20].
2.1.2. Zinc coatings
Zinc galvanic coatings are obtained from a slightly acidic
electrolyte containing ZnSO
4
7H
2
O (150 g L
-1
); NH
4
Cl
(30 g L
-1
); H
3
BO
3
(30 g L
-1
). The deposition conditions
applied are: current density of 2 A dm
-2
, pH value in the
range 4.55.0, room temperature, metallurgical zinc
anodes. The coatings are electrodeposited without
stirring or circulation of the electrolyte.
2.2. Sample preparation
Both sides of the steel plates with dimensions of
20101 mm (total working area of 4 cm
2
) are
electrochemically coated with Zn or alloy galvanic
coatings. The thickness of the layers obtained on this
substrate is preliminary calculated to be approximately
10 m.
2.3. Corrosion medium
A model corrosion medium of free aerated 5% NaCl
solution with pH ~ 6.3 at ambient room temperature of
about 19
o
C is used during the investigations. At least
three samples of each coating types (including the pure
zinc) have been investigated to ensure reproducibility of
the experimental results.
2.4. Sample characterization
2.4.1. Corrosion investigations
All investigations are carried out in a common three-
electrode experimental cell with a Luggin-capillary for
minimizing the ohmic resistance of the corrosion medium.
The platinum plate is used as a counter electrode. The
1184
V.l D. Bachvarov, et al.
corrosion potentials during the test are measured with
respect to the saturated calomel electrode (SCE).
2.4.1.1. Potentiodynamic (PD) polarization curves
Potentiodynamic polarization measurements are carried
out at a scan rate of 1 mV s
-1
using a VersaStat 4 (PAR)
device. Prior to the start of the test, the probes were
maintained (temporized) for a defnite period in the
medium under conditions of the open circuit potential
(OCP).
2.4.1.2. Polarization resistance (Rp) measurements
Polarization resistance is an indicator for the protective
ability of the coatings. The measurements are carried
out for a prolonged interval of 30 days while the Rp
values are taken at selected time intervals (days).
The experiments are conducted using an apparature
Corrovit - in the range of 25 mV relative to the
corrosion potential.
The SternGeary equation gives the fundamental
reason to apply this method which states that higher
Rp value (in cm
2
) corresponds to higher corrosion
resistance and to a lower corrosion current, i.e.,
Rp ~ 1 / I
corr
[24,25].
2.4.2. Phase composition and surface morphology
2.4.2.1. X-ray diffraction analysis
X-ray diffraction (XRD) analysis is applied to investigate
the phase composition and the changes occurring
after the corrosion treatment. These are, for example,
new corrosion products which can affect the protective
ability. The apparature used is X-ray diffractometer
DRON-3 (Bragg-Brentano arrangement, CuK
a
-radiation
and scintillation counter). XRD patterns are recorded
in a step scanning mode, in steps of 0.02
o
(2Q) and a
counting time of 1 s step
-1
. The PowderCell program [26]
is used in data processing.
2.4.2.2. Scanning electron microscopy and microprobe
analysis
Scanning electron microscopy (SEM) is used to observe
the surface morphology and to register the changes that
appear after the test. The apparature is a scanning
electron microscope JEOL JSM-5300, Japan coupled
with EDX device.
3. Results and discussion
3.1. Potentiodynamic polarization curves
Generally, this method is applied to characterize the
cathodic and anodic behavior. The results for the selected
alloy samples and pure zinc (given for comparison) are
demonstrated in Fig. 1. The corrosion potential of the
Zn coating is the highly negative one ( 1046 mV),
curve 1. Under conditions of external anodic polarization,
this electrodeposit demonstrates the highest anodic
current density and almost fully disappears at a potential
value of about -540 mV leaving the iron substrate
practically unprotected. The length of the PD curves
shows that the alloy coatings (curves 2-4) last about
two times longer compared to the pure zinc under these
conditions.
The Zn
76
Ni
18
P
6
alloy with the highest Ni and P
contents curve 4 characterizes the lowest anodic
current density compared to all other coatings including
the pure zinc up to potential values of about -250 mV. This
provides proof for its increased corrosion resistance.
Similar is the behavior of the Zn
86
Ni
11
P
3
alloy -
curve 3. Both alloy samples consist of the -phase
(Zn-Ni), and their PD curves show lower anodic current
densities compared to Zn
90
Ni
10
P
0
during the whole
investigated potential zone.
The alloy Zn
90
Ni
10
P
0
- curve 2 consists of the -phase
Zn-Ni and the intermetallic compound Ni
5
Zn
21
(see also
XRD section below). This sample demonstrates the
most active anodic dissolution (highest anodic current
density) during polarization.
The potentiodynamic curve of the substrate
(curve 5) is included for more clarity concerning the
protective action of the alloys. The PD curves of the latter
are placed at more negative potentials (between -1050
and -900 mV) compared to the steel. This shows that
the investigated coatings will play the role of over-layers
protecting the substrate and dissolving predominantly
during the anodic polarization process.
3.2. Polarization resistance (Rp) measurements
In contrast to the previous investigations, these data are
obtained under OCP conditions during the test. The only
period when OCP was not reached is the time when
the polarization resistance was measured for about
1020 minutes. Generally, this method is accepted as
more appropriate for the investigation of real corrosion
characteristics at a prolonged time interval.
The results obtained during 30 days of immersion in
the model medium are shown in Fig. 2. The data of the
pure zinc is given as a comparison line 1. This coating
demonstrates the lowest Rp values, but it must be noted
that at the end of the investigation there were practically
no visible red spots (appearing of so called red rust)
on the surface of the zinc. This is practical proof that
the pure zinc protected the steel substrate although to
a lower degree compared to the alloys.
The polarization resistance of the alloy Zn
76
Ni
18
P
6
line

4 demonstrates an increasing tendency in its
1185
Corrosion properties of Zn-Ni-P
alloys in neutral model medium
protective ability (increasing Rp values) up to the end of
the frst 7-8 days. Thereafter, this parameter decreased
by approximately one third and remained almost
unchanged until the end of the whole test. Quantitatively
very close but with lower protective characteristics was
the behavior of the alloy Zn
86
Ni
11
P
3
line 3.
The coating with the composition Zn
90
Ni
10
P
0
line 2
- shows increased Rp values only after the frst 5 days
and thereafter during the rest of the period. The reason
for this result seems to be the alloy composition which
consists of the -phase Zn-Ni and of the intermetallic
compound Ni
5
Zn
21
(see EDX and XRD sections).
It can be assumed that greater amounts of corrosion
products appear to have played a signifcant role in
the impeding of the penetration of the aggressive test
medium into the depth of the coating.
3.3. EDX analysis
The differences in the chemical composition before
and after the corrosion treatment in the model medium
obtained via EDX analysis are summarized in Table 1.
The demonstrated data present the results after 10 and
30 days of immersion.
Additionally, Table 1 shows the phase composition
changes during the investigation which are registered
by the XRD analysis (see Chapter 3.4. below).
Generally, it can be summarized that the newly
appeared corrosion products are zinc-based -
Zn
5
(OH)
8
Cl
2
H
2
O, Zn
5
(OH)
6
(CO
3
)
2
and ZnO. They are
characterized with a low product of solubility values
[9,10,27-29]. These products seem to be one of the
main reasons for the enhanced corrosion resistance of
the samples. They ensure a strong barrier effect as well
10
-7
10
-6
10
-5
10
-4
10
-3
10
-2
10
-1
10
0
-0.2 -0.4 -0.6 -0.8 -1.0
3
3
2
2
4
4
1
1
5
5

l
g

I
,

A
.
c
m
-
2
E, V (SCE)
-1.2
Figure 1. Potentiodynamic polarization curves in 5% NaCl of: (1) Zn; (2) Zn
90
Ni
10
P
0
; (3) Zn
86
Ni
11
P
3
; (4) Zn
76
Ni
18
P
6
; (5) substrate.
0 5 10 15 20 25 30 35
0
5000
10000
15000
1
3
4
2
Time (days)
R
p
,

(
o
h
m
.
c
m
2
)


Figure 2. Polarization resistance measurements of: (1) Zn; (2) Zn
90
Ni
10
P
0
; (3) Zn
86
Ni
11
P
3
; (4) Zn
76
Ni
18
P
6
.


1186
V.l D. Bachvarov, et al.
as greater diffusion limitations for the model solution
which result in a delay of the corrosion rate of the steel
substrate.
In general, the main observed tendency is that the
Zn, Ni and P amounts decrease to different degrees
during the test especially after 10 days. Thereafter, their
concentration remains almost constant.
3.4. X-ray diffraction analysis
Fig. 3 shows the XRD patterns of the alloy Zn
90
Ni
10
P
0.

The non-treated (as received) coating consists of the
-phase Zn-Ni and the intermetallic compound Ni
5
Zn
21
.
In addition, some lines of the iron substrate also appear
in the pattern. The Zn/Ni ratio in the alloy before the
corrosion treatment is 8.5.
After 10 days of the corrosion treatment the lines
of Ni
5
Zn
21
gradually disappear, but some traces can be
still registered at 2~80
o
. Simultaneously, the coating
thickness decreases - the lines of the iron substrate
become more intensive. The Zn/Ni ratio changes
drastically to 51.2 which indicates that the Ni content is
strongly diminished (~ 8.7 times). In addition, the peaks
of some newly appeared Zn-based corrosion products
can be observed in the sample ZnO, Zn
5
(OH)
8
Cl
2
H
2
O
and Zn
5
(OH)
6
(CO
3
)
2
. After 30 days the Zn/Ni ratio is
55.8 which indicates that the Ni content is additionally
decreased although to a smaller degree.
These results can be compared to the data from
the Rp measurements. During the frst 3-4 days the
polarization resistance value of that sample was very
low, close to the pure zinc. After this period, the Rp of
the alloy began to increase most probably due to the
presence of a mixture of the abovementioned Zn-based
products which delay the corrosion process.
XRD patterns of the ternary Zn
86
Ni
11
P
3
alloy are
presented in Fig. 4. Contrary to the previous coating,
this one contains only the -phase Zn-Ni. After 10 days
the amount of the -phase decreased, the coating
dissolved steadily and became thinner - the lines of
the iron increased. In that case the Zn/Ni ratio did not
change signifcantly before treatment it was 8.2; after
10 days 9.5 at the end of the investigation it was 8.9.
During the frst 10 days, the Rp values of that alloy
were higher compared to the previous case. The Zn/Ni
ratio after the 10-th day, increased slightly in relation to
the non-treated sample. These observations lead to the
conclusion that in such a case Ni dissolves faster than
the zinc. The P content decreased about 15 times after
a 30 day immersion in the model medium.
Fig. 5 shows the XRD patterns of the non-treated
ternary alloy Zn
76
Ni
18
P
6
as well as the samples treated in
the model medium during 10 and 30 days, respectively.
The composition the alloy consisted only of the -phase
Zn-Ni. In addition, some lines of the iron substrate could
also be observed. The Zn/Ni ratio before the corrosion
treatment was 4.3 most probably due to the Ni content
being the highest one compared to the other samples.
After a 10 day immersion in 5% NaCl, the coating
thickness decreased. The Zn/Ni ratio changed to 9.3
which indicated that the Ni content was strongly reduced
(~3 times).
This observation can be compared with the data from
the Rp measurements. During the frst 7-8 days the Rp
value of that sample was the highest one from all treated
Table 1. Chemical and phase composition of the samples before and after corrosion treatment.
Sample type Corrosion
treatment
Element composition, wt.% Phase composition
Zn Ni Cl
Zn
90
Ni
10
P
0
non-treated 89.6 10.4 0 0 0 -phase (Zn-Ni); Ni
5
Zn
21
after 10 days 61.4 1.2 0 37.0 0.4
-phase; ZnO; Ni
5
Zn
21
Zn
5
(OH)
8
Cl
2
H
2
O Zn
5
(OH)
6
(CO
3
)
2
after 30 days 61.4 1.1 0 36.0 1.5
-phase; ZnO; Ni
5
Zn
21
Zn
5
(OH)
8
Cl
2
H
2
O Zn
5
(OH)
6
(CO
3
)
2
Zn
86
Ni
11
P
3
non-treated 86.5 10.5 3.0 0 0 -phase (Zn-Ni)
after 10 days 57.8 6.1 0.3 34.5 1.3
-phase; ZnO
Zn
5
(OH)
8
Cl
2
H
2
O
after 30 days 56.0 6.3 0.2 36.2 1.3
-phase; ZnO
Zn
5
(OH)
8
Cl
2
H
2
O Zn
5
(OH)
6
(CO
3
)
2
Zn
76
Ni
18
P
6
non-treated 76.3 17.7 6.0 0 0 -phase (Zn-Ni)
after 10 days 56.0 6.0 0.5 36.5 1.0
-phase; ZnO
Zn
5
(OH)
8
Cl
2
H
2
O
Zn
5
(OH)
6
(CO
3
)
2
after 30 days 56.0 6.0 0.2 36.2 1.6
-phase; ZnO
Zn
5
(OH)
8
Cl
2
H
2
O Zn
5
(OH)
6
(CO
3
)
2
1187
Corrosion properties of Zn-Ni-P
alloys in neutral model medium
alloys. Thereafter the Rp data decreased with about one
third remaining and practically unchanged until the end
of the investigation. After their initial decrease, the Ni
and Zn contents remained almost constant (~6 wt.%
and ~56 wt.% respectively). There were no changes
in these values after 30 days of the investigation. Most
probably, the relative high Ni and P amounts lead to
better protective characteristics at the beginning. The
P amount strongly decreased (about 30 times after
30 days test) compared to its initial content in that alloy.
3.5. Scanning electron microscopy
The surface morphology of the Zn
90
Ni
10
P
0
alloy before
and after 30 days of corrosion treatment is demonstrated
in Fig. 6. The non-treated sample is characterized
with relative uniform, smooth and compact surface
morphology (Fig. 6A). There are practically no cracks
or damages. After 30 days of treatment the amount of
the corrosion products was good and it seemed that the
latter was agglomerated to a defnite degree in a dense
layer (Fig. 6B). This lead to better sealing off the surface
and to an improved protective ability, respectively.
The as-received sample of the ternary Zn
86
Ni
11
P
3

alloy is presented in Fig. 7A. The surface is more uneven
compared to the previous case and some relative small
holes can be observed. After 30 days immersion in the
model medium, the newly appeared corrosion products
are almost randomly distributed which has in general
a positive infuence on the protective characteristics
(Fig. 7B).
Fig. 8A presents the surface morphology of a non-
treated sample of the ternary Zn
86
Ni
11
P
6
alloy. The
surface is more disarranged compared to the Zn
90
Ni
10
P
0

alloy and consists of small-sized agglomerates. It seems
that their adhesion to the substrate is lower compared
to both other coating types since some places look like
0 10 20 30 40 50 60 70 80
0
200
400
600
Fe
c
c
c
c
c,d
d
c
c,d


I
n
t
e
n
s
i
t
y
,

(
a
.
u
.
)
2, (degrees)
Fe
a,b
a,d
h
30 days
0 10 20 30 40 50 60 70 80
0
200
400
600
d c
c
c
2, (degrees)
c
b
d
a,d
c,d
c,d
Fe


I
n
t
e
n
s
i
t
y
,

(
a
.
u
.
)
Fe
a,b

h
10 days
0 10 20 30 40 50 60 70 80
0
200
400
600
b
b
a
Fe
b
a
a
Fe
a,b a
I
n
t
e
n
s
i
t
y
,

(
a
.
u
.
)
2, (degrees)
Nontreated
Figure 3. XRD patterns of Zn
90
Ni
10
P
0
before and after corrosion treatment: (a) -phase(Zn-Ni); (b) Ni
5
Zn
21
; (c) Zn
5
(OH)
8
Cl
2
H
2
O; (d) ZnO;
(h) Zn
5
(OH)
6
(CO
3
)
2
.

1188
V.l D. Bachvarov, et al.
they are upright. At the end of the corrosion treatment,
the newly appeared products were very close in their
morphology to these of Zn
86
Ni
11
P
3
alloy (Fig. 8B).
4. Discussion
The results of the corrosion properties of the investigated
alloy coatings can be explained based on the role of
their chemical and phase composition. The new zinc-
based corrosion products as a result of the treatment
in the model medium have a low product of solubility
values. Thus, it can be concluded that they will impede
the permeation of the corrosion medium into the depth
acting as a barrier. It is known that zinc is the more
electronegative element compared to the Ni. And so,
the zinc dissolves predominantly in the model medium
under these conditions [9,10,28,29].
The corrosion process is accompanied also by the
hydrogen evolution process which rate depends on the
nature of the compound. For example, the hydrogen
overvoltage on the zinc is higher compared to that of
the nickel. Since the ternary alloy has a heterogenic
structure it can be assumed that the Ni and Ni-P areas
are cathodic compared to the rest of the matrix. In
these zones the hydrogen overvoltage is lower, and the
reduction processes are stronger. This leads to the
release of greater hydrogen amounts. Simultaneously,
the dissolution rate of the zinc in the surrounding anodic
areas rich on zinc (-phase) increases. However,
in this case it would be very diffcult to give a precise
quantitative evaluation of this effect.
The alloy Zn
90
Ni
10
P
0
consists of the Zn-Ni -phase
and the intermetallic compound Ni
5
Zn
21
which has
a bcc structure. Some investigators have found that
the presence of this compound leads to enhanced
0 10 20 30 40 50 60 70 80
0
200
400
600
h
d
c
c
c
a
a
a
Fe
h
a
c d


I
n
t
e
n
s
i
t
y
,

(
a
.
u
.
)
2, (degrees)
Fe
a,d
c,d
30 days
0 10 20 30 40 50 60 70 80
0
200
400
600
c
c
a
a
a
Fe
a
c
d
10 days

I
n
t
e
n
s
i
t
y
,

(
a
.
u
.
)
2, (degrees)
Fe
a,d
c,d
d
0 10 20 30 40 50 60 70 80
0
200
400
600
Fe
Fe
a
a
a
a a a
Nontreated

I
n
t
e
n
s
i
t
y
,

(
a
.
u
.
)
2, (degrees)
Figure 4. XRD patterns of Zn
86
Ni
11
P
3
alloy before and after corrosion treatment: (a) -phase(Zn-Ni); (c) Zn
5
(OH)
8
Cl
2
H
2
O; (d) ZnO;
(h) Zn
5
(OH)
6
(CO
3
)
2
.

1189
Corrosion properties of Zn-Ni-P
alloys in neutral model medium
0 10 20 30 40 50 60 70 80
0
200
400
600
a
a
c
c
c
I
n
t
e
n
s
i
t
y
,

(
a
.
u
.
)
2, (degrees)
30 days
d
a


Fe
Fe
c,d
a,d
h
a
0 10 20 30 40 50 60 70 80
0
200
400
600
Fe
c
c
a
a
a
I
n
t
e
n
s
i
t
y
,

(
a
.
u
.
)
2, (degrees)
10 days
a
Fe
a,d
c,d
h
0 20 40 60 80
0
200
400
600
I
n
t
e
n
s
i
t
y
,

(
a
.
u
.
)
2, (degrees)
a
a
Fe
Fe a
a
a
Nontreated
Figure 5. XRD patterns of Zn
76
Ni
18
P
6
alloy before and after corrosion treatment: (a) -phase(Zn-Ni); (c) Zn
5
(OH)
8
Cl
2
H
2
O; (d) ZnO;
(h) Zn
5
(OH)
6
(CO
3
)
2
.

B A
Figure 6. Surface morphology of Zn
90
Ni
10
P
0
alloy: (A) as received; (B) after 30 days of corrosion treatment.


1190
V.l D. Bachvarov, et al.
corrosion resistance [30-33]. As abovementioned,
it was registered that this intermetallic compound
disappeared almost fully after 10 days of immersion into
the corrosion medium. It could be assumed that the rate
of the dissolution process of this alloy is a sum of the
dissolution rates of the zinc from the -phase and zinc
from the intermetallic compound. The expected result
will accelerate the forming of new corrosion products
which will seal up the substrate. However, it seems that
under conditions of external anodic polarization (PD
curves) the time is insuffcient for forming products in
suffcient amounts to cover the whole sample surface
so the dissolution process remains active.
There are practically no data concerning the
potential value of Ni
5
Zn
21
in the medium. Nevertheless,
two possible variants could be discussed that may
explain this behavior:
1. The potential value of the intermetallic phase is
anodic compared to the Zn-Ni -phase. It will begin to
dissolve as frst followed by the dissolution of the Zn
from the -phase. The fnal result will be the formation of
corrosion products.
2. The potential value of Ni
5
Zn
21
is cathodic compared
to the -phase. This leads frst to intensive dissolution
of the Zn from the surrounding -phase. A process of
forming Zn-based corrosion products will be registered
here as well. It can be expected that some parts of the
cathodic phase will tear off during the process followed
by intensive dissolution of the already lesser protected
underlayer/substrate.
The alloys Zn
76
Ni
18
P
6
and

Zn
86
Ni
11
P
3
consist of the
Zn-Ni -phase which is proved by XRD analysis. From
the electrochemical standpoint, it can be presumed
that part of the nickel is bound with P in a separate

B A
Figure 7. Surface morphology of Zn
86
Ni
11
P
3
alloy: (A) as received; (B) after 30 days of corrosion treatment.

B A
Figure 8. Surface morphology of Zn
76
Ni
18
P
6
alloy: (A) as received; (B) after 30 days of corrosion treatment.


1191
Corrosion properties of Zn-Ni-P
alloys in neutral model medium
amorphous phase (Ni-P) the latter acting as a strong
cathodic zone in the alloy matrix. This will also lead to
an accelerated rate of the forming process of corrosion
products. The indications for this supposition are as
follows:
- Zn does not co-deposit with phosphorous in the
absence of nickel ions in the bath [20];
- The -phase is registered via the XRD method
but no peaks of a crystalline Ni - P based phase can
detected in the XRD patterns;
- The halo of the amorphous Ni - P phase is placed
in a zone which is covered by other compounds at 2Q
between 35 and 55 degrees.
In both alloys Ni and P amounts decrease strongly
indicating they take part in the dissolution process. The
surrounding zinc phase will dissolve faster leading to
the separation of some Ni-P containing sections of the
coating.
In all cases a similar behavior infuences the
formation of new corrosion products with a low product
of solubility on the sample surface which impedes the
penetration of the model medium. Finally, after a defnite
period of time, the corrosion products are not suffcient
in quantity to cover the damaged zone (or will be with
insuffcient thickness).
5. Conclusion
The obtained Zn-Ni-P alloy coatings demonstrate better
protective characteristics in regard to the steel substrate
compared to the pure zinc layer in a test medium with
chloride ions as corrosion activators.
This is based on the phase inhomogeneity and the
processes that have occurred. The alloys consist of two
phases. In the case of Zn
90
Ni
10
P
0
these are the -phase
Zn-Ni and the intermetallic compound Ni
5
Zn
21
. In the
case of two other alloys the phases are the -phase Zn-
Ni and the amorphous compound Ni-P. These phases
play an important role in the process of the forming of
zinc-based corrosion products like Zn
5
(OH)
8
Cl
2
H
2
O,
Zn
5
(OH)
6
(CO
3
)
2
and ZnO. All three distinguish
themselves as having a low product of solubility values.
The result is an additional accumulation of products
on the surface which impedes the penetration of the
aggressive test medium into the depth leading to an
improved protection of the steel substrate.
Acknowledgement
The authors gratefully acknowledge the fnancial support
of Project BG 051PO001-3.3.06-0038.
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