Microstructure and corrosion behaviour of pulsed plasma-nitrided

AISI H13 tool steel

Rodrigo L.O. Basso
a
, Heloise O. Pastore
b
, Vanessa Schmidt
a
, Israel J.R. Baumvol
a,c
, Silvia A.C. Abarca
d
,
Fernando S. de Souza
d
, Almir Spinelli
d
, Carlos A. Figueroa
a
, Cristiano Giacomelli
a,
*
a
Centro de Cincias Exatas e Tecnologia, Universidade de Caxias do Sul, 95070-560 Caxias do Sul, RS, Brazil
b
Instituto de Qumica, Universidade Estadual de Campinas, 13084-862 Campinas, SP, Brazil
c
Instituto de Fsica, Universidade Federal do Rio Grande do Sul, 91501-970 Porto Alegre, RS, Brazil
d
Departamento de Qumica, Universidade Federal de Santa Catarina, 88040-900 Florianpolis, SC, Brazil
a r t i c l e i n f o
Article history:
Received 8 March 2010
Accepted 25 May 2010
Available online 1 June 2010
Keywords:
A. Steel
B. Polarization
B. XRD
B. SEM
C. Pitting corrosion
a b s t r a c t
The effect of pulsed plasma nitriding temperature and time on the pitting corrosion behaviour of AISI H13
tool steel in 0.9% NaCl solutions was investigated by cyclic polarization. The pitting potential (E
pit
) was
found to be dependent on the composition, microstructure and morphology of the surface layers, whose
properties were determined by X-ray diffraction and scanning electron microscopy techniques. The best
corrosion protection was observed for samples nitrided at 480 C and 520 C. Under such experimental
conditions the E
pit
-values shifted up to 1.25 V in the positive direction.
2010 Elsevier Ltd. All rights reserved.
1. Introduction
Pulsed plasma nitriding is a thermochemical process exten-
sively applied in materials science and surface engineering due
to its well-known potential for improving properties such as hard-
ness, wear, and corrosion resistance of metallic parts [1,2]. This
surface treatment technique consists of the implantation of nitro-
gen species at low energies (63 eV) into the steel substrate, and
their subsequent diffusion into the bulk at temperatures above
300 C. The interaction of nitrogen and steel constituents leads to
the formation of different types of metallic nitrides, which form
the so-called nitride layer. Starting from the solid surface, such
a modied layer usually comprises an oxide layer, a compound
zone, and a diffusion zone [3,4]. The resulting structure of these
domains depends on several processing parameters such as the
concentration of alloying elements, exposure time, substrate
temperature, and gaseous mixture [5,6].
The presence of a nitride layer obviously changes the mecha-
nisms of interactionbetweenmetallic materials and their surround-
ings, thus affecting their stability in aggressive environments [79].
In the case of austenitic steels, in particular, the incorporation of
nitrogen imparts better mechanical properties (friction and wear
resistance), but the dissolution kinetics (corrosion resistance) re-
mains closely related to the composition of the corrosive medium
[10,11].
In this context, the AISI H13 tool steel is largely employed in
industrial processes that take place in aggressive environments.
For example, this steel is commonly used in the fabrication of
moulds, casting dies and screws for poly(vinyl chloride) (PVC)
extrusion and the injection mould industry. One drawback associ-
ated with the high temperature processing of PVC-containing
materials is the non-negligible concentration of free chloride spe-
cies originating from the cleavage of CCl bonds, which may
strongly accelerate corrosion and wear rates.
However, this problem can be avoided by plasma nitriding the
AISI H13 tool steel [12,13]. Hard iron nitrides are originated during
the plasma treatment owing to nitrogen diffusion in the near-
surface region at temperatures below the eutectic point
(T
e
593 C) [14]. Usually, two distinctive phases corresponding
to the e-Fe
2-3
N and c
0
-Fe
4
N nitrides are obtained, whose high hard-
ness improves the strength, friction and wear resistance [15,16].
However, the highest wear resistance is normally achieved when
the close-packed hexagonal e-Fe
2-3
N phase is primarily at the sur-
face of the specimens. This is so because the composite nitride
layer of the e-Fe
2-3
N and c
0
-Fe
4
N phases is, in fact, stressed due
to a crystal lattice mismatch [1720].
0010-938X/$ - see front matter 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2010.05.036
* Corresponding author. Present address: Universidade Federal de Santa Maria
(UFSM), Centro de Cincias Naturais e Exatas (CCNE), Av. Roraima, 1000, Cid.
Universitria, Prdio 18, Bairro Camobi. 97105-900 Santa Maria, RS, Brazil. Tel.: +55
8291224932; fax: +55 8232141384.
E-mail address: cgiacomelli@pq.cnpq.br (C. Giacomelli).
Corrosion Science 52 (2010) 31333139
Contents lists available at ScienceDirect
Corrosion Science
j our nal homepage: www. el sevi er. com/ l ocat e/ cor sci
Recent work has shown that the pitting corrosion resistance of
nitrocarburized AISI H13 tool steel can be signicantly improved
by nitride layers consisting of e-Fe
23
(C,N) and c
0
-Fe
4
N phases
[21,22]. However, the effect of the nitride layer microstructure
on the pitting corrosion behaviour of AISI H13 tool steel is still
not fully understood. In this study, we address this question by
analysing the inuence of plasma processing parameters (temper-
ature and time) on the corrosion behaviour and microstructure of
pulsed plasma-nitrided AISI H13 tool steel.
2. Experimental
2.1. Nitriding process
AISI H13 tool steel samples (20 10 2 mm) with nominal
composition of 90.6 Fe, 0.5 C, 0.4 Mn, 1.0 Si, 5.1 Cr, 1.4 Mo, and
0.9 V (wt.%) were used in this study. Before plasma nitriding, sam-
ples were polished with diamond powder (mesh size = 1.0 lm) and
ultrasonically cleaned in ethanol. The nitriding process was carried
out in an automatic hot-wall Plasmatec 450 pulsed plasma system
with 60 A/1000 V of maximum capacity. The substrate tempera-
ture was the same as the reactor temperature, and will be referred
to as the nitriding or processing temperature. In all cases, the plas-
ma was generated by a pulsed DC power supply operating at 7.1 A
and 380 V with a duty cycle of 0.25 (pulse on: 50 ls; pulse off:
150 ls). Before nitriding and during the heating step to reach the
processing temperature, the specimens were ion-bombarded for
4 h in an Ar/H
2
80/20 v/v plasma for cleaning purposes. A H
2
/N
2
80/20 v/v gas mixture ow at 400 Pa was used throughout the
nitriding process. Samples were submitted to plasma nitriding
either at temperatures ranging from 360 to 520 C for 4 h, or at a
constant temperature of 400 C and nitriding time ranging from
1 to 36 h. After processing, the samples were left to cool down
slowly ( 6 h) inside a vacuum chamber.
2.2. XRD and SEM analyses
The samples for XRD and SEM analyses were mounted in con-
ductive Bakelite (Bakelite + copper powder) and mirror-polished
with colloidal silica (mesh size = 0.05 lm). The nitrided layers
were revealed at room temperature by chemical etching with Nital
(2% v/v nitric acid in absolute ethanol). Micrographs of cross-
sections of nitrided layers were recorded using a Shimadzu
SSX-550 scanning electron microscope. The phase composition of
the compound layers was determined by XRD analysis using a
Shimadzu XRD-6000 diffractometer. The diffractograms were re-
corded at room temperature using the BraggBrentano geometry
with monochromatic radiation (Cu Ka, k = 0.15418 nm).
2.3. Electrochemical measurements
Corrosion tests were carried out with an EG&G PAR model 263A
potentiostat/galvanostat interfaced to a personal computer using
the EG&G-PAR SoftCorr II Model 252/352 software for data
acquisition and analysis. The electrochemical cell contained ve
openings: three of them were used for the electrodes, and two
served either for nitrogen bubbling prior to the experiments or
for keeping an inert atmosphere with a gentle nitrogen ow
through the cell during the experiments. The counter electrode
(CE) was a graphite rod, and the reference electrode (RE) was a sat-
urated calomel electrode (SCE) connected to the cell by a salt
bridge and a LugginHabber capillary. Unless otherwise indicated,
all potentials in the text are quoted with respect to this reference
electrode. The working electrode (WE) was a 0.55 cm
2
(geometrical
surface area) AISI H13 tool steel disc mounted in a glass tube with
Araldite

epoxy. Prior to the experiments, the electrode surface

was degreased with acetone, rinsed with deionised water, and
gently dried with nitrogen [23].
Cyclic potentiodynamic polarization curves were recorded
according to the ASTM G61 standard, which is recommended for
evaluating the pitting corrosion tendency of materials in chlo-
ride-containing media. In this pitting experiment, the open circuit
potential (OCP) was initially measured over 30 min. The potential
scan was then started from the OCP-value in the positive direction
until a threshold current density of 6.0 mA/cm
2
was reached. At
this point, the potentiodynamic scan was reversed to the negative
direction, and continued down to 0.25 V/OCP. The pitting poten-
tial (E
pit
) was taken as the value at which the current sharply in-
creased during the positive scan. The values reported hereinafter
correspond to an average of three measurements, and exhibit stan-
dard deviations of 215 mV.
3. Results and discussion
The morphology and microstructure of nitrided layers produced
on near-surface regions of AISI H13 tool steel by plasma treatment
at different temperatures and exposure times were determined by
SEM and XRD, respectively. SEM images can reveal up to two dis-
tinct types of surface layers, depending on the treatment parame-
ters. The SEM image in Fig. 1 shows two distinct layers, as obtained
for a sample plasma nitrided at 520 C for 4 h. One can see an out-
ermost layer well-known as compound layer or white layer, and
below it there is a modied region also known as diffusion layer
[3,4]. SEM micrographs of cross-sections of samples nitrided here
at different temperatures for 4 h are shown in Fig. 2. A non-
compact compound layer was generally obtained for samples trea-
ted at temperatures below 480 C (Fig. 2AC), whereas a compact
compound layer became evident when the nitriding process was
carried out at temperatures as high as 520 C (Fig. 2D). This tem-
perature-induced transition was corroborated by the XRD analysis,
as indicated by the results given in Fig. 3. One single diffraction
peak was observed at 2h = 44.0 for untreated AISI H13 substrates,
which was attributed to the a-ferrite phase. After plasma nitriding,
the e-Fe
2-3
N phase with characteristic diffraction peaks at 2h =
38.3, 41.0, 43.6 and 57.6 was identied for the whole tempera-
ture range investigated in this study. The peak at 2h = 43.6 was
slightly displaced towards higher angles for samples submitted
to pulsed plasma nitriding at high temperatures, as previously
Fig. 1. SEM micrograph of cross-section of a AISI H13 tool steel samples after
plasma nitriding for 4 h at 520 C. Tree different well-dened regions can be seen in
this image.
3134 R.L.O. Basso et al. / Corrosion Science 52 (2010) 31333139
reported in the literature [13]. The diffractogram also revealed the
appearance of diffraction peaks at 2h = 41.0 and 47.6 for
T P440 C (see arrows in Fig. 3), which are associated to the pres-
ence of c
0
-Fe
4
N phase in the modied layer [24]. The diffraction
peak at 2h = 46could, in principle, be attributed to expanded mar-
tensite phase [25,26] or c
0
-Fe
4
N phase [27]. However, the set of
diffraction peaks identied in this study clearly indicates the for-
mation of the c
0
-Fe
4
N phase.
The low diffusivity of nitrogen at low temperatures is very
likely at the origin of the formation of a non-compact compound
layer in which the e-Fe
2-3
N phase was predominant. For this rea-
son, the formation of c
0
-Fe
4
N is usually hindered at low tempera-
tures [28]. However, the synthesis of the latter is favoured above
440 C, as indicated by the progressive increase in the intensity
of its characteristic diffraction peaks as a function of the processing
temperature. This variation continues until a major transition oc-
curs between 480 and 520 C (see diffractograms in Fig. 3). These
results are consistent with the precipitation of e-Fe
2-3
N and
c
0
-Fe
4
N phases, thus producing the compact compound layer iden-
tied by SEM (Fig. 2D).
The diffraction line at 2h = 37.2 is typically associated with the
CrN phase, which is well-known to precipitate during plasma
nitriding at high temperatures (above 440 C in the present case)
[29,30]. No evidence of the formation of the Cr
2
N phase was found
in the diffractograms recorded for treated samples.
Considering the results reported above, different nitride layers
can be synthesized on the surface of AISI H13 tool steel by adjusting
the plasma processing temperature. Briey, samples nitrided at
T 6 400 C exhibit a modied region near the surface whose
structure consists mainly of the e-Fe
2-3
N phase. The formation of
c
0
-Fe
4
NandCrNphases is favouredabove440 C. Aclear microstruc-
tural rearrangement that leads to the precipitation of e-Fe
2-3
N and
c
0
-Fe
4
Nphases to forma compact compoundlayer, takes place with-
in the range of 480520 C.
The corrosion behaviour of pulsed plasma-nitrided AISI H13
tool steel in 0.9% NaCl solutions reected clearly the variations in
terms of the microstructure and phase composition of the near-
surface layers described above. Cyclic polarization experiments
were carried out in order to evaluate the pitting corrosion resis-
tance, which was the main purpose of this study. Before cyclic
polarization, the open circuit potential (OCP) was measured over
30 min. This is an electrochemical parameter that can provide
valuable information on the resistance of passive surface lms
against degradation (corrosion) via non-destructive analysis. The
OCP-value is generally dictated by the structure, chemical compo-
sition and thickness of the protective lm, as well as by the mor-
phology and nature of the lm/solution interface [31].
The results are shown in Fig. 4A for representative samples. In
general, the OCP decreased very soon after the electrode immer-
sion in the aggressive medium, and remained virtually constant
thereafter. Interestingly, the values measured after 30 min of expo-
sure are strongly dependent on the plasma processing protocol
(i.e., on the structure and composition of the near-surface layer)
as evidenced by data given in Table 1, entries 16. The average
OCP increased as a function of nitriding temperature from
0.797 V for untreated H13 specimens up to 0.265 V/SCE for
Fig. 2. SEM micrographs of cross-sections of AISI H13 tool steel samples after plasma nitriding for 4 h at 360 C (A), 440 C (B), 480 C (C), and 520 C (D).
Fig. 3. XRD patterns of AISI H13 tool steel surface after plasma nitriding for 4 h at
different temperatures, as indicated.
R.L.O. Basso et al. / Corrosion Science 52 (2010) 31333139 3135
samples nitrided at T = 440 C. Above this temperature, a sudden
potential decrease to 0.555 V/SCE was observed, followed by
another increase to 0.288 V/SCE for specimens nitrided at T =
520 C. The increases in the OCP-values (up to 500 mV in
selected cases) described above for plasma-nitrided AISI H13 sam-
ples immersed in de-aerated 0.9% NaCl solutions are considerably
higher than those previously reported in the literature for the same
material in aerated 3.5% NaCl after surface treatment via plasma
immersion ion implantation (60 mV on average) [21,32]. It
should be noted, however, that this study was carried out in a less
aggressive environment, and therefore such differences must be
cautiously interpreted. To the best of our knowledge, the OCP-
value of AISI H13 in de-aerated 0.9% NaCl solutions has not been
previously reported.
The cyclic polarization curves shown in Fig. 4B were typical of
materials in the passive state with critical pitting corrosion poten-
tials (E
pit
), whose values revealed essentially the same behaviour as
that described above. According to the data summarized in Table 1,
the E
pit
-values tend to increase with the nitriding temperature, in
spite of a remarkable decrease for T = 480 C. Most importantly,
these experiments proved that the E
pit
can be displaced by
approximately 1.25 V in the positive direction (DE
pit
= [+0.787
V/SCE (0.472 V/SCE)] = +1.25 V), therefore implying that the
pitting corrosion tendency is considerably reduced. Furthermore,
the dissolution processes after pit formation were considerably
less active for nitrided samples, as evidenced by the increase in
the slope of E vs. log(i) curves in Fig. 4B.
These results corroborate the variations in the nature of nitride
layers formed at different plasma processing temperatures. Within
the 360440 C temperature range the corrosion resistance in-
creases because of the formation of a e-Fe
2-3
N surface layer that
retains chromium atoms in its crystalline structure. Indeed, this
phase has been reported to be the most corrosion resistant among
those formed during the plasma nitriding of steels [17,19,20]. The
formation of CrN as the substrate temperature exceeds 440 C (see
discussion related to Fig. 3) is apparently at the origin of the corro-
sion resistance decrease, in good agreement with results reported
elsewhere [29,30]. On raising the nitriding temperature to 520 C,
the pitting corrosion resistance was markedly recovered (i.e.,
E
pit
-values increased again) due to the precipitation of both
e-Fe
2-3
N and c
0
-Fe
4
N phases. Such a compound layer imparts bet-
ter corrosion protection because it is more compact than those
generated below 520 C.
In an attempt to further improve the pitting corrosion resis-
tance of plasma-nitrided AISI H13 tool steel, the processing tem-
perature was xed at 400 C and the effect of processing time
was evaluated. Fig. 4 shows the SEM micrographs of cross-sections
of the samples nitrided for different periods of time. The images
suggest the presence of a diffusion layer in the near-surface region,
and the absence of a well-dened compound layer as a conse-
quence of the low substrate temperature during the surface mod-
ication process, as discussed above. The thickness of the layer on
the steel surface was determined from SEM images. The data pre-
sented in Table 2 conrm that the layer thickness increases with
the increase in the nitriding time, as expected. Needle-shaped
structures typical of c
0
-Fe
4
N nitrides [3] were evidenced on the
surface layer of specimens nitrided for relatively long times
(36 h) as indicated in Fig. 6. In fact, the c
0
-Fe
4
N phase can be pro-
duced not only at high temperatures (see above) but also at low
temperatures when longer nitriding times are selected [3,33,34].
Fig. 4. Representative open circuit potential (A) and cyclic potentiodynamic
polarization curves (B) recorded in 0.9% NaCl solutions for AISI H13 steel specimens
after plasma nitriding for 4 h at different temperatures, as indicated.
Table 1
Corrosion parameters obtained from cyclic potentiodynamic polarization curves
recorded in 0.9% NaCl solutions for AISI H13 tool steel specimens before and after
plasma nitriding under different conditions.
Entry Nitriding
time (h)
Substrate
temperature (C)
OCP (V/SCE) E
pit
(V/SCE)
1-H13 0.797 0.472
2 4 360 0.529 0.292
3 4 400 0.490 +0.062
4 4 440 0.265 +0.445
5 4 480 0.555 0.288
6 4 520 0.288 +0.787
7 1 400 0.520 0.241
8 4 400 0.490 +0.062
9 9 400 0.357 +0.665
10 16 400 0.395 +0.725
11 36 400 0.424 +0.580
Table 2
Layer thickness obtained from SEM images for AISI H13 tool steel samples nitrided at
400 C for different periods of time.
Nitriding time (h) Layer thickness (lm)
01 25.2
04 36.1
09 44.0
16 50.0
36 66.8
3136 R.L.O. Basso et al. / Corrosion Science 52 (2010) 31333139
The ndings described above were conrmed by the XRD re-
sults (Fig. 7). In general, the interpretation of diffraction peaks de-
scribed in detail above also applies to the present case. Depending
on the nitriding time, three different phases corresponding to a-
ferrite (steel matrix), e-Fe
2-3
N and c
0
-Fe
4
N were identied in the
modied layer. The c
0
-Fe
4
N phase, however, was only detected
unambiguously for samples nitrided for long treatment periods
(36 h) at 400 C. Furthermore, no compact compound layer of e-
Fe
2-3
N and c
0
-Fe
4
N was detected under these experimental condi-
tions, as observed in the SEM imaging analysis (Fig. 5). This is in
part due to the fact that nitrogen diffusion is not sufcient to allow
such a structural rearrangement to occur within the nitriding time
scale investigated in this study. Therefore, the main phase in the
nitride layer should be e-Fe
2-3
N. According to XRD results, the e-
Fe
2-3
N phase is present in the diffusion layer and if the SEM images
do not show a compact compound layer, then this phase precipi-
tated as dispersed nitrides in the diffusion layer near the surface
region. Importantly, the precipitation of CrN could be effectively
avoided by selecting a reasonably low nitriding temperature and
preferentially for periods of time up to 16 h, since no diffraction
peaks characteristic of such a nitride are seen in Fig. 7 under such
conditions.
The corrosion properties were found to depend on the micro-
structure changes that were induced by the variation of the nitrid-
ing time. The OCP-values showed almost no variation after
immersion in 0.9% NaCl (Fig. 8A), implying that reasonably stable
lm/solution interfaces were produced during the surface treat-
ment. However, an exception was found for samples nitrided for
1 h (the shortest time). In this case, a slight increase in the OCP oc-
curred during immersion, but the small amplitude of this variation
(DOCP 50 mV) means that the results are not conclusive. The
average OCP-values measured after 30 min of exposure (Table 1,
entries 711) increased with nitriding time from 0.797 V/SCE
for untreated H13 specimens up to 0.357 V/SCE for samples ni-
trided for 9 h. A small decrease to 0.424 V/SCE was then observed
Fig. 5. SEM micrographs of cross-sections of AISI H13 tool steel samples after plasma nitriding at 400 C for 1 h (A), 9 h (B), 16 h (C), and 36 h (D).
Fig. 6. SEM micrograph taken at high magnication for a cross-section of a AISI H13
tool steel sample after plasma nitriding at 400 C for 36 h.
Fig. 7. XRD patterns of AISI H13 tool steel surface after plasma nitriding at 400 C
for different exposure times, as indicated.
R.L.O. Basso et al. / Corrosion Science 52 (2010) 31333139 3137
for longer treatment times due to the presence of the c
0
-Fe
4
N phase
whose formation is favoured during long nitriding periods (Fig. 7).
Interestingly, however, the E
pit
-values did not immediately reect
this drawback in terms of OCP-values (see Table 1, entries 711).
The E
pit
increased from0.472 V/SCE for untreated H13 specimens
up to +0.725 V/SCE for samples nitrided for 16 h, with a small
reduction to +0.580 being observed for samples nitrided for 36 h.
In fact, the reduction in the E
pit
value in the latter case can be asso-
ciated with the CrN precipitation.
The cyclic polarization curves (Fig. 8B) showed an interesting
feature for this series of samples. The current density continued
to increase by almost one order of magnitude once the threshold
current was achieved and the potential scan direction was re-
verted, as indicated by the dotted line. This behaviour suggests a
very active and localized electrode dissolution (pitting corrosion).
Nevertheless, the onset of such a process can be signicantly re-
tarded by plasma nitriding.
4. Conclusions
The microstructure and composition of nitride layers produced
by plasma surface modication of AISI H13 tool steel can be con-
trolled by suitably selecting the substrate temperature and nitrid-
ing time during pulsed plasma processing. These parameters have
a direct effect on the pitting corrosion behaviour of the resulting
materials in 0.9% NaCl solutions.
The results of the present investigation indicate that e-Fe
2-3
N is
the main phase obtained at nitriding temperatures below 400 C.
The precipitation of this phase on the surface as well as in the dif-
fusion layer near the surface region can signicantly improve the
pitting corrosion resistance of AISI H13 tool steel. The formation
of a non-compact compound layer of e-Fe
2-3
N and c
0
-Fe
4
N phases
above 400 C, in addition to the precipitation of CrN at tempera-
tures higher than 440 C, leads to a decrease in the pitting corro-
sion resistance. However, this drawback can be successfully
avoided by raising the substrate temperature to 520 C. Under such
conditions, a compact compound layer of e-Fe
2-3
N and c
0
-Fe
4
N can
be produced, which offers the best pitting corrosion protection, as
conrmed by a substantial 1.25-V increase in the E
pit
-values.
The pitting corrosion resistance can also be improved by plasma
treatment at 400 C during periods of time varying between 1 and
36 h. At such a low substrate temperature the precipitation of CrN
is suppressed, and the c
0
-Fe
4
N phase does not appreciably affect
the corrosion performance, which remains practically unchanged
for nitriding times longer than 9 h.
Acknowledgments
The authors are grateful to UCS, CNPq, CAPES and FAPESP for
nancial support. We are also indebted to the Laboratrio de
Implantao Inica e Tratamento de Superfcies (LIITS). I.J.R.B.,
A.S., C.G., C.A.F., and H.O.P. are CNPq fellows.
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