Materials and Design 32 (2011) 26352643

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Materials and Design

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Wear assessment of plasma nitrided AISI H11 steel

H. Forati Rad, A. Amadeh , H. Moradi
School of Metallurgy and Materials Engineering, University College of Engineering, University of Tehan, P.O. Box 11155-4563, Tehran, Iran

a r t i c l e i n f o a b s t r a c t

Article history: Plasma nitriding is one of the effective methods for improvement of the hardness, wear and corrosion
Received 9 August 2010 resistance of steels. In this research AISI H11 hot working tool steel was plasma nitrided in various gas
Accepted 15 January 2011 mixtures for different times and temperatures. The morphology, size and composition of nitride nanopar-
Available online 22 January 2011
ticles formed on the surface of the specimens were investigated using scanning electron microscopy
(SEM), atomic force microscopy (AFM), X-ray diffraction (XRD). The wear behavior of plasma nitrided
Keywords: samples was studied by means of unlubricated pin-on-disc method under constant load of 80 N, sliding
A. Ferrous metals and alloys
speed of 1 m/s, sliding distance of 2000 m at room temperature. The results showed plasma nitriding pro-
C. Coatings
E. Wear
cess improved the wear behavior of H11 steel. The increase in time and temperature of plasma nitriding
decreased the hardness and increased the wear weigh loss of the specimens.
2011 Elsevier Ltd All rights reserved.

1. Introduction nism of plasma diffusion treatments (plasma nitriding, plasma

In industries, mechanical components have to operate under se-
vere conditions such as high load, speed or temperature and hostile
chemical environment [1]. Hot working tool steel possesses the un-
ique combinations of good mechanical properties and toughness
but poor resistance to sliding wear [2]. Consequently, there has
been ever-growing interest in using surface engineering technol-
ogy to change the surface composition and morphology, and thus
to improve wear resistance of hot working tool steel [1,2]. The pos-
sibilities of using such plasma techniques as ion implantation [3,4],
plasma ion implantation [5] or plasma immersion ion implantation
[68] and physical vapor deposition (PVD) to modify the surface
properties of these materials have all been investigated. Plasma
ion implantation (PIII) and physical vapor deposition (PVD) meth-
ods can produce coating layers at lower temperatures and are
therefore less likely to have detrimental effects on substrate
mechanical properties. However, low-temperature ion implanta-
tion methods tend to produce only very thin compound and shal-
low nitrogen diffusion layers. PVD coatings produce a very hard
coating on a relatively soft substrate and this can lead to coating
fracture, delamination and excessive wear under conditions of high
normal load. Glow discharge plasma nitriding, on the other hand, is
one of the most important plasma surface engineering techniques.
It has been widely used in industry over the past decades to im-
prove the hardness, wear and corrosion resistance and fatigue
strength of various metallic materials such as low alloy steels, tita-
nium alloys and hot working tool steels [912]. The basic mecha-
Corresponding author. Tel.: +98 21 82084090; fax: +98 21 88006076.
E-mail address: amadeh@ut.ac.ir (A. Amadeh).
carburizing and plasma boriding) is the formation of FeN precip-
itates as the result of a reaction between plasma and the surface of
the metal. In addition, the plasma mass transfer plays an important
role on the formation of nitride precipitates [13]. Nitride precipi-
tates formed on the surface consist of different phases such as c0 -
Fe4N, e-Fe23N and other MxNy precipitates. The morphology of
these precipitates is effectively inuenced by gas composition,
temperature and time of plasma nitriding process [14]. Variation
of size and density of nitride precipitates has a considerable effect
on surface hardness, wear behavior and mechanical properties of
the samples.
The aim of the present paper is to study the morphology and
size of nitride nanoprecipitates formed on the surface and wear
behavior of plasma nitrided H11 steel disc against a rotating SiC
pins was studied.
2. Experimental procedure
2.1. Materials
Commercially available AISI H11 steel was used as the substrate
for all coating procedures. Cubic samples (15  15  15 mm3) with
nominal composition listed in Table 1 were cut from AISI H11 steel.
The specimens were austenitized at 1020 C for 30 min, quenched
in oil media and then tempered at 560 C for 2 h in an electric fur-
nace. The surface of the samples was mechanically ground to 1200
grit silicon carbide paper. The ground samples were ultrasonically
cleaned in distilled water and detergent for 10 min. This procedure
was repeated with only distilled water for 10 min and then with
acetone for another 10 min.

0261-3069/$ - see front matter 2011 Elsevier Ltd All rights reserved.
doi:10.1016/j.matdes.2011.01.027
2636 H. Forati Rad et al. / Materials and Design 32 (2011) 26352643

Table 1 Table 3
Nominal composition of AISI H11 steel (wt.%). Thickness of compound and diffusion layers of nitrided specimens.

C Si Mn Cr Mo Thickness (lm) S1 S2 S3 S4 S5 S6
0.40.5 1.11.2 0.40.5 4.75 1.11.3 Compound layer 14 28 10 8 9 3
Ni V Cu P, S Fe Diffusion layer 71 75 90 95 70 80

0.050.1 0.5 0.10.5 <0.001 Balance

ranged from 250 to 2000 m for the nitrided samples and 2000 m
for the untreated sample. All tests were conducted in air and with-
Table 2
Plasma nitriding conditions of the specimens.
out lubrication. Before and after wear test, the disk specimens were
weighed to a precision of 0.1 mg and the weight change, was con-
Sample number Nitriding time (h) Nitriding temperature (C)
sidered as wear weight-loss.
S1 5 500
S2 7 500
S3 5 540 3. Results and discussion
S4 7 540
S5 5 580
3.1. Microstructural investigations
S6 7 580

Fig. 1 shows the SEM micrograph of the cross section of the

After cleaning, the specimens were placed into plasma nitriding
chamber and the chamber was evacuated to 0.5 mbar. Prior to ion
nitriding, the specimens were sputtered by hydrogen for 15 min.
under a voltage of 500 V and a pressure of 5 mbar to remove the
surface contaminates. The samples were treated by pulsed plasma
nitriding in a hot wall plasma nitriding apparatus with 70% duty
cycle, 10 kHz frequency in 75%N2 + 25%H2 gas composition for dif-
ferent times and temperatures as described in Table 2.
The morphology, size of nanoprecipitates as well as the worn
surfaces were studied using a Camscan scanning electron micro-
scope (SEM) and DTM atomic force microscope (AFM). Before
investigation the cross section, a thin layer of nickel was electrode-
posited on the surface of the specimens to prevent the destruction
of nitride layer during further cutting. Phase analysis was per-
formed by X-ray diffraction apparatus (Seifert 3003TT) operating
at 30 kV and 30 mA with Cu Ka radiation. The surface microhard-
ness was measured using a Reicher-Duremat 4000E apparatus at a
load of 80 gf and a dwell time of 10 s.
2.2. Wear tests
Tribological behavior of the untreated and plasma nitrided H11
steel were evaluated using a pin-on-disc custom made tribotester.
The H11 steel disc (56 mm diameter and 8 mm thickness) was
rotating against a stationary SiC pin of 2 mm diameter at a speed
of 1 m/s. The nominal diameter of the wear track was 35 mm
and the normal contact load was 80 N. The sliding distances were
sample treated for 5 h at 580 C. A white compound layer (exclud-
ing the nickel layer) as well as a dark diffusion layer can be distin-
guished in the cross section of the specimens. It is reported that the
threshold condition for the formation of compound layer is depen-
dent on time, temperature and nitriding potential [9]. The thick-
ness of compound and diffusion layers for nitrided specimens is
listed in Table 3. As seen the thickness of both the diffusion and
compound layer is inuenced by the treatment time and tempera-
ture. The thickness of diffusion layer increases by increasing both
of time and temperature until 540 C. At 580 C although, as the re-
sult of the increase in surface sputtering, the thickness of diffusion
layer decreases with respect to other nitriding temperatures but
the increase in processing time increases the thickness of this layer
due to the promotion in diffusion of nitrogen ions. The thickness of
compound layer increases with nitriding time at 500 C and then
decreases by increasing the nitriding time or temperature. Increas-
ing the nitriding temperature results in a greater amount of sput-
tering and so the thickness of compound layer decreases [15].
Fig. 2 shows the SEM images of the surface of the sample ni-
trided at 500, 540 and 580 C for 5 and 7 h in 75%N2 + 25%H2 gas
composition. The average size of nitride nanoprecipitates for the
sample nitrided at 500 C for 5 h is 118 nm which increases to
145 nm for the specimen treated for 7 h at the same temperature.
Fig. 2c and d reveal the agglomeration of nanoprecipitates, espe-
cially at higher temperature and/or exposure time. In this atmo-
sphere, due to high concentration of nitrogen ions and the
presence of weighty nonionized nitrogen molecules in plasma
media, the surface sputtering increases. On the other hand, the

Fig. 1. SEM micrograph of the cross section of the sample nitrided for 5 h at 580 C.
 H. Forati Rad et al. / Materials and Design 32 (2011) 26352643
Fig. 2. SEM micrographs of the surface of the samples plasma nitrided in 75%N2 + 25%H2 atmosphere at: (a) 500 C for 5 h, (b) 500 C for 7 h, (c) 540 C for 5 h, (d) 540 C for
7 h, (e) 580 C for 5 h, (f) 580 C for 7 h.
nitrogen atoms have lower energy and tend to recombine to form
molecular N2 on the surface. The combination of these effects to-
gether with the agglomeration of nitride precipitates leads to the
formation of micro-pores on the surface of the samples (dark
points) [11,15].
Fig. 3 shows the AFM image as well as the distribution function
of the size of nitride precipitates formed on the surface of the sam-
ple nitrided for 5 h at 500 C in 75%N2 + 25%H2. It is clear that the
size of all the precipitates is less than 120 nm and the precipitates
with 45.6 nm diameter have the greatest content.
3.2. Phase analysis
Fig. 4 depicts the XRD patterns of the samples nitrided at differ-
ent conditions in 75%N2 + 25%H2. At low nitriding time and tem-
perature, the composition of nanoprecipitates and compound
layer consists of a mixture of e and c0 phases. By increasing the
time and/or temperature, the intensity of diffraction peaks of e
2637
phase decreases, while the amount of c0 phase increases. c0 phase
forms at higher times and/or temperatures of nitriding process
due to, (i) the surface sputtering that leads to surface decarburizing
and so, provides the appropriate conditions for the formation of
this phase, and (ii) the depletion of the surface from nitrogen ow-
ing to the diffusion of nitrogen ions to the depth of the specimen
and lack of complete substitution of these ions from plasma media.
In this situation, the conditions unlimber for e ? c0 phase transfor-
mation which leads to a decrease in the amount of e phase.
3.3. Microhardness measurement
Fig. 5 illustrates the surface proles from the surface through
the depth of plasma.
As seen, the highest surface hardness has been achieved for the
sample nitrided for 7 h at 500 C which contains, according to XRD
patterns, the most percentage of e phase. c0 -Fe4N phase, has fcc
crystalline structure and shows lower hardness with respect to e-
2638 H. Forati Rad et al. / Materials and Design 32 (2011) 26352643

Fig. 3. AFM image of the surface of the sample nitrided at 500 C for 5 h (a) and distribution function of the size of precipitates (b).

Fe23N phase with hcp crystalline structure. The surface hardness

reduces by increasing the nitriding time and temperature due to
the transformation of e to c0 phase. The reduction of surface hard-
ness for the samples treated at 540 C can also be attributed to fur-
ther tempering of steel substrate (540 C is near to the tempering
temperature of H11 steel) [16,17]. Moreover, the hardness de-
creases gradually from the surface towards the depth of the sam-
ple, which is crucial for the maintenance of the ductility of
surface engineered layers. The variation in hardness distribution
veries the results of microstructural investigations and implies
that the change in nitriding conditions produces different size
and distribution of precipitation in nitrided layer which can affect
the tribological behavior [11].

3.4. Wear behavior

Overall wear weight loss for untreated and plasma nitrited sam-
ples after 2000 m sliding distance is shown in Fig. 6. As expected,
the untreated specimen exhibits poor wear resistance with respect
to plasma nitrided samples, that is, plasma nitriding process effec-
tively improves the wear resistance of steel. Fig. 6 also shows that
the wear resistance of the nitrided specimens increases with Fig. 4. XRD patterns of the samples nitrided at different temperatures and times in
increasing the surface hardness, which in agreement with Achards 75%N2 + 25%H2.
 H. Forati Rad et al. / Materials and Design 32 (2011) 26352643 2639

Fig. 5. The hardness proles of plasma nitrided specimens.

Fig. 6. Wear rate for untreated and plasma nitrited samples after 2000 m sliding distance.

Fig. 7. Wear weight loss versus sliding distance of plasma nitrided H11 steel.
2640 H. Forati Rad et al. / Materials and Design 32 (2011) 26352643

Table 4
EDS analysis of compact layer formed on worn surface (point a in Fig. 8).

Element O Si Cr Fe
Weight% 20.3 0.9 4.4 74.5

Table 5
EDS analysis of point b in Fig. 8.

Element O Si Cr N W Fe
Weight% 5.4 0.9 4.4 4.8 1.6 83.2

talline structures in comparison with bcc and/or fcc structure

Fig. 8. SEM micrograph of worn surface of untreated specimens after 2000 m
sliding distance.
equation, Q KWH
, where Q is wear volume in sliding distance, W is
vertical load and H is surface hardness [18].
The lowest wear rate is related to S2 sample that has the highest
hardness and the greatest amount of e phase. Normally, hcp crys-
shows better tribological properties due to their limited sliding
systems. The number of sliding systems in hcp materials at low
temperature is one while in the fcc materials are twelve [19]. It
was mentioned that fracture properties of surface layer also play
an important role on the wear behavior of specimen [20]. Although
the wear rate of S4, S5 and S6 is higher than untreated sample, but
they exhibit greater wear weight loss with respect to other nitride
samples. This difference can be attributed to the fact that these
samples have thin compound layer that can be broken in small
sliding distance and produce abrasive particles resulting in severe
scrape wear and increase the wear rate of the samples.

Fig. 9. SEM micrographs of worn surfaces of S2 sample after (a) 250 m, (b) 750 m and (c) 2000 m sliding distance.
 H. Forati Rad et al. / Materials and Design 32 (2011) 26352643 2641

Fig. 10. SEM image of abrasive particles on the surface (a) and EDS analysis of these particles (b) in S2 specimen after 2000 m sliding distance.

Fig. 7 represents the wear weight loss versus sliding distance.
With regards to good thickness compound layer in the S1 and S2
samples (15 and 28 lm, respectively), these specimens have a stea-
dy-state wear in overall sliding distance. By decreasing the thickness
of compound layer, it can be broken in small sliding distances and
produce abrasive particles that result in high wear rate. According
to Fig. 7 because of low thickness of compound layer in S6 sample,
this layer breaks down in the rst stage of wear test (250 m) and gen-
erates abrasive particles, which result in an increase in the slope of
the curve. For S3, S4 and S5 samples at the primary stage of wear test,
the slope of curve is low dealing with good wear resistance, but with
increasing the sliding distance, the compound layer of these samples
breaks too, and results in suddenly increase in wear weight loss.
SEM micrograph of worn surface of untreated specimens after
2000 m sliding distance is shown in Fig. 8. As seen, a compact and
smooth tribological layer is formed on the surface. Shear grooves
are also found on the worn surfaces of the unnitrided disks, indi-
cating ductile fracture due to its low surface strength [11]. EDS
analysis of point a in Fig. 8, listed in Table 4, shows the presence
very amount of oxygen in this layer. Consequent to the pin and
disk wear, abrasive particles are produced. These particles create
deep wear scratches on the surface. Free moving of theses oxide
particles between pin and disk decreases the size of the particles.
The accumulated wear debris particles can be compacted and
subsequently sintered to form solid compact layers on the worn
surface known as glaze layer. EDS analysis of the center area
of wear line (point b in Fig. 8) listed in Table 5 shows a little
amount of oxygen in this area. In this area because of high con-
tact between pin and disk and the presence of a low hardness
sublayer, which does not support sufciently the surface layer,
the oxide layer is removed. All these results suggest that the wear
behavior of untreated steel is dominated by severe adhesion
accompanied with abrasive wear leading to large metallic wear
debris and higher wear rate [11].
Fig. 9 presents the SEM images of worn surfaces of S2 specimen
after 250, 750 and 2000 m sliding distance. This specimen shows

Fig. 11. Friction coefcient of S2 (a), and S6 (b) specimens at different sliding distances.
2642 H. Forati Rad et al. / Materials and Design 32 (2011) 26352643
Fig. 12. SEM micrograph of the cross section of S2 specimen after 2000 m sliding
distance.
Fig. 13. SEM micrograph of worn surface of S5 specimen after 2000 m sliding
distance.
the highest surface hardness between nitrided samples. After
250 m sliding distance, the surface sample remains approximately
unchanged and wear rate is very low. At longer sliding distances
(750 and 2000 m), tribological oxide layers, slight grooves and
small debris are formed on the surface. These surfaces show that
a mild adhesive and abrasive wear takes place on this sample.
SEM image and EDS analysis of wear debris particles formed on
the surface of S2 specimen after 2000 m sliding distance is shown
in Fig. 10. EDS analysis reveals a high percentage of oxygen sug-
gesting that these are oxide particles. It can be observed in
Fig. 11a that the coefcient of friction of this specimen is 0.39.
For this sample, the initial friction coefcient is high due to surface
roughness, and then reduces to a steady value after about 50 m of
sliding distance [12]. Due to high hardness of the sublayer, the
oxide layers are protected and act as a solid lubricant and thus it
is very effective in reducing the contact area, which decreases
the friction coefcient and the wear rate of this sample [11,21].
As shown in Fig. 12, in this sample the compound layer is protected
even after 2000 m sliding distance. It is reported that compound
layer can increase the resistance to both adhesive and abrasive
wear. The adhesive wear may be reduced by hardening the surface
which reduces the contact area and inhibits extensive intermetallic
contact and adhesion between the sliding counter faces [22].
Fig. 13 reveals the SEM image of worn surface of S6 specimen
after 2000 m sliding distance. In this gure severe grooves are
formed on the surface resulting in the breakdown of the compound
layer that forms the abrasive particles. The friction coefcient of
this sample is 0.78 (Fig. 11b) that is two times of the coefcient
of friction of S2 specimen. This fact shows that the formation of
abrasive particles increases the friction coefcient and the wear
rate of the sample.
4. Conclusions
Wear behavior of plasma nitrided AISI H11 tool steel was inves-
tigated. The thickness of compound layer as well as the average
size of nitride nanoprecipitates varied as a function of nitriding
time or temperature. The composition of nanoprecipitates and
compound layer consisted of a mixture of e and c0 phases.
The surface hardness of nitrided steel increased by increasing
the amount of e phase. The lowest wear rate was related to the
sample which had the highest hardness and the most amount of
e phase. For this sample the compound layer was protected even
after 2000 m sliding distance, and so resulted in good wear
behavior.
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