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

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

sample treated for 5 h at 580 C. A white compound layer (exclud-
After cleaning, the specimens were placed into plasma nitriding ing the nickel layer) as well as a dark diffusion layer can be distin-
chamber and the chamber was evacuated to 0.5 mbar. Prior to ion guished in the cross section of the specimens. It is reported that the
nitriding, the specimens were sputtered by hydrogen for 15 min. threshold condition for the formation of compound layer is depen-
under a voltage of 500 V and a pressure of 5 mbar to remove the dent on time, temperature and nitriding potential [9]. The thick-
surface contaminates. The samples were treated by pulsed plasma ness of compound and diffusion layers for nitrided specimens is
nitriding in a hot wall plasma nitriding apparatus with 70% duty listed in Table 3. As seen the thickness of both the diffusion and
cycle, 10 kHz frequency in 75%N2 + 25%H2 gas composition for dif- compound layer is inuenced by the treatment time and tempera-
ferent times and temperatures as described in Table 2. ture. The thickness of diffusion layer increases by increasing both
The morphology, size of nanoprecipitates as well as the worn of time and temperature until 540 C. At 580 C although, as the re-
surfaces were studied using a Camscan scanning electron micro- sult of the increase in surface sputtering, the thickness of diffusion
scope (SEM) and DTM atomic force microscope (AFM). Before layer decreases with respect to other nitriding temperatures but
investigation the cross section, a thin layer of nickel was electrode- the increase in processing time increases the thickness of this layer
posited on the surface of the specimens to prevent the destruction due to the promotion in diffusion of nitrogen ions. The thickness of
of nitride layer during further cutting. Phase analysis was per- compound layer increases with nitriding time at 500 C and then
formed by X-ray diffraction apparatus (Seifert 3003TT) operating decreases by increasing the nitriding time or temperature. Increas-
at 30 kV and 30 mA with Cu Ka radiation. The surface microhard- ing the nitriding temperature results in a greater amount of sput-
ness was measured using a Reicher-Duremat 4000E apparatus at a tering and so the thickness of compound layer decreases [15].
load of 80 gf and a dwell time of 10 s. 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
2.2. Wear tests composition. The average size of nitride nanoprecipitates for the
sample nitrided at 500 C for 5 h is 118 nm which increases to
Tribological behavior of the untreated and plasma nitrided H11 145 nm for the specimen treated for 7 h at the same temperature.
steel were evaluated using a pin-on-disc custom made tribotester. Fig. 2c and d reveal the agglomeration of nanoprecipitates, espe-
The H11 steel disc (56 mm diameter and 8 mm thickness) was cially at higher temperature and/or exposure time. In this atmo-
rotating against a stationary SiC pin of 2 mm diameter at a speed sphere, due to high concentration of nitrogen ions and the
of 1 m/s. The nominal diameter of the wear track was 35 mm presence of weighty nonionized nitrogen molecules in plasma
and the normal contact load was 80 N. The sliding distances were 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 2637

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 phase decreases, while the amount of c0 phase increases. c0 phase
molecular N2 on the surface. The combination of these effects to- forms at higher times and/or temperatures of nitriding process
gether with the agglomeration of nitride precipitates leads to the due to, (i) the surface sputtering that leads to surface decarburizing
formation of micro-pores on the surface of the samples (dark and so, provides the appropriate conditions for the formation of
points) [11,15]. this phase, and (ii) the depletion of the surface from nitrogen ow-
Fig. 3 shows the AFM image as well as the distribution function ing to the diffusion of nitrogen ions to the depth of the specimen
of the size of nitride precipitates formed on the surface of the sam- and lack of complete substitution of these ions from plasma media.
ple nitrided for 5 h at 500 C in 75%N2 + 25%H2. It is clear that the In this situation, the conditions unlimber for e ? c0 phase transfor-
size of all the precipitates is less than 120 nm and the precipitates mation which leads to a decrease in the amount of e phase.
with 45.6 nm diameter have the greatest content.

3.3. Microhardness measurement

3.2. Phase analysis
Fig. 5 illustrates the surface proles from the surface through
Fig. 4 depicts the XRD patterns of the samples nitrided at differ- the depth of plasma.
ent conditions in 75%N2 + 25%H2. At low nitriding time and tem- As seen, the highest surface hardness has been achieved for the
perature, the composition of nanoprecipitates and compound sample nitrided for 7 h at 500 C which contains, according to XRD
layer consists of a mixture of e and c0 phases. By increasing the patterns, the most percentage of e phase. c0 -Fe4N phase, has fcc
time and/or temperature, the intensity of diffraction peaks of e 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

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
Fig. 8. SEM micrograph of worn surface of untreated specimens after 2000 m
was mentioned that fracture properties of surface layer also play
sliding distance. 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
equation, Q KWH
, where Q is wear volume in sliding distance, W is samples. This difference can be attributed to the fact that these
vertical load and H is surface hardness [18]. samples have thin compound layer that can be broken in small
The lowest wear rate is related to S2 sample that has the highest sliding distance and produce abrasive particles resulting in severe
hardness and the greatest amount of e phase. Normally, hcp crys- 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. analysis of point a in Fig. 8, listed in Table 4, shows the presence
With regards to good thickness compound layer in the S1 and S2 very amount of oxygen in this layer. Consequent to the pin and
samples (15 and 28 lm, respectively), these specimens have a stea- disk wear, abrasive particles are produced. These particles create
dy-state wear in overall sliding distance. By decreasing the thickness deep wear scratches on the surface. Free moving of theses oxide
of compound layer, it can be broken in small sliding distances and particles between pin and disk decreases the size of the particles.
produce abrasive particles that result in high wear rate. According The accumulated wear debris particles can be compacted and
to Fig. 7 because of low thickness of compound layer in S6 sample, subsequently sintered to form solid compact layers on the worn
this layer breaks down in the rst stage of wear test (250 m) and gen- surface known as glaze layer. EDS analysis of the center area
erates abrasive particles, which result in an increase in the slope of of wear line (point b in Fig. 8) listed in Table 5 shows a little
the curve. For S3, S4 and S5 samples at the primary stage of wear test, amount of oxygen in this area. In this area because of high con-
the slope of curve is low dealing with good wear resistance, but with tact between pin and disk and the presence of a low hardness
increasing the sliding distance, the compound layer of these samples sublayer, which does not support sufciently the surface layer,
breaks too, and results in suddenly increase in wear weight loss. the oxide layer is removed. All these results suggest that the wear
SEM micrograph of worn surface of untreated specimens after behavior of untreated steel is dominated by severe adhesion
2000 m sliding distance is shown in Fig. 8. As seen, a compact and accompanied with abrasive wear leading to large metallic wear
smooth tribological layer is formed on the surface. Shear grooves debris and higher wear rate [11].
are also found on the worn surfaces of the unnitrided disks, indi- Fig. 9 presents the SEM images of worn surfaces of S2 specimen
cating ductile fracture due to its low surface strength [11]. EDS 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

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

Fig. 12. SEM micrograph of the cross section of S2 specimen after 2000 m sliding
Wear behavior of plasma nitrided AISI H11 tool steel was inves-
distance. 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.

References

[1] Liu Y, Yang D, He Sh, Ye Zh. Dry sliding wear of Ti6Al4V alloy at low
temperature in vacuum. Space Technol Proc 2006;6:30916.
[2] El-Tayeb NSM, Yap TC, Venkatesh VC, Brevern PV. Modeling of cryogenic
frictional behaviour of titanium alloys using response surface methodology
approach. Mater Des 2009;30:402334.
[3] Toth A, Bell T, Bertoti I, Mohai M, Zelei B. Surface modication of polyethylene
by low keV ion beams. Nucl Instrum Methods Phys Res Sect B Beam Interact
Mater Atoms 1999;148:11315.
[4] Ikeda D, Ogawa M, Hara Y, Nishimura Y, Odusanya O, Azuma K, et al. Effect of
nitrogen plasma-based ion implantation on joint prosthetic material. Surf Coat
Technol 2002;156:3015.
[5] Muthukumaran V, Selladurai V, Nandhakumar S, Senthilkumar M.
Experimental investigation on corrosion and hardness of ion implanted AISI
316L stainless steel. Mater Des 2010;31:28137.
[6] Dong H, Bell T. Plasma immersion ion implantation of UHMWPE. J Mater Sci
Lett 2000;19:11479.
[7] Shi W, Li XY, Dong H. Improved wear resistance of ultra-high molecular weight
Fig. 13. SEM micrograph of worn surface of S5 specimen after 2000 m sliding polyethylene by plasma immersion ion implantation. Wear 2001;250:54452.
distance. [8] Saklakoglu IE, Saklakoglu N, Short KT, Collins GA. Characterization of austenitic
stainless steel after plasma immersion nitrogen and carbon implantation.
Mater Des 2007;28:165763.
[9] Oliveira SD, Tschiptschin AP, Pinedo CE. Simultaneous plasma nitriding and
the highest surface hardness between nitrided samples. After ageing treatments of precipitation hardenable plastic mould steel. Mater Des
250 m sliding distance, the surface sample remains approximately 2007;28:17148.
[10] Habig KH. Wear protection of steels by boriding, vanadizing, nitriding,
unchanged and wear rate is very low. At longer sliding distances carburising, and hardening. Mater Des 1980;2:8392.
(750 and 2000 m), tribological oxide layers, slight grooves and [11] Yang J, Liu Y, Ye Z, Yang D, He Sh. Microstructural and tribological
small debris are formed on the surface. These surfaces show that characterization of plasma- and gas-nitrided 2Cr13 steel in vacuum. Mater
Des 2011;32:80814.
a mild adhesive and abrasive wear takes place on this sample. [12] Karakan M, Alsaran A, elik A. Effect of process time on structural and
SEM image and EDS analysis of wear debris particles formed on tribological properties of ferritic plasma nitrocarburized AISI 4140 steel. Mater
the surface of S2 specimen after 2000 m sliding distance is shown Des 2004;25:34953.
[13] Grill A. Cold plasma in materials fabrication from fundamental to
in Fig. 10. EDS analysis reveals a high percentage of oxygen sug-
application. IEEE Press; 1980.
gesting that these are oxide particles. It can be observed in [14] Priest JM, Baldwin MJ, Fewell MP. The action of hydrogen in low-pressure r.f.-
Fig. 11a that the coefcient of friction of this specimen is 0.39. plasma nitriding. Surf Coat Technol 2001;145:15263.
[15] Fattah M, Mahboubi F. Comparison of ferritic and austenitic plasma nitriding
For this sample, the initial friction coefcient is high due to surface
and nitrocarburizing behavior of AISI 4140 low alloy steel. Mater Des
roughness, and then reduces to a steady value after about 50 m of 2010;31:391521.
sliding distance [12]. Due to high hardness of the sublayer, the [16] Ruset C, Ciuca S, Grigore E. The inuence of the sputtering process on the
oxide layers are protected and act as a solid lubricant and thus it constitution of the compound layers obtained by plasma nitriding. Surf Coat
Technol 2003;174175:12015.
is very effective in reducing the contact area, which decreases [17] Karakan M, Alsaran A, Celik A. Effects of various gas mixtures on plasma
the friction coefcient and the wear rate of this sample [11,21]. nitriding behavior of AISI 5140 steel. Mater Charact 2003;49:2416.
 H. Forati Rad et al. / Materials and Design 32 (2011) 26352643 2643

[18] Hutchings M. Tribology: friction and wear engineering materials. Cambridge, [21] Liu RL, Yan MF. Improvement of wear and corrosion resistances of 174PH
London: Edward Arnold; 1992. stainless steel by plasma nitrocarburizing. Mater Des 2010;31:23559.
[19] Berns H, Fisher A. Tribological stability of metallic materials at elevated [22] Whittle RDT, Scott VD. Sliding-wear evaluation of nitrided austenitic alloys.
temperatures. Wear 1993;162164:4419. Mater Technol 1984;11:2315.
[20] Karamis MB, Gerekcioglu E. Wear behavior of plasma nitrided steels at
ambient and elevated temperatures. Wear 2000;243:7684.