JOURNAL OF RARE EARTHS, Vol. 27, No. 6, Dec. 2009, p.

1056

Effect of rare earths on mechanical properties of plasma nitrocarburized

surface layer of 17-4PH steel
LIU Ruiliang (), YAN Mufu (), WU Danlei ()
(National Key Laboratory for Precision Hot Processing of Metals, School of Materials Science and Engineering, Harbin Institute of Technology, Harbin 150001, China)
Received 11 May 2009; revised 10 October 2009

Abstract: The aim of this investigation is to reveal the influence of rare earths (RE) addition on mechanical properties of plasma nitrocarburized 17-4PH steel. The nitrocarburized layers were characterized by optical microscope, scanning electron microscope equipped with energy dispersive X-ray analyzer, X-ray diffractometer, microhardness tester and pin-on-disc tribometer. The results showed that RE atoms
could diffuse into the surface layer of 17-4PH steel plasma nitrocarburized at 500qC for 4 h and did not change the phase structure of the surface layer. The presence of RE in the surface layer increased thickness, toughness, microhardness and wear resistance of the nitrocarburized
layer. Additionally, grain boundary and micro-crack parallel to the surface have been depressed by plasma nitrocarburizing with RE addition.
The severe plastic deformation, adhesion and abrasive wear produced during wear of the experimental steel could be changed into mild micro-abrasion and slight micro-crack wear by plasma nitrocarburizing without and with RE addition, respectively.
Keywords: 17-4PH steel; plasma nitrocarburizing; mechanical properties; rare earths

17-4PH martensitic stainless steel has been widely utilized in the aerospace, chemical, petrochemical, food processing, paper and general metalworking industries because
of its very good combination of strength, toughness, corrosion resistance and ease of fabrication[1]. However, 17-4PH
steel has poor tribological properties when sliding against
some engineering materials. Therefore, it cannot meets
challenging design requirements of high strength, high
toughness and good wear resistance in some application
fields. Several surface modifying such as gas nitriding[2,3],
ion implantation[4], plasma nitriding[58] and salt bath nitrocarburizing[9] have been carried out for improving wear
properties of this steel.
The effects of RE on thermochemical treatments have
been studied from 1980s[10]. It has been found that RE elements can diffuse into the surface layer and at the same time
can also help carbon and nitrogen atoms to diffuse to a significant depth during gas carburizing and carbonitriding of
steels[1115]. However, the effect of RE addition during
plasma nitriding on mechanical properties of the surface
layer of stainless steel has not been reported until now. In
this paper, the authors attempt to reveal the microstructure
and wear properties of the surface layer of 17-4PH steel
plasma nitrocarburized with and without RE addition.

1 Experimental
1.1 Materials
The as-received 17-4PH steel with the chemical composition (wt.%) 0.06C, 17.22Cr, 3.91Ni, 3.01Cu, 0.16Nb, 0.81Si,
0.76Mo, and balance Fe was used. The steel was solution
treated at 1040 C for 1 h and then cooled in oil. The samples were machined to 13 mm13 mm6 mm and its surface
being plasma nitrocarburized were manually ground using
silicon carbide papers from 240 to 800 grades. The samples
for wear test were machined to the dimension of 40 mm
3 mm.
1.2

Plasma nitrocarburizing with and without RE

addition

Nitrocarburizing of 17-4PH steel was performed in a 30 kW

pulse plasma nitriding furnace. RE reagents, in the form of
mixed compounds of RE salt and its oxide mainly bearing
La and Ce, were dissolved in ethanol and then introduced
into the furnace along with N2 and H2 gases. Then the samples were nitrocarburized at 500 C for 4 h with and without
RE addition. After the treatment, the samples were slowly
cooled to room temperature in the furnace. The detailed

Foundation item: Project supported by the National Natural Science Foundation of China (50871035), the Ph.D. Programs Foundation of Ministry of Education of
China (20060213017)
Corresponding author: YAN Mufu (E-mail: yanmufu@hit.edu.cn, ruiliangliu@126.com; Tel.: +86-451-86418617)
DOI: 10.1016/S1002-0721(08)60388-9

LIU Ruiliang et al., Effect of rare earths on mechanical properties of plasma nitrocarburized surface layer of 17-4PH steel

2 Results and discussion

Table 1 Treatment information of the samples

Treatment

N2:H2:C2H5OH
(RE)

Temperature/

1057

Time/

Voltage/

Pa

500

600650

200

P13

1:3:0.5

P13+RE

1:3:0.5(RE)

P00

Solution treated+quenched 17-4PH steel (Untreated)

Pressure/

treatment information for the experimental steel is shown in

Table 1.
1.3 Characterization
The nitrocarburized layers etched by Marbles reagent
were observed by optical microscope (OM, type CMM-33E).
The surface phase structure of the nitrocarburized layers
were analyzed by X-ray diffractometer (XRD, type
D/max-rB) using Cu K radiation (=0.15405 nm). The RE
content in the nitrocarburized layer was examined by scanning electron microscope (SEM, type S-4700) equipped
with energy dispersive X-ray analyzer (EDS).
The hardness of the nitrocarburized surface was measured
by Vickers hardness tester (type HV-1000) under a test load
of 0.1 N for 15 s. Tribological properties of the untreated
and plasma nitrocarburized 17-4PH steel were evaluated by
pin-on-disc tribometer (type POD-1). During the test, the
steel sample (disc) was rotating at a speed of 200 r/min (0.1
m/s) for 180, 600 and 11280 s (i.e. 18 m, 60 m and 1128 m)
against a stationary WC ball of diameter 5 mm, and the normal contact load was 10 N. All tests were conducted in air
and without lubrication. The morphology of worn surface
was observed by SEM (type S-570). The mass losses were
measured using an electronic balance (type FA2201B) with
an accuracy of 104 g. The wear loss rates were calculated
using Eq. (1):
w
k
(1)
s
wherew is the mass loss in mg, s is the sliding distance in m.

2.1 Effect of RE on microstructure and phase structure

of plasma nitrocarburized layer
2.1.1 Microstructure of nitrocarburized layer The microstructures of the surface layer of 17-4PH steel plasma nitrocarburized are shown in Fig. 1. It can be seen that the layer
depth is a little thinner without RE than with RE addition
after plasma nitrocarburizing and their thickness are about
50 and 55 m, respectively. Further observation shows that
there exist visible grain boundaries and micro-cracks parallel to the treated surface nitrocarburized without RE addition
(Fig. 1(a)), which will remarkably affect mechanical properties of the surface layer. However, this kind of grain
boundaries and micro-cracks were restrained by plasma nitrocarburizing with RE addition, as shown in Fig. 1(b)),
which can be beneficial to the improvement of the wear resistance of the surface layer.
2.1.2 Phase structure of nitrocarburized layer XRD patterns of the surface layer of 17-4PH steel plasma nitrocarburized with and without RE addition are shown in Fig. 2.
Obviously, RE addition does not change the phase structure
of nitrocarburized surface layer, i.e., the surface layer consists mainly of -Fe4N, D-Fe and CrN phases.
However, addition of RE apparently increases the intensity of -Fe4N phase diffraction peaks (111) and (200),
i.e., the proportion of -Fe4N phases in the surface layer is
higher with RE than without RE addition, which results in
the increase of hardness and wear resistance of the modified
layer.
2.1.3 Element analysis of nitrocarburized layer Fig. 3
gives the EDS results of element content about 30 m distance from surface of plasma RE nitrocarburized 17-4PH
steel. Obviously, the formation of nitrocarburized layer results mainly from certain amount of nitrogen and carbon
atoms diffused into the surface layer of experimental steel.

Fig. 1 Morphologies of the surface layer of 17-4PH steel plasma nitrocarburized at 500qC for 4 h without RE (a) and with RE (b) addition

1058

JOURNAL OF RARE EARTHS, Vol. 27, No. 6, Dec. 2009

Fig. 2 XRD patterns of the surface layer of 17-4PH steel plasma nitrocarburized at 500qC for 4 h without RE (a) and with RE (b) addition

Fig. 3 EDS results of element content in the surface layer (30 m distance from surface) of 17-4PH steel plasma RE nitrocarburized at
500qC for 4 h

More importantly, the amount of La and Ce are all more

than 1.3 wt.% at the same position. The presence of La and
Ce improves the microstructure of nitrocarburized layer (see
Fig.1 (b)), which will also affect mechanical properties of
the surface layer.
2.2 Hardness and toughness of plasma nitrocarburized
layer
2.2.1 Surface hardness of nitrocarburized layer Fig. 4
shows the surface hardness of 17-4PH steel treated under
different conditions. It can be seen that the hardness of
plasma nitrocarburized surface with and without RE addition are all higher than 1400 HV which is about 3.9 times
harder than the untreated 17-4PH (360 HV). The obvious
increase in microhardness is due mainly to the formation of
nitrides in the surface layer.
In addition, the surface hardness of the plasma RE nitrocarburized layer is about 60 HV higher than that of plasma
nitrocarburized one. This is attributed mainly to the microstructure improvement and the change of phase proportion
in plasma RE nitrocarburized layer, as shown in Figs. 1 and

2. Furthermore, because the atomic radius of RE is larger

than that of iron atom, diffusion of RE atoms diffused into
surface layer can produce a lot of lattice distortion regions
where nitrogen and carbon atoms are easy to reside, which
favors the diffusion of carbon atoms and the formation of a
lot of dispersed nitrides/carbonitrides. Thus, dispersion
strengthening could lead to the increase in hardness[1012].

Fig. 4 Surface hardness of 17-4PH steel treated under different

conditions

LIU Ruiliang et al., Effect of rare earths on mechanical properties of plasma nitrocarburized surface layer of 17-4PH steel

2.2.2 Toughness of nitrocarburized layer The toughness of

nitrocarburized layer can be characterized by Vickers hardness[16]. The indentation morphologies in the surface layer of
17-4PH steel plasma nitrocarburized with and without RE
addition are shown in Fig. 5.
It can be seen that there are two kinds of indentation morphologies. The severe crack with long tail was produced in
plasma nitrocarburized surface layer (see Fig. 5(a)) when the
microhardness test was carried out employing a test load of
0.5 N. However, there is only slight crack formed in plasma
RE nitrocarburized surface layer under the same test condition, as shown in Fig. 5(b), i.e., the addition of RE can
greatly increase the toughness of surface layer. Obviously,
the improvement of toughness is related to the microstructure shown in Fig. 1.

1059

plasma nitrocarburizing. Moreover, lower proportion of

D-Fe phase and the improvement of microstructure in RE
plasma nitrocarburized layer lead further to the decrease in
the coefficient of friction and wear rate.
2.3.2 Worn morphology and wear mechanism Fig. 8
shows the worn morphology of the untreated 17-4PH steel.
It can be seen wear occurs due to severe plastic deformation
and adhesion with traces of abrasion as well as micro-cracks.
The poor wear resistance is directly evidenced by the deep
and wide wear track on the sample surface (Fig.8 (a)). It also

2.3 Tribological properties

2.3.1 Coefficient of friction and wear rate The coefficient
of friction the 17-4PH steel treated under different conditions is shown in Fig. 6. The results show that the coefficient
of friction of the steel surface layer decreased to 0.45 and
0.35 from original 0.50 using plasma nitrocarburizing without and with RE addition, respectively. The wear rates of the
three samples are shown in Fig. 7. We can see that the wear
rates are 26.9103, 0.9103 and 0.5103 mg/m for the untreated, nitrocarburized and RE nitrocarburized samples, respectively. Thus, plasma nitrocarburizing treatment can apparently decrease the wear rate of the steel.
The change of the coefficient of friction and wear rate
depends on the phase structure and its proportion as well as
the microstructure in surface layer. The decrease of the coefficient of friction and wear rate results mainly from the
existence of -Fe4N, D-Fe and CrN phases produced by

Fig. 6 Coefficient of friction for 17-4PH steel treated under different conditions

Fig. 7 Wear rate of 17-4PH steel treated under different conditions

after sliding 1128 m at room temperature (Load: 10 N;
Slider: WC ball)

Fig. 5 Indentation morphologies in surface layer of 17-4PH steel

plasma nitrocarburized without RE (a) and with RE (b)
addition

Fig. 8 SEM images of the worn surface of the untreated 17-4PH

steel after sliding 18 m with a WC ball under a load of 10 N
(a) Wear track; (b) Enlarged detail of Fig. 8(a)

1060

can be seen that the worn surface is severely deformed and

scored, which leads to significant roughening and tearing of
the surface and generation of plate-like metallic wear debris
(Fig. 8(b)). It is a typical morphology of adhesive wear[17].
The wear track on the 17-4PH steel surface nitrocarburized without RE addition is shallow and superficial, as
shown in Fig. 9(a). The worn surface was in a mild mode
characterized by micro-abrasion and surface polishing with
the formation of some micro-cracks and micro-craters, and
no obvious sign of plastic deformation and adhesive wear
were observed (Fig. 9(b)). There is only polished appearance
with some fine wear products trapped in the valleys of the
original grinding marks. Obviously, the wear of the nitrocarburized sample is caused mainly by micro-abrasion action of the slider, followed by some wear debris pushed to
the edges of wear track and trapped in valleys of the original
grinding marks.
Fig. 10 shows the worn morphology of plasma RE nitrocarburized 17-4PH steel. The wear track on the surface is
even shallower. The worn surface is almost free from plastic
deformation, only some micro-cracks and micro-polishing
trace are included, which is much smoother than that shown

Fig. 9 SEM images of the worn surface of plasma nitrocarburized

17-4PH steel after sliding 60 m with a WC ball under a load
of 10 N
(a) Wear track; (b) Enlarged detail of Fig. 9(a)

Fig. 10 SEM images of the worn surface of plasma RE nitrocarburized 17-4PH steel after sliding distance 60 m with a
WC ball under a load of 10 N
(a) Wear track; (b) Enlarged detail of Fig. 10(a)

JOURNAL OF RARE EARTHS, Vol. 27, No. 6, Dec. 2009

in Fig. 9(b). The production of few oxidative wear in Fig. 10

(a) may contribute to micro-polishing wear, since the
stainless steel surface has the tendency to form oxide film
under ambient condition.
In a word, the higher wear resistance of the surface nitrocarburized with RE than without RE addition is based
mainly on the fact that RE atoms diffused into the surface
layer of steel 17-4PH, and improved the microstructure, and
increased the microhardness and toughness of the modified
layer.

3 Conclusions
(1) RE atoms such as La and Ce could diffuse into the
surface layer of 17-4PH steel and did not change the phase
constitution (-Fe4N, D-Fe and CrN) of the surface layer
during plasma nitrocarburizing at 500 qC for 4 h. The presence of RE atom in the surface layer increased thickness,
toughness, microhardness and wear resistance of the surface
layer.
(2) The grain boundary and micro-crack (parallel to surface) produced during plasma nitrocarburizing could be depressed by plasma nitrocarburizing with RE addition. The
severe plastic deformation, adhesion and abrasive wear
produced during wear of the experimental steel could be
changed into mild micro-abrasion and slight micro-crack
wear by plasma nitrocarburizing without and with RE addition.
Acknowledgements: The authors gratefully acknowledge the National Natural Science Foundation of China (50871035), the Ph.D.
Programs Foundation of Ministry of Education of China
(20060213017) for financial support of this research work.

References:
[1] Sun Y, Bell T. Low Temperature plasma nitriding characteristics of precipitation hardening stainless steel. Surface Engineering, 2003, 19(5): 331.
[2] Kochmaski P, Nowacki J. Activated gas nitriding of 17-4PH
stainless steel. Surface & Coatings Technology, 2006, 200:
6558.
[3] Kochmanski P, Nowacki J. Influence of initial heat treatment
of 17-4PH stainless steel on gas nitriding kinetics. Surface &
Coatings Technology, 2008, 202: 4834.
[4] Manova D, Thorwarth G, Mndl S, Neumann H, Strizker B,
Rauschenbach B. Variable lattice expansion in martensitic
stainless steel after nitrogen ion implantation. Nuclear Instruments and Methods in Physics Research B, 2006, 242: 285.
[5] Leyland A, Lewis D B, Stevenson P R. Low temperature
plasma diffusion treatment of stainless steels for improved
wear resistance. Surface & Coatings Technology, 1993, 62:

LIU Ruiliang et al., Effect of rare earths on mechanical properties of plasma nitrocarburized surface layer of 17-4PH steel
608.
[6] Esfandiari M, Dong H. Plasma surface engineering of precipitation hardening stainless steel. Surface Engineering, 2006,
22(2): 86.
[7] Esfandiari M, Dong H. The corrosion and corrosion-wear behavior of plasma nitrided 17-4PH precipitation hardening
stainless steel. Surface & Coatings Technology, 2007, 202:
466.
[8] Li G J, Wang J, Li C. Microstructure and dry-sliding wear
properties of DC plasma nitrided 17-4PH stainless steel. Nuclear Instruments and Methods in Physics Research B, 2008,
266: 1964.
[9] Li G J, Wang J, Peng Q, Li C, Wang Y, Shen B L. Influence
of salt bath nitrocarburizing and post-oxidation process on surface microstructure evolution of 17-4PH stainless steel. Journal of Materials Processing Technology, 2008, 207: 187.
[10] Wei Y D, Liu Z R, Wang C Y. A note on coating of surface
diffusion infiltration of RE on steel 20 and Armco iron by
chemical process. Acta Metallurgica Sinica (in Chin.), 1983,
19: B197.
[11] Zhu F Y, Cai C H, Meng Q C, Yan M F, Liu Z R. Observation
and analysis of the microstructure in carburized surface layer

1061

of steel 20Cr2Ni4A treated with conventional and rare earth

carburizing process. Journal of Rare Earths, 1996, 14: 154.
[12] Bell T, Sun Y, Liu Z R, Yan M F. Rare earth surface engineering. Heat Treatment of Metals, 2000, 27: 1.
[13] Yan M F, Pan W, Bell T, Liu Z R. The effect of rare earth
catalyst on carburising kinetics in a sealed quench furnace
with endothermic atmosphere. Applied Surface Science, 2001,
173: 91.
[14] Yan M F, Sun Y, Bell T, Liu Z R, Xia L F. Effect of temperature and phase constitution on kinetics of diffusion. Journal of
Rare Earths, 2002, 20: 330.
[15] Yan M F, Sun Y, Bell T, Liu Z R, Xia L F. Diffusion of La in
plasma RE ion nitrided surface layer and its effect on nitrogen
concentration profiles and phase structures. Acta Metallurgica
Sinica (in Chin.), 2000, 36: 487.
[16] Anstis G R, Chantikul P, Lawn B R, Marshall D B. A critical
evaluation of indentation techniques for measuring fracture
toughness. Journal of the American Ceramic Society, 1981, 64:
533.
[17] Sun Y, Bell T. Dry sliding wear resistance of low temperature
plasma carburised austenitic stainless steel, Wear, 2002, 253:
689.