j o u r n a l o f m a t e r i a l s p r o c e s s i n g t e c h n o l o g y 2 0 7 ( 2 0 0 8 ) 187192

journal homepage: www.elsevier.com/locate/jmatprotec

Inuence of salt bath nitrocarburizing and post-oxidation

process on surface microstructure evolution of 17-4PH
stainless steel
Gui-jiang Li a , Jun Wang a , Qian Peng b , Cong Li b , Ying Wang b , Bao-luo Shen a,
a
b

College of Materials Science and Engineering, Sichuan University, Chengdu 610064, China
Nuclear Power Institute of China, Chengdu 610041, China

a r t i c l e

i n f o

a b s t r a c t

Article history:

The effect of QuenchPolishQuench complex salt bath heat-treatment (QPQ) on surface

Received 18 October 2007

microstructure of the 17-4PH stainless steel (SS) was investigated. A bright zone (compound

Received in revised form

-Fe2 (N,C)) is formed at the outermost surface of the nitrocarburized sample, followed by a

12 December 2007

zone (mixture Fe3 N/Fe4 N/CrN/-Fe) which is slightly etched. A thin oxides zone (Fe3 O4 /FeO)

Accepted 16 December 2007

is formed at the outer surface of the post-oxidized sample, followed by a zone (mixture
Cr2 N/-Fe2 (N,C) and the inner zone (CrN/N ). A signicantly high amount of oxygen is found
at the outermost surface of the post-oxidized sample. The push-effect of oxygen leads to

Keywords:

the peak nitrogen concentration, while the peak carbon concentration at the front of the

17-4PH stainless steel

nitrided layer is due to the push-effect of nitrogen. High microhardness values (>1200 HV0.1 )

QPQ salt bath

is obtained at the surface and then drops abruptly at the case/core interface to substrate

Microstructure

microhardness value for both of the nitrocarburized and post-oxidized samples.

X-ray diffraction

2007 Elsevier B.V. All rights reserved.

SEM

1.

Introduction

17-4 Precipitation-hardened stainless steel (17-4PH) is more

commonly appropriate to a variety of applications including oil eld valve parts, chemical process equipments,

nuclear reactor components, gears, fasteners (Kochmanski

and Nowacki, 2006; Ping Li et al., 2006). However, the wider
applications are restrained by their relatively poor wear and
corrosion properties. This necessitates the development of
advanced surface engineering techniques to address the problem. In fact, the previous study (Yeung et al., 1997; Li et al.,
1997; Luo et al., 2005) suggests that the performance of surface corrosionresistance provided by QuenchPolishQuench

complex salt bath heat-treatment process (QPQ) is better than

that provided by hard chrome plating or other galvanic layers.
Besides, it is reported that a corrosionresistance compound
layer, which can be formed after the nitriding process, could be
further improved when dipped to an oxidizing salt melt (Anon,
1984). Consequently, QPQ salt bath process is considered as
an effective engineering technology to improve the corrosion
properties mentioned above. It is a new type of harmful free to
environment process that originates from complex salt bath
nitriding technology where a combination property of high
fatigue resistance and good wear and corrosion resistance can
be achieved (Kunst, 1987). Materials properties are supposed
to be closely related to the microstructure, so the good proper-

Corresponding author at: College of Materials Science and Engineering, Sichuan University, Chengdu 610064, China. Tel.: +86 13688456619;
fax: +86 28 85402231.
E-mail address: shen baoluo@163.com (B.-l. Shen).
0924-0136/$ see front matter 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.jmatprotec.2007.12.082

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ties mentioned above are probably connected with the typical

surface microstructure obtained by QPQ. Unfortunately, in
the present literatures, there is no attention paid on detail
research on its surface microstructure. Therefore, the aim of
the study is focused on making an attempt to investigate the
inuence of QPQ process on surface micro-structure of 17-4PH
stainless steels, using X-ray diffraction (XRD), micro-hardness,
scanning electron microscopy (SEM) and glow discharge optical spectroscopy (GDOS).

2.

Experiment

2.1.

QPQ salt bath surface-treatment

The engineering of QPQ salt bath surface modied technology, which mainly consists of six steps: (1) degreasing, (2)
pre-heating, (3) nitriding, (4) oxidizing, (5) washing, (6) oil
immersion (Yeung et al., 1997) is one of the processes of
nitro-carburizing in a cyanidecyanate salt bath TF1 with
post-oxidation in a nitratenitrite salt bath AB1(Marusic et
al., 2006). During the process, the nascent nitrogen which
comes from the dissociation of CNO (Yeung et al., 1997):
4CNO CO3 2 + 2CN + CO + 2[N], diffuses into the lattices
from surface to the core resulting in formation of nitrides
compound. In the meantime, a few number of nascent carbon which comes from the dissociation of CO: 2CO CO2 + C
(Yeung et al., 1997) also permeates together with nitrogen. Finally, additional processes of post-oxidation after
nitro-carburizing have also been applied to further improve
properties of steels.

2.2.

Material and treatments

The samples were prepared from grade 17-4PH stainless steel

with the following compositions shown in Table 1.
Each sample of martensitic stainless steel which is treated
by solid solution treatment at 1040 C and then tempered at
595 C had dimensions of about 10 mm 10 mm 10 mm. All
of the at surfaces of each sample were ground and polished to
a mirror nish and then ultrasonically cleaned with acetone,
alcohol and distilled water in succession before QPQ treatment. The samples of 17-4PH steel grade 1 were preheated
to 350 C for 5 min in air and then nitro-carburized in the QPQ
TF1 salt bath at 580 C for 2 h (Fig. 1). After that a group of nitro-

Table 1 The main composition of 17-4PH stainless

steels (wt. %)
Element

wt. %

C
Cr
Ni
Cu
Mn
Si
P
Nb
Mo
Fe

0.04
16.39
4.32
3.40
0.30
0.60
0.023
0.36
Trace
Balance

carburized samples marked as 2 was cooled in warm water

(classical salt bath nitro-carburizing process) and the other
group of nitro-carburized 17-4PH samples 3 was exposed to
further post-oxidation in AB1 salt bath at 400 C for 10 min and
then cooled in warm water to room temperature. This group of
nitro-carburized 17-4PH samples marked as 3 was polished
and exposed again to further post-oxidation in AB1 salt bath at
400 C for 5 min and then cooled in warm water to room temperature. Detailed description of the QPQ process can refer to
Tenifer process found in literature (Wahl, 1984).

2.3.

Characterization

The structural changes in the modied layer were investigated using cross-sections for optical microscopy and Type
JSM5910-LV scanning electron microscopy. Information about
the nitrogen, carbon and oxygen depth proles is obtained
by glow discharge optical spectroscopy (GDOS). X-ray diffractometer Type Dmax-1400 with Cu K radiation was used to
determine the phases present in the modied layer, as well
as for the structural characterization of layers as a function
of depth. The latter was accomplished by carefully removing consecutive layers by mechanical polishing and analyzing
the new surfaces as described above. Micro-hardness testing
was performed on cross-sectioned samples. To preserve the
nitrided, hard surfaces from failure, a thin copper foil clamped
to the nitrided surface was carried out. Loads of 100 g and dwell
times of 15 s were employed. Three to ve indentations placed
at the same depth into the treated layer were used to prepare
the micro-hardness proles on a type of HV-1000 tester

Fig. 1 Thermo-chemical treatments of test samples made of stainless steel grade 17-4PH.

j o u r n a l o f m a t e r i a l s p r o c e s s i n g t e c h n o l o g y 2 0 7 ( 2 0 0 8 ) 187192

3.

Results and discussion

3.1.

Microstructure

189

Fig. 2a and b shows the cross-sectional microstructure of 17-4

PH treated by QPQ process. As can be seen from the optical
micrograph (OM) shown in Fig. 2(a), depth of the total nitrocarburized layer is observed to be approximately 45 m. A
bright zone of approximately 10 m is formed at the outermost surface of the nitrocarburized sample, followed by a zone
of about 35 m depth which is slightly etched and composed
of Fe3 N, Fe4 N, CrN and -Fe mixture. This indicates that the
subsurface zone which contains CrN and -Fe is susceptible
to etching in Nital contrary to the compound zone -Fe2 (N,C)
produced at the surface. When the post-oxidation treatment
is conducted at 400 C, the secondary electron image (SEI)
of the post-oxidized sample shows that depth of the total
post-oxidized layer is observed to be approximately 65 m.
A distinctly thin oxides (Fe3 O4 + FeO) zone of approximately
5 m is formed at the outermost surface (Fig. 2b), followed
by a compact zone of approximately 10 m (Cr2 N/-Fe2 (N,C)
mixture). The formation of a thin oxidized zone is probably
due to the oxidation reaction of the iron with the absorbed
oxygen on the surface. In addition, the inner zone which

Fig. 3 Depth prole of oxygen, nitrogen and carbon as a

function of distance from the surface: (a) nitrocarburized
and (b) post-oxidized.

is composed of CrN and N (Kim, 2003) is observed to be

approximately 50 m.

3.2.

Fig. 2 Micrograph of cross-section of the treated layer for

17-4PH: (a) nitrocarburized (OM) and (b) post-oxidized (SEI).

Elemental concentration prole

Fig. 3a and b shows the elemental concentration prole of

cross-section of the nitrocarburized and post-oxidized samples as a function of depth. As has been shown in Fig. 3(a),
a nitrogen maximum can be observed at the surface for
the nitrocarburized samples. Besides, a distribution prole of
nitrogen close to exponential decay in the range 4050 m
is also observed. This indicates the end of the treated layer.
On the other hand, the carbon and oxygen shows a gradually
decreasing to the core level from surface to the substrate. This
is probably due to the formation of the -Fe2 (N,C) nitride at the
surface and the formation of Fe3 N, Fe4 N and CrN at the subsurface. In Fig. 3b, a high oxygen concentration about 20 wt.% is
recorded, but it decreases abruptly from 20 to 5 wt.% with the
depth increasing beyond 5 m. By contrast, a peak nitrogen
concentration at about 5 m is observed. This is thought to
be due to the push-effect of oxygen (Tsujikawa et al., 2005).
It is inferred that the nitrogen accumulation inversely prevents oxygen from diffusing further. As a result, a relatively
high oxygen concentration is observed only in the rst 5 m.

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Fig. 5 XRD patterns of the structural characterization of

QPQ nitrided layers as a function of depth (000: untreated).

Fig. 4 XRD patterns of 17-4PH samples: (a) nitrocarburized

and (b) post-oxidized.

Whats more, it is evident that the leading edge of the prole is characterized by a rather rapid decay of the nitrogen
concentration on a scale of approximately 5 m. The turning
point of the prole is taken for end of the layer, and thus a
thickness of approximately 65 m is obtained for the postoxidized sample. This is in agreement with the microstructure
of the treated layer shown in Fig. 2b. Similarly, according to the
results provided by Tsujikawa et al. (2005), a relatively high
peak concentration of carbon is obtained at the front of the
nitrided layer due to the push-effect of nitrogen.

3.3.
XRD analysis for the nitro-carburized and
post-oxidized samples
Fig. 4 shows the X-ray diffraction patterns on the nitrocarburized and post-oxidized samples. According to Fig. 4a,
it is believed that the treated samples are possibly composed of nitride compound with the following order: Fe23 N,
Fe23 N + Fe4 N, Fe4 N from the treated surface towards the core.
A relatively stable CrN nitride is much easier to form at such
nitrocarburizing temperature as 580 C because Crnitrides
formation is favored due to their high negative enthalpy and
low Cr diffusivity in the matrix at temperature higher than
450 C (Foerster et al., 2007). As a result, there are additional
diffraction peaks of CrN and ferrite (-Fe). During the oxidation process, it is assumed that a chemical reaction between
the outward ux of iron cations and the absorbed oxygen
takes place at the outermost surface, thus the formation of
a Fe3 O4 /FeO zone at the outermost surface is obtained as well
as an accumulation of nitrogen atoms at the subsurface (Jutte
et al., 1997). This accumulation of nitrogen is the result of
the push-effect of oxygen. So this local nitrogen enrichment
facilitates the nuclei -Fe2 (N,C)1x formation at the subsur-

face, leading to the conversion of Fe3 (N,C) or  -Fe4 N1x into

-Fe2 (N,C)1x as conrmed by the detailed XRD depth analysis
in Fig. 5. Probably, Cr2 N is supposed to be more stable than
CrN at post-oxidation temperature 400 C, thereby, transformation of CrN into Cr2 N occurs together with the conversion
of Fe23 (N,C) or  -Fe4 N1x into oxides (Fe3 O4 and FeO) (Somers
and Mittemeijer, 1990; Somers et al., 1992, 1994; Graat et al.,
1998).
To conrm further the phase composition involved in the
post-oxidized sample, detailed XRD depth analysis is conducted at a depth of 15, 25, 35, 45 and 60 m below the top
surface and the results are shown in Fig. 5. The results of XRD
analyses of the treated samples are summarized in Table 2
in order to understand conveniently the phase compositions
evolution. As can be seen from Fig. 5, the intensity value of
diffraction peaks related to Fe3 O4 phase decreases as depth
increasing from 15 to 25 m. But their peaks disappear with
the thickness increasing over the depth of 35 m. This illustrates that post-oxidation only takes place at distance from
depth of about 25 m to the surface. Besides, no peak of -Fe
is found. Thus, it appears that the Fe3 O4 phase forms partially
at the expense of -Fe. In addition, the peak shift towards a
lower 2 value for -Fe indicates the lattice expansion. This
expansion is considered to be the result of post-oxidation,
since it is believed that post-oxidation leads to nitrogen diffusing inward and the formation of N . Furthermore, microstrains
can be induced by dissolution of nitrogen in the martensitic
matrix and also by the formation of CrN nitrides of varied stoichiometries and sizes, thus the broad peaks are observed. As
also observed in Fig. 5, the preexisting martensitic structure
remains present, so another reason for the peak broadening
can be attributed to the CrN and the martensite (-Fe) diffraction peak overlapping.

3.4.

Cross-sectional hardness prole

Fig. 6 shows micro-hardness proles of cross-sections of nitrocarburized and post-oxidized samples as a function of depth.
It can be observed that high microhardness values (>1200
HV0.1 ) is obtained at the surface and then drops abruptly at the
case/core interface to substrate microhardness value. Corre-

-Fe
CrN + -Fe + N

191

CrN + -Fe
CrN + -Fe + N
CrN + -Fe
CrN + -Fe + N
Fe4 N + CrN + -Fe
Fe3 O4 + Fe4 N + CrN
Fe4 N + CrN + -Fe
Fe3 O4 + Fe4 N + CrN
Nitro-carburized
Post-oxidized

Fe2 (N,C) + Fe3 N + Fe4 N + CrN + -Fe

Fe3 O4 + FeO + Fe2 (N,C) + Cr2 N + -Fe

25 m
15 m
0 m
Process

Table 2 The phase composition of various depths of nitrided layer of 17-4PH

35 m

45 m

60 m

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Fig. 6 Hardness prole of various nitrided layers of

17-4PH as a function of nitrided depth.

lating the nitrogen concentration results (see Fig. 3a) with the
surface hardnesses (see Fig. 6), it is suggested that the nitrocarburized layer thickness is veried to be about 45 m. In the
rst 20 m, the nitrocarburized sample exhibits higher microhardness than the post-oxidized sample due to formation of
a single -Fe2 (N,C) compound zone. However, its microhardness is becoming lower than that of the post-oxidized samples
with the depth increasing beyond 20 m. This is probably due
to the formation of N in the post-oxidized samples. Similarly,
as can be seen in Fig. 6, the microhardness prole of the postoxidized samples also shows the presence of a sharp change
in hardness between the case (post-oxidized layer) and the
core (matrix). The microhardness prole of the post-oxidized
sample is observed to be in agreement with the nitrogen concentration prole in Fig. 3b. So this conrms the fact that the
post-oxidized layer is approximately 65 m as shown in Fig. 2b.

4.

Conclusion

A bright zone of approximately 10 m is formed at the most

outer surface of the nitrocarburized sample, followed by a
zone of about 35 m depth composed of Fe3 N, Fe4 N, CrN and
-Fe mixture. A distinctly thin oxides (Fe3 O4 + FeO) zone of
approximately 5 m is formed at the most outer surface of the
post-oxidized sample, followed by a compact zone of approximately 10 m (Cr2 N/-Fe2 (N,C) mixture). The inner zone which
is composed of CrN and N is observed to be approximately
50 m.
After post-oxidation process, a signicantly high amount
of oxygen is found at the outermost surface. The peak concentration of the nitrogen prole which can be ascribed to the
push-effect of oxygen is obtained at the subsurface. Similarly,
the carbon prole shows a relatively high peak concentration
at the front of the nitrided layer due to the push-effect of
nitrogen. The advancing part of the prole is similar for the
nitrogen and carbon proles.
High microhardness values (>1200 HV0.1 ) is obtained at the
surface and then drops abruptly at the case/core interface to
substrate microhardness value for both of the nitrocarburized
and post-oxidized samples.

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Acknowledgements
The authors gratefully acknowledge support of this work by
Nuclear Power Institute of China and QPQ heat treatment
department of Chengdu Tool Institute.

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