Journal of Materials Processing Technology 157–158 (2004) 415–421

Structure and properties of X150CrMo12 steel after

PVDM-R by magnetron deposition of chromium
nitride coatings with next heat treatment
R. Shishkova , M. Jordanovb , W. Kwaśnyc,∗
a Department of Material Science and Technology of Materials, University of Russe, 8 Studentska Street, 7017 Russe, Bulgaria
b Department of Engineering and Pedagogy, Technical University of Sofia, 59 Burgasko Shosse, 8800 Sliven, Bulgaria
c Institute of Engineering Materials and Biomaterials, Silesian University of Technology, Konarskiego St. 18a, 44-100 Gliwice, Poland

Abstract

The CrN coatings have been deposited on X150CrMo12 steel substrates by sputtering of a sintered chromium target at metallizing tem-
peratures Ts , ranging between 450 and 850 ◦ C and bias voltage Us , ranging from 0 to −200 V by the method of “Plasma Vacuum Diffusive
Metallizing-Reactive scheme” (PVDM-R) in a single-chamber vacuum furnace with a graphite heater and a heat-isolative chamber, made of
carbon wool. The method is based on the diffusive interaction between the substrate and condensate, transforming the condensate into a diffu-
sive coating with or without a residual condensate, during the metallizing. The covered samples are hardened at temperature 1020 ± 10 ◦ C and
tempered at 200 ◦ C in vacuum. The kinetics and mechanism of the structure forming of the coatings are investigated. The chemical and phase
composition of the coatings, the lattice parameter and texture coefficient are determined by XRD and GDOES analyses. Their micro-hardness
and Young’s modulus also have been investigated. The microstructure and the type of the coatings before and after heat treatment have been
determined.
It is determined that with pure chromium or ferro-chromium target for time 60 min is possible with previously or accompanied deposition
of condensate on X150CrMo12 steel substrates (by direct or indirect process) and next vacuum heating treatment are forming chromium-
carbide or chromium-nitride vacuum-diffusion coating with KDC = 1 with thickness, which are equal to the both ranges, which have practical
importance: 4–8 ␮m or 10–20 ␮m.
It is concluded that the plasma-vacuum deposition process of vacuum condensates, built only of CrN on the steel X150CrMo12 or another
steel of this group, cannot be used as a preliminary process, because the vacuum heat treatment (hardening and tempering) change the type
of the coverage from vacuum coating to vacuum-diffusive coating with changing phase composition.
© 2004 Published by Elsevier B.V.

Keywords: Magnetron sputtering; CrN coatings; Heat treatment; Hardness; Young’s modulus; Texture coefficient

1. Introduction The vacuum methods, based respectively on the physi-

The chromium-based protective wear-resistant and dec-
orative coatings have a structure and properties analogous
to those of the TiN coatings and even exceed them in
some aspects [1,3,5,8,9]. They possess a higher corrosion-
resistance [1,2,7], better heat-resistance and according to
some authors—a lower friction coefficient etc. [1,3,4,6].
∗ Corresponding author.
E-mail address: wkwasny@zmn.mt.polsl.gliwice.pl (W. Kwaśny).
cal vapor deposition (PVD) and chemical vapor deposition
(CVD) have been predominantly developed and used for their
obtaining. Among the PVD methods the magnetron sputter-
ing and arc-evaporation have imposed lately as the most per-
spective methods.
In last years investigations for developing of a new and per-
spective method for Plasma Vacuum Diffusive Metallizing
(PVDM) have been carried out. At this method the condensate
is deposited in a vacuum furnace on heated metal substrates
by magnetron sputtering. The diffusive interaction between
the condensate and the substrate creates a coating of diffusive

0924-0136/$ – see front matter © 2004 Published by Elsevier B.V.

doi:10.1016/j.jmatprotec.2004.09.065
416 R. Shishkov et al. / Journal of Materials Processing Technology 157–158 (2004) 415–421
type. The character and the type of the coating are defined
by the coefficient of diffusion, KDC [11], which is the rela-
tion between the thickness of the intermediate diffusive layer,
created on the borderline layer/substrate and the total thick-
ness of the coating. When 0 < KDC < 0.1 the coating is defined
as a vacuum condensate with diffusive connection with the
substrate (VC with DC). At values 0.1 < KDC < 0.3 it is de-
fined as a transitional coating (TR C), and at 0.3 < KDC < 1.0
as a vacuum-diffusive coating with residuary condensate
(VDC with RC). When KDC = 1 the coating is a vacuum-
diffusive coating without residuary condensate (VDC
without RC).
At a great interest of applied and theoretical way is the va-
riety of the method—the so-called Plasma Vacuum Diffusive
Metallizing-Reactive scheme (PVDM-R). In this scheme by
sputtering in reactive environment is depositing condensate,
whose contents are equal to the wanted coating. For exam-
ple, forming of a chromium-carbide coating on parts, which
are poor of carbon, as a low-carbon stainless steel, ␣-Fe, Cu
and other [10–12]. In those cases it is hard to create diffusive
chromium-carbide coating by the other methods, for which
previous carbonizing process has to done, but it is not always
possible and technologically profitable.
The aim of the present work is to study the possibility to
obtain CrN coatings in a vacuum furnace by plasma vac-
uum diffusion reactive metallizing process (PVDM-R) of
the sintered chromium target at high temperatures and next
heat treatment, and also to explore possibility of deposition
of these hard and wear-resistant coatings to be transformed
from a final treatment into an initial one, which will create
a possibility to improve this way the working properties of
a large number of non-heat-resistant and semi-heat-resistant
steels.
2. Experimental procedure
The coatings have been deposited in a single-chamber vac-
uum furnace with a built-in DC unbalanced magnetron. Af-
Fig. 1. Schematic presentation of the heat treatment process of the substrates after deposition of CrN coatings.
ter reaching an initial vacuum of 6 × 10−4 to 7 × 10−4 mbar,
before depositing the films, the substrates have been heated
to the corresponding metallizing temperature Ts , rang-
ing between 450 and 850 ◦ C. Reaching the vacuum of
7 × 10−4 mbar, cleaning is carried out under the conditions
of glow discharge in Ar flow at 1 × 10−1 mbar for 10 min
at 900 V. A sintered pure 99.998% chromium target has been
sputtered at a pressure of 8 × 10−3 to 9 × 10−3 mbar in a flow
gas mixture of Ar (2.6 sccm) and N2 (26 sccm), for 60 min
at a sputtering power of 3.2 kW (Isp = 8 A), providing con-
densation rates of 40–85 nm/min for a target-to-substrate dis-
tance Lt–s = 70 mm. The metallizing temperature Ts have been
changed between 450 and 850 ◦ C and the substrate bias Us
has been 0 V, except the experiments at 500 ◦ C, which have
been carried out at substrate potentials of 0, −50, −100 and
−200 V, respectively. Samples of semi-heat-resistant steel
X150CrMo12 (1.45–1.65% C, 11–12.5% Cr, 0.15–0.30% V,
0.40–0.60% Mo, 0.15–0.40% Mn, 0.15–0.35% Si, 0–0.03%
S, 0–0.03% P) have been used for substrates. After the depo-
sition, on the coated substrates is subjected to vacuum heat
treatment (VHT) in a two-chamber vacuum furnace together
with real parts at a technological standard process for the
given substrate material. As it is shown in Fig. 1, the heat-
ing up process to temperature of hardening (1020 ± 10 ◦ C)
includes an intermediate keeping at 850 ◦ C for 60 min. Af-
ter the hardening, the tempering on 200 ◦ C in vacuum was
made.
The chemical composition of the films has been deter-
mined by Ar glow discharge optical emission spectroscopy
(GDOES), using a LECO 750GDS® Instrument.
The phase composition, crystallographic structure and
axial texture of the films have been analysed by X-ray
diffraction (XRD) using Co K␣ radiation. The microhard-
ness and Young’s modulus have been determined by a Vick-
ers Nanoindentation tester FISCHERSCOPE® H100 us-
ing a load force of 50 mN. The morphology and thick-
ness of the films have been investigated on a cross-section,
using a NIKON® -OPTIPHOT metallographic micro-
scope.
 R. Shishkov et al. / Journal of Materials Processing Technology 157–158 (2004) 415–421
3. Results and discussion
3.1. Microstructure and topography
The exploring of the coatings topography separates them
into two groups. The coatings from the first group, obtained
up to Ts = 600 ◦ C fit to Zone II of the Thornton’s zone model,
while those from second group, obtained at 650 ◦ C and es-
pecially obtained at 850 ◦ C fit to Zone III of the Thornton’s
zone model [13–15]. The boundary between the zones is in
essence, the recrystallization temperature of the condensate
material. For nitrides and carbides this temperature is about
(0.7–0.8) Ts and in the given case for CrN it corresponds to
600–650 ◦ C. The recrystallization process means intensive
volume diffusion and a possibility for a diffusive interaction
with the substrate [11,12].
The microstructure investigations on a cross-section
shows that till Ts = 600 ◦ C the coatings are mono-layered and
are extremely disperse having a columned structure. They do
not change their type and belong to the vacuum condensates
with micro-diffusive bond to the substrate [11]. In the coat-
ings at 650 ◦ C it is difficult to be observed, but at 850 ◦ C a
condensate CrN and a thin underlayer between the coating
and the substrate can be seen.
The microstructure of the CrN coatings, deposited on
X150CrMo12 substrates at 650 and 850 ◦ C temperatures,
after VHT is a vacuum-diffusive coatings without residual
condensate of CrN. They consist of two basic underlayers: an
outer one having a grey colour built of alloyed Cr2 N + Cr2 CN
and an inner one, which is more dense and lighter, consisting
of alloyed chromium carbides.
3.2. Phase composition and texture
The basic changes in the coatings, accompanied by in-
creasing the temperature of magnetron deposition, lead to
the change of the texture and the phase composition of the
coatings.
The kind and the degree of texture are determined by many
factors, but a resultant vector of energetic influence can show
the general action of more of them. It is sum of the vectors:
of energetic influences of the target (by the radiation of the
zone of sputtering); of the stream of the metal steam (density
and angle of the attack); of the radiation heater, of the ion
bombardment of the plating with bias voltage, the influence
of the secondary plasma of the unbalanced DC magnetron,
etc.
The trend of the forming condensate is to direct its crystal
structure in direction, which have to make sure maximal heat
going and mass transportation.
The phase composition of the coating in this case is deter-
mined basically by the degree of diffusive interaction between
the condensate and the substrate. For it basic meaning has the
temperature of metallizing and the chemical composition of
the substrate.
According to the XRD analysis till 650 ◦ C the coatings
have only one phase, CrN. Because of the low thickness of
417
Fig. 2. Diffraction patterns of CrN coatings, deposited on X150CrMo12
steel substrates at 650 ◦ C/60min: (a) before VHT; (b) after VHT (hardening
at 1020 ◦ C in oil and tempering at 200 ◦ C in vacuum).
the coatings (2.13–5.74 ␮m) in the X-ray patterns appear also
lines of ferrite out of the substrate.
Till 600 ◦ C the phase CrN have an orientation 3 1 1 and
2 0 0, but at 650 ◦ C appear the line 1 1 1 (Fig. 2a).
In the XRD patterns of the coatings, deposited at 850 ◦ C,
the line 1 1 1 has stronger intensity and appeared some of
the lines of the phase (CrFeMe)2 CN, but they have very little
intensity (Fig. 3a).
The crystal lattice of the CrN is strongly deformed in the
interval Ts = 450–850 ◦ C and the lattice parameter is less than
the theoretical one. When increasing Ts the lattice parameter
is increasing and the deformations tends to a decreasing. This
result is in relation with the lessening the quantity of the N2
on one hand and increase the quantity of the Cr on the other
hand.
The increase of the substrate bias to a negative direction
increase the deformations which according to 3 1 1 tends to
4.23 × 10−3 nm at Us = −200 V.
According to the X-ray patterns the coatings have a well-
expressed texture. The level of the texture is defined by cal-
culating the coefficient of texture δhkl by method, which
often is used for vacuum condensates [3]. The variation of
texture coefficient δhkl of the CrN coatings as a function
of the metallizing temperature Ts and bias voltage Us of an
X150CrMo12 substrates is shown in Fig. 4. The increase of
Ts without a bias voltage changes the preferred orientation
3 1 1 at 450 ◦ C into a mixed orientation 3 1 1 and 2 0 0
at Ts = 55–600 ◦ C and then into 2 0 0 at 850 ◦ C (Fig. 4a).
This is explained with increasing of the surface movement
of adsorbed atoms when increasing the substrate tempera-
ture, which helps for their closer disposition. The effect of
418 R. Shishkov et al. / Journal of Materials Processing Technology 157–158 (2004) 415–421
Fig. 3. Diffraction patterns of CrN coatings, deposited on X150CrMo12
steel substrates at 850 ◦ C/60min: (a) before VHT; (b) after VHT (hardening
at 1020 ◦ C in oil and tempering at 200 ◦ C in vacuum).
the bias is similar to that when increasing the temperature.
At Us = −50 V the coating is textured on direction 3 1 1,
at Us = −100 V the orientation becomes mixed 3 1 1 and
2 0 0, and at Us = −200 V is changed to strongly mono-axis
orientation 2 0 0 (Fig. 4b), which is more dense direction
Fig. 4. Texture coefficient δhkl of the coatings as a function of the deposi-
tion temperature Ts (a) and bias voltage Us (b) of an X150CrMo12 substrates.
than 3 1 1. The variation of the texture from less compact-
ness to more compactness orientation when increasing the
temperature (respective bias voltage) has been observed and
confirmed by other scientists [2–4].
The coatings deposited at 850 ◦ C have two-phase com-
position, CrN and (Cr, Me)2 CN. This speaks of a diffusive
interaction between the condensate and substrate (the carbon
from the substrate and the nitrogen from the condensate) at
the explored conditions. As a result the phase (Cr, Me)2 CN is
formed. It showed a little displacement of the X-ray patterns
due to the diffusion of other elements (mainly Fe and also W,
Mo, V, Ti, Si), which are signed with “Me”. This is confirmed
by the GDOES analysis.
A considerable modification in phase composition is
showed of the coatings deposition at 650 and 850 ◦ C after
VHT. The level of the diffusion interaction between the con-
densate and substrate, defines the phase composition of the
coatings. In this case the temperature of metallization and the
composition of the substrate are of a great interest. The phase
transformations occur according the following sequence:
(1) For the condensate: CrN → Cr2 N → (Cr, Me)2 N → (Cr,
Me)2 CN → (Cr, Me)23 C6 → (Cr, Me)7 C3 .
(2) For the substrate: (Cr, Me)2 CN → (Cr, Me)7 C3 .
The way of obtaining the phase (Cr, Me)2 CN in the con-
densate and the substrate are different and depends on the
velocity of diffusion of the different elements, or on the vari-
ation of the chemical compositions in order of the triple dia-
grams Cr–CrN–CrC and Cr–Fe–C.
After VHT in the coatings, deposited at 650 ◦ C the phase
CrN is missing. This phase is transformed firstly into a nitride
Cr2 N, then into a carbonitride (Cr, Me)2 CN and finally into
a carbide (Cr, Me)23 C6 (Fig. 2b). The coatings deposited at
850 ◦ C after VHT are transformed from a mono-phase CrN
to a three-phase composition (Cr2 N + (Cr, Me)2 CN + (Cr,
Me)23 C6 ) (Fig. 3b).
At both the temperatures it is observed that the patterns
of the phase (Cr, Me)7 C3 , coming from the substrate. The
specificity of the coatings deposited at 650 ◦ C after VHT, is
the phase (Cr, Me)23 C6 , which either is missing, or is in very
small quantity. This shows a stronger diffusion in comparison
with the coatings deposited at 850 ◦ C.
3.3. Chemical composition
All the coatings deposited in Ts between 450 and 600 ◦ C
have the same structure and arrangement of the elements in
depth. According to the general model the coatings are VC
with diffusion bond [11]. Until 850 ◦ C, the coatings are clas-
sified as transitional ones depending on their total thickness.
The depth profile outlines four zones [10], but in the coating
deposited at 650 and 850 ◦ C after VHT additional underlay-
ers appear.
The heat treatment of the coatings in this case leads to a
significant redistribution of the elements of the condensate
and the substrate. This causes a forming, by a phase recrys-
 R. Shishkov et al. / Journal of Materials Processing Technology 157–158 (2004) 415–421 419

Fig. 5. GDOES profile of CrN coating on X150CrMo12 steel after heat treatment obtained at: (a) Ts = 650 ◦ C, Lt–s = 70 mm, Us = 0 V and (b) Ts = 850 ◦ C,
Lt–s = 70 mm, Us = 0 V.

tallization, of a transitive diffusive layer consisted of two
underlayers δtdl = (δs→c + δc→s ). After VHT, the coatings de-
posited at 650 and 850 ◦ C on X150CrMo12 steel substrates
are transformed into VDC without RC. In the coatings de-
posited at 650 ◦ C the first underlayer δ1s→c is equal by chem-
ical composition to the (Cr, Me)2 CN phase from the ternary
diagram Cr–CrN–CrC, while the second underlayer δs→c is
equal to (Cr, Me)23 C6 from the diagram Cr–Fe–C (Fig. 5a).
In the substrate it is formed an underlayer δc→s with chemical
composition equal to the phases (Cr, Me)7 C3 + ␣-(Fe, Cr).
Its phase composition is the same as the steel, but the
difference is only in the quantity of the phases. Actually,
the underlayer δc→s is gradually transformed in a diffusive
influence zone in the substrate (DIZS ). It is due to the stopping
role of the underlayer δ2s→c , which has a carbide structure.
Rz in Fig. 5 is the zone of roughness of substrate before
deposition of the condensate.
In the coatings deposited at 850 ◦ C, after VHT the outer
diffusive underlayer is with different chemical composition
and consists of phases (CrN + Cr2 N), Fig. 5b. The underlayer
420 R. Shishkov et al. / Journal of Materials Processing Technology 157–158 (2004) 415–421
δc→s situated in the substrate at the side of the condensate is
built of the phases (Cr, Me)7 C3 + ␣-(Fe, Cr).
Its phase composition is like the phase composition of
the steel, and the only difference is in the relation between
the phases. This is a reason for making difficult difference by
the metallographic analysis, because of the gradual transition
δc→s to DIZS . Reason for this is the border-function of the
δ2s→c , which has carbide composition. After its forming and
reaching certain thickness it slows or even stops the diffusion
of the Cr and N2 by the condensate. This provokes dispers-
ing of the input quantities of N2 and Cr to the inside volume
of the substrate. This frees space for entering of carbon in
the condensate and forming of the diffusive underlayers of
the transitional diffusive layer (TDL). Mainly this is due to
the composition of austenite by secondary heating for VHT
and the high Ts . At this high temperature the structure of the
substrate is the austenite, which has low quantity of carbon
(≈0.4–0.5% C). This is due to the high quantity of the Cr,
which provokes displace of the line “ES” in the Fe–Fe3 C di-
agram. Meanwhile the austenite is alloyed only with Cr—the
element which saturates the substrate by the condensate.
Obviously, the second heating for hardening from
Ts = 1020 ◦ C has led to an extra reallocation of the elements
in the condensate and the substrate. Firstly because of the
dissolve of chrome carbides from TDL at Ts = 1020 ◦ C have
started again the diffusive processes of redistribution of the
N2 from the condensate and of C and Fe from the substrate.
This has led to dissolving of TDL by the side of the substrate
and its increasing by the side of the condensate, by transform-
ing of the CrN into Cr2 N. These diffusive processes lead to
Fig. 6. Universal hardness, HU, and effective Young’s modulus, E, of the
coatings as a function of the deposition temperature Ts (a) and bias voltage
Us (b) of X150CrMo12 steel substrates.
transforming the last in the δ1s→c , which slowly is moving to
the surface of the coating. This is accompanied by its gradual
increase of the thickness. Meanwhile, its composition has en-
riched by the elements V, Mn, etc. coming from the substrate.
The remaining under δ1s→c enriched of Cr and N2 zone from
the ex-condensate, after enrichment with C is transforming
into δ2s→c , which consisted of the phase (Cr, Me)23 C6 .
3.4. Microhardness and Young’s modulus
The coatings, obtained in the temperature interval
Ts = 450–850 ◦ C (before and after VHT) and bias voltage
Us = 0 to −200 V have a universal hardness HU and effec-
tive Young’s modulus, E, measured on a plane, as shown in
Fig. 6.
The result is in connection with the lowering of the in-
ternal stresses and also with the increase of the N2 content.
Generally, the not so far high hardness is in addition to the
significant axial texture, according to 2 0 0.
The coatings obtained at 850 ◦ C have the lowest hardness.
In this case the recrystallization in the coating has finished.
4. Conclusions
• The coatings obtained in the interval 450–600 ◦ C have a
light gray color. Their topography and microstructure cor-
respond to Zone II of the Thornton’s zone model. These
obtained at 650 ◦ C and especially at 850 ◦ C are dark gray
color and correspond to Zone III of Thornton’s model.
• Up to 850 ◦ C the coatings are with micro-diffusive bond
to the substrate and built mainly of the phase CrN. Four
zones can be distinguished in them: Zone I is situated at the
surface and has an increased content of Cr, C and O2 at the
expense of the N2 ; Zone II is the main part of the coating
with a constant ratio among the elements; Zones III and
IV are zones of a diffusive influence in the condensate and
substrate, respectively.
• The hardening heat treatment of the system
CrN/X150CrMo12 steel transform the type of the
coating from a vacuum condensate with a micro-diffusive
bond to the substrate into a vacuum-diffusive coating
with or without residual condensate, changing from
chromium-carbonitride to chromium-carbide phase
composition.
• The plasma-vacuum deposition process of vacuum con-
densates built only of CrN on the semi-heat-resistant steel
X150CrMo12 or another steel of this group cannot be used
as a preliminary process, because the vacuum heat treat-
ment (hardening and tempering) changes the type of the
coatings and their phase composition.
• Chromium-carbide or chromium-nitride vacuum-diffusion
coating with KDC = 1 can be obtained on X150CrMo12
steel substrates by previous or accompanied deposition of
condensate sputtering a chromium or ferro-chromium tar-
 R. Shishkov et al. / Journal of Materials Processing Technology 157–158 (2004) 415–421
get for time of 60 min (direct or indirect process) combined
with a vacuum heat treatment.
References
[1] D.B. Lee, Surf. Coat. Technol. 173 (2003) 81.
[2] C. Fernandez-Ramos, J.C. Sanchez-Lopez, A. Justo, T.C. Rojas, I.
Papst, F. Hofer, A. Fernandez, Surf. Coat. Technol. 180–181 (2004)
526.
[3] L. Cunha, M. Andritschky, L. Rebouta, K. Pischow, Surf. Coat. Tech-
nol. 116–119 (1999) 1152.
[4] C. Gautier, J. Machet, Thin Solid Films 295 (1997) 43.
[5] C. Heau, R. Fillit, F. Vaux, F. Pascaretti, Surf. Coat. Technol.
120–121 (1999) 200.
[6] W. Heinke, A. Leyland, A. Matthews, G. Berg, C. Friedrich, E.
Broszeit, Thin Solid Films 270 (1995) 431.
[7] M. Hirai, Y. Ueno, T. Suzuki, W. Jiang, C. Grigoriu, K. Yatsui, Jpn.
J. Appl. Phys. 40 (2001) 1052.
421
[8] M. Jordanov, D. Tzaneva, P. Petrov, M. Ilieva, Mashin’s Mechanics
44 (2002) 83 (in Bulgarian).
[9] M. Oden, C. Ericsson, G. Hakansson, H. Ljungcrantz, Surf. Coat.
Technol. 114 (1999) 39.
[10] A. Rutkowska, M. Dabrowski, Zeszyty naukowe-Mechanika 38
(1995) 191 (in Polish).
[11] R. Shishkov, M. Jordanov, M. Vnoucek, Proceedings of the
11th International Scientific Conference, AMME’2002, 2002, p.
483.
[12] R. Shishkov, E. Lisichkova, Vacuum 46 (11) (1995) 1337.
[13] R. Shishkov, E. Lisichkova, Plasma vacuum-diffusive metallizing
method, Patent No. 48518/03.06.94, Sofia-Bulgaria (1994).
[14] J. Thornton, Rev. Mater. Sci. 7 (1977) 239.
[15] J. Thornton, J. Thin, Thin Solid Films 54 (1978) 23.
Further reading
[16] J. Thornton, D. Hoffman, Thin Solid Films 171 (1989) 5.