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Residual stresses in the substrate and in the PVD coating have a signicant inuence on the coating adhesion and
lifespan of machining as well as forming tools. Therefore, the understanding and control of the system's residual
stresses will lead to a better performance of the coated components. Moreover, although investigations were
conducted in the eld of stress analysis of PVD coatings, they do not focus on interdependencies of residual
stresses in the substrate and in the coating.
In this investigation, three different metallographically prepared substrates were used. SiC grinding, diamond
grinding, and SiC grinding and plasma nitriding preparations were selected, due to the substantial differences
in their nal residual stress states. Additionally, a Ti/TiAlN multilayer coating and a reference TiAlN monolayer
were deposited on each pre-treated substrate.
Their initial and nal residual stress states were measured by means of X-ray diffraction. In addition to the
residual stress analyses, tribo-mechanical tests, such as nano-indentation, ball-on-disc, and scratch tests were
performed in order to correlate the results with these residual stress states.
2014 Elsevier B.V. All rights reserved.
1. Introduction
In order to ensure a sufcient protection for industrially used tools
against wear, a functionalization of component surfaces, PVD protective
layers are applied. Depending on the requirements of the application,
single or multilayer PVD coatings can be used for this purpose.
Ti-based ceramic coating systems, such as TiN, TiCN, or TiAlN, are widely
used in the industry due to their high wear resistance [18]. In
particular, TiAlN possesses outstanding coating properties with a
maximum hardness of about 2832 GPa [9]. In addition, the aluminum
content in the coating ensures a high temperature resistance up to
800 C [10]. The formation of a thin, dense and well adhering protective
layer of aluminum oxide, which acts as a diffusion barrier and thus minimizes diffusion-induced wear, is responsible for this behavior [9,11,12].
Due to the possibility to produce near net-shaped coatings utilizing the
PVD technique, forming tools with a very high surface quality can be
coated. Besides the mostly low surface roughness of the tools,
unfavorable residual stresses in the composite system make it more
complicated to achieve a good adhesion. The residual stresses in
the coating and in the substrate affect the adhesive and cohesive damage processes at the coating/substrate interface, which can either
promote or prevent a failure of the coating [13]. Suitable substrate
Corresponding author at: Institute of Materials Engineering, Technische Universitt
Dortmund, Leonhard-Euler-Str. 2, 44227, Dortmund, Germany.
E-mail address: tobias.sprute@tu-dortmund.de (T. Sprute).
http://dx.doi.org/10.1016/j.surfcoat.2014.08.075
0257-8972/ 2014 Elsevier B.V. All rights reserved.
370
wear protection, the multilayer starts with a Ti-layer on the surface of the
substrate and ends with a hard TiAlN layer. Moreover, the topography and
morphology of the deposited coatings were evaluated by using a scanning
electron microscope as well. An additional EDX detector was used in order
to analyze the chemical composition of the ceramic layers.
Additionally, mechanical properties such as the coating hardness
and Young's modulus were determined by means of nanoindentation
tests (G200 Agilent Technology, USA). A depth controlled penetration
was performed at room temperature and, in order to avoid the inuence
of the substrate on the properties of the thin lm, the results were evaluated in a range from 10 to 15% of the total coating thickness, which was
in this case between 100 and 400 nm.
With the purpose of determining the tribological properties of the
coatings, ball on disc tests at room temperature were conducted using
a tribometer (high temperature tribometer CSM, Switzerland) equipped
with a WC/Co ball as counterpart to the rotating samples with the aim of
analyzing the wear coefcient and with 51CrV4 pins as a counterpart to
obtain the friction coefcients of the different systems. 51CrV4 is a steel
used for quenching and tempering according to DIN EN 10083, and it is
usually used in the automotive and mechanical engineering industry
on components formed of metal such as gear parts, pinions, and shafts.
During the experiment, which consists of 8000 rotations, no external
lubricant was used and both the normal force and linear velocity of the
rotating discs were kept constant at 5 N and 40 cm/s, respectively. The
wear coefcient was evaluated by analyzing the wear tracks with an optical 3D surface analyzer (Innite Focus Alicona, Austria) that consists of
a confocal microscope connected to an image analyzer software, and the
wear mechanisms evidenced by SEM.
The scratch tester Revetest (CSM, Switzerland) was utilized to examine the adhesion between the PVD coatings and the steel substrates
at room temperature. For this, scratch tracks were generated with a
total length of 10 mm. The force was steadily and linearly increased
from 0 to 100 N and the results were analyzed using SEM in combination with an EDX-detector (Oxford Instruments, UK).
The residual stress evaluation was executed by means of a diffractometer (Bruker Advance D8), using the sin2 method [38]. Fe-K radiation was used instead of the usually used Cu-K radiation, in order to
avoid the uorescence radiation from the substrate [39].
Before proceeding with the residual stress measurements, phase
analyses of the metallic substrate, TiAlN monolayer, and Ti/TiAlN multilayer were performed to determine the present phases and to establish
the 2 angles related to the Bragg law, which thereafter are used for the
determination of the residual stresses. Consequently, the Fe 220 peak
found at an angle of 2 equaling 145 was selected to measure the residual stresses in the substrate. This specic reection was chosen instead
of other Fe reections, due to the high value of the angle 2 which benets the sensitivity of the sin2 method, where small changes in the lattice spacing, d, result in a corresponding shift of the diffraction angle 2.
For the analysis of the residual stresses in the coating systems, the
TiAlN 220 peak was selected and Fe-K radiation was used as well.
The reections were scanned and afterwards tted by the Pearson function to determine the positions of the peak. The X-ray elastic constants
of Fe were calculated by elastic single crystal constants. For the TiAlN
coatings, the XEC were calculated after Voigt by utilizing the experimentally determined macroscopic elastic moduli of these coatings.
To analyze the residual stresses in the substrates after the deposition
of monolayer and multilayer coating systems with X-ray diffraction,
several conditions need to be considered. In homogeneous materials,
the following relationship between the beam intensities at the moment
when the X-ray enters and leaves the specimen (hereinafter denoted as
I0 and If, respectively) holds true:
I f z I0 exp k z:
371
Fig. 1. Residual stress depth proles in the substrate for the different substrate pretreatments.
1
a 1 ta
c k
c
1
n
c k
a
b
1 ta
1 tb :
c
c
Eqs. (2) and (3) stand for the phases a, b and c, respectively.
Here, n is the total number of layers of phases a and b and t stands
for the thickness of the single sub-layers. In this particular case, a
corresponds to TiAlN, b to Ti metallic interlayers, and c to the
substrate material.
Afterwards, using Eqs. (2) and (3), the penetration depths of the
X-rays, for the reection Fe 220, in the different systems used for this
Fig. 2. Coating thickness from TiAlN monolayer and Ti/TiAlN multilayer systems.
372
Fig. 3. a. SEM images of the TiAlN monolayer system deposited on the different pretreated substrates. b. SEM images of the Ti/TiAlN multilayer system deposited on the different pretreated
substrates.
Fig. 4. Arithmetic average roughness Ra of the substrates before coating deposition and after deposition of both mono- and multilayer.
373
Fig. 5. Topography SEM pictures of the mono- and multilayer deposited on different pretreated substrates.
at.-% with N
at.-% without N
Ti
Al
N
19.98 0.43
25.18 0.35
54.84 0.78
43.66 0.21
56.34 0.21
374
Fig. 6. X-ray phase diffractogram of the Ti/TiAlN multilayer system, Fe-K radiation.
deposited on the diamond grinded substrate presents a slightly columnar structure. However, the selected process parameters were constant
for all systems.
In addition, the comparable structures and morphologies of all
deposited coatings can also be attributed to the similar nucleation on
the surface of the substrate. It can be assumed that the surface roughnesses of the differently treated substrates prior to the deposition are
responsible for this behavior [4749]. The values are in the range of
Ra = 101 nm and Ra = 149 nm (Fig. 4). Due to the slight roughening
during the nitriding process by sputtering the substrate material, the
nitrided substrate has the highest roughness with Ra = 149 nm [43].
The SiC and diamond grinded substrates possess lower roughness
values of Ra = 116 nm and Ra = 101 nm, respectively. The trend observed for the different roughness values is constant both before and
after the deposition of the coatings. Thus, it can be noted that the roughness of the substrates before the deposition affects the roughness of the
different coatings. However, in general, the roughness values increase
after the coating deposition of mono- and multilayer systems due to
the sum of the substrate roughness and the intrinsic roughness of the
coating itself [47].
The initial roughness of the surface of the substrates is not only
reected in the roughness values after the coating application, but also
in the topography images of the systems (see Fig. 5). Here, the same
trend as in the roughness values can be observed. The coated surface
of the nitrided base material has a coarser texture than that of the
grinded and coated samples.
The chemical composition of TiAlN was determined by an EDX analysis. The chemical composition of the monolayer and the ceramic layers
of the multilayer system are shown in Table 1. The alternating Ti layers
used in the multilayers consist of pure Ti. Due to the fact that light
elements are difcult to determine quantitatively by EDX, the composition is examined with and without N. According to the literature,
sputtered coatings with an Al/Ti ratio of about 3/2, generally exhibit
fcc NaCl-type crystallographic structure with excellent tribomechanical properties [9,50]. Nonetheless, different investigations as
the ones performed by Makino [51] and Greczynski [52] should be
considered, since both authors have attributed the obtaining of cubic
or hexagonal phases to the use of different deposition techniques,
instead of different Al contents in the TiAlN structure.
3.3. Development of residual stresses
Residual stress depth proles for each substrate pre-treatment were
developed in order to determine the residual stress state at different
depths from the surface of the substrate and to evaluate their gradient,
Fig. 1. Hereby, the substrate was electrolytically polished one step after
the other to a depth of approximately 120 m, and residual stress evaluations were conducted for every step. In the detailed graph, shown in
Fig. 1, it can be observed that the residual stress states for the three different substrate pre-treatments present a very low gradient in depths
between 0 and 10 m. The penetration depth of the X-rays during the
different residual stress measurements in the substrate of these samples
reaches up to 10 m, being located within the above described region.
The residual stress measurements of the three different pre-treated
substrates before and after deposition, in this case, do not depend on
the deposited coating and thus are comparable.
Moreover, in order to measure the residual stresses in the coatings,
phase analyses were performed on the mono- and multilayers to dene
the most suitable reection. Fig. 6 shows a phase diffractogram of a Ti/
TiAlN multilayer system, deposited onto the substrate which was
Fig. 7. Residual stress evolution for the different substrates before and after deposition of TiAlN monolayer, Fe 220 reection.
375
Fig. 8. Residual stress evolution for the different substrates before and after deposition of Ti/TiAlN multilayer, Fe 220 reection.
376
Fig. 10. Mechanical properties of the TiAlN monolayer and Ti/TiAlN multilayer deposited on different pretreated substrates.
Fig. 11. H/E ratio of the TiAlN monolayer and Ti/TiAlN multilayer deposited on different pretreated substrates.
377
Fig. 12. Critical load of the TiAlN monolayer and Ti/TiAlN multilayer deposited on different pretreated substrates.
mechanical and physical bonding between the coating and the substrate, subsequently increasing the critical load value [67]. However,
the various hardness results of the substrate materials exhibit greater
differences than the roughness values. Thus, a major effect on the
critical load value is rather attributed to the hardness than to the roughness differences, even though these two parameters are closely linked in
this case.
3.5. Tribological behavior
Fig. 13 shows the wear coefcient obtained for the different coating/
substrate systems evaluated within this research. Hereby, the abrasive
wear mechanism was identied as a consequence of the high hardness
of the tribological counterpart used, WC/Co. Moreover, both the TiAlN
monolayer and Ti/TiAlN multilayer have shown a reduction of the
wear coefcient with increasing hardness and compressive residual
stresses in the substrate. In addition, the wear resistance correlates
with critical load and thus adhesive bonding of the coating on the substrate material. Therefore, the highest wear values were obtained at
the coatings deposited on SiC prepared substrates and the lowest values
onto nitride substrates.
Furthermore, Ti/TiAlN coatings have shown a poor tribological
behavior during wear resistance tests, which is evident in the higher
wear coefcient than this obtained for TiAlN monolayers, deposited on
the same type of substrate. This trend might result from the Ti metallic
interlayer thickness which, despite stopping the crack propagation, further reduces the system stability, as Ti interlayers can be plastically
Fig. 13. Wear coefcient of the TiAlN monolayer and Ti/TiAlN multilayer deposited on different pretreated substrates.
378
Fig. 14. Friction coefcient of the TiAlN monolayer and Ti/TiAlN multilayer deposited on different pretreated substrates using WC/Co and 51CrV4 counterparts.
Acknowledgment
The authors gratefully acknowledge the DFG (German Science
Foundation) for the nancial support for this work within the projects
Ti 343/34-1 and Fi 686/8-1.
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