Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
Vacuum
journal homepage: www.elsevier.com/locate/vacuum
UR Mcanique Applique, Ingnierie et Industrialisation (M.A.2I), ENIT, BP 37, Le Belvdre, 1002 Tunis, Tunisia
Laboratoire Bourguignon des Matriaux et Procds (LaBoMaP), Centre Arts et Mtiers ParisTech de Cluny, Rue Porte de Paris, F-71250 Cluny, France
c
Department of Physics, University of Alabama at Birmingham, USA
d
Photothermal Laboratory, I PEI 8000 Nabeul, Tunisia
b
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 20 February 2011
Received in revised form
5 September 2011
Accepted 18 September 2011
Cr/CrN/CrAlN, CrN/CrAlN and Cr/CrN thin layers were deposited by PVD (Physical Vapor Deposition). The
multilayers were obtained from the combined deposition of different layers Cr, CrN and CrAlN thick lms
on on AISI4140 steel and silicon substrates at 200 C, and evaluated with respect to fundamental
properties such as structure and thermal properties. Cr, CrN and CrAlN single layers were also prepared
for comparison purposes. The structural and morphological properties of PVD layers were characterized
by X-ray diffraction (XRD) and scanning electron microscopy (SEM) coupled with EDS WDS microanalyses, stresses were determined by the Newtons rings methods using the Stoneys equation and
surface hardening and hardness proles were evaluated by micro hardness measurements. The XRD data
and HRTEM showed that both the Cr/CrN, CrN/CrAlN and Cr/CrN/CrAlN multilayer coatings exhibited
B1NaCl structure with a prominent reection along (200) plane, and CrAlN sub-layer microstructures
composed of nanocrystallites uniformly embedded in an amorphous matrix. The innovation of this work
was to use the thickness of three different coating types to determine the thermal properties. Furthermore, an empirical equation was developed for the thermal properties variations with temperature of
AISI4140 steel coated with different multilayer coatings. The thermal conductivity of CrAlN single layered
was lower than the multilayer and the bulk material AISI4140. Moreover, the inuences of structure and
composition of the multilayer coatings on the thermal properties are discussed.
The thermal conductivity of nanoscale thin lm is remarkably lower than that of bulk materials
because of its various size effects.
2011 Elsevier Ltd. All rights reserved.
Keywords:
Multilayers Cr/CrN/CrAlN
Thermal conductivity
PVD
Model
1. Introduction
Thin lms based on carbides and nitrides of transition metals
have been very successful in improving the performance of cutting
tools. Although TiN is the most widely used in industrial applications, CrN has been gaining importance in recent years due to its
superior corrosion and wear resistance, friction behavior and low
internal stress [1e3]. However, there are an increasing number of
applications where properties of single layer coatings are not
sufcient. Recent research is focused on the development of
nanolayered multilayer coatings in order to meet the requirements
in terms of hardness, thermal stability, coefcient of friction,
corrosion resistance and internal stress [4e11]. Nanolayered
* Corresponding author. Laboratoire Bourguignon des Matriaux et Procds
(LaBoMaP), Centre Arts et Mtiers ParisTech de Cluny, Rue Porte de Paris, F-71250
Cluny, France. Tel.: 33 (06) 85 30 58 95.
E-mail address: tlilii_brahim@yahoo.fr (B. Tlili).
0042-207X/$ e see front matter 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.vacuum.2011.09.008
1049
2 !
1
Es
ts
1
1
tf
6 1 ns
R R0
(1)
where Es and ns are Youngs modulus (181 GPa) and Poissons ratio
(0.28) of silicon (100), respectively [17]. The Es =1 ns term is the
biaxial modulus of the Si (100) substrate (E 1.805 1011 N/mm2).
Both ts and tf are the thicknesses of the Si substrate and of the layer,
respectively, while R0 and R are the curvature radius before and
after deposition, respectively.
2.2. Photo-thermal deection (PTD)
The thermal properties are determined by photo-thermal
deection (PTD) [23,24] which is a non-destructive technique. In
Table 1
Chemical composition of AISI4140 steel.
C
Mn
Si
S
Cr
P
Mo
0.410
0.770
0.280
0.026
1.020
0.019
0.160
Table 2
Deposition conditions.
Coatings
Time of
Bias voltages (-V)
deposition
Al
Cr
(min)
Cr
CrN
CrAlN
Cr/CrN
CrN/CrAlN
Cr/CrN/CrAlN
60
60
60
51
105
99
4
//
//
//
//
//
0
0
-300
//
//
//
-900
0
-900
//
//
//
100
80
//
//
//
//
0
20
//
//
//
//
1050
p
2l dn
x
jjj
jT je mf
nmf dTf 0
x
5p
4 q
mf
4
(2)
(3)
where l is the width of the pump beam in the direction of the probe
laser beam, n, mf, and Tf are the refractive index, the thermal
Tf x; t T0 esf x ejut
Tn x; t Xn esn x Yn esn x Zn ean x ejut
Tn1 x; t Xn1 esn1 xln Yn1 esn1 xln Zn1 ean xln ejut
T1 x X1 es1 xln .l2 Y1 es1 xln .l2 Z1 ea1 xln .l2 ejut
Ts x Xs ess xln .l1 Ys ess xln .l1 Zs eas xln .l1 ejut
if ln ln1 x ln
if ln . ls x ln . l1
if 0 x lf
if ln x 0
if ln . l1 x ln . l2
if ln . ls x ln . l1
Ff x; t Kf sf T0 esf x ejut
if 0 x lf
an an x jut
e
Z e
sn n
an1
Z
ean xln ejut
sn1 n1
if ln x 0
if ln ln1 x ln
if ln . l1 x ln . l2
if ln . ls x ln . l1
if ln . ls x ln . l1
1051
Xi1
Xi
xi ln ln1 . li @ Yi1 A Mi @ Yi A
Ei1
Ei
Then
1
0 1
0
X1
Xn
m11
@ Y1 A M2 $M3 .Mn @ Yn A @ m21
E1
En
m31
m12
m22
m32
10 1
Xn
m13
m23 A@ Yn A
m33
En
Xn
Fig. 3. Schematic representation of the probe beam deection.
10
1
1
Xn1
1 rn1 A@ Yn1 A
0 En =En1
En1
10 1
0
s
s
n ln
Xn
e
e n ln
ean ln
s
s
a
l
l
l
@
cn e n n cn e n n cn rn e n n A@ Yn A
En
0
0
1
1
@1
0
1
En
1
En
1 gT0 1 r3 ; Yn 1 gT0 1 r3 :
2
2
2
2
And
X1
m11
m
1 gT0 1 rn En 12 1 gT0
2
2
1 rn En m13 En
and
Y1
1
0 1
Xn1
Xn
Gn @ Yn1 A Dn @ Yn A
En1
En
m21
m
1 gT0 1 rn En 22 1 gT0
2
2
1 rn En m23 En :
Or too
X1 m11 1 g m12 1 g
or
1
0 1
0 1
Xn1
Xn
Xn
1
@ Yn1 A G $Dn @ Yn A Mn @ Yn A
n
En1
En
En
Where
1
Gn @ 1
0
1
1
rn1 A;
En =En1
1
1
0
esn ln
Dn @ cn esn ln
0
esn ln
cn esn ln
0
m12 1 rn 2m13
T0
m11 1 rn
2
En
2
and
Y1 m21 1 g m22 1 g
m22 1 rn 2m23
1
ean ln
cn rn ean ln A
1
and
Mn
(4)
T0
m21 1 rn
2
En
:
2
1 bes1 l1 h1 T0 h2 En 1 bes1 l1 h3 T0 h4 En
r1 bea1 l1 E1 0
G1
n $Dn :
What gives:
1 bh1 es1 l1 1 bh3 es1 l1 T0
1 bh4 es1 l1 1 bh2 es1 l1 En r1 bea1 l1 E1
1052
Finally
Fig. 5. XRD patterns of uncoated AISI4140 steel and multilayers such as CrN/CrAlN and
Cr/CrN/CrAlN on AISI4140 samples.
Table 3
Composition, atomic ratios, total thicknesses and roughnesses of the mono and multilayers.
Coatings
N Content
(at. %)
Al Content
(at. %)
Cr Content
(at. %)
Atomic ratio
N/(Cr Al)
Total
thickness (nm)
Roughness (mm)
Arithmetic roughness (Ra)
Cr
CrN
CrAlN
CrAlN/CrN/Cr
CrAlN/CrN
0
48
48.2
51.8
52
0
0
4
4.2
5
98
51
48
42.9
41.3
0
0.95
1.04
1.2
1.2
860
690
980
1500
1500
0.1
0.1
0.1
0.1
0.13
0.12
0.12
0.12
0.12
0.11
1053
0,6
0,5
r (-GPa)
0,4
0,3
0,2
0,1
0,0
Fig. 6. SEM cross-section observation of a Cr/CrN/CrAlN coated sample.
Cr
CrN
Fig. 7. (A) Cross-section TEM image and (B) HRTEM image of a CrAlN lm.
1054
40
1,0
Cr
Experimental
0,8
0,6
Phase (degree)
Normalized amplitude
35
Cr
Experimental
0,4
-1
-1
-1
-4 2 -1
25
20
15
10
Theoretical curve
-1
Theoretical curve
30
-4 2 -1
2
4
6
8 10 12 14 16 18
Square root modulation frequency (Hz1/2 )
2
4
6
8 10 12 14 16 18
Square root modulation frequency ( Hz1/2 )
Fig. 9. Normalized amplitude and phase evolution of the photo-thermal signal vs. the square root frequency of the deposited Cr layers.
1,0
CrN/Cr
Experimental
Theoretical curve
35
30
0,8
0,7
0,6
0,5
0,4
CrN/Cr
Experimental
Theoretical curve
-1 -1
-4 2 -1
Phase (degree)
Normalized amplitude
0,9
-1 -1
-4 2 -1
25
-4 2 -1
20
15
10
-4 2 -1
5
0,3
4
6
8
10 12 14 16 18
1/2
Square root modulation frequency (Hz )
4
6
8
10 12 14 16 18
Square root modulation frequency (Hz 1/2)
Fig. 10. Normalized amplitude and phase evolution of the photo-thermal signal vs. the square root frequency of the deposited Cr/CrN layers.
Fig. 11 show that the CrAlN layer presents the following values
K 2.8 W m1 K1 and D 0.052 104 m2 s1 of thermal
conductivity and diffusivity, respectively.
The thermal conductivity of the coating can be containing
a large error due to inaccurate parameters used as input in the
calculations. Especially, the coating to substrate thickness ratio is
small; the calculated conductivity value will be extremely sensitive
to errors in the input parameters. In general, the accuracy of the
laser ash technique for two or three layers strongly depends on
1,0
30
0,9
25
0,8
0,7
0,6
0,5
0,4
CrAlN/CrN/Cr
Experimental
Theoretical curve
K1=93,9 W.m-1.K-1; D1=0,79.10-4m2.s-1
K2=11 W.m-1.K-1; D2=0,23.10-4m2.s-1
K3=2.8 W.m-1.K-1; D3=0,052.10-4m2.s-1
4
6
8 10 12 14 16 18
Square root modulation frequency (Hz1/2 )
Phase (degree)
Normalized amplitude
20
CrAlN/CrN/Cr
15
10
5
Experimental
Theoretical curve
K1=93,9W.m-1.K-1; D1=0,79.10-4m2.s-1
K2=11W.m-1.K-1; D2=0,23.10-4m2.s-1
K3=2.8W.m-1.K-1; D3=0,052.10-4m2.s-1
4
6
8 10 12 14 16 18
Square root modulation frequency ( Hz1/2 )
Fig. 11. Normalized amplitude and phase evolution of the photo-thermal signal vs. the square root frequency of the deposited Cr/CrN/CrAlN layers.
Thermal
conductivity
(W m1 K1)
Thermal
diffusivity
(106 m2 s1)
AISI4140
Cr
CrN
CrAlN
CrN/Cr
CrAlN/CrN/Cr
26 0.01
93.9 0.01
11 0.015
2.8 0.012
9 0.012
0.79 0.01
0.23 0.013
0.052 0.001
Equivalent thermal
conductivity (W m1 K1)
1
1
eCr eCrN
Ke
eCr eCrN KCr KCrN
number of interface pores associated with the formation of nonuniform interfaces between layers, which causes increased
phonon scattering.
4. Conclusion
13.1 0.012
4.6 0.013
1055
1
1
eCr eCrN eCrAlN
Ke
eCr eCrN eCrAlN KCr KCrN KCrAlN
for the stacking Cr/CrN/CrAlN.
In a model developed by Ghrib et al. [25,26] the overall coating
conductivity results from the combined effect of these two zones
(amorphous and crystallites). Essential parts of this two-zone
model were modied in this work describing the total thermal
resistance of a coating as a series combination of the thermal
resistance of the inner zone and of the outer zone, providing a good
agreement between model and measured data.
We note from the values summarized in Table 4 that the CrAlN
layer has lower thermal properties compared with the Cr and CrN
layers, so it can act as a thermal insulator. The conductivity value of
CrAlN is extremely low compared to those of the monolayer of Cr
and CrN. This is well known and can be explained by the columnar
microstructure which is characterized by elongated inter-columnar
pores that are predominantly aligned perpendicular to the plane of
the coating [34,35]. In the CrAlN layer, the heat ow is mainly
parallel to these inter-columnar gaps, the heat transfer is not
effectively reduced. However, the primary columns exhibit
a feathery structure with inter-columnar pore [36]. These ne intercolumnar gaps contribute to a moderate reduction in the thermal
conductivity as they are generally inclined to the heat ow. For that
reason, the thermal conductivity of CrN coatings is still signicantly
lower than the thermal conductivity of the fully dense Cr layer. This
result suggests that the structure of the Cr and CrN coating near the
interface to the metallic substrate has a markedly different thermal
conductivity. Structural differences of Cr/CrN/CrAlN and Cr/CrN
PVD multilayers can be roughly divided into two zones, the negrained inner zone (Cr/CrN lm) and the coarse columnar outer
zone (CrAlN coating). The thermal conductivity of the ne grain
inner zone is much higher than the thermal conductivity of the
outer zone. This effect is attributed to the higher grain boundary
density as well as numerous oblique columnar boundaries in the
outer zone [37]. Thus, the thermal conductivity is dominated by
phonon scattering at defect/grain boundaries in this part of the
coating, and this results in a lower conductivity of around
2.5 W m1 K1 at room temperature. Moreover, the decreased
thermal conductivity of Cr/CrN/CrAlN multilayers is attributed to
the increased total porosity resulting from an increase in the
1056
[27]
[28]
[29]
[30]
[31]
[32]
[33]
[34]
[35]
[36]
[37]