Professional Documents
Culture Documents
6
Macro- and
Micromechanical and
Tribological Properties
Bharat Bhushan and Bal K. Gupta
1.0
INTRODUCTION
2.0
[56][57][76][131][133][139][147][199][223][224][261][263][272][287][301][302][305][306] re-
Eq. (1)
BHN =
2W
D( D D 2 d 2 )
W
Dh
Eq. (2)
Meyer hardness =
4W
d2
R = C1 C 2 t
where C1 and C2 are constants for a given indenter size, shape, and
hardness scale, and t is the penetration depth in millimeters between the major and minor loads. Although Rockwell hardness
increases with Brinell hardness, the two are not proportional and the
dimensions of the Rockwell hardness are not force per unit area. In
fact, the Rockwell hardness number cannot be assigned any dimensions, since it is defined in an arbitrary Eq. (3).
A variety of combinations of indenters and major loads are
possible; the most commonly used are HRB or R B, which uses
1.59-mm diameter (1/16 inch) ball as the indenter and a major load
of 100 kg; HRC, or RC, which uses a cone as the indenter and a major
load of 150 kg; and HRA or RA, which uses a cone as the indenter
and a major load of 60 kg. Rockwell B is used for soft metals and
Rockwell C and A are used for hard metals.
2.2
Eq. (4)
HV =
1.8544W
d2
Eq. (5)
HK =
14.229W
l2
(b)
Figure 2. Geometry and indentation with (a) a Vickers indenter and (b) a Knoop
indenter.
2.3
In this section, we review nanoindentation hardness apparatuses in which the indent is imaged after the load has been removed,
as well as the depth-sensing indentation apparatuses in which the
load-indentation depth are continuously monitored during the loading and unloading processes. Earlier work by Alekhin, et al.,[6]
Ternovskii, et al.,[279] and Bulychev, et al.,[72] led to the development
of depth-sensing apparatuses. Prototype depth-sensing hardness apparatuses developed by several research groups are reviewed by
Bhushan.[38][39] A commercial depth-sensing nanoindentation hardness test apparatus manufactured by Nano Instruments Inc., is extensively used and is described in detail.
Nanoindentation Hardness Apparatuses With Imaging of
Indents After Unloading. For completeness, we first describe a
commercially available microindentation hardness apparatus (Model
No. Micro-Duromet 4000), that uses a built-in light optical microscope for imaging of indents after the sample is unloaded. It is
manufactured by C. Reichert Optische Werke AG, A-1171, Vienna,
Box 95, Austria.[233] The indenters case is of the size of a microscope objective mounted on the objective revolver. The load range for
this design is from 0.5 mN to 2 N; therefore it is used for thicker films.
A commercial nanoindentation hardness apparatus for use inside a scanning electron microscope (SEM), (Model No. UHMT-3)
for imaging the indents after the sample is unloaded, is manufactured
by Anton Paar K.G., A-8054, Graz, Austria. The apparatus is mounted
on the goniometer stage of the SEM. In this setup, the indenter is
mounted on a double-leaf spring cantilever, and is moved against the
sample by an electromagnetic system to attain the required indentation load, which is measured by strain gages mounted on the leaf
springs.[22][23] After the required load has been reached and the dwell
time has elapsed, the sample is unloaded, and the indentation diagonal is measured by an SEM.
Depth-Sensing Nanoindentation Hardness Apparatus and
Its Modifications. General Description and Principle of Operation.
The most commonly used commercial depth-sensing nanoindentation
(a)
(b)
Figure 3. Schematics of the Nanoindenter II (a) showing the major componentsthe indenter head, an optical microscope and a X-Y-Z motorized precision table
and (b) showing the details of indenter head and controls (microscope which is
directly behind indenter and massive U bar are not shown for clarity).[16]
The Nanoindenter also comes with a continuous stiffness measurement device.[217][229] This device makes possible the continuous
measurement of the stiffness of a sample, which allows the elastic
modulus to be calculated, as a continuous function of time (or
indentation depth). Useful data can be obtained from indents with
depths as small as 20 nm. Because of the relatively small time
constant of the measurements, the device is particularly useful in
studies of time-dependent properties of materials.
Weihs, et al.,[295] used acoustic emission (AE) sensors to detect
cracking during indentation tests using Nanoindenter. Acoustic emission (AE), measurement is a very sensitive technique to monitor
cracking of the surfaces and subsurfaces. The nucleation and growth
of cracks result in a sudden release of energy within a solid, then
some of the energy is dissipated in the form of elastic waves. These
waves are generated by sudden changes in stress, and in displacement that accompany the deformation. If the release of energy is
sufficiently large and rapid, then elastic waves in the ultrasonic
frequency regime (acoustic emission) will be generated, and these
can be detected using piezoelectric transducers (PZTs), via expansion and compression of the PZT crystals.[38][249][312] The energy
dissipated during crack growth can be estimated by the rise time of
the AE signal. Weihs, et al.,[295] mounted commercial transducer
with W impregnated epoxy backing for damping underneath the
sample. The transducer converts the AE signal into voltage, that is
amplified by an oscilloscope, and used for continuous display of AE
signal. Any correlation between the AE signal, and the load-displacement curves can be observed (also see Refs. 302 and 306).
The Berkovich Indenter. The main requirements for the indenter are high elastic modulus, no plastic deformation, low friction,
smooth surface, and a well defined geometry that is capable of
making a well defined indentation impression. The first four requirements are satisfied by choosing the diamond material for the tip. A
well defined perfect tip shape is difficult to achieve. Berkovich is a
three-sided pyramid, and provides a sharply pointed tip compared to
the Vickers or Knoop indenters, which are four-sided pyramids and
Eq. (6a)
(a)
(b)
l = 0.866a
and
Eq. (6c)
h
1
=
a 7.44
The projected contact area (A) for the assumed geometry is given as
Eq. (7)
A = 0.433a2 = 23.97h2
Figure 5. Schematics of stress-strain curves, typical indentation curves, deformed surfaces after tip removal, and residual impressions of indentation, for
ideal elastic, rigid-perfectly plastic, elastic-perfectly plastic (ideal) and real
elastic-plastic solids.
All engineering surfaces follow real elastic-plastic deformation behavior with work hardening.[151] The deformation pattern of a
real elastic-plastic sample during and after indentation is shown
schematically in Fig. 6. In this figure, we have defined the contact
depth (hc) as the depth of indenter in contact with the sample under
load. The depth measured during the indentation (h) includes the
depression of the sample around the indentation in addition to the
contact depth. The depression of the sample around the indentation
(hs = h-hc) is caused by elastic displacements and must be subtracted
from the data to obtain the actual depth of indentation or actual
hardness. At peak load, the load and displacement are Wmax and hmax,
respectively, and the radius of the contact circle is a. Upon unloading, the elastic displacements in the contact region are recovered and
when the indenter is fully withdrawn, the final depth of the residual
hardness impression is h f.
where =0.72 for the conical indenter, =0.75 for the paraboloid of
revolution, and =1 for the flat punch, and Smax is the stiffness (=1/
compliance), equal to the slope of unloading curve (dW/dh) at the
maximum load. Oliver and Pharr[218] assumed that behavior of
Berkovich indenter is similar to that of conical indenter, since crosssectional areas of both types of indenters varies as the square of the
contact depth, and their geometries are singular at the tip. Therefore,
for Berkovich indenter, ~ 0.72. Thus hc is slightly larger than
plastic indentation depth (hp) which is given by
Eq. (8b)
Displacement, h
Figure 7. Schematic of load-displacement curve.
A = 24 .5hc2
1/ 2
= F ( hc )
(a)
(b)
Figure 8. (a) Predicted projected contact area as a function of indentation depth
curves for various tip radii and measured data, (b) predicted load as a function of
indentation depth curves for various tip radii and measured data.[254]
Oliver and Pharr [218] proposed an easier method for determining area functions that requires no imaging. Their method is based
only on one assumption, that Youngs modulus is independent of
indentation depth. They also proposed a method to determine loadframe compliance. We first describe the methods for determining of
load frame compliance followed by the method for area function.
They modeled the load frame and the specimen as two springs in
series, thus
Eq. (10)
C = Cs + C f
C = dh/dW
Eq. (11b)
Cs =
1
2 Er
1/ 2
where
2
2
1 1 vs 1 vi
=
+
Er
Es
Ei
and dW/dh is the slope of the unloading curve at the maximum load
(Fig. 7), Er, Es, and Ei are the reduced modulus and elastic moduli of
the specimen and the indenter, and s and i are the Poissons ratios
of the specimen and indenter. C (or S) is the experimentally measured compliance (or stiffness) at the maximum load during unloading and A is the projected contact area at the maximum load.
From Eqs. (10) and (11), we get
1/ 2
Eq. (12)
C = Cf +
1
2 Er A
A=
1
1
2
4 E r (C C f ) 2
from which an initial guess at the area function was made by fitting A
as a function hc data to an eighth order polynomial
Eq. (14)
HB = Wmax / A
uncorrected shape
corrected shape
H =Hf
Vf
V
+ Hs
Vs
V
H =Hf X3
Vf
V
+ Hs
Vs
V
Eq. (17b)
H = Hs
Vf
V
+ Hs X 3
Vs
V
Eq. (17c)
Ef Hs
X =
H f Es
harder or softer than the film. For the case of a soft film on a harder
substrate, the effect of substrate on film hardness can be described as
Eq. (18a)
s hc
H
= 1 + f 1 exp
t
f
Hs
Ef
Hs
E s
where Ef and Es are the Youngs moduli, f and s are the yield
strengths and Hf and Hs are the hardnesses of the film and substrate,
respectively. H is the hardness of the composite, hc is the contact
indentation depth, and tf is the film thickness. Similarly for the case
of a hard film on a softer substrate, the hardness can be expressed as
Hf
H
s
H
hc
f
= 1 +
1 exp
1
2
Eq. (18b) H s
tf
E
Hs
f f
Es
s
(a)
(b)
Figure 11. Effect of relative yield strengths of the film and the substrate on the
composite hardness for (a) a soft film on a hard substrate and (b) a hard film on a
soft substrate.[35]
(a)
(b)
Figure 12. Effect of relative Youngs moduli of the film and the substrate on the
composite hardness for (a) a soft film on a hard substrate and (b) a hard film on a
soft substrate.[35]
t f
1
exp
1
A
dh 1 2 E f
=
C=
+b
2
2
dW 2 A 1 v f
t f 1 v i
+
+ E exp
E i
A
s
Viscoelastic/Plastic Properties. Most materials including ceramics, and even diamond are found to creep at temperatures well
below half their melting points, even at room temperature. Indentation creep and indentation load relaxation (ILR) tests are used for
measurement of the time-dependent flow of materials. These offer an
advantage of being able to probe the deformation properties of a thin
film as a function of indentation depth and location.
In the indentation creep test, the hardness indenter maintains its
load over a period of time under well controlled conditions, and
changes in indentation size are monitored.[19][144][178][206][290][297]
Nanoindenters are also used for indentation creep studies.[178][182][234][235] Indentation creep is influenced by a large number of variables, such as the materials plastic deformation properties, diffusion constants, normal load of indenter, duration of the
indentation, and the test temperature.
In a typical ILR test, the indenter is first pushed into the sample
at a fixed displacement rate until a predetermined load or displacement is achieved, and the position of the indenter is then fixed. The
material below the indenter is elastically supported, and will continue to deform in an nonelastic manner, thereby tending to push the
indenter farther into the sample. Load relaxation is achieved by
conversion of elastic strain in the sample into inelastic strain in the
sample. During the test, the load and position of the indenter, and the
specimen are continuously monitored. Normally the indenter motion
Eq. (21)
K IC
E
= B
H
1/ 2
W
3/2
c
Figure 15. Indentations in fused quartz made with the cube corner indenter
showing radial cracking at indentation loads of (a) 12 g and (b) 0.45 g.[232]
Eq. (22)
K Ic
E
= c
H
1
4
8
f W 3
(a)
(b)
(c)
Eq. (23)
W
c = 1 cr W 1 / 4
W
where
2 =
1t c3 / 2 H 1 / 2
(K Ic )interface
2.5
Macro-, micro-, and nanoscratch techniques are used to measure scratch resistance of surfaces from bulk materials to a few
nanometer thick films. Adhesion describes the sticking together of
two materials. Adhesion strength, in practical sense, is the stress
required to remove a coating from a substrate. Indentation, described
earlier, and scratch on micro-and nanoscales are the two commonly
used techniques to measure adhesion of thin hard films with good
adhesion to the substrate (>70 MPa).[37][46][60][76][199]
Scratching the surface with a fingernail, or a knife, is probably
one of the oldest methods for determining the adhesion of paints and
other coatings. Scratch tests to measure adhesion of films was first
introduced by Heavens.[139] A smoothly round chrome-steel stylus
with a tungsten carbide, or Rockwell C diamond tip (in the form of
120 cone with a hemispherical tip of 200 mm radius),[196][223]
[224][261][287] or Vickers pyramidal indenter,[70][73] for macro-and
microscratching a conical diamond indenter (with a 1 m or 5 m of
tip radius and 60 of included angle), for nanoscratching[56][131]
[132][302][305][306] is drawn across the coating surface. A vertical load is
applied to the scratch tip, and is gradually increased during scratching until the coating is completely removed. The minimum or critical
load at which the coating is detached or completely removed is used
as a measure of adhesion.[2][30][70][73][76][80][119][147][149][153][170][196]
[199][223][225][253][261][287][288][299][301][302][305][306] It is a most commonly used technique to measure adhesion of hard coatings with
strong interfacial adhesion (>70 MPa).
For a scratch geometry shown in Fig. 18, surface hardness H is
given by
Eq. (24)
H=
Wcr
a2
Eq. (25a)
t = H tan
=
Wcr
a2
a
2
R a 2
1/ 2
or
Eq. (25b)
Wcr
if R >> a
aR
where Wcr is the critical normal load, a is the contact radius and R is
the stylus radius.
Eq. (26)
a 2 2 EWad 2
Wc =
2 t
Figure 19. Schematic illustration of the scratch method for adhesion measurement.
(a)
(b)
Figure 20. (a) Optical micrographs of channels produced during scribing from
right to left under various stylus loads in Crofer 1700 coated with sputtered
TiN about 1.5 m thick. (b) Acoustic emission signal maxima and minima
taken from the curves recorded within the scratch channel length between 0.5
and 2.5 mm.[149]
scratch block with two Allen head screws. The scratch tip can be a
Berkovich indenter, or a conventional conical diamond tip with a tip
radius of about 1 to 20 m, and an included angle of 60 to 90
(typically 1 m or 5 m of tip radius with 60 of included
angle.)[56][131][133][302][306] The tip radius does not have to be very
small as it will get blunt readily.
Figure 21. Schematic of the tangential force option hardware (not to scale and
the front and rear prongs not shown).[16]
During scratching, a load is applied up to a specified indentation load or up to a specified indentation depth, and the lateral motion
of the sample is measured. In addition, of course, load and indentation depth are monitored. Scratches can be made either at the constant load, or at ramp up load. Measurement of lateral force allows
the calculations of coefficient of friction during scratching. The
resolution of the capacitance proves to measure tangential load is
about 50 N, therefore, a minimum load of about 0.5 mN can be
measured, or a minimum normal load of about 5 mN should be used
for a sample with coefficient of friction of about 0.1. Microscopy of
the scratch produced at ramp up load allows the measurement of
critical load required to break up of the film (if any) and scratch
width, and general observations of scratch morphology. Additional
parameters which are used to control the scratch are scratch length
(m), draw acceleration (m/s2), and draw velocity (m/s). The
latter parameters control the speed with which the scratch is performed. The default values of 10 m/s2 and 10 m/s provide safe
rates for performing the scratch. Draw velocity is limited by the
maximum rate of data acquisition (during a scratch the maximum
rate is approximately 2/s) and the length of the desired scratch. Thus,
a scratch with a desired 20 points over 1 mm must have a draw
velocity no greater than 100 m/s.
Wu[302] has used the scratch technique to study the adhesion of
diamondlike carbon and zirconia films deposited on Si(100) substrates. Figure 22 shows the scratch morphology at increasing normal loads, and typical scratch data (normal load, tangential load and
acoustic emission, as well as calculated apparent coefficient of
friction). We note that all three monitored outputs (LC, TG, and AE),
detected the first spallation event of the carbon coating by showing
sudden changes in their output signals. Correlation between the
delamination pattern and the sudden change in the scratch loading is
clearly observed.
Figure 22. Scratch morphology and scratch loading curves of 0.11-m thick
d-c sputtered diamondlike carbon film on a Si substrate.[302]
after the removal of the normal load. It appears that the scratch depth
after scratching indicates the final depth which reflects the extent of
permanent damage and ploughing of the tip into the sample surface.
We believe that the scratch depths after scratching are probably more
relevant for visualizing the damage that can occur in real applications. The abrupt increase in the coefficient of friction and scratch
depth is associated with damage to the coating. The cathodic arc
coating exhibits an almost constant low coefficient of friction of
about 0.10.15 during the initial stages and an abrupt increase in
friction when normal load exceeds the critical load, the load sufficient to damage the coating. Sputtered carbon coating exhibits a
gradual increase in the coefficient of friction with increasing normal
load from the beginning of the scratch.
Figure 23. Coefficient of friction profile during scratching and scratch depth
during and after scratching as a function of normal load for scratches made on
20 nm thick carbon coatings deposited on silicon by cathodic arc and sputtering
deposition techniques.[132]
Figure 24. SEM images of various regions and coefficient of friction profiles as
a function of normal load for 500 m long scratches made on single-crystal
silicon (111) at 2 to 20 mN.[56]
Figure 25. Surface profiles for scratched (a) (111) single-crystal silicon, (b)
PECVD-oxide coated Si, (c) dry-oxidized Si and (d) C+-implanted Si. The loads
used for various scratches at ten cycles are indicated in the plot.[51]
Accelerated friction and wear tests on macroscale are conducted to rank the friction and wear resistance of coatings, or bulk
materials to optimize their selection or development for specific
applications. After these coatings or bulk materials have been ranked
by accelerated friction and wear tests, the most promising candidates
Counterface material
Coefficient of friction
Bulk materials
Aluminum
Aluminum
1.0
Copper
Copper
0.8
Silver
Silver
0.9
Brass
Brass
0.4
Cast iron
Cast iron
0.6
Mild steel
Brass
Bronze
Copper
0.4
0.25
0.25
0.3
Mild steel
0.8
Aluminum
Nickel
Silver
Copper
Brass
Bronze
Babbitt
Graphite
PTFE
0.5
0.7
0.5
0.8
0.3
0.3
0.3
0.15
0.1
Tool steel
Tool steel
0.4
Nickel
Brass
Polyethylene
PTFE
Nickel
0.25
0.25
0.1
1.1
Chromium
Chromium
0.4
Silicon nitride
Silicon nitride
0.3
Mild steel
(Contd.)
Table 1. (Contd.)
Materials pair
Bulk
material/Coating
and Substrate
Tungsten carbide
Counterface material
Coefficient of friction
Tungsten carbide
0.35
Natural diamond
Steel
Natural diamond
0.4
0.05
PTFE
PTFE
0.05
Coatings/Surface
treatments
MoS2 (Sputtered)
Steel
0.050.1 (Ambient)
WC-Co
0.02 (Vacuum)
Steel
0.10.2 (Ambient)
Steel
0.40.6 (Dry)
0.030.1
Silver/Gold (Sputtered)
Steel
0.10.25
Al2O3 (CVD)
Steel
0.20.5
TiN (Sputtered)
Steel
0.150.5
TiC(Sputtered)
Steel
0.20.5
Diamond(HFCVD)/Si
Steel
0.10.2
a-C:H (Sputtered)
Steel
0.150.3
a-C:H (PEPVD)
Steel
0.150.3
Figure 26. Schematic illustration of typical interface geometries used for sliding
friction and wear tests: (a) pin-on-disk, (b) pin-on-flat, (c) pin-on-cylinder, (d)
thrust washer, (e) pin-into-bushing, (f) rectangular flats on rotating cylinder, (g)
crossed cylinders and (h) four ball.[46]
Rolling-Contact Fatigue Wear Tests. A number of rollingcontact fatigue (RCF) tests are used for testing materials and lubricants for rolling-contact applications such as rolling element bearings, and gears. In RCF test apparatus, basically a pair of driven
rollers are pressed against one another, and the surface damage on
roller surfaces is monitored with the number of cycles. The surface
damage could be the appearance of cracks, change in surface texture
or roughness, or spalling of material. In general, rolling-contact
fatigue (RCF) wear is compared in terms of number of cycles
sufficient to result a specific damage on the rollers. The most commonly used interface geometries used to rank coatings and materials
in terms of their resistance to rolling-contact fatigue wear are schematically shown in Fig. 27. The disk-on-disk test apparatus (Fig.
27a) uses two disks or a ball-on-disk rotating against each other
on their outer surfaces (edge loaded). The rotating four ball test
3.2
and is subtracted from the friction profiles of each scan, the misalignment effect can be eliminated. By following procedures developed
by Ruan and Bhushan[242] voltage corresponding to normal and
friction forces can be converted to force units. By making measurements at various normal loads, the average value of the coefficient of
friction is obtained which can then be used to convert the friction
profile to the coefficient of friction profile. Thus, any directionality
and local variation of friction can be measured. Surface topography data can be measured simultaneously with the friction data, and
a local relationship between the two profiles can be established.
Figure 30. Surface profile of an as-polished unlubricated disk showing the worn
region (center 2 m 2 m) after one cycle of wear. The normal load and the
number of test cycles are indicated in the figure.[53]
Figure 31. Wear depth as a function of load for both lubricated and unlubricated
as-polished disks after one cycle.[53]
3.3
Reduction of friction and wear are critical to successful performance of micromechanical elements requiring relative motion. Since
electrostatic forces, van der Waals forces, and viscous drag forces in
liquids change in proportion to the surface area of the element, these
become dominant over electromagnetic forces, and inertial forces,
which are in proportion to the volume of the element. In MEMS, the
electrostatic and van der Waals forces are the major sources of the
normal force which directly affect the friction force. Wear of sliding
components also need to be minimized. One of the MEMS devices in
which friction and wear issues are critical, is a micromotor. Friction
and wear studies have been conducted on actual or simulated MEMS
components, as well as on the coupons in conventional accelerated
tribological tests.
To in-situ measure static friction of rotor-bearing interface in a
micromotor, Tai and Muller[274] measured the starting torque (voltage)
and pausing position for different starting positions under a constant
bias voltage. A friction-torque model was used to obtain the coefficient
coefficient of static friction was then obtained from a plot of tangential force as a function of normal force. Figure 34 shows the tangential force as a function of normal force for the sputtered SiO2 coating
from a fused silica target against itself in different environments. The
tangential force versus normal force plots for the SiO2/ SiO2 pair in
air before baking is 0.54, in air after baking is 0.21, and in high
vacuum of 10-5 torr is 0.36.[95]
Figure 33. Schematic of the setup used to measure static friction between two
flats samples at very low loads.[95]
Figure 34. Tangential force versus normal force plots for SiO2/ SiO 2, pair in
ambient air as well as in high vacuum (10-5 torr). The coefficient of friction is
0.54 before baking the sample and 0.21 after. The coefficient of friction is 0.36 at
10-5 torr after the sample was baked.[95]
weight rotating on a threaded rod. The arm holding the bullet was
translated horizontally by a translation table using a piezoelectric
positioning device. The push of the piezoelectric positioning device
was controlled by a high voltage power supply, supervised by a
programmable controller. The tangential force on a bullet was measured by a charge mode piezoelectric force sensor. The sliding test
was performed by lowering the bullet onto the substrate, adjusting
the normal force on the bullet, and pushing the bullet forward using
the translational device until slippage was observed on the forcedisplacement curve. The bullet was then raised. Deng and Ko[95]
used this setup to measure friction between various material/ coating
pairs in ambient air, in UHV (8 10-10 torr), argon, and oxygen
environments. The coefficients of friction obtained by using this
setup are compared in Table 4. The values of coefficients of friction
obtained by using this setup were found to be very close to those
values obtained from in situ friction measurements in micromotors.[95]
Figure 35. Schematic of the setup used to measure static friction between a
coated bullet and a flat in controlled environment.[95]
(a)
(b)
Figure 36. Schematic of the setup used to measure static and kinetic friction
between two flat samples.[212]
4.0
Drilled holes in
circular arrangements
Specimen holder
Frequency
counter
Power supply
Test structure
X-rotation/
translation
Y-translation
Y-rotation
Substrate
Adjustable
base plate
DC motor
Figure 37. (a) SEM images of triangles micromachined on silicon by photolithography; total area of contact of triangle A and B is 1.88 10-1 mm-2 and 2.36
10 -2 mm -2, respectively. (b) Sample holder with circular arranged holes for the
placement of test triangles. (c) Schematic of the set-up used for sliding triangles
on a rotating disk. [28]
Figure 41. Effect of composition of precursor gas on the film density of diamond
films deposited by MW/RF plasma-assisted CVD using methane mixed with
argon and hydrogen.[236]
Figure 42. Effect of ion energy on the film density of amorphous carbon
films deposited by ion beam deposition with e/m selection.[146][193][240]
Figure 43. (a) Effect of substrate biasing on the film density of amorphous
carbon films deposited by rf capacitively coupled plasma-assisted CVD using
benzene-based precursor gas,[163] methane based precursor gas,[207] and hydrocarbon vapor,[300] and (b) effect of substrate biasing on hydrogen content of
amorphous carbon films deposited by rf capacitively coupled plasma-assisted
CVD using benzene-based precursor gas,[163] methane based precursor gas,[207]
and hydrocarbon vapor;[300] and by rf inductively coupled plasma-assisted CVD
using methane based precursor gas.[222]
4.2
Mechanical Properties
present some representative results on the mechanical and tribological properties on the micro- and nanoscale, of diamond, a-C, and aC:H coatings reported by various authors.
Hardness And Youngs Modulus of Elasticity. High cohesive energy, short bond length and covalent bonding in diamond
result in the highest hardness and Youngs modulus of elasticity. In
polycrystalline diamond films, even in the presence of high strength
of interatomic forces, the mechanical properties significantly vary
with the operative deformation mechanisms, which vary with the
microstructure and other structural features like voids, impurities,
defects, and texture.[265] The micromechanical characterization studies of a-C and a-C:H films deposited by various PVD and CVD
techniques have been done by various research groups. [56][83]
[116][132][133][246] Since these coatings are much smoother than polycrystalline diamond films, it is comparatively easy to obtain reproducible hardness, and elastic modulus values by nanoindentation. In
this section, we focus on the micromechanical properties of diamond
and a-C and a-C:H coatings. The information on the hardness and
elastic modulus measured by conventional methods can be found in
various reviews.[236][283][284]
Very few studies have been conducted on the micromechanical
properties measurements of diamond films. Beetz et al.[29] and OHern
and McHargue[213] have made nanoindentation measurements on
polycrystalline diamond films deposited on silicon by HFCVD using
methane and hydrogen mixture precursor gas. Beetz et al.[29] deposited films at two methane concentrations (0.11 and 0.99% CH4 in
H2), 1 kPa partial pressure, and at about 800900C substrate temperature. The films deposited at lower methane concentration exhibit
larger size grain size of about 58 m; and the films deposited at
higher methane concentration exhibit smaller size grain size of
about 0.5 m. The load-displacement plots of nanoindentation, and
SEM images of two polycrystalline diamond films deposited by
Beetz et al. [29] are shown in Fig. 44.[29] We note that the coarsegrained films exhibit almost an elastic deformation, whereas
the fine-grained diamond films exhibit a little hysteresis in the
Seino et al.[251] and Seino and Nagai[252] deposited polycrystalline diamond films by MPCVD with 0.51 micron grain size at 4 kPa
partial pressure, 0.1 to 5% methane in a H2 mixture, and 500 W
microwave power, and measured the hardness by Vickers indentation at 210 mN, and elastic modulus of a free standing film by a
vibrating reed apparatus. The effect of methane concentration in
precursor gas on the hardness and elastic modulus is shown in Fig.
47.[251] We note that films deposited at lower methane concentration
of 0.1% exhibit the highest hardness of about 94 GPa and elastic
modulus of about 960 GPa and hardness and elastic modulus decrease with increasing methane concentration resulting in an increase in sp2-bonded carbon fraction in diamond films. The high
hardness, and elastic modulus values of MPCVD diamond films
deposited at lower methane concentration are very close to those of
natural diamond ranging from 80 to 100 GPa.[66]
Figure 47. Effect of methane concentration on the hardness and elastic modulus
of diamond films deposited by MPCVD using 0.1 to 5% CH4 in H2 gas. [251]
The data reported by various authors indicate that the polycrystalline diamond films exhibit hardness and elastic modulus values
very close to those of natural diamond. More systematic study on
micromechanical characterization is needed to better understand the
dependence of deposition parameters, effects of diamond crystallite orientation, surface morphology, grain size, and role of atomic
hydrogen in the growth process on the mechanical behavior of
diamond films.
Figure 51. Effect of hydrogen content of the hardness of a-C:H films deposited
by magnetron sputtering using a graphite target and by varying hydrogen concentration from 0.5 to 15 % in Ar + H2 gas mixture.[83]
Figure 52. The effect of substrate bias voltage on the hardness of amorphous
carbon films deposited by rf capacitively coupled plasma-assisted CVD using
methane based precursor gas and biasing from -100 to -1250 V,[116] and 75% CH4
and 25% Ar precursor gas and biasing from -50 to -600 V,[92] and benzene-based
precursor gas at 3 kPa partial pressure.[163]
Pappas and Hopwood[222] studied the effect of various deposition parameters on the hardness, measured by Knoop indentation, of
a-C:H films deposited on silicon by RF induction plasma-assisted
CVD. Shown in Fig. 53 are the effects of substrate biasing, RF
induction power, Ar concentration in methane-based precursor gas,
and precursor gas flow on the hardness of a-C:H films. Like RF
(a)
(b)
(c)
(d)
The hardness and elastic modulus of metal-containing amorphous carbon films (Me-C:H) were measured using Nanoindenter by
Wang et al.[291] Figure 54 shows the dependence of metal concentrations on the hardness, and elastic modulus of Ti-C:H films deposited
on silicon by DC magnetron sputtering and Ta-C:H films deposited
by combining RF capacitively coupled plasma-assisted CVD at three
substrate temperatures, i.e., 20, 270, and 20270C in the presence
of methane-based plasma. Both the hardness and elastic modulus
profiles as a function of metal concentration in films passes through
a peak at about 50 to 60% metal. A model for explaining the increase
in hardness and elastic modulus of Me-C:H with metal concentration
need to be developed.
Figure 54. The dependence of hardness and elastic modulus Me-C:H films
deposited by rf plasma CVD combined with reactive rf glow discharge sputtering
using argon+acetylene precursor gas at different percentages of acetylene and
substrate temperatures. Films shown by S1 were deposited at 270C, S2 at 20C,
and S3 at temperatures between 20 to 270C.[291]
Figure 56. The adhesion, measured by microscratching, of 20-nm thick amorphous carbon films deposited on silicon by cathodic arc, direct ion beam, rf
plasma-enhanced CVD, and DC magnetron sputtering.[132]
The scratch depth profiles obtained during and after the scratches
on all samples are plotted with respect to initial profile after cylindrical curvature removed, Fig. 56. Reduction in scratch depth after
scratching is observed. The reduction in scratch depth after scratching is attributed to an elastic recovery after the removal of the normal
load. It appears that the scratch depth after scratching indicates the
final depths which reflect the extent of permanent damage and
ploughing of the tip into the sample surface. We believe that the
scratch depths after scratching are probably more relevant for visualizing the damage that can occur in real applications.
The higher scratch resistance/adhesion of cathodic arc carbon
coatings is attributed to an atomic intermixing at the coating-substrate interface because of high kinetic energy (2 keV) plasma
formed during the cathodic arc deposition process.[9] The atomic
intermixing at the interface provides a graded compositional transition between the coating and the substrate materials. In all other
coatings used in this study, the kinetic energy of the plasma was
insufficient for atomic intermixing.
4.3
Tribological Properties
SEM images of these films indicating that the grain size of diamond
crystallites varies from 20100 nm to 3.3 mm. The fine-grained films
(grain size ~ 20100 nm) are smooth, and contain a significant
amount of nondiamond carbon, whereas the coarse-grained films
(grain size ~ 1.13.3 mm) are rough and contain a little amount of
nondiamond carbon. The coefficients of friction of these films against
bulk diamond pins at 1N in humid air and dry nitrogen are shown in
Fig. 58. As expected, smooth films exhibit low coefficients of
friction of 0.030.04 in humid air, as well as in dry nitrogen. Rough
films exhibit slightly higher coefficients of friction of 0.050.07.
Measurements in high vacuum of 10-7 torr show very high coefficient of friction approaching 1.51.8.[203] The authors believe that in
humid air and nitrogen, friction arises from abrasion from a diamond
pin sliding on the diamond film, and high vacuum adhesion between
the sliding surfaces. They also observed that the friction in air and
nitrogen increases with the surface roughness, whereas in vacuum it
is independent of surface roughness.
(a)
(b)
(c)
Figure 57. SEM images of diamond films deposited by MPCVD. (a) Fine-grain
(20-100 nm) diamond film on (100) silicon; surface roughness rms = 15 nm. (b)
Medium-grain (1100 nm) diamond film on (100) silicon; surface roughness rms
= 63 nm. (c) Coarse-grain (3300 nm) diamond film on -SiC silicon; surface
roughness rms = 160 nm.[203]
(a)
(b)
(c)
Figure 60. (a) Coefficient of friction of diamond films whose surface morphologies
are shown in Fig. 59, slid against a diamond coated silicon nitride, silicon nitride,
alumina, zirconia, and steel at 4.2N load, 35 mm s-1 sliding speed, and 5585%
relative humidity and (b) average wear rate of slider materials slid for 1 h against
the three diamond films.[115]
Figure 61. SEM and AFM images of (a) as-deposited coarse-grained films,
(b) as-deposited fine-grained films polished diamond films, (c) chemomechanically-polished coarse-grained films, and (d) laser-polished coarse-grained
films, deposited by HFCVD.[129]
Since a-C and a-C:H coatings can be deposited at lower temperatures (< 200300C) on substrates ranging from soft polymers to
hard ceramic substrates without significantly affecting their surface
topography, numerous studies have been performed to correlate the
friction and wear properties of carbon films to their properties, and
subsequently to their deposition conditions.[9][106][107][116][120][122]
[125][131][133][143][293][294] Like hardness and elastic modulus, friction
and wear properties of a-C and a-C:H coatings vary dramatically
with the deposition conditions. The environment plays a crucial role
in the friction and wear properties of a-C:H coatings because of their
lower thermal stabilities, the a-C:H coatings start to graphitize by
hydrogen loss above 400C.[102][197][202] In this section, we present
some representative data to illustrate the effect of deposition conditions, and the environment on the friction and wear properties of a-C
and a-C:H coatings. For more detailed information reader can refer
to a review by Grill.[120]
Ball surface
Figure 63. The optical images of the diamond surface and the alumina ball after
the sliding tests on (a) as-deposited coarse-grained films, (b) chemomechanicallypolished coarse-grained films, (c) as-deposited fine-grained films polished films,
and (d) natural diamond.[129]
Figure 65. Coefficient of friction of a-C coatings deposited at different ion beam
energies and substrate temperatures sliding against an alumina ball at 0.2 N
normal load under 50 10% relative humidity and 21 2C temperature.[293]
Figure 66. The coefficient of friction of a-C coatings deposited by cathodic arc
deposition on silicon slid against diamond at 0.3 N as a function of pulsed bias
voltage for pulse duty cycles of 10 and 33%.[9]
Friction Coefficient
Gangopadhyay et al.[116] deposited a-C:H films by RF capacitively coupled plasma-assisted CVD using methane-based precursor
gas at substrate biasing ranging from -100 to -1250 V corresponding
to ion energies from 30 to 400 eV. The effect of substrate biasing on
the coefficient of friction of a-C:H films slid against steel ball at 4.2
N in ambient humidity of 70% RH are compared in Fig. 67. We note
that films deposited at the lowest (-100 V) and the highest (-1250 V)
biasing exhibit high coefficient of friction in the range of 0.2 to 0.3,
while films deposited at the biasing from -200 to -300 V, exhibit the
lowest coefficient of friction of about 0.08. The lowest coefficient of
friction in these films can related to their high hardness of about 16
GPa, Fig. 52. Gangopadhyay et al. [116] have also studied the effect of
humidity on the friction and wear properties of the films deposited at
a substrate biasing of -350 V, and found that both friction and wear
increases with the relative humidity, Fig. 68. They observed a more
uniform transfer film on a steel ball at lower humidity (4%) than the
film at higher humidity (67%). Enke et al.[104] reported a low coefficient of friction of about 0.010.02 for RF PECVD deposited a-C:H
films using acetylene and argon mixture precursor gas at a relative
humidity of 1% and an increase in the coefficient of friction to 0.19
as relative humidity was increased to 100%.
Figure 68. Effect of relative humidity on (a) the coefficient of friction and (b)
wear volume of a-C:H films deposited at -350 V bias voltage by rf capacitively
coupled plasma-assisted CVD properties of a-C:H films.[116]
films that exhibit a high coefficient of friction (in dry oxygen) iron
was transferred to the coating. Miyoshi et al.[202] deposited 0.25-m
thick for 30 kHz AC-PECVD a-C:H films, using methane and butane
precursor gases. They found low coefficients of friction of 0.02 and
0.06 between these films and diamond in dry nitrogen and ambient
air, respectively. The a-C:H coatings exhibit coefficients of friction
of 0.15 and 0.25 when slid against silicon nitride in dry nitrogen and
humid air, respectively. This increase in friction is due to the silicon
oxide films produced on the surface of silicon nitride pins in humid air.
Erdemir et al.[108] studied the nature of transfer layers formed
on M50 steel balls during sliding against 1.5 m thick ion-beam
deposited carbon coatings on M50 steel disks. These coatings exhibited a low coefficient of friction of about 0.12 at initial stage of
sliding against M50 steel ball in nitrogen at 5N normal load under
ambient temperature. The coefficient of friction decreased with
continuing sliding, and reached to a value of about 0.07 toward the
end of 1 km sliding test, and to about 0.03 toward the end of a long
test. Ultra low friction of these carbon films was attributed to the
formation of transfer films that were rich in carbon and had a
disordered graphitic structure.
Memming et al.[197] annealed a-C:H films at 550C to study the
effect of hydrogen depletion during annealing on the friction and
wear properties. They found the annealing resulted in a high coefficient of friction of 0.68 in vacuum, as well as in dry nitrogen.
Miyoshi et al.[202] also observed a similar increase in the coefficient
of friction on annealing; Miyoshi and co-workers suggested the
formation of a graphite layer through a two stage process: a carburization stage resulting in hydrogen depletion and a polymerization
stage resulting in the formation of graphite crystallites.
Grill et al.[123] reported the effects of substrate temperature and
substrate biasing on the friction and wear properties of RF PECVD
a-C:H coatings deposited on silicon using acetylene. The coefficient
of friction of a-C:H films (hydrogen content-40%) sliding against
a steel ball in 4070%, relative humidity was decreased from
0.35 0.04 to 0.20 0.04 as the substrate temperature increased from
100oC to 250C. The substrate biasing did not show any significant
variation in friction. The insensitivity of the coefficient of friction to
the annealing temperature was similar to what was reported by
Memming et al.[197] and Miyoshi[201] in humid air.
Kim et al.[156] reported the effects of oxygen and humidity on
friction and wear of RF PECVD a-C coatings deposited on silicon
from methane and hydrogen mixture. The coefficient of friction of
these films against silicon nitride ball varied from 0.2 in 50% humid
argon and 100% humid air, to 0.06 in dry argon, Fig. 69. The
variations in friction were attributed to a transfer layer, produced by
friction, that covered the contact surface of the ball in all cases.[156]
Low friction in dry argon was resulted from the material (unoxidized
DLC debris) transferred from the carbon coating to the silicon nitride
ball. The oxidized DLC debris (carbonyl compounds) formed on the
a-C coating, as well as on the silicon nitride ball in air, and humid
argon increases the friction.[156] The lowest wear rates were observed
in dry environments. The humidity increases the wear rates of a-C
coatings in 50 and 100% argon, and humidity saturated air by five times.
Wear of these coatings was dominated by the tribochemistry in air
and humid argon, but in dry argon it is controlled by adhesive wear.
Figure 69. Coefficient of friction and wear rate of a-C coatings sliding against
silicon nitride ball in air and argon as a function of relative humidity. The test
conditions were as follows: silicon nitride ball diameter-7.94 mm, sliding speed18.7 0.8 mm s-1, load- 9.8 N, environment-ambient temperature.[156]
5.0
CLOSURE
The micromechanical and microtribological properties measurements can be made on ultrathin coatings, and on the skin of bulk
materials by simulating single asperity contact scratching and sliding situations by using a nanoindenter, an atomic force microscope,
and a friction force microscope. Depth profiles of various mechanical properties such as elastic-plastic deformation behavior, hardness,
Youngs modulus of elasticity, fracture toughness, fatigue, and coating-substrate adhesion can be obtained by making nanoindentations
at different loads by using a nanoindenter. The evolution of wear on
a typical surface can be observed by using an atomic force microscope or a friction force microscope.
Diamond films deposited by plasma enhanced CVD exhibit
hardness, elastic modulus, friction, and wear properties comparable
to those of natural diamond. High friction (0.4) of rough CVD
diamond films having grain size of diamond crystallites in the range
of 1020 m and rms roughness of about 700 nm can be reduced to
0.08 by polishing by using chemomechanical, and laser polishing
techniques. Properties of amorphous and hydrogenated amorphous
carbon coatings can be tailored by optimizing the deposition parameters. Amorphous carbon coatings with a hardness of more than 40
GPa can be deposited by cathodic arc deposition. The friction and
wear properties and wear mechanisms of amorphous and hydrogenated amorphous carbon coatings are found be very sensitive to the
test environment.
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