Thin Solid Films, 154 (1987) 387-401

387

EVALUATION OF ADHESION STRENGTH OF THIN HARD COATINGS*

T. ARAI, H. FUJITA AND M. WATANABE

Toyota Central Research and Development Laboratories Inc., 41-1 Ala Yokomichi, Oaza Nagakute,
Nagakute-cho, Aichi-gun. Aichi-ken 480-l I (Japan)
(Received May 12, 1987)

Extensive research has been carried out in order to study the feasibility of
various methods for evaluating the adhesion strength of thin hard coatings,
produced by a wide variety of coating methods, to steels.
Indentation, scratch, hammering, rolling with slip, and coining and metal
stamping tests were employed and some of them were concluded to be of no use for
such thin hard coatings which have large adhesion strength.
Carbide and nitride coatings produced by high temperature processes such as
chemical vapour deposition (CVD) and salt bath immersion showed less failure by
all testing methods than those produced by low temperature processes such as
physical vapour deposition, low temperature CVD and chromium plating. How-
ever, TiN coatings formed by plasma-assisted CVD at low temperature showed less
failure than those formed by sputtering and ion plating.

1. INTRODUCTION

Some methods have been developed for forming various types of hard coatings
onto dies, jigs, tools and machine components in order to improve their resistance to
seizure and wear. The durability of any such material depends not only on the
seizure and wear resistance of the coatings but also strongly on adhesion to the
substrate. It is, therefore, very important to evaluate the adhesion strength.
The adhesion strength of a coating is considered to be the amount of energy
which is required to separate it from the substrate, but the energy is very difficult to
measure. Therefore, the force which is required to separate the coatings from the
substrate is often employed to indicate the adhesion strength. Low adhesion
strength, as of a paint, is easy to determine, and a number of methods are known’-3.
There is, however, not yet any method that is optimum for evaluating large
adhesion strengths, although some indirect methods have been developed4. Among

* Paper presented at the 14th International Conference on Metallurgical Coatings, San Diego, CA,
U.S.A., March 23-27, 1987.

0040-6090/87/$3.50 0 Elsevier Sequoia/Printed in The Netherlands

388 T. ARAI, H. FUJITA, M. WATANABE

these methods, the scratch test is often used for coatings produced by chemical
vapour deposition (CVD) and physical vapour deposition (PVD), and this has
recently made remarkable progress 5~ ’ . Some attempts have been made to study the
adhesion ofcoatings from the point of view of dynamics9~i0, and acoustic emission is
utilized for detecting flaking. This method is simple but does not always determine
the adhesion strength of coatings correctly.
Various fields of industry experience different modes of flaking with different
kinds of coatings under different conditions of service. Thus there is often a great
difference between the results of a laboratory study and the experience in industry,
even if, for example, only the comparison of the types of surface coatings is
considered.
We have therefore tested various types of surface coatings by using various
methods. The coatings are the thin film coatings which are mainly employed to im-
prove the wear resistance of surfaces, e.g. those formed by PVD, such as ion plating
(IP) and sputtering, CVD at ordinary temperature (HT), medium” temperature
(MT) and low’* temperature (LT), plasma-assisted CVD (PCVD) at low tempera-
ture13 and salt bath immersion carbide coating14p16, as well as by conventional
chromium electroplating. A number of laboratory and semi-industrial methods
were used in which different amounts of stress are applied in different directions to
the coatings and the interface to the substrate.

2. EXPERIMENTAL DETAILS

The test methods involved indentation, scratch, hammering, metal stamping,

coining and rolling with slip tests, as shown in Fig. 1. The indentation test was
conducted by employing a Rockwell hardness tester and applying a diamond
indenter of the C scale to the surface of the sample. The resulting damage of the

I I
I I
INDENTATION
I
SCRATCH
I
HAMMERING
I
METAL
STAMPING
I
COINING

I
ROLLING
WITH SLIP

yB FLAKING FLAKING
FLAKING CRACKING
55 CRACKING FLAKING
is CRACKING CHIPPING
CHIPPING
WEAR
2s

Fig. 1. Main stress concerned and failures observed in six tests.

ADHESION STRENGTH OF THIN HARD COATINGS 389

coating around the indentation was examined by scanning electron microscopy

(SEM), electron beam scanning (EBS) and optical microscopy.
The scratch test was carried out by employing a Heidon 14 surface testing
machine and applying a graded load to a diamond indenter having a conical angle of
90” and a tip radius of 25 urn to scratch the surface of a sample. The scratch channels
were examined by SEM, EBS and optical microscopy.
The hammering test was performed by using a cemented carbide ball having a
diameter of 6.35 mm to strike the surface of a sample repeatedly at a load of 304 N.
The number of times for which the surface was struck until the coating disappeared
to expose the substrate surface was counted.
The metal stamping test was conducted by using coated dies for bending a cold-
rolled low carbon steel strip having a width of 10 mm and a thickness of 0.8 mm into
a U-shape continuously until the coating disappeared from the die corner.
The coining test was also conducted by using a coated punch for coining a cold-
rolled low carbon steel strip having a width of 10 mm and a thickness of 1.6 mm
continuously until the coating disappeared from the punch corner.
The rolling with slip test was conducted by using an Amsler tester and applying
a rolling stress with a slip of 10% to a pair of 40 mm diameter sample rings coated
with the same material until the coating disappeared.
Table I shows the coating conditions tested, the thickness of the layer, the
surface roughness and the substrate hardness of the samples made of M2 steel.
Before being coated, each sample was hardened (1200 “C, 30 min; oil quenched and
tempered three times at 560°C for 2 h) so that the substrate hardness was
61-63 HRC. Each of the samples for the stamping, coining and rolling tests was
ground to a surface roughness R,,, of 0.5 urn. Each of the samples for the
indentation, scratch and hammering tests was lapped with diamond paste to a
surface roughness R,,, of 0.1 urn. All the samples were then coated. For the samples
produced by CVD at high and medium temperatures and salt bath immersion
coating only, reheating hardening was carried out with a vacuum furnace under the
following conditions: nitrogen cooling at 1190 “C for 30 min and tempering three
times at 560 “C for 2 h.
The samples prepared by PVD, PCVD and CVD at low temperature were all
tested without any additional finishing. The samples which had been prepared by
CVD at high and medium temperatures and salt bath immersion carbide coating
were all tested after lapping. The chromium-plated samples for the indentation,
scratch and hammering tests were finished by lapping before testing. The chromium-
plated samples for the metal stamping, coining and rolling with slip tests were
finished by grinding to receive an accurately designed shape.
Chromium electroplating, IP and CVD were carried out by commercial
processors under their recommended conditions. Sputtering, PCVD and salt bath
immersion coating were carried out by ourselves, as we are the developers of these
processes. Some of the specimens had been cut from a commercially available gear
cutter TIN coated by IP.
In most cases, specimen preparation and coating were repeated several times
because it is commonly suggested that substrate surface preparation affects the
quality of coatings”.
TABLE I
SAMPLESTESTED %
0

Coating Material Lot Thickness Hardness Surface roughness R,,, (pm) Coating condition
oroces of layer of substrate
(b-4 WW Indentation, scratch, Metal stamping,
hammering coining, rolling

Electroplating Cr 25 62.1-63.6 0.03-O. 1 0.330.8 Silicofluoride

3 bath, 52 + 2 ‘C,
6 35k5Ame2
16
PVD
IP TiN 1 62.0-63.8 28O’C”
L
4
1
3
0.3 67.0
0.5
Sputtering TiN 2 62.0-63.0 Presputtering
2 No presputtering
PCVD TiN 2 62.0-63.0 550 ‘C
TiC 2
CVD
LT w-c 9 61.2262.0
MT Ti(C, N) 17 61.0-62.3 850 ‘C
HT TiN 6 6 1.5562.9 9OOC
TiC 6 61.5-62.4 0.4 l-3 1020°C
TiC + TiN 1 61.5562.0 0.0330.1 TIC, 1020 “C;
TIN. 900 ‘C
Salt bath immersion vc 2 60.9-61.0 1025 -C
2 4
3 I

“Estimated on the basis of the hardness of the carbon steel substrate.

ADHESION STRENGTH OF THIN HARD COATINGS 391

3. RESULTS

As a result of the six types of tests, the coatings showed wear, chipping and
cracking in addition to flaking as shown in Figs. 2-6. Table II gives our definition of
each of these failures.

3.1. Indentation test

Figure 2 shows the results. The chromium-plated samples exhibited only
cracking. The majority of the PVD coatings showed only cracking, or cracking and
flaking in a small area surrounded by cracks. There were, however, some PVD
coatings that had flaked off in a large annular area surrounding the indentation. The
coatings formed by CVD at high temperature and salt bath immersion produced
only cracking, or cracking and flaking in a small area surrounded by cracks.

CRACKING

FLAKING

Fig. 2. Failures observed at each load in the indentation test.

3.2. Scratch test

Figure 3 shows that the chromium coatings cracked with slight chipping at the
shoulder of the scratch channel. The coatings formed by IP showed slight chipping
in some samples. Small amounts of flaking appeared in some samples coated by IP,
sputtering and PCVD. However, the samples coated by sputtering under obviously
poor conditions exhibited flaking in a large area around the scratch.
The majority of the coatings formed by CVD at high temperature and salt bath
immersion carbide coating showed only surface chipping that did not reach the
substrate.

3.3. Hammering test

Figure 4 shows the number of shots which resulted in the disappearance of the
coatings. The disappearance of the TiN coatings formed by IP and the W-C
coatings formed by CVD at low temperature was due to flaking, and that of the
other coatings was due to chipping. It is worthy of notice that the gear cutter TiN
392 T. ARAI, H. FUJITA, M. WATANABE

TABLE II
DEFINITIONS OF VARIOUS FAILURES OBSERVED IN SIX TESTS

Failure Lkjinition Model

Wear Progressive very fine loss of coatings from the surface due to
abrasion or adhesion as a result of relative motion at the surface

Chipping Intermittent irregular particle loss ofcoating from the surface as a

result of fine cracking

Cracking Cracks vertically across the coating without noticeable loss of

coating from the interface

Flaking Separation of particles from the interface in the form of flakes

coated by IP, lots 6 and 7, which had been found to provide a greatly improved tool
life, showed flaking after only a small number of shots.

3.4. Metal stumping test

Clear flaking of the chromium coatings (lot l), TIN coatings formed by IP (lots 1
and 3) and by sputtering (lot 2) and W-C coatings formed by low temperature CVD
resulted from only a small number of shots, as shown in Fig. 5. However, other
chromium coatings and the TIN coatings formed by IP and by sputtering showed no
flaking even after a large number of shots. Remarkable wear was observed on
chromium platings.
No flaking of any of the coatings formed by PCVD, CVD at high temperature
and salt bath immersion carbide coating resulted from even a large number of shots.

3.5. Coining test

Flaking was observed even after a small number of shots in TIN coatings
formed by IP (lot 2) and W-C coatings as shown in Fig. 6. In contrast, the TIN
coatings formed by IP (lot 5) showed only a small degree of flaking despite a large
number of shots. Therefore, the coining test, as well as the metal stamping test,
confirmed that the quality of the TIN coatings formed by TP differed greatly from
one lot to another.
No flaking of any of the coatings formed by PCVD, high temperature CVD and
salt bath immersion carbide coating resulted from even a large number of shots.

3.6. Rolling with slip test

The rolling with slip test caused flaking of all the coatings, as shown in Fig. 7. It
 THICKNESS
FAILURES
PROCESS ;f)iy Lot. OF LOAD(N)
OBSERVED
LAYER (pm) 1 2 3
m h n A t
PLATING Cr
@-‘ --

CRACKING
I P TiN - - - -
4 @@@AA n
2 @@@@AAA A
SPUTTERING O--V-
\, v v
i; CHIPPING.
PCVD
A
@
DO0
SMALL FLAKING
@
I TiC+TiN 1 7 0
2 . 0 0
SALT BATH VC 4
7 0 LARGE FLAKING

Fig. 3. Failures observed at each load in the scratch test.

394 T. ARAI, H. FUJITA, M. WATANABE

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ADHESION STRENGTH OF THIN HARD COATINGS 397

M.T. CVD TilC.Nl a SALT BATH VC 0

NUMBER OF REVOLUTION
Fig. 7. Load us. number of revolutions that caused flaking in the rolling with slip test.

may be that chipping occurred first on the edge and induced flaking. However, none
of the other failures that were observed in the other tests was found.
The coatings formed by high temperature CVD and the carbide coatings
formed by salt bath immersion showed a very high degree of durability compared
with that of, for example, the TiN coatings formed by IP.

4. DISCUSSION

The majority of the tests employed here caused not only flaking but also other
failures, such as wear, chipping and cracking, irrespective of the type of coating.
Unless an adhesive having an adhesion strength which is higher than that of the
coatings to be tested is employed, flaking can be induced only by a force applied to
the coating-substrate interface through a loading material which is brought into
contact with the surface of the coatings or is penetrated into the substrate beneath.
The magnitude and direction of the force which is applied to the interface are
governed by the properties of the coating, such as its thickness, mechanical
properties and residual stress, and the friction between the coating surface and the
loading material as shown in Fig. 8. Furthermore, the mode in which the force is
applied to the interface varies with the properties of the coatings even when the same
method is employed. Therefore, the adhesion strength of any such coatings is quite
difficult to determine correctly, whichever method is employed.
The magnitude of the force which acts on the interface during the indentation or
scratch test ought to depend not only on the load which is applied to the indenter but
398 T. ARAI, H. FUJITA, M. WATANABE

* Thickness
* Mechanical &perty Coating
* Residual stress
+-

Fig. 8. Various factors that should be considered in evaluating flaking

also on the positional relationship between the depth of the indentations and the
interface. This positional relationship depends strongly on the thickness of the
coating, its mechanical properties etc. The indentation test estimates the capacity of
the coating to follow the plastic deformation of the substrate. Flaking hardly occurs
when the coating is either elastic or brittle because the deformation and cracking
release the applied stress. Flaking occurs in the coating which is unable to deform
with the substrate and flakes at a lower stress than the stress for cracking. In the
scratch test, the shearing stress can be applied to the interface parallel to it when the
indenter does not reach the interface. However, flaking does not occur when the
stress at the interface is relaxed by plastic deformation or cracking. Flaking therefore
occurs in the coating with an extremely low adhesion strength, similarly to the
indentation test. The scratch test relies on the critical load detected by acoustic
signal to determine the adhesion strength of coatings. However, the acoustic
emission can also result from chipping and cracking18, so the scratch test should be
limited to specified cases, e.g. the same coatings and same thickness. If the coatings
have a low adhesion strength as a result of, for example, inappropriate coating
treatment, it can be detected because flaking occurs in a large area around the
indentation or scratch. Thus it is concluded that this method is useful for
determining the coatings having an extremely low adhesion strength which are
likely to be produced by low temperature methods such as PVD and plating.
Steinmann and Hintermann reported that the critical load increases with the
coating thickness8, but the effect of-coating thickness was unclear in our study
because of poor experimental data.
The hammering test was used to strike the surface of the coatings repeatedly at
a small load without large plastic deformation as occurred in the indentation test. In
this test it is clear that the durability of coating depends on the thickness of layer
when the failure is dominated by chipping. The shear stress at the interface is
dominant for flaking in the metal stamping, coining and rolling tests. This shear
stress depends on the thickness and antiscoring property of the coatings.
It is very difficult to apply the same shear stress to the interface because the
TABLE III
SUMMARY OF THE RESULTS OF THE SIX TYPES OF TEST

Coating Material Lot Thickness Degree offailurefor the following test9

process of layer
(Pm) Indentation Scratch Hammering Metal Coining Rolling
stamping with slip

Electroplating Cr 25 x
3 0 @
6 0 @
16 0 0 0 A (wear) A (wear) x

PVD
IP TiN 1
2
4
1
3
0.3
0.5
Sputtering TiN 2
2

PCVD TIN 1 2 A 0
TIC 1 2 0 0
CVD
LT w-c Aor 0 x x
MT Ti(C, N) c3
HT TIN @ 0
TIC @ 0 0
TiC+TiN A or 0
Salt bath vc

‘Less failure in the order x > A > 0 > @.

400 T. ARAI, H. FUJITA, M. WATANABE

antiscoring properties of the coatings are different”. The antiscoring properties of

the coatings in this report are superior to those of steel dies. Therefore the shear
stresses at the interface are not so large. Nevertheless, the W-C coatings produced
by low temperature CVD etc. showed flaking. This is therefore interpreted as
meaning that the adhesion strengths ofthese coatings are low. In the rolling test, large
shear stresses were available at the interface, so all the coatings flaked.
The hammering, metal stamping, coining and rolling with slip tests employ
modes of loading which can be seen very frequently in industry and can, therefore, be
said to be useful for the practical evaluation of any coatings. Nevertheless, careful
consideration is needed even for such a test in the examination of the test results, as
they involve a great many factors varying on a case-to-case basis.
Table III summarizes the results of the six types of tests. It can generally be
concluded that the coatings which are formed by high temperature treatment, such
as salt bath immersion or CVD at high temperature and medium temperature,
showed less failure than those formed by any other method.
The W-C coatings formed by CVD at a low temperature, chromium coatings
and TIN coatings formed by IP are obviously inferior in durability to the coatings
obtained at a high temperature. Moreover, their durability greatly differs from one
lot of products to another.

5. SUMMARY

The adhesion strengths of various types of coatings have been tested by using
six methods; the following conclusions have been obtained.
(1) Whichever method is employed, it is impossible to apply the same stress to
the interface in a way which is not affected by the type or thickness of the coatings
and many other factors. Moreover, other failures such as wear, chipping and
cracking, accompanied by flaking in most cases, also depend on the type and
thickness of the coatings etc. These problems make it difficult to evaluate the correct
adhesion strength.
(2) The indentation, scratch or hammering test can be considered to be useful to
determine the coatings having an extremely low adhesion strength.
(3) The rolling with slip test can clarify the difference in durability between
different kinds of coatings.
(4) The coatings which are formed by a high temperature treatment, such as salt
bath immersion or CVD, have been found to be less prone to failure than any other
type of coating, irrespective of the testing method employed.
(5) The W-C coatings formed by CVD at a low temperature, the TIN coatings
formed by IP and sputtering, and the chromium coatings are definitely inferior in
durability to those formed by treatment at a high temperature. Moreover, their
durability differs substantially from one lot of products to another.

ACKNOWLEDGMENTS

We, the authors, wish to thank Messrs. Y. Ohta, Y. Tsuchiya and Y. Takada for
their cooperation through a large number of tests.
ADHESION STRENGTH OF THIN HARD COATINGS 401

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