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Surface and Coatings Technology 154 (2002) 304–313
Surface and Coatings Technology 154 (2002) 304–313

Relationships between hardness, Young’s modulus and elastic recovery in hard nanocomposite coatings

J. Musil*, F. Kunc, H. Zeman, H. Polakova´ ´

Department of Physics, University of West Bohemia, P.O. Box 314, 306 14 Plzen,ˇ

Czech Republic

Received 19 November 2001; accepted in revised form 11 December 2001

Abstract

The paper is devoted to an assessment of the mechanical behavior of hard and superhard nanocomposite coatings from loadingy unloading curves measured by a computer-controlled Fischerscope H 100 microhardness tester and a maximum depth d of the diamond indenter impression into the coating at a given load L. It is shown that: (1) the area between the loadingyunloading curve and the value of d decreases with increasing (i) hardness H, (ii) effective Young’s modulus E sEy(1yn ) and (iii) universal hardness HU, where E and n are the Young’s modulus and the Poisson ratio, respectively; and (2) there is no simple

max

*

max

2

relation between the mechanical response of the coating and H or E alone; however, this response is strongly dependent on the ratio HyE . The last fact gives a possibility of tailoring the mechanical properties of a coating for a given application, e.g. to prepare coatings with high hardness H, high resistance to plastic deformation (;H yE ), high elastic recovery W , but with low

E

(G60 GPa) coatings. It is shown that a high elastic recovery W G80% of superhard films with HG60 GPa (1) strongly decreases the gradient dHydL and (2) shifts the region L, where H(L)fconstant and the hardness H is correctly measured, to higher values

of L. This means that the lowest load L used in the hardness measurement must be higher than L used in measurements of coatings with H-60 GPa to prevent the value of H measured from being significantly higher than the real hardness of the coating. 2002 Elsevier Science B.V. All rights reserved.

and high d . Special attention is also given to the analysis of problems in accurately measuring the hardness of superhard

*

*

3

*2

e

*

max

e

Keywords:

Nanocomposite films; Mechanical properties; Microindentation measurements; Magnetron sputtering

1. Introduction

It is well known that the properties of every material are closely connected to its structure. The structure, however, depends on the phase and chemical composi- tion of the material, and this in turn is strongly depend- ent on the preparation method. Therefore, the development of new materials becomes a complex and difficult task. First, the relationship between the structure of the material and the conditions of its preparation must be found; this argument is particularly valid for materials produced in the form of coatings. Increasingly, thin-film coating techniques are being used as a flexible method to produce new materials—many of which cannot yet be synthesized by conventional methods.

*Corresponding author. Tel.: q420-19-7423136; fax: q420-19-

7422825.

E-mail address: musil@kfy.zcu.cz (J. Musil).

Hard materials are currently characterized by their hardness, H, effective Young’s modulus E sEy(1yn ) and elastic recovery W , where E and n are the Young’s modulus and the Poisson ratio, respectively. For hard coatings, these quantities can easily be determined from loadingyunloading curves measured by nanoindentation or instrumented microhardness testing. Recently, for instance, such measurements were used to characterize the macrostresses generated in CN films during depo- sition by reactive magnetron sputtering of a graphite target in pure nitrogen discharge w1x. Here, it was shown that stresses in CN films deposited onto a Si(001) substrate can be directly correlated with the film micros- tructure (low stresses for an underdense columnar struc-

ture and high stresses for a dense, distorted turbostratic-like cross-linked microstructure) and partic- ularly that W increases, and maximum penetration depth

d

of the diamond indenter decreases, with increasing

H (and vice versa). Similar experimental results have

*

2

e

x

x

e

max

0257-8972/02/$- see front matter 2002 Elsevier Science B.V. All rights reserved. PII: S0257-8972 Ž 01 . 01714-5

J. Musil et al. / Surface and Coatings Technology 154 (2002) 304–313

305

/ Surface and Coatings Technology 154 (2002) 304–313 305 Fig. 1. Typical indentation load–displacement curve

Fig. 1. Typical indentation load–displacement curve measured using a microhardness tester. Areas I and II represent plastic deformation and elastic recovery, respectively.

also been reported by Karlsson et al. w2x. They showed that for arc-evaporated TiC N films, the value of

decreases with both increasing stress s and H. On

the contrary, Matthews and Leyland w3x discussed the importance of the elastic modulus E and the ratio HyE in determining the endurance capability of a surface

coating, especially its ability to accommodate substrate deflections under load. Recent experiments, however, have shown that hard nanocomposite coatings with the same hardness can, according to their chemical composition, exhibit differ-

* w4,5x.

This means that there is a possibility of tailoring the mechanical properties of a material for a given appli- cation, but there is no simple relationship between all three quantities, H, E and W , that characterizes this mechanical behavior. Therefore, it is necessary to find some general relationships between H, E and W . This task is the main subject of the article.

0.15

0.85

d max

ent values of the effective Young’s modulus E

*

e

*

e

max ent values of the effective Young’s modulus E * e * e Fig. 2. The

Fig. 2. The loadingyunloading curves of the hard (13 GPa) and super- hard (46 GPa) Cr–Ni–N nanocomposite coatings.

The article deals with (i) a systematic investigation

of the loadingyunloading curves of different nanocom- posite coatings prepared by magnetron sputtering, (ii)

correlations between H, E

and W and (iii) the effect

*

e

of H and E on the resistance of materials to plastic

deformation.

*

2. Experimental details

All hard and superhard nanocomposite coatings

reported in this article were prepared by DC reactive sputtering using an unbalanced magnetron equipped with alloyed or composite targets with a diameter of 100

mm.

The nanocomposite coatings were characterized using a computer-controlled Fischerscope H 100 microhard- ness tester equipped with a Vickers diamond indenter. The hardness H and universal hardness HU measured by this instrument are defined by the following formulae

w6,7x:

HsL

HUsL yŽ26.43d

where the diamond indenter penetration depths d and

are defined in Fig. 1. The hardness H is determined

from the plastic component of the coating deformation only. On the contrary, the universal hardness HU is determined by both plastic and elastic components of

the coating deformation. Therefore, the value of HU is

lower than the value of H. Each hardness value was determined as a result of 10 indentation tests. The typical thickness of the coatings is approximately 4 mm. This ensures that all coatings fulfil the criterion

dyhF0.1, which guarantees that measurement of the

hardness is not significantly influenced by the substrate,

d max

max

yŽ26.43d

max

cor

.

max

.

2

2

(1)

(2)

cor

where d and h are the depth of the diamond indenter impression into the coating and the thickness of the coating, respectively.

3. Loadingyunloading curves

The evaluation of microhardness, H, effective Young’s modulus E sEy(1yn ) and elastic recovery W from the loadingyunloading curves measured by an instru- mented microhardness tester is a standard methodology used for the characterization of coating materials. A typical loadingyunloading curve is shown in Fig. 1. The area between the loading and unloading curve represents the energy dissipated in the coating due to plastic deformation, and the area under the unloading curve represents the elastic energy for deformation. From measured values of H and E , it is easy to calculate the ratio H yE , which is proportional to the resistance of the coating to plastic deformation w8x. This essentially means that the higher the resistance to plastic deforma- tion, the higher is the ratio H yE . In general therefore,

3

*

*2

2

*

3

*2

e

306

J. Musil et al. / Surface and Coatings Technology 154 (2002) 304–313

Table 1 Mechanical parameters of hard (12.7 GPa) and superhard (46 GPa) Cr–Ni–N films measured at the diamond indenter load Ls20 mN

 

E * w GPa x

W e w % x

HU w GPa x

3

H yE w GPa x

*2

HyE * w mm x

d max

H

w GPa x

12.7

273

35

7.9

0.03

0.05

0.31

46.0

352

71

14.0

0.78

0.13

0.23

Table 2 Mechanical parameters of films with approximately the same hardness H and different values of E measured at the diamond indenter load Ls20 mN

*

 

H w GPa x

E * w GPa x

W e w % x

HU w GPa x

3

H yE w GPa x

*2

HyE *

d max

w mm x

Film

Zr–Y–N

31.6

229

80.3

9.9

0.60

0.137

0.195

Zr–Y–N

32.1

296

73.4

11.9

0.38

0.108

0.178

Cr–Ni–N

39.2

307

74

12.6

0.64

0.128

0.246

Ti–Mo–N

43

442

68

15.9

0.41

0.097

0.218

Al–Cu–N

47

313

84

12.9

1.06

0.15

0.24

Ti–Mo–N

46

413

75

15.5

0.57

0.11

0.22

a low E becomes desirable, as it allows the given load to be distributed over a wider area. This argument

(although valid) is in contradiction to conventional linear-elastic fracture mechanics theory, which predicates

a high modulus (to prevent crack growth) for ‘tough’ materials.

*

3.1. Effect of hardness H

The effect of coating hardness H on the loadingy unloading curves is shown in Fig. 2, with typical loadingyunloading curves measured for soft (12.7 GPa) and superhard (46 GPa) coatings. Fig. 2 compares two Cr–Ni–N nanocomposite films, prepared under different deposition conditions, the mechanical quantities of which are summarized in Table 1. As expected, the area between the loading and unloading curve and the max-

Table 3 Mechanical parameters of films with the same resistance to plastic deformation, i.e. H yE fconstant measured at the diamond indenter load Ls20 mN

3

*2

 

H w GPa x

E * w GPa x

W e w % x

HU w GPa x

3

H yE w GPa x

*2

HyE *

d max

w mm x

Film

Cr–Ni–N

31.8

253

74

10.7

0.50

0.126

0.267

Cr–Ni–N

34.5

287

75

11.8

0.50

0.120

0.254

Ti–Mo–N

44.5

401

77

15.1

0.55

0.110

0.224

imum depth d of the diamond indenter penetration into the film decreases with increasing H of the film.

Moreover, from Table 1 it is evident that the Cr–Ni–N film with a higher hardness (46 GPa) exhibits higher values of E , W , H yE and HU. This is the main difference in the mechanical response of the hard and superhard films to the diamond impression into their surface.

*

max

e

3

*2

3.2. Effect of Young’s modulus E

There is no simple relation between the film hardness H and its effective Young’s modulus E . Experiments show that it is possible to produce films with the same hardness H and different values of E ; see Table 2. This means that films with the same hardness can exhibit different resistance to plastic deformation. The effect of different values of E on the loadingyunloading curves at the same (i) hardness H and (ii) resistance to plastic deformation H yE is shown in Fig. 3a,b. Mechanical quantities characterizing the films that exhibit the same resistance to plastic deformation are summarized in Table 3. From Fig. 3a and Table 2, it is clearly evident that an increase in E results in (a) a decrease in W , H yE and d , and (b) an increase in HU. For films with the same resistance to plastic deformation (Fig. 3b and Table 3) the value W , however, slightly increases with increasing E . This is due to the fact that with increasing

max

*

*

3

*2

*

e

*

*

e

3

*2

to the fact that with increasing max * * 3 *2 * e * * e

Fig. 3. Effect of increasing effective Young’s modulus E

same hardness H of approximately 46 GPa and (b) films with the same resistance to plastic deformation (H yE

* on the maximum depth d

max

of the diamond indenter impression for (a) films with the

3

*2

f0.5 GPa).

J. Musil et al. / Surface and Coatings Technology 154 (2002) 304–313

307

/ Surface and Coatings Technology 154 (2002) 304–313 307 Fig. 4. The dependence of the film

Fig. 4. The dependence of the film hardness H as a function of effec- tive Young’s modulus E for selected hard nanocomposite and binary nitride films magnetron-sputtered under different deposition condi- tions w4,5x.

*

E , the hardness H increases and the ratio HyE decreas- es. This experiment clearly shows that the mechanical behavior of a hard film strongly depends on the com- bination of its hardness H and effective Young’s modu- lus E . Recent experiments show that the relationship between hardness H and effective elastic modulus E in the hard film can be controlled by the choice of (i) its chemical composition (see Fig. 4) and (ii) the deposi- tion parameters used for its formation (see for instance w4,5,9x). Fig. 4 gives experimental evidence that the production of films exhibiting the same hardness H and different values of E is possible. This means that, in principle, it is possible to tailor films with prescribed mechanical properties for a given application.

*

*

*

*

*

mechanical properties for a given application. * * * * * Fig. 5. The loading y

Fig. 5. The loadingyunloading curves of two Ti–Al–V–N films exhib- iting different hardness H and the same elastic recovery W .

e

different hardness H and the same elastic recovery W . e Fig. 6. The loading y

Fig. 6. The loadingyunloading curves of two Ti–Al–V–N films exhib- iting the same hardness H and different values of elastic recovery W , and one Ti–Al–V–N film with low H (11 GPa), low W (41%) and high plastic deformation, i.e. low H yE ratio.

e

3

*2

e

3.3. Effect of elastic recovery W e

3.3.1. Films with different H and the same W e

In general, the effective Young’s modulus E increas- es with increasing hardness H. This is the simplest situation. In this case, the resistance to plastic deforma- tion H yE increases with increasing H because the ratio HyE is approximately constant (Table 4). The same ratio HyE approximately correlates with the same elastic recovery W . On the contrary, as can be expected, the maximum indentation depth d decreases with increasing H. Typical loadingyunloading curves of two Ti–Al–V–N films with different hardness values H and the same elastic recovery W are given in Fig. 5. Table 4 shows that the films with the same elastic recovery W can exhibit a very different resistance to plastic deformation characterized by the ratio H yE . The harder the film, the higher is E and the higher is the resistance to plastic deformation. The most important finding that follows from the experiment described above is the fact that hard nano- composite coatings with very different hardness can even exhibit the same elastic recovery W , provided that the ratio HyE is approximately constant.

*

3

*2

*

*

e

max

e

e

3

*2

*

e

*

Table 4 Mechanical parameters of two Ti–Al–V–N films with the same elas- tic recovery W measured at the diamond indenter load Ls20 mN

e

H

E * w GPa x

W e w % x

HU w GPa x

3

H yE w GPa x

*2

HyE *

d max

w GPa x

 

w mm x

26.0

233

71

9.7

0.32

0.112

0.28

45.6

405

72

15.4

0.58

0.113

0.22

308

J. Musil et al. / Surface and Coatings Technology 154 (2002) 304–313

al. / Surface and Coatings Technology 154 (2002) 304–313 Fig. 7. Micrographs of the diamond indenter

Fig. 7. Micrographs of the diamond indenter impressions into super- hard Al–Cu–N and Zr–Cu–N films sputter-deposited on steel sub- strates under different loads ranging from 200 to 1000 mN.

3.3.2. Films with different W and the same H The loadingyunloading curves of two Ti–Al–V–N films with the same hardness (Hf37 GPa; see Table 5) and different values of W are given in Fig. 6. For comparison, the loadingyunloading curves for a soft film with Hs11 GPa is also given in Fig. 6. This experiment shows that the film with lower E (250 GPa) exhibits (i) smaller area between the loading and unloading curves and (ii) greater d and higher ratio H yE and (iii) lower values of HU compared with the films with higher E (399 GPa), see Table 5. From this experiment two important conclusions can be drawn:

3

*2

*

e

e

max

*

1. Hard films with the same (plastic) indentation hard- ness Hf37 GPa can exhibit very different values of universal hardness HU. The value of HU is greater for the film with the greater value of E . This is due to the difference in the method of H and HU evaluation. The hardness H is evaluated from the

*

and HU evaluation. The hardness H is evaluated from the * Fig. 8. Microhardness H of

Fig. 8. Microhardness H of 2.4-mm-thick Ti–Al–N, 4-mm-thick Ti– B and 6-mm-thick Zr–Cu–N films magnetron-sputtered on 15330 CSN steel substrate as a function of the diamond indenter load L.

plastic deformation only). On the contrary, in evalu- ation of the HU, both plastic and elastic deformations are considered. This means that the accuracy of H determination will decrease with increasing W , and more reliable hardness values of films with high elastic recovery W )70% will be given by the universal hardness HU values and not by H. 2. The hard film (Hf37 GPa) with high elastic recov- ery (W f80%) (i) allows deeper penetration of the diamond indenter tip compared with the film that exhibits a lower W (63%) and (ii) therefore exhibits a higher resistance to plastic deformation (Table 5). This experiment shows the possibility of creating new, very elastic, hard materials. On the other hand, deeper penetration of the diamond indenter into the hard elastic film can complicate the evaluation of its

toughness from cracks formed under higher indenter

e

e

e

e

loads L.

In addition, there may be an elastic contribution from

the substrate to the HU values measured (even at dy hF0.1), which might not influence H, but could influ-

ence the HU value measured. It could be envisaged in

some circumstances that H would be too high (due to elastic recovery of the coating) and HU too low (due to elastic contribution from the lower modulus sub-

Table 5 Mechanical parameters of three Ti–Al–V–N films, the load- ingyunloading curves of which are displayed in Fig. 6, measured at the diamond indenter load Ls20 mN

Film

H w GPa x

E * w GPa x

W e w % x

HU w GPa x

3

H yE w GPa x

*2

HyE * d max w mm x

Ti–Al–V–N

11

238

41

6.8

0.023

0.046

0.342

Ti–Al–V–N

38

250

81

10.7

0.878

0.152

0.266

Ti–Al–V–N

36

399

63

14.5

0.296

0.090

0.229

J. Musil et al. / Surface and Coatings Technology 154 (2002) 304–313

309

/ Surface and Coatings Technology 154 (2002) 304–313 309 Fig. 9. Dependence of the hardness H

Fig. 9. Dependence of the hardness H and the ratio dyh of the indenter impression depth d and the film thickness h for 4-mm-thick Ti–B film magnetron-sputtered from TiB target at: magnetron current I s1 A; substrate bias U sy50 V; substrate ion current density i s 1 mAycm ; substrate temperature T s550 8C; and argon pressure p s p s0.6 Pa.

T

2

s

2

s

d

s

Ar

strate). Thus, the ‘true’ hardness value would lie some- where between H and HU.

4. Micrographs of diamond indenter impressions

It is claimed that the fracture toughness of films can be determined from the measured dependence of the length of ‘radial cracks’ on the applied diamond indenter load L w10x. We therefore created a series of diamond

indenter impressions in the surface of the films tested under different values of L. Superhard films with high ()60%) elastic recovery W exhibit quite unique, and at first sight, unexpected behavior. Fig. 7 displays diamond indenter impressions into 3-mm-thick superhard Al–Cu–N and Zr–Cu–N films created under different loads ranging from 200 to 1000 mN. The mechanical parameters of these films measured at Ls20 mN are summarized in Table 6. From Fig. 7, it is evident that (i) the high loads L)400 and )600 mN for the Al–Cu–N and Zr–Cu–N film,

respectively, are necessary to generate cracks in the film and (ii) no radial, but only circular cracks are created (a similar deformation mechanism is reported in w10x).

A lower value of L, which is sufficient to generate a

circular crack in the Al–Cu–N film, can easily be explained by greater penetration of the diamond indenter tip into the film surface (see Table 6). The maximum penetration depth d decreases with increasing HU or

H (Figs. 3 and 6 and Tables 3 and 5). Therefore, lower

into the Zr–Cu–N film results in higher L, com-

d max

pared to the Al–Cu–N film, necessary to generate a circular crack. This experiment clearly indicates that generation of the crack in the film is not sufficient to evaluate the film toughness. The formation of cracks depends not only on the diamond indenter load L, but also on (i) the mechanical behavior of the film (HU, E , H yE ), (ii) the stress andyor adhesion state of the coatingy

e

max

*

3

*2

stress and y or adhesion state of the coating y e max * 3 *2 Fig.

Fig. 10. The dependence Hs f (L) for 7-mm-thick Ti–B film and HUs f (H) for two 4-mm- and 7-mm-thick Ti–B films, measured under different

2

values of L , magnetron-sputtered at: I s1 A; U sy50 V; i s1 mAy cm ; T s550 8C; and p

d

s

s

s

Ar

s0.6 Pa, from a TiB target.

2

Table 6 Mechanical parameters of superhard Al–Cu–N and Zr–Cu–N nanocomposite films magnetron sputtered on steel substrates and measured at the diamond indenter load Ls20 mN

 

H w GPa x

HU w GPa x

E * w GPa x

W e w % x

3

H yE w GPa x

*2

HyE * w mm x

h w mm x

d max

w mm x

Film

Al–Cu–N

47

12.55

313

84

1.06

0.150

3.3

0.242

Zr–Cu–N

56

15.38

399

81

1.08

0.140

3.0

0.220

310

J. Musil et al. / Surface and Coatings Technology 154 (2002) 304–313

al. / Surface and Coatings Technology 154 (2002) 304–313 Fig. 11. The dependence HU s f

Fig. 11. The dependence HUs f (H) and HUs f (W ) for Ti–B and Al–Si–Cu–N films magnetron-sputtered from a TiB Al–Si–Cu wAlSi (90y10 at.%) alloyed target with a Cu fixing ringx target, respectively.

e

2

target and a composite

substrate interface (i.e. the propensity for film delami- nation) and (iii) the mechanical behavior of the substrate. The accurate determination of film toughness, therefore, still remains an open problem.

5. Correctness of measurement of the quantifiable mechanical properties of hard and superhard coatings

The basic mechanical properties of hard and superhard coatings, i.e. the microhardness H, effective Young’s modulus E and elastic recovery W , are evaluated from loadingyunloading curves measured by nanoindentation or instrumented microhardness testing. The determina- tion of these quantities for thin films is, however, difficult because they vary strongly with the diamond indenter load L used in their measurement. To obtain real values of H, E and W , the load L has to be correctly chosen.

*

*

e

e

The correct value of the microhardness H is that value which (1) does not depend on L and (2) is not affected by the substrate. Therefore, too low values of L — at which H strongly varies with increasing L (due to problems with determination of the true contact area between the indentor and surface of its impression) and too high values of L — at which the ratio of the indenter depth d and the film thickness h is greater than a maximum value wusually (dyh) s0.1 is recommended not to be exceeded for ‘plastic’ hardness of hard coatings on, say, tool steel, cemented carbides substrates and

silicon wafersx, cannot be used in determination of the correct value H. This means that there is a certain interval of L in which the measured hardness H(L)fconstant and only the value H within this interval for L is a correct value of the hardness of the film measured.

For films with hardness HF50 GPa, the decrease in H with increasing L from Ls0 is very steep, and the

max

J. Musil et al. / Surface and Coatings Technology 154 (2002) 304–313

311

/ Surface and Coatings Technology 154 (2002) 304–313 311 Fig. 12. H as a function of

Fig. 12. H as a function of E sEy(1yn ) for Ti–Si–N, Zr–Y–N, Zr–Cu–N and Ti–Mo–N nanocomposite films sputtered at different

. H was measured at an

deposition conditions, i.e. T , U , i and p indenter load of 20 mN.

s

*

2

N 2

ss

interval L for which H(L)fconstant is already reached

for relatively small values of L. In this case, a relatively low load of Ls20 mN lies in the interval where H almost does not depend on L and the correct value of the film hardness H is measured. A maximum

L

limited by the ratio dyhs0.1, and this is higher for

increasing thickness of the film; see the Zr–Cu–N film

in Fig. 8. A completely different situation occurs in the case

where superhard films with hardness H)50 GPa are measured; see the dependence H(L) for 4-mm-thick Ti–

B film given in Fig. 8. For a superhard Ti–B film, the

hardness H very slowly decreases with increasing L, and

a much higher (G50 mN) load L has to be used to

reach the interval of L where H(L)fconstant. In this case, the interval L ranges from approximately 50 to 150 mN. The corresponding interval of the ratio dyh also shifts to higher values and ranges from approxi- mately 0.08 to 0.15; see Fig. 9. This means that correct measurement of the mechanical behavior of hard films with high hardness above 60 GPa, which always exhibit high elastic recovery W G70%, has to be carried out at higher ratios of dyh (up to approx. 0.15) compared to those allowed in the measurement of hard films with H-50 GPa, i.e. when a maximum value of the ratio (dyh) s0.1 should not be overcome. This finding is of fundamental importance. The hardness of superhard ()60 GPa) films H measured at L-50 mN is higher than the correct value of the hardness H of the film measured, i.e. H )H .

value that gives the correct value of H is

correct

max

correct

e

max

meas.

correct

meas.

correct

5.1. Universal hardness

The hardness H of the film is determined from a plastic component of the film deformation induced by

from a plastic component of the film deformation induced by Fig. 13. W as a function

Fig. 13. W as a function of (a) H, (b) E sEy(1yn ) and (c) H yE for Ti–Si–N, Zr–Y–N, Zr–Cu–N and Ti–Mo–N nanocom- posite films sputtered at different deposition conditions, i.e. T , U , i and p . W was measured at an indenter load of 20 mN.

s

3

*2

e

Ne

2

s

s

*

2

the diamond indenter during its penetration into the surface of the film according to Eq. (1). Therefore, this is also known as ‘plastic’ hardness. The accuracy of the hardness measurement, however, decreases for high hardness values H)60 GPa, because the elastic recovery W of the film achieves very high values of up to 70– 90% and the plastic deformation of the film strongly decreases (the area between the loading and unloading curves is very small and represents only 30–10% of the total deformation energy). Therefore, some investigators suggest use of the universal hardness HU for the characterization of superhard films. The correctness of this suggestion also confirms the experiment displayed in Fig. 6. Here, films with almost the same hardness H

e

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J. Musil et al. / Surface and Coatings Technology 154 (2002) 304–313

al. / Surface and Coatings Technology 154 (2002) 304–313 Fig. 14. H y E as a

Fig. 14. H yE as a function of H for Ti–Si–N, Zr–Y–N, Zr–Cu–

N and Ti–Mo–N nanocomposite films sputtered at different deposi-

tion conditions, i.e. T , U , i and indenter load of 20 mN.

p

were measured at an

3

*2

N 2

. H and E

*

s

ss

exhibit different values of the universal hardness, with HU being greater for the film with lower penetration of the diamond indenter into its surface. The universal hardness HU, however, also exhibits specific features, and therefore this quantity has to be used correctly. The main features of HU are the following.

1. The universal hardness HU first increases with increasing H, but above some critical value of hard- ness H , HU practically does not change with increas- ing H)H (Fig. 10). This is a direct consequence of the correction procedure used in the evaluation of the HU at low values of L. 2. The universal hardness HU depends not only on hardness H, but also on elastic recovery W of the film (Fig. 11). HU first increases with increasing W , but starting at approximately W f75%, HU saturates at a value of approximately (i) 20 GPa for the superhard Ti–B film and (ii) 11.5 GPa for the hard Al–Si–Cu–N film. This experiment clearly shows that:

HU cannot be used to characterize hard films exhibiting a high elastic recovery W G80%;

High values of W G80% are exhibited not only in superhard ()40 GPa) films, but also in some hard (-40 GPa) films; and c. HU of films with high elastic recovery W G80% can have very different values, which are strongly dependent on their hardness H and effective Young’s modulus E .

c

c

e

e

e

a

b

e

e

e

*

This experiment shows that the universal hardness HU cannot be reliably used to characterize superhard films that exhibit high elastic recovery exceeding 70%.

6. Relationships between basic mechanical parame-

ters in hard and superhard coatings

The mechanical behavior of hard and superhard coat- ings is well characterized, not only by their hardness H, but also by their effective Young’s modulus E sEy (1yn ) and elastic recovery W . Moreover, values of H and E measured permit simple calculation of the ratio H yE , which gives information on the resistance of the material to plastic deformation w8x. The higher this

3

2

*

*2

e

*

is, the higher is the ratio H yE . The likelihood of plastic deformation is therefore significantly reduced in materials with high H and low E . In general, low E

is desirable, as it allows the load to be distributed over

3

*2

*

*

*

a wider area. Typical relationships between H, E , W

e

and the ratio H yE for four selected nanocomposite

coatings—Ti–Si–N w11x, Zr–Y–N w12x, Zr–Cu–N w13x

and Ti–Mo–N w9x—are given in Figs. 12–14.

3

*2

7. Conclusions

The main results reported in this paper can be sum- marized as follows.

1. A comparison of two hard nanocomposite films

shows that the maximum depth d of the diamond indenter impression is higher (i) the lower is H, E ,

yE and HU and (ii) the higher is the ratio Hy

* (Tables 1 and 2). This fact does not exclude the

possibility that films with smaller resistance to plastic

deformation (;H yE ) and lower values of W can exhibit lower d and larger area between the loading and unloading curves when the ratio HyE is lower, compared to films with higher values of H yE , i.e. with (generally) low E and thus higher HyE (Fig. 6 and Table 5). This complex relation between the

inherent mechanical properties of hard coatings gives,

E

H 3

max

*

*2

3

*2

e

*2

*

max

*

3

*

however, the possibility of producing films with different mechanical behavior. This possibility is based on the fact that a film with a given hardness

H can exhibit substantially different values of E .

Therefore, very elastic films with high resistance to plastic deformation (high H yE ratio) or hard films with high plastic deformation (low H yE ratio) can be formed (Fig. 6).

2. Hard nanocomposite coatings with very different hardness can exhibit the same elastic recovery W e (Fig. 5).

3. The same value of the ratio HyE correlates well

*

3

*2

3

*2

*

with similar elastic recovery W behavior.

e

4. The correct value of the hardness of superhard ()60 GPa) films has to be measured at higher loads L, ranging from approximately 50 to 150 mN, because only in this interval of L is the hardness H(L)fconstant. This is a consequence of the fact that a gradient of the decrease in H with L (increasing from Ls0) decreases with increasing elastic recovery

J. Musil et al. / Surface and Coatings Technology 154 (2002) 304–313

313

of superhard films, and the region H(L)fconstant

shifts to higher values of L. 5. The possibility of creating films with similar hardness

W

e

*

and different values of E allows the tailoring of films with given mechanical properties. 6. The universal hardness HU cannot be reliably used for characterization of superhard (G60 GPa) films, because HU saturates and does not depend on W for

e

W G80%.

e

Acknowledgments

This work was supported in part by the Ministry of Education of the Czech Republic under Project Nos MSM 235200002, ME 173y2001 and ME 203y2001. Constructive comments from the referees of this article, with regard to presentation of the results, are acknowl- edged with thanks.

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