Powder Metallurgy and Metal Ceramics, Vol. 47, Nos.

7-8, 2008

EXCHANGE OF EXPERIENCE

INSTRUMENTAL INDENTATION FOR EXAMINING

THE PROPERTIES OF SECONDARY STRUCTURES
OF METALS AND COATINGS

V. F. Gorban’1
UDC 621.762

The structure and properties of the surface layers of metals and coatings in the initial state and after
friction contact are examined. Substantial increase in the hardness of surface layers after friction is
mainly associated with the formation of nanostructure due to shear strains. Deformation does not
noticeably change the properties of surface layers when the nanostructure has been formed in the
initial material. The relationship is established between the wear resistance and the following
properties of the initial coatings and secondary structures: plasticity, stress relaxation coefficient,
and their structural component.
Keywords: coating, deformation, secondary structures, hardness, plasticity characteristic, stress
relaxation coefficient, wear resistance.

Currently, coatings are widely used to increase the life of various products, including friction pairs. Modern
technologies allow changing the structure, phase composition, and properties of coatings so as to endow them with
the necessary combinations of physical and mechanical properties.
In friction, as well as in other processes of deformation, the structure of the surface layer changes, which is
accompanied by structural adaptation. Some of the structures forming in friction exist virtually indefinitely in a
metastable state even after cessation of friction, others gradually, with different periods, relax into the equilibrium
state, and still others disappear almost immediately after the termination of friction. Among the other features of
frictional interaction is the locality of deformation during friction, which entails nonuniform surface hardening.
The changes occurring in frictional contact of metal–metal pairs are studied in many publications [1–3],
which discovered the formation of secondary structures, including oxygen-doped ones [4]. It should be noted that
the secondary structures are a sophisticated object of research. Their properties are mainly determined by analyzing
the chemical and phase compositions. The mechanical characteristics are difficult to determine because of small
thickness (2–4 μm).
The objective of the present paper is to examine the influence of frictional contact in coating–iron and
metal–iron pairs on the physical and chemical changes in the surface layer, to assess the level of these changes, and
to ascertain their effect on service properties.

1Institute
for Problems of Materials Science, National Academy of Sciences of Ukraine, Kiev, Ukraine;
e-mail: gvf@ipms.kiev.ua.
Translated from Poroshkovaya Metallurgiya, Vol. 47, No. 7–8 (462), pp. 146–155, 2008. Original article
submitted December 27, 2007.

1068-1302/08/0708-0493 ©2008 Springer Science+Business Media, Inc. 493

 MATERIAL AND EXPERIMENTAL PROCEDURE
The objects of study are chromium monocrystal, 65G steel, VТ-1-0 titanium, Ti3SiC2 laminate, and
chromium-based coatings produced using different techniques.
To examine the properties of secondary structures, we used the method of indentation under low loads with
plotting indentation diagrams, holding under a constant load, and unloading. The Oliver–Pharr technique [5] allows
determining the hardness and elastic modulus at the indentation point. Moreover, indentation diagrams can be used
to determine material characteristics such as the plasticity and stress-relaxation coefficients [6].
Indentation was carried out at room temperature using a Berkovich diamond pyramid. The rate of dynamic
loading was 0.01 to 0.3 N/sec. After the continuously increased load had reached its maximum level, it was held for
50 sec to examine the effect of holding under a constant load. The errors of determining the load R and indentation
depth h were 10–3 N and ± 5 nm, respectively.
Figure 1 shows an indentation program, where hmax = hs + hc is the indentation depth after loading to
P = Pmax and subsequent holding at that level until the stop of the indenter (cessation of creep). It includes the
elastic strain εel, the plastic strain εres, and the elastic deflection εel.def near the indenter. Here hs is the design
indentation depth (determined by the Oliver–Pharr technique) that represents the elastic deflection of the material
around the indenter under the maximum load; hc is the design indentation depth (determined by the Oliver–Pharr
technique) at which the indenter and the material are in contact until the maximum level of loading (Pmax) is
reached (at this depth, the indentation obeys the law of conservation of similarity under any load). The indentation
depth hres is the one remaining after complete unloading (R = 0). It includes the plastic strain (εpl), the failure strain
near the indenter (εf), and the remaining elastic strain (εel′). Thus, the residual strain εres = εel′ + εpl + εf.
In addition to the determination of Oliver–Pharr hardness, we can calculate the work (Adisp.mat) done by the
indenter to displace a volume of material (which is found from the indentation diagram bounded by the lines
OABhc) to determine hardness considering that it is equal to the work done to displace a volume of material. In our
case:
H = Adisp.mat/h 3c = (Atot – As)/h 3c . (1)
Calculating the work, we can find the contribution of the plastic strain to the total work done to move the
indenter:
Kpl = Atot – Ael/Atot, (2)
where Atot is the total area under the indentation curve; Ael is the area under the indentation curve bounded by the
lines hresBhtot.

450 Holding
А В 6.0

5.0
Hardness, GPa

4
ng
di
Load, g

a 4.0
Lo g 3
in
oad 3.0
l 2
Un
2.0 1
hs
О
0 hocт hc hmax 4
10 20 30 40 50 60 70 80 90
Indentation depth Load, g
Fig. 1 Fig. 2
Fig. 1. Indentation diagram
Fig. 2. Hardness of surface layers (regardless of elastic deformation) of titanium alloy versus indenter
load: 1) initial state; 2) 90% rolling; 3) friction; 4) ECAP

494
 The indentation depth at the maximum load and after stress relaxation is used to determine the relaxation
coefficient Krel, which represents the susceptibility of a material to creep:
Krel = Arel. stress/Atot = (hmax – hA) ⋅ P/Atot, (3)
where hA is the indentation depth at the maximum load.
The friction area was examined with scanning electron microscopy, Auger spectroscopy, X-ray phase and
X-ray diffraction analyses.
The properties of the secondary structures were determined after 1000 and 3000 m of end friction of the
material against high-strength cast iron at a velocity of 3 m/sec and under pressure of 1 MPa. The wear resistance of
the coatings was examined in the presence of boundary lubrication at a velocity of 14 m/sec, pressure of 3 MPa,
temperature of 473 K, and test duration of 40 h.

DISCUSSION OF RESULTS
An analysis of the properties of the starting materials (Table 1) reveals a minor difference between the
values of hardness determined from the indentation depth Hhc and the work done to displace a volume HA. This
suggests that the properties of the materials are uniform throughout the depth. The difference between the elastic
moduli of the starting chromium and the thermal-spray chromium coating is due to the coating porosity, which is 10
to 15%.
A specific feature of frictional contact is the nonuniform deformation processes in the surface layer. The
reason is that contact occurs locally, where there are projections on the surface, which results in areas with different
hardness, from initial to maximum possible for this friction pair. For example, the hardness of chromium with initial
hardness of 1.5 GPa reaches 7–8 GPa in separate areas even after 1000 m of frictional contact (Table 2).
The hardness in the surface layer of chromium deformed by 90% and more does not exceed 3–4 GPa if it is
highly saturated with interstitial impurities. At the same time, studies of the frictional deformation of a chromium
monocrystal [7] show that there are sites with much higher strains where hardness reaches 7 GPa at an average surface

TABLE 1. Initial Characteristics of the Surface Layer

Material HA, GPa Hh, GPa E, GPa Kpl Krel, %

Chromium 1.52 1.55 270 0.960 21–24

Flame-spray chromium coating 5.4 5.46 210 0.850 8.8–9.8
Titanium VT-1-0 1.57 1.53 95 0.905 13–15
Steel 65G 3.15 3.2 220 0.860 3.1–3.4
High-strength cast iron 3.16 3.24 210 0.880 3.3–3.5
Ti3SiC2 9.2 9.25 260 0.830 7.5–8.5
CrN + TiN (24 layers) 28.9 27.1 460 0.678 2.6–3.1

TABLE 2. Characteristics of the Surface Layer after Friction

Material HA, GPa Hh, GPa E, GPa Kpl Krel, %

Chromium 8.8 8.0 259 0.880 8.0–11.3

Flame-spray chromium coating 14.3 13.5 270 0.720 6.2–8.2
Titanium VT-1-0 5.7 5.1 103 0.712 4.7–5.5
Steel 65G 13.1 12.5 224 0.650 2.4–3.0
High-strength cast iron 8.6 8.2 200 0.770 2.1–2.5
Ti3SiC2 17.4 15.2 240 0.650 6.1–6.6
CrN + TiN (24 layers) 45.3 44.0 460 0.467 2.4–3.0

495
 45.0

40.0 After friction

20.0
Hardness, GPa

35.0 Before friction

Hardness, GPa
16.0
30.0
Before friction
25.0 12.0 1.97 mm

20.0 8.0
After friction 1.98 mm
15.0
4.0
50 100 150 200 250 5 15 25 35 45 55 65 75 85
Load, g Load, g
Fig. 3 Fig. 4
Fig. 3. Hardness (no elastic edging) versus applied load for a 24-layer (CrN + TiN)-based coating
Fig. 4. Surface hardness of a flame-sprayed chromium coating (elastic deformation neglected) versus
applied load before and after friction (indentation depth under finite load is indicated)

strain of 36%. This difference in hardness between frictional and deformation structures may be attributed to the
fact that shear strains cause the frictional surface layer to undergo substantial restructurization in a short time.
After several passes in equal-channel angular pressing (ECAP), nanostructures form in plastic materials
under shear strains [8]. Comparing the hardness of titanium alloy deformed by ECAP, friction, and rolling shows
that its levels after ECAP and friction are close to each other and much higher than the hardness of the 90% rolled
alloy (Fig. 2). It should be noted that the structure after ECAP is much more uniform throughout the depth than that
after friction. In the latter case, structural changes localize in a thin surface layer, which is the reason why the
hardness decreases more dramatically with the movement of the indenter (Fig. 2, curve 3).
The hardness of the surface layers abruptly increased after friction in the majority of the materials tested.
For example, hardness increased from 3.2 to 12.5 GPa in the 65G steel and from 9.2 to 15.2 GPa in the Ti3SiC2
nanolaminate. This substantial increase of hardness in local areas of secondary frictional structures is due to
structural changes.
The surface hardness of CrN+TiN laminate did not change considerably and stayed between 35 and 40 GPa
(Fig. 3). The reason is that this material has a nanostructure even in the initial state and the subsequent deformation
cannot considerably affect the decrease in the size of structural components.
A similar change in the hardness of secondary structures is observed in partially amorphized coatings. For
example, the surface hardness of Fe80B20 detonation-spray coatings with the amorphous phase content ranging from
66 to 83% did not change in abrasion tests. Their hardness before the tests was 6 to 8 GPa and the elastic modulus
70 to 90 GPa, which is due to heterogeneous structure [9].
It should be noted that the values of hardness of the secondary structures determined from the work and
depth differ substantially. This suggests that the material properties are nonuniform throughout the depth.
Determining hardness from the indentation depth, we a priori assume uniform material properties, whereas the
work represents the material properties at each point of the indentation diagram. The hardness on the surface of
secondary structures is much higher than at the maximum indentation depth, which is due to the effect of the
substrate material. This is clearly demonstrated by the curve of hardness versus applied load (Fig. 4).
The difference in hardness between the surface layer and matrix affects the integral hardness, which is
clearly demonstrated with an example of a 24-layer CrN + TiN coating (Table 3). Its thickness is 2.4 μm.
At an indentation depth of 0.3 μm, the values of hardness do not differ and the elastic modulus and
plasticity coefficient are at a level typical of nitrides. As the load is increased, the indentation becomes deeper, the

496
 TABLE 3. Properties of a 24-Layer (CrN + TiN)-Based Coating Depending on the Indentation Depth

Indentation depth, µm HA, GPa Hh, GPa E, GPa Kpl

0.3 45.3 44.0 460 0.540

1.3 33.9 26.1 295 0.625
2.8 21.9 17.3 260 0.678

elastic modulus abruptly decreases close to the level of the substrate material because of the effect of the substrate,
the plasticity coefficient increases, and the difference between the values of hardness determined from the work and
depth become more and more noticeable.
Such a dependence of hardness on the indentation depth is typical of the secondary structures in all the
materials tested. For example, Fig. 4 shows how the hardness depends on the applied load for a thermal-sprayed
chromium coating. The hardness of the friction surface (calculated regardless of elastic deformation) reaches
22 GPa, which is due to the nanostructure in the surface layer. Fragmented structures, 20 to 50 μm in size, on the
friction surface of thermal-spray chromium coatings were observed in [10], though the starting coating had cellular
structure 1 to 5 µm is size. The hardness of nanoscale chromium coatings produced by vacuum deposition was
pointed out in [11, 12] to be 20–28 GPa.
An X-ray phase analysis of chromium coatings before and after friction revealed that there were phase
transformations during frictional contact. Nonstoichiometric chromium oxides CrO and Cr3O4 transformed into
Cr2O3 during friction, the amount of free oxygen in the chromium matrix increased. The oxygen content in the
secondary structures increases from 12–15 to 24–30%. Similar processes were observed in secondary frictional
structures in iron-based materials [4].
As secondary frictional structures are hardened, the contribution of plastic deformation to the total work of
indentation and the level of stress relaxation decrease.
To ascertain the effect of grain size, strength, plasticity, and stress relaxation on wear resistance, we
conducted comparative tests of chromium coatings produced by various technologies. The reason why chromium
coatings have been chosen for tests is that they are widely used in world’s engine technology. However, the major
drawback of the chromium electrodeposition technology is hexavalent chromium contamination of the environment.
A quest for alternative environmentally safe coatings is currently well underway.
Thermal-spray chromium coatings are advantageous over electrodeposited ones in the possibility to control
porosity and, hence, to highly increase the oil absorption power of piston rings (from 0.004 ⋅ 106 for
electrodeposited coatings to 0.12 ⋅ 106 for thermal-spray coatings) and in stability of structure and mechanical
properties up to 1100°C (electrodeposited chromium coatings begin to abruptly lose hardness at 900°C). The
contact temperatures in uprated engines are known to reach 1000°C, which explains the dramatically reduced life of
piston rings with electrodeposited chromium coating.
Electrodeposited chromium coatings are very hard (8–10 GPa) and consist of grains 20–40 μm in size
(Table 4). Thermal spraying fails to produce chromium coatings with a combination of properties typical of
electrodeposited coatings.
To obtain lamellas with dimensions comparable to those in electrodeposited coatings, a chromium wire
4 mm in diameter was thermal-spray coated. The hardness of the resulting coating did not exceed 5.5 GPa. To
increase the hardness of thermal-spray chromium coatings, we applied the detonation- and supersonic-spray
technologies with 20–40 μm chromium powders. The hardness of such coatings is comparable to the hardness of
electrodeposited coatings. However, the size of the structural components of these coatings did not exceed 10 μm.
Wear studies of chromium coatings produced by different technologies show that coatings with small
structural components and low stress relaxation wear quicker. The main characteristic of wear resistance of friction
pairs is total wear. According to this characteristic, thermal-spray chromium coatings with greatest plasticity and
stress relaxation exhibit the maximum wear resistance.

497
 TABLE 4. Wear-Resistance and Surface Characteristics of Chromium Coatings before and after Friction
Depending on Coating Technology

Wear, µm
Technology Hrec, GPa Kpl Krel, % Lamella size
Cast iron Coating

Thermal 5.4/11.8* 0.850/0.730 8.8–9.8/6.2–8.2 11 39 10–30

Plasma 6.4/10.8 0.830/0.740 5.0–5.4/3.4–5.0 38 58 5–10
Supersonic 7.45/12.2 0.773/0.731 3.2–3.7/2.9–3.1 32 120 4–8

Detonation 8.0–9.6/12.6 0.755/0.726 3.4–3.9/2.5–2.9 21 140 2–7

Electrodeposition 8.5–9.4/11.5 0.777/0.740 5.2–5.8/3.5–4.0 45 42 30–40

* Before friction/after friction.

Table 4 indicates that the maximum hardness of the secondary structures in chromium coatings differs
insignificantly. Nevertheless, thermal-spray chromium coatings with high plasticity and higher susceptibility to
stress relaxation have high wear resistance. The reason is that the hardness at which cracks can be reached by
increasing the friction distance.
Both the size of the structural component and the susceptibility to stress relaxation contribute to the
enhancement of the wear resistance of electrodeposited chromium coatings, compared with detonation- and plasma-
spray coatings. In hard coatings, the maximum level of hardening is reached quickly, while a low level of stress
relaxation causes the thermal energy generated in frictional contact to relax as cracks, which mainly occur at the
boundaries of structural components. The smaller the lamellas, the less the cohesive strength in the coating because
of the oxide films formed during spraying and the more intensive the wear, which is typical of detonation- and
supersonic-spray coatings.
CONCLUSIONS
The high hardness of the secondary structures of metals and coatings is mainly associated with the
formation of a nanostructure in areas of frictional contact under the action of shear strains. If a starting material has
a nanostructure, deformation processes during friction do not noticeably change the properties of surface layers. The
relaxation coefficient and the size of structure have an influence on wear resistance under boundary friction
conditions. The method of indentation with plotting of indentation diagrams allows us to reveal how the properties
change throughout the depth of secondary structures.

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