Nanoniechanical Properties of TiN/TiC Multilayer Coatings
The structure, the composition and mechanical properties of TiN/TiC multilayer coatings are investigated. All coatings were deposited on H13 hot work tool steel by the pulsed-DC plasma assisted chemical vapor deposition (PACVD). Nanoindentation and nanoscratch tests were carried out by the atomic fo...
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Інститут проблем міцності ім. Г.С. Писаренко НАН України
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irk-123456789-1126962020-11-24T18:21:55Z Nanoniechanical Properties of TiN/TiC Multilayer Coatings Azadi, M. Sabour Rouhaghdam, A. Научно-технический раздел The structure, the composition and mechanical properties of TiN/TiC multilayer coatings are investigated. All coatings were deposited on H13 hot work tool steel by the pulsed-DC plasma assisted chemical vapor deposition (PACVD). Nanoindentation and nanoscratch tests were carried out by the atomic force microscopy (AFM). The objective is to determine mechanical properties such as hardness, elastic modulus, surface roughness and friction coefficient. The grazing incidence X-ray diffraction (GIXRD) and the field emission scanning electron microscopy (FE-SEM) were also used to study the crystalline structure of coatings. Increasing the number of layers in coatings increased the elastic modulus and the hardness. Overall superior mechanical properties such as high hardness, the elastic modulus and the scratch resistance rendered to multilayer coatings with 10 layers. This type of coating can be suitable for wear resistance applications. Досліджено структуру, склад і механічні властивості багатошарових покриттів TiN/ TiC. Всі покриття наносились на зразки з інструментальної сталі марки Н13 методом вакуум-плазмового хімічного осадження парів із пульсуючим розрядом постійного струму. За допомогою атомно-силового мікроскопа було проведено випробування на проникнення наноіндентора та наноцарапання. У результаті визначено такі механічні характеристики: твердість, модуль пружності, шорсткість поверхні і коефіцієнт тертя. Для вивчення кристалічної структури покриттів використовувались метод ковзної рентгенівської дифракції і тунельна сканувальна мікроскопія. Показано, що збільшення кількості шарів покриттів приводить до росту модуля пружності і твердості. Установлено, що покриття з десяти шарів мають високі механічні характеристики (твердість, модуль пружності, опір царапанню), тому покриття такого типу рекомендуються для використання у випадку, якщо потребується їх підвищена зносостійкість. Исследованы структура, состав и механические свойства многослойных покрытий TiN/TiC. Все покрытия наносилиcь на образцы из инструментальной стали марки H13 методом вакуум-плазменного химического осаждения паров с пульсирующим разрядом постоянного тока. С помощью атомно-силового микроскопа были выполнены испытания по внедрению наноиндентора и наноцарапанию. В результате определены такие механические характеристики: твердость, модуль упругости, шероховатость поверхности и коэффициент трения. Для изучения кристаллической структуры покрытий использовались метод скользящей рентгеновской дифракции и туннельная сканирующая микроскопия. Показано, что с увеличением количества слоев покрытий повышаются модуль упругости и твердость. Установлено, что десятислойные покрытия имеют высокие механические характеристики (твердость, модуль упругости, сопротивление царапанию), поэтому покрытия такого типа рекомендуются для использования в случаях, если требуется их повышенная износостойкость. 2014 Article Nanoniechanical Properties of TiN/TiC Multilayer Coatings / M. Azadi, A. Sabour Rouhaghdam // Проблемы прочности. — 2014. — № 1. — С. 149-161. — Бібліогр.: 34 назв. — англ. 0556-171X http://dspace.nbuv.gov.ua/handle/123456789/112696 539.4 en Проблемы прочности Інститут проблем міцності ім. Г.С. Писаренко НАН України |
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Научно-технический раздел Научно-технический раздел Azadi, M. Sabour Rouhaghdam, A. Nanoniechanical Properties of TiN/TiC Multilayer Coatings Проблемы прочности |
| description |
The structure, the composition and mechanical properties of TiN/TiC multilayer coatings are investigated. All coatings were deposited on H13 hot work tool steel by the pulsed-DC plasma assisted chemical vapor deposition (PACVD). Nanoindentation and nanoscratch tests were carried out by the atomic force microscopy (AFM). The objective is to determine mechanical properties such as hardness, elastic modulus, surface roughness and friction coefficient. The grazing incidence X-ray diffraction (GIXRD) and the field emission scanning electron microscopy (FE-SEM) were also used to study the crystalline structure of coatings. Increasing the number of layers in coatings increased the elastic modulus and the hardness. Overall superior mechanical properties such as high hardness, the elastic modulus and the scratch resistance rendered to multilayer coatings with 10 layers. This type of coating can be suitable for wear resistance applications. |
| format |
Article |
| author |
Azadi, M. Sabour Rouhaghdam, A. |
| author_facet |
Azadi, M. Sabour Rouhaghdam, A. |
| author_sort |
Azadi, M. |
| title |
Nanoniechanical Properties of TiN/TiC Multilayer Coatings |
| title_short |
Nanoniechanical Properties of TiN/TiC Multilayer Coatings |
| title_full |
Nanoniechanical Properties of TiN/TiC Multilayer Coatings |
| title_fullStr |
Nanoniechanical Properties of TiN/TiC Multilayer Coatings |
| title_full_unstemmed |
Nanoniechanical Properties of TiN/TiC Multilayer Coatings |
| title_sort |
nanoniechanical properties of tin/tic multilayer coatings |
| publisher |
Інститут проблем міцності ім. Г.С. Писаренко НАН України |
| publishDate |
2014 |
| topic_facet |
Научно-технический раздел |
| url |
http://dspace.nbuv.gov.ua/handle/123456789/112696 |
| citation_txt |
Nanoniechanical Properties of TiN/TiC Multilayer Coatings / M. Azadi, A. Sabour Rouhaghdam // Проблемы прочности. — 2014. — № 1. — С. 149-161. — Бібліогр.: 34 назв. — англ. |
| series |
Проблемы прочности |
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AT azadim nanoniechanicalpropertiesoftinticmultilayercoatings AT sabourrouhaghdama nanoniechanicalpropertiesoftinticmultilayercoatings |
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2025-07-08T04:25:19Z |
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2025-07-08T04:25:19Z |
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1837051381505064960 |
| fulltext |
UDC 539.4
Nanomechanical Properties of TiN/TiC Multilayer Coatings
M. Azadi
1
and A. Sabour Rouhaghdam
Tarbiat Modares University, Tehran, Iran
1 mahbub.azadi@gmail.com
ÓÄÊ 539.4
Íàíîìåõàíè÷åñêèå ñâîéñòâà ìíîãîñëîéíûõ ïîêðûòèé TiN/TiC
Ì. Àçàäè, À. Ñàáóð Ðóõàãäàì
Òàðáèàò Ìîäàðåñ óíèâåðñèòåò, Òåãåðàí, Èðàí
Èññëåäîâàíû ñòðóêòóðà, ñîñòàâ è ìåõàíè÷åñêèå ñâîéñòâà ìíîãîñëîéíûõ ïîêðûòèé TiN/TiC.
Âñå ïîêðûòèÿ íàíîñèëècü íà îáðàçöû èç èíñòðóìåíòàëüíîé ñòàëè ìàðêè H13 ìåòîäîì
âàêóóì-ïëàçìåííîãî õèìè÷åñêîãî îñàæäåíèÿ ïàðîâ ñ ïóëüñèðóþùèì ðàçðÿäîì ïîñòîÿííîãî
òîêà. Ñ ïîìîùüþ àòîìíî-ñèëîâîãî ìèêðîñêîïà áûëè âûïîëíåíû èñïûòàíèÿ ïî âíåäðåíèþ
íàíîèíäåíòîðà è íàíîöàðàïàíèþ.  ðåçóëüòàòå îïðåäåëåíû òàêèå ìåõàíè÷åñêèå õàðàêòåðèñ-
òèêè: òâåðäîñòü, ìîäóëü óïðóãîñòè, øåðîõîâàòîñòü ïîâåðõíîñòè è êîýôôèöèåíò òðåíèÿ.
Äëÿ èçó÷åíèÿ êðèñòàëëè÷åñêîé ñòðóêòóðû ïîêðûòèé èñïîëüçîâàëèñü ìåòîä ñêîëüçÿùåé ðåíò-
ãåíîâñêîé äèôðàêöèè è òóííåëüíàÿ ñêàíèðóþùàÿ ìèêðîñêîïèÿ. Ïîêàçàíî, ÷òî ñ óâåëè÷åíèåì
êîëè÷åñòâà ñëîåâ ïîêðûòèé ïîâûøàþòñÿ ìîäóëü óïðóãîñòè è òâåðäîñòü. Óñòàíîâëåíî, ÷òî
äåñÿòèñëîéíûå ïîêðûòèÿ èìåþò âûñîêèå ìåõàíè÷åñêèå õàðàêòåðèñòèêè (òâåðäîñòü, ìîäóëü
óïðóãîñòè, ñîïðîòèâëåíèå öàðàïàíèþ), ïîýòîìó ïîêðûòèÿ òàêîãî òèïà ðåêîìåíäóþòñÿ äëÿ
èñïîëüçîâàíèÿ â ñëó÷àÿõ, åñëè òðåáóåòñÿ èõ ïîâûøåííàÿ èçíîñîñòîéêîñòü.
Êëþ÷åâûå ñëîâà: TiN/TiC ïîêðûòèÿ, âàêóóì-ïëàçìåííîå õèìè÷åñêîå îñàæäåíèå ïàðîâ,
àòîìíî-ñèëîâîé ìèêðîñêîï, íàíîèíäåíòèðîâàíèå, íàíîöàðàïàíèå.
Introduction. Hard coatings such as titanium carbide (TiC) and titanium nitride (TiN)
are widely used in various industries. This is due to their unique properties such as high
hardness and elastic modulus, satisfactory corrosion and wear resistance, good electrical
and thermal conductivities, a well as high melting temperature [1–3]. Since single-layer
coatings due to their specific characteristics exhibit less efficient performance than
multilayer ones, in recent papers various multilayer coatings were investigated, which have
a number of advantages over single-layer coatings. They combine attractive properties of
several materials, as well as exhibit some completely new properties that are not observed
in single-layer coatings. Each layer in a multilayer coating contributes to the surface with
its specific properties. Multilayer coatings have been found to possess better mechanical
properties than single-layer ones: for example, higher hardness, fracture toughness and
strength [4, 5].
Thin coatings can be deposited by different methods, such as physical vapor and
thermal chemical vapor techniques. During implementation of the first method , the coating
adhesion strength decreases due to low temperature, whereas the second method implies a
high temperature, due to which grain growth occurs and quality of coatings’ properties is
deteriorated [6, 7]. On the other hand, the pulsed-DC plasma-assisted chemical vapor
deposition (PACVD) is a proper technique for depositing thin coatings over different
substrates, due to the possibility of achieving the same properties at lower temperatures.
Control of composition and thickness of coatings is performed by adjusting plasma
© M. AZADI, A. SABOUR ROUHAGHDAM, 2014
ISSN 0556-171X. Ïðîáëåìû ïðî÷íîñòè, 2014, ¹ 1 149
parameters. Moreover, rotation of the complex specimen is no more required [6, 8–9]. It is
noteworthy that researchers have been studied TiN/TiC multilayer coatings obtained by
other techniques [7, 10], but only few studies were dedicated to the PACVD technique. In
addition, due to brittleness of TiC layer, most researchers studied TiN/Ti(C,N)/TiC coatings
[7]. Thus, there are only scarce research results on TiN/TiC multilayer coatings. However,
such properties as hardness of TiN/TiC double-layer coatings obtained using the PACVD
were investigated by Kim et al. [6]. Takahashi et al. [11] also prepared the compositionally
graded TiC/TiN films by the liquid injection PACVD and studied the composition and
structure of graded TiC/TiN films deposited over silicon substrates.
The objective of this study was to deposit TiN/TiC multilayer coatings over H13 hot
work tool steel by the PACVD technique and then to evaluate the influence of the number
of layers on nanoindentation characteristics and the scratch resistance of TiN/TiC multilayer
coatings. The crystalline structure of coatings is determined by the grazing incidence X-ray
diffraction (GIXRD) and the field emission scanning electron microscopy (FE-SEM). The
surface morphology, roughness and nanomechanical properties, such as the elastic modulus,
hardness, wear and scratch resistance are determined by the atomic force microscopy
(AFM) with NanoScope and Hysitron TriboScope instruments.
1. Material and Methods. H13 hot work tool steel specimens with the composition
listed in Table 1 were heat-treated, in order to increase their hardness. Specimens were
prepared by grinding up to surface roughness of 2000 and cleaned with alkali solution in
ultrasonic bath at 100�C for 10 min. In order to increase the adhesion of coatings to the
substrate and to increase the load capacity of coatings, a plasma nitriding operation with
parameters listed in Table 2 was performed. In the plasma nitriding process, the flow ratio
of hydrogen to nitrogen was fixed about 3 to prevent the white layer formation [12].
TiN/TiC multilayer and single-layer coatings were deposited in a PACVD reactor,
using a TiCl4–Ar–CH4–H2–N2 gas mixture. The plasma was triggered by a pulsed-DC
power supply. The total pressure in the reaction chamber was 2–6 mbar. Fixed flow rates of
argon, hydrogen and titanium chloride, methane and nitrogen were 500, 1600, 50, 1200,
and 250 sccm, respectively. The duty cycle for all specimens was 33%. A negative bias
voltage was fixed at 600–650 V during the process in the chamber with height and diameter
of 70�50 cm. The substrate temperature was controlled by an auxiliary heating system, in
addition to the intrinsic sputtering effect. Other experimental conditions are listed in Table 3.
The TiN layer was deposited firstly, in order to have a better adhesion to the substrate [7].
The thickness of each (TiN/TiC) layer in multilayer coatings was controlled by adjusting
the feeding time of reactant gases, based on the reference of the deposition rate in TiN/TiC
single-layer coatings. The thickness of layers varied from 0.2 to 2 �m.
M. Azadi and A. Sabour Rouhaghdam
150 ISSN 0556-171X. Ïðîáëåìû ïðî÷íîñòè, 2014, ¹ 1
T a b l e 1
Chemical Composition of the Substrate (wt.%)
C Si Cr Mo V Mn Ni Cu Fe
0.45 0.69 5.72 1.14 2.23 0.27 0.15 0.24 balance
T a b l e 2
Parameters Used in the Plasma Nitriding Process
Temperature
(�C)
Pressure
(mbar)
Duty cycle
(%)
Voltage
(V)
Time
(min)
Hydrogen
(sccm)
Nitrogen
(sccm)
Argon
(sccm)
470 2 33 650 60 1600 500 500
In this paper, the GIXRD with test specifications of �� �2 (the incidence angle) and
the radiation of 1.5418 Å: CuK� was used. For coatings, the cross section was observed by
the FE-SEM.
The surface morphology and roughness of coatings were measured by the AFM.
Nanomechanical properties such as the elastic modulus (E) and hardness (H) were
determined by the nanoindentation (the Hysitron TriboScope instrument). The nano-
mechanical test instrument with the two-dimensional transducer, complete software and the
Berkovich diamond indenter was used after calibrating instruments including the compliance.
The indentation time was 10 s. The sensor of the transducer recorded values for the normal
force and the normal depth. Five indentation tests for each specimen were conducted in this
study. In the AFM part, the NanoScope instrument was also used. Recently, emerging
technologies such as the AFM and the surface force apparatus have opened the possibility
to study friction and wear phenomena in a molecular scale. This allows one to measure
frictional forces between contacting molecules at the nanonewton level [13]. The nano-
scratch test has extended the applicability range of the nanoindentation device. The scratch
was made by moving the indenter laterally with continuous penetration into the specimen.
Every scratch had 4 �m length, and it took 30 s to conduct a scratch test. The friction
coefficient of coatings was measured through the nanoscratch test. The normal load of the
scratch test was ramped from zero to 2000 �N. The normal force, the lateral force, the
normal displacement, and the lateral displacement during the scratch test were recorded
with respect to the time. Three scratch tests for each specimen were also conducted in this
study.
2. Results and Discussion.
2.1. X-Ray Diffraction. Phases of deposited films were identified by the GIXRD.
Figure 1 demonstrates the GIXRD pattern obtained from TiN/TiC multilayer and single-
layer coatings. These diffraction patterns show the orientation in the direction of crystalline
planes including (1 1 1), (2 0 0), (2 2 0), (3 1 1), and (2 2 2) planes. The literature reported
that these peaks corresponded to TiN and TiC layers [14]. In multilayer coatings, the peak
width and the intensity were more than the peak for TiC or TiN single-layer coatings. Due
to the near position of the peak characteristic of the TiC phase or the TiN phase, the peak
separation for each layer was not observed in multilayer coatings. This result (overlaying of
peaks for each layer in multilayer coatings) was consistent with the result of other
researches [15, 16]. The study of the crystal structure of deposited layer coatings showed a
texture in the (2 0 0) orientation for all specimens. Therefore, the (2 0 0) plane which had
the lowest surface energy was the preferred structure, although the (1 1 1) texture was the
common structure of these 4 coatings [17]. In multilayer coatings, depositing of the first
layer (the TiN layer) had no effect on the preferred orientation of the grain growth in the
second layer (the TiC layer). However, increasing the number of layers (from 2 to 10)
caused the increasing tendency in the (1 1 1) texture.
2.2. Microstructure of Coatings. The cross section of single-layer and multilayer
coatings was observed by the FE-SEM, as shown in Fig. 2. The total thickness of TiN/TiC
multilayer coatings was 2–3 �m, approximately. Investigation of the morphology of all
coatings demonstrated a fine-grained structure, whereas coatings which were deposited by
the physical vapor deposition [18] had a columnar structure. Layers are closely integrated,
Nanomechanical Properties of TiN/TiC Multilayer Coatings
ISSN 0556-171X. Ïðîáëåìû ïðî÷íîñòè, 2014, ¹ 1 151
T a b l e 3
Parameters Used in the Coating Deposition Process
Time
(min)
Temperature
(�C)
Titanium chloride
(sccm)
Methane
(sccm)
Nitrogen
(sccm)
80 450–470 50 80 250
152 ISSN 0556-171X. Ïðîáëåìû ïðî÷íîñòè, 2014, ¹ 1
M. Azadi and A. Sabour Rouhaghdam
a c
b d
Fig. 1. GIXRD test results for specimens including TiN (a), TiC (b), and multilayer coatings with 2 (c)
and 10 (d) layers.
a b
c d
Fig. 2. Cross section FE-SEM images for specimens including TiN (a), TiC (b), and multilayer
coatings with 2 (c) and 6 (d) layers.
and the interface between the film and the substrate is flat without pores and defects. This
indicates good interfacial bonding properties. By increasing the number of layers, the
coating possessed smaller grain structure and the structure became increasingly densed, as
reported by Liu et al. [19]. Thus, few spaces and defects have appeared in the coatings. The
existence of the multilayer interface structure can reduce the internal stress of the film. As
is shown in Fig. 2b, images demonstrate that if the substrate surface is not completely flat,
coatings are deposited even in down hills of the surface, and a uniform coating is formed.
This is due to the high power throwing property, which is intrinsic only to the PACVD
process. The interface between TiN layers and TiC layers in multilayer coatings is not quite
sharp (Fig. 2c and 2d).
2.3. Surface Morphology. The AFM was carried out to quantitatively study the
surface morphology of specimens in relation with an increase of the number of layers in
TiN/TiC multilayer coatings. Figure 3 shows AFM images for coatings that were analyzed
in 2�2 �m. Lighter areas of AFM images represent those regions with a higher height.
Figure 3 demonstrates that asperities were distributed over a broader range of heights on
multilayer coatings, compared to single-layer coatings. This is also confirmed by the
roughness and values of the root mean square roughness profile of the surface height
( ).Rrms The grain height in TiN single-layer coating attains the smallest value and is about
65 nm. Some sub-grains in TiN single-layer coating were also observed. As the number of
layers in TiN/TiC multilayer coatings was changed from 2 to 10, the grains’ height
increased from 81 nm to 89 nm. Thus, about the 25–36% enhancement is observed for
multilayer coatings, in comparison to the grain height of TiN single-layer coatings. The
morphology of grains in TiN single-layer coatings is similar to pyramidal or granular
structures, while the grains’ shape in other coatings is spherical.
Figure 4 shows the relation between roughness and grain height versus the number of
layers, where Ra is defined as the mean value of the surface height relative to the center
plane, while Rrms is the root mean square roughness profile of the surface height within
the scanned area [8]. The results obtained indicate that Ra and Rrms are affected by the
structure and the material. TiC single-layer coatings exhibit lower surface roughness than
other coatings. Increase in the number of layers from 2 to 10 in TiN/TiC multilayer coatings
results in the increase of the surface roughness. Variation of the surface roughness with the
number of layers exhibits a trend similar to the grain height variation, as is shown in Fig. 4.
When the number of layers in TiN/TiC multilayer coatings was increased from 2 to 10, the
surface roughness (Ra ) also increased from 20 to 26 nm. This corresponds to about 11–
44% increase, as compared to the surface roughness of TiC single-layer coatings. It is
noteworthy that the surface roughness of coatings is directly related to the surface preparation
of the substrate. If the level of the preparation is higher, the coating surface roughness is
decreased. In other words, in case of a single-layer coating, when the layer is directly
deposited onto the mirror surface of the substrate, the surface roughness attains the minimum
value. Therefore, multilayer coatings with 10 layers have the maximum surface roughness
among other coatings. As established by Morant et al. [20], there is a relation between
increasing the surface roughness and increasing the number of layers in multilayer coatings.
2.4. Nanoindentation. Nanoindentation experiments were performed to study
mechanical characteristics as a function of the multilayer wavelength. The dependences
between nanohardness, elastic modulus and the number of layers in multilayer coatings are
shown in Fig. 5.
The thickness of coatings exceeds the total indentation depth by more than ten times.
Hence, hardness and elastic modulus were calculated only for coatings (with no consideration
of the substrate effect). For better comparison, hardness values of TiN and TiC single-layer
coatings were also reported. Mechanical properties such as hardness (H) and the elastic
modulus (E) were calculated by fitting the unloading part of the P h� curve via the
Oliver–Pharr method [21–23].
ISSN 0556-171X. Ïðîáëåìû ïðî÷íîñòè, 2014, ¹ 1 153
Nanomechanical Properties of TiN/TiC Multilayer Coatings
Via this method, the contact hardness (Hc ) can be obtained from Eq. (1):
H
P
A
P
h
c
c
� �
max max
max
,
� 2 (1)
where � is a non-dimensional geometrical constant, � � � tan ,2 c in which is the
inner angle of the effective cone, approximating the pyramidal indenter tip geometry. The
value of 24.5 for � is associated with the ideal Vickers or Berkovich pyramidal indenter,
with of 70.38 [8]. Thus, the hardness is related to the maximum displacement ( )maxh in
154 ISSN 0556-171X. Ïðîáëåìû ïðî÷íîñòè, 2014, ¹ 1
M. Azadi and A. Sabour Rouhaghdam
a b
c d
e
Fig. 3. The three-dimensional AFM image of the surface topography including TiN (a), TiC (b),
multilayer coatings with 2 (c), 6 (d), and 10 (e) layers.
the load–displacement curve. As TiN single-layer coatings have the maximum displacement
(Fig. 6), they exhibit lower hardness than other coatings.
ISSN 0556-171X. Ïðîáëåìû ïðî÷íîñòè, 2014, ¹ 1 155
Nanomechanical Properties of TiN/TiC Multilayer Coatings
Fig. 4. Relation between roughness (Ra and Rrms), grain height, and the number of layers.
Fig. 5. Relation between nanohardness, elastic modulus, and the number of layers.
Fig. 6. The loading–unloading curve of specimens including TiC, TiN, and multilayer coatings with
10 layers.
All hardness values of multilayer coatings are about 24.6–26.7 GPa, while hardness of
TiN and TiC single-layer coatings are about 19.4–24.4 GPa, respectively. The first value
(19.4 GPa) was also established by Kim et al. [24]. Moreover, hardness of all multilayer
coatings exceeds that of TiC and TiN single-layer ones. As the number of layers is
increased, an enhancement can be observed. The hardness of multilayer coatings has
reached its maximum value of 26.7 GPa in case of 10 layers. While hardness is related to
composition and structure of single-layer coatings, high hardness values can be also
atrributed to the role of interfaces as effective obstacles for the lattice dislocation slip and
the dominant deformation mechanism in multilayer coatings [5, 17]. The maximum
hardness by interface strengthening can be described by the following simple equation.
Consider a multilayer structure containing two layers, one of which (layer A) has a low
shear modulus, while the other (layer B) has a high shear modulus. Therefore,
H H
G G
m
A
B A
max
( )sin
,�
�3
2
�
�
(2)
G
E
�
2 1( )
,
�
(3)
where H A is hardness of layer A (with a lower shear modulus), G is shear modulus, � is
angle between the interface and the slip plane of layers, and m is the Taylor factor. The
value of m can be estimated as 0.3 for transition metal nitrides in NaCl type structures.
Poisson’s ratio (�) is 0.24–0.25 for TiC and TiN coatings. Hardness and elastic modulus
values of individual layers are obtained through nanoindentation tests [21]. Thus,
H H E EA B Amax . ( ).�
�0 1044 (4)
Results for TiN/TiC multilayer coatings show a difference between experimental data
of nanoindentation tests and results derived from interface characteristics through Eq. (4).
We have found that this difference is caused by dislocation blocking in the system of
multilayer coatings. Therefore, the highest hardness was found for multilayer coatings with
10 layers, reaching the maximum value of 26.7 GPa. Thus, the increase in hardness is equal
to 38% , which is higher the expected referent value (34%) from the rule-of-mixtures
applied to TiC and TiN coatings. Explanation for this hardness enhancement in TiN/TiC
multilayer coatings can be based on interfaces acting on dislocations and Hall–Petch
models, which provide a good overall picture of hardness enhancements [25].
The PACVD is a technique which allows one to generate compressive stresses in the
most coatings [26]. In addition, as established by Ding et al. [27], increase in the number
of layers in multilayer coatings results in augmentation of the compressive stress and
hardness values [28]. Thus, hardness of TiN/TiC multilayer coatings was also increased due
to generation of the compressive stresses. Enhanced hardness values have been also
observed in the process of material bombardment by high-energy ions during deposition of
coatings with high compressive stresses in [8].
The stiffness (S dP dh� ) of the contact can be used to calculate the reduced elastic
modulus (Er ) via the following equation:
E
S
A h
r
p c
�
1
2
�
( )
, (5)
where A hp c( ) is the projected area of the indentation at the contact depth (hc ) and
is a
geometrical constant A hp c( ) is often approximated by a fitting polynomial for the
156 ISSN 0556-171X. Ïðîáëåìû ïðî÷íîñòè, 2014, ¹ 1
M. Azadi and A. Sabour Rouhaghdam
Berkovich tip [29]. The area function of this indenter is calibrated by the B270 glass. The
variation of E with the number of layers exhibited a trend similar to that of the variation of
H , as shown in Fig. 5. During the increase in the number of layers, the elastic modulus was
reported to increase linearly.
The wear resistance can be predicted by the elasticity index (H E), describing the
elastic strain prior to failure. This ratio is the measure of the ability to absorb the energy
elastically. In addition, H E2 defines the resistance to fracture (the Irwin–Orowan–
Griffith case). Tough materials are characterized by high H E2 [30]. High H E and
H E2 values are intrinsic to multilayer coatings, in contrast to single-layer ones, as it is
shown in Table 4. Although for a long time the hardness has been regarded as a primary
material property affecting the wear resistance, the elastic strain prior to failure seems to be
a suitable parameter for predicting the wear resistance [9, 22, 31]. Thus, with increase in
the number of layers from 2 to 10 in TiN/TiC multilayer coatings, the wear resistance or the
H E ratio is also increased (by about 7%, in comparison to TiC single-layer coatings),
while the fracture toughness or the H E2 ratio is also increased (by about 17%, in
comparison to TiC single-layer coatings).
2.5. Nanoscratch. The AFM has been shown to be a powerful tool to investigate the
nanofriction behavior of several surfaces, including metals, ceramics and polymers [32].
Friction coefficients (ratio of the measured friction force to the applied normal force) for all
coatings were calculated as an average of about 400 data points over the entire sliding
distance. Figure 7 shows variation of friction coefficients with the scratch time. Based on
the nanoscratch data, changes in the relative elastic-plastic response can be monitored.
During the running-in time, due to the interaction between the tip and asperities on
coatings, the friction coefficient (�) is increased. At the initial stage, the friction coefficient
is controlled by the film roughness and the build-up of a transfer layer (tribolayer). At the
second stage, friction and wear are controlled by the nature of the tribolayer [33]. The
average value of friction coefficients (�) for all multilayer coatings was approximately
0.3–0.34. The minimum average value of friction coefficients (0.28) was related to TiN
single-layer coatings. Thus, when the number of layers was increased, the increase in the
friction coefficient was also observed. This result shows that multilayer coatings have
better scratch resistance, as compared to TiN single-layer ones. This suggests a dependency
between the surface asperity, roughness, hardness, and the friction coefficient by this scale
for TiN/TiC multilayer coatings. This occurrs when the loading rate, scratching speed,
indenter tip radius and the indenter material remain unchanged during the scratch test.
ISSN 0556-171X. Ïðîáëåìû ïðî÷íîñòè, 2014, ¹ 1 157
Nanomechanical Properties of TiN/TiC Multilayer Coatings
T a b l e 4
Nanomechanical Properties Obtained by the AFM
Coatings
type
Number
of layers
H E H E2 � Lateral
force
(�N)
Normal
displacement
(nm)
TiN n �1 0.0713 1.46 0.28 673�10 157�2
TiC n �1 0.0876 2.12 0.33 727�10 86�2
2 layers n � 2 0.0880 1.85 0.30 690�10 134�2
4 layers n � 4 0.0898 2.26 0.31 681�10 112�2
6 layers n � 6 0.0910 2.36 0.33 685�10 105�2
10 layers n �10 0.0935 2.49 0.34 734�10 88�2
According to Recco et al. [34], when the coating hardness is increased, the friction
coefficient is also increased. Variation of the friction coefficient in TiN single-layer
coatings with the scratch time was approximately fixed and the diagram was continuous
over the scratch time, but similar diagrams for other coatings were discontinuous, whereas
this discontinuity exhibited a certain improvement in the scratch resistance. When the
number of layers in multilayer coatings is increased, variation of friction coefficients is
slowly increased over the scratch time. According to the lateral (shear) force shown in
Table 4, the critical load for multilayer coatings with 10 layers is higher than that in other
158 ISSN 0556-171X. Ïðîáëåìû ïðî÷íîñòè, 2014, ¹ 1
M. Azadi and A. Sabour Rouhaghdam
a b
c d
e
Fig. 7. Friction coefficient versus time for different specimens including TiN (a), TiC (b), multilayer
coatings with 2 (c), 6 (d), 10 (e) layers.
coatings, whereas the critical loads for other multilayer coatings are lower than in TiC
single-layer coatings. The normal displacement that describes the scratch depth turned ot to
be similar in multilayer coatings with 10 layers and TiC single-layer ones. This indicates
that the scratch resistance of multilayer coatings, especially those with 10 layers, is higher
than that of TiN single-layer coatings.
Conclusions. TiN/TiC multilayer coatings were successfully deposited by the pulsed-
DC PACVD with the number of layers ranging from 2 to 10. High hardness values (about
26.7 GPa) are observed for TiN/TiC multilayer coatings deposited with 10 layers. The
enhanced hardness of multilayer coatings is attributed to several interfaces which block the
dislocation motion across the interface between Ti–C and Ti–N layers. This is due to
differences in the shear moduli of materials in the individual layers. The values of hardness
and elastic modulus of TiN/TiC multilayer coatings are found to be slightly higher than
those observed in single-layer coatings. The results obtained show that the TiN film has the
smallest grain height, whereas the TiC film has the lowest surface roughness. By increasing
the number of layers from 2 to 10 in multilayer coatings, it became possible to increase the
grain height, surface roughness, hardness, elastic modulus, as well as wear and scratch
resistance of the coatings.
Ð å ç þ ì å
Äîñë³äæåíî ñòðóêòóðó, ñêëàä ³ ìåõàí³÷í³ âëàñòèâîñò³ áàãàòîøàðîâèõ ïîêðèòò³â TiN/
TiC. Âñ³ ïîêðèòòÿ íàíîñèëèñü íà çðàçêè ç ³íñòðóìåíòàëüíî¿ ñòàë³ ìàðêè Í13 ìåòîäîì
âàêóóì-ïëàçìîâîãî õ³ì³÷íîãî îñàäæåííÿ ïàð³â ³ç ïóëüñóþ÷èì ðîçðÿäîì ïîñò³éíîãî
ñòðóìó. Çà äîïîìîãîþ àòîìíî-ñèëîâîãî ì³êðîñêîïà áóëî ïðîâåäåíî âèïðîáóâàííÿ íà
ïðîíèêíåííÿ íàíî³íäåíòîðà òà íàíîöàðàïàííÿ. Ó ðåçóëüòàò³ âèçíà÷åíî òàê³ ìåõàí³÷í³
õàðàêòåðèñòèêè: òâåðä³ñòü, ìîäóëü ïðóæíîñò³, øîðñòê³ñòü ïîâåðõí³ ³ êîåô³ö³ºíò òåðòÿ.
Äëÿ âèâ÷åííÿ êðèñòàë³÷íî¿ ñòðóêòóðè ïîêðèòò³â âèêîðèñòîâóâàëèñü ìåòîä êîâçíî¿
ðåíòãåí³âñüêî¿ äèôðàêö³¿ ³ òóíåëüíà ñêàíóâàëüíà ì³êðîñêîï³ÿ. Ïîêàçàíî, ùî çá³ëüøåí-
íÿ ê³ëüêîñò³ øàð³â ïîêðèòò³â ïðèâîäèòü äî ðîñòó ìîäóëÿ ïðóæíîñò³ ³ òâåðäîñò³. Óñòà-
íîâëåíî, ùî ïîêðèòòÿ ç äåñÿòè øàð³â ìàþòü âèñîê³ ìåõàí³÷í³ õàðàêòåðèñòèêè (òâåð-
ä³ñòü, ìîäóëü ïðóæíîñò³, îï³ð öàðàïàííþ), òîìó ïîêðèòòÿ òàêîãî òèïó ðåêîìåíäó-
þòüñÿ äëÿ âèêîðèñòàííÿ ó âèïàäêó, ÿêùî ïîòðåáóºòüñÿ ¿õ ï³äâèùåíà çíîñîñò³éê³ñòü.
1. H. Liepack, K. Bartsch, W. Brückner, A. Leonhardt, “Mechanical behavior of
PACVD TiC–amorphous carbon composite layers,” Surf. Coat. Technol., 183, 69–73
(2004).
2. N. Kumar, R. Krishnan, D. Dinesh Kumar, et al., “Tribological properties of
nanostructured TiC coatings deposited on steel and silicon substrates using pulse laser
deposition technique,” Tribology – Mater. Surf. Interfaces, 5, 1–9 (2011).
3. A. Shanaghi, A. Sabour Rouhaghdam, S. Ahangarani, et al., “Effects of duty cycle on
microstructure and corrosion behavior of TiC coatings prepared by DC pulsed plasma
CVD,” Appl. Surf. Sci., 258, 3051–3057 (2012).
4. P. Panjan, M. Ekada, D. Kek-Merl, et al., “Deposition and characterization of
Ti0.5Al0.5N/CrN multilayer coating sputtered at low temperature,” MTAEC9, 37 (3-4),
123–127 (2003).
5. J. Lim, J. Lee, H. Ahn, and K. T. Rie, “Mechanical properties of TiNyTiB2
multilayers deposited by plasma enhanced chemical vapor deposition,” Surf. Coat.
Technol., 174-175, 720–724 (2003).
6. D. Kim, Y. Cho, M. Lee, et al, “Properties of TiN–TiC coatings using plasma-assisted
chemical vapor deposition,” Surf. Coat. Technol., 116-119, 906–910 (1999).
Nanomechanical Properties of TiN/TiC Multilayer Coatings
ISSN 0556-171X. Ïðîáëåìû ïðî÷íîñòè, 2014, ¹ 1 159
7. Y. Zhao, G. Lin, J. Xiao, et al., “TiN/TiC multilayer films deposited by pulse biased
arc ion plating,” Vacuum, 85, 14 (2010).
8. A. Shanaghi, A. Sabour Rouhaghdam, S. Ahangarani, and P. K. Chu, “Effect of
plasma CVD operating temperature on nanomechanical properties of TiC nano-
structured coating investigated by atomic force microscopy,” Mater. Res. Bull., 47,
2200–2205 (2012).
9. H. L. Wang, J. L. He, and M. H. Hon, “Sliding wear resistance of TiCN coatings on
tool steel made by plasma-enhanced chemical vapor deposition,” Wear, 169, 195–200
(1993).
10. Y. Iwai, T. Miyajima, A. Mizuno, et al., “Micro-slurry-jet erosion (MSE) testing of
CVD TiC/TiN and TiC coatings,” Wear, 267, 264–269 (2009).
11. M. Takahashi and S. Shimada, “Preparation of composite and compositionally graded
TiC–TiN films by liquid injection plasma-enhanced CVD,” Solid State Ionics, 172,
249–252 (2004).
12. S. Ma, Y. Li, and K. Xu, “The composite of nitrided steel of H13 and TiN coatings by
plasma duplex treatment and the effect of pre-nitriding,” Surf. Coat. Technol., 137,
116–121 (2001).
13. K. Holmberg, A. Matthews, and H. Ronkainen, “Coatings tribology-contact
mechanisms and surface design,” Tribol. Int., 31, 107–120 (1998).
14. A. Devia, V. Benavides, E. Restrepo, et al., “Influence substrate temperature on
structural properties of TiN/TiC bilayers produced by pulsed arc techniques,” Vacuum,
81, 378–384 (2006).
15. D. E. Wolfe, J. Singh, and K. Narasimhan, “Synthesis and characterization of
multilayered TiC–TiB2 coatings deposited by ion beam assisted, electron beam
physical vapor deposition (EB-PVD),” Surf. Coat. Technol., 165, 8–25 (2003).
16. K. T. Rie, A. Gebauer, J. Wohle, et al., “Synthesis of TiN/TiCN/TiC layer systems on
steel and cermet substrates by PACVD,” Surf. Coat. Technol., 74-75, 375–381
(1995).
17. C. Jarms, H. R. Stock, H. Berndt, et al., “Influence of the PACVD process parameters
on the properties of titanium carbide thin films,” Surf. Coat.Technol., 98, 1547–1552
(1998).
18. Y. T. Pei, D. Galvan, J. Th. M. De Hosson, and C. Strondl, “Advanced TiC/a-C:H
nanocomposite coatings deposited by magnetron sputtering,” J. Europ. Ceram. Soc.,
26, 565–570 (2006).
19. C. Liu, K. Liu, H. Yan, et al., “Mechanical properties of TiN/NbN multilayered films
prepared by PVD coating,” Adv. Ceram. Sci. Eng. (ACSE), 2, 16–22 (2013).
20. C. Morant, P. Prieto, A. Forn, et al., “Hardness enchancement by CN–TiCN–TiN
multilayer films,” Surf. Coat. Technol., 180-181, 512–518 (2004).
21. S. H. Kim, Y. J. Baik, and D. Kwon, “Analysis of interfacial strengthening from
composite hardness of TiN/VN and TiN/NbN multilayer hard coatings,” Surf. Coat.
Technol., 187, 47–53 (2004).
22. K. H. T. Raman, M. S. R. N. Kiran, U. Ramamurty, and G. Mohan Rao, “Structure
and mechanical properties of Ti–C films deposited using combination of pulsed DC
and normal DC magnetron co-sputtering,” Appl. Surf. Sci., 258, 8629–8635 (2012).
23. W. C. Oliver and G. M. Phar, “An improved technique for determining hardness and
elastic modulus using load and displacement sensing indentation experiments,” J.
Mater. Res., 7, 1564–1583 (1992).
M. Azadi and A. Sabour Rouhaghdam
160 ISSN 0556-171X. Ïðîáëåìû ïðî÷íîñòè, 2014, ¹ 1
24. S. H. Kim, H. Park, K. H. Lee, et al., “Structure and mechanical properties of titanium
nitride thin films grown by reactive pulsed laser deposition,” Process. Res., 10, 49–53
(2009).
25. J. C. Caicedo, C. Amaya, L. Yate, et al., “TiCN/TiN/CN multilayer coatings with
enhanced mechanical properties,” Appl. Surf. Sci., 256, 5898–5904 (2010).
26. K. Holmberg, H. Ronkainen, A. Laukkanen, et al., “Residual stresses in TiN, DLC
and MoS2 coated surfaces with regard to their tribological fracture behavior,” Wear,
267, 2142–2156 (2009).
27. J. Ding, Y. Meng, and S. Wen, “Mechanical properties and fracture toughness of
multilayer hard coatings using nanoindentation,” Thin Solid Films, 371, 178–182
(2000).
28. A. J. McGinnis, T. R. Watkins, and K. Jagannadham, “Residual stresses in a
multilayer system of coatings,” Int. Centre Diffr. Data, 41, 443–454 (1999).
29. S. Jian, G. Chen, and T. Lin, “Berkovich nanoindentation on AlN thin films,”
Nanoscale Res. Lett., 5, 935–940 (2010).
30. J. M. Lackner, L. Major, and M. Kot, “Microscale interpretation of tribological
phenomena in Ti/TiN soft-hard multilayer coatings on soft austenite steel substrates,”
Bull. Polish Acad. Sci. (Tech. Sci.), 59, 343–355 (2011).
31. Y. T. Pei, D. Galvan, J. Th. M. De Hosson, and A. Cavaleiro, “Nanostructured
TiC/a-C coatings for low friction and wear resistant applications,” Surf. Coat. Technol.,
198, 44–50 (2005).
32. L. Ipaz, A. Esguerra-Arce, W. Aperador, et al., “Nanofriction study using atomic
force microscopy (AFM) of multilayers based in titanium, chromium and aluminum,”
in: A. Mendez-Vilas (Ed.), Current Microscopy Contributions to Advances Science
and Technology (2012), pp. 1395–1403.
33. D. G. Liu, J. P. Tu, C. D. Gu, et al., “Tribological and mechanical behaviors of
TiN/CNx multilayer films deposited by magnetron sputtering,” Thin Solid Films, 519,
4842–4848 (2011).
34. A. A. C. Recco, C. C. Vifara, A. Sinator, and A. P. Tschiptschin, “Energy dissipation
in depthsensing indentation as a characteristic of the nanoscratch behavior of coatings,”
Wear, 267, 1146–1152 (2009).
Received 19. 09. 2013
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/NLD (Gebruik deze instellingen om Adobe PDF-documenten te maken voor kwaliteitsafdrukken op desktopprinters en proofers. De gemaakte PDF-documenten kunnen worden geopend met Acrobat en Adobe Reader 5.0 en hoger.)
/NOR <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>
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/ENU (Use these settings to create Adobe PDF documents for quality printing on desktop printers and proofers. Created PDF documents can be opened with Acrobat and Adobe Reader 5.0 and later.)
>>
/Namespace [
(Adobe)
(Common)
(1.0)
]
/OtherNamespaces [
<<
/AsReaderSpreads false
/CropImagesToFrames true
/ErrorControl /WarnAndContinue
/FlattenerIgnoreSpreadOverrides false
/IncludeGuidesGrids false
/IncludeNonPrinting false
/IncludeSlug false
/Namespace [
(Adobe)
(InDesign)
(4.0)
]
/OmitPlacedBitmaps false
/OmitPlacedEPS false
/OmitPlacedPDF false
/SimulateOverprint /Legacy
>>
<<
/AddBleedMarks false
/AddColorBars false
/AddCropMarks false
/AddPageInfo false
/AddRegMarks false
/ConvertColors /NoConversion
/DestinationProfileName ()
/DestinationProfileSelector /NA
/Downsample16BitImages true
/FlattenerPreset <<
/PresetSelector /MediumResolution
>>
/FormElements false
/GenerateStructure true
/IncludeBookmarks false
/IncludeHyperlinks false
/IncludeInteractive false
/IncludeLayers false
/IncludeProfiles true
/MultimediaHandling /UseObjectSettings
/Namespace [
(Adobe)
(CreativeSuite)
(2.0)
]
/PDFXOutputIntentProfileSelector /NA
/PreserveEditing true
/UntaggedCMYKHandling /LeaveUntagged
/UntaggedRGBHandling /LeaveUntagged
/UseDocumentBleed false
>>
]
>> setdistillerparams
<<
/HWResolution [2400 2400]
/PageSize [612.000 792.000]
>> setpagedevice
|