UNIVERSITY OF TECHNOLOGY

Proudction And Metallurgy Department

Metallurgy branches

Study Corrosion Behavior of Co-Cr-Mo

Alloy Coated By PACVD

Project Submitted to the Department of Production

Engineering and Metallurgy/ University of Technology in a
Partial Fulfillment of the Requirements for the Degree of
B.Sc. in Metallurgical Engineering

Submitted by

YUSUR A. ABDULRAHMAN Lena M. Muslih

Supervised by

Asst. Prof. Dr. Ali. M. Resen Mahdi M. Hanon

1444A.H 2023A.D
 Chapter 1 : Introduction
1.1 Introduction 01

1.2 Diamond like Carbon Coating 02

1.3 History and Literature Survey 03

1.4 Aim Of Work 04

Chapter 2 : Theoretical part

2.1 Introduction 05

2.2 Cobalt alloys

2.3 Applications of Co-Cr-Mo alloy 07

2.4 Surface Modification 08

2.5 diamond-like carbon (DLC) 09

2.6 Structure of DLC coatings

2.7 Deposition Methods of DLC coatings 13

2.8 PAVCD TECHNOLOGY

2.9 Deposition Mechanism 15

2.10 Advantages of PAVCD 17

2.11 DLC Coating Characteristics

2.12 Applications Of DCL Coating 18
 Chapter 3 : Experimental
Work
3.1 Introduction 19 3.6 Roughness Measurement
3.2 Materials 3.7 Microhardness Measurment
3.3 Sample Prepartation 20 3.8 Corrosion Test 22

3.4 Coating Phase

3.5 Optical Microscopy 21

Chapter 4 : Results and discussion

4.1 Optical Microstructure 23

4.2 Roughness Measurements

4.3 Hardness Results
4.4 Corrosion Test Result 24

Chapter 5 : Conclusions and

Recommendations
5.1 Conclusion Recommendations 25

5.2 Recommendations

References
References 26
CHAPTER 1

Introduction
CHAPTER ONE : INTRODUCTION

1.1 introduction

The materials used in biomedical engineering shouldhave adequate

mechanical properties. The propertiesrequired for the biomaterial under
consideration depend on the field of application [1]. Like with structural
materials used in other fields of application, there are a few fundamental
properties determining mechanical behaviour of a structure in this particular
case, too: stiffness, strength, toughness and hardness. Considering the
environment in which they are used, the biomaterials should be corrosion-
and wear-resistant, assuming that the debris should be minimized. Finally,
these structures should have good machining ability, as they should be
frequently subjected to reshaping during operation [2].
Decades of basic and clinical experimentation have re- sulted in a vast array
of prosthetic designs and material combinations. However, there is still any
consensus on which designs are the most appropriate and successful. All
material combinations have certain drawbacks. Ac-cording to Wang [3], “All
prostheses will fail sometime. It is a race between the life of the patient and
the life of the prosthesis” [1-3]. Therefore, the duty of researchers is
continuing the search for finding better combinations of materials for
artificial joints.
Co-Cr-Mo alloy is one of the most important materials. It have many
application for many fields. One of applications is biomedical applications.
Co-Cr-Mo alloy used in human body such as total replacement in knee and hip
joint [4-6].
The material combinations used today include a polymer component for the
acetabular cup in the hip joint, or a tibial plateau in the knee joint, and a
metallic or ceramic counterface for the femoral head in the hip joint, or a
metallic counterface for the femoral condyle the dissolution of Cr ion and the
uncertainty of that being a carcinogenic component is one of the main
concerns in the case of Co–Cr–Mo sliding against the same, in addition to the
tribological behaviour of the material pair. Surface modification of Co–Cr–Mo
alloy material with an inert coating such as high quality DLC film may
prolong the life of the component as well as reduce the release of Cr ions [7-
10].

01
CHAPTER ONE : INTRODUCTION

1.2 Diamond like Carbon Coating

DLC define as a metastable of amorphous carbon have respectable portion of

SP3 bond types [ 1 ]. It is different of diamond by color, hardness, and
microstructure. It has amorphous phase permits to incorporation of other
elements such as silicon, Ni, H and etc [3]. During the past two decades,
diamond-like carbon (DLC) films have attracted an overwhelming interest
from both industry and the research community. These films offer a wide
range of exceptional physical, mechanical, biomedical and tribological
properties that make them scientifically very fascinating and commercially
essential for numerous industrial applications. Mechanically, certain DLC
films are extremely hard (as hard as 90 GPa ) and resilient, while
tribologically they provide some of the lowest known friction and wear
coefficients. Their optical and electrical properties are also extraordinary
and can be tailored to meet the specific requirements of a given application.
Because of their excellent chemical inertness, these films are resistant to
corrosive and/or oxidative attacks in acidic and saline media. The
combination of such a wide range of outstanding properties in one material
is rather uncommon, so DLC can be very useful in meeting the
multifunctional application needs of advanced mechanical systems. In fact,
these films are now used in numerous industrial applications, including
razor blades, magnetic hard discs, critical engine parts, mechanical face
seals, scratch-resistant glasses, invasive and implantable medical devices
and microelectromechanical systems. DLC films are primarily made of
carbon atoms that are extracted or derived from carbon-containing sources,
such as solid carbon targets and liquid and gaseous forms of hydrocarbons
and fullerenes [11] .

02
CHAPTER ONE : INTRODUCTION

1.3 History and Literature Survey

Historically, the earliest research on DLC films can be traced back to 1953.
Even though Eisenberg and Chabot are often considered as the true pioneers
of this technology (mainly because of their comprehensive studies in the
early 1970s [15], Schmellenmeier had produced such carbon films back in
1953 and hence he was probably the earliest pioneer of DLC technology [16].
From the start of their studies, these scientists have immediately realized
that these carbon films were rather unique and possessed some unusual
mechanical and electrical properties. For one thing, they were mechanically
very hard and resistant to scratching; they also possessed high dielectric
constants, high index of refraction and excellent optical transparency.
Furthermore, these early DLC films were chemically inert and hard to
remove or etch out from coated surfaces by dipping into strong acidic
solutions. During the mid-1970s, Holland et al and a few other researchers
also developed an interest in DLC films. These researchers were able to
derive DLC from a number of gaseous hydrocarbon sources by applying an
r.f . bias to the substrate materials and thus creating a plasma [17 ,18 ]. In
this respect, their deposition process was somewhat different from the
one that Eisenberg and Chabot had used. Weissmental and his co-workers
were the very first group of scientists who performed extensive electron
microscopy and electronenergy loss spectroscopy work on DLC films to
elucidate their structural and chemical nature [19]. Some of the earlier
researchers had thought that these films were perhaps made of crystalline
diamond, but the microscopicwork byWeissmental et al proved otherwise;
these films were made of amorphous carbon.

03
CHAPTER ONE : INTRODUCTION

Despite their several attractive properties, DLC films did not draw
much attention throughout the 1970s and even until the mid-1980s.
This neglect may, in part, have been due to the fact that around the
same time, the creation of crystalline diamond films using low-
pressure chemical vapour deposition (CVD) had been announced, and
most researcherswereworking on the hot topic of diamond but not on
something like it [20, 21]. However, inherent difficulties plagued the
large-scale production of diamond as thin films or free-standing large
crystals that everybody was dreaming of producing at reasonable
costs. Nevertheless, these dedicated research activities resulted in
the development of high-quality diamond films that are now used in
key industrial applications [22, 23]. Lastly Ali Mezher in 2022 study the
formation of DLC Using PACVD to coat Co-Cr-Mo alloy. DLCs by using
acetylene gas flow rate 40 sccm and voltage is 1600 v with Voltage
between electrodes is 250 v for (PACVD) results coating film with 83%
diamond like carbon (sp3) with thickness is 100 lm. Observations of
surface indicate by suing both SEM and AFM indicate no crack and
smooth surface with surface roughness is 0.679 mm in DLCs. Raman
tested to determine the amount diamond like carbon (sp3) is 83%.that
meaning the minimum of hydrogen content. Hardness tested to
indicate increasing up to three times [1].

1.4 Aim of work

While DLCs is new technique needs many research to allow for using in
biomedical applications. This led us to investigate a preliminary study on the
chemical behavior of DLC coating ofdifferent parameter, to evaluate and
optimise for the best DLC parameters of PACVD. Depending on the literatures
mention above and choose another parameter to determine the best
condition of gas flow rate and voltage between electrodes. the study will be
carried out using the custom-made Co–Cr–Mo, the quality of the film varies
greatly on the deposition condition. In this article we discuss multilayer of
thick DLC coatings.

04
CHAPTER 2
Theoretical part ​
CHAPTER TWO : THEORETICAL PART ​

2.1 Introduction

This chapter dial with the cobalt alloys and its applications then explain the surface
method to modify the surface characteristic to improvement the surface properties.
The DLC definition and its structure then the methods of deposition of DLC are
explaining. The plasma assisted chemical vapor deposition PACVD explaining with
mechanism of deposition. Finally explain some of applications of DLC coating.

2.2 Cobalt alloys

Cobalt (Co) alloys have been in use since 1907 when Elwood Haynes obtained the
first patents cobalt–chromium compositions [24]. Historically, many of the
commercial cobalt-base alloys are derived from the cobalt–chromium–tungsten and
cobalt–chromium–molybdenum ternaries.
Co-Cr-Mo alloy specified in standards ASTM, 2018 Edition, November 15, 2018 as alloy
ASTM F75 [25]. Chemical composition of Standard Specification Co-Cr-Mo alloy shown
in table 2.1 [25]. Cobalt-28 Chromium-6 Molybdenum Alloy Castings and Casting Alloy
used for Surgical Implants (UNS R30075). This specification covers the chemical,
mechanical, and metallurgical requirements for cobalt-28 chromium-6 molybdenum
alloy unfinished investment product castings for surgical implant applications and
casting alloy in the form of shot, bar, or ingots to be used in the manufacture of
surgical implants. Table 2.2 shows the mechanical properties of ASTM F75 [25]. This
specification does not apply to completed surgical implants made from castings [1].
Generally Cobalt alloys have good magnetic properties, corrosion resistance, wear
resistance, and high temperature strength. These properties arise from the
crystallographic nature of cobalt, the solid-solution-strengthening effects of Cr, W,
and Mo, the formation of metal carbides, and the corrosion resistance imparted by
Cr. Relatively harder Co-alloys is used for resistance to wear. On the other hand the
tougher Cobalt compositions are used for high-temperature applications such as
gas-turbine vanes and buckets. Co-based alloys are also used to produce artificial
joints thanks to their excellent biocompatibility. Although in terms of properties,
nickel-based alloys have taken the majority share of the superalloy market, Co-
alloys give superior hot corrosion resistance to gas turbine atmospheres, due to
their high Cr content, and they show superior thermal fatigue resistance and
weldability over Ni-alloys.

05
CHAPTER TWO : THEORETICAL PART ​

TABLE 2.1 STANDARD COMPOSITION OF CO-CR-MO ALLOY ASTM F75 [25].

TABLE 2.2 SHOWS THE MECHANICAL PROPERTIES OF ASTM F75 [25]

06
CHAPTER TWO : THEORETICAL PART ​

The values stated in either SI units or inch-pound units are to be regarded separately
as standard. The values stated in each system may not be exact equivalents;
therefore, each system shall be used independently of the other. Combining values
from the two systems may result in non-conformance with the standard.

2.3 Applications of Co-Cr-Mo alloy

Table 2 .3 summarizes the applications of Co-Cr alloys. Cast Co-28Cr-6Mo (ASTM F 75)
alloy has been used in the stem, ball, and cup of artificial hip joints including both
metal-on-UHMWPE and metal-on-metal joints as well as in the sliding components of
artificial knee joints. Since artificial knee joints have complicated shapes,
investment casting is essential for their production. Wrought Co-28Cr-6Mo Alloy 1
and Alloy 2 (ASTM F 799 and F 1537) have been used in the joint replace- ments for
hips, knees, shoulders, and so on. The Co-Cr alloys in the Co-Cr- W-Ni (ASTM F 90/F
1091), Co-Ni-Cr-Mo (ASTM F 562), and Co-Cr-Fe-Ni-Mo (ASTM F 1058) systems are used
for wrought produ cts that require a large defor mation to fabricate. Since they
exhibit excellent hot and cold workability and can be strengthened by cold working,
they have been used in fixation wires, vascular stents, springs, catheters, surgical
clips, orthodontic dental arch wires, and so on .

TABLE 2.3 THE APPLICATION OF CO-CR-MO ALLOY [27]

07
CHAPTER TWO : THEORETICAL PART ​

2.4 Surface Modification

Surface modification is the act of modifying the surface of a material by bringing

physical, chemical or biological characteristics different from the ones originally
found on the surface of a material [27].

This modification is usually made to solid materials, but it is possible to find

examples of the modification to the surface of specific liquids [28].

The modification of Co-Cr-Mo alloy can be done by different methods with a view to
altering a wide range of characteristics of the surface, such as: roughness,[1]
hydrophilicity,[2] surface charge,[3] surface energy, biocompatibility[2][4] and
reactivity [5].
During the past two decades, diamond-like carbon (DLC) films have attracted an
overwhelming interest from both industry and the research community. These films
offer a wide range of exceptional physical, mechanical, biomedical and
tribologicalproperties that make them scientifically very fascinating and
commercially essential for numerous industrial applications. Mechanically, certain
DLC films are extremely hard (as hard as 90 GPa) and resilient, while tribologically
they provide some of the lowest known friction and wear coefficients. Their optical
and electrical properties are alsoextraordinary and can be tailored to meet the
specific requirements of a given application. Because of their excellent chemical
inertness, these films are resistant to corrosive and/or oxidative attacks in acidic
and saline media. The combination of such a wide range of outstanding properties in
one material is rather uncommon, so DLC can be very useful in meeting the
multifunctional application needs of advancedmechanical systems. In fact, these
films are now used in numerous industrial applications, including razor blades,
magnetic hard discs, critical engine parts,mechanical face seals, scratch-resistant
glasses, invasive and implantable medical devices and microelectromechanical
systems.

08
CHAPTER TWO : THEORETICAL PART ​

2.5 diamond-like carbon (DLC)

DLC films are primarily made of carbon atoms that are extracted or derived from
carbon-containing sources, such as solid carbon targets and liquid and gaseous
forms of hydrocarbons and fullerenes.
Depending on the type of carbon source being used during the film deposition, the
type of bonds (i.e. sp1, sp2, sp3) that hold carbon atoms together in DLC may vary a
great deal and can affect their mechanical, electrical, optical and tribological
properties.
Recent systematic studies of DLC films have confirmed that the presence or
absence of certain elemental species, such as hydrogen, nitrogen, sulfur, silicon,
tungsten, titanium and fluorine, in their microstructure can also play significant
roles in their properties.
DLC coating is highly chemically inactive and has no reactive potential with acids
and alkalis. Diamond-like carbon coatings are a stable, amorphous, high-density
carbon layer that prevents corrosion and oxidation. Also, this inert state of the
diamond-like carbon coating is useful for reducing surface interaction with other
metals and for reducing cold welding

2.6 Structure of DLC coatings

Has three different types of bonding configurations, namely sp³, sp2 and sp¹ as
shown in figure 2.1 . In diamond, carbon has four sp³ hybridized orbitals. These sp³
orbitals contribute to the formation of four equal carbon-carbon bonds with
adjacent atoms, which produces the tetrahedral structure of diamond. This
covalently bonded tetrahedral structure is the origin of the superior properties of
diamond, like high hardness and high thermal conductivity. Graphite has three
trigonally directed sp² hybrid orbitals, which lie in plane. Each carbon atom in plane
is bonded to three other carbon atoms with strong covalent bonds. The layers of
carbon atoms are attracted to each other by weak van der Waals forces producing
the layered structure of graphite. The layers can cleave easily, which accounts for
the typical low friction property of graphite [Guy 1976, Bhushan 1999]. The diamond-
like carbon films have a mixed sp³/sp2 structure with different proportions of sp³
and sp2 bonds depending on the deposition techniques and deposition parameters
used.

09
CHAPTER TWO : THEORETICAL PART ​

The structure is claimed to consist of sp² bonded clusters embedded in an

amorphous sp³ bonded carbon matrix [ Dischler 1987, Robertson 1992]. One major
group of diamond-like carbon coatings is the hydrogenated amorphous carbon, a-C
:H , coatings. The hydrogen content of a-C :H films can differ considerably depending
on the deposition method, hydrocarbon source gas and the deposition parameters
used. For a-C :H films, hydrogen is important for obtaining a wide optical gap and
high electrical resistivity and stabilizing the diamond structure by maintaining the
sp³ hybridization configuration [ Donnet & Grill 1997]. Another group of DLC coatings
is the metastable form of amorphous carbon (a-C). For a-C films, hydrogen is
generally treated as an impurity. The hydrogen-free form of amorphous carbon,
which is highly sp³ bonded, is known as tetrahedral amorphous carbon, ta-C. It is
also referred to as amorphous diamond because the structure is locally tetrahedral,
like diamond, even if the structure is disordered on a larger scale. The compositions
of diamond-like carbons can be displayed on a ternary phase diagram of sp³ ratio, sp²
ratio and hydrogen content of the film, as shown in Figure. The sp² bonded graphitic
carbon lies in the lower left-hand corner. Phases that have too high a content of
hydrogen cannot form an interconnected molecular structure, but form gas or liquid
molecules, and lie at the lower right-hand corner of the diagram. The typical a-C :H
coatings are situated in the middle of the diagram showing a varying ratio of
sp³/sp2 bonding and hydrogen content. The ta-C coatings are situated on the left
side depending on the ratio of sp³/sp² bonding [Robertson 1999]. DLC coatings are
formed when ionized and decomposed hydrocarbon or carbon species hit the surface
with energies ranging from several tens of eV to 200 eV [Angus 1987]. All methods for
the deposition of DLC films are non-equilibrium processes characterized by the
interaction of energetic ions with the surface of the growing films. The methods can
be divided into chemical vapour deposition and physical vapour deposition
techniques. The CVD techniques, such as d.c. plasma and radio frequency ( r.f .)
plasma assisted chemical vapour deposition, and PVD techniques, like sputter
deposition, ion-plating techniques and ion beam techniques can be used for
depositing the hydrogenated a-C :H coatings. The PVD techniques, such as
magnetron sputtering, mass selected ion beam (MSIB), cathodic arc and laser
plasma deposition can be used for hydrogen-free a-C and ta-C coatings [ Weissmantel
1985, Neuville & Matthews 1997, Robertson 1999]. DLC coatings can be deposited at
temperatures that are below 200 °C [ Donnet 1995] to 325 °C [ Donnet & Grill 1997].
This property makes it possible to deposit DLC coatings on most relevant
engineering materials, including polymers.

10
CHAPTER TWO : THEORETICAL PART ​

DLC coating which is also referred to as a nanocomposite coating of a range of

substrate materials to display the unique properties of natural diamond such as
high hardness, wear resistance, low friction, electrical insulation, and many more. In
this regard, the main desirable property among these groups of properties is the
hardness of the material obtained. However, DLC coating can be applied using
multiple deposition techniques.

FIGURE 2.1 TERNARY PHASE DIAGRAM OF SP, SP' AND HYDROGEN

CONTENTS OF VARIOUS FORMS OF DIAMOND-LIKE CARBON
[ROBERTSON 1999]

DLC coatings come in a variety of forms, including:

1- form a-C (hydrogen-free amorphous carbon)
2-ta-C form (amorphous carbon without hydrogen tetrahedral)
3-a-C form: H (hydrogen amorphous carbon
4-from aC:H:Me (Me = W, Ti, amorphous carbon saturated with hydrogen)
5-Form aC:H:Si (this is an amorphous carbon doped Si with hydrogen)
6-Form aC:H:X (amorphous carbon that is not metal-doped with hydrogen)
7-of aC: Me (Me = Ti, a metal-doped hydrogen-free amorphous carbon)
8-The form ta-C:H (an amorphous carbon tetrahedral bonded to hydrogen

11
CHAPTER TWO : THEORETICAL PART ​

The amorphous carbon is all that isotropic carbon with structures riddled with
defects and molecular irregularities. The term allotrope refers to a single chemical
element, such as a carbon atom, forming different molecular structures; some are
crystalline, others, as in this case, are amorphous.
Amorphous carbon lacks the long-range crystalline structure that characterizes
diamond and graphite. This means that the structural pattern remains more or less
consistent if you view regions of the solid very close together; and when they are
apart, their differences become apparent.
The physical and chemical properties or properties of amorphous carbon are also
different from those of graphite and diamond. For example, there is the famous
charcoal, which is a product of wood combustion (top photo). This is not gliding, and
it's not shiny either
There are several types of amorphous carbon in nature and these types can also be
obtained synthetically. Among the different forms of amorphous carbon are carbon
black, activated carbon, soot, and charcoal.
Amorphous carbon has important uses in the power generation industry, as well as
in the textile and health industries.
Synthetic amorphous carbon is produced by cathodic arc deposition, and spraying
techniques. In an artificial way, diamond-like amorphous carbon coatings or
amorphous carbon films are also synthesized.

Amorphous carbon element often abbreviated as BC or BC, it includes activated

carbon and carbon black. Varieties of this group are obtained by incomplete
combustion of animal and plant materials; That is, they burn with a commensurate
lack of oxygen.
They have a higher proportion of sp2 bonds in their molecular structure or
organization. It can be imagined as a series of grouped planes, with different
orientations in space, the product of the tetrahedral carbon that establishes the
heterogeneity in the whole. Among them, nanocomposites with electronic
applications and materials development have been synthesized.
Tetrahedral amorphous carbon Abbreviated as ta-C, it is also called diamond-like
carbon. It contains a high percentage of sp3 hybrid links.
Amorphous carbon films or coatings with an amorphous tetrahedral structure
belong to this classification. It lacks hydrogen, has a high hardness, and many of its
physical properties are similar to those of diamond.
Molecularly, it consists of tetrahedral carbons that do not have a long range
structural pattern; whereas in diamond, the arrangement remains constant in
different regions of the crystal. ta-C can introduce a specific arrangement or
modularity feature of a crystal, but only in a short range.

12
CHAPTER TWO : THEORETICAL PART ​

2.7 Deposition Methods of DLC coatings

Many methods have been developed for the deposition of DLC coatings, from a
variety of carbonaceous precursor materials. They include:
•Direct ion beam deposition,
•Pulsed laser ablation,
•Filtered cathodic arc deposition,
•Ion beam conversion of condensed precursor,
• Magnetron sputtering,
•RF plasma-activated chemical vapor deposition,
• Plasma source ion implantation and deposition

2.8 PACVD Technology

PACVD The most popular laboratory deposition method is rf PECVD [ 29 ]. The

reactor consists of two electrodes of different area. The rf power is usually
capacitively coupled to the smaller electrode on which the substrate is mounted,
and the other electrode (often including the reactor walls) is earthed. The rf power
produces a plasma between the electrodes. The higher mobility of electrons than
ions in the plasma creates a sheath next to the electrodes with an excess of ions.
This has a positive space charge, so the plasma develops a positive voltage with
respect to the electrodes, which equalises the mean electron and ion current to the
wall [ 30 ], as shown in Fig. 2.2 . The sheaths act as diodes, so that the electrodes
acquire de self-bias voltages equal to their peak if voltage. The rf voltage is divided
between the sheaths of the two electrodes as in a capacitive divider, according to
their inverse capacitance. Thus, the de self-bias voltage varies inversely with the
electrode areas [ 27, 30 ].

13
CHAPTER TWO : THEORETICAL PART ​

FIGURE ( 2.2 ) ELECTRON AND ION DISTRIBUTION BETWEEN NEUTRAL PLASMA AND WALLS.

PACVD is the abbreviated form of Plasma Assisted Chemical Vapor

Deposition. This deposition method is widely used in the deposition of
diamond-like carbon coatings. This process is vacuum dependent and all
PACVD processes occur in a gaseous state.
Unlike PVD, the gas deposition process makes it suitable for 3D coating
without spinning. PACVD coatings contain about 3% sp70 bonds and are
amorphous. The sp3 bond represents the super hardness property (3-
10GPa) of the coating. At temperatures below 40°C, PACVD can deposit
coatings for a wide range of non-conductive and conductive substrate
materials.

14
CHAPTER TWO : THEORETICAL PART ​

2.9 Deposition mechanism

The key property of DLC is its sp bonding. The deposition process which promotes
sp 3 bonding is a physical process, ion bombardment [6-8 ,17, 29 , 31 ]. The highest
sp³ fractions are formed by C ions with ion energy around 100 eV. To see how this
occurs, it is useful to first consider the hydrogen-free carbon, ta-C, and then a-C :H .
The atomistic description of the deposition mechanism has developed as follows.
Fig. 2 and 3 compares the ion ranges and yields for various processes of C and H ions
in carbon [ 32 ]. Spencer et al. [ 33 ] proposed various mechanisms such as that the
sp³ sites arise from the sp³/sp² mixture by a preferential sputtering of the sp² sites.
However, Lifshitz et al. [34] noted that this process would not work because
sputtering yield (efficiency) of carbon. In addition, the sputtering yield depends
primarily on an atom's cohesive energy, which is almost the same for the sp² and sp³
sites, so there is little difference in sputtering yields. Weissmantel [ 35 ] suggested
that the sp³ bonding arose from a shock wave of the displacement spike of the ion
cascade. This picture has some similarities to later models, but the shock wave is
more appropriate to higher ion energies and higher ion masses.

FIGURE 2 MASS SPECTRA DISSOCIATION PATTERN OF C2H4, CH4 AND C2H2

AT DIFFERENT PRESSURES

15
CHAPTER TWO : THEORETICAL PART ​

Lifshitz et al. [34] used Auger analysis of the depth profiles of medium energy C ions
incident on Ni substrates to show that the growth was sub-surface. They denoted
this process as 'subplantation (low energy subsurface implantation). They then
proposed that the sp sites accumulate by a preferential displacement of sp sites.
Moller [102] modelled this idea in more detail. The sp and sp' atoms would be
displaced at certain rates into interstitial sites, and then fall back at similar rates
into sp² and sp' sites. The fraction of sp sites increases if there is a preferential
displacement of sp² atoms. This idea arose from some early estimates of the
displacement threshold in graphite and diamond of 25 and 80 eV, respectively
[15,36]. However, more recent direct measurements of the displacement threshold
find similar values for graphite (35 eV) and diamond (37-47 eV) [37-40], so preferential
displacement is not correct. It should be noted that the displacement threshold of
graphite is quite anisotropic because of its layer structure, and Banhart [108] still
takes the displacement threshold for sp² sites to be lower. McKenzie et al. [41], and
McKenzie [42] noted that sp³ bonded graphite occupies 50% more volume than sp
bonded diamond. This leads to the phase diagram of diamond and graphite shown in
Fig. 4, with diamond stable at higher pressures above the Berman-Simon line.
McKenzie [42] and Davis [43] proposed that the role of the ion beam is to create a
compressive stress in the film, which will move the film above the Berman-Simon
line and so stabilisethe high pressure diamond (-like) phase. Of course, in all these
models, the phase once created is quenched into the growing film. Robertson [39-44]
proposed that the subplantation created a metastable increase in density, which
tends to cause the local bonding to change to sp³ Preferential displacement is not
needed. Only subsurface growth in a restricted volume is needed to get sp bonding.
The difference between these viewpoints is discussed shortly. Various numerical
and analytical simulations prove the basic idea of subplantation [45,46]. The
unsolved problem is in the details of the relaxation process, which suppresses sp'
bonding at higher ion energies and higher deposition temperatures. Let us consider
the atomic scale processes in more detail [39-41]. In the energy range of interest, 10-
1000 eV, the carbon ions have a range of a few nm and they loose their energy
largely by elastic collisions with the target atoms (nuclear stopping). The elastic
collisions of ions in solids can be simplified to the binary collision approximation, in
which the collisions occur as a sequence of J. independent pair collisions. The cross-
section of the collisions decreases as the energy is raised, as this is the repulsive
part of the inter-atomic potential. Thus, an ion of zero energy incident on a surface
sees an impenetrable wall of touching spheres. At a higher ion energy, the atomic
radii decrease, so the interstices look wider. At some energy, the ion can pass
through an interstice and so penetrate the surface layer.

16
CHAPTER TWO : THEORETICAL PART ​

2.10 Advantages of PACVD

PACVD has many advantages, including:

1-Subsequent treatment is not required
2-It can be deposited on a wide range of substrate
3-No distortion occurs on a high-resolution substrate
4-Uses an invasive process that allows for a uniform coating

2.11 DLC Coating Characteristics

Solids consisting primarily of carbon possess excellent mechanical
properties. These properties displayed by DLC coatings include:
1-mechanical properties
2-Low coefficient of friction
3-Corrosion resistance
4-electrical properties
5-Surface properties of DLC coating

17
CHAPTER TWO : THEORETICAL PART ​

2.12 Application of DCL Coating

Applications of diamond-like carbon coatings is the physical and mechanical

properties of DLC films make them suitable for a variety of applications, many of
them exploiting the attractive tribologicalcharacteristics of DLC. The DLC coatings
used in industrial applications can be divided into two major categories, namely
undoped single-layer DLC films and DLC films with the addition of other elements.
The former are used when contact pressures are relatively low, shear stresses are
low and/or heat generation is minor. Some examples of such applications are found
in knives used in the textile industry to cut through many layers of synthetic fibre,
and dies used in the extrusion of polystyrene in the packing industry. For high shear
stress applications, DLC coatings with interfacial bonding layers and alloyed or
layered coating structures are typically used. Such applications range from gears for
aircraft landing-flap controls, ball bearing races or cages, journal bearings,
compressor screws, and extrusion dies in cutting tools for aluminium[Matthews &
Eskildsen 1994]. In addition, a number of moving parts inside automobile engines
and, for example, diesel engine injection systems, have been coated and wear rates
have been successfully reduced [Bloyse 2000]. DLC coatings have also been used as
anti- reflection coatings on germanium and silicon optics and solar cells or for the
protective coating on zinc sulphide IR windows. The scratching resistance of metal
objects has been improved by DLC coatings. DLC has been proposed for biomedical
applications, such as orthopaedic pins and screws and for bearing surfaces of
artificial joints [Lettington 1998]. One widely used application for DLC coatings is the
protection of the hard disc drives and other magnetic recording media [Talke, 2000].
The softer DLC films are mostly used for components, whereas hard DLC films are
widely used as tool coatings [Grischke et al. 2000].

18
CHAPTER 3
Experimental Work
CHAPTER THREE : EXPERIMENTAL WORK ​

3.1 Introduction

This chapter explains the experimental methodologies for preparation of Co-Cr-Mo

alloy to coating by PACVD and characterization of coating sample then tested by
corrosion test to identify the corrosion behavior for coated samples and comparison
with uncoated.

3.2 Materials
Co-Cr-Mo alloy has the chemical composition (64.8%Co, 28.5%Cr, 5.0Mo, 0.5Mn and
0.4C) EDS was showed in Fig 3.1. This test has been done in (Department of Applied
Sciences - University of Technology).

FIG 3.1 EDS OF CO-CR-MO ALLOY.

19
CHAPTER THREE : EXPERIMENTAL WORK ​

3.3 Sample preparation

Preparation samples firstly done by Three types of surface grinding (400, 600 and
800) grit SIC grind were used by using emery papers to obtain the best surface rough
to enhance the bonding with substrate. Then some of the samples polished by
clothe and using diamond paste for final finishing and to obtain smooth surface. All
the samples are cleaning by ultrasonic for 15 min in acetone and , then all samples
were leaved to dry at room temperature before depositing..

3.4 Coating Phase

After preparation of samples, placed in the PACVD chamber. The chamber of PACVD
which have cooled copper plates substrate holder and electrodes. The chamber
evacuated for sufficient pressure. Deposition parameters are summarized in Table 2.
Ethylene (H2C4) carbon-carrying gas is introduced into the chamber during the
coating stage of the process. The gas introduced into the chamber is the source of
the amorphous carbon DLC coating. This carbon-carrying gas introduced into the
chamber is then ionized by the auxiliary anodes.
This then undergoes what is known as the cracking or separation of hydrogen and
carbon in the gas. There is an application of an electric charge on the carousel that
pulls ionized hydrogen and carbon atoms into the gas.

20
CHAPTER THREE : EXPERIMENTAL WORK ​

3.5 Optical microscopy

Optical microscopy is important to ensure that a sample can be viewed as clearly as

possible and used for characterizing the coating morphology and measuring
thickness coating layer. This will provide information about its microscopic
appearance.
This test was done in the department of engineering production and metallurgy
with type (MTM-1A). The microstructure and cross section of all samples were
performed and tested by the same microscope to characterize morphology layers in
addition to measure thickness of layers.

3.6 Roughness Measurement

Optical microscopy is important to ensure that a sample can be viewed as clearly as

possible and used for characterizing the coating morphology and measuring
thickness coating layer. This will provide information about its microscopic
appearance. This test was done in the department of engineering production and
metallurgy with type (MTM-1A). The microstructure and cross section of all samples
were performed and tested by the same microscope to characterize morphology
layers in addition to measure thickness of layers.

3.7 Microhardness Measurements

Optical microscopy is important to ensure that a sample can be viewed as clearly as
possible and used for characterizing the coating morphology and measuring
thickness coating layer. This will provide information about its microscopic
appearance. This test was done in the department of engineering production and
metallurgy with type (MTM-1A). The microstructure and cross section of all samples
were performed and tested by the same microscope to characterize morphology
layers in addition to measure thickness of layers.

21
CHAPTER THREE : EXPERIMENTAL WORK ​

3.8 Corrosion tests

The corrosion resistance of samples with (10 x 10x) mm, for both coated and un
coated in somebody fluid ( SBF ) solution. Prepared the SBF solution at 25ºC by
adding the chemical compounds with the specific concentration for each compound
that are given in Tables 3.3 in 1 liter of distilled water and then the solutions were
stirred by means of magnetic stirrer for 30 min. The investigated potential range
was adjusted to be from -1000 mV to +1500 mV. The complementation of test was
done in (department of engineering production and metallurgy) by using a
potentiostat type (WENKING M, LAB.), Advanced Electrochemical System, made in
German. The measurement of the corrosion current density ( i corr ) and corrosion
potential ( E corr ) was done by analyzing the data values (current-voltage) using
potentiostat software.

22
CHAPTER 4
Results and Discussion
CHAPTER FOUR : RESULTS AND DISCUSSION

4.1 Optical Microstructure

Figure 4.1 shows the optical microstructure for coating sample. Its show that the
coating layer have smooth and uniform distribution without any crack or pores. The
thickness measured at cross section founded about 165 ±5 µm

4.2 Roughness Measurement

Roughness Measurement result of both DLC coating and un-coating samples are
0.524 and 2.8 µm respectively. That indicate the deposition of DLC reduce the
rroughness due to the mechanism of the DLC deposition. Were the fine atomic layer
of DLC increase the surface properties.

4.3 Hardness results

Results of hardness test indicate the increasing of hardness with coating more than
2 time of the as its sample. The hardness of coating samples is 1130 Hv, while in
substate was about 410 Hv. That increasing of hardness due to nature of coating.
DLC coating have high hardness near to diamond further called like diamond.

23
CHAPTER FOUR : RESULTS AND DISCUSSION

4.4 Corrosion tests results

The polarization curves regarding Co-Cr-Mo alloy with and without coatings in the
SBF’ solution at 37 °C shown in figure 4.2

The un coating sample results the Ecorr 1586 mV with icorr current density of
corrosion is 206.9A/cm2,while the both the Ecorr and icorr for coating samples are
1389 mV , and 2.6 A/cm2respectively. From data above indicated the increasing of
corrosion resistance more than 100 times. That increasing of resistance due to the
DLC coating acts as a barrier coating with ceramic nature coating increase the
resistivity on materials and the nature of smooth layer as shown in both
microscopic and roughness test without any cracks or pores prevent penetration of
the SBF solution to CO-Cr-Mo alloy surface.

24
CHAPTER 5
Conclusions and
recommendations
CHAPTER FIVE : CONCLUSIONS AND RECCOMMENDARION

5.1 Conclusions recommendations

From the result that explained in results chapter. The following Conclusions can
summarized:
1. Plasma assisted CVD technique (PACVD) is useful method for Coatings of Co-Cr-Mo
alloy by using Ethylene (H2C4) carbon-carrying gas.
2. The surface of coating layer smooth and uniform distribution without any crack or
pores. The thickness measured at cross section founded about 165 ±5 µm.
3. Roughness of both DLC coating and un-coating samples are 0.524 and 2.8 µm
respectively.
4. Increasing of hardness with coating more than 2 time of the as its sample. The
hardness of coating samples is 1130 Hv, while in substate was about 410 Hv.
5. The increasing of corrosion resistance more than 100 times. uncoating sample
results the Ecorr 1586 mV with icorr current density of corrosion is 206.9 A/cm2,while
the both the Ecorr and icorr for coating samples are 1389 mV , and 2.6 A/cm2
respectively.

5.2 Recommendations

1. Using another types of carrying gas such as CH4 and comparing the result with our
result.
2. Study the tribological behavior such as wear test with dry and wet types.

25
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