EVALUATION OF MECHANICAL, WEAR AND

CORROSION PROPERTIES OF MICROCRYSTALLINE

COATING ON TITANIUM ALLOY OT4-1

Chandrappa Ka, Anoop Joshib*, Anush Cc, Likith B Kongd

a
Associate Professor, Siddaganga Institute of Technology, Tumakuru, Karnataka,
India
b,c,d
Undergraduate research scholar, Siddaganga Institute of Technology, Tumakuru,
Karnataka, India

*
[email protected]

Abstract. Thin-film barrier coating on titanium alloy substrate has a vast range of applications
among which aeronautic and marine applications are significant. Talking about 2 very different
aspects, whose requirements and applications are way apart. Titanium has always been
beneficial in both these products’ applications. The introduction of titanium in aerospace and
marine locomotive parts will have significant importance on parameters like pressure
withstanding capacity and corrosion resistance. Four different specimens of OT4-1 Titanium
alloy will be coated with Titanium Nitrate (TiN), Aluminium Chromium Nitride (AlCrNa pro),
Diamond-like Carbon (DLC), and Tungsten Carbide Carbon (WCC). All the above mentioned
are coated for 4 µm over the substrate. TiN and AlCrNa pro coatings are carried out in the Arc
evaporation method, DLC coating was conducted using Plasma-assisted Chemical Vapour
deposition and WCC coating was performed using sputtering process. Here an attempt has been
made to improve Hardness, Wear and Corrosion by introducing a thin film coating on the base
metal OT4-1.

Keywords. Titanium Alloy, Microhardness, Pin-on-disc Wear, Electro-chemical Corrosion,

Physical Vapor Deposition, Sputtering

1. Introduction

Titanium amalgams, because of their fantastic blend of low thickness, high solidarity to weight
proportion, great erosion obstruction and biocompatibility, are generally utilized in the aviation, auto,
compound and biomedical ventures [1-3]. Titanium has a density of roughly 4.5 g/cm3, which is higher
than that of other light metals of structural importance such as aluminium or magnesium but nearly half
that of steels. Titanium also possesses good mechanical resistance to yield and fracture, an elastic
modulus of roughly 115 GPa, and excellent corrosion resistance.
Titanium also has exceptionally low thermal conductivity and thermal expansion coefficients, about 22
W/mK and 84 * 10-6/c, which are nearly one order of magnitude and 1/3 of those of aluminium,
respectively.
In terms of crystalline structure, titanium allows for an allotropic transformation in which the crystal
lattice transitions from a compact hexagonal (CH) structure at room temperature to a body-centred cubic
(BCC) structure at temperatures that are highly dependent on the alloy's specific chemical composition.
In the case of pure titanium, the compact hexagonal crystalline structure (or phase) is often maintained
up to 882°C, a temperature that is generally accorded the β-transus (Fig. 2). At higher temperatures, the
stable structure is a body-centred cubic (phase) structure that can be maintained up to 1670°C, the
melting point of pure titanium.

Fig. 1 Allotropic transformation in commercially pure titanium

The following are the key qualities of commercial titanium alloys:

• The elastic modulus that increases with the concentration of interstitial elements (C, N, O, and
H) and aluminum, but can also decrease when -stabilizers are added.
• Hardness that rises with the presence of -stabilizing substances (some alloys, as will be
explained in more detail below, can be hardened by means of a thermal solubilization treatment
with subsequent aging).
• Maximum creep resistance of 0.6 Tf (Tf is the melting temperature expressed in Kelvin
degrees).
• Titanium alloys have a high resistance to specific mechanical fatigue (fatigue limit relative to
density), which is superior to any other metal alloy with the same mechanical strength.

Table. 1 Properties of Commercially available Pure Titanium (theoretical)

Molecular Weight 47.86
Appearance Slivery
Melting Point 1668o c
Boiling Point 3560o c
Density 4.54 g/cm3
Crystal Phase/ Structure Hexagonal
Poisson’s Ratio 0.32
Specific Heat 0.125 Cal/g/K @ 25o c
Tensile Strength 140 MPa
Thermal Conductivity 21.9 W/(m-K) @ 298.2 K
Youngs Modulus 116 GPa
 1.1. Type of Titanium Alloys

Aircraft titanium alloys are classified into three kinds based on phase composition: mixed (+), and Ti-
8Al-1Mo-1V [4], Ti-6Al-2Zr-1Mo-1V [8], and so on. It primarily contains elements such as Al, which
can increase the tensile strength and creep stress of the alloy, reduce the density of titanium alloy, and
improve the specific strength; [9] examples include Ti-6Al-6V-2Sn, Ti-6Al-2Sn-2Cr-2Mo-2Cr-Si, and
Ti-6Al-2Sn-2Cr-2Mo-2Cr-2Mo-2Cr-2Mo-2Cr-2Mo-2Cr-2Mo-2C It has a high enough stable element
content to be the primary structural material for airframes and wings; (+) examples are Ti-6Al-4V, Ti-
6Al-2Sn-4Zr-6 Mo[10], and others. Titanium Alloys are utilized in the Boeing 787 for 15%, the SU-57
for 18%, the J-20 for 20%, the FC-31 fighters for 25%, the B-2 for 26%, the F35 for about 27%, and
the F22 for up to 41%, among other applications [4, 5].
Titanium and its alloys are a driving force at the technological edge. Titanium synthesis with other
materials to generate composites has been investigated for mechanical behavior involving parameters
such as fracture strength and its connection to alloy interface, yield strength, tensile moduli, reaction to
para and ortho load applications, and load transformation. The reported results were so encouraging
that it prompted other explorations into the realm of composites incorporating dispersions of TiO2 and
other material particles with cast alloys.

1.2. Introduction to Titanium Wrought alloy OT4-1

At room temperature, the OT4-1 composition lies in two phases of the region in the Ti-Al-Mn phase
diagram, and there is a strong partitioning of Al to the phase and Mn to the phase in the OT4-1 alloy,
which stabilizes a small amount of phase in the microstructure, resulting in improved workability and
strength. The evaporation of volatile substances from molten metal causes pressure buildup at the melt
surface.
The strength of the OT4-1 alloys is nearly constant up to 2% and increases as the proportion of
aluminum increases. Tensile characteristics at various annealing temperatures reveal a small loss in
strength when annealed at 610°C and 690°C. The strength of the alloy which is controlled by grain size
shows a linear relation with yield strength.

OT4-1 is a titanium composite utilized for high-temperature applications in the aeronautic trade. These
materials are widely utilized in process enterprises, paper, and material plants, extractive metallurgy,
the oil business, clinical sciences, and designing parts like steam and gas turbine sharp edges,
associating bars driving rods, and so on. Thus, assessing its mechanical properties after coating the
surface with different materials is very fundamental. In this way, concentrating on formability aspects
is valuable further. The rising utilization of titanium composites in load-bearing components causes a
requirement for examination into their solidarity qualities. [44]
The chemical composition of the alloy OT 4-1 (Ti-Al-Mn system) is as follows (in weight percent): Al,
1.0 - 2.5; Mn, 0.7 - 2.5. The impurity concentration shall not exceed (weight percent) C, 0.10. [39]
Table 2 shows the composition of the sheet.
Table 2: Chemical Composition of OT4-1

Fe C Si Mn N Ti Al Zr O H Impurity

max 0.3 max 0.1 max 0.12 0.7 max 0.05 94.33 - 1.5 - max 0.3 max 0.15 max 0.012 other 0.3
-2 97.5 2.5
2. Experiment

2.1. Materials and Methodology

The equivalent of Japanese ST-A90 titanium is the titanium alloy OT4-1 (Ti-Al-Mn). Its chemical
make-up is shown in Table 1 for your study. This substance, which is often utilized in the aerospace
sector, is thought to be superplastic between 800-900 C [19]. Special metals and alloys that can survive
high temperatures, resist corrosion, and have a high strength to weight ratio are in great demand today.
[1,9] The aerospace industry uses the titanium alloy OT 4-1 for high-temperature applications. These
materials are widely utilized in the processing industry, in paper and textile factories, in extractive
metallurgy, in the oil business, in the medical field, and in some engineered parts including crankshafts,
connecting rods, and steam and gas turbine blades.
A low alloy titanium alloy with high ductility and low strength is OT 4-1. The alloy, which is based on
the Ti-Al-Mn system [7], is primarily designed for sheet semi-products, including structural goods, as
well as forgings, stampings, rods, forms, pipes, wire, and other semi-products. [3-6]
The 1mm OT 4-1 sheet was received in the cool rolled and strengthened condition. The piece of the
plates was affirmed by the Inductive coupled plasma optical spectrometer strategy and viewed as
Russian Grade Titanium amalgam OT4-1. The elements of the Inductive coupled plasma optical
spectrometer were:
• Multi-element, a sequential technique with wavelength range: 190-750 NM
• The Plasma produced by the electrode radio frequency discharge.
• A High-resolution grating with RF source.
• It can produce a very high temperature up to 10,000o K.
• The Capability of analysis from ppm to percentage level.

By using the deformation process, alloy OT4-1 is used to manufacture semi-finished products (sheets,
strips, foils, plates, bars, rod, profiles, tubes, forgings and forged blanks), as well as ingots.
Longitudinally welded pipes for industrial pipelines, operating at conventional pressure PN (Pu) not
exceeding 10 MPa and temperature not exceeding 400oc. The alloy OT4-1 is used for the manufacture
of aircraft parts such as wing panels, flaps, and inner wing kits when it is in the annealed condition.
It is frequently necessary to alter the surface characteristics of titanium alloy products, for example, to
enhance the alloy's solderability or change the product's look. The PVD process of depositing metals
and alloys is one way to improve surface characteristics. The process of creating the product is greatly
complicated by the hard oxide coating that covers the surface of titanium and its alloys.

2.2. Processing Techniques

Physical Vapour Deposition is the general methodology used in coating the substrates. It is a process
that takes place under high vacuum and, in most situations, at temperatures ranging from 150 to 500
°C. In the PVD process, the high purity solid coating material (metals such as titanium, chromium, and
aluminum) is either heated to a high temperature or blasted with ions (sputtering). A reactive gas is also
injected at this time, such as a gas containing carbon or nitrogen, and it reacts with the metal vapour to
generate a coating that is thin and very sticky and is then deposited on the substrate. By rotating the
components along numerous axes at a steady speed, a homogeneous coating thickness may be achieved.
It is possible to carefully adjust coating qualities, including hardness, structure, chemical and
temperature resistance, and adhesion.
Arc evaporation, Sputtering, Ion plating, and Enhanced Sputtering are examples of PVD techniques.
 2.2.1. Arc Evaporation

In this procedure, the solid, metallic coating material is swept over by an arc with a diameter
ranging from microns to only a few tenths of a micron, which causes it to evaporate. The nearly
full ionization of the evaporated material as a result of the high current and power densities
utilized results in the creation of a high-energy plasma.
When metal ions combine with a reactive gas injected into the chamber, they deposit as a thin,
extremely adherent coating on the target tools or components.

1. Argon
2. Reactive Gas
3. Arc Sources (coating material
and backing plate)
4. Substrate
5. Vacuum pump

Fig. 2 Arc Evaporation Process

Titanium Nitride (TiN) and Aluminum Chromium Nitride (AlCroNa Pro) coating was carried out using
Arc Evaporation method. TiN coating specification are listed in the table 3 and AlCroNa Pro
specification are mentioned in the table 4.

Table. 3 Arc Evaporation specification for Titanium Nitride coating

Coating Material TiN

Coating color gold-yellow
Coating Hardness HIT [GPa] 30 +/- 3
Coefficient of friction (dry) vs. steel ~ 0.6
Intrinsic stress [GPa] -2 +/- 1
Max. service temp [oC] 600
Process Temperature [oC] < 500

Table. 4 Arc Evaporation specification of AlCroNa pro coating

 Coating Material AlCrN-based
Coating color Bright grey
Coating Hardness HIT [GPa] 36 +/- 3
Coefficient of friction (dry) vs. steel ~ 0.6
Intrinsic stress [GPa] -3 +/- 1
Max. service temp [oC] 1100
Process Temperature [oC] < 500

2.2.2. Plasma Assisted Chemical Vapour Deposition (PACVD)

This process produces metal-free carbon coatings using high frequency electric voltage. This
procedure's setup is comparable to that of sputtering, which is usually combined with CVD.
In PACVD, the vacuum chamber is filled with a gas containing the coating components, and
an AC voltage-powered discharge is then ignited.
As a result, the tools and components are coated in a thick layer of free carbon and hydrogen
atoms (ions and radicals). The applied voltage can be changed to affect the coating's qualities.
Diamond like Carbon coating was carried out through PACVD method. Table 5 mentions the
specification of the DLC coating.

1. Argon
2. Reactive gas
3. Substrate
4. Planar magnetron
evaporation source
(Coating Material)
5. High-frequency connection
6. Vacuum pump

Fig. 3 PACVD process of Diamond like Carbon coating

 Table. 5 PACVD coating specification of DLC coating

Coating Material a-C:H

Coating Colour Black
Coating Hardness HIT [GPa] ~ 15-25
Coefficient of friction (dry) vs. steel 0.1-0.2
Max service temp [oC] 300
Process temperature [oC] < 250

2.2.3. Sputtering
The material that will be coated in the sputtering process is heated first and then ion etched by being
attacked with argon ions in the vacuum chamber. This results in a pure and clean metal surface devoid
of atomic contamination, which is required for the optimal coating adhesion.
The coating material-containing sputtering sources are then subjected to a strong negative voltage.
Positive argon ions are created as a result of the electrical gas discharge and are driven toward the
coated material, where they atomize it. The hard coating's non-metallic component is subsequently
reacted with vaporized, atomized metal in a gaseous phase.
In the end, a thin, compact covering with the correct structure and composition is deposited. Tungsten
Carbide Carbon coating was carried out using Sputtering method. Table 6 depicts mentions the
specification of WCC coating.

1. Argon
2. Reactive gas
3. Planar magnetron evaporation
source (coating material)
4. Substrate
5. Vacuum pump

Fig. 4 Sputtering Process for Tungsten Carbide coating

 Table. 6 Sputtering coating specification for WCC

Coating Material a-C:H:Me (WC/C)

Coating Colour Anthracite

Coating hardness HIT [GPa] 10 – 15

Coefficient of friction (dry) vs. steel 0.1 – 0.2

Max. service temp [oC] 300

Process Temperature [oC] < 250

2.3. Testing Methods

Mechanical testing, thermal testing, electrical testing, corrosion, radiation, and biological degradation
testing, and nondestructive testing are the five major subcategories of materials testing. Mechanical
testing is performed to determine a material's mechanical characteristics as it functions in a specific
environment. Microhardness is the mechanical test that was conducted to find out the hardness of the
materials before and after coating. Corrosion testing assesses a material's corrosion resistance under a
variety of environmental variables such as temperature, humidity, and salt water. The procedure used
to assess the corrosion resistance of the substrates before and after coating was Electrochemical
Corrosion resistance test. The outcome of a wear test is acquired from deformation, scratches, and
indentations on the interacting surfaces. The wear test measures the changes in conditions caused by
friction. The wear testing approach utilized to assess the wear rate of the titanium alloy before and after
coating is pin-on-disc.

2.3.1. Microstructure
Materials' characteristics, which in turn impact their viability for various purposes, can be significantly
influenced by their microstructure. In any engineering design, choosing and using the right materials is
essential to assuring the quality and safety of your project. Hitachi SU1500 Scanning Electron
Microscope was used to analysis the microstructural properties of the titanium alloy OT4-1 before and
after coating.
2.3.2. Microhardness
When a consistent compressive force is applied, a solid material's hardness may be calculated as a
measure of its resistance to permanently changing form. Different methods, such as indentation,
scraping, cutting, mechanical wear, or bending, might cause the distortion. Since strength, ductility, and
fatigue resistance are all mechanical qualities that are closely related to hardness, hardness testing is a
straightforward, quick, and reasonably priced way to check the quality of a material.
Vickers Hardness method is used to calculate the hardness of the coated and uncoated specimens. A
pyramid-shaped diamond indenter creates an imprint under load that is measured as part of the Vickers
hardness test. The indenter is a square-based pyramid with faces at 68o, edges at 148o, and opposing
sides that meet at an angle of 136o at the top.
The Vickers diamond hardness number, HV, is calculated using the actual surface area of the imprint
Ac and the indenter load L.

HV = L/Ac = (2L/d2) sin(136o/2) = 1.8544 (L/d2),

where L is measured in kgf and d (mm) is the diagonal length measured from corner to corner on the
remaining impression in the specimen surface. To measure the size of the impression, which is
normally no greater than 0.5 mm, a calibrated microscope with a tolerance of 1/1000 mm is
employed. Vickers hardness is indicated as HV, and the units are commonly stated as kgf/mm2 or
MPa (the value in kgf/mm2 multiplied by 9.8065).

2.3.3. Wear Test

Wear is a process of surface contact that results in material loss and surface deformation as a result of
mechanical action between the sliding sides. Wear can also refer to the plastic deformation's dimension
loss. The results of a wear test, on the other hand, are derived from deformation, scratches, and
indentations on the interacting surfaces, and they quantify the changes in circumstances brought on by
friction.

Fig. 5 Pin on disc machine (DUCOM – TR 20-LE)

Pin on disk machine (DUCOM – TR 20-LE) as shown in the Fig. 5 was used to forecast the wear and
friction behavior of the coated and uncoated Titanium Alloy samples OT4-1. The most common wear
test procedures, according to research by Glaeser and Ruff, were pin-on-disc and pin-on-flat. Additional
applications include material wear and friction of pin-on-disc, characteristics at high temperatures and
under regulated the atmospheres. This testing procedure is pretty typical to apply thin coats. As per
ASTM G99 guidelines, the tests were carried out at room temperature in an unlubricated setting. The
parameters of the exam comprised, Load - Force values in Newtons at the worn contact; Speed - The
relative sliding speed between the contacting surfaces expressed in meters per second or revolutions per
minute. Time - The amount of time that the load is delivered on the specimen while the disc rotates at
the sliding speed.

2.3.4. Corrosion Test

Corrosion is an unwelcome phenomenon that results in the destruction or deterioration of materials,
having detrimental effects such as the closing of a plant, pollution from pipeline breaks, negative effects
on the environment and human health, loss of productivity and products, tainted products from metal
leaching, etc.
For a successful coating, proper coating application, including substrate preparation, is essential, and
corrosion testing offers a quick way to assess how well your process is working. In conditions with high
relative humidity, water can permeate coatings, causing blistering below as the substrate corrodes.
Additionally, coatings can sustain degradation that causes filiform corrosion, the coating to separate
totally from the substrate, or a combination of these.
2.3.4.1. Potentiodynamic Polarization Test
One of the most extensively used methods for gauging specimen corrosion is the potentio-dynamic
polarization test. Between the working electrode and the reference electrode, the potential difference is
measured. The two electrodes are subjected to a difference, and the current generated is measured.
Pitting corrosion behavior is investigated using polarisation curves derived from the electrochemical
system of a Gill AC unit used for corrosion testing. The basic electrochemical system with
electrochemical fat cell employed in this investigation is depicted in Figure 6. Programs to assess
corrosion kinetic parameters like Icorr, Ecorr, ba and bc, where ba and bc are the anodic and cathodic
slope of the polarization curve, are included into this instrument itself.

Fig. 6 Electrochemical Cell of GILL AC unit

3. Results and discussion

3.1. Microstructure

Microstructure analysis is conducted to check the coatings’ bonding strength with the base metal, to
check for appearance of pores and uniformity of the coating on the material. By this, the coating
methodology can be decided which is perfect for the given application. Magnifications are limited to
low and intermediate magnifications (100x-1000x). Preparation of the samples before coating is also
skipped due to the low thickness of the coating.
Figure 7 depicts the microstructure of a material which is used for further processing of cooling to study
the behavior of mechanical properties. In these SEM images, it is concluded that structure is uniform
with alloying elements of Aluminum and Manganese.

a. b.

Fig. 7 SEM images of polished OT4-1 at (a) x500 and (b) x2500
Figure 8 results obtained after the base material is coated with Titanium Nitrate (TiN) with Arc
Evaporation method of coating with a coating thickness of 4µm. Due to the variability in the spreading
of the coated material on the base substrate, voids have seemed to be visible and overcrowding of the
coated material which results in the non-uniformity of the structure. The analysis of this image indicates
proper controlling of coating and sintering method, for uniformity of coating thickness

a. b.

Fig. 8 SEM images of OT4-1 coated with Titanium Nitrate at (a) x1000 and (b) x200

Referring Fig. 9 SEM images of base substrate coated with AlCroNa Pro indicates improper distribution
of the coated material, with varying thickness of coating, from 1µm to 4µm. Hence there is a variation
in the microhardness value at different zones of the coated surface

a. b.
Fig. 9 SEM images of OT4-1 coated with AlCroNa Pro at (a) x500 and (b) x1000

Figure 10 are the microstructure results of base substrate coated with Diamond like Carbon, indicating
the perfectness of coating thickness and a suitable method for improving the mechanical properties for
many engineering applications such as aerospace, marine, etc. Due to the high frequency current used
during PACVD process of coating, DLC coating showed excellent surface finish which resulted in a
smooth mirror surface. The coating procedure resulted in a smaller number of pores compared to TiN
or AlCroNa Pro coating indicating a successful coating procedure.

a. b.
 Fig. 10 SEM images of OT4-1 coated with DLC at (a) x200 and (b) x500

Figure 11 are the images of base substrate coated with Tungsten Carbide Carbon, which indicates
optimized method for obtaining uniform coating thickness and maintaining uniformity in the structure
and properties. This coated material on the base metal can be considered further studies for facture
analysis and life cycle analysis. Sputtering method of coating resulted in a matte like surface finish with
the least number of pores. The coating material is spread out evenly throughout the material resulting
is excellent bonding of the material to the base substrate.

a. b.

Fig. 11 SEM images of OT4-1 coated with WCC at (a) x200 and (b) x500

3.2. Microhardness

Vickers microhardness method was used to evaluate the hardness values of OT4-1 before and after
coating. The samples were subjected to 100 kgf force for 15 sec using the diamond indenter. The initial
application of force is for 8 sec and then the test force is maintained for 15 sec. The hardness was
sampled at 10 different locations across the metal for an average value of hardness. The measured
hardness number is indicated as HV, which is Vickers hardness number. This can be converted to MPa
by multiplying the number by 9.8065.
The base metal OT4-1 showed average hardness values of 334.35 HV or 3278.98 MPa without
annealing at room temperature. Titanium nitrate coating on the base metal OT4-1 increased its hardness
by 1.5 times with average hardness number of 500.72 HV or 4910.57 MPa. The hardness values of the
base metal OT4-1 and OT4-1 after TiN coating is shown in the Figure 12. X-axis shows 10 different
readings across the sample and Y-axis shows hardness value in MPa.

Fig. 12 Microhardness comparison of OT4-1 and OT4-1 after Titanium Nitrate coating
AlCroNa Pro coating showed steady values of 875.7 HV or 8588.07 MPa with a maximum hardness
value of 9288.40 MPa. The peak value is due to the presence of Aluminum with covers 29.5 % weight
of the coating. Figure 13 shows the graph comparing the hardness values of OT4-1 and AlCroNa Pro
coated OT4-1.

Fig. 13 Microhardness comparison of OT4-1 and OT4-1 after AlCroNa Pro coating

Carbon based coating i.e., Diamond-like-Carbon and Tungsten carbide Carbon coating showed average
values of 16140.28 MPa and 17086.02 MPa respectively. The hardness values have increased by 5.1 to
5.6 times the base metal OT4-1. But DLC coating showed irregular values ranging from 15367.56 MPa
till 18540.13 MPa. WCC coating on the other hand shows stable values of microhardness. Figure 14
shows the microhardness values of DLC coating compared with OT4-1 and Figure 15 depicts the
microhardness values of WCC coating and OT4-1.

Fig. 14 Microhardness comparison of OT4-1 and OT4-1 after DLC coating

As it is clear Tungsten carbide carbo coating showed the highest hardness value compared to the other
coatings. The reason behind this is based on how tungsten carbide is manufactured. Ball mills are used
to combine powdered tungsten carbide and cobalt, and a binder ingredient is added to keep the powders
together throughout the next stage of the process, which is compaction or pressing. During the
compaction operations, hydraulic presses or isostatic presses are used to compact the powders into a
shape that approximates the design of the finished product. Ordinary metalworking equipment may now
be used to machine the powder compact. This is referred to as "Green Machining" at times. Fine powder
particles must be removed with attention since they may pose a health concern; thus, effective extraction
processes are required. After "Green Machining," the powder compact is ready to be sintered. Typically,
this is done in a vacuum furnace at temperatures ranging from 1300 to 1600°C. During the sintering
process, the tungsten carbide and cobalt matrix fuse together, resulting in a dense "Hard Metal". The
material is so hard after sintering that it can only be machined by diamond grinding, a specialized kind
of micro machining that is somewhat costly since it cannot remove huge amounts of material.

Fig. 15 Microhardness comparison of OT4-1 and OT4-1 after WCC coating

Furthermore, WC particles operate as internal balls that refine grain; therefore, hardness values are
raised by increasing WC % owing to grain refinement, according to the Hall-Petch equation, which
stipulates that particle size reduction improves hardness. Furthermore, the generated Cr-carbide phases
improve toughness.

3.3. Wear Rate

This section examines the wear characteristics of OT4-1 samples before and after coating when exposed
to a 25 N load against a stainless-steel disc. The wear rate of the samples was determined using a pin
on disc wear testing system supplied by DUCOM Instruments, Bangalore and purchased using funds
from the Research Laboratory Upgradation Fund. The spinning hardened steel disc of 40 cm diameter,
0.11 µm surface roughness, and hardness of 840 HV is used in the pin on disc wear testing equipment
(Figure 5).
The samples were loaded on the horizontal arm of the apparatus under a load of 2.5 kg which is
approximately 25 N. The machine was controlled to run the test for 10 minutes per sample with the disc
rotating at a speed of 500 rpm. The results were in the form of graph with amount of Wear in micrometer
at the X-axis and different data points in the Y-axis.
The equation W = M/ ρD is utilized in this research to compute the wear rate (mm3/m) of the samples
based on the mass loss measurements acquired during the wear test. M is the mass loss in g, ρ is the
sample density in g/cc, and D is the sliding distance in m. It was feasible to quantify the weight reduction
of the pins by comparing the weight of the worn pins before and after the trials using an electronic scale
with 0.01 mg accuracy. Before each experiment, the steel disc surface was carefully cleaned with
acetone.
 Table. 7 Weights of the sample before and after the wear test.
Weight before wear Weight after wear Difference in
Sample name
test (g) test (g) weight (g)
OT4-1 1.9476 1.848 0.0996
TiN coating OT4-1 2.6 2.555 0.045
AlCroNa Pro coated OT4-1 2.676 2.639 0.037
DLC coated OT4-1 2.56 2.522 0.038
WCC coated OT4-1 2.710 2.686 0.024

Volume of the sample need to be evaluated in 2 steps, below figure 16 shows the sketch of the sample
used for the wear test. The volume should be calculated for the first rectangle on top then the volume
should be calculated for the rectangle below. Volume can be calculated by the formula, V=l × b × h,
where l is the length in cm, b is the breath in cm and h is the height in cm (0.1 cm).

Fig. 16 Dimensions of the samples used

Volume of the first rectangle will be -

V1 = l × b × h
V1 = 1 × 0.8 × 0.1
V1 = 0.08 cm3
Volume of the remaining part of the sample will be –
V2 = l × b × h
V2 = 2 × 2 × 0.1
V2 = 0.4 cm3
Total Volume of the sample will be the sum of the volumes of the individual parts –
Total Volume = V1 + V2
V = 0.08 + 0.4
V= 0.48 cm3
To calculate the density of the sample, we use the formula ρ = M/V, where M is the initial mass of the
samples and V is the volume of the sample. Table 8 shows the densities of the different samples
calculated using their initial weight.

Table. 8 Densities of the different samples used in wear test

Sample Density (g/cc)
OT4-1 4.0575
TiN coated OT4-1 5.416
AlCroNa Pro coated OT4-1 5.575
DLC coated OT4-1 5.3458
WCC coated OT4-1 5.6458

To calculate the sliding distance can be calculated using the formula D = πdN/1000, where d is the
length of the specimen in contact with the disc in cm, N is the load applied on the pin in N. The load
applied on the pin was standard throughout the experiment, 25 N. The length of the sample that was in
contact with the disc in 2cm.
Therefore, D = πdN/1000
D = π × 2 × 25/ 1000
D = 0.15707 cm
Now, to calculate wear rate, we have all the variables, i.e., weight lost in g, Density in g/cc and Sliding
distance. Applying the variables to the equation W = M/ρD, we get the wear rate of the specific samples
in mm3/m.
Table. 9 Wear rate observed in different specimens
Sample Wear rate (mm3/m)
OT4-1 0.15635
TiN coated OT4-1 0.05292
AlCroNa Pro coated OT4-1 0.04227
DLC coated OT4-1 0.04527
WCC coated OT4-1 0.02707

By examining the wear rate of the samples obtained in Table 9, it appears that Archard's law was broken,
which stipulates that the hardness of the material is one of the most significant elements of the wear
rate [44]. The wear volume may be calculated using the Archard equation W = k × Wn × s/H, however
one issue is the hardness H of the softer material at the sliding interface. Because wear at the
boundary/mixed or hydrodynamic regime only occurs in the few microns range, this hardness is difficult
to quantify, because bulk hardness is involved utilizing Vickers and Rockwell techniques, and the top
surface generally experiences strain hardening while sliding.
Following images show a comparison graph of wear in the coated and uncoated samples of OT4-1.
 OT4-1

TiN + OT4-1

Fig. 17 Wear of uncoated OT4-1 and TiN coated OT4-1

Fig. 18 Wear of uncoated OT4-1 and AlCroNa Pro coated OT4-1

Fig. 19 Wear of uncoated OT4-1 and DLC coated OT4-1

 Fig. 20 Wear of uncoated OT4-1 and WCC coated OT4-1

When the wear losses of samples are compared, it is discovered that the losses in coated specimens are
fewer than those in uncoated specimens. DLC coating has the lowest surface roughness of the coatings.
The major source of this outcome is the change in gas fluxes during the coating process. When the
acquired results are compared, the order of the samples' average surface roughness values is TiN >DLC
> AlCroNa Pro > WCC. The wear widths on the samples were found to be uniform and almost parallel
to each other. As a result, the wear rate of the wear track is used to calculate the amount of wear in the
specimens.
The friction force in the WCC and AlCroNa pro coating is 5.3 N which is almost 1.5 times lesser than
the uncoated sample, 6.8 N. This result aligns with the results we obtained above.

3.4. Corrosion Resistance

Using the electrochemical workstation, Gill AC with ACM instrument version 5 software, the
electrochemical measurements were performed in a non-stirred environment without aerating the
solutions. The moulded test coupon was used as the working electrode, the platinum electrode served
as an auxiliary electrode, and the saturated calomel electrode served as the reference electrode in a
typical three electrode cell. Test coupon was exposed to potentio-dynamic polarisation tests without
any surface treatment.
The medium in which the test conducted was 3.5 % NaCl solution. The usual salt content of sea water
is 3.5 %. Since NaCl is the most prevalent and prolific corrosive chemical on earth. Additionally, the
0.6 molar NaCl solution is recognized by ASTM standard. The weight percentage of a 0.6 molar
solution is again 3.5 %.
The specimen was polarised to -300 mV catholically and +1000 mV anodically with respect to the OCP
at a scan rate of 21.6727 mV/min to capture the potentio-dynamic current-potential curves. The
specimens were induced in the test for a time period of 60 minutes.
All corrosion investigations must measure OCP since electrochemical methods like EIS work at this
pressure. Potentio-dynamic polarisation is accomplished by drifting the system from its equilibrium
condition. In both situations, OCP fills a crucial function without which the outcomes of
electrochemical analyses would suffer.
Evident shifts in the anodic and cathodic branches occur at lower corrosion current density (Icorr).
Additionally, in comparison to the blank, the corrosion potential (Ecorr) changes to the cathodic side.
To guarantee accuracy, the linear Tafel areas of the cathodic curves were extrapolated to OCP in order
to calculate the corrosion current densities (Icorr), as the anodic branches in NaCl electrolytes do not
show linear Tafel regions [46].
Electrochemical polarization parameters, like Ecorr, Icorr, Icorr(inh), cathodic Tafel slope (-βc)
calculated from the Potentio-dynamic polarization studies in given medium are presented in Table 10.

Table. 10 Polarization data for the corrosion of OT4-1 samples before and after coating in 3.5 % NaCl
solution

Icorr Icorr(inh) -βc

Sample Ecorr (mV)
(µA/cm2) (µA/cm2) (mV/dec)

OT4-1 299.27 0.5589 0.1542 189

TiN coated OT4-1 277.62 0.6435 0.0655 139

AlCroNa Pro coated OT4-1 220.13 1.2686 0.04963 134

DLC coated OT4-1 271.15 3.9875 0.113 137

WCC coated OT4-1 255.23 2.375 0.06021 134

The rate of corrosion V(corr) was calculated using this equation -

V(corr) (mm/year) = K × Icorr × M/ ρ × n ….. (1)
where K denotes corrosion rate and is equal to 0.00327 mm g A-1 cm-1 y-1, establishing the unit of
corrosion rate in millimetres per year. Icorr is the current density in A cm2, is the density of the
corroding specimen, M is the molar mass, and n is the metal's valence.
The inhibition efficiency (η) of NaCl solution was determined as the function of surface coverage (θ)
using this equation –
η (%) = θ × 100 ….. (2)
The surface coverage (θ) is computed using –
θ = Icorr - Icorr(inh) / Icorr ….. (3)
To calculate Molar Mass of the sample, Moles = Mass / RAM (assuming percentage composition).
OT4-1 constitute mainly of Titanium (Ti), Aluminum (Al) and Manganese (Mn). Molar mass of Ti =
47.9 g/mol; Al = 26.98 g/mol; Mn = 54. 94 g/mol.
Percentage of the above-mentioned elements in the alloy are – Ti = 95.5%, Al = 2.5%, Mn = 2%.
Therefore, the masses of the elements are – 95.5 g is Titanium, 2.5 g of Aluminum and 3 g of
Manganese.
By applying the molar mass formula to the above elements, we get –
MM (Ti) = Mass/RAM
 MM (Ti) = 95.5/47.9
MM (Ti) = 1.997 mol
Similarly, MM (Al) = 0.0926 mol and MM (Mn) = 0.0364 mol. Hence the total Molar Mass of the
substrate is –
MM = MM (Ti) + MM (Al) + MM (Mn)
MM = 1.997 + 0.0926 + 0.0364
MM = 2.126 mol
The valency of an element is When an element creates chemical compounds or molecules, its ability to
combine with other atoms is measured by its valence or valency. Valency of Titanium is 4, Valency of
Aluminum is 3 and Valency of Manganese is 7. Hence the total valency of the alloy is –
Valency (n) = V (Ti) + V (Al) + V(Mn)
Valency (n) = 4 + 3 + 7
Valency (n) = 14
Now using equation (1), Corrosion rate can be calculated by substituting all the variables.
Equation (3) depicts the surface coverage (θ) formula, which can be calculated using values in Table
10.
θ = Icorr - Icorr(inh) / Icorr
θ(OT4-1) = 0.5589 – 0.1542 / 0.5589
θ(OT4-1) = 0.4047/0.5589
θ(OT4-1) = 0.7241
Similarly, θ(TiN) = 0.8989, θ(AlCroNa Pro) = 0.9608, θ(DLC) = 0.9716, θ(WCC) = 0.9746. Table 11
shows the corrosion rates and inhibition efficiency of the coated and uncoated samples.

Table. 11 Corrosion rate and Inhibition efficiency of the coated and uncoated substrates in 3.5% NaCl
solution
Corrosion Rate, V(corr)
Sample Inhibition efficiency, η (%)
(mm/year)
OT4-1 5.84 × 10-5 72.41
TiN coated OT4-1 6.90 × 10-4 89.89
AlCroNa Pro coated OT4-1 1.115 × 10-4 96.08
DLC coated OT4-1 3.703 × 10-4 97.16
WCC coated OT4-1 2.113 × 10-4 97.46

Following figures compares the Tofel plot of the uncoated sample of OT4-1 with each of the coatings
on the base metal. The red and grey lines are the results of Uncoated OT4-1 metal and blue, purple
and orange line are the results of coated OT4-1.
 Fig. 21 Potentio-dynamic polarization curves of uncoated OT4-1 and TiN coated OT4-1

Fig. 22 Potentio-dynamic polarization curves of uncoated OT4-1 and AlCroNa Pro coated OT4-1
Fig. 23 Potentio-dynamic polarization curves of uncoated OT4-1 and DLC coated OT4-1

Fig. 24 Potentio-dynamic polarization curves of uncoated OT4-1 and WCC coated OT4-1
Figure 22 depicts the Tafel curves of the OT4-1 with an AlCroNa Pro coating and after an
electrochemical corrosion test. The best corrosion resistance performance was indicated by the sample's
minimum corrosion potential and maximum passive current density at room temperature. The
polarisation curves revealed that Titanium Nitrate coating had the lowest corrosion resistance due to its
lowest corrosion current density and highest corrosion potentials.
As per the earlier examination, the primary part of as-stored AlCroNa Pro coatings was a fcc-(Cr,Al)N
stage, as confirmed by the coatings' plentiful beads and particles. After cooling to room temperature,
the amount of particles that drops on the outer layer of the (Cr,Al)N stage radically decreased as it split
into hcp-AlN and CrN stages. making actual touch with the substrate. hcp-AlN, - FeCr, and minor
amounts of CrN, Cr2N, and Al2O3 stages made up most of these coatings right now. The examples
covered with AlCroNa Pro had the most elevated corrosion resistance since it is notable that the hcp-
AlN, Al2O3, CrN, and Cr2N stages major areas of strength for having obstruction [45].

4. Conclusion

This chapter is the compilation of different mechanical and chemical properties of the Titanium alloy
OT4-1. The coating characteristics have also been studied by coating the samples with Titanium Nitrate,
AlCroNa Pro, Diamond like Carbon, Tungsten Carbide Carbon. The respective coated samples have
been tested out for various tests like Microstructure Analysis, Microhardness, Wear Resistance and
Corrosion Resistance. The project also compares the results obtained from the coated sample and
uncoated sample, comparing them and suggesting a suitable coating methodology and coating material
for different use purposes. The concluded points of the results are as follows-

4.1. Microstructure Analysis

The SEM images captured of the sample are at low to intermediate magnification. Since the coating
layer is just 4 µm, we skipped the sample preparation procedure mentioned according to ASTM E3-11.
After analyzing various images at different zoom length of the specimens It can be concluded that
PACVD and sputtering method of coating provide the best coating solution, when compared to Arc
Evaporation method. TiN and AlCroNa Pro layer were coated on to the base metal using arc evaporating
method. The images show many pores of various sizes on the coating which may lead to many
discrepancies. On the other hand, microstructure of DLC coating and WCC coating, which were
administered using PACVD and sputtering method had little to no pores. They also produced excellent
surface finish compared to Arc evaporation.

4.2. Microhardness

Microhardness of the samples were tested using Vickers Hardness method. The diamond indenter
produced a force 100 kgf for 15 seconds on the sample, the diagonals lengths of the indentation produce
the hardness value of the samples in HV. The uncoated sample showed an average value of 3278.98
MPa, which a bit lower than the industry standard titanium alloy Ti-6AL-4V which has a hardness value
of approximately 3600 MPa. TiN and AlCroNa Pro coating showed gradual increment in hardness value
at 4910.57 MPa and 8588 MPa respectively. These coating showed an improvement in hardness of
almost 1.5 – 2.6 times the base metal OT4-1. WCC and DLC coating showed extreme hardness with an
average value of 17140.28 MPa and 16068.2 MPa respectively. These coating increased the hardness
of the base metal by at least 5 times. These levels of hardness are very difficult to process when coated
on large equipment’s. the Figure 25 shows the graph of microhardness value of all coating in
comparison with the base metal OT4-1.

Fig. 25 Microhardness values of Uncoated OT4-1 and all coated samples of OT4-1

4.3. Wear Resistance

The coated and uncoated samples of Titanium alloy OT4-1 were tested for wear resistance using Pin-
on-disc wear testing machine. The specimens were subjected to 2.5kg or approximately 25 N of force
on a rotating disc of 40 cm diameter which was running at a speed of 500 rpm for 10 minutes. Following
the results of microhardness Tungsten carbide carbon was the most wear resistant coating, with a wear
rate of 0.02707 mm3/m, which is almost 6 times more wear resistant than the uncoated sample OT4-1,
which showed a wear rate of 0.15635 mm3/m. AlCroNa Pro coating showed the next best wear rate of
0.04227 mm3/m/, which is approximately 3.7 times more wear resistant than uncoated sample OT4-1.
This coating lost less weigh when measured after the testing compared to DLC coating. Therefore, the
most wear resistant coating were Tungsten Carbide and AlCroNa pro followed by DLC and TiN. Figure
26 shows a graph of all coating on OT4-1 in order of its wear rate from lowest to highest.

Fig. 26 Wear of coated samples, DLC, TiN, AlCroNa Pro, WCC

4.4. Corrosion Resistance

Titanium and its alloys do not show any type of rust until at least 1200 hours of them being exposed to
corrosive medium. Since replicating this is difficult, an Electrochemical workstation was used to test
the corrosion resistance of the samples. The medium in which the test conducted was 3.5% NaCl
solution. This specimen was polarised to -300 mV catholically and +1000 mV anodically with respect
to the OCP at a scan rate of 21.6727 mV/min. the potentio-dynamic polarisation curves obtained after
testing showed that AlCroNa Pro followed by WCC coating consumed the most current. The same two
coating showed least corrosion rate of 1.115 × 10-4 and 2.113 × 10-4 respectively in comparison with
the uncoated sample OT4-1. The coating of AlCroNa pro improved the base metals’ corrosion
resistance by 47.6%. Figure 27 shows the Tofel graphs of all coated specimens in comparison with
uncoated sample OT4-1. Red lines are the uncoated OT4-1, pinks ones are TiN coated OT4-1, grey
describe the DLC coating, yellow lines are WCC coating and blue is the AlCroNa Pro coating.

TiN

OT4-1

AlCroNa Pro

WCC

DLC

Fig. 26 Potentio-dynamic polarization curves of AlCroNa Pro, WCC, DLC, TiN coated samples and
uncoated sample OT4-1
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