Minor Project

“Characterization and Nano-indentation Analysis

of Ni-W-P-TiO2 Coatings”

By
Hrishitava Sarkar
Class Roll Number-002111201164

Under the Supervision of

Prof. Gautam Majumdar

Department of Mechanical Engineering

Faculty of Engineering & Technology
Jadavpur University
Kolkata-700032

2023
Acknowledgement:
I extend my heartfelt appreciation to all the individuals and organizations who have been a part of this
minor project and have contributed to its successful completion. I would like to express my gratitude
to my project supervisor Prof. Gautam Majumdar for his guidance, expertise, and constant support
throughout the project duration.

I also acknowledge the important role of Mr. Biplab Baran Mandal and Mr. Rupam Mandal for helping
me to conduct the experiments successfully in laboratories. With their help, it became possible for me
to conduct the annealing and access the nono-indentation results.

Furthermore, I would like to acknowledge the support received from the Surface Engineering lab,
Jadavpur University for granting permission to conduct the research and providing necessary
resources. I am indebted to the entire Mechanical Engineering Department, Jadavpur University for
providing me with the facilities required during the course of project work. Finally, I would thank my
family for being supportive to me in every step of my life which boosts my energy to move forward in
my academic and future career life.

Hrishitava Sarkar

Date:
 Faculty of Engineering and Technology, Jadavpur University

CERTIFICATE OF SUPERVISOR

I hereby recommend that the project presented under my supervision by Mr Hrishitava

Sarkar entitled “Characterization and Nano-indentation Analysis of Ni-W-P-TiO2
Coatings” be accepted in fulfilment of the requirements for the minor project.

Countersigned by

Prof. Gautam Majumdar

Project Supervisor
 Table of Contents

I. Abstract 01
II. Introduction 02
III. Literature Review 04
IV. Objective 05
V. Methodology 05
VI. Experimental Setup 06
VII. Characterization Techniques 09
VIII. Comparison and Validation 13
IX. Results and Discussion 14
X. Conclusion 15
XI. Future Scope of Work 16
XII. References 17
I. Abstract:
This comprehensive project endeavors to delve into the intricate dynamics governing electroless
plating, with a focused exploration of deposition intricacies and the characterization Ni-W-P-TiO2
coating. Beyond optimizing deposition rates, the study aims to provide an in-depth understanding of
surface properties, encompassing roughness, microhardness, corrosion resistance, and wear resistance.
A distinctive aspect of this research involves a specialized emphasis on nanoindentation analysis. This
entails a meticulous comparison of experimental nanoindentation data for elastic modulus and
Poisson's ratio with predictions derived from the finite element analysis tool ABAQUS. Employing
advanced characterization techniques such as scanning electron microscopy (SEM), X-ray diffraction
(XRD), and microhardness testing, this study seeks to contribute nuanced insights to the existing body
of knowledge.

1
II. Introduction:
Electroless coating, also referred to as autocatalytic coating, represents a sophisticated method for
depositing a thin layer of metal or alternative materials onto a substrate, distinguishing itself from
electroplating by eliminating the need for an external electrical power source. Unlike electroplating,
which relies on an electric current, electroless coating offers a distinct set of advantages, making it a
preferred choice in various industries.
One noteworthy advantage is its ability to uniformly coat complex shapes and non-conductive
materials, a feat that traditional electroplating struggles to achieve. This unique attribute positions
electroless coating as an invaluable technique in industries such as automotive, electronics, and
aerospace, where diverse shapes and materials are commonplace. The process not only enhances the
substrate's corrosion resistance but also contributes to improved wear resistance, hardness, and
overall aesthetic appearance.
Despite its numerous benefits, electroless coating is not without its challenges. Potential drawbacks
include the prospect of high costs, intricacies in control mechanisms, environmental considerations
related to waste disposal, demanding requirements for surface preparation, limited compatibility with
certain materials, challenges in achieving precise thickness control, and the need for meticulous
maintenance of chemical baths. These considerations underscore the importance of a balanced
evaluation, as manufacturers weigh the advantages against the drawbacks, tailoring their choices to
specific needs and applications.
The versatility of electroless coating extends across a multitude of industries, including automotive,
electronics, aerospace, metal finishing, medical devices, plastics, and machinery. Its widespread
application stems from its ability to provide durable and functional treatments for various substrates,
offering corrosion resistance, wear protection, enhanced conductivity, and improved appearance. In
essence, while acknowledging the complexities and trade-offs involved, the unique advantages of
electroless coating solidify its status as a widely embraced method in the manufacturing sector.

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Advantages of Electroless Coating:
Electroless plating, distinguished by its ability to deposit uniform layers of metal or composite coatings
without the need for an external electrical power source, presents several notable advantages. Firstly,
the process ensures a consistent thickness of the coating on complex geometries and intricate surfaces,
providing a level of uniformity challenging to achieve through traditional electroplating methods. This
attribute makes electroless plating particularly advantageous in industries where intricate components
and irregular shapes are prevalent, such as electronics and aerospace.
Additionally, electroless plating offers enhanced corrosion resistance and hardness to the coated
materials, augmenting their durability and longevity. The uniform deposition facilitates the coating of
internal surfaces and recessed areas, further expanding its application in diverse fields. The adaptability
of the electroless plating process to a variety of substrates, including non-conductive materials, widens
its scope of application, rendering it a versatile and indispensable tool in surface engineering.
Disadvantages of Electroless Coating:
However, the electroless plating technique is not without its challenges. One significant disadvantage
lies in the waste generated during the process, particularly in terms of the chemical baths and solutions
employed. The disposal of these chemicals requires careful consideration to mitigate environmental
impact and adhere to regulatory standards. The chemicals used in electroless plating, often containing
toxic elements, necessitate meticulous handling and disposal procedures to ensure environmental
sustainability.
Moreover, the uniformity achieved by electroless plating can be a limitation in certain scenarios. In
applications where selective coating or variation in coating thickness is required, electroless plating
may not offer the desired level of control. The process also demands precise control of parameters
such as temperature, pH, and concentration, adding complexity to the operational procedures.
Despite these challenges, the advantages of electroless plating in terms of uniformity, corrosion
resistance, and applicability to diverse substrates underscore its continued significance in modern
surface engineering.

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III. Literature Review:
Ni-P Coating:
Nickel-Phosphorus (Ni-P) coatings stand as a stalwart in the realm of electroless plating, renowned for
their multifaceted properties and versatile applications. The corrosion-resistant nature of Ni-P coatings
makes them indispensable in industries where materials face challenging environments. Furthermore,
their commendable hardness adds an extra layer of durability, making them a preferred choice in
sectors such as automotive, electronics, and chemical processing. The homogeneous and conformal
deposition achieved through electroless Ni-P plating is particularly advantageous for complex and
irregular geometries, setting it apart as a key player in surface engineering.[1][2][3]

Ni-W-P Coating:
Nickel-Tungsten-Phosphorus (Ni-W-P) coatings emerge as a distinct evolution, offering heightened
mechanical properties compared to their Ni-P counterparts. The incorporation of tungsten introduces
a notable increase in hardness and wear resistance, making Ni-W-P coatings a preferred choice in
applications where durability is paramount. Industries such as aerospace and manufacturing leverage
the exceptional wear resistance of Ni-W-P coatings to enhance the lifespan and performance of critical
components. The intricate interplay of nickel, tungsten, and phosphorus in the matrix forms a robust
alloy, expanding the horizons of electroless plating capabilities.[4][5][6]

Ni-W-P-TiO2 Coating:
The synthesis of Nickel-Tungsten-Phosphorus-Titanium Dioxide (Ni-W-P-TiO2) coatings represents
a cutting-edge exploration within the electroless plating landscape. The integration of TiO2
nanoparticles introduces a new dimension to the coating, aiming to enhance properties such as hardness
and wear resistance. TiO2, known for its exceptional hardness and stability, is strategically
incorporated to fortify the coating matrix. The literature surrounding Ni-W-P-TiO2 coatings
emphasizes the need for a meticulous optimization of deposition parameters to harness the full
potential of this composite coating. Industries seeking to push the boundaries of performance in terms
of both mechanical strength and environmental resilience look to Ni-W-P-TiO2 coatings as a promising
avenue for innovation.[7][8]

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IV. Objective:
The primary objective of this project is to conduct an exhaustive assessment of surface properties,
coupled with a specialized focus on nano-indentation analysis. This entails a unique endeavour to
bridge the gap between experimental nano-indentation data and finite element analysis predictions,
contributing a nuanced layer to the overall exploration.

V. Methodology:
The electroless plating process is executed with meticulous precision, with critical variables such as
bath composition, temperature, and deposition time carefully controlled. The experimentation protocol
is designed not only to optimize deposition rates but also to ensure the reproducibility and reliability
of the obtained coatings. For nano-indentation analysis, specialized equipment and protocols are
employed to acquire experimental data for elastic modulus and Poisson's ratio, adding a layer of
precision to the mechanical property assessment.

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VI. Experimental Setup:
The various components of the experimental setup are as followed:
1. Electronic weighing machine: An electronic weighing scale is useful for making accurate
measurements of the weight of the chemicals.

Fig - Weighing Scale

2. Beakers: This are used for preparation of the bath and is used as the primary apparatus where the
process of electroless coating takes place.

Fig –Beakers
3. Graduated cylinders: These are some cylindrical apparatus with several markings up and down
the length of the container with the primary function dealing with proper measurement of a specific
volume of liquid with precision.

Fig - Graduated Cylinders

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4. Pipettes: Pipettes are of varying sizes, designed for accomplishing specific goals of volumes.
These are narrow glass cylindrical pipes, used for measuring an exact volume of liquid and placing it
into another container.

Fig - Pipettes (from eiscolab.com)

5. Magnetic Stirrer: A magnetic stirrer with hotplate a device widely used in laboratories and consists
of a rotating magnet or a stationary electromagnet that creates a rotating magnetic field. It is also used
for heating a solution in uniform, slow and controlled manner.

Fig - Magnetic Stirrer with Hotplate.

6. Laboratory thermometers: Laboratory thermometers are used to measure the temperature of
substances, air, systems, and other objects in a laboratory.

Fig - Lab Thermometer

7
7. Nano-Indenter: A nano-indenter is a precision instrument used for nano-mechanical testing,
employing a sharp, calibrated tip to measure mechanical properties such as hardness and elastic
modulus at the nanoscale level.

Fig – Nano-Indenter
8. Furnace: The furnace is used to anneal the coating at 400°C

Fig - Furnace

8
VII. Characterization Techniques:
The nano-indentation results of the Ni-P-W-TiO2 coating were acquired using a Berkovich-type
indenter. The investigation encompassed the generation of a load-versus-displacement graph specific
to the coating.

Additionally, a comprehensive dataset, including load, indentation depth, contact area, and reduced
elastic modulus, was compiled in tabular form from the aforementioned nano-indentation test.

9
A correlation among the reduced elastic modulus, Young's modulus of the indenter, Poisson's ratio of
the indenter, Young's modulus of the tested material, and Poisson's ratio of the tested material was
discerned from pertinent research papers.[9]

𝟏 𝟏−𝒗𝟐𝒊 𝟏−𝒗𝟐
= +
𝑬𝒓 𝑬𝒊 𝑬

The properties of the Berkovich indenter used in the experiment were:

Young’s Modulus, Ei = 1147 GPa and Poisson’s ratio νi = 0.07
Consequently, the only variables yet to be determined were the Poisson's ratio and elastic modulus of
the Ni-P-W-TiO2 coating. Employing the aforementioned equation, a prospective dataset was derived,
presenting potential values for the Poisson's ratio and elastic modulus.

Prospective dataset for As Plated Condition

Prospective dataset for Annealed at 400°C

Subsequently, the nano-indentation experiment was computationally simulated in ABAQUS using the
finite element method, employing the values derived from the prospective dataset.
The load displacement graph obtained from simulation was analysed using the following algorithm:

10
For Coating annealed at 400°C (Run-I):

Simulation for Coating annealed at 400°C (Run-I)

The load-displacement graph was obtained from the simulation.

Graph Obtained for ν=0.25 and E=102.09GPa

11
For Coating annealed at 400°C (Run-II):

Simulation for Coating annealed at 400°C (Run-I)

The load-displacement graph was obtained from the simulation.

Graph Obtained for ν=0.23 and E=103.14GPa

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VIII. Comparison and Validation:
The load-displacement graphs derived from simulations in both Run-I and Run-II were validated
against the existing experimental load-displacement graphs from the corresponding experiments. The
comparison revealed minimal deviation between the experimental and simulation results, affirming
the reliability of the simulations.
For Run-I:

For Run-II:

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IX. Results and Discussion:
Subsequently, the nano-indentation experiment was computationally simulated in ABAQUS using the
finite element method, employing the values derived from the prospective dataset. The comparison of
results between the experimental and simulated approaches reveals a discernible range for the Young's
modulus and Poisson's ratio of the Ni-P-W-TiO2 coating, annealed at 400°C, estimated to be between
0.24 and 0.25 and 102.09 GPa to 103.14 GPa, respectively. Nevertheless, it is imperative to
acknowledge certain limitations in achieving high accuracy and precision within the obtained results,
primarily attributed to constraints in computational analysis using the student software version.
Despite these computational limitations, the predictive model implemented in this study offers a cost-
effective alternative for forecasting material properties, thereby mitigating the associated experimental
costs. However, the model's inherent simplicity and reliance on computational approximations
necessitate a cautious interpretation of the obtained results. Consequently, it is recommended that
future investigations employ dedicated tests specifically designed for determining elastic modulus and
Poisson's ratio, thereby ensuring the validation and refinement of the predicted values.
In conclusion, while this study presents a valuable and cost-effective prediction model for estimating
material properties, it is essential to recognize its inherent limitations and the preliminary nature of the
results. The pursuit of greater accuracy and precision remains contingent upon accessing more robust
computational resources and conducting comprehensive experimental validations in subsequent
research endeavors.

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X. Conclusion:
In conclusion, this research endeavours to provide a comprehensive and detailed exploration into the
electroless plating mechanisms and performance details of Ni-W-P-TiO2 coatings. The incorporation
of nano-indentation analysis adds an innovative dimension, facilitating a nuanced understanding of the
electroless coatings mechanical behaviour at a nanoscale.
In summary, while this project has provided valuable insights and a cost-effective approach to
predicting material properties, it is essential to acknowledge the preliminary nature of the results and
the need for further validation and refinement in future studies. The pursuit of greater accuracy remains
an ongoing endeavour, necessitating access to advanced computational resources and a commitment
to rigorous experimental validations.

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XI. Future Scope of Work:
The field of electroless plating presents a plethora of promising opportunities for future advancements.
Notably, electroless plating has found widespread application across diverse industries, including
nanotechnology, renewable energy, 3D printing, and electronics. Its ability to precisely coat small
specimens makes it particularly valuable in the nanotechnology sector, where precision is paramount.
As manufacturing technologies continue to evolve, electroless coating holds the potential to play a
pivotal role in the 3D printing industry. Integration of electroless coating into the manufacturing
processes of 3D printers could significantly enhance the performance of the final products. This
integration may pave the way for innovations that improve the durability, conductivity, or other key
properties of 3D-printed objects, thereby expanding the capabilities of this rapidly advancing industry.
Moreover, the anticipatory simulation of mechanical properties, coupled with the integration of
predictive Artificial Intelligence (AI) and Machine Learning (ML) models, represents a pioneering
approach poised to alleviate the financial burden associated with preliminary experimental research.
This strategic combination not only offers the prospect of predicting mechanical properties but also
holds the potential to democratize the research landscape by making it more accessible and cost-
effective.
By harnessing simulation techniques, researchers can proactively estimate mechanical properties,
enabling a more informed and targeted approach to experimentation. The incorporation of predictive
AI and ML models further enhances the efficiency of this process, providing valuable insights into
material behaviours and characteristics. The synergy of simulation and predictive modelling aligns
with a broader trend in research toward leveraging advanced technologies to optimize resource
utilization.
This innovative methodology not only streamlines the initial stages of research but also fosters
inclusivity within the scientific community. The reduction in experimentation costs allows a broader
spectrum of researchers, including those with limited resources, to actively engage in meaningful
exploration and hypothesis testing. Consequently, the convergence of simulation and predictive
AI/ML models not only advances the efficiency of research but also contributes to a more equitable
distribution of scientific opportunities.
In conclusion, the integration of simulation-based predictions and predictive AI/ML models marks a
transformative paradigm in research methodology, promising to make scientific exploration more
accessible, cost-effective, and inclusive. This approach has the potential to reshape the dynamics of
preliminary research stages, facilitating a more democratized and collaborative research environment.

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XII. References:
[1] W. Riedel, Electroless Nickel Plating, Finishing Publications Ltd., 1991, p.2.
[2] M.H. Staia , E.J. Castillo , E.S. Puchi , B. Lewis , H.E. Hintermann, Wear
performance and mechanism of electroless Ni-P coating
[3] G.O. Mallory, J.B. Hajdu (Eds.), Electroless Plating: Fundamentals and
Applications, American Electroplaters and Surface Finisher Society, Orlando, FL,
1990
[4] J.N. Balaraju, K.S. Rajam, Surf. Coat. Technol. 195 (2005) 154.
[5] Chen XM, Li GY, Lian JS. Deposition of electroless Ni-P/Ni-W-P duplex coatings
on AZ91D magnesium alloy. Transactions of the Nonferrous Metals Society of China
2008;18(Suppl 1):s323-s328.
[6] Balaraju JN, Rajam KS. Electroless deposition of Ni-Cu-P, Ni-W-P and Ni-W-Cu-
P alloys. Surface and Coatings Technology 2005;195(2-3):154-161.
[7] J. Novaković, P. Vassiliou, Kl. Samara, T. Argyropoulos (2006)
Electroless NiP–TiO2 composite coatings: Their production and properties
Surface & Coatings Technology, 201
[8] Mandal, B.B., Kumar, V. & Oraon, B. Optimization, Prediction, and
Characterization of Electroless Ni-W-P-nanoTiO2 Composite Coatings on Pipeline
Steel. Arab J Sci Eng (2023).
[9] Michel Yetna N’Jock, Francine Roudet, I. Idriss, Olivier Bartier, Didier
Chicot.,Work-of-indentation coupled to contact stiffness for calculating elastic
modulus by instrumented indentation. Mechanics of Materials, Elsevier, 2016, 94,
170-179.

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